JP2006137876A - Ink for inkjet recording curable by radiation irradiation and method for producing lithographic printing plate using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ink for inkjet recording, which has high sensitivity to radiation irradiation, can form high-quality images, and has good storage stability and to provide a method for producing a lithographic printing plate, which requires no development treatment and enables formation of high-quality images with high printing durability. <P>SOLUTION: The ink for inkjet recording contains a color material, a polymerizable compound, and a photopolymerization initiation system and is curable by radiation irradiation, wherein the photopolymerization initiation system contains a sensitizing dye containing one or more types of compound selected from the group consisting of compounds, one of which compounds is represented by general formula (XIV) (formulae (XV) to (XXVI) are not shown) and a polymerization initiator. The method for producing a lithographic printing plate comprises injecting the ink on a hydrophilic support and then irradiating the resultant, so as to obtain a hydrophobic image. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an inkjet recording ink and a method for producing a lithographic printing plate using the same. Specifically, it is highly sensitive to radiation irradiation, can form high-quality images, has excellent storage stability, and does not require development processing, high printing durability, and high The present invention relates to a method for producing a lithographic printing plate capable of forming an image having an image quality.

As an image recording method for forming an image on a support such as paper based on an image data signal, there are an electrophotographic method, a sublimation type and a melt type thermal transfer method, an ink jet method and the like. In particular, the ink jet method ejects ink only to a required image portion and forms an image directly on a support, so that the ink can be used efficiently. Furthermore, it is excellent in that the apparatus is simple and has low noise.
In the inkjet image recording method, in order to fix the ejected ink on the support, a method of drying the ink in the air to remove the solvent, and a method of using an ink that can be cured by irradiation with radiation such as ultraviolet rays. Etc. are adopted. In particular, inks for ink jet recording that can be cured by irradiation with radiation such as ultraviolet rays (radiation curable ink for ink jet recording) have a relatively low odor, are quick-drying, have no ink absorbability, and are usually recorded directly. It is possible to obtain an image having no blur, high sensitivity, and high adhesion to the support even when the support is difficult. For example, Patent Document 1 provides an inkjet recording ink that has low irritation and sensitization and high safety even when applied to the skin. When such a radiation curable ink for ink jet recording is employed, there is a demand for sufficiently high sensitivity to radiation and high image quality of an image formed by a fixed ink. If the sensitivity to radiation is sufficiently high, there are many benefits such as high curability, reduction of power consumption of the radiation source, extension of life by reducing the load on the radiation source, prevention of low molecular weight substances due to insufficient curing, etc. Arise. In addition, high sensitivity is achieved particularly when the ink for inkjet recording is used as an image portion of a lithographic printing plate for offset printing, and the curing strength of the image portion is increased, and a lithographic printing plate having high printing durability can be obtained. It will be.
In general, as a method for increasing the sensitivity to radiation in a radiation curable polymerizable compound, use of various polymerization initiation systems is disclosed (Non-patent Document 1). However, there is no example in which an ink for ink-jet recording employs a polymerization initiation system that satisfies sufficient sensitivity and storage stability for scanning exposure. Also, there is no known use of a radiation curable ink jet recording ink satisfying the formation of high printing durability, high quality images, and storage stability for a lithographic printing plate.

JP 2003-192943 A Bruce M. Monroe et al., Chemical Revue, Vol. 93, (1993), pp. 435-448.

  Therefore, the object of the present invention is high sensitivity to low-output radiation, can form a high-quality image, does not require ink for inkjet recording with good storage stability, and development processing, An object of the present invention is to provide a method for producing a lithographic printing plate capable of forming a high printing durability and high quality image.

（一般式（XIV）中、Ａ¹はＳ又はＮＲ⁵⁰を表し、ここでＲ⁵⁰はアルキル基又はアリール基を表し、Ｌ²は隣接するＡ¹及び隣接する炭素原子と共同して前記増感色素の塩基性核を形成する非金属原子団を表し、Ｒ⁵¹及びＲ⁵²はそれぞれ独立に一価の非金属原子団を表すか、又は、互いに結合して前記増感色素の酸性核を形成する非金属原子団を表し、ＷはO又はＳを表す。）、

(一般式（XVI）中、Ａ²はＳ又はＮＲ⁵⁹を表し、ここでＲ⁵⁹はアルキル基又はアリール基を表し、Ｌ⁴は隣接するＡ²及び隣接する炭素原子と共同して前記増感色素の塩基性核を形成する非金属原子団を表し、Ｒ⁵³、Ｒ⁵⁴、Ｒ⁵⁵、Ｒ⁵⁶、Ｒ⁵⁷及びＲ⁵⁸はそれぞれ独立に一価の非金属原子団を表す。)、

（一般式（XVII）中、Ａ³及びＡ⁴はそれぞれ独立にＳ、ＮＲ⁶⁰又はＮＲ⁶³を表し、ここでＲ⁶⁰及びＲ⁶³はそれぞれ独立にアルキル基又はアリール基を表し、Ｌ⁵及びＬ⁶はそれぞれ独立に、隣接するＡ³、Ａ⁴及び隣接する炭素原子と共同して前記増感色素の塩基性核を形成する非金属原子団を表し、Ｒ⁶¹及びＲ⁶²はそれぞれ独立に一価の非金属原子団を表すか、又は、互いに結合して脂肪族環又は芳香族環を形成する。）

（一般式（XVIII）中、Ｒ⁶⁶は芳香族環又はヘテロ環を表し、Ａ⁵はＯ、Ｓ又はＮＲ⁶⁷を表し、Ｒ⁶⁴、Ｒ⁶⁵及びＲ⁶⁷はそれぞれ独立に一価の非金属原子団を表すか、又は、Ｒ⁶⁴とＲ⁶⁷及びＲ⁶⁵とＲ⁶⁷はそれぞれ互いに結合して脂肪族環又は芳香族環を形成する。）

（一般式（XIX）中、R¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸およびR⁹は、それぞれ独立に一価の非金属原子団を表し、但し、Ｒ¹およびＲ³のうちの少なくとも一つは、下記部分構造式（XIX-1）に示す一価の有機残基で表され、又は、R¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸およびR⁹は、それぞれ独立に、脂肪族環または芳香族環を形成するため結合する。

（部分構造式（XIX-1）中、R¹⁰は、一価の非金属原子団を表すか、又は、前記一般式（XIX）中のR¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸またはR⁹と脂肪族環または芳香族環を形成するため結合し、Ｚは隣接する原子と共同して５員環酸性核を形成するのに必要な２価の非金属原子団を表す。））

（一般式（XX）中、Ｒは一価の非金属原子団であり、Ｘは一価の非金属原子団であり、それぞれ互いに結合することができ、Ｙは５員環または６員環を表す。）

（一般式（XXI）中、Ａｒは芳香環を表し、Ａは−ＮＲ³Ｒ⁴、−ＳＲ⁵または−ＯＲ⁶を表し、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵及びＲ⁶はそれぞれ独立に一価の非金属原子団を表し、Ｚ^-は電荷の中和に必要なカウンターイオンを表す。）

（一般式（XXII）中、Ｙは、独立に酸素原子または硫黄原子を表し、Ｒ₁およびＲ₂は、それぞれ独立に水素原子以外の一価の非金属原子団を表し、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、Ｒ₇、Ｒ₈、Ｒ₉、Ｒ₁₀、Ｒ₁₁およびＲ₁₂は、それぞれ独立に一価の非金属原子団を表す。）

（一般式(XXIII)中、Ｘは、酸素原子または硫黄原子を表し、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、Ｒ₇およびＲ₈は、それぞれ独立に一価の非金属原子団を表し、Ａは炭素数２０以下のアリール基またはヘテロアリール基を表す。）

(一般式（XXIV）中、Ｘは、酸素原子または硫黄原子を表し、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、Ｒ₇およびＲ₈は、それぞれ独立に一価の非金属原子団を表す。)

（一般式(XXV)中、Ｘ₁〜Ｘ₅はそれぞれ独立に一価の非金属原子団を表し、Ｚはアリール基、またはヘテロアリール基を表す。）

（一般式（XXVI）中、Ｙは隣接するＮおよび炭素原子と共同して含窒素ヘテロ環を形成する非金属原子団を表し、Ｘは一価の非金属原子団を表す。） As a result of repeated studies, the present inventors can use a specific sensitizing dye together with a polymerization initiator to form a high-quality image that is highly sensitive to irradiation with low-power radiation. It was found that an ink for ink jet recording having good storage stability can be obtained. It was also found that when applied to a lithographic printing plate, it satisfies high printing durability and high-quality image formation and storage stability.
That is, the present invention
An ink for inkjet recording, which contains a colorant, a polymerizable compound, and a polymerization initiation system and is curable by irradiation with radiation, wherein the polymerization initiation system is represented by the following general formulas (XIV) and (XVI): The present invention relates to an ink for ink jet recording, comprising a sensitizing dye containing one or more compounds selected from the group consisting of compounds represented by (XXVI) and a polymerization initiator.

(In the general formula (XIV), A ¹ represents S or NR ⁵⁰ , wherein R ⁵⁰ represents an alkyl group or an aryl group, and L ² represents the sensitization in cooperation with the adjacent A ¹ and the adjacent carbon atom. Represents a non-metallic atomic group that forms a basic nucleus of the dye, and R ⁵¹ and R ⁵² each independently represent a monovalent non-metallic atomic group, or are bonded to each other to form an acidic nucleus of the sensitizing dye. And W represents O or S).

(In the general formula (XVI), A ² represents S or NR ⁵⁹ , wherein R ⁵⁹ represents an alkyl group or an aryl group, and L ⁴ represents the sensitization in combination with the adjacent A ² and the adjacent carbon atom. Represents a non-metallic atomic group forming a basic nucleus of the dye, and R ⁵³ , R ⁵⁴ , R ⁵⁵ , R ⁵⁶ , R ⁵⁷ and R ⁵⁸ each independently represents a monovalent non-metallic atomic group).

(In General Formula (XVII), A ³ and A ⁴ each independently represent S, NR ⁶⁰ or NR ⁶³ , wherein R ⁶⁰ and R ⁶³ each independently represent an alkyl group or an aryl group, and L ⁵ and L ⁶ independently represents a nonmetallic atomic group that forms a basic nucleus of the sensitizing dye in combination with adjacent A ³ , A ⁴ and adjacent carbon atoms, and R ⁶¹ and R ⁶² each independently Represents a non-valent metal valence group, or is bonded to each other to form an aliphatic ring or an aromatic ring.)

(In the general formula (XVIII), R ⁶⁶ represents an aromatic ring or a hetero ring, A ⁵ represents O, S or NR ⁶⁷ , and R ⁶⁴ , R ⁶⁵ and R ⁶⁷ each independently represents a monovalent nonmetallic atom. Or R ⁶⁴ and R ⁶⁷ and R ⁶⁵ and R ⁶⁷ are bonded to each other to form an aliphatic ring or an aromatic ring.)

(In the general formula (XIX), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ each independently represents a monovalent nonmetallic atomic group, provided that , R ¹ and R ³ are each represented by a monovalent organic residue represented by the following partial structural formula (XIX-1), or R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently bonded to form an aliphatic ring or an aromatic ring.

(In the partial structural formula (XIX-1), R ¹⁰ represents a monovalent nonmetallic atomic group, or R ¹ , R ² , R ³ , R ⁴ , R ^{5 in the} general formula (XIX). , R ⁶ , R ⁷ , R ⁸ or R ⁹ are bonded to form an aliphatic ring or an aromatic ring, and Z is divalent necessary to form a 5-membered acidic nucleus together with adjacent atoms. Represents a nonmetallic atomic group of

(In the general formula (XX), R is a monovalent nonmetallic atomic group, X is a monovalent nonmetallic atomic group, and each can be bonded to each other, and Y is a 5-membered or 6-membered ring. To express.)

(In the general formula (XXI), Ar represents an aromatic ring, A represents —NR ³ R ⁴ , —SR ⁵ or —OR ⁶ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ^6. Each independently represents a monovalent non-metallic atomic group, and Z ⁻ represents a counter ion necessary for charge neutralization.)

(In General Formula (XXII), Y independently represents an oxygen atom or a sulfur atom, R ₁ and R ₂ each independently represent a monovalent nonmetallic atomic group other than a hydrogen atom, and R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ and R ₁₂ each independently represents a monovalent nonmetallic atomic group.)

(In the general formula (XXIII), X represents an oxygen atom or a sulfur atom, and R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are each independently monovalent. Represents a nonmetallic atomic group, and A represents an aryl group or heteroaryl group having 20 or less carbon atoms.)

(In the general formula (XXIV), X represents an oxygen atom or a sulfur atom, and R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are each independently monovalent. Represents a non-metallic atomic group.)

(In the general formula (XXV), X _{1 to} X ₅ each independently represents a monovalent nonmetallic atomic group, and Z represents an aryl group or a heteroaryl group.)

(In general formula (XXVI), Y represents a nonmetallic atomic group that forms a nitrogen-containing heterocycle in cooperation with adjacent N and carbon atoms, and X represents a monovalent nonmetallic atomic group.)

2. The present invention also provides a method for forming an image on a support,
(a) applying the inkjet recording ink according to claim 1 on the support;
(b) curing the inkjet recording ink by irradiating the inkjet recording ink with radiation having a peak wavelength of 350 to 420 nm with an irradiation energy of 2000 mJ / cm ² or less; and
(c) the cured ink jet recording ink forms an image on the support,
A method comprising:
3. Furthermore, the present invention relates to the method described in 2 above, wherein the sensitizing dye contained in the ink jet recording ink has a maximum absorption value at 350 to 420 nm.
4). In addition, the present invention is a method for producing a lithographic printing plate having a support and an image formed on the support,
(1) a step of ejecting the ink for inkjet recording described in 1 above onto the support; and
(2) A step of irradiating the support on which the ink is ejected to cure the ink and forming an image formed by curing the ink on the support;
And a method comprising:

High sensitivity to radiation, high-quality images can be formed, ink composition for ink-jet recording with good storage stability, and development processing is unnecessary, high printing durability, and high image quality The present invention relates to a method for producing a lithographic printing plate capable of forming an image.
The present invention provides an ink jet recording ink that is highly sensitive to short-wavelength radiation having a peak wavelength of, for example, 350 to 450 nm, can form high-quality images, and has good storage stability. The In addition, the present invention provides a method for producing a lithographic printing plate that does not require a development process and that can form a high printing durability and high-quality image.

As described above, the present invention is an ink jet recording ink that contains a colorant, a polymerizable compound, and a polymerization initiation system and is curable by irradiation with radiation, wherein the polymerization initiation system is a polymerization initiator. And an sensitizing dye. The present invention relates to an ink for ink jet recording. Hereinafter, the present invention will be described in detail.
(1) Polymerization Initiating System The ink for inkjet recording of the present invention includes a polymerization initiating system. The polymerization initiation system includes a sensitizing dye, a polymerization initiator, and optionally other additives.

一般式（XIV）中、Ａ¹はＳ又はＮＲ⁵⁰、好ましくはＳを表す。ここでＲ⁵⁰はアルキル基又はアリール基を表す。ここで、アルキル基及びアリール基は、置換されていてもよい。
好ましいアルキル基の例としては、炭素原子数が１から２０までの直鎖状、分岐状、および環状のアルキル基を挙げることができ、その具体例としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、トリデシル基、ヘキサデシル基、オクタデシル基、エイコシル基、イソプロピル基、イソブチル基、ｓ−ブチル基、ｔ−ブチル基、イソペンチル基、ネオペンチル基、１−メチルブチル基、イソヘキシル基、２−エチルヘキシル基、２−メチルヘキシル基、シクロヘキシル基、シクロペンチル基、２−ノルボルニル基を挙げることができる。これらの中では、炭素原子数１から１２までの直鎖状、炭素原子数３から１２までの分岐状、ならびに炭素原子数５から１０までの環状のアルキル基がより好ましい。
置換アルキル基の置換基としては、水素を除く一価の非金属原子団が用いられ、好ましい例としては、ハロゲン原子（−Ｆ、−Ｂｒ、−Ｃｌ、−Ｉ）、ヒドロキシル基、アルコキシ基、アリーロキシ基、メルカプト基、アルキルチオ基、アリールチオ基、アルキルジチオ基、アリールジチオ基、アミノ基、Ｎ−アルキルアミノ基、Ｎ，Ｎ−ジアルキルアミノ基、Ｎ−アリールアミノ基、Ｎ，Ｎ−ジアリールアミノ基、Ｎ−アルキル−Ｎ−アリールアミノ基、アシルオキシ基、カルバモイルオキシ基、Ｎ−アルキルカルバモイルオキシ基、Ｎ−アリールカルバモイルオキシ基、Ｎ，Ｎ−ジアルキルカルバモイルオキシ基、Ｎ，Ｎ−ジアリールカルバモイルオキシ基、Ｎ−アルキル−Ｎ−アリールカルバモイルオキシ基、アルキルスルホキシ基、アリールスルホキシ基、アシルチオ基、アシルアミノ基、Ｎ−アルキルアシルアミノ基、Ｎ−アリールアシルアミノ基、ウレイド基、Ｎ′−アルキルウレイド基、Ｎ′，Ｎ′−ジアルキルウレイド基、Ｎ′−アリールウレイド基、Ｎ′，Ｎ′−ジアリールウレイド基、Ｎ′−アルキル−Ｎ′−アリールウレイド基、Ｎ−アルキルウレイド基、Ｎ−アリールウレイド基、Ｎ′−アルキル−Ｎ−アルキルウレイド基、Ｎ′−アルキル−Ｎ−アリールウレイド基、Ｎ′，Ｎ′−ジアルキル−Ｎ−アルキルウレイド基、Ｎ′，Ｎ′−ジアルキル−Ｎ−アリールウレイド基、Ｎ′−アリール−Ｎ−アルキルウレイド基、Ｎ′−アリール−Ｎ−アリールウレイド基、Ｎ′，Ｎ′−ジアリール−Ｎ−アルキルウレイド基、Ｎ′，Ｎ′−ジアリール−Ｎ−アリールウレイド基、Ｎ′−アルキル−Ｎ′−アリール−Ｎ−アルキルウレイド基、Ｎ′−アルキル−Ｎ′−アリール−Ｎ−アリールウレイド基、 (1-1) Sensitizing dye The sensitizing dye of the present invention contains one or more compounds selected from the group consisting of compounds represented by the following general formula (XIV) and general formulas (XVI) to (XXVI). .
(1-1-1) Types of sensitizing dye

In the general formula (XIV), A ¹ represents S or NR ⁵⁰ , preferably S. Here, R ⁵⁰ represents an alkyl group or an aryl group. Here, the alkyl group and the aryl group may be substituted.
Examples of preferable alkyl groups include linear, branched, and cyclic alkyl groups having 1 to 20 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, a propyl group, Butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, octadecyl, eicosyl, isopropyl, isobutyl, s-butyl, Examples thereof include t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group and 2-norbornyl group. Of these, linear alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, and cyclic alkyl groups having 5 to 10 carbon atoms are more preferable.
As the substituent of the substituted alkyl group, a monovalent nonmetallic atomic group excluding hydrogen is used, and preferred examples include a halogen atom (—F, —Br, —Cl, —I), a hydroxyl group, an alkoxy group, Aryloxy group, mercapto group, alkylthio group, arylthio group, alkyldithio group, aryldithio group, amino group, N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diarylamino group N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N-arylcarbamoyloxy group, alkylsulfoxy group, Reelsulfoxy group, acylthio group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N'-alkylureido group, N ', N'-dialkylureido group, N'-arylureido Group, N ′, N′-diarylureido group, N′-alkyl-N′-arylureido group, N-alkylureido group, N-arylureido group, N′-alkyl-N-alkylureido group, N′- Alkyl-N-arylureido group, N ', N'-dialkyl-N-alkylureido group, N', N'-dialkyl-N-arylureido group, N'-aryl-N-alkylureido group, N'- Aryl-N-arylureido group, N ′, N′-diaryl-N-alkylureido group, N ′, N′-diaryl-N-ary Ruureido group, N'- alkyl -N'- aryl -N- alkylureido group, N'- alkyl -N'- aryl -N- arylureido group,

Alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N -Aryloxycarbonylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N- di arylcarbamoyl, N- alkyl -N- arylcarbamoyl groups, alkylsulfinyl groups, arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfo group (-SO ₃ H) and its conjugated base group (hereinafter Sulfonate group), alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diaryls Rufinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-diaryl Sulfamoyl group, N-alkyl-N-arylsulfamoyl group, phosphono group (—PO ₃ H ₂ ) and its conjugate base group (hereinafter referred to as phosphonate group), dialkyl phosphono group (—PO ₃ (alkyl) ) _2), diaryl phosphono group (-PO ₃ (aryl) _2), alkyl aryl phosphono group ( PO ₃ (alkyl) (aryl)), monoalkyl phosphono group (-PO ₃ H (alkyl)) and its conjugated base group (hereinafter referred to as alkyl phosphonophenyl group),

Monoaryl phosphono group (—PO ₃ H (aryl)) and its conjugate base group (hereinafter referred to as aryl phosphonate group), phosphonooxy group (—OPO ₃ H ₂ ) and its conjugate base group (hereinafter referred to as phosphine group) A dialkylphosphonooxy group (—OPO ₃ (alkyl) ₂ ), a diarylphosphonooxy group (—OPO ₃ (aryl) ₂ ), an alkylarylphosphonooxy group (—OPO ₃ (alkyl)) (aryl)), a monoalkylphosphonooxy group (—OPO ₃ H (alkyl)) and its conjugate base group (hereinafter referred to as an alkylphosphonatooxy group), a monoarylphosphonooxy group (—OPO ₃ H (aryl) )) And conjugated base groups thereof (hereinafter referred to as arylphosphonateoxy groups), cyano groups, nitro groups, aryl groups, heteroaryl groups, alkenyl groups, and alkynyl groups. .

  Specific examples of the alkyl group in these substituents include the above-described alkyl groups, and specific examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, a xylyl group, a mesityl group, and a cumenyl group. , Chlorophenyl group, bromophenyl group, chloromethylphenyl group, hydroxyphenyl group, methoxyphenyl group, ethoxyphenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group, methylamino Phenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, ethoxyphenylcarbonyl group, phenoxycarbonylphenyl group, N-phenylcarbamoylphenyl group, phenyl group Cyanophenyl group, sulfophenyl group, sulfonatophenyl group, phosphonophenyl phenyl group, phosphonophenyl phenyl group and the like.

As the heteroaryl group, a monocyclic or polycyclic aromatic ring containing at least one of nitrogen, oxygen and sulfur atoms is used, and preferably 5 or 6 members such as furan, pyrrole or pyridine. Ring aromatic substituents can be used.
Examples of the alkenyl group include a vinyl group, 1-propenyl group, 1-butenyl group, cinnamyl group, 2-chloro-1-ethenyl group, and the like. Examples of the alkynyl group include ethynyl group, 1- A propynyl group, a 1-butynyl group, a trimethylsilylethynyl group, etc. are mentioned. Examples of G ¹ in the acyl group (G ¹ CO—) include hydrogen and the above alkyl groups and aryl groups. Among these substituents, even more preferred are halogen atoms (—F, —Br, —Cl, —I), alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, N-alkylamino groups, N, N -Dialkylamino group, acyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, acylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group Group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, sulfo group, sulfonate group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfa group Moyl group, N-aryl sulf Moyl group, N-alkyl-N-arylsulfamoyl group, phosphono group, phosphonate group, dialkyl phosphono group, diaryl phosphono group, monoalkyl phosphono group, alkyl phosphonate group, monoaryl phosphono group, aryl phosphine group Examples include an onato group, a phosphonooxy group, a phosphonateoxy group, an aryl group, and an alkenyl group.

  On the other hand, examples of the alkylene group in the substituted alkyl group include divalent organic residues obtained by removing any one of the hydrogen atoms on the alkyl group having 1 to 20 carbon atoms. Can include linear alkylene groups having 1 to 12 carbon atoms, branched chains having 3 to 12 carbon atoms, and cyclic alkylene groups having 5 to 10 carbon atoms.

Specific examples of the substituted alkyl group preferable as R ⁵⁰ obtained by combining the substituent and the alkylene group include chloromethyl group, bromomethyl group, 2-chloroethyl group, trifluoromethyl group, methoxymethyl group, methoxyethoxyethyl. Group, allyloxymethyl group, phenoxymethyl group, methylthiomethyl group, tolylthiomethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyloxymethyl group, benzoyloxymethyl group, N-cyclohexylcarbamoyloxyethyl group N-phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxoethyl group, 2-oxopropyl group, carboxypropyl group, methoxycarbonylethyl group, Ruoxycarbonylbutyl group, chlorophenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl group, N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, N-methyl-N- ( Sulfophenyl) carbamoylmethyl group, sulfobutyl group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N-dipropylsulfamoylpropyl group, N-tolylsulfamoylpropyl group, N- Methyl-N- (phosphonophenyl) sulfamoyloctyl group, phosphonobutyl group, phosphonatohexyl group, diethylphosphonobutyl group, diphenylphosphonopropyl group, methylphosphonobutyl group, methylphosphonatobutyl group, tolylpho Phonohexyl group, tolylphosphonatohexyl group, phosphonooxypropyl group, phosphonatooxybutyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-methyl-1-phenylethyl group, p-methylbenzyl group, Cinnamyl group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2-methylallyl group, 2-methylpropenylmethyl group, 2-propynyl group, 2-butynyl group, 3-butynyl group and the like can be mentioned. .

Specific examples of preferred aryl groups for R ⁵⁰ include those in which 1 to 3 benzene rings form a condensed ring, and those in which a benzene ring and a 5-membered unsaturated ring form a condensed ring. Examples include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenaphthenyl group, and a fluorenyl group. Among these, a phenyl group and a naphthyl group are more preferable.
The aryl group may be substituted. As a specific example of a substituted aryl group preferable as R ⁵⁰ , those having a monovalent nonmetallic atomic group excluding hydrogen as a substituent on the ring-forming carbon atom of the aforementioned aryl group are used. Examples of preferred substituents include the alkyl groups, substituted alkyl groups, and those previously shown as substituents in the substituted alkyl group. Preferred examples of such a substituted aryl group include biphenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, fluorophenyl group, chloromethylphenyl group, trifluoromethylphenyl group. Hydroxyphenyl group, methoxyphenyl group, methoxyethoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, methylthiophenyl group, tolylthiophenyl group, ethylaminophenyl group, diethylaminophenyl group, morpholinophenyl group, acetyloxyphenyl group, Benzoyloxyphenyl group, N-cyclohexylcarbamoyloxyphenyl group, N-phenylcarbamoyloxyphenyl group, acetylaminophenyl group, N-methylbenzoylaminophenyl group, carbo Cyphenyl group, methoxycarbonylphenyl group, allyloxycarbonylphenyl group, chlorophenoxycarbonylphenyl group, carbamoylphenyl group, N-methylcarbamoylphenyl group, N, N-dipropylcarbamoylphenyl group, N- (methoxyphenyl) carbamoylphenyl group N-methyl-N- (sulfophenyl) carbamoylphenyl group, sulfophenyl group, sulfonatophenyl group, sulfamoylphenyl group, N-ethylsulfamoylphenyl group, N, N-dipropylsulfamoylphenyl group, N-tolylsulfamoylphenyl group, N-methyl-N- (phosphonophenyl) sulfamoylphenyl group, phosphonophenyl group, phosphonatophenyl group, diethylphosphonophenyl group, diphenylphosphono Enyl group, methylphosphonophenyl group, methylphosphonatophenyl group, tolylphosphonophenyl group, tolylphosphonatophenyl group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2-methylallylphenyl group, 2- Examples thereof include a methylpropenylphenyl group, a 2-propynylphenyl group, a 2-butynylphenyl group, and a 3-butynylphenyl group.

R ⁵¹ and R ⁵² each independently represent a monovalent nonmetallic atomic group. Examples of the monovalent nonmetallic atomic group include a hydrogen atom, a halogen atom (—F, —Br, —Cl, —I), a hydroxyl group, an alkoxy group, an aryloxy group, a mercapto group, an alkylthio group, an arylthio group, an alkyl group. Dithio group, aryldithio group, amino group, N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, acyloxy group , Carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N-arylcarbamoyloxy group, alkylsulfo Xyl group, arylsulfoxy group, acylthio group, acylamido Group, N-alkylacylamino group, N-arylacylamino group, ureido group, N′-alkylureido group, N ′, N′-dialkylureido group, N′-arylureido group, N ′, N′-diaryl Ureido group, N'-alkyl-N'-arylureido group, N-alkylureido group, N-arylureido group, N'-alkyl-N-alkylureido group, N'-alkyl-N-arylureido group, N ', N'-dialkyl-N-alkylureido group, N', N'-dialkyl-N-arylureido group, N'-aryl-N-alkylureido group, N'-aryl-N-arylureido group, N ', N'-diaryl-N-alkylureido group, N', N'-diaryl-N-arylureido group, N'-alkyl-N'-aryl N-alkylureido group, N′-alkyl-N′-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N— Aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, alkylsulfinyl group, arylsulfinyl group, alkyls Sulfonyl group, arylsulfonyl group, sulfo group (—SO ₃ H) and its conjugate base group (hereinafter referred to as sulfonate group), alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkylsulfinamoyl group, N , N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, phosphono group (—PO ₃ H ₂ ) and Its conjugated base group (hereinafter referred to as phosphonate group), dialkylphosphono group (—PO ₃ (alk yl) ₂ ), diaryl phosphono group (—PO ₃ (aryl) ₂ ), alkylaryl phosphono group (—PO ₃ (alkyl) (aryl)), monoalkyl phosphono group (—PO ₃ H (alkyl)) And its conjugate base group (hereinafter referred to as alkyl phosphonate group), monoaryl phosphono group (—PO ₃ H (aryl)) and its conjugate base group (hereinafter referred to as aryl phosphonate group), phosphonooxy group (—OPO ₃ H ₂ ) and its conjugate base group (hereinafter referred to as phosphonatooxy group), dialkylphosphonooxy group (—OPO ₃ (alkyl) ₂ ), diarylphosphonooxy group (—OPO ₃ (aryl)) ₂ ), an alkylarylphosphonooxy group (—OPO ₃ (alkyl) (aryl)), a monoalkylphosphonooxy group (—OPO ₃ H (alkyl)) and a conjugated base group thereof (hereinafter referred to as an alkylphosphonatooxy group) Call) Monoaryl phosphonooxy group (-OPO ₃ H (aryl)) and its conjugated base group (hereinafter referred to as aryl phosphite Hona preparative group), a cyano group, a nitro group, a substituted or unsubstituted aryl group, a heteroaryl group, Examples thereof include an alkenyl group and an alkynyl group, and more specific examples thereof are those described above for R ⁵⁰ .

R ⁵¹ and R ⁵² may represent a nonmetallic atomic group that is bonded to each other to form an acidic nucleus of the sensitizing dye. Here, examples of acidic nuclei include acidic nuclei in merocyanine pigments described in LGBrooker et al., J. Am. Chem. Soc., 73, 5326-5358 (1951). .
Specific examples of the acidic nucleus include a 1,3-dicarbonyl nucleus (for example, 1,3-indandione, 1,3-cyclohexanedione, 5,5-dimethylcyclohexanedione, 1,3-dioxane-4,6- Dione etc.), pyrazolinone nucleus (for example, 3-methyl-1-phenyl-2-pyrazolin-5-one, 1-phenyl-2-pyrazolin-5-one, 1- (2-benzothiazolyl) -3-methyl-2-pyrazolin -5-one etc.), isoxazolinone nuclei (eg 3-phenyl-2-isoxazolin-5-one, 3-methyl-2-isoxazolin-5-one etc.), oxindole nuclei (eg 1 -Alkyl-2,3-dihydro-2-oxindole, etc.), 2,4,6-trioxohexahydropyrimidine nucleus (eg barbituric acid or 2-thio Barbituric acid and its N-substituted derivatives, such as 1,3-diethylbarbituric acid, 1,3-diethyl-2-thiobarbituric acid, 1,3-dibutylbarbituric acid, 1,3-dibutyl-2-thiobarbituric acid, 1,3-diphenylbarbituric acid, 1,3-diphenyl-2-thiobarbituric acid, 1,3-dimethoxycarbonylmethylbarbituric acid, 1,3-dimethoxycarbonylmethyl-2-thiobarbituric acid, etc.), 2-thio- 2,4-thiazolidinedione nuclei (eg, rhodanine and its N-substituted derivatives such as 3-methylrhodanine, 3-ethylrhodanine, 3-phenylrhodanine, 3-allylrhodanine, 3-benzylrhodanine, 3 -Carboxymethyl rhodanine, 3-carboxyethyl rhodanine, 3-methoxycarbonylmethyl -Danine, 3-hydroxyethylrhodanine, 3-morpholinoethylrhodanine, etc.), 2-thio-2,4-oxazolidinedione nucleus (ie 2-thio-2,4- (3H, 4H) -oxazoledione) Nucleus, such as 2-ethyl-2-thio-2,4-oxazolidinedione), thianaphthenone nucleus (such as 3 (2H) -thianaphthenone, 3 (2H) -thianaphthenone-1,1-dioxide), 2 -Thio-2,5-thiazolidinedione nucleus (for example, 3-ethyl-2-thio-2,5-thiazolidinedione, etc.), 2,4-thiazolidinedione nucleus (for example, 2,4-thiazolidinedione, 3-ethyl- 2,4-thiazolidinedione, 3-phenyl-2,4-thiazolidinedione, etc.), thiazolidinone nucleus (for example, 4-thiazolidinone, 3-e Til-4-thiazolidinone, 2-ethylmercapto-4-thizolidinone, 2-methylphenylamino-4-thizolidinone, etc.), 2-imino-2-oxazolin-4-one nucleus (ie, pseudohydantoin nucleus), 2,4 An imidazolidinedione nucleus (ie, a hydantoin nucleus such as 2,4-imidazolidinedione, 3-ethyl-2,4-imidazolidinedione, 1,3-diethyl-2,4-imidazolidinedione, etc.), 2 A thio-2,4-imidazolidinedione nucleus (ie a thiohydantoin nucleus such as 2-thio-2,4-imidazolidinedione, 3-ethyl-2-thio-2,4-imidazolidinedione, 1, 3-diethyl-2-thio-2,4-imidazolidinedione, etc.), imidazolin-5-one nucleus (for example, 2-propylmercapto-2-imidazole) Phosphorus-5-one, etc.), furan-5-one nucleus, 4-hydroxy-2 (1H) -pyridinone nucleus (eg, N-methyl-4-hydroxy-2 (1H) -pyridinone, N-methyl-4- Hydroxy-2 (1H) -quinolinone, N-butyl-4-hydroxy-2 (1H) -quinolinone, etc.), 4-hydroxy-2H-pyran-2-one nucleus (for example, 4-hydroxycoumarin etc.), thioindo A xyl nucleus (for example, 5-methylthioindoxyl etc.) etc. are mention | raise | lifted and these acidic nuclei may have a substituent further.

L ² represents a nonmetallic atomic group that forms a basic nucleus of the sensitizing dye in cooperation with the adjacent A ¹ and the adjacent carbon atom. Here, examples of the basic nucleus include heterocycles such as 5-, 6-, and 7-membered nitrogen-containing or sulfur-containing heterocycles, and preferably 5- or 6-membered heterocycles.
Here, as an example of the nitrogen-containing heterocycle, the basic nucleus in the merocyanine dyes described in LGBrooker et al., J. Am. Chem. Soc., 73, 5326-5358 (1951). Any of those known as constituents can be suitably used. Specific examples include thiazoles (for example, thiazole, 4-methylthiazole, 4-phenylthiazole, 5-methylthiazole, 5-phenylthiazole, 4,5-dimethylthiazole, 4,5-diphenylthiazole, 4,5- Di (p-methoxyphenylthiazole), 4- (2-thienyl) thiazole, etc.), benzothiazoles (for example, benzothiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, 7- Chlorobenzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, 5-bromobenzothiazole, 4-phenylbenzothiazole, 5-phenylbenzothiazole, 4-methoxybenzothiazole, 5-methoxybenzo Cheer , 6-methoxybenzothiazole, 5-iodobenzothiazole, 6-iodobenzothiazole, 4-ethoxybenzothiazole, 5-ethoxybenzothiazole, tetrahydrobenzothiazole, 5,6-dimethoxybenzothiazole, 5,6-di Oxymethylenebenzothiazole, 5-hydroxybenzothiazole, 6-hydroxybenzothiazole, 6-dimethylaminobenzothiazole, 5-ethoxycarbonylbenzothiazole, etc.), naphthothiazoles (for example, naphtho [1,2] thiazole, naphtho [ 2,1] thiazole, 5-methoxynaphtho [2,1] thiazole, 5-ethoxynaphtho [2,1] thiazole, 8-methoxynaphtho [1,2] thiazole, 7-methoxynaphtho [1,2] thiazole, Etc.), Chianafu -7 ', 6', 4,5-thiazole (for example, 4'-methoxythianaphtheno-7 ', 6', 4,5-thiazole, etc.), oxazole (for example, 4-methyloxazole, 5 -Methyl oxazole, 4-phenyl oxazole, 4,5-diphenyl oxazole, 4-ethyl oxazole, 4,5-dimethyl oxazole, 5-phenyl oxazole, etc.), benzoxazoles (benzoxazole, 5-chlorobenzoxazole, 5- Methylbenzoxazole, 5-phenylbenzoxazole, 6-methylbenzoxazole, 5,6-dimethylbenzoxazole, 4,6-dimethylbenzoxazole, 6-methoxybenzoxazole, 5-methoxybenzoxazole, 4-ethoxybenzoxazole, 5-chlorobenzo Oxazole, 6-methoxybenzoxazole, 5-hydroxybenzoxazole, 6-hydroxybenzoxazole, etc.), naphthoxazoles (for example, naphtho [1,2] oxazole, naphtho [2,1] oxazole, etc.), selenazoles (For example, 4-methylselenazole, 4-phenylselenazole, etc.), benzoselenazoles (for example, benzoselenazole, 5-chlorobenzoselenazole, 5-methoxybenzoselenazole, 5-hydroxybenzoselenazole, Tetrahydrobenzoselenazole, etc.), naphthoselenazoles (eg, naphtho [1,2] selenazole, naphtho [2,1] selenazole, etc.), thiazolines (eg, thiazoline, 4-methylthiazoline, etc.), 2 Quinolines (eg quino 3-methylquinoline, 5-methylquinoline, 7-methylquinoline, 8-methylquinoline, 6-chloroquinoline, 8-chloroquinoline, 6-methoxyquinoline, 6-ethoxyquinoline, 6-hydroxyquinoline, 8-hydroxy Quinoline, etc.), 4-quinolines (eg, quinoline, 6-methoxyquinoline, 7-methylquinoline, 8-methylquinoline, etc.), 1-isoquinolines (eg, isoquinoline, 3,4-dihydroisoquinoline, etc.) , 3-isoquinolines (for example, isoquinoline etc.), benzimidazoles (for example, 1,3-diethylbenzimidazole, 1-ethyl-3-phenylbenzimidazole, etc.), 3,3-dialkylindolenins (for example, 3,3-dimethylindolenine, 3,3,5, -trimethylin Renin, 3,3,7, - trimethyl indolenine, etc.), 2-pyridines (e.g., pyridine, 5-methyl-pyridine, etc.), 4-pyridine (e.g., may be mentioned pyridine, and the like) and the like.

Examples of the sulfur-containing heterocycle include a dithiol partial structure in dyes described in JP-A-3-296759. Specific examples of the dithiol include benzodithiols (for example, benzodithiol, 5-t-butylbenzodithiol, 5-methylbenzodithiol, etc.), naphthodithiols (for example, naphtho [1,2] dithiol, naphtho [2 , 1] dithiol, etc.), dithiols (for example, 4,5-dimethyldithiols, 4-phenyldithiols, 4-methoxycarbonyldithiols, 4,5-dimethoxycarbonylbenzodithiols, 4,5-ditrifluoro) Methyldithiol, 4,5-dicyanodithiol, 4-methoxycarbonylmethyldithiol, 4-carboxymethyldithiol, etc.).
W represents O or S.
The following sensitizing dyes having the structures represented by the general formulas (XIV-1) and (XIV-2) have high sensitizing ability and are very excellent in storage stability. Therefore, the compound represented by the general formula (XIV) is particularly preferable.

In the general formulas (XIV-1) and (XIV-2), R ₁ has the same meaning as R ⁵⁰ , X ₁ and X ₂ have the same meanings as R ⁵¹ and R ⁵² , respectively, Synonymous with formula (XIV), Z represents O or S. R ₂ and R ₃ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, or a heteroaryl group, and R ₂ and R ₃ are bonded to each other to form a 5-, 6-, or 7-membered ring May be. Specific examples of R ₂ and R ₃ include the examples of the substituted or unsubstituted alkyl group and aryl group described above as examples of R ⁵⁰ .

Preferred specific examples of the compound represented by the general formula (XIV) are shown below. Note that the present invention is not limited to this. Further, the isomer by the double bond connecting the acidic nucleus and the basic nucleus is not clear, and the present invention is not limited to either isomer.

一般式（XVI）中、Ａ²はＳ又はＮＲ⁵⁹を表し、ここでＲ⁵⁹はアルキル基又はアリール基を表す。ここで、アルキル基及びアリール基は、置換されていてもよい。
Ｒ⁵⁹の好ましい例について具体的に述べる。好ましいアルキル基の例としては、炭素原子数が１から２０までの直鎖状、分岐状、および環状のアルキル基を挙げることができ、その具体例としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、トリデシル基、ヘキサデシル基、オクタデシル基、エイコシル基、イソプロピル基、イソブチル基、ｓ−ブチル基、ｔ−ブチル基、イソペンチル基、ネオペンチル基、１−メチルブチル基、イソヘキシル基、２−エチルヘキシル基、２−メチルヘキシル基、シクロヘキシル基、シクロペンチル基、２−ノルボルニル基を挙げることができる。これらの中では、炭素原子数１から１２までの直鎖状、炭素原子数３から１２までの分岐状、ならびに炭素原子数５から１０までの環状のアルキル基がより好ましい。

In the general formula (XVI), A ² represents S or NR ⁵⁹ , where R ⁵⁹ represents an alkyl group or an aryl group. Here, the alkyl group and the aryl group may be substituted.
Specifically described for preferred embodiments of R ^59. Examples of preferable alkyl groups include linear, branched, and cyclic alkyl groups having 1 to 20 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, a propyl group, Butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, octadecyl, eicosyl, isopropyl, isobutyl, s-butyl, Examples thereof include t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group and 2-norbornyl group. Of these, linear alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, and cyclic alkyl groups having 5 to 10 carbon atoms are more preferable.

As the substituent of the substituted alkyl group, a monovalent non-metallic atomic group other than hydrogen is used. Preferred examples include halogen atoms (—F, —Br, —Cl, —I), hydroxyl groups, alkoxy groups. Group, aryloxy group, mercapto group, alkylthio group, arylthio group, alkyldithio group, aryldithio group, amino group, N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diaryl Amino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy Group, N-alkyl-N-arylcarbamoyloxy group, alkylsulfoxy , Arylsulfoxy group, acyloxy group, acylthio group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N′-alkylureido group, N ′, N′-dialkylureido group, N '-Arylureido group, N', N'-diarylureido group, N'-alkyl-N'-arylureido group, N-alkylureido group, N-arylureido group, N'-alkyl-N-alkylureido group N′-alkyl-N-arylureido group, N ′, N′-dialkyl-N-alkylureido group, N ′, N′-dialkyl-N-arylureido group, N′-aryl-N-alkylureido group N′-aryl-N-arylureido group, N ′, N′-diaryl-N-alkylureido group, N ′, N′-diaryl-N-aryluree Id group, N′-alkyl-N′-aryl-N-alkylureido group, N′-alkyl-N′-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl- N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group, formyl group, acyl group, carboxyl group , Alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N-arylcarbamoyl group An alkylsulfinyl group, An arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfo group (—SO ₃ H) and a conjugate base group thereof (hereinafter referred to as a sulfonate group),

Alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N- Alkyl-N-arylsulfamoyl group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-diarylsulfamoyl group, N -Alkyl-N-arylsulfamoyl group, phosphono group (-PO ₃ H ₂ ) and its conjugate base group (hereinafter referred to as phosphonate group), dialkyl phosphono group (-PO ₃ (alkyl) ₂ ), diaryl phosphine group phono group _{(-PO 3 (aryl) 2)} , alkyl aryl phosphono group _{(-PO 3 (alkyl) (aryl} )), -Alkyl phosphono group (-PO ₃ H (alkyl)) and its conjugated base group (hereinafter referred to as alkyl phosphonophenyl group), monoaryl phosphono group (-PO ₃ H (aryl)) and its conjugated base group ( Hereinafter referred to as aryl phosphonate group), phosphonooxy group (—OPO ₃ H ₂ ) and its conjugate base group (hereinafter referred to as phosphonateoxy group), dialkyl phosphonooxy group (—OPO ₃ (alkyl) ₂ ), diaryl phosphonooxy group (-OPO3 (aryl) 2), alkylaryl phosphonooxy group _{(-OPO 3 (alkyl) (aryl} )), monoalkyl phosphonooxy group (-OPO ₃ H (alkyl)) and Its conjugated base group (hereinafter referred to as alkyl phosphonatooxy group), monoaryl phosphonooxy group (—OPO ₃ H (aryl)) and its conjugated base group (hereinafter referred to as aryl phosphonate). And a cyano group, a nitro group, an aryl group, a heteroaryl group, an alkenyl group, an alkynyl group, and a silyl group.

  Specific examples of the alkyl group in these substituents include the above-described alkyl group, which may further have a substituent. Specific examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, Tolyl group, xylyl group, mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, chloromethylphenyl group, hydroxyphenyl group, methoxyphenyl group, ethoxyphenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, Methylthiophenyl group, phenylthiophenyl group, methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, ethoxyphenylcarbonyl group, phenoxycarbonylphenyl group, N-phenyl group Ba carbamoylphenyl group include a phenyl group, cyanophenyl group, sulfophenyl group, sulfonatophenyl group, phosphonophenyl phenyl group, a phosphonophenyl phenyl group.

  As the heteroaryl group, a group derived from a monocyclic or polycyclic aromatic ring containing at least one of nitrogen, oxygen and sulfur atoms is used, and examples of the heteroaryl ring in the particularly preferred heteroaryl group include Is, for example, thiophene, thiathrene, furan, pyran, isobenzofuran, chromene, xanthene, phenoxazine, pyrrole, pyrazole, isothiazole, isoxazole, pyrazine, pyrimidine, pyridazine, indolizine, isoindolizine, indolizine, indazole, indazole, Purine, quinolidine, isoquinoline, phthalazine, naphthyridine, quinazoline, sinoline, pteridine, carbazole, carboline, phenanthrine, acridine, perimidine, phenanthrolin, phthalazine, phenalazine, phenoxazine, fura Emissions, phenoxazine and the like, and these are further may be benzo-fused or may have a substituent.

Examples of alkenyl groups include vinyl, 1-propenyl, 1-butenyl, cinnamyl, 2-chloro-1-ethenyl, etc. Examples of alkynyl include ethynyl, 1 -Propynyl group, 1-butynyl group, trimethylsilylethynyl group and the like. Examples of G ¹ in the acyl group (G ¹ CO—) include hydrogen and the above alkyl groups and aryl groups. Among these substituents, even more preferred are halogen atoms (—F, —Br, —Cl, —I), alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, N-alkylamino groups, N, N -Dialkylamino group, acyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, acylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group Group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, sulfo group, sulfonate group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfa group Moyl group, N-aryl sulf Moyl group, N-alkyl-N-arylsulfamoyl group, phosphono group, phosphonate group, dialkyl phosphono group, diaryl phosphono group, monoalkyl phosphono group, alkyl phosphonate group, monoaryl phosphono group, aryl phosphine group Examples include an onato group, a phosphonooxy group, a phosphonateoxy group, an aryl group, an alkenyl group, and an alkylidene group (such as a methylene group).

  On the other hand, examples of the alkylene group in the substituted alkyl group include divalent organic residues obtained by removing any one of the hydrogen atoms on the alkyl group having 1 to 20 carbon atoms. Can include linear alkylene groups having 1 to 12 carbon atoms, branched chains having 3 to 12 carbon atoms, and cyclic alkylene groups having 5 to 10 carbon atoms.

Specific examples of preferred substituted alkyl groups as R ⁵⁹ obtained by combining the above substituents and alkylene groups include chloromethyl group, bromomethyl group, 2-chloroethyl group, trifluoromethyl group, methoxymethyl group, methoxyethoxyethyl. Group, allyloxymethyl group, phenoxymethyl group, methylthiomethyl group, tolylthiomethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyloxymethyl group, benzoyloxymethyl group, N-cyclohexylcarbamoyloxyethyl group N-phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxoethyl group, 2-oxopropyl group, carboxypropyl group, methoxycarbonylethyl group Allyloxycarbonylbutyl group, chlorophenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl group, N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, N-methyl-N- ( Sulfophenyl) carbamoylmethyl group, sulfobutyl group, sulfonatopropyl group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N-dipropylsulfamoylpropyl group, N-tolylsulfamoyl group Propyl group, N-methyl-N- (phosphonophenyl) sulfamoyloctyl group, phosphonobutyl group, phosphonatohexyl group, diethylphosphonobutyl group, diphenylphosphonopropyl group, methylphosphonobutyl group, methylphosphine Onatobutyl group, tolylphosphonohexyl group, tolylphosphonatohexyl group, phosphonooxypropyl group, phosphonatoxybutyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-methyl-1-phenylethyl group, p -Methylbenzyl group, cinnamyl group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2-methylallyl group, 2-methylpropenylmethyl group, 2-propynyl group, 2-butynyl group, 3-butynyl group, etc. Can be mentioned.

Specific examples of preferred aryl groups as R ⁵⁹ include those in which 1 to 3 benzene rings form a condensed ring, and those in which a benzene ring and a 5-membered unsaturated ring form a condensed ring. Examples include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenaphthenyl group, and a fluorenyl group. Among these, a phenyl group and a naphthyl group are more preferable.

Specific examples of preferred substituted aryl groups for R ⁵⁹ include those having a monovalent non-metallic atomic group other than hydrogen as a substituent on the ring-forming carbon atom of the aryl group. Examples of preferred substituents include the alkyl groups, substituted alkyl groups, and those previously shown as substituents in the substituted alkyl group. Preferred examples of such a substituted aryl group include biphenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, fluorophenyl group, chloromethylphenyl group, trifluoromethylphenyl group. Hydroxyphenyl group, methoxyphenyl group, methoxyethoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, methylthiophenyl group, tolylthiophenyl group, ethylaminophenyl group, diethylaminophenyl group, morpholinophenyl group, acetyloxyphenyl group, Benzoyloxyphenyl group, N-cyclohexylcarbamoyloxyphenyl group, N-phenylcarbamoyloxyphenyl group, acetylaminophenyl group, N-methylbenzoylaminophenyl group, cal Xiphenyl group, methoxycarbonylphenyl group, allyloxycarbonylphenyl group, chlorophenoxycarbonylphenyl group, carbamoylphenyl group, N-methylcarbamoylphenyl group, N, N-dipropylcarbamoylphenyl group, N- (methoxyphenyl) carbamoylphenyl group N-methyl-N- (sulfophenyl) carbamoylphenyl group, sulfophenyl group, sulfonatophenyl group, sulfamoylphenyl group, N-ethylsulfamoylphenyl group, N, N-dipropylsulfamoylphenyl group, N-tolylsulfamoylphenyl group, N-methyl-N- (phosphonophenyl) sulfamoylphenyl group, phosphonophenyl group, phosphonatophenyl group, diethylphosphonophenyl group, diphenylphosphoro Phenyl group, methylphosphonophenyl group, methylphosphonatophenyl group, tolylphosphonophenyl group, tolylphosphonatephenyl group, allylphenyl group, 1-propenylmethylphenyl group, 2-butenylphenyl group, 2-methylallylphenyl Group, 2-methylpropenylphenyl group, 2-propynylphenyl group, 2-butynylphenyl group, 3-butynylphenyl group, and the like.

L ² represents a nonmetallic atomic group that forms a basic nucleus of the sensitizing dye in cooperation with the adjacent A ² and the adjacent carbon atom. A heterocyclic ring is suitable as the basic nucleus. Examples of such a heterocyclic ring include 5-, 6-, and 7-membered nitrogen-containing or sulfur-containing heterocyclic rings that may have a condensed ring, and preferably 5- or 6-membered heterocyclic rings.

  Examples of nitrogen-containing heterocycles form the basic nucleus in merocyanine dyes described in, for example, LGBrooker et al., J. Am. Chem. Soc., 73, 5326-5358 (1951) and references Any known material can be suitably used. Specific examples include thiazoles (for example, thiazole, 4-methylthiazole, 4-phenylthiazole, 5-methylthiazole, 5-phenylthiazole, 4,5-dimethylthiazole, 4,5-diphenylthiazole, 4,5- Di (p-methoxyphenylthiazole), 4- (2-thienyl) thiazole, 4,5-di (2-furyl) thiazole, etc.), benzothiazoles (for example, benzothiazole, 4-chlorobenzothiazole, 5-chloro Benzothiazole, 6-chlorobenzothiazole, 7-chlorobenzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, 5-bromobenzothiazole, 4-phenylbenzothiazole, 5-phenylbenzothiazole 4-methoxybenzo Azole, 5-methoxybenzothiazole, 6-methoxybenzothiazole, 5-iodobenzothiazole, 6-iodobenzothiazole, 4-ethoxybenzothiazole, 5-ethoxybenzothiazole, tetrahydrobenzothiazole, 5,6-dimethoxybenzothiazole, 5,6-dioxymethylenebenzothiazole, 5-hydroxybenzothiazole, 6-hydroxybenzothiazole, 6-dimethylaminobenzothiazole, 5-ethoxycarbonylbenzothiazole, etc.), naphthothiazoles (for example, naphtho [1,2 ] Thiazole, naphtho [2,1] thiazole, 5-methoxynaphtho [2,1] thiazole, 5-ethoxynaphtho [2,1] thiazole, 8-methoxynaphtho [1,2] thiazole, 7-methoxynaphtho [ , 2] thiazole, etc.), thianaphtheno-7 ′, 6 ′, 4,5-thiazole (for example, 4′-methoxythianaphtheno-7 ′, 6 ′, 4,5-thiazole, etc.), oxazole ( For example, 4-methyl oxazole, 5-methyl oxazole, 4-phenyl oxazole, 4,5-diphenyl oxazole, 4-ethyl oxazole, 4,5-dimethyl oxazole, 5-phenyl oxazole, etc.), benzoxazoles (benzoxazole, 5-chlorobenzoxazole, 5-methylbenzoxazole, 5-phenylbenzoxazole, 6-methylbenzoxazole, 5,6-dimethylbenzoxazole, 4,6-dimethylbenzoxazole, 6-methoxybenzoxazole, 5-methoxybenzo Oxazole, 4-ethoxybe Nzooxazole, 5-chlorobenzoxazole, 6-methoxybenzoxazole, 5-hydroxybenzoxazole, 6-hydroxybenzoxazole, etc.), naphthoxazoles (for example, naphtho [1,2] oxazole, naphtho [2,1 Oxazole, etc.), selenazoles (eg, 4-methylselenazole, 4-phenylselenazole, etc.), benzoselenazoles (eg, benzoselenazole, 5-chlorobenzoselenazole, 5-methoxybenzoselenazole) , 5-hydroxybenzoselenazole, tetrahydrobenzoselenazole, etc.), naphthoselenazoles (for example, naphtho [1,2] selenazole, naphtho [2,1] selenazole, etc.), thiazolines (for example, thiazoline, 4 -Methyl thiazoline, , 5-dimethylthiazoline, 4-phenylthiazoline, 4,5-di (2-furyl) thiazoline, 4,5-diphenylthiazoline, 4,5-di (p-methoxyphenyl) thiazoline, etc.), 2-quinolines ( For example, quinoline, 3-methylquinoline, 5-methylquinoline, 7-methylquinoline, 8-methylquinoline, 6-chloroquinoline, 8-chloroquinoline, 6-methoxyquinoline, 6-ethoxyquinoline, 6-hydroxyquinoline, 8 -Hydroxyquinoline, etc.), 4-quinolines (eg, quinoline, 6-methoxyquinoline, 7-methylquinoline, 8-methylquinoline, etc.), 1-isoquinolines (eg, isoquinoline, 3,4-dihydroisoquinoline, Etc.), 3-isoquinolines (for example, isoquinoline etc.), benzimidazoles For example, 1,3-dimethylbenzimidazole, 1,3-diethylbenzimidazole, 1-ethyl-3-phenylbenzimidazole, etc., 3,3-dialkylindolenine (for example, 3,3-dimethylindolenine, 3,3,5-trimethylindolenine, 3,3,7-trimethylindolenine, etc.), 2-pyridines (eg, pyridine, 5-methylpyridine, etc.), 4-pyridine (eg, pyridine, etc.), etc. Can be mentioned. Moreover, the substituents of these rings may combine to form a ring.

Examples of the sulfur-containing heterocycle include a dithiol partial structure in dyes described in JP-A-3-296759.
Specific examples include benzodithiols (eg, benzodithiol, 5-t-butylbenzodithiol, 5-methylbenzodithiol, etc.), naphthodithiols (eg, naphtho [1,2] dithiol, naphtho [2,1 Dithiols, etc.), dithiols (for example, 4,5-dimethyldithiols, 4-phenyldithiols, 4-methoxycarbonyldithiols, 4,5-dimethoxycarbonyldithiols, 4,5-diethoxycarbonyldithiols) 4,5-ditrifluoromethyldithiol, 4,5-dicyanodithiol, 4-methoxycarbonylmethyldithiol, 4-carboxymethyldithiol, etc.).

Among the examples of nitrogen-containing or sulfur heterocycles formed by L ^{4 in combination} with adjacent A ² and adjacent carbon atoms in the general formula (XVI) described above, the following partial structural formula (XVI-1) The dye having the structure represented is particularly preferable because it gives a photopolymerizable composition having high sensitizing ability and excellent storage stability. In the formula (XVI), a dye having a structure represented by the partial structural formula (XVI-1) is a novel compound.

In the formula (XVI-1), A has the same meaning as A ^{2 in the} formula (XVI), R ₈ and R ₉ each independently represents a group of a monovalent nonmetallic atomic group, and R ₈ and R ₉ are They may combine with each other to form a 5- to 8-membered ring.
R ₈ and R ₉ are particularly preferably a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. As specific examples of these substituents, those exemplified as the example of R ⁵⁹ described above can be used. Particularly preferred R ₈ and R ₉ are each independently an alkyl group having 1 to 6 carbon atoms which may be branched, a phenyl group which may have a substituent, a furyl group which may have a substituent, A thienyl group and an alkoxycarbonyl group; Further, when R ₈ and R ₉ are bonded to each other to form a 5-, 6-, or 7-membered ring, it is particularly preferable to form a benzene ring or a naphthalene ring, or trimethylene (— (CH ₂ ) ₃ —). , Tetramethylene (— (CH ₂ ) ₄ —).

R ⁵³ , R ⁵⁴ , R ⁵⁵ , R ⁵⁶ , R ⁵⁷ and R ⁵⁸ each independently represent a monovalent nonmetallic atomic group. R ⁵³ , R ⁵⁴ , R ⁵⁵ , R ⁵⁶ , R ⁵⁷ and R ⁵⁸ are more preferably a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an alkenyl group, a substituted alkenyl group, Hydroxyl group, substituted oxy group, mercapto group, substituted thio group, amino group, substituted amino group, substituted carbonyl group, sulfo group, sulfonate group, substituted sulfinyl group, substituted sulfonyl group, phosphono group, substituted phosphono group, phosphonate group, substituted The thing which is any of a phosphonate group, a cyano group, a nitro group, and a silyl group can be mentioned. As preferred examples of these substituents, any of those exemplified as the aforementioned R ⁵⁹ examples can be suitably used.

R ⁵³ and R ⁵⁴ may combine with each other to form an aliphatic ring, and may form a spiro ring with a ring containing a carbon atom to which they are bonded. Preferred examples of the aliphatic ring include 3-membered ring, 5-membered ring, 6-membered ring, 7-membered ring and 8-membered aliphatic ring, and more preferred are 3-membered ring, 5-membered ring and 6-membered ring. A cyclic aliphatic ring can be mentioned. These may further have a substituent on the carbon atom constituting them. (Examples of the substituent include the examples of the substituent in the substituted alkyl group mentioned above as the example of R ^59. In addition, a part of the ring-constituting carbon may be substituted with a hetero atom (oxygen atom, sulfur atom, nitrogen atom, etc.). Preferred examples of these include cyclopropane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane, cyclo-1,3-dioxapentane ring, cyclopentene ring, cyclohexene ring, cyclohexane ring, Examples include a heptene ring, a cyclooctene ring, a cyclo-1,3-dioxapentene ring, and a cyclo-1,3-dioxahexene ring.

Further, those in which R ⁵⁵ and R ⁵⁶ , R ⁵⁶ and R ⁵⁷ , R ⁵⁷ and R ⁵⁸ are bonded to each other to form an aliphatic or aromatic ring can also be suitably used. Examples of such aliphatic rings include 5-membered, 6-membered, 7-membered and 8-membered aliphatic rings, and more preferably 5-membered and 6-membered aliphatic rings. A ring can be mentioned. These may further have a substituent on the carbon atom constituting them. (Examples of the substituent include the examples of the substituent in the substituted alkyl group described above as the example of R ^59. In addition, a part of the ring-constituting carbon may be substituted with a hetero atom (oxygen atom, sulfur atom, nitrogen atom, etc.). Preferred examples of these include benzocyclopentene ring, benzocyclohexene ring, benzocycloheptene ring, benzocyclo in cooperation with the benzene ring containing the carbon atom to which they are bonded in the following partial structure (XVI-2). Examples include an octene ring, a 1,3-benzocyclohexadiene ring, a 1,3-dihydro-1,3-dioxaindene ring, and a julolidine ring. Examples of forming an aromatic ring include those that form a naphthalene or anthracene ring in cooperation with a benzene ring containing a carbon atom to which they are bonded, and more preferably those that form a naphthalene ring. It is done. A substituent may be present on the carbon atoms constituting these (as examples of the substituent, the substituents on the substituted alkyl group exemplified above for R ⁵⁹ can be given).

Among these, more preferable R ⁵³ and R ⁵⁴ include a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, a substituted carbonyl group, and a trialkylsilyl group, and R ^{55 to} R ^{As 58} , hydrogen atom, halogen atom, alkyl group, substituted alkyl group, aryl group, substituted aryl group, hydroxyl group, substituted oxy group, mercapto group, substituted thio group, amino group, substituted amino group, substituted carbonyl group, More preferred.

Specific examples of the partial structure (XVI-2) having preferable R ^{53 to} R ⁵⁸ are specifically shown below.

The compound represented by the general formula (XVI) includes a basic nucleus formed by the above A ² and L ^{4 in} cooperation with adjacent carbon atoms, and 1,3 represented by the partial structural formula (XIV-2). It can be constructed by sequentially combining a dihydro-1-oxo-2H-indenylidene skeleton. Preferred specific examples of the compound represented by the general formula (XVI) are shown below, but the present invention is not limited thereto.

一般式（XVII）中、Ａ³及びＡ⁴はそれぞれ独立にＳ、ＮＲ⁶⁰又はＮＲ⁶³を表し、ここでＲ⁶⁰及びＲ⁶³はそれぞれ独立にアルキル基又はアリール基を表す。ここでいうアルキル基及びアリール基は置換されていてもよい。
ここで、Ｒ⁶⁰、Ｒ⁶³として非置換アルキル基の好ましい例について具体的に述べる。好ましいアルキル基の例としては、炭素原子数が１から２０までの直鎖状、分岐状、および環状のアルキル基を挙げることができ、その具体例としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、トリデシル基、ヘキサデシル基、オクタデシル基、エイコシル基、イソプロピル基、イソブチル基、ｓ−ブチル基、ｔ−ブチル基、イソペンチル基、ネオペンチル基、１−メチルブチル基、イソヘキシル基、２−エチルヘキシル基、２−メチルヘキシル基、シクロヘキシル基、シクロペンチル基、２−ノルボルニル基を挙げることができる。

In general formula (XVII), A ³ and A ⁴ each independently represent S, NR ⁶⁰ or NR ⁶³ , wherein R ⁶⁰ and R ⁶³ each independently represent an alkyl group or an aryl group. The alkyl group and aryl group here may be substituted.
Here, preferred examples of the unsubstituted alkyl group as R ⁶⁰ and R ⁶³ will be specifically described. Examples of preferable alkyl groups include linear, branched, and cyclic alkyl groups having 1 to 20 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, a propyl group, Butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, octadecyl, eicosyl, isopropyl, isobutyl, s-butyl, Examples thereof include t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group and 2-norbornyl group.

As the substituent of the substituted alkyl group preferable as R ⁶⁰ and R ⁶³ , a monovalent nonmetallic atomic group excluding hydrogen is used, and preferable examples include a halogen atom (—F, —Br, —Cl, —I). , Hydroxyl group, alkoxy group, aryloxy group, mercapto group, alkylthio group, arylthio group, alkyldithio group, aryldithio group, amino group, N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N-arylcarbamoyloxy group Alkylsulfoxy group, arylsulfoxy group, acylthio group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N′-alkylureido group, N ′, N′-dialkylureido group N'-arylureido group, N ', N'-diarylureido group, N'-alkyl-N'-arylureido group, N-alkylureido group, N-arylureido group, N'-alkyl-N-alkyl Ureido group, N′-alkyl-N-arylureido group, N ′, N′-dialkyl-N-alkylureido group, N ′, N′-dialkyl-N-arylureido group, N′-aryl-N-alkyl Ureido group, N′-aryl-N-arylureido group, N ′, N′-diaryl-N-alkylureido group, N ′, N -Diaryl-N-arylureido group, N'-alkyl-N'-aryl-N-alkylureido group, N'-alkyl-N'-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino Group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group, formyl group , Acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl -N-aryl carbonate Bamoiru group, alkylsulfinyl group, arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfo group (-SO ₃ H) and its conjugated base group (hereinafter referred to as sulfonato group), alkoxy sulfonyl group, aryloxy sulfonyl group, Sulfinamoyl group, N-alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group Sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl Group, phosphono group (—PO ₃ H ₂ ) and conjugated salts thereof Group (hereinafter referred to as phosphonate group), dialkyl phosphono group (—PO ₃ (alkyl) ₂ ), diaryl phosphono group (—PO ₃ (aryl) ₂ ), alkylaryl phosphono group (—PO ₃ (alkyl) ) (aryl)), monoalkyl phosphono group (—PO ₃ H (alkyl)) and its conjugate base group (hereinafter referred to as alkyl phosphonate group), monoaryl phosphono group (—PO ₃ H (aryl)) And its conjugate base group (hereinafter referred to as arylphosphonate group), phosphonooxy group (—OPO ₃ H ₂ ) and its conjugate base group (hereinafter referred to as phosphonateoxy group), dialkylphosphonooxy group (— OPO ₃ (alkyl) ₂ ), diaryl phosphonooxy group (—OPO ₃ (aryl) ₂ ), alkylaryl phosphonooxy group (—OPO ₃ (alkyl) (aryl)), monoalkyl phosphonooxy group (—OPO) ₃ (alkyl)) and its conjugated base group (hereinafter referred to as alkyl phosphonophenyl group), monoaryl phosphonooxy group (-OPO ₃ H (aryl)) and its conjugated base group (hereinafter, the aryl phosphite Hona preparative group A cyano group, a nitro group, an aryl group, a heteroaryl group, an alkenyl group, and an alkynyl group.

  Specific examples of the alkyl group in the substituent of these substituted alkyl groups include the aforementioned alkyl groups. Specific examples of the aryl group in the substituent of the substituted alkyl group include phenyl group, biphenyl group, naphthyl group, tolyl group, xylyl group, mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, chloromethylphenyl group, Hydroxyphenyl group, methoxyphenyl group, ethoxyphenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group, methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, Carboxyphenyl group, methoxycarbonylphenyl group, ethoxyphenylcarbonyl group, phenoxycarbonylphenyl group, N-phenylcarbamoylphenyl group, phenyl group, cyanophenyl group, sulfophenyl group, sulfo Tofeniru group, phosphono phenyl group, and a phosphonophenyl phenyl group.

  Moreover, as the heteroaryl group in the substituent of the substituted alkyl group, a monocyclic or polycyclic aromatic ring containing at least one of nitrogen, oxygen and sulfur atoms is used, preferably furan, pyrrole, pyridine, 5-membered or 6-membered aromatic substituents such as

Examples of the alkenyl group in the substituent of the substituted alkyl group include vinyl group, 1-propenyl group, 1-butenyl group, cinnamyl group, 2-chloro-1-ethenyl group, and the like. Examples of alkynyl group Examples thereof include an ethynyl group, a 1-propynyl group, a 1-butynyl group, and a trimethylsilylethynyl group. Further, Examples of G ¹ in the acyl group (G ¹ CO-) in the substituent of the substituted alkyl group include a hydrogen atom and the above-described alkyl group, an aryl group. Of these substituents, halogen atoms (-F, -Br, -Cl, -I), alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, N-alkylamino groups, N, N are more preferable. -Dialkylamino group, acyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, acylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group Group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, sulfo group, sulfonate group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfa group Moyl group, N-arylsulfa Moyl group, N-alkyl-N-arylsulfamoyl group, phosphono group, phosphonate group, dialkyl phosphono group, diaryl phosphono group, monoalkyl phosphono group, alkyl phosphonate group, monoaryl phosphono group, aryl phosphine group Examples include an onato group, a phosphonooxy group, a phosphonateoxy group, an aryl group, and an alkenyl group.

  On the other hand, examples of the alkylene group in the substituted alkyl group include divalent organic residues obtained by removing any one of the hydrogen atoms on the alkyl group having 1 to 20 carbon atoms. Can include linear alkylene groups having 1 to 12 carbon atoms, branched chains having 3 to 12 carbon atoms, and cyclic alkylene groups having 5 to 10 carbon atoms.

  Specific examples of the preferred substituted alkyl group obtained by combining the substituent and the alkylene group include a chloromethyl group, a bromomethyl group, a 2-chloroethyl group, a trifluoromethyl group, a methoxymethyl group, a methoxyethoxyethyl group, and allyloxy. Methyl group, phenoxymethyl group, methylthiomethyl group, tolylthiomethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyloxymethyl group, benzoyloxymethyl group, N-cyclohexylcarbamoyloxyethyl group, N-phenyl Carbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxoethyl group, 2-oxopropyl group, carboxypropyl group, methoxycarbonylethyl group, allyloxycarbonyl Bonylbutyl, chlorophenoxycarbonylmethyl, carbamoylmethyl, N-methylcarbamoylethyl, N, N-dipropylcarbamoylmethyl, N- (methoxyphenyl) carbamoylethyl, N-methyl-N- (sulfophenyl) Carbamoylmethyl group, sulfobutyl group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N-dipropylsulfamoylpropyl group, N-tolylsulfamoylpropyl group, N-methyl-N -(Phosphonophenyl) sulfamoyloctyl group, phosphonobutyl group, phosphonatohexyl group, diethylphosphonobutyl group, diphenylphosphonopropyl group, methylphosphonobutyl group, methylphosphonatobutyl group, tolylphosphonohexyl Group, tolylphosphonatohexyl group, phosphonooxypropyl group, phosphonatooxybutyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-methyl-1-phenylethyl group, p-methylbenzyl group, cinnamyl Group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2-methylallyl group, 2-methylpropenylmethyl group, 2-propynyl group, 2-butynyl group, 3-butynyl group and the like.

Specific examples of preferred unsubstituted aryl groups as R ⁶⁰ and R ⁶³ include those in which 1 to 3 benzene rings form a condensed ring, and those in which a benzene ring and a 5-membered unsaturated ring form a condensed ring. Specific examples include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenaphthenyl group, and a fluorenyl group. Among these, a phenyl group and a naphthyl group are more preferable.

Specific examples of preferred substituted aryl groups as R ⁶⁰ and R ⁶³ include those having a monovalent nonmetallic atomic group excluding hydrogen as a substituent on the ring-forming carbon atom of the aforementioned aryl group. Examples of preferred substituents include the alkyl groups, substituted alkyl groups, and those previously shown as substituents in the substituted alkyl group. Preferred examples of such a substituted aryl group include biphenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, fluorophenyl group, chloromethylphenyl group, trifluoromethylphenyl group. Hydroxyphenyl group, methoxyphenyl group, methoxyethoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, methylthiophenyl group, tolylthiophenyl group, ethylaminophenyl group, diethylaminophenyl group, morpholinophenyl group, acetyloxyphenyl group, Benzoyloxyphenyl group, N-cyclohexylcarbamoyloxyphenyl group, N-phenylcarbamoyloxyphenyl group, acetylaminophenyl group, N-methylbenzoylaminophenyl group, carbo Cyphenyl group, methoxycarbonylphenyl group, allyloxycarbonylphenyl group, chlorophenoxycarbonylphenyl group, carbamoylphenyl group, N-methylcarbamoylphenyl group, N, N-dipropylcarbamoylphenyl group, N- (methoxyphenyl) carbamoylphenyl group N-methyl-N- (sulfophenyl) carbamoylphenyl group, sulfophenyl group, sulfonatophenyl group, sulfamoylphenyl group, N-ethylsulfamoylphenyl group, N, N-dipropylsulfamoylphenyl group, N-tolylsulfamoylphenyl group, N-methyl-N- (phosphonophenyl) sulfamoylphenyl group, phosphonophenyl group, phosphonatophenyl group, diethylphosphonophenyl group, diphenylphosphono Enyl group, methylphosphonophenyl group, methylphosphonatophenyl group, tolylphosphonophenyl group, tolylphosphonatophenyl group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2-methylallylphenyl group, 2- Examples thereof include a methylpropenylphenyl group, a 2-propynylphenyl group, a 2-butynylphenyl group, and a 3-butynylphenyl group.

L ⁵ and L ⁶ each independently represents a nonmetallic atomic group that forms a basic nucleus of the sensitizing dye in combination with adjacent A ³ , A ⁴ and adjacent carbon atoms. Here, examples of the basic nucleus include a heterocyclic ring. Examples of such a heterocycle include 5-, 6-, and 7-membered nitrogen-containing, oxygen-containing, or sulfur-containing heterocycles, and preferably 5- or 6-membered heterocycles.

  Examples of nitrogen-containing heterocycles include, for example, the basic nucleus in merocyanine dyes described in LGBrooker et al., J. Am. Chem. Soc., 73, 5326-5358 (1951). Any of those known to be used can be suitably used. Specific examples include thiazoles (for example, thiazole, 4-methylthiazole, 4-phenylthiazole, 5-methylthiazole, 5-phenylthiazole, 4,5-dimethylthiazole, 4,5-diphenylthiazole, 4,5- Di (p-methoxyphenylthiazole), 4- (2-thienyl) thiazole, etc.), benzothiazoles (for example, benzothiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, 7- Chlorobenzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, 5-bromobenzothiazole, 4-phenylbenzothiazole, 5-phenylbenzothiazole, 4-methoxybenzothiazole, 5-methoxybenzo Cheer , 6-methoxybenzothiazole, 5-iodobenzothiazole, 6-iodobenzothiazole, 4-ethoxybenzothiazole, 5-ethoxybenzothiazole, tetrahydrobenzothiazole, 5,6-dimethoxybenzothiazole, 5,6-di Oxymethylenebenzothiazole, 5-hydroxybenzothiazole, 6-hydroxybenzothiazole, 6-dimethylaminobenzothiazole, 5-ethoxycarbonylbenzothiazole, etc.), naphthothiazoles (for example, naphtho [1,2] thiazole, naphtho [ 2,1] thiazole, 5-methoxynaphtho [2,1] thiazole, 5-ethoxynaphtho [2,1] thiazole, 8-methoxynaphtho [1,2] thiazole, 7-methoxynaphtho [1,2] thiazole, Etc.), Chianafu -7 ', 6', 4,5-thiazole (for example, 4'-methoxythianaphtheno-7 ', 6', 4,5-thiazole, etc.), oxazole (for example, 4-methyloxazole, 5 -Methyl oxazole, 4-phenyl oxazole, 4,5-diphenyl oxazole, 4-ethyl oxazole, 4,5-dimethyl oxazole, 5-phenyl oxazole, etc.), benzoxazoles (benzoxazole, 5-chlorobenzoxazole, 5- Methylbenzoxazole, 5-phenylbenzoxazole, 6-methylbenzoxazole, 5,6-dimethylbenzoxazole, 4,6-dimethylbenzoxazole, 6-methoxybenzoxazole, 5-methoxybenzoxazole, 4-ethoxybenzoxazole, 5-black Benzoxazole, 6-methoxybenzoxazole, 5-hydroxybenzoxazole, 6-hydroxybenzoxazole, etc.), naphthoxazoles (for example, naphtho [1,2] oxazole, naphtho [2,1] oxazole, etc.), selenazole (Eg, 4-methylselenazole, 4-phenylselenazole, etc.), benzoselenazoles (eg, benzoselenazole, 5-chlorobenzoselenazole, 5-methoxybenzoselenazole, 5-hydroxybenzoselenazole) , Tetrahydrobenzoselenazole, etc.), naphthoselenazoles (eg, naphtho [1,2] selenazole, naphtho [2,1] selenazole, etc.), thiazolines (eg, thiazoline, 4-methylthiazoline, etc.), 2-quinolines (eg Quinoline, 3-methylquinoline, 5-methylquinoline, 7-methylquinoline, 8-methylquinoline, 6-chloroquinoline, 8-chloroquinoline, 6-methoxyquinoline, 6-ethoxyquinoline, 6-hydroxyquinoline, 8- Hydroxyquinoline, etc.), 4-quinolines (eg, quinoline, 6-methoxyquinoline, 7-methylquinoline, 8-methylquinoline, etc.), 1-isoquinolines (eg, isoquinoline, 3,4-dihydroisoquinoline, etc.) ), 3-isoquinolines (for example, isoquinoline and the like), benzimidazoles (for example, 1,3-diethylbenzimidazole, 1-ethyl-3-phenylbenzimidazole, and the like), 3,3-dialkylindolenins (for example, 3,3-dimethylindolenine, 3,3,5, -trimethyl Indolenine, 3,3,7, -trimethylindolenine, etc.), 2-pyridines (eg, pyridine, 5-methylpyridine, etc.), 4-pyridine (eg, pyridine, etc.) and the like. In, these basic nuclei can be used as alkylidene derivatives obtained by dihydrolysis.

R ⁶¹ and R ⁶² each independently represent a monovalent nonmetallic atomic group, or are bonded to each other to form an aliphatic ring or an aromatic ring.
Preferably, R ⁶¹ and R ⁶² each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or these groups are substituted or unsubstituted via an alkylene group or the like. Can be linked to form an aliphatic ring or an aromatic ring. When bonded to each other to form a ring, the ring can be formed via an oxygen atom, a nitrogen atom, a sulfur atom, or the like in addition to the carbon atom. Examples of preferred rings include a ring through a substituted or unsubstituted alkylene group, an ether bond, an ester bond, an amide bond, and the like. Here, preferred examples of the substituted or unsubstituted alkyl group, the substituted or unsubstituted aryl group, and the substituent are the same as those described in the description of R ⁶⁰ and R ⁶³ in the general formula (XVII). Can be mentioned.

Of the examples of nitrogen-containing or sulfur heterocycles formed by L ⁵ and L ^{6 in combination} with the aforementioned A ³ , A ⁴ and adjacent carbon atoms in the general formula (XVII) described above, the following general formula ( The dye having the structure represented by XVII-1) is particularly excellent in exposure suitability at 350 to 450 nm, has a high sensitizing ability, and provides a photopolymerizable composition having excellent storage stability. Particularly preferred.

In the formula, R ₁ , R ₂ , R ₃ and R ₄ have the same meanings as R ⁶² , R ⁶¹ , R ⁶⁰ and R ^{63 in} formula (XVII); X ₁ and X ₂ are each independently an O atom , S atom, Se atom, NR ₉ or CR ₁₀ R ₁₁ , wherein R ₉ , R ₁₀ and R ₁₁ are each independently an alkyl group having 1 to 6 carbon atoms or a substituted or unsubstituted phenyl group. And R _{5 to} R ₈ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a substituted or unsubstituted phenyl group, chlorine or bromine; And R ₅ and R ₆ can be linked together to form an aliphatic ring or an aromatic ring, or R ₇ and R ₈ can be bonded to each other. When forming a ring mutually, formation of a ring can also be via an oxygen atom, a nitrogen atom, a sulfur atom, etc. other than a carbon atom. Examples of preferred rings include a ring through a substituted or unsubstituted alkylene group, an ether bond, an ester bond, an amide bond, and the like. Here, preferred examples of the substituted or unsubstituted alkyl group, the substituted or unsubstituted aryl group, and the substituent are the same as those described in the description of R ⁶⁰ and R ⁶³ in the general formula (XVII). Can be mentioned.

More preferably in the embodiment of the present invention; X ₁ = X ₂ and S or C (CH ₃ ) ₂ ; R ₁ + R ₂ (when R ₁ and R ₂ are bonded to each other to form a ring) ) Is — (CH ₂ ) ₂ — or — (CH ₂ CHR ₁₄ CH ₂ ) — (wherein R ₁₄ is H or t-butyl); R ₃ = R ₄ and CH ₃ or C ₂ represents H _5; R ₁ and R ₂ is H; and R ₅ and R ₆ are either each is hydrogen, or combine to form a aromatic ring together, and with R ₇ Each R ₈ is either hydrogen or is bonded to each other to form an aromatic ring. In addition, regarding the substituted or unsubstituted alkyl group, alkylene group, and substituent in the general formula (XVII-1), the same as those exemplified in the general formula (XVII) can be mentioned.

Preferable examples of the compound represented by the general formula (XVII) include the following. Any sensitizing dye of the present invention that satisfies the above structural requirements can be suitably used, and the present invention is not limited by the following chemical structural formula.

  The sensitizing dye represented by the general formula (XVII) or (XVII-1) of the present invention can be prepared by a Claisen-Schmidt condensation method using a base catalyst of 2 equivalents of an appropriate aldehyde and 1 equivalent of an appropriate ketone. . A method by hydrolysis of carbocyanine dyes is described in US Pat. No. 3,672,906. A synthetic method by condensation of a ketone with an azotium salt is described in Slominskii et al., Khim. Geterotsikl. Soedin., 711 712 (1974); Chem. Abst., 81, 77828f (1974).

一般式（XVIII）中、Ａ⁵はＯ、Ｓ又はＮＲ⁶⁷を表し、Ｒ⁶⁴、Ｒ⁶⁵及びＲ⁶⁷はそれぞれ独立に一価の非金属原子団を表すか、又は、Ｒ⁶⁴とＲ⁶⁷及びＲ⁶⁵とＲ⁶⁷はそれぞれ互いに結合して脂肪族環又は芳香族環を形成する。
Ｒ⁶⁴、Ｒ⁶⁵及びＲ⁶⁷は、それぞれ独立に、一価の非金属原子団を示す。ここで、一価の非金属原子団としては、例えば、水素原子、置換もしくは非置換のアルキル基、置換もしくは非置換のアルケニル基、置換もしくは非置換のアリール基、置換もしくは非置換の芳香族複素環残基、置換もしくは非置換のアルコキシ基、置換もしくは非置換のアルキルチオ基、ヒドロキシル基、ハロゲン原子を表す。

In general formula (XVIII), A ⁵ represents O, S or NR ⁶⁷ , and R ⁶⁴ , R ⁶⁵ and R ⁶⁷ each independently represent a monovalent nonmetallic atomic group, or R ⁶⁴ and R ⁶⁷ and R ⁶⁵ and R ⁶⁷ are bonded to each other to form an aliphatic ring or an aromatic ring.
R ⁶⁴ , R ⁶⁵ and R ⁶⁷ each independently represent a monovalent nonmetallic atomic group. Here, examples of the monovalent nonmetallic atomic group include a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aromatic complex, and the like. It represents a ring residue, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group, a hydroxyl group, or a halogen atom.

Preferable examples of R ⁶⁴ , R ⁶⁵ and R ⁶⁷ will be specifically described. Examples of preferable alkyl groups include linear, branched, and cyclic alkyl groups having 1 to 20 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, a propyl group, Butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, octadecyl, eicosyl, isopropyl, isobutyl, s-butyl, Examples thereof include t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group and 2-norbornyl group. Of these, linear alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, and cyclic alkyl groups having 5 to 10 carbon atoms are more preferable.

As the substituent of the substituted alkyl group, a monovalent nonmetallic atomic group excluding hydrogen is used, and preferred examples include a halogen atom (—F, —Br, —Cl, —I), a hydroxyl group, an alkoxy group, Aryloxy group, mercapto group, alkylthio group, arylthio group, alkyldithio group, aryldithio group, amino group, N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diarylamino group N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N-arylcarbamoyloxy group, alkylsulfoxy group, Reelsulfoxy group, acylthio group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N'-alkylureido group, N ', N'-dialkylureido group, N'-arylureido Group, N ′, N′-diarylureido group, N′-alkyl-N′-arylureido group, N-alkylureido group, N-arylureido group, N′-alkyl-N-alkylureido group, N′- Alkyl-N-arylureido group, N ', N'-dialkyl-N-alkylureido group, N', N'-dialkyl-N-arylureido group, N'-aryl-N-alkylureido group, N'- Aryl-N-arylureido group, N ′, N′-diaryl-N-alkylureido group, N ′, N′-diaryl-N-ary Luureido group, N′-alkyl-N′-aryl-N-alkylureido group, N′-alkyl-N′-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl- N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group, formyl group, acyl group, carboxyl group , Alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N-arylcarbamoyl group , Alkylsul Finyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfo group (—SO ₃ H) and its conjugate base group (hereinafter referred to as sulfonate group), alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N -Alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, phosphono group (-PO ₃ H ₂₎ and its conjugated base group (hereinafter, phosphonato And referred), a dialkyl phosphono group _{(-PO 3 (alkyl) 2)} , diaryl phosphono group _{(-PO 3 (aryl) 2)} , alkyl aryl phosphono group _{(-PO 3 (alkyl) (aryl} )), mono Alkyl phosphono group (—PO ₃ H (alkyl)) and its conjugate base group (hereinafter referred to as alkyl phosphonate group), monoaryl phosphono group (—PO ₃ H (aryl)) and its conjugate base group (hereinafter referred to as “alkyl phosphonate group”) , Arylphosphonate group), phosphonooxy group (—OPO ₃ H ₂ ) and its conjugate base group (hereinafter referred to as phosphonateoxy group), dialkylphosphonooxy group (—OPO ₃ (alkyl) ₂ ) , Diarylphosphonooxy group (—OPO ₃ (aryl) ₂ ), alkylarylphosphonooxy group (—OPO ₃ (alkyl) (aryl)), monoalkylphosphonooxy group (—OPO ₃ H (alkyl)) and its Conjugated base group Hereinafter referred to as alkyl phosphonophenyl group), monoaryl phosphonooxy group (-OPO ₃ H (aryl)) and its conjugated base group (hereinafter referred to as aryl phosphite Hona preparative group), a cyano group, a nitro group, an aryl Group, heteroaryl group, alkenyl group, alkynyl group.

  Specific examples of the alkyl group in these substituents include the above-described alkyl groups, and specific examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, a xylyl group, a mesityl group, and a cumenyl group. , Chlorophenyl group, bromophenyl group, chloromethylphenyl group, hydroxyphenyl group, methoxyphenyl group, ethoxyphenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group, methylamino Phenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, ethoxyphenylcarbonyl group, phenoxycarbonylphenyl group, N-phenylcarbamoylphenyl group, phenyl group Cyanophenyl group, sulfophenyl group, sulfonatophenyl group, phosphonophenyl phenyl group, phosphonophenyl phenyl group and the like.

  As the heteroaryl group, a monocyclic or polycyclic aromatic ring containing at least one of nitrogen, oxygen and sulfur atoms is used. Examples of particularly preferred heteroaryl groups include thiophene, thiathrene, furan, Pyran, isobenzofuran, chromene, xanthene, phenoxazine, pyrrole, pyrazole, isothiazole, isoxazole, pyrazine, pyrimidine, pyridazine, indolizine, isoindolizine, indoyl, indazole, purine, quinolidine, isoquinoline, phthalazine, naphthyridine, Quinazoline, cinolin, pteridine, carbazole, carboline, phenanthrine, acridine, perimidine, phenanthroline, phthalazine, phenazazine, phenoxazine, furazane, phenoxazine, etc. It further may be benzo-fused, or may have a substituent.

Examples of alkenyl groups include vinyl, 1-propenyl, 1-butenyl, cinnamyl, 2-chloro-1-ethenyl, etc. Examples of alkynyl include ethynyl, 1 -Propynyl group, 1-butynyl group, trimethylsilylethynyl group and the like. Examples of G ¹ in the acyl group (G ¹ CO—) include hydrogen and the above alkyl groups and aryl groups. Among these substituents, even more preferred are halogen atoms (—F, —Br, —Cl, —I), alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, N-alkylamino groups, N, N -Dialkylamino group, acyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, acylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group Group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, sulfo group, sulfonate group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfa group Moyl group, N-aryl sulf Moyl group, N-alkyl-N-arylsulfamoyl group, phosphono group, phosphonate group, dialkyl phosphono group, diaryl phosphono group, monoalkyl phosphono group, alkyl phosphonate group, monoaryl phosphono group, aryl phosphine group Examples include an onato group, a phosphonooxy group, a phosphonateoxy group, an aryl group, and an alkenyl group.

  On the other hand, examples of the alkylene group in the substituted alkyl group include divalent organic residues obtained by removing any one of the hydrogen atoms on the alkyl group having 1 to 20 carbon atoms. Can include linear alkylene groups having 1 to 12 carbon atoms, branched chains having 3 to 12 carbon atoms, and cyclic alkylene groups having 5 to 10 carbon atoms.

Specific examples of preferred substituted alkyl groups as R ⁶⁴ , R ⁶⁵ and R ⁶⁷ obtained by combining the substituent with an alkylene group include chloromethyl, bromomethyl, 2-chloroethyl, trifluoromethyl, methoxy Methyl group, methoxyethoxyethyl group, allyloxymethyl group, phenoxymethyl group, methylthiomethyl group, tolylthiomethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyloxymethyl group, benzoyloxymethyl group, N -Cyclohexylcarbamoyloxyethyl group, N-phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxoethyl group, 2-oxopropyl group, carboxypropyl group, methoxycarboni Ruethyl group, allyloxycarbonylbutyl group, chlorophenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl group, N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, N-methyl- N- (sulfophenyl) carbamoylmethyl group, sulfobutyl group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N-dipropylsulfamoylpropyl group, N-tolylsulfamoylpropyl group N-methyl-N- (phosphonophenyl) sulfamoyloctyl group, phosphonobutyl group, phosphonatohexyl group, diethylphosphonobutyl group, diphenylphosphonopropyl group, methylphosphonobutyl group, methylphosphonatobuty Group, tolylphosphonohexyl group, tolylphosphonatohexyl group, phosphonooxypropyl group, phosphonateoxybutyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-methyl-1-phenylethyl group, p- Methylbenzyl group, cinnamyl group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2-methylallyl group, 2-methylpropenylmethyl group, 2-propynyl group, 2-butynyl group, 3-butynyl group, etc. Can be mentioned.

Specific examples of preferred aryl groups as R ⁶⁴ , R ⁶⁵ and R ⁶⁷ include ^those in which 1 to 3 benzene rings form a condensed ring, and those in which a benzene ring and a 5-membered unsaturated ring form a condensed ring. Specific examples include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenaphthenyl group, and a fluorenyl group. Among these, a phenyl group and a naphthyl group are more preferable. .

Specific examples of preferred substituted aryl groups as R ⁶⁴ , R ⁶⁵ and R ⁶⁷ include those having a monovalent non-metallic atomic group excluding hydrogen as a substituent on the ring-forming carbon atom of the aryl group described above. . Examples of preferred substituents include the alkyl groups, substituted alkyl groups, and those previously shown as substituents in the substituted alkyl group. Preferred examples of such a substituted aryl group include biphenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, fluorophenyl group, chloromethylphenyl group, trifluoromethylphenyl group. Hydroxyphenyl group, methoxyphenyl group, methoxyethoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, methylthiophenyl group, tolylthiophenyl group, ethylaminophenyl group, diethylaminophenyl group, morpholinophenyl group, acetyloxyphenyl group, Benzoyloxyphenyl group, N-cyclohexylcarbamoyloxyphenyl group, N-phenylcarbamoyloxyphenyl group, acetylaminophenyl group, N-methylbenzoylaminophenyl group, carbo Cyphenyl group, methoxycarbonylphenyl group, allyloxycarbonylphenyl group, chlorophenoxycarbonylphenyl group, carbamoylphenyl group, N-methylcarbamoylphenyl group, N, N-dipropylcarbamoylphenyl group, N- (methoxyphenyl) carbamoylphenyl group N-methyl-N- (sulfophenyl) carbamoylphenyl group, sulfophenyl group, sulfonatophenyl group, sulfamoylphenyl group, N-ethylsulfamoylphenyl group, N, N-dipropylsulfamoylphenyl group, N-tolylsulfamoylphenyl group, N-methyl-N- (phosphonophenyl) sulfamoylphenyl group, phosphonophenyl group, phosphonatophenyl group, diethylphosphonophenyl group, diphenylphosphono Enyl group, methylphosphonophenyl group, methylphosphonatophenyl group, tolylphosphonophenyl group, tolylphosphonatophenyl group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2-methylallylphenyl group, 2- Examples thereof include a methylpropenylphenyl group, a 2-propynylphenyl group, a 2-butynylphenyl group, and a 3-butynylphenyl group.

R ⁶⁶ represents a substituted or unsubstituted aromatic ring or heterocyclic ring. The aromatic ring or heterocycle which may have a substituent is an organic compound having a cyclic structure, and the atoms constituting the ring include not only carbon atoms but also O, S, N and other heteroatoms. It may be a thing. Specific examples include the structures described in the organic compound nomenclature TEBIKI (Chemical Doujinshi) P27-P40.

The sensitizing dye represented by the general formula (XVIII) of the present invention comprises an acidic nucleus as shown above, an acidic nucleus having an active methylene group, and a substituted or unsubstituted aromatic ring or heterocyclic ring. Although obtained by a condensation reaction, these can be synthesized with reference to JP-B-59-28329. Preferable specific examples of the compound represented by the general formula (XVIII) include those shown below. Note that the present invention is not limited to this. Further, the isomer by the double bond connecting the acidic nucleus and the basic nucleus is not clear, and the present invention is not limited to either isomer.

一般式(XIX)は、カルバゾール系増感色素である。
一般式（XIX）中、R¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸およびR⁹は、それぞれ独立に一価の非金属原子団を表し、但し、Ｒ¹およびＲ³のうちの少なくとも一つは、下記部分構造式（XIX-1）に示す一価の有機残基で表され、R¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸およびR⁹は、それぞれ独立に、脂肪族環または芳香族環を形成するため結合することができる。

General formula (XIX) is a carbazole sensitizing dye.
In general formula (XIX), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ each independently represent a monovalent nonmetallic atomic group, provided that At least one of R ¹ and R ³ is represented by a monovalent organic residue represented by the following partial structural formula (XIX-1), and R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ can each independently be joined to form an aliphatic ring or an aromatic ring.

（部分構造式（XIX-1）中、R¹⁰は、一価の非金属原子団を表し、Ｚは隣接する原子と共同して５員環酸性核を形成するのに必要な２価の非金属原子団を表し、R¹⁰は前記一般式（XIX）中のR¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸またはR⁹と脂肪族環または芳香族環を形成するため結合することができる。）

(In the partial structural formula (XIX-1), R ¹⁰ represents a monovalent non-metallic atomic group, and Z represents a divalent non-metallic group necessary for forming a five-membered acidic nucleus together with adjacent atoms. Represents a metal atomic group, and R ¹⁰ represents R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ or R ^{9 in the} general formula (XIX) and an aliphatic ring or aromatic Can be joined to form a ring.)

The general formula (XIX) and the partial structural formula (XIX-1) will be described in detail. R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom or a monovalent nonmetallic atomic group, preferably Substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted aryl group, substituted or unsubstituted aromatic heterocyclic residue, substituted or unsubstituted alkoxy group, substituted or unsubstituted alkylthio Represents a group, a hydroxy group, or a halogen atom.

Preferable examples of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ will be specifically described. Examples of preferable alkyl groups include linear, branched, and cyclic alkyl groups having 1 to 20 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, a propyl group, Butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, octadecyl, eicosyl, isopropyl, isobutyl, s-butyl, Examples thereof include t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group and 2-norbornyl group. Of these, linear alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, and cyclic alkyl groups having 5 to 10 carbon atoms are more preferable.

  As the substituent of the substituted alkyl group, a monovalent nonmetallic atomic group excluding hydrogen is used, and preferred examples include a halogen atom (—F, —Br, —Cl, —I), a hydroxyl group, an alkoxy group, Aryloxy group, mercapto group, alkylthio group, arylthio group, alkyldithio group, aryldithio group, amino group, N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diarylamino group N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N-arylcarbamoyloxy group, alkylsulfoxy group,

Arylsulfoxy group, acylthio group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N′-alkylureido group, N ′, N′-dialkylureido group, N′-arylureido Group, N ′, N′-diarylureido group, N′-alkyl-N′-arylureido group, N-alkylureido group, N-arylureido group, N′-alkyl-N-alkylureido group, N′- Alkyl-N-arylureido group, N ', N'-dialkyl-N-alkylureido group, N', N'-dialkyl-N-arylureido group, N'-aryl-N-alkylureido group, N'- Aryl-N-arylureido group, N ′, N′-diaryl-N-alkylureido group, N ′, N′-diaryl-N-ary Ruureido group, N'- alkyl -N'- aryl -N- alkylureido group, N'- alkyl -N'- aryl -N- arylureido group,

Alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N -Aryloxycarbonylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N- di arylcarbamoyl, N- alkyl -N- arylcarbamoyl groups, alkylsulfinyl groups, arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfo group (-SO ₃ H) and its conjugated base group (hereinafter Called sulfonato group), alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diaryls Rufinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-diaryl Sulfamoyl group, N-alkyl-N-arylsulfamoyl group,

Phosphono group (—PO ₃ H ₂ ) and its conjugate base group (hereinafter referred to as “phosphonate group”), dialkyl phosphono group (—PO ₃ (alkyl) ₂ ), diaryl phosphono group (—PO ₃ (aryl) ₂ ) , Alkylaryl phosphono group (—PO ₃ (alkyl) (aryl)), monoalkyl phosphono group (—PO ₃ H (alkyl)) and its conjugate base group (hereinafter referred to as alkyl phosphonate group), monoaryl Phosphono group (—PO ₃ H (aryl)) and its conjugate base group (hereinafter referred to as aryl phosphonate group), phosphonooxy group (—OPO ₃ H ₂ ) and its conjugate base group (hereinafter referred to as “phosphonateoxy”) Group), dialkyl phosphonooxy group (—OPO ₃ (alkyl) ₂ ), diaryl phosphonooxy group (—OPO ₃ (aryl) ₂ ), alkylaryl phosphonooxy group (—OPO ₃ (alkyl) (aryl) )), -Alkyl phosphonooxy group (-OPO ₃ H (alkyl)) and its conjugated base group (hereinafter referred to as alkyl phosphonophenyl group), monoaryl phosphonooxy group (-OPO ₃ H (aryl)) and its conjugate Examples include a base group (hereinafter referred to as an arylphosphonatooxy group), a cyano group, a nitro group, an aryl group, a heteroaryl group, an alkenyl group, and an alkynyl group.

  Specific examples of the alkyl group in these substituents include the above-described alkyl groups, and specific examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, a xylyl group, a mesityl group, and a cumenyl group. , Chlorophenyl group, bromophenyl group, chloromethylphenyl group, hydroxyphenyl group, methoxyphenyl group, ethoxyphenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group, methylamino Phenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, ethoxyphenylcarbonyl group, phenoxycarbonylphenyl group, N-phenylcarbamoylphenyl group, cyanophene Group, sulfophenyl group, sulfonatophenyl group, phosphonophenyl phenyl group, and a phosphonophenyl phenyl group.

As the heteroaryl group, a monocyclic or polycyclic aromatic ring containing at least one of nitrogen, oxygen and sulfur atoms is used. Examples of particularly preferred heteroaryl groups include thiophene, thiathrene, furan, Pyran, isobenzofuran, chromene, xanthene, phenoxazine, pyrrole, pyrazole, isothiazole, isoxazole, pyrazine, pyrimidine, pyridazine, indolizine, isoindolizine, indoyl, indazole, purine, quinolidine, isoquinoline, phthalazine, naphthyridine, Quinazoline, sinoline, pteridine, carbazole, carboline, phenanthrine, acridine, perimidine, phenanthroline, phthalazine, phenazazine, phenoxazine, furazane, phenoxazine, etc. These further may be benzo-fused or may have a substituent.
Examples of alkenyl groups include vinyl, 1-propenyl, 1-butenyl, cinnamyl, 2-chloro-1-ethenyl, etc. Examples of alkynyl include ethynyl, 1 -Propynyl group, 1-butynyl group, trimethylsilylethynyl group and the like.

Examples of G ¹ in the acyl group (G ¹ CO—) include hydrogen and the above alkyl groups and aryl groups. Among these substituents, even more preferred are halogen atoms (—F, —Br, —Cl, —I), alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, N-alkylamino groups, N, N— Dialkylamino group, acyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, acylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, sulfo group, sulfonate group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group Group, N-arylsulfa Yl group, N-alkyl-N-arylsulfamoyl group, phosphono group, phosphonate group, dialkyl phosphono group, diaryl phosphono group, monoalkyl phosphono group, alkyl phosphonate group, monoaryl phosphono group, aryl phosphine group Examples include an onato group, a phosphonooxy group, a phosphonateoxy group, an aryl group, and an alkenyl group.

  On the other hand, examples of the alkylene group in the substituted alkyl group include divalent organic residues obtained by removing any one of the hydrogen atoms on the alkyl group having 1 to 20 carbon atoms. Can include linear alkylene groups having 1 to 12 carbon atoms, branched chains having 3 to 12 carbon atoms, and cyclic alkylene groups having 5 to 10 carbon atoms.

Preferred substituents of the substituted alkyl group as R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ obtained by combining the substituent and the alkylene group are Specific examples of the preferable substituted alkyl group include, but are not limited to, chloromethyl group, bromomethyl group, 2-chloroethyl group, trifluoromethyl group, methoxymethyl group, methoxyethoxyethyl group, allyloxymethyl group, and phenoxymethyl group. , Methylthiomethyl group, tolylthiomethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyloxymethyl group, benzoyloxymethyl group, N-cyclohexylcarbamoyloxyethyl group, N-phenylcarbamoyloxyethyl group, acetyl Aminoethyl group, N-methylbenzoylaminopropyl group, 2- Xoxoethyl group, 2-oxopropyl group, carboxypropyl group, methoxycarbonylethyl group, allyloxycarbonylbutyl group, chlorophenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl group, N, N-dipropylcarbamoylmethyl group N- (methoxyphenyl) carbamoylethyl group, N-methyl-N- (sulfophenyl) carbamoylmethyl group, sulfobutyl group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N- Dipropylsulfamoylpropyl group, N-tolylsulfamoylpropyl group,

N-methyl-N- (phosphonophenyl) sulfamoyloctyl group, phosphonobutyl group, phosphonatohexyl group, diethylphosphonobutyl group, diphenylphosphonopropyl group, methylphosphonobutyl group, methylphosphonatobutyl group , Tolylphosphonohexyl group, tolylphosphonatohexyl group, phosphonooxypropyl group, phosphonateoxybutyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-methyl-1-phenylethyl group, p-methyl Benzyl group, cinnamyl group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2-methylallyl group, 2-methylpropenylmethyl group, 2-propynyl group, 2-butynyl group, 3-butynyl group, etc. be able to.

Specific examples of preferred aryl groups as R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ include 1 to 3 benzene rings as condensed rings. And those in which a benzene ring and a 5-membered unsaturated ring form a condensed ring. Specific examples include phenyl, naphthyl, anthryl, phenanthryl, indenyl, acenaphthenyl, fluorenyl. Group, and among these, a phenyl group and a naphthyl group are more preferable.
Specific examples of the substituted aryl group preferable as R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ include a ring-forming carbon atom of the aforementioned aryl group. As the substituent, those having a monovalent nonmetallic atomic group excluding hydrogen are used. Examples of preferred substituents include the alkyl groups, substituted alkyl groups, and those previously shown as substituents in the substituted alkyl group. Preferred examples of such a substituted aryl group include biphenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, fluorophenyl group, chloromethylphenyl group, trifluoromethylphenyl group. Hydroxyphenyl group, methoxyphenyl group, methoxyethoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, methylthiophenyl group, tolylthiophenyl group, ethylaminophenyl group, diethylaminophenyl group, morpholinophenyl group, acetyloxyphenyl group, Benzoyloxyphenyl group, N-cyclohexylcarbamoyloxyphenyl group, N-phenylcarbamoyloxyphenyl group, acetylaminophenyl group, N-methylbenzoylaminophenyl group, carbo Cyphenyl group, methoxycarbonylphenyl group, allyloxycarbonylphenyl group, chlorophenoxycarbonylphenyl group, carbamoylphenyl group, N-methylcarbamoylphenyl group, N, N-dipropylcarbamoylphenyl group, N- (methoxyphenyl) carbamoylphenyl group N-methyl-N- (sulfophenyl) carbamoylphenyl group,

Sulfophenyl group, sulfonatophenyl group, sulfamoylphenyl group, N-ethylsulfamoylphenyl group, N, N-dipropylsulfamoylphenyl group, N-tolylsulfamoylphenyl group, N-methyl-N- (Phosphonophenyl) sulfamoylphenyl group, phosphonophenyl group, phosphonatophenyl group, diethylphosphonophenyl group, diphenylphosphonophenyl group, methylphosphonophenyl group, methylphosphonatophenyl group, tolylphosphonophenyl group , Tolylphosphonate phenyl group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2-methylallylphenyl group, 2-methylpropenylphenyl group, 2-propynylphenyl group, 2-butynylphenyl group, 3- List butynylphenyl groups, etc. It can be.

部分構造式（XIX-1）中、Ｚは隣接する原子と共同して置換基を有しても良い５員環酸性核を形成するのに必要な２価の非金属原子団を表し、酸性核の具体例としては、１，３−ジカルボニル核（例えば、１，３−インダンジオン、１，３−ジオキサン−４，６−ジオン等）、ピラゾリノン核（例えば、３−メチル−１−フェニル−２−ピラゾリン−５−オン、１−フェニル−２−ピラゾリン−５−オン、１−（２−ベンゾチアゾリル）−３−メチル−２−ピラゾリン−５−オン等）、イソオキサゾリノン核（例えば、３−フェニル−２−イソオキサゾリン−５−オン、３−メチル−２−イソオキサゾリン−５−オン等）、オキシインドール核（例えば、１−アルキル−２，３−ジヒドロ−２−オキシインドール等）、２−チオ−２，４−チアゾリジンジオン核（例えば、ローダニンおよびそのＮ置換誘導体、例えば、３−メチルローダニン、３−エチルローダニン、３−フェニルローダニン、３−アリルローダニン、３−ベンジルローダニン、３−カルボキシメチルローダニン、３−カルボキシエチルローダニン、３−メトキシカルボニルメチルローダニン、３−ヒドロキシエチルローダニン、３−モルフォリノエチルローダニン等）、２−チオ−２，４−オキサゾリジンジオン核（即ち、２−チオ−２，４−（３Ｈ，４Ｈ）−オキサゾールジオン核、例えば、２−エチル−２−チオ−２，４−オキサゾリジンジオン等）、チアナフテノン核（例えば、３（２Ｈ）−チアナフテノン、３（２Ｈ）−チアノフテノン−１，１−ジオキサイド等）、２−チオー２，５−チアゾリジンジオン核（例えば、３−エチル−２−チオ−２，５−チアゾリジンジオン等）、２，４−チアゾリジンジオン核（例えば、２，４−チアゾリジンジオン、３−エチル−４−チアゾリジンジオン、３−フェニル−２，４−チアゾリジンジオン等）、チアゾリジノン核（例えば、４−チアゾリジノン、３−エチル−４−チアゾリジノン、２−エチルメルカプト−４−チアゾリジノン、２−メチルフェニルアミノ−４−チアゾリジノン等）、２−イミノ−２−オキサゾリン−４−オン核（即ち、擬ヒダントイン核）、２，４−イミダゾリジンジオン核（即ち、ヒダントイン核、例えば、２，４−イミダゾリジンジオン、３−エチル−２，４−イミダゾリジンジオン、１，３−ジエチル−２，４−イミダゾリジンジオン等）、２−チオ−２，４−イミダゾリジンジオン核（即ち、チオヒダントイン核、例えば、２−チオ−２，４−イミダゾリジンジオン、３−エチル−２−チオ−２，４−イミダゾリジンジオン、１，３−ジエチル−２−チオ−２，４−イミダゾリジンジオン等）、イミダゾリン−５−オン核（例えば、２−プロピルメルカプト−２−イミダゾリン−５−オン等）、フラン−５−オン核、チオインドキシル核（例えば、５−メチルチオインドキシル等）が挙げられ、これらの酸性核はさらに置換基を有してもよい。 Next, Z in the general formula (XIX) and the partial structural formula (XIX-1) will be described.

In the partial structural formula (XIX-1), Z represents a divalent nonmetallic atomic group necessary for forming a 5-membered ring acidic nucleus which may have a substituent in cooperation with an adjacent atom, and is acidic. Specific examples of the nucleus include a 1,3-dicarbonyl nucleus (for example, 1,3-indandione, 1,3-dioxane-4,6-dione, etc.), a pyrazolinone nucleus (for example, 3-methyl-1-phenyl). -2-pyrazolin-5-one, 1-phenyl-2-pyrazolin-5-one, 1- (2-benzothiazolyl) -3-methyl-2-pyrazolin-5-one, etc.), isoxazolinone nucleus (for example , 3-phenyl-2-isoxazolin-5-one, 3-methyl-2-isoxazolin-5-one, etc.), oxindole nucleus (for example, 1-alkyl-2,3-dihydro-2-oxindole, etc.) ), 2-thio-2,4-thia Lysine dione nuclei (eg, rhodanine and its N-substituted derivatives such as 3-methyl rhodanine, 3-ethyl rhodanine, 3-phenyl rhodanine, 3-allyl rhodanine, 3-benzyl rhodanine, 3-carboxymethyl rhodanine 3-carboxyethylrhodanine, 3-methoxycarbonylmethylrhodanine, 3-hydroxyethylrhodanine, 3-morpholinoethylrhodanine, etc.), 2-thio-2,4-oxazolidinedione nucleus (ie 2-thio -2,4- (3H, 4H) -oxazoledione nuclei such as 2-ethyl-2-thio-2,4-oxazolidinedione, etc., thianaphthenone nuclei (eg 3 (2H) -thianaphthenone, 3 (2H) -Thianoftenone-1,1-dioxide, etc.), 2-thio-2,5-thiazolidinedione Nucleus (for example, 3-ethyl-2-thio-2,5-thiazolidinedione, etc.), 2,4-thiazolidinedione nucleus (for example, 2,4-thiazolidinedione, 3-ethyl-4-thiazolidinedione, 3-phenyl) -2,4-thiazolidinedione, etc.), thiazolidinone nucleus (for example, 4-thiazolidinone, 3-ethyl-4-thiazolidinone, 2-ethylmercapto-4-thiazolidinone, 2-methylphenylamino-4-thiazolidinone, etc.), 2- Imino-2-oxazolin-4-one nucleus (ie pseudohydantoin nucleus), 2,4-imidazolidinedione nucleus (ie hydantoin nucleus such as 2,4-imidazolidinedione, 3-ethyl-2,4- Imidazolidinedione, 1,3-diethyl-2,4-imidazolidinedione, etc.), 2-thio-2,4-imidazoli Thiohydantoin nuclei such as 2-thio-2,4-imidazolidinedione, 3-ethyl-2-thio-2,4-imidazolidinedione, 1,3-diethyl-2-thio-2 , 4-imidazolidinedione, etc.), imidazolin-5-one nucleus (eg, 2-propylmercapto-2-imidazolin-5-one), furan-5-one nucleus, thioindoxyl nucleus (eg, 5-methylthio) Indoxyl etc.), and these acidic nuclei may further have a substituent.

Of the carbazole-based sensitizing dyes represented by the general formula (XIX) and the partial structural formula (XIX-1) described above, the dye having a structure represented by the following general formulas (2) to (6) is: This is particularly preferred because it provides an ink for ink jet recording including a polymerization initiating system that has high sensitization ability and excellent storage stability.

In the general formulas (2) to (6), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are the above general formula (XIX) and a moiety X ¹ , X ² , X ³ and X ⁴ are each independently O atom, S atom or N R ²⁰ , and Y is O atom, S atom or N R ^21. Each of R ^{11 to} R ²¹ independently represents a hydrogen atom or a monovalent non-metallic atomic group, and may form an aliphatic ring or an aromatic ring, each of which may have a substituent. Can be combined.

General formulas (2) to (6) will be described in detail. In general formulas (2) to (6), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ have the same meanings as in general formula (XIX). R ^{11 to} R ²¹ each independently represents a hydrogen atom or a monovalent nonmetallic atomic group, preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted group. An aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group, a hydroxyl group, and a halogen atom are represented. R ^{13 to} R ¹⁹ can be bonded to each other to form an aliphatic ring or an aromatic ring which may have a substituent. Preferred examples of R ^{11 to} R ²¹ are described in the description of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ^{10 in} the general formula (XIX). Examples similar to those described above are given.

In the general formulas (2) to (6), X ¹ , X ² , X ³ and X ⁴ each independently represent an O atom, S atom or N R ²⁰ , and Y represents an O atom, S atom or N R ²¹ . .

The sensitizing dyes represented by the general formula (XIX) and the general formulas (2) to (6) are an acidic nucleus as shown above, an acidic nucleus having an active methylene group, a substituted or unsubstituted one. These can be obtained by condensation reaction with carbazole carbaldehyde, which can be synthesized with reference to JP-B-59-28329. Preferred specific examples (D1) to (D31) of the compound represented by the general formula (XIX) are shown below, but the present invention is not limited thereto. In addition, the isomer due to the double bond connecting the acidic nucleus and the carbazole skeleton is not clear, and the present invention is not limited to either isomer.

一般式（XX）中、Ｒは一価の非金属原子団であり、Ｘは一価の非金属原子団であり、それぞれ互いに結合することができ、Ｙは５員環または６員環を表す。
ここで、一般式（XX）について詳しく説明する。Ｒはそれぞれ独立に一価の非金属原子団を表す。この様な置換基Ｒの好ましい具体例としては、水素原子、アルキル基、置換アルキル基、ハロゲン原子（−Ｆ、−Ｂｒ、−Ｃｌ、−Ｉ）、ヒドロキシル基、アルコキシ基、アリーロキシ基、メルカプト基、アルキルチオ基、アリールチオ基、アルキルジチオ基、アリールジチオ基、アミノ基、Ｎ−アルキルアミノ基、Ｎ，Ｎ−ジアルキルアミノ基、Ｎ−アリールアミノ基、Ｎ，Ｎ−ジアリールアミノ基、Ｎ−アルキル−Ｎ−アリールアミノ基、アシルオキシ基、カルバモイルオキシ基、Ｎ−アルキルカルバモイルオキシ基、Ｎ−アリールカルバモイルオキシ基、Ｎ，Ｎ−ジアルキルカルバモイルオキシ基、Ｎ，Ｎ−ジアリールカルバモイルオキシ基、Ｎ−アルキル−Ｎ−アリールカルバモイルオキシ基、アルキルスルホキシ基、アリールスルホキシ基、アシルチオ基、アシルアミノ基、Ｎ−アルキルアシルアミノ基、Ｎ−アリールアシルアミノ基、ウレイド基、Ｎ′−アルキルウレイド基、Ｎ′，Ｎ′−ジアルキルウレイド基、Ｎ′−アリールウレイド基、Ｎ′，Ｎ′−ジアリールウレイド基、Ｎ′−アルキル−Ｎ′−アリールウレイド基、Ｎ−アルキルウレイド基、Ｎ−アリールウレイド基、Ｎ′−アルキル−Ｎ−アルキルウレイド基、Ｎ′−アルキル−Ｎ−アリールウレイド基、Ｎ′，Ｎ′−ジアルキル−Ｎ−アルキルウレイド基、Ｎ′，Ｎ′−ジアルキル−Ｎ−アリールウレイド基、Ｎ′−アリール−Ｎ−アルキルウレイド基、Ｎ′−アリール−Ｎ−アリールウレイド基、Ｎ′，Ｎ′−ジアリール−Ｎ−アルキルウレイド基、Ｎ′，Ｎ′−ジアリール−Ｎ−アリールウレイド基、Ｎ′−アルキル−Ｎ′−アリール−Ｎ−アルキルウレイド基、Ｎ′−アルキル−Ｎ′−アリール−Ｎ−アリールウレイド基、

In general formula (XX), R is a monovalent nonmetallic atomic group, X is a monovalent nonmetallic atomic group, and can be bonded to each other, and Y represents a 5-membered ring or a 6-membered ring. .
Here, the general formula (XX) will be described in detail. Each R independently represents a monovalent nonmetallic atomic group. Preferred examples of such a substituent R include a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom (—F, —Br, —Cl, —I), a hydroxyl group, an alkoxy group, an aryloxy group, a mercapto group. , Alkylthio group, arylthio group, alkyldithio group, aryldithio group, amino group, N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diarylamino group, N-alkyl- N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N -Arylcarbamoyloxy group, alkylsulfoxy group, arylsulfuryl group Xyl group, acylthio group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N′-alkylureido group, N ′, N′-dialkylureido group, N′-arylureido group, N ', N'-diarylureido group, N'-alkyl-N'-arylureido group, N-alkylureido group, N-arylureido group, N'-alkyl-N-alkylureido group, N'-alkyl- N-arylureido group, N ′, N′-dialkyl-N-alkylureido group, N ′, N′-dialkyl-N-arylureido group, N′-aryl-N-alkylureido group, N′-aryl- N-arylureido group, N ′, N′-diaryl-N-alkylureido group, N ′, N′-diaryl-N-arylureido , N'- alkyl -N'- aryl -N- alkylureido group, N'- alkyl -N'- aryl -N- arylureido group,

Alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N -Aryloxycarbonylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N- di arylcarbamoyl, N- alkyl -N- arylcarbamoyl groups, alkylsulfinyl groups, arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfo group (-SO ₃ H) and its conjugated base group (hereinafter Called sulfonato group), alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diaryls Rufinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-diaryl Sulfamoyl group, N-alkyl-N-arylsulfamoyl group,

Phosphono group (—PO ₃ H ₂ ) and its conjugate base group (hereinafter referred to as “phosphonate group”), dialkyl phosphono group (—PO ₃ (alkyl) ₂ ), diaryl phosphono group (—PO ₃ (aryl) ₂ ) , Alkylaryl phosphono group (—PO ₃ (alkyl) (aryl)), monoalkyl phosphono group (—PO ₃ H (alkyl)) and its conjugate base group (hereinafter referred to as alkyl phosphonate group), monoaryl Phosphono group (—PO ₃ H (aryl)) and its conjugate base group (hereinafter referred to as aryl phosphonate group), phosphonooxy group (—OPO ₃ H ₂ ) and its conjugate base group (hereinafter referred to as “phosphonateoxy”) Group), dialkyl phosphonooxy group (—OPO ₃ (alkyl) ₂ ), diaryl phosphonooxy group (—OPO ₃ (aryl) ₂ ), alkylaryl phosphonooxy group (—OPO ₃ (alkyl) (aryl) )), -Alkyl phosphonooxy group (-OPO ₃ H (alkyl)) and its conjugated base group (hereinafter referred to as alkyl phosphonophenyl group), monoaryl phosphonooxy group (-OPO ₃ H (aryl)) and its conjugate Examples include a base group (hereinafter referred to as an arylphosphonatooxy group), a cyano group, a nitro group, an aryl group, a heteroaryl group, an alkenyl group, and an alkynyl group.

  Preferable examples of the alkyl group in these substituents include linear, branched and cyclic alkyl groups having 1 to 20 carbon atoms. Specific examples thereof include a methyl group, Ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, hexadecyl group, octadecyl group, eicosyl group, isopropyl group, isobutyl group S-butyl group, t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group, 2-norbornyl group. it can. Of these, linear alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, and cyclic alkyl groups having 5 to 10 carbon atoms are more preferable.

  On the other hand, examples of the alkylene group in the substituted alkyl group include divalent organic residues obtained by removing any one of the hydrogen atoms on the alkyl group having 1 to 20 carbon atoms. Can include linear alkylene groups having 1 to 12 carbon atoms, branched chains having 3 to 12 carbon atoms, and cyclic alkylene groups having 5 to 10 carbon atoms. The substituent of the substituted alkyl group is arbitrary, but preferred examples of the substituted alkyl group include chloromethyl group, bromomethyl group, 2-chloroethyl group, trifluoromethyl group, methoxymethyl group, methoxyethoxyethyl group, allyloxy. Methyl group, phenoxymethyl group, methylthiomethyl group, tolylthiomethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyloxymethyl group, benzoyloxymethyl group, N-cyclohexylcarbamoyloxyethyl group, N-phenyl Carbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxoethyl group, 2-oxopropyl group, carboxypropyl group, methoxycarbonylethyl group, allyloxycarbonylbutyl Chlorophenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl group, N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, N-methyl-N- (sulfophenyl) carbamoylmethyl Group, sulfobutyl group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N-dipropylsulfamoylpropyl group, N-tolylsulfamoylpropyl group,

N-methyl-N- (phosphonophenyl) sulfamoyloctyl group, phosphonobutyl group, phosphonatohexyl group, diethylphosphonobutyl group, diphenylphosphonopropyl group, methylphosphonobutyl group, methylphosphonatobutyl group , Tolylphosphonohexyl group, tolylphosphonatohexyl group, phosphonooxypropyl group, phosphonateoxybutyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-methyl-1-phenylethyl group, p-methyl Benzyl group, cinnamyl group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2-methylallyl group, 2-methylpropenylmethyl group, 2-propynyl group, 2-butynyl group, 3-butynyl group, etc. be able to.

  Specific examples of the aryl group in these substituents include those in which 1 to 3 benzene rings form a condensed ring, and those in which a benzene ring and a 5-membered unsaturated ring form a condensed ring. Specific examples thereof include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenaphthenyl group, and a fluorenyl group. Among these, a phenyl group and a naphthyl group are more preferable.

  Specific examples of the substituted aryl group include those having a monovalent nonmetallic atomic group excluding hydrogen as a substituent on the ring-forming carbon atom of the aryl group. Preferred specific examples of the substituted aryl group include a biphenyl group, a tolyl group, a xylyl group, a mesityl group, a cumenyl group, a chlorophenyl group, a bromophenyl group, a fluorophenyl group, a chloromethylphenyl group, a trifluoromethylphenyl group, and a hydroxyphenyl group. , Methoxyphenyl group, methoxyethoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, methylthiophenyl group, tolylthiophenyl group, ethylaminophenyl group, diethylaminophenyl group, morpholinophenyl group, acetyloxyphenyl group, benzoyloxyphenyl group N-cyclohexylcarbamoyloxyphenyl group, N-phenylcarbamoyloxyphenyl group, acetylaminophenyl group, N-methylbenzoylaminophenyl group, carboxypheny Group, methoxycarbonylphenyl group, allyloxycarbonylphenyl group, chlorophenoxycarbonylphenyl group, carbamoylphenyl group, N-methylcarbamoylphenyl group, N, N-dipropylcarbamoylphenyl group, N- (methoxyphenyl) carbamoylphenyl group, N-methyl-N- (sulfophenyl) carbamoylphenyl group,

Sulfophenyl group, sulfonatophenyl group, sulfamoylphenyl group, N-ethylsulfamoylphenyl group, N, N-dipropylsulfamoylphenyl group, N-tolylsulfamoylphenyl group, N-methyl-N- (Phosphonophenyl) sulfamoylphenyl group, phosphonophenyl group, phosphonatophenyl group, diethylphosphonophenyl group, diphenylphosphonophenyl group, methylphosphonophenyl group, methylphosphonatophenyl group, tolylphosphonophenyl group , Tolylphosphonatophenyl group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2-methylallylphenyl group, 2-methylpropenylphenyl group, 2-propynylphenyl group, 2-butynylphenyl group, 3- List butynylphenyl groups, etc. Can.

  As the heteroaryl group, a monocyclic or polycyclic aromatic ring containing at least one of nitrogen, oxygen and sulfur atoms is used, and preferably a 5-membered or 6-membered ring such as furan, pyrrole or pyridine. Aromatic substituents can be used.

  Examples of alkenyl groups include vinyl, 1-propenyl, 1-butenyl, cinnamyl, 2-chloro-1-ethenyl, etc. Examples of alkynyl include ethynyl, 1 -Propynyl group, 1-butynyl group, trimethylsilylethynyl group and the like.

Examples of G ¹ in the acyl group (G ¹ CO—) include hydrogen and the above alkyl groups and aryl groups. Among these substituents, even more preferred are halogen atoms (—F, —Br, —Cl, —I), alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, N-alkylamino groups, N, N— Dialkylamino group, acyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, acylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, sulfo group, sulfonate group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group Group, N-arylsulfa Yl group, N-alkyl-N-arylsulfamoyl group, phosphono group, phosphonate group, dialkyl phosphono group, diaryl phosphono group, monoalkyl phosphono group, alkyl phosphonate group, monoaryl phosphono group, aryl phosphine group Examples include an onato group, a phosphonooxy group, a phosphonateoxy group, an aryl group, and an alkenyl group.

  R described above is selected from various practical viewpoints in addition to performance such as photosensitivity, photosensitive wavelength, and stability. For example, in terms of compatibility improvement in the composition system, prevention of crystal precipitation, when developing, solubility in a developing solution, dispersibility, difficulty in precipitation, raw material price, ease of synthesis, It is appropriately selected in consideration of economic viewpoints such as ease of purification. In this respect, examples of particularly preferable substituents include a hydrogen atom, a halogen atom (—F, —Br, —Cl, —I), a lower alkyl group having 1 to 6 carbon atoms (methyl group, ethyl group, Propyl group, isopropyl group, allyl group, 2-methylpropenyl group, etc.), alkyl-substituted aminoalkylene group (the alkyl group is a linear or branched alkyl group having 1 to 6 carbon atoms and having 5 to 7 carbon atoms) And examples of the alkylene group include mono-, di-, and tri-methylene groups having 1 to 3 carbon atoms.

  Specific examples of the aryl group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenaphthenyl group, and a fluorenyl group. Specific examples of the substituted aryl group include a biphenyl group, a tolyl group, Xylyl, mesityl, cumenyl, chlorophenyl, bromophenyl, fluorophenyl, chloromethylphenyl, trifluoromethylphenyl, hydroxyphenyl, methoxyphenyl, methoxyethoxyphenyl, allyloxyphenyl, phenoxy Phenyl group, methylthiophenyl group, tolylthiophenyl group, ethylaminophenyl group, diethylaminophenyl group, morpholinophenyl group, acetyloxyphenyl group, benzoyloxyphenyl group, N-cyclohexylcarbamo Oxy phenyl group, N- phenylcarbamoyloxy phenyl group, an acetylamino phenyl group, N- methyl-benzoylamino phenyl group,

Carboxyphenyl group, methoxycarbonylphenyl group, allyloxycarbonylphenyl group, chlorophenoxycarbonylphenyl group, carbamoylphenyl group, N-methylcarbamoylphenyl group, N, N-dipropylcarbamoylphenyl group, N- (methoxyphenyl) carbamoylphenyl Group, N-methyl-N- (sulfophenyl) carbamoylphenyl group, sulfophenyl group, sulfonatophenyl group, sulfamoylphenyl group, N-ethylsulfamoylphenyl group, N, N-dipropylsulfamoylphenyl group N-tolylsulfamoylphenyl group, N-methyl-N- (phosphonophenyl) sulfamoylphenyl group, phosphonophenyl group, phosphonatophenyl group, diethylphosphonophenyl group, diphenylphosphine Ionophenyl group, methylphosphonophenyl group, methylphosphonatophenyl group, tolylphosphonophenyl group, tolylphosphonatophenyl group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2-methylallylphenyl group, 2- Examples thereof include a methylpropenylphenyl group, a 2-propynylphenyl group, a 2-butynylphenyl group, and a 3-butynylphenyl group.

As the heteroaryl group, a monocyclic or polycyclic aromatic ring containing at least one of nitrogen, oxygen and sulfur atoms is used, and preferably a 5-membered or 6-membered ring such as furan, pyrrole or pyridine. Aromatic substituents can be used. As an example of the substituted heteroaryl group, a monovalent nonmetallic atomic group can be used, and specifically, any of those exemplified as examples of R can be used. Examples of particularly preferred heteroaryl groups include, for example, thiophene, thiathrene, furan, pyran, isobenzofuran, chromene, xanthene, phenoxazine, pyrrole, pyrazole, isothiazole, isoxazole, pyrazine, pyrimidine, pyridazine, indolizine, Indolizines, indoles, indazoles, purines, quinolidines, isoquinolines, phthalazines, naphthyridines, quinazolines, sinolines, pteridines, carbazoles, carbolines, phenanthrines, acridines, perimidines, phenanthrolins, phenalzazines, furansans, etc. It may be benzo-fused or may have a substituent.

X in the general formula (XX) is a monovalent nonmetallic atomic group, and the monovalent nonmetallic atomic group is the same as that defined in R above.
Y in the general formula (XX) represents a 5-membered ring or a 6-membered ring. Examples of the 5-membered ring and 6-membered ring include an aliphatic or aromatic 5-membered ring or 6-membered ring defined by the above formula (XVII).

Further, the general formula (XX) may be the following general formula (2), (3) or (4).

In general formulas (2) to (4), R represents a hydrogen atom or a monovalent nonmetallic atomic group, and can be bonded to each other. Ar represents an aromatic ring or a heteroaromatic ring, and A represents any of —NR ¹¹ R ¹² , —SR ¹³ or —OR ¹⁴ .
-NR < ¹¹ > R < ¹² >, -SR < ¹³ > and -OR < ¹⁴ > are those in which any one of the aromatic ring and the nitrogen atom, sulfur atom or oxygen atom in general formula (XX) is directly bonded. Atoms R ^{11 to} R ¹⁴ represent a hydrogen atom or a monovalent nonmetallic atomic group, and specific examples thereof include those described for R in the general formula (XX).

Y in the general formula (3) represents a 5-membered ring or 6-membered ring which may have a substituent. The definition of a 5-membered ring or a 6-membered ring is the same as the general formula (XX).
X in the general formula (4) represents NR, O, S, or Se.
The sensitizing dyes represented by the general formula (XX) and the general formulas (2) to (4) of the present invention are 1) Vaz, CJF et al .: Indian J. Chem. Sect. B, 14, 1976, 709. -711; 2) Grozinger, Karl. G .: Sorcek, Ronald J .; Oliver, James T: Eur. J. Med. Chem. Chem. Ther., EN, 20, 6, 1985, 487-491; 3) Takahashi, Ueda: Yakugaku Zasshi, 72, 1952, 506, Chem. Abstr., 1953, 6406; Preferred specific examples (D-1) to (D-42) of the compounds represented by the general formula (XX) and the general formulas (2) to (4) are shown below, but the present invention is limited thereto. is not. Further, the isomer by the double bond connecting the acidic nucleus and the basic nucleus is not clear, and the present invention is not limited to either isomer.

一般式（XXI）中、Ａｒは芳香環を表し、Ａは−ＮＲ³Ｒ⁴、−ＳＲ⁵または−ＯＲ⁶を表し、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵及びＲ⁶はそれぞれ独立に一価の非金属原子団を表す。ここで、一価の非金属原子団とは、一般式(XIV)のＲ⁵¹およびＲ⁵²と同一の定義である。
Ｚ^-は電荷の中和に必要なカウンターイオンを表す。但し、増感色素のカチオン部がアニオン性の置換基を有する場合は必ずしも必要ではない。具体的には、Ｚ^-は、ハロゲンイオン、過塩素酸イオン、テトラフルオロボレートイオン、へキサフルオロホスフェートイオン、およびスルホン酸イオンからなる群より選択される対イオンが挙げられ、好ましくは、ハロゲンイオン、過塩素酸イオン、へキサフルオロフオスフエートイオン、およびアリールスルホン酸イオンである。

In general formula (XXI), Ar represents an aromatic ring, A represents —NR ³ R ⁴ , —SR ⁵ or —OR ⁶ , and R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ represent Each independently represents a monovalent nonmetallic atomic group. Here, the monovalent nonmetallic atomic group has the same definition as R ⁵¹ and R ^{52 in} the general formula (XIV).
Z ⁻ represents a counter ion necessary for charge neutralization. However, it is not always necessary when the cation portion of the sensitizing dye has an anionic substituent. Specifically, Z ⁻ includes a counter ion selected from the group consisting of a halogen ion, a perchlorate ion, a tetrafluoroborate ion, a hexafluorophosphate ion, and a sulfonate ion, and preferably a halogen ion Perchlorate ion, hexafluorophosphite ion, and aryl sulfonate ion.

Moreover, it is preferable that general formula (XXI) is following General formula (2)-(4).

The general formula (2) will be described in detail. R ¹¹ to R ¹⁸ each independently represents a monovalent nonmetallic atomic group. Preferable specific examples of such a substituent include a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom (—F, —Br, —Cl, —I), a hydroxyl group, an alkoxy group, an aryloxy group, a mercapto group, Alkylthio group, arylthio group, alkyldithio group, aryldithio group, amino group, N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diarylamino group, N-alkyl-N -Arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N- Arylcarbamoyloxy group, alkylsulfoxy group,

Arylsulfoxy group, acylthio group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N′-alkylureido group, N ′, N′-dialkylureido group, N′-arylureido Group, N ′, N′-diarylureido group, N′-alkyl-N′-arylureido group, N-alkylureido group, N-arylureido group, N′-alkyl-N-alkylureido group, N′- Alkyl-N-arylureido group, N ', N'-dialkyl-N-alkylureido group, N', N'-dialkyl-N-arylureido group, N'-aryl-N-alkylureido group, N'- Aryl-N-arylureido group, N ′, N′-diaryl-N-alkylureido group, N ′, N′-diaryl-N-ary Ruureido group, N'- alkyl -N'- aryl -N- alkylureido group, N'- alkyl -N'- aryl -N- arylureido group,

Alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N -Aryloxycarbonylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfo group (-SO3H) and its conjugate base group (hereinafter, Sulfonate group), alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diaryls Rufinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-diaryl Sulfamoyl group, N-alkyl-N-arylsulfamoyl group,

Phosphono group (—PO ₃ H ₂ ) and its conjugate base group (hereinafter referred to as “phosphonate group”), dialkyl phosphono group (—PO ₃ (alkyl) ₂ ), diaryl phosphono group (—PO ₃ (aryl) ₂ ) , Alkylaryl phosphono group (—PO ₃ (alkyl) (aryl)), monoalkyl phosphono group (—PO ₃ H (alkyl)) and its conjugate base group (hereinafter referred to as alkyl phosphonate group), monoaryl Phosphono group (—PO ₃ H (aryl)) and its conjugate base group (hereinafter referred to as aryl phosphonate group), phosphonooxy group (—OPO ₃ H ₂ ) and its conjugate base group (hereinafter referred to as “phosphonateoxy”) Group), dialkyl phosphonooxy group (—OPO ₃ (alkyl) ₂ ), diaryl phosphonooxy group (—OPO ₃ (aryl) ₂ ), alkylaryl phosphonooxy group (—OPO ₃ (alkyl) (aryl) )), -Alkyl phosphonooxy group (-OPO ₃ H (alkyl)) and its conjugated base group (hereinafter referred to as alkyl phosphonophenyl group), monoaryl phosphonooxy group (-OPO ₃ H (aryl)) and its conjugate Examples include a base group (hereinafter referred to as an arylphosphonatooxy group), a cyano group, a nitro group, an aryl group, a heteroaryl group, an alkenyl group, and an alkynyl group.

  Preferable examples of the alkyl group in these substituents include linear, branched and cyclic alkyl groups having 1 to 20 carbon atoms. Specific examples thereof include a methyl group, Ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, hexadecyl group, octadecyl group, eicosyl group, isopropyl group, isobutyl group S-butyl group, t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group, 2-norbornyl group. it can. Of these, linear alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, and cyclic alkyl groups having 5 to 10 carbon atoms are more preferable.

On the other hand, examples of the alkylene group in the substituted alkyl group include divalent organic residues obtained by removing any one of the hydrogen atoms on the alkyl group having 1 to 20 carbon atoms. Can include linear alkylene groups having 1 to 12 carbon atoms, branched chains having 3 to 12 carbon atoms, and cyclic alkylene groups having 5 to 10 carbon atoms. The substituent of the substituted alkyl group is arbitrary, but preferred examples of the substituted alkyl group include chloromethyl group, bromomethyl group, 2-chloroethyl group, trifluoromethyl group, methoxymethyl group, methoxyethoxyethyl group, allyloxy. Methyl group, phenoxymethyl group, methylthiomethyl group, tolylthiomethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyloxymethyl group, benzoyloxymethyl group,

N-cyclohexylcarbamoyloxyethyl group, N-phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxoethyl group, 2-oxopropyl group, carboxypropyl group, methoxycarbonylethyl group, allyl Oxycarbonylbutyl group, chlorophenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl group, N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, N-methyl-N- (sulfo) Phenyl) carbamoylmethyl group, sulfobutyl group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N-dipropylsulfamoylpropyl group, N-tolylsulfamoyl group Propyl group,

N-methyl-N- (phosphonophenyl) sulfamoyloctyl group, phosphonobutyl group, phosphonatohexyl group, diethylphosphonobutyl group, diphenylphosphonopropyl group, methylphosphonobutyl group, methylphosphonatobutyl group , Tolylphosphonohexyl group, tolylphosphonatohexyl group, phosphonooxypropyl group, phosphonateoxybutyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-methyl-1-phenylethyl group, p-methyl Benzyl group, cinnamyl group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2-methylallyl group, 2-methylpropenylmethyl group, 2-propynyl group, 2-butynyl group, 3-butynyl group, etc. be able to.

  Specific examples of the aryl group in these substituents include those in which 1 to 3 benzene rings form a condensed ring, and those in which a benzene ring and a 5-membered unsaturated ring form a condensed ring. Specific examples thereof include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenaphthenyl group, and a fluorenyl group. Among these, a phenyl group and a naphthyl group are more preferable.

  Specific examples of the substituted aryl group include those having a monovalent nonmetallic atomic group excluding hydrogen as a substituent on the ring-forming carbon atom of the aryl group. Preferred specific examples of the substituted aryl group include a biphenyl group, a tolyl group, a xylyl group, a mesityl group, a cumenyl group, a chlorophenyl group, a bromophenyl group, a fluorophenyl group, a chloromethylphenyl group, a trifluoromethylphenyl group, and a hydroxyphenyl group. , Methoxyphenyl group, methoxyethoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, methylthiophenyl group, tolylthiophenyl group, ethylaminophenyl group, diethylaminophenyl group, morpholinophenyl group, acetyloxyphenyl group, benzoyloxyphenyl group N-cyclohexylcarbamoyloxyphenyl group, N-phenylcarbamoyloxyphenyl group, acetylaminophenyl group, N-methylbenzoylaminophenyl group, carboxypheny Group, methoxycarbonylphenyl group, allyloxycarbonylphenyl group, chlorophenoxycarbonylphenyl group, carbamoylphenyl group, N-methylcarbamoylphenyl group, N, N-dipropylcarbamoylphenyl group, N- (methoxyphenyl) carbamoylphenyl group, N-methyl-N- (sulfophenyl) carbamoylphenyl group,

Sulfophenyl group, sulfonatophenyl group, sulfamoylphenyl group, N-ethylsulfamoylphenyl group, N, N-dipropylsulfamoylphenyl group, N-tolylsulfamoylphenyl group, N-methyl-N- (Phosphonophenyl) sulfamoylphenyl group, phosphonophenyl group, phosphonatophenyl group, diethylphosphonophenyl group, diphenylphosphonophenyl group, methylphosphonophenyl group, methylphosphonatophenyl group, tolylphosphonophenyl group , Tolylphosphonatophenyl group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2-methylallylphenyl group, 2-methylpropenylphenyl group, 2-propynylphenyl group, 2-butynylphenyl group, 3- List butynylphenyl groups, etc. Can.

  As the heteroaryl group, a monocyclic or polycyclic aromatic ring containing at least one of nitrogen, oxygen and sulfur atoms is used, and preferably a 5-membered or 6-membered ring such as furan, pyrrole or pyridine. Aromatic substituents can be used.

  Examples of alkenyl groups include vinyl, 1-propenyl, 1-butenyl, cinnamyl, 2-chloro-1-ethenyl, etc. Examples of alkynyl include ethynyl, 1 -Propynyl group, 1-butynyl group, trimethylsilylethynyl group and the like.

Examples of G ¹ in the acyl group (G ¹ CO—) include hydrogen and the above alkyl groups and aryl groups. Among these substituents, even more preferred are halogen atoms (—F, —Br, —Cl, —I), alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, N-alkylamino groups, N, N— Dialkylamino group, acyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, acylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, sulfo group, sulfonate group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group Group, N-arylsulfa Yl group, N-alkyl-N-arylsulfamoyl group, phosphono group, phosphonate group, dialkyl phosphono group, diaryl phosphono group, monoalkyl phosphono group, alkyl phosphonate group, monoaryl phosphono group, aryl phosphine group Examples include an onato group, a phosphonooxy group, a phosphonateoxy group, an aryl group, and an alkenyl group.

R ¹¹ to R ¹⁸ described above are selected from various practical viewpoints in addition to performance such as photosensitivity, photosensitive wavelength, and stability. For example, in terms of compatibility improvement in the composition system, prevention of crystal precipitation, when developing, solubility in a developing solution, dispersibility, difficulty in precipitation, raw material price, ease of synthesis, It is appropriately selected in consideration of economic viewpoints such as ease of purification. In this respect, examples of particularly preferable substituents include a hydrogen atom, a halogen atom (—F, —Br, —Cl, —I), a lower alkyl group having 1 to 6 carbon atoms (methyl group, ethyl group, Propyl group, isopropyl group, allyl group, 2-methylpropenyl group, etc.), alkyl-substituted aminoalkylene group (the alkyl group is a linear or branched alkyl group having 1 to 6 carbon atoms and having 5 to 7 carbon atoms) And examples of the alkylene group include mono-, di-, and tri-methylene groups having 1 to 3 carbon atoms.

  Specific examples of the aryl group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenaphthenyl group, and a fluorenyl group. Specific examples of the substituted aryl group include a biphenyl group, a tolyl group, Xylyl, mesityl, cumenyl, chlorophenyl, bromophenyl, fluorophenyl, chloromethylphenyl, trifluoromethylphenyl, hydroxyphenyl, methoxyphenyl, methoxyethoxyphenyl, allyloxyphenyl, phenoxy Phenyl group, methylthiophenyl group, tolylthiophenyl group, ethylaminophenyl group, diethylaminophenyl group, morpholinophenyl group, acetyloxyphenyl group, benzoyloxyphenyl group, N-cyclohexylcarbamo Oxy phenyl group, N- phenylcarbamoyloxy phenyl group, an acetylamino phenyl group, N- methyl-benzoylamino phenyl group,

Carboxyphenyl group, methoxycarbonylphenyl group, allyloxycarbonylphenyl group, chlorophenoxycarbonylphenyl group, carbamoylphenyl group, N-methylcarbamoylphenyl group, N, N-dipropylcarbamoylphenyl group, N- (methoxyphenyl) carbamoylphenyl Group, N-methyl-N- (sulfophenyl) carbamoylphenyl group, sulfophenyl group, sulfonatophenyl group, sulfamoylphenyl group, N-ethylsulfamoylphenyl group, N, N-dipropylsulfamoylphenyl group N-tolylsulfamoylphenyl group, N-methyl-N- (phosphonophenyl) sulfamoylphenyl group, phosphonophenyl group, phosphonatophenyl group, diethylphosphonophenyl group, diphenylphosphine Ionophenyl group, methylphosphonophenyl group, methylphosphonatophenyl group, tolylphosphonophenyl group, tolylphosphonatophenyl group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2-methylallylphenyl group, 2- Examples thereof include a methylpropenylphenyl group, a 2-propynylphenyl group, a 2-butynylphenyl group, and a 3-butynylphenyl group.

As the heteroaryl group, a monocyclic or polycyclic aromatic ring containing at least one of nitrogen, oxygen and sulfur atoms is used, and preferably a 5-membered or 6-membered ring such as furan, pyrrole or pyridine. Aromatic substituents can be used. As an example of the substituted heteroaryl group, a monovalent non-metallic atomic group can be used. Specifically, any of those exemplified as R ^{11 to} R ^{18 in} the general formula (2) can be used. it can. Examples of particularly preferred heteroaryl groups include, for example, thiophene, thiathrene, furan, pyran, isobenzofuran, chromene, xanthene, phenoxazine, pyrrole, pyrazole, isothiazole, isoxazole, pyrazine, pyrimidine, pyridazine, indolizine, Indolizines, indoles, indazoles, purines, quinolidines, isoquinolines, phthalazines, naphthyridines, quinazolines, sinolines, pteridines, carbazoles, carbolines, phenanthrines, acridines, perimidines, phenanthrolins, phenalzazines, furansans, etc. It may be benzo-fused or may have a substituent.

Next, —NR ¹⁹ R ²⁰ , —SR ²¹ and —OR ²² in the general formula (2) will be described. —NR ¹⁹ R ²⁰ , —SR ²¹ and —OR ²² are located in any one of R ¹¹ , R ¹³ and R ¹⁵ in the general formula (2), and are an aromatic ring and a nitrogen atom, sulfur atom or oxygen atom. One of them is directly bonded, and R ¹⁹ R ²⁰ bonded to a nitrogen atom, R ²¹ bonded to a sulfur atom, and R ²² bonded to an oxygen atom represent a hydrogen atom or a monovalent nonmetallic atomic group. Specific examples thereof include the same as those described for R ^{11 to} R ¹⁸ in the general formula (2).

  Y in the general formula (3) represents a 5-membered ring or 6-membered ring which may have a substituent.

X in the said General formula (4) represents either NR < ⁹ >, O, S, or Se. R ²³ and R ²⁴ have the same meanings as those described for R ^{11 to} R ¹⁸ in the general formula (2).

The sensitizing dyes represented by the general formula (XXI) and general formulas (2) to (4) of the present invention are disclosed in JP-A 20000-80297, US 98-12525, Dyes Pigm. (1994), 24 (2 ), 93-8. (Gadjev, N .; Deligeorgiev, T .; Kanev, I .; Tasseva, M .; Sabnis, R.), Dyes Pigm. (1991), 17 (2), 153-62, etc. Can be synthesized with reference to. Preferred specific examples (D-1) to (D-40) of the compounds represented by general formula (XXI) and general formulas (2) to (4) are shown below, but the present invention is limited thereto. is not. Further, the isomer by the double bond connecting the acidic nucleus and the basic nucleus is not clear, and the present invention is not limited to either isomer.

一般式（XXII）中、Ｙは、独立に酸素原子または硫黄原子を表し、Ｒ₁およびＲ₂は、それぞれ独立に水素原子以外の一価の非金属原子団を表し、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、Ｒ₇、Ｒ₈、Ｒ₉、Ｒ₁₀、Ｒ₁₁およびＲ₁₂は、それぞれ独立に一価の非金属原子団を表す。

In general formula (XXII), Y independently represents an oxygen atom or a sulfur atom, R ₁ and R ₂ each independently represent a monovalent nonmetallic atomic group other than a hydrogen atom, R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ and R ₁₂ each independently represent a monovalent nonmetallic atomic group.

Hereinafter, the general formula (XXII) will be described in detail below.
In general formula (XXII), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ and R ₁₂ (hereinafter referred to as R _{1 to} R ₁₂ and The monovalent non-metallic atomic group represented by (which may be abbreviated) is preferably a hydrogen atom (excluding R ₁ and R ₂ ), a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, substituted Or an unsubstituted aryl group, a substituted or unsubstituted aromatic heterocyclic group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group, a hydroxyl group, an acyl group, and a halogen Represents an atom.

Preferable examples of R _{1 to} R ₁₂ will be specifically described.
Examples of preferable alkyl groups include linear, branched, and cyclic alkyl groups having 1 to 20 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, a propyl group, Butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, octadecyl, eicosyl, isopropyl, isobutyl, s-butyl, Examples thereof include t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group and 2-norbornyl group. Of these, linear alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, and cyclic alkyl groups having 5 to 10 carbon atoms are more preferable.

As the substituent of the substituted alkyl group, a monovalent nonmetallic atomic group excluding hydrogen is used, and preferred examples include a halogen atom (—F, —Br, —Cl, —I), a hydroxyl group, an alkoxy group, Aryloxy group, mercapto group, alkylthio group, arylthio group, alkyldithio group, aryldithio group, amino group, N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diarylamino group N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N-arylcarbamoyloxy group, alkylsulfoxy group, Reel sulphoxide group, an acylthio group, an acylamino group, N- alkylacylamino group, N- arylacylamino group, a ureido group, N'- alkylureido group, N ', N'- dialkyl ureido group,
N'-arylureido group, N ', N'-diarylureido group, N'-alkyl-N'-arylureido group, N-alkylureido group, N-arylureido group, N'-alkyl-N-alkylureido Group, N′-alkyl-N-arylureido group, N ′, N′-dialkyl-N-alkylureido group, N ′, N′-dialkyl-N-arylureido group, N′-aryl-N-alkylureido group Group, N′-aryl-N-arylureido group, N ′, N′-diaryl-N-alkylureido group, N ′, N′-diaryl-N-arylureido group, N′-alkyl-N′-aryl -N-alkylureido group, N'-alkyl-N'-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonyl Mino group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group, formyl Group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N- An alkyl-N-arylcarbamoyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfo group (—SO ₃ H) and a conjugate base group thereof (hereinafter referred to as a sulfonate group), an alkoxysulfonyl group, Ant Roxysulfonyl group, sulfinamoyl group, N-alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-aryl Sulfinamoyl group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N- An arylsulfamoyl group, a phosphono group (—PO ₃ H ₂ ) and a conjugate base group thereof (hereinafter referred to as a phosphonate group),

Dialkyl phosphono group (—PO ₃ (alkyl) ₂ ), diaryl phosphono group (—PO ₃ (aryl) ₂ ), alkylaryl phosphono group (—PO ₃ (alkyl) (aryl)), monoalkyl phosphono group (—PO ₃ H (alkyl)) and its conjugate base group (hereinafter referred to as alkyl phosphonate group), monoaryl phosphono group (—PO ₃ H (aryl)) and its conjugate base group (hereinafter referred to as aryl phosphonate) Group), phosphonooxy group (—OPO ₃ H ₂ ) and its conjugate base group (hereinafter referred to as phosphonatooxy group), dialkyl phosphonooxy group (—OPO ₃ (alkyl) ₂ ), diaryl phosphono Oxy group (—OPO ₃ (aryl) ₂ ), alkylaryl phosphonooxy group (—OPO ₃ (alkyl) (aryl)), monoalkyl phosphonooxy group (—OPO ₃ H (alkyl)) and its conjugate base group (After that, Kill phosphodiesterase referred to isocyanatomethyl group), monoaryl phosphonooxy group (-OPO ₃ H (aryl)) and its conjugated base group (hereinafter referred to as aryl phosphite Hona preparative group), a cyano group, a nitro group, an aryl group, A heteroaryl group, an alkenyl group, and an alkynyl group are mentioned.

  Specific examples of the alkyl group in these substituents include the above-described alkyl groups, and specific examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, a xylyl group, a mesityl group, and a cumenyl group. , Chlorophenyl group, bromophenyl group, chloromethylphenyl group, hydroxyphenyl group, methoxyphenyl group, ethoxyphenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group, methylamino Phenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, ethoxyphenylcarbonyl group, phenoxycarbonylphenyl group, N-phenylcarbamoylphenyl group, phenyl group Cyanophenyl group, sulfophenyl group, sulfonatophenyl group, phosphonophenyl phenyl group, phosphonophenyl phenyl group and the like.

As the aromatic heterocyclic group preferable as R _{1 to} R ₁₂ , a monocyclic or polycyclic aromatic ring containing at least one of nitrogen, oxygen, and sulfur atoms is used. Examples of particularly preferable aromatic heterocyclic groups As, for example, thiophene, thiathrene, furan, pyran, isobenzofuran, chromene, xanthene, phenoxazine, pyrrole, pyrazole, isothiazole, isoxazole, pyrazine, pyrimidine, pyridazine, indolizine, isoindolizine, indoisine, indazole , Purine, quinolidine, isoquinoline, phthalazine, naphthyridine, quinazoline, cinolin, pteridine, carbazole, carboline, phenanthrine, acridine, perimidine, phenanthrolin, phthalazine, phenalazine, phenoxazine, furazane, phenoxy Jin and etc., and these are further may be benzo-fused or may have a substituent.

Examples of preferable alkenyl groups as R _{1 to} R ₁₂ include vinyl group, 1-propenyl group, 1-butenyl group, cinnamyl group, 2-chloro-1-ethenyl group, and the like. Examples of alkynyl group Examples thereof include ethynyl group, 1-propynyl group, 1-butynyl group, trimethylsilylethynyl group and the like. Examples of G ¹ in the acyl group (G ¹ CO—) include hydrogen and the above alkyl groups and aryl groups.

  Among these substituents, even more preferred are halogen atoms (—F, —Br, —Cl, —I), alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, N-alkylamino groups, N, N -Dialkylamino group, acyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, acylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group Group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, sulfo group, sulfonate group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfa group Moyl group, N-aryl sulf Moyl group, N-alkyl-N-arylsulfamoyl group, phosphono group, phosphonate group, dialkyl phosphono group, diaryl phosphono group, monoalkyl phosphono group, alkyl phosphonate group, monoaryl phosphono group, aryl phosphine group Examples include an onato group, a phosphonooxy group, a phosphonateoxy group, an aryl group, and an alkenyl group.

  On the other hand, examples of the alkylene group in the substituted alkyl group include divalent organic residues obtained by removing any one of the hydrogen atoms on the alkyl group having 1 to 20 carbon atoms. Can include linear alkylene groups having 1 to 12 carbon atoms, branched chains having 3 to 12 carbon atoms, and cyclic alkylene groups having 5 to 10 carbon atoms.

Specific examples of the substituted alkyl group preferable as R _{1 to} R ₁₂ obtained by combining the substituent and the alkylene group include a chloromethyl group, a bromomethyl group, a 2-chloroethyl group, a trifluoromethyl group, a methoxymethyl group, Methoxyethoxyethyl group, allyloxymethyl group, phenoxymethyl group, methylthiomethyl group, tolylthiomethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyloxymethyl group, benzoyloxymethyl group, N-cyclohexylcarbamoyl Oxyethyl group, N-phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxoethyl group, 2-oxopropyl group, carboxypropyl group, methoxycarbonylethyl Allyloxycarbonylbutyl group, chlorophenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl group, N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, N-methyl-N- (Sulfophenyl) carbamoylmethyl group, sulfobutyl group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N-dipropylsulfamoylpropyl group, N-tolylsulfamoylpropyl group, N -Methyl-N- (phosphonophenyl) sulfamoyloctyl group, phosphonobutyl group, phosphonatohexyl group, diethylphosphonobutyl group, diphenylphosphonopropyl group, methylphosphonobutyl group, methylphosphonatobutyl group, G Ruphonohexyl group, tolylphosphonatohexyl group, phosphonooxypropyl group, phosphonatooxybutyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-methyl-1-phenylethyl group, p-methylbenzyl Groups, cinnamyl groups, allyl groups, 1-propenylmethyl groups, 2-butenyl groups, 2-methylallyl groups, 2-methylpropenylmethyl groups, 2-propynyl groups, 2-butynyl groups, 3-butynyl groups, etc. Can do.

Furthermore, specific examples of preferred aryl groups as R _{1 to} R ₁₂ include those in which 1 to 3 benzene rings form a condensed ring, and those in which a benzene ring and a 5-membered unsaturated ring form a condensed ring. Specific examples include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenaphthenyl group, and a fluorenyl group. Among these, a phenyl group and a naphthyl group are more preferable.

Specific examples of preferred substituted aryl groups as R _{1 to} R ₁₂ include those having a monovalent non-metallic atomic group excluding hydrogen as a substituent on the ring-forming carbon atom of the aforementioned aryl group. Examples of preferred substituents include the alkyl groups, substituted alkyl groups, and those previously shown as substituents in the substituted alkyl group. Preferred examples of such a substituted aryl group include biphenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, fluorophenyl group, chloromethylphenyl group, trifluoromethylphenyl group. Hydroxyphenyl group, methoxyphenyl group, methoxyethoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, methylthiophenyl group, tolylthiophenyl group, ethylaminophenyl group, diethylaminophenyl group, morpholinophenyl group, acetyloxyphenyl group, Benzoyloxyphenyl group, N-cyclohexylcarbamoyloxyphenyl group, N-phenylcarbamoyloxyphenyl group, acetylaminophenyl group, N-methylbenzoylaminophenyl group, carbo Cyphenyl group, methoxycarbonylphenyl group, allyloxycarbonylphenyl group, chlorophenoxycarbonylphenyl group, carbamoylphenyl group, N-methylcarbamoylphenyl group, N, N-dipropylcarbamoylphenyl group, N- (methoxyphenyl) carbamoylphenyl group N-methyl-N- (sulfophenyl) carbamoylphenyl group, sulfophenyl group, sulfonatophenyl group, sulfamoylphenyl group, N-ethylsulfamoylphenyl group, N, N-dipropylsulfamoylphenyl group, N-tolylsulfamoylphenyl group, N-methyl-N- (phosphonophenyl) sulfamoylphenyl group, phosphonophenyl group, phosphonatophenyl group, diethylphosphonophenyl group, diphenylphosphono Enyl group, methylphosphonophenyl group, methylphosphonatophenyl group, tolylphosphonophenyl group, tolylphosphonatophenyl group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2-methylallylphenyl group, 2- Examples thereof include a methylpropenylphenyl group, a 2-propynylphenyl group, a 2-butynylphenyl group, and a 3-butynylphenyl group.

In addition, as a more preferable example of R < ₁ > and R < ₂ >, a substituted or unsubstituted alkyl group is mentioned from a viewpoint of improving compatibility with another photosensitive composition. Further, when an acylphosphine compound is used as the activator compound described later, Y is preferably a sulfur atom in terms of sensitivity.

Preferred specific examples (D1) to (D23) of the compound represented by the general formula (XXII) are shown below, but the present invention is not limited thereto. In the following formulae, Me represents a methyl group, Et represents an ethyl group, and Hex represents an n-hexyl group.

一般式(XXIII)中、Ｘは、酸素原子または硫黄原子を表し、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、Ｒ₇、およびＲ₈は、それぞれ独立に一価の非金属原子団を表し、Ａは炭素数２０以下のアリール基またはヘテロアリール基を表す。ここで、アリール基又はヘテロアリール基は置換されていてもよい。

In general formula (XXIII), X represents an oxygen atom or a sulfur atom, and R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , and R ₈ are each independently monovalent. Represents a non-metallic atomic group, and A represents an aryl group or heteroaryl group having 20 or less carbon atoms. Here, the aryl group or heteroaryl group may be substituted.

Hereinafter, the general formula (XXIII) will be described in detail below.
As the monovalent non-metallic atomic group represented by R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , and R ₈ (hereinafter sometimes abbreviated as R _{1 to} R ₆ ), A hydrogen atom, a halogen atom, and a substituted or unsubstituted alkyl group having 20 or less carbon atoms, an alkoxy group, an acyl group, an aryl group, an aralkyl group, an alkenyl group, an alkylthio group, an aryloxy group, an arylthio group, a heteroaryl group, And alkylsulfone groups.

  Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  Examples of the substituted or unsubstituted alkyl group include linear, branched or cyclic alkyl groups, alkoxyalkyl groups, alkoxyalkoxyalkyl groups, alkoxyalkoxyalkoxyalkyl groups, alkoxycarbonylalkyl groups, alkoxycarbonyloxyalkyl groups, alkoxyalkoxycarbonyloxy groups. Alkyl group, hydroxyalkyl group, hydroxyalkoxyalkyl group, hydroxyalkoxyalkoxyalkyl group, cyanoalkyl group, acyloxyalkyl group, acyloxyalkoxyalkyl group, acyloxyalkoxyalkoxyalkyl group, alkyl halide, sulfonealkyl group, alkylcarbonylaminoalkyl group , Alkylsulfonaminoalkyl group, sulfonamidoalkyl group, alkylaminoalkyl group Aminoalkyl groups, and they are selected from alkyl sulfonic alkyl group.

  As the linear, branched or cyclic alkyl group, in consideration of processability by application to polycarbonate, acrylic, epoxy, polyolefin substrates, etc., a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n- Butyl group, iso-butyl group, sec-butyl group, t-butyl group, n-pentyl group, iso-pentyl group, 2-methylbutyl group, 1-methylbutyl group, neo-pentyl group, 1,2-dimethylpropyl group 1,1-dimethylpropyl group, cyclo-pentyl group, n-hexyl group, 4-methylpentyl group, 3-methylpentyl group, 2-methylpentyl group, 1-methylpentyl group, 3,3-dimethylbutyl group 2,3-dimethylbutyl group, 1,3-dimethylbutyl group, 2,2-dimethylbutyl group, 1,2-dimethylbutyl 1,1-dimethylbutyl group, 3-ethylbutyl group, 2-ethylbutyl group, 1-ethylbutyl group, 1,2,2-trimethylbutyl group, 1,1,2-trimethylbutyl group, 1-ethyl-2- Methylpropyl group, cyclo-hexyl group, n-heptyl group, 2-methylhexyl group, 3-methylhexyl group, 4-methylhexyl group, 5-methylhexyl group, 2,4-dimethylpentyl group, n-octyl group 2-ethylhexyl group, 2,5-dimethylhexyl group, 2,5,5-trimethylpentyl group, 2,4-dimethylhexyl group, 2,2,4-trimethylpentyl group, 3,5,5-trimethylhexyl Group, n-nonyl group, n-decyl group, 4-ethyloctyl group, 4-ethyl-4,5-methylhexyl group, n-undecyl group, n-dodecyl group, 1, , 5,7-tetraethyloctyl group, 4-butyloctyl group, 6,6-diethyloctyl group, n-tridecyl group, 6-methyl-4-butyloctyl group, n-tetradecyl group, n-pentadecyl group, 3, 5-dimethylheptyl group, 2,6-dimethylheptyl group, 2,4-dimethylheptyl group, 2,2,5,5-tetramethylhexyl group, 1-cyclo-pentyl-2,2-dimethylpropyl group, 1 -Cyclo-hexyl-2,2-dimethylpropyl group and the like can be mentioned.

  Examples of alkoxyalkyl groups include methoxymethyl, ethoxymethyl, propoxymethyl, butoxymethyl, methoxyethyl, ethoxyethyl, propoxyethyl, butoxyethyl, n-hexyloxyethyl, 4-methyl. Pentoxyethyl group, 1,3-dimethylbutoxyethyl group, 2-ethylhexyloxyethyl group, n-octyloxyethyl group, 3,5,5-trimethylhexyloxyethyl group, 2-methyl-1-iso-propylpropoxy Ethyl group, 3-methyl-1-iso-propylbutyloxyethyl group, 2-ethoxy-1-methylethyl group, 3-methoxybutyl group, 3,3,3-trifluoropropoxyethyl group, 3,3,3 -A trichloropropoxyethyl group etc. are mentioned.

  Examples of alkoxyalkoxyalkyl groups include methoxyethoxyethyl group, ethoxyethoxyethyl group, propoxyethoxyethyl group, butoxyethoxyethyl group, hexyloxyethoxyethyl group, 1,2-dimethylpropoxyethoxyethyl group, 3-methyl-1 -Iso-butylbutoxyethoxyethyl group, 2-methoxy-1-methylethoxyethyl group, 2-butoxy-1-methylethoxyethyl group, 2- (2'-ethoxy-1'-methylethoxy) -1-methylethyl Group, 3,3,3-trifluoropropoxyethoxyethyl group, 3,3,3-trichloropropoxyethoxyethyl group and the like.

  Examples of alkoxyalkoxyalkoxyalkyl groups include methoxyethoxyethoxyethyl group, ethoxyethoxyethoxyethyl group, butoxyethoxyethoxyethyl group, 2,2,2-trifluoroethoxyethoxyethoxyethyl group, 2,2,2-trichloroethoxy An ethoxyethoxyethyl group etc. are mentioned.

  Examples of alkoxycarbonylalkyl groups include methoxycarbonylmethyl, ethoxycarbonylmethyl, butoxycarbonylmethyl, methoxycarbonylethyl, ethoxycarbonylethyl, butoxycarbonylethyl, 2,2,3,3-tetrafluoropropoxy Examples thereof include a carbonylmethyl group and a 2,2,3,3-tetrachloropropoxycarbonylmethyl group.

  Examples of alkoxycarbonyloxyalkyl groups include methoxycarbonyloxyethyl, ethoxycarbonyloxyethyl, butoxycarbonyloxyethyl, 2,2,2-trifluoroethoxycarbonyloxyethyl, 2,2,2-trichloroethoxy Examples thereof include a carbonyloxyethyl group.

  Examples of alkoxyalkoxycarbonyloxyalkyl groups include methoxyethoxycarbonyloxyethyl group, ethoxyethoxycarbonyloxyethyl group, butoxyethoxycarbonyloxyethyl group, 2,2,2-trifluoroethoxyethoxycarbonyloxyethyl group, 2,2 , 2-trichloroethoxyethoxycarbonyloxyethyl group and the like.

  Examples of the hydroxyalkyl group include 2-hydroxyethyl group, 4-hydroxyethyl group, 2-hydroxy-3-methoxypropyl group, 2-hydroxy-3-chloropropyl group, 2-hydroxy-3-ethoxypropyl group, Examples include 3-butoxy-2-hydroxypropyl group, 2-hydroxy-3-phenoxypropyl group, 2-hydroxypropyl group, 2-hydroxybutyl group and the like.

  Examples of hydroxyalkoxyalkyl groups include hydroxyethoxyethyl group, 2- (2′-hydroxy-1′-methylethoxy) -1-methylethyl group, 2- (3′-fluoro-2′-hydroxypropoxy) ethyl. Group, 2- (3′-chloro-2′-hydroxypropoxy) ethyl group and the like.

  Examples of hydroxyalkoxyalkoxyalkyl groups include hydroxyethoxyethoxyethyl group, [2 ′-(2′-hydroxy-1′-methylethoxy) -1′-methylethoxy] ethoxyethyl group, [2 ′-(2 ′). -Fluoro-1'-hydroxyethoxy) -1'-methylethoxy] ethoxyethyl group, [2 '-(2'-chloro-1'-hydroxyethoxy) -1'-methylethoxy] ethoxyethyl group, and the like. .

  Examples of the cyanoalkyl group include 2-cyanoethyl group, 4-cyanobutyl group, 2-cyano-3-methoxypropyl group, 2-cyano-3-chloropropyl group, 2-cyano-3-ethoxypropyl group, 3- Examples include butoxy-2-cyanopropyl group, 2-cyano-3-phenoxypropyl group, 2-cyanopropyl group, and 2-cyanobutyl group.

  Examples of the acyloxyalkyl group include an acetoxyethyl group, a propionyloxyethyl group, a butyryloxyethyl group, a valeryloxyethyl group, a 1-ethylpentylcarbonyloxyethyl group, and a 2,4,4-trimethylpentylcarbonyloxyethyl group. , 3-fluorobutyryloxyethyl group, 3-chlorobutyryloxyethyl group and the like.

  Examples of the acyloxyalkoxyalkyl group include acetoxyethoxyethyl group, propionyloxyethoxyethyl group, valeryloxyethoxyethyl group, 1-ethylpentylcarbonyloxyethoxyethyl group, 2,4,4-trimethylpentylcarbonyloxyethoxyethyl group , 2-fluoropropionyloxyethoxyethyl group, 2-chloropropionyloxyethoxyethyl group, and the like.

  Examples of acyloxyalkoxyalkoxyalkyl groups include acetoxyethoxyethoxyethyl group, propionyloxyethoxyethoxyethyl group, valeryloxyethoxyethoxyethyl group, 1-ethylpentylcarbonyloxyethoxyethoxyethyl group, 2,4,4-trimethylpentyl Examples include carbonyloxyethoxyethoxyethyl group, 2-fluoropropionyloxyethoxyethoxyethyl group, and 2-chloropropionyloxyethoxyethoxyethyl group.

  Examples of the halogenated alkyl group include a chloromethyl group, a chloroethyl group, a 2,2,2-trifluoroethyl group, a trifluoromethyl group, a bromomethyl group, and a methyl iodide group.

  Examples of the sulfonealkyl group include a sulfonemethyl group, a sulfoneethyl group, and a sulfonepropyl group.

  Examples of the alkylcarbonylaminoalkyl group include a methylcarbonylaminoethyl group, an ethylcarbonylaminoethyl group, a propylcarbonylaminoethyl group, a cyclohexylcarbonylaminoethyl group, a succiniminoethyl group, and the like.

  Examples of the alkylsulfonaminoalkyl group include methylsulfonaminoethyl group, ethylsulfonaminoethyl group, propylsulfonaminoethyl group and the like.

  Examples of the sulfonamidoalkyl group include a sulfonamidomethyl group, a sulfonamidoethyl group, and a sulfonamidopropyl group.

  Examples of alkylaminoalkyl groups include N-methylaminomethyl, N, N-dimethylaminomethyl, N, N-diethylaminomethyl, N, N-dipropylaminomethyl, N, N-dibutylaminomethyl. Groups and the like.

  Examples of the aminoalkyl group include an aminomethyl group, an aminoethyl group, an aminopropyl group, and the like.

Examples of alkyl sulfone alkyl groups include methyl sulfone methyl group, ethyl sulfone methyl group, butyl sulfone methyl group, methyl sulfone ethyl group, ethyl sulfone ethyl group, butyl sulfone ethyl group, 2,2,3,3-tetrafluoropropyl Examples thereof include a sulfonemethyl group and a 2,2,3,3-tetrachloropropylsulfonemethyl group.

  Examples of the substituted or unsubstituted alkoxy group include an alkoxy group having the same substituent as the alkyl group listed above, and preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, n Examples include lower butoxy groups such as -butoxy group, iso-butoxy group, sec-butoxy group, t-butoxy group, n-pentoxy group, iso-pentoxy group, neo-pentoxy group, and 2-methylbutoxy group.

  Examples of the substituted or unsubstituted acyl group include an acyl group having the same substituent as the above-described alkyl group, preferably a formyl group, a methylcarbonyl group, an ethylcarbonyl group, an n-propylcarbonyl group, iso-propylcarbonyl group, n-butylcarbonyl group, iso-butylcarbonyl group, sec-butylcarbonyl group, t-butylcarbonyl group, n-pentylcarbonyl group, iso-pentylcarbonyl group, neo-pentylcarbonyl group, 2- Examples thereof include a methylbutylcarbonyl group and a nitrobenzylcarbonyl group.

  Examples of the substituted or unsubstituted aryl group are aryl groups having the same substituents as the alkyl groups listed above, and preferably a phenyl group, a nitrophenyl group, a cyanophenyl group, a hydroxyphenyl group, a methylphenyl group. Group, trifluoromethylphenyl group, naphthyl group, nitronaphthyl group, cyanonaphthyl group, hydroxynaphthyl group, methylnaphthyl group, trifluoromethylnaphthyl group and the like.

  Examples of the substituted or unsubstituted aralkyl group are aralkyl groups having the same substituents as the alkyl groups listed above, preferably benzyl group, nitrobenzyl group, cyanobenzyl group, hydroxybenzyl group, methylbenzyl group. Group, trifluoromethylbenzyl group, naphthylmethyl group, nitronaphthylmethyl group, cyanonaphthylmethyl group, hydroxynaphthylmethyl group, methylnaphthylmethyl group, trifluoromethylnaphthylmethyl group and the like.

  Examples of the substituted or unsubstituted alkenyl group are alkenyl groups having the same substituents as the alkyl groups listed above, and are preferably a propenyl group, a 1-butenyl group, an iso-butenyl group, and a 1-pentenyl group. 2-pentenyl group, 2-methyl-1-butenyl group, 3-methyl-1-butenyl group, 2-methyl-2-butenyl group, 2,2-dicyanovinyl group, 2-cyano-2-methylcarboxyl vinyl And lower alkenyl groups such as 2-cyano-2-methylsulfonvinyl group.

  Examples of the substituted or unsubstituted alkylthio group include an alkylthio group having the same substituent as the above-described alkyl group, preferably a methylthio group, an ethylthio group, an n-propylthio group, an iso-propylthio group, n Lower alkylthio such as -butylthio group, iso-butylthio group, sec-butylthio group, t-butylthio group, n-pentylthio group, iso-pentylthio group, neo-pentylthio group, 2-methylbutylthio group, methylcarboxylethylthio group Groups.

  Examples of the substituted or unsubstituted aryloxy group are aryloxy groups having the same substituents as the aryl groups listed above, preferably a phenoxy group, a 2-methylphenoxy group, a 4-methylphenoxy group, 4-t-butylphenoxy group, 2-methoxyphenoxy group, 4-iso-propylphenoxy group and the like can be mentioned.

  Examples of the substituted or unsubstituted arylthio group are arylthio groups having the same substituents as the above-mentioned aryl groups, preferably a phenylthio group, a 4-methylphenylthio group, a 2-methoxyphenylthio group, 4-t-butylphenylthio group etc. are mentioned.

  Examples of substituted or unsubstituted heteroaryl groups include pyrrolyl, thienyl, furanyl, oxazoyl, isoxazoyl, oxadiazoyl, imidazolyl, benzoxazoyl, benzothiazoyl, benzoimidazolyl, benzofuranyl Group, indoyl group and the like.

  Examples of the substituted or unsubstituted alkylsulfone group are alkylsulfone groups having the same substituents as the above-mentioned alkyl groups, and preferably methylsulfone group, ethylsulfone group, n-propylsulfone group, iso -Propylsulfone group, n-butylsulfone group, iso-butylsulfone group, sec-butylsulfone group, t-butylsulfone group, n-pentylsulfone group, iso-butylsulfone group, neo-pentylsulfone group, 2-methyl A butyl sulfone group, 2-hydroxyethyl sulfone group, 2-cyanoethyl sulfone group, etc. are mentioned.

Preferable specific examples of A include substituted or unsubstituted aryl groups, substituted or unsubstituted heteroaryl groups and the like mentioned as specific examples of R _{1 to} R ₈ . A is selected so as not to be the same as the compound represented by the following general formula (XXIV).

More preferable examples of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , and R ₈ are substituted or unsubstituted from the viewpoint of enhancing compatibility with other photosensitive compositions. Of the alkyl group. Further, when an acylphosphine compound is used as an activator compound described later, X is preferably a sulfur atom in terms of sensitivity. A is more preferably an aryl group having an amino group.

The compound represented by the general formula (XXIII) of the present invention can be obtained by a known method, for example, J. Org. Am. Chem. Soc. 63, 3203 (1941) and the like. That is, it can be produced by reacting a compound represented by the following general formula (2) with a compound represented by the following general formula (3) using hydrochloric acid or the like as a catalyst.

(In formulas (2) and (3), R _{1 to} R ₈ , X and A have the same meaning as defined in general formula (XXIII).)
Preferred specific examples (D1) to (D21) of the compound represented by the general formula (XXIII) are shown below, but the present invention is not limited thereto.

In general formula (XXIV), X represents an oxygen atom or a sulfur atom, and R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are each independently a monovalent non-valent group. Represents a metal atomic group.

General formula (XXIV) will be described in detail below.
As the monovalent non-metallic atomic group represented by R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , and R ₈ (hereinafter sometimes abbreviated as R _{1 to} R ₆ ), A hydrogen atom, a halogen atom, and a substituted or unsubstituted alkyl group having 20 or less carbon atoms, an alkoxy group, an acyl group, an aryl group, an aralkyl group, an alkenyl group, an alkylthio group, an aryloxy group, an arylthio group, a heteroaryl group, And alkylsulfone groups.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  Examples of the substituted or unsubstituted alkyl group include linear, branched or cyclic alkyl groups, alkoxyalkyl groups, alkoxyalkoxyalkyl groups, alkoxyalkoxyalkoxyalkyl groups, alkoxycarbonylalkyl groups, alkoxycarbonyloxyalkyl groups, alkoxyalkoxycarbonyloxy groups. Alkyl group, hydroxyalkyl group, hydroxyalkoxyalkyl group, hydroxyalkoxyalkoxyalkyl group, cyanoalkyl group, acyloxyalkyl group, acyloxyalkoxyalkyl group, acyloxyalkoxyalkoxyalkyl group, alkyl halide, sulfonealkyl group, alkylcarbonylaminoalkyl group , Alkylsulfonaminoalkyl group, sulfonamidoalkyl group, alkylaminoalkyl group Aminoalkyl groups, and they are selected from alkyl sulfonic alkyl group.

As the linear, branched or cyclic alkyl group, in consideration of processability by application to a polycarbonate, acrylic, epoxy, polyolefin substrate or the like, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n- Butyl group, iso-butyl group, sec-butyl group, t-butyl group, n-pentyl group, iso-pentyl group, 2-methylbutyl group, 1-methylbutyl group, neo-pentyl group, 1,2-dimethylpropyl group 1,1-dimethylpropyl group, cyclo-pentyl group, n-hexyl group, 4-methylpentyl group, 3-methylpentyl group, 2-methylpentyl group, 1-methylpentyl group, 3,3-dimethylbutyl group 2,3-dimethylbutyl group, 1,3-dimethylbutyl group, 2,2-dimethylbutyl group, 1,2-dimethylbutyl group 1,1-dimethylbutyl group, 3-ethylbutyl group, 2-ethylbutyl group, 1-ethylbutyl group, 1,2,2-trimethylbutyl group, 1,1,2-trimethylbutyl group, 1-ethyl-2- Methylpropyl group, cyclo-hexyl group, n-heptyl group, 2-methylhexyl group, 3-methylhexyl group, 4-methylhexyl group, 5-methylhexyl group, 2,4-dimethylpentyl group, n-octyl group 2-ethylhexyl group, 2,5-dimethylhexyl group, 2,5,5-trimethylpentyl group, 2,4-dimethylhexyl group, 2,2,4-trimethylpentyl group, 3,5,5-trimethylhexyl Group, n-nonyl group, n-decyl group, 4-ethyloctyl group, 4-ethyl-4,5-methylhexyl group, n-undecyl group, n-dodecyl group, 1, , 5,7-tetraethyloctyl group, 4-butyloctyl group, 6,6-diethyloctyl group, n-tridecyl group, 6-methyl-4-butyloctyl group, n-tetradecyl group, n-pentadecyl group, 3, 5-dimethylheptyl group, 2,6-dimethylheptyl group, 2,4-dimethylheptyl group, 2,2,5,5-tetramethylhexyl group, 1-cyclo-pentyl-2,2-dimethylpropyl group, 1 -Cyclo-hexyl-2,2-dimethylpropyl group and the like can be mentioned.

  Examples of alkoxyalkyl groups include methoxymethyl, ethoxymethyl, propoxymethyl, butoxymethyl, methoxyethyl, ethoxyethyl, propoxyethyl, butoxyethyl, n-hexyloxyethyl, 4-methyl. Pentoxyethyl group, 1,3-dimethylbutoxyethyl group, 2-ethylhexyloxyethyl group, n-octyloxyethyl group, 3,5,5-trimethylhexyloxyethyl group, 2-methyl-1-iso-propylpropoxy Ethyl group, 3-methyl-1-iso-propylbutyloxyethyl group, 2-ethoxy-1-methylethyl group, 3-methoxybutyl group, 3,3,3-trifluoropropoxyethyl group, 3,3,3 -A trichloropropoxyethyl group etc. are mentioned.

  Examples of alkoxyalkoxyalkyl groups include methoxyethoxyethyl group, ethoxyethoxyethyl group, propoxyethoxyethyl group, butoxyethoxyethyl group, hexyloxyethoxyethyl group, 1,2-dimethylpropoxyethoxyethyl group, 3-methyl-1 -Iso-butylbutoxyethoxyethyl group, 2-methoxy-1-methylethoxyethyl group, 2-butoxy-1-methylethoxyethyl group, 2- (2'-ethoxy-1'-methylethoxy) -1-methylethyl Group, 3,3,3-trifluoropropoxyethoxyethyl group, 3,3,3-trichloropropoxyethoxyethyl group and the like.

Examples of alkoxyalkoxyalkoxyalkyl groups include methoxyethoxyethoxyethyl group, ethoxyethoxyethoxyethyl group, butoxyethoxyethoxyethyl group, 2,2,2-trifluoroethoxyethoxyethoxyethyl group, 2,2,2-trichloroethoxy An ethoxyethoxyethyl group etc. are mentioned.
Examples of alkoxycarbonylalkyl groups include methoxycarbonylmethyl, ethoxycarbonylmethyl, butoxycarbonylmethyl, methoxycarbonylethyl, ethoxycarbonylethyl, butoxycarbonylethyl, 2,2,3,3-tetrafluoropropoxy Examples thereof include a carbonylmethyl group and a 2,2,3,3-tetrachloropropoxycarbonylmethyl group.

Examples of alkoxycarbonyloxyalkyl groups include methoxycarbonyloxyethyl, ethoxycarbonyloxyethyl, butoxycarbonyloxyethyl, 2,2,2-trifluoroethoxycarbonyloxyethyl, 2,2,2-trichloroethoxy Examples thereof include a carbonyloxyethyl group.
Examples of the alkoxyalkoxycarbonyloxyalkyl group include methoxyethoxycarbonyloxyethyl group, ethoxyethoxycarbonyloxyethyl group, butoxyethoxycarbonyloxyethyl group, 2,2,2-trifluoroethoxyethoxycarbonyloxyethyl group, 2,2 , 2-trichloroethoxyethoxycarbonyloxyethyl group and the like.

Examples of the hydroxyalkyl group include 2-hydroxyethyl group, 4-hydroxyethyl group, 2-hydroxy-3-methoxypropyl group, 2-hydroxy-3-chloropropyl group, 2-hydroxy-3-ethoxypropyl group, Examples include 3-butoxy-2-hydroxypropyl group, 2-hydroxy-3-phenoxypropyl group, 2-hydroxypropyl group, 2-hydroxybutyl group and the like.
Examples of hydroxyalkoxyalkyl groups include hydroxyethoxyethyl, 2- (2′-hydroxy-1′-methylethoxy) -1-methylethyl, 2- (3′-fluoro-2′-hydroxypropoxy) ethyl Group, 2- (3′-chloro-2′-hydroxypropoxy) ethyl group and the like.

Examples of hydroxyalkoxyalkoxyalkyl groups include hydroxyethoxyethoxyethyl group, [2 ′-(2′-hydroxy-1′-methylethoxy) -1′-methylethoxy] ethoxyethyl group, [2 ′-(2 ′). -Fluoro-1'-hydroxyethoxy) -1'-methylethoxy] ethoxyethyl group, [2 '-(2'-chloro-1'-hydroxyethoxy) -1'-methylethoxy] ethoxyethyl group, and the like. .
Examples of the cyanoalkyl group include 2-cyanoethyl group, 4-cyanobutyl group, 2-cyano-3-methoxypropyl group, 2-cyano-3-chloropropyl group, 2-cyano-3-ethoxypropyl group, 3- Examples include butoxy-2-cyanopropyl group, 2-cyano-3-phenoxypropyl group, 2-cyanopropyl group, and 2-cyanobutyl group.

Examples of the acyloxyalkyl group include an acetoxyethyl group, a propionyloxyethyl group, a butyryloxyethyl group, a valeryloxyethyl group, a 1-ethylpentylcarbonyloxyethyl group, and a 2,4,4-trimethylpentylcarbonyloxyethyl group. , 3-fluorobutyryloxyethyl group, 3-chlorobutyryloxyethyl group, and the like.
Examples of acyloxyalkoxyalkyl groups include acetoxyethoxyethyl group, propionyloxyethoxyethyl group, valeryloxyethoxyethyl group, 1-ethylpentylcarbonyloxyethoxyethyl group, 2,4,4-trimethylpentylcarbonyloxyethoxyethyl group , 2-fluoropropionyloxyethoxyethyl group, 2-chloropropionyloxyethoxyethyl group, and the like.

Examples of acyloxyalkoxyalkoxyalkyl groups include acetoxyethoxyethoxyethyl group, propionyloxyethoxyethoxyethyl group, valeryloxyethoxyethoxyethyl group, 1-ethylpentylcarbonyloxyethoxyethoxyethyl group, 2,4,4-trimethylpentyl. Examples include carbonyloxyethoxyethoxyethyl group, 2-fluoropropionyloxyethoxyethoxyethyl group, 2-chloropropionyloxyethoxyethoxyethyl group, and the like.
Examples of the halogenated alkyl group include a chloromethyl group, a chloroethyl group, a 2,2,2-trifluoroethyl group, a trifluoromethyl group, a bromomethyl group, and a methyl iodide group.

Examples of the sulfonealkyl group include a sulfonemethyl group, a sulfoneethyl group, and a sulfonepropyl group.
Examples of the alkylcarbonylaminoalkyl group include a methylcarbonylaminoethyl group, an ethylcarbonylaminoethyl group, a propylcarbonylaminoethyl group, a cyclohexylcarbonylaminoethyl group, a succiniminoethyl group, and the like.
Examples of the alkylsulfonaminoalkyl group include a methylsulfonaminoethyl group, an ethylsulfonaminoethyl group, a propylsulfonaminoethyl group, and the like.
Examples of the sulfonamidoalkyl group include a sulfonamidomethyl group, a sulfonamidoethyl group, and a sulfonamidopropyl group.

Examples of alkylaminoalkyl groups include N-methylaminomethyl, N, N-dimethylaminomethyl, N, N-diethylaminomethyl, N, N-dipropylaminomethyl, N, N-dibutylaminomethyl. Groups and the like.
Examples of the aminoalkyl group include an aminomethyl group, an aminoethyl group, and an aminopropyl group.
Examples of alkyl sulfone alkyl groups include methyl sulfone methyl group, ethyl sulfone methyl group, butyl sulfone methyl group, methyl sulfone ethyl group, ethyl sulfone ethyl group, butyl sulfone ethyl group, 2,2,3,3-tetrafluoropropyl Examples thereof include a sulfonemethyl group and a 2,2,3,3-tetrachloropropylsulfonemethyl group.
Examples of the substituted or unsubstituted alkoxy group include an alkoxy group having the same substituent as the alkyl group listed above, and preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, n Examples include lower butoxy groups such as -butoxy group, iso-butoxy group, sec-butoxy group, t-butoxy group, n-pentoxy group, iso-pentoxy group, neo-pentoxy group, and 2-methylbutoxy group.

Examples of the substituted or unsubstituted acyl group are acyl groups having the same substituents as the alkyl groups listed above, preferably a formyl group, a methylcarbonyl group, an ethylcarbonyl group, an n-propylcarbonyl group, iso-propylcarbonyl group, n-butylcarbonyl group, iso-butylcarbonyl group, sec-butylcarbonyl group, t-butylcarbonyl group, n-pentylcarbonyl group, iso-pentylcarbonyl group, neo-pentylcarbonyl group, 2- Examples thereof include a methylbutylcarbonyl group and a nitrobenzylcarbonyl group.
Examples of the substituted or unsubstituted aryl group are aryl groups having the same substituents as the alkyl groups listed above, and preferably a phenyl group, a nitrophenyl group, a cyanophenyl group, a hydroxyphenyl group, a methylphenyl group. Group, trifluoromethylphenyl group, naphthyl group, nitronaphthyl group, cyanonaphthyl group, hydroxynaphthyl group, methylnaphthyl group, trifluoromethylnaphthyl group and the like.

Examples of the substituted or unsubstituted aralkyl group are aralkyl groups having the same substituents as the alkyl groups listed above, preferably benzyl group, nitrobenzyl group, cyanobenzyl group, hydroxybenzyl group, methylbenzyl Group, trifluoromethylbenzyl group, naphthylmethyl group, nitronaphthylmethyl group, cyanonaphthylmethyl group, hydroxynaphthylmethyl group, methylnaphthylmethyl group, trifluoromethylnaphthylmethyl group and the like.
Examples of the substituted or unsubstituted alkenyl group are alkenyl groups having the same substituents as the alkyl groups listed above, and are preferably a propenyl group, a 1-butenyl group, an iso-butenyl group, and a 1-pentenyl group. 2-pentenyl group, 2-methyl-1-butenyl group, 3-methyl-1-butenyl group, 2-methyl-2-butenyl group, 2,2-dicyanovinyl group, 2-cyano-2-methylcarboxyl vinyl And lower alkenyl groups such as 2-cyano-2-methylsulfonvinyl group.

Examples of the substituted or unsubstituted alkylthio group are alkylthio groups having the same substituents as the alkyl groups listed above, and preferably a methylthio group, an ethylthio group, an n-propylthio group, an iso-propylthio group, n Lower alkylthio such as -butylthio group, iso-butylthio group, sec-butylthio group, t-butylthio group, n-pentylthio group, iso-pentylthio group, neo-pentylthio group, 2-methylbutylthio group, methylcarboxylethylthio group Groups.
Examples of the substituted or unsubstituted aryloxy group are aryloxy groups having the same substituents as the aryl groups listed above, preferably a phenoxy group, a 2-methylphenoxy group, a 4-methylphenoxy group, Examples include 4-t-butylphenoxy group, 2-methoxyphenoxy group, 4-iso-propylphenoxy group.
Examples of the substituted or unsubstituted arylthio group are arylthio groups having the same substituents as the above-mentioned aryl groups, preferably a phenylthio group, a 4-methylphenylthio group, a 2-methoxyphenylthio group, 4-t-butylphenylthio group etc. are mentioned.

  Examples of substituted or unsubstituted heteroaryl groups include pyrrolyl, thienyl, furanyl, oxazoyl, isoxazoyl, oxadiazoyl, imidazolyl, benzoxazoyl, benzothiazoyl, benzoimidazolyl, benzofuranyl Group, indoyl group and the like.

  Examples of the substituted or unsubstituted alkylsulfone group are alkylsulfone groups having the same substituents as the above-mentioned alkyl groups, and preferably methylsulfone group, ethylsulfone group, n-propylsulfone group, iso -Propylsulfone group, n-butylsulfone group, iso-butylsulfone group, sec-butylsulfone group, t-butylsulfone group, n-pentylsulfone group, iso-butylsulfone group, neo-pentylsulfone group, 2-methyl A butyl sulfone group, 2-hydroxyethyl sulfone group, 2-cyanoethyl sulfone group, etc. are mentioned.

More preferable examples of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , and R ₈ are substituted or unsubstituted from the viewpoint of enhancing compatibility with other photosensitive compositions. Of the alkyl group. Further, when an acylphosphine compound is used as an activator compound described later, X is preferably a sulfur atom in terms of sensitivity.

  The compound represented by the general formula (XXIV) of the present invention can be obtained by a known method, for example, J. Org. Am. Chem. Soc. 63, 3203 (1941) and the like. That is, it can be produced by reacting a compound represented by the general formula (XXIV-1) with a compound represented by the general formula (XXIV-2) using hydrochloric acid or the like as a catalyst.

(In the formulas (XXIV-1) and (XXIV-2), R _{1 to} R ₈ , X ₁ and X ₂ have the same meaning as defined in the general formula (XXIV).)
Preferred specific examples (D1) to (D19) of the compound represented by the general formula (XXIV) are shown below, but the present invention is not limited thereto. In the following formula, Hex means an n-hexyl group.

一般式(XXV)中、Ｘ₁〜Ｘ₅はそれぞれ独立に一価の非金属原子団を表し、Ｚはアリール基、またはヘテロアリール基を表す。

In the general formula (XXV), X _{1 to} X ₅ each independently represents a monovalent nonmetallic atomic group, and Z represents an aryl group or a heteroaryl group.

Hereinafter, the general formula (XXV) will be described in detail. X ₁ to X ₅ each independently represents a monovalent nonmetallic atomic group. Preferable specific examples of such a substituent include a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom (—F, —Br, —Cl, —I), a hydroxyl group, an alkoxy group, an aryloxy group, a mercapto group, Alkylthio group, arylthio group, alkyldithio group, aryldithio group, amino group, N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diarylamino group, N-alkyl-N -Arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N- Arylcarbamoyloxy group, alkylsulfoxy group,

Arylsulfoxy group, acylthio group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N′-alkylureido group, N ′, N′-dialkylureido group, N′-arylureido Group, N ′, N′-diarylureido group, N′-alkyl-N′-arylureido group, N-alkylureido group, N-arylureido group, N′-alkyl-N-alkylureido group, N′- Alkyl-N-arylureido group, N ', N'-dialkyl-N-alkylureido group, N', N'-dialkyl-N-arylureido group, N'-aryl-N-alkylureido group, N'- Aryl-N-arylureido group, N ′, N′-diaryl-N-alkylureido group, N ′, N′-diaryl-N-ary Ruureido group, N'- alkyl -N'- aryl -N- alkylureido group, N'- alkyl -N'- aryl -N- arylureido group,

Alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N -Aryloxycarbonylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N-arylcarbamoyl group,

Alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfo group (—SO ₃ H) and its conjugate base group (hereinafter referred to as sulfonate group), alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group,

Phosphono group (—PO ₃ H ₂ ) and its conjugate base group (hereinafter referred to as “phosphonate group”), dialkyl phosphono group (—PO ₃ (alkyl) ₂ ), diaryl phosphono group (—PO ₃ (aryl) ₂ ) , Alkylaryl phosphono group (—PO ₃ (alkyl) (aryl)), monoalkyl phosphono group (—PO ₃ H (alkyl)) and its conjugate base group (hereinafter referred to as alkyl phosphonate group), monoaryl Phosphono group (—PO ₃ H (aryl)) and its conjugate base group (hereinafter referred to as aryl phosphonate group), phosphonooxy group (—OPO ₃ H ₂ ) and its conjugate base group (hereinafter referred to as “phosphonateoxy”) Group), dialkyl phosphonooxy group (—OPO ₃ (alkyl) ₂ ), diaryl phosphonooxy group (—OPO ₃ (aryl) ₂ ), alkylaryl phosphonooxy group (—OPO ₃ (alkyl) (aryl) )), -Alkyl phosphonooxy group (-OPO ₃ H (alkyl)) and its conjugated base group (hereinafter referred to as alkyl phosphonophenyl group), monoaryl phosphonooxy group (-OPO ₃ H (aryl)) and its conjugate Examples include a base group (hereinafter referred to as an arylphosphonatooxy group), a cyano group, a nitro group, an aryl group, a heteroaryl group, an alkenyl group, and an alkynyl group.

  Preferable examples of the alkyl group in these substituents include linear, branched and cyclic alkyl groups having 1 to 20 carbon atoms. Specific examples thereof include a methyl group, Ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, hexadecyl group, octadecyl group, eicosyl group, isopropyl group, isobutyl group S-butyl group, t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group, 2-norbornyl group. it can. Of these, linear alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, and cyclic alkyl groups having 5 to 10 carbon atoms are more preferable.

  On the other hand, examples of the alkylene group in the substituted alkyl group include divalent organic residues obtained by removing any one of the hydrogen atoms on the alkyl group having 1 to 20 carbon atoms. Can include linear alkylene groups having 1 to 12 carbon atoms, branched chains having 3 to 12 carbon atoms, and cyclic alkylene groups having 5 to 10 carbon atoms. The substituent of the substituted alkyl group is arbitrary, but preferred examples of the substituted alkyl group include chloromethyl group, bromomethyl group, 2-chloroethyl group, trifluoromethyl group, methoxymethyl group, methoxyethoxyethyl group, allyloxy. Methyl group, phenoxymethyl group, methylthiomethyl group, tolylthiomethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyloxymethyl group, benzoyloxymethyl group, N-cyclohexylcarbamoyloxyethyl group, N-phenyl Carbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxoethyl group, 2-oxopropyl group, carboxypropyl group, methoxycarbonylethyl group, allyloxycarbonylbutyl Chlorophenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl group, N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, N-methyl-N- (sulfophenyl) carbamoylmethyl Group, sulfobutyl group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N-dipropylsulfamoylpropyl group, N-tolylsulfamoylpropyl group,

N-methyl-N- (phosphonophenyl) sulfamoyloctyl group, phosphonobutyl group, phosphonatohexyl group, diethylphosphonobutyl group, diphenylphosphonopropyl group, methylphosphonobutyl group, methylphosphonatobutyl group , Tolylphosphonohexyl group, tolylphosphonatohexyl group, phosphonooxypropyl group, phosphonateoxybutyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-methyl-1-phenylethyl group, p-methyl Benzyl group, cinnamyl group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2-methylallyl group, 2-methylpropenylmethyl group, 2-propynyl group, 2-butynyl group, 3-butynyl group, etc. be able to.

  Specific examples of the aryl group in these substituents include those in which 1 to 3 benzene rings form a condensed ring, and those in which a benzene ring and a 5-membered unsaturated ring form a condensed ring. Specific examples thereof include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenaphthenyl group, and a fluorenyl group. Among these, a phenyl group and a naphthyl group are more preferable.

  Specific examples of the substituted aryl group include those having a monovalent nonmetallic atomic group excluding hydrogen as a substituent on the ring-forming carbon atom of the aryl group. Preferred specific examples of the substituted aryl group include a biphenyl group, a tolyl group, a xylyl group, a mesityl group, a cumenyl group, a chlorophenyl group, a bromophenyl group, a fluorophenyl group, a chloromethylphenyl group, a trifluoromethylphenyl group, and a hydroxyphenyl group. , Methoxyphenyl group, methoxyethoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, methylthiophenyl group, tolylthiophenyl group, ethylaminophenyl group, diethylaminophenyl group, morpholinophenyl group, acetyloxyphenyl group, benzoyloxyphenyl group N-cyclohexylcarbamoyloxyphenyl group, N-phenylcarbamoyloxyphenyl group, acetylaminophenyl group, N-methylbenzoylaminophenyl group, carboxypheny Group, methoxycarbonylphenyl group, allyloxycarbonylphenyl group, chlorophenoxycarbonylphenyl group, carbamoylphenyl group, N-methylcarbamoylphenyl group, N, N-dipropylcarbamoylphenyl group, N- (methoxyphenyl) carbamoylphenyl group, N-methyl-N- (sulfophenyl) carbamoylphenyl group,

Sulfophenyl group, sulfonatophenyl group, sulfamoylphenyl group, N-ethylsulfamoylphenyl group, N, N-dipropylsulfamoylphenyl group, N-tolylsulfamoylphenyl group, N-methyl-N- (Phosphonophenyl) sulfamoylphenyl group, phosphonophenyl group, phosphonatophenyl group, diethylphosphonophenyl group, diphenylphosphonophenyl group, methylphosphonophenyl group, methylphosphonatophenyl group, tolylphosphonophenyl group , Tolylphosphonatophenyl group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2-methylallylphenyl group, 2-methylpropenylphenyl group, 2-propynylphenyl group, 2-butynylphenyl group, 3- List butynylphenyl groups, etc. Can.

  As the heteroaryl group, a monocyclic or polycyclic aromatic ring containing at least one of nitrogen, oxygen and sulfur atoms is used, and preferably a 5-membered or 6-membered ring such as furan, pyrrole or pyridine. Aromatic substituents can be used.

  Examples of alkenyl groups include vinyl, 1-propenyl, 1-butenyl, cinnamyl, 2-chloro-1-ethenyl, etc. Examples of alkynyl include ethynyl, 1 -Propynyl group, 1-butynyl group, trimethylsilylethynyl group and the like.

Examples of G ¹ in the acyl group (G ¹ CO—) include hydrogen and the above alkyl groups and aryl groups. Among these substituents, even more preferred are halogen atoms (—F, —Br, —Cl, —I), alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, N-alkylamino groups, N, N— Dialkylamino group, acyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, acylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, sulfo group, sulfonate group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group Group, N-arylsulfa Yl group, N-alkyl-N-arylsulfamoyl group, phosphono group, phosphonate group, dialkyl phosphono group, diaryl phosphono group, monoalkyl phosphono group, alkyl phosphonate group, monoaryl phosphono group, aryl phosphine group Examples include an onato group, a phosphonooxy group, a phosphonateoxy group, an aryl group, and an alkenyl group.

X ₁ to X ₅ described above are selected from various practical viewpoints in addition to performance such as photosensitivity, photosensitive wavelength, and stability. For example, in terms of compatibility improvement in the composition system, prevention of crystal precipitation, when developing, solubility in a developing solution, dispersibility, difficulty in precipitation, raw material price, ease of synthesis, It is appropriately selected in consideration of economic viewpoints such as ease of purification. In this respect, examples of particularly preferable substituents include a hydrogen atom, a halogen atom (—F, —Br, —Cl, —I), a lower alkyl group having 1 to 6 carbon atoms (methyl group, ethyl group, Propyl group, isopropyl group, allyl group, 2-methylpropenyl group, etc.), alkyl-substituted aminoalkylene group (the alkyl group is a linear or branched alkyl group having 1 to 6 carbon atoms and having 5 to 7 carbon atoms) And examples of the alkylene group include mono-, di-, and tri-methylene groups having 1 to 3 carbon atoms.

Next, Z in the general formula (XXV) will be described. Z represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. As the aryl group, one in which 1 to 3 benzene rings form a condensed ring, or one in which a benzene ring and a 5-membered unsaturated ring form a condensed ring can be used. As the substituent of the substituted aryl group, a monovalent non-metallic atomic group can be used, and specifically, any of those exemplified as examples of X ₁ to X ₅ can be used.

  Specific examples of particularly preferred aryl groups as Z include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenaphthenyl group, and a fluorenyl group. Specific examples of the substituted aryl group include a biphenyl group. , Tolyl group, xylyl group, mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, fluorophenyl group, chloromethylphenyl group, trifluoromethylphenyl group, hydroxyphenyl group, methoxyphenyl group, methoxyethoxyphenyl group, allyloxy Phenyl group, phenoxyphenyl group, methylthiophenyl group, tolylthiophenyl group, ethylaminophenyl group, diethylaminophenyl group, morpholinophenyl group, acetyloxyphenyl group, benzoyloxyphenyl group, N-silane Rohe alkoxy carbamoyl oxyphenyl group, N- phenylcarbamoyloxy phenyl group, an acetylamino phenyl group, N- methyl-benzoylamino phenyl group,

Carboxyphenyl group, methoxycarbonylphenyl group, allyloxycarbonylphenyl group, chlorophenoxycarbonylphenyl group, carbamoylphenyl group, N-methylcarbamoylphenyl group, N, N-dipropylcarbamoylphenyl group, N- (methoxyphenyl) carbamoylphenyl Group, N-methyl-N- (sulfophenyl) carbamoylphenyl group, sulfophenyl group, sulfonatophenyl group, sulfamoylphenyl group, N-ethylsulfamoylphenyl group, N, N-dipropylsulfamoylphenyl group N-tolylsulfamoylphenyl group, N-methyl-N- (phosphonophenyl) sulfamoylphenyl group, phosphonophenyl group, phosphonatophenyl group, diethylphosphonophenyl group, diphenylphosphine Ionophenyl group, methylphosphonophenyl group, methylphosphonatophenyl group, tolylphosphonophenyl group, tolylphosphonatophenyl group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2-methylallylphenyl group, 2- Examples thereof include a methylpropenylphenyl group, a 2-propynylphenyl group, a 2-butynylphenyl group, and a 3-butynylphenyl group.

  As the heteroaryl group, a monocyclic or polycyclic aromatic ring containing at least one of nitrogen, oxygen and sulfur atoms is used, and preferably a 5-membered or 6-membered ring such as furan, pyrrole or pyridine. Aromatic substituents can be used. As an example of the substituted heteroaryl group, a monovalent non-metallic atomic group can be used, and specifically, any of those exemplified as examples of X1 to X5 can be used. Examples of particularly preferred heteroaryl groups include, for example, thiophene, thiathrene, furan, pyran, isobenzofuran, chromene, xanthene, phenoxazine, pyrrole, pyrazole, isothiazole, isoxazole, pyrazine, pyrimidine, pyridazine, indolizine, Indolizines, indoles, indazoles, purines, quinolidines, isoquinolines, phthalazines, naphthyridines, quinazolines, sinolines, pteridines, carbazoles, carbolines, phenanthrines, acridines, perimidines, phenanthrolins, phenalzazines, furansans, etc. It may be benzo-fused or may have a substituent.

  Z described above is selected from various practical viewpoints in addition to performance such as photosensitivity, photosensitive wavelength, and stability. For example, in terms of compatibility improvement in the composition system, prevention of crystal precipitation, when developing, solubility in a developing solution, dispersibility, difficulty in precipitation, raw material price, ease of synthesis, It is appropriately selected in consideration of economic viewpoints such as ease of purification. According to the general synthesis method described later, since Z is caused by the corresponding carboxylic acid derivative Z-COOH, it is economically advantageous to use relatively inexpensive ZCOOH.

  From this point of view, phenyl nucleus-substituted benzoic acids and nucleus-substituted naphthoic acids are preferred as ZCOOH. Specifically, benzoic acid, o-toluic acid, m-toluic acid, p-ethylbenzoic acid, p-isopropylbenzoic acid, p-butylbenzoic acid, p-tert-butylbenzoic acid, 3,4-dimethylbenzoic acid Acid, 3,5-dimethylbenzoic acid, o-anisic acid, m-anisic acid, p-anisic acid, 3,4-dimethoxybenzoic acid (baratrmic acid), 2,3-dimethoxybenzoic acid (o-veratormic acid) , O-ethoxybenzoic acid, 3-methoxy-4-methylbenzoic acid, p-ethoxybenzoic acid, p-propoxybenzoic acid, o-bromobenzoic acid, p-bromobenzoic acid, o-chlorobenzoic acid, m-chloro Benzoic acid, p-fluorobenzoic acid, 3,4-dichlorobenzoic acid, o-hydroxybenzoic acid, p-hydroxybenzoic acid, m-hydroxybenzoic acid, 4-hydroxy-3-methoxybenzoic acid Benzoic acid such as perfume acid, o-biphenylcarboxylic acid, 4-biphenylcarboxylic acid, o-benzoylbenzoic acid, p-acetamidobenzoic acid, m-dimethylaminobenzoic acid, p-methylaminobenzoic acid, m-cyanobenzoic acid, etc. Acids, naphthoic acid, 2-chloro-1-naphthoic acid, 5-chloro-1-naphthoic acid, 8-chloro-1-naphthoic acid, 4-fluoro-1-naphthoic acid, 4-bromo-1-naphthoic acid 5-iodo-1-naphthoic acid, 5,8-dichloro-1-naphthoic acid, 1-chloro-2-naphthoic acid, 3-chloro-2-naphthoic acid, 5-chloro-2-naphthoic acid, 4, 5-dichloro-2-naphthoic acid, 1-bromo-2-naphthoic acid, 4,5-dichloro-2-naphthoic acid, 1-bromo-2-naphthoic acid, 2-methyl-1-naphthoic acid, 8-methyl -2 -Naphthoic acid etc. are mentioned. In the naphthofuranone compound of the present invention, the photosensitive wavelength can be easily controlled by selecting the structure of Z. For example, the purpose of obtaining a highly sensitive starting system in the long wave region up to around 500 nm is achieved by using 4-dialkylaminobenzoic acid as ZCOOH as described in JP-B-61-55513. it can.

In the following, examples of the general formula (XXV) of the present invention are shown as chemical structural formulas (D1) to (D37) as more specific descriptions. The general formula (XXV) of the present invention is the structural requirement described above. Any of those satisfying the above conditions can be suitably used, and the present invention is not limited by the following chemical structural formula.

一般式（XXVI）中、Ｙは隣接するＮおよび炭素原子と共同して含窒素ヘテロ環を形成する非金属原子団を表し、Ｘは一価の非金属原子団を表す。

In general formula (XXVI), Y represents a nonmetallic atomic group that forms a nitrogen-containing heterocycle in cooperation with adjacent N and carbon atoms, and X represents a monovalent nonmetallic atomic group.

  The general formula (XXVI) will be described in detail. Y represents a non-metallic atomic group that forms a nitrogen-containing heterocycle together with an adjacent N atom and an adjacent carbon atom. Examples of preferred nitrogen-containing heterocycles include cyanine as described in, for example, FM Hamer, The Chemistry of Heterocyclic Compounds Vol. 18, “The Cyanine Dyes and Related Compounds” (1964), John Willille & Sons (New York). The nitrogen-containing heterocyclic group which comprises a base (Group) compound group can be mentioned.

  Specific examples include thiazoles (for example, thiazole, 4-methylthiazole, 4-phenylthiazole, 5-methylthiazole, 5-phenylthiazole, 4,5-dimethylthiazole, 4,5-diphenylthiazole, 4,5- Di (p-methoxyphenylthiazole), 4- (2-thienyl) thiazole, etc.), benzothiazoles (for example, benzothiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, 7- Chlorobenzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, 5-bromobenzothiazole, 4-phenylbenzothiazole, 5-phenylbenzothiazole, 4-methoxybenzothiazole, 5-methoxybenzo Cheer , 6-methoxybenzothiazole, 5-iodobenzothiazole, 6-iodobenzothiazole, 4-ethoxybenzothiazole, 5-ethoxybenzothiazole, tetrahydrobenzothiazole, 5,6-dimethoxybenzothiazole, 5,6-di Oxymethylenebenzothiazole, 5-hydroxybenzothiazole, 6-hydroxybenzothiazole, 6-dimethylaminobenzothiazole, 5-ethoxycarbonylbenzothiazole, etc.),

Naphthothiazoles (for example, naphtho [1,2] thiazole, naphtho [2,1] thiazole, 5-methoxynaphtho [2,1] thiazole, 5-ethoxynaphtho [2,1] thiazole, 8-methoxynaphtho [1 , 2] thiazole, 7-methoxynaphtho [1,2] thiazole, etc.), thianaphtheno-7 ′, 6 ′, 4,5-thiazole (for example, 4′-methoxythianaphtheno-7 ′, 6 ′, 4) , 5-thiazole, etc.), oxazoles (for example, 4-methyloxazole, 5-methyloxazole, 4-phenyloxazole, 4,5-diphenyloxazole, 4-ethyloxazole, 4,5-dimethyloxazole, 5-phenyl Oxazole), benzoxazoles (benzoxazole, 5-chlorobenzoxazole, 5-methyl Benzoxazole, 5-phenylbenzoxazole, 6-methylbenzoxazole, 5,6-dimethylbenzoxazole, 4,6-dimethylbenzoxazole, 6-methoxybenzoxazole, 5-methoxybenzoxazole, 4-ethoxybenzoxazole, 5 -Chlorobenzoxazole, 6-methoxybenzoxazole, 5-hydroxybenzoxazole, 6-hydroxybenzoxazole, etc.),

Naphthoxazoles (eg, naphtho [1,2] oxazole, naphtho [2,1] oxazole, etc.), selenazoles (eg, 4-methylselenazole, 4-phenylselenazole, etc.), benzoselenazoles ( For example, benzoselenazole, 5-chlorobenzoselenazole, 5-methoxybenzoselenazole, 5-hydroxybenzoselenazole, tetrahydrobenzoselenazole, etc.), naphthoselenazoles (for example, naphtho [1,2] selenazole, Naphtho [2,1] selenazole, etc.], thiazolines (eg, thiazoline, 4-methylthiazoline, etc.), 2-quinolines (eg, quinoline, 3-methylquinoline, 5-methylquinoline, 7-methylquinoline, 8-methylquinoline, 6-chloroquinoline, 8-chloroquino , 6-methoxyquinoline, 6-ethoxyquinoline, 6-hydroxyquinoline, 8-hydroxyquinoline, etc.), 4-quinolines (for example, quinoline, 6-methoxyquinoline, 7-methylquinoline, 8-methylquinoline, etc.) ), 1-isoquinolines (eg, isoquinoline, 3,4-dihydroisoquinoline, etc.), 3-isoquinolines (eg, isoquinoline, etc.), imidazoles (eg, imidazole, etc.),

Benzimidazoles (for example, 1,3-diethylbenzimidazole, 1-ethyl-3-phenylbenzimidazole, etc.), 3,3-dialkylindolenines (for example, 3,3-dimethylindolenine, 3,3, 5, -trimethylindolenine, 3,3,7, -trimethylindolenine, etc.), 2-pyridines (eg, pyridine, 5-methylpyridine, etc.), 4-pyridine (eg, pyridine, etc.) and the like. In addition, diazoles (for example, 1,3,4-oxadiazole, 1,3,4-thiadiazole, 1,3,4-selenadiazole, etc.), triazoles (for example, 1,2,4- Other than triazole), pyrazines, quinoxalines, triazines (eg, 1,3,5-triazine, etc.), phenanthridine, 2H pyrrole , Pyrazoles, isothiazoles, isoxazoles, pyrimidines, pyridazines, indazoles, phthalazines, naphthyridines, quinazolines, cinnolines, pteridines, β-carbolines, perimidines, furazanes, etc. Used.

  In these nitrogen-containing heterocycles formed by Y in combination with adjacent N and adjacent carbon atoms, the hydrogen atoms constituting them can be replaced with arbitrary substituents. Preferred examples of such a substituent include an alkyl group, a substituted alkyl group, a halogen atom (—F, —Br, —Cl, —I), a hydroxyl group, an alkoxy group, an aryloxy group, a mercapto group, an alkylthio group, an arylthio group. Group, alkyldithio group, aryldithio group, amino group, N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group , Acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N-arylcarbamoyloxy group Alkylsulfoxy group, arylsulfoxy group, Thio group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N′-alkylureido group, N ′, N′-dialkylureido group, N′-arylureido group, N ′, N′-diarylureido group, N′-alkyl-N′-arylureido group, N-alkylureido group,

N-arylureido group, N'-alkyl-N-alkylureido group, N'-alkyl-N-arylureido group, N ', N'-dialkyl-N-alkylureido group, N', N'-dialkyl- N-arylureido group, N'-aryl-N-alkylureido group, N'-aryl-N-arylureido group, N ', N'-diaryl-N-alkylureido group, N', N'-diaryl- N-arylureido group, N′-alkyl-N′-aryl-N-alkylureido group, N′-alkyl-N′-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N -Alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N- Lucoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkyl Carbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group,

Sulfo group (—SO ₃ H) and its conjugate base group (hereinafter referred to as “sulfonato group”), alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkylsulfinamoyl group, N, N-dialkylsulfinamoyl Group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfa Moyl group, N-arylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, phosphono group (—PO ₃ H ₂ ) and its conjugate base group (hereinafter, Phosphonate group), dialkyl phosphono group (—PO ₃ (alkyl) ₂ ), diaryl phosphono group (— PO ₃ (aryl) ₂ ), alkylaryl phosphono group (—PO ₃ (alkyl) (aryl)), monoalkyl phosphono group (—PO ₃ H (alkyl)) and its conjugate base group (hereinafter referred to as alkyl phosphonate) Group), monoarylphosphono group (—PO ₃ H (aryl)) and its conjugate base group (hereinafter referred to as arylphosphonate group), phosphonooxy group (—OPO ₃ H ₂ ) and its conjugate base A group (hereinafter referred to as a phosphonatoxy group), a dialkylphosphonooxy group (—OPO ₃ (alkyl) ₂ ),

Diarylphosphonooxy group (—OPO ₃ (aryl) ₂ ), alkylarylphosphonooxy group (—OPO ₃ (alkyl) (aryl)), monoalkylphosphonooxy group (—OPO ₃ H (alkyl)) and its A conjugated base group (hereinafter referred to as an alkylphosphonatooxy group), a monoarylphosphonooxy group (—OPO ₃ H (aryl)) and a conjugated base group (hereinafter referred to as an arylphosphonatooxy group), a cyano group, Examples thereof include a nitro group, an aryl group, a heteroaryl group, an alkenyl group, and an alkynyl group.

  Preferable examples of the alkyl group in these substituents include linear, branched and cyclic alkyl groups having 1 to 20 carbon atoms. Specific examples thereof include a methyl group, Ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, hexadecyl group, octadecyl group, eicosyl group, isopropyl group, isobutyl group S-butyl group, t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group, 2-norbornyl group. it can. Of these, linear alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, and cyclic alkyl groups having 5 to 10 carbon atoms are more preferable.

  On the other hand, examples of the alkylene group in the substituted alkyl group include divalent organic residues obtained by removing any one of the hydrogen atoms on the alkyl group having 1 to 20 carbon atoms. Can include linear alkylene groups having 1 to 12 carbon atoms, branched chains having 3 to 12 carbon atoms, and cyclic alkylene groups having 5 to 10 carbon atoms.

  The substituent of the substituted alkyl group is arbitrary, but preferred examples of the substituted alkyl group include chloromethyl group, bromomethyl group, 2-chloroethyl group, trifluoromethyl group, methoxymethyl group, methoxyethoxyethyl group, allyloxy. Methyl group, phenoxymethyl group, methylthiomethyl group, tolylthiomethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyloxymethyl group, benzoyloxymethyl group, N-cyclohexylcarbamoyloxyethyl group, N-phenyl Carbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxoethyl group, 2-oxopropyl group, carboxypropyl group, methoxycarbonylethyl group, allyloxycarbonylbutyl Chlorophenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl group, N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, N-methyl-N- (sulfophenyl) carbamoylmethyl Group, sulfobutyl group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N-dipropylsulfamoylpropyl group, N-tolylsulfamoylpropyl group, N-methyl-N- ( (Phosphonophenyl) sulfamoyloctyl group, phosphonobutyl group, phosphonatohexyl group, diethylphosphonobutyl group, diphenylphosphonopropyl group, methylphosphonobutyl group, methylphosphonatobutyl group, tolylphosphonohexyl group, Thrill Suphonatohexyl group, phosphonooxypropyl group, phosphonatoxybutyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-methyl-1-phenylethyl group, p-methylbenzyl group, cinnamyl group, allyl group 1-propenylmethyl group, 2-butenyl group, 2-methylallyl group, 2-methylpropenylmethyl group, 2-propynyl group, 2-butynyl group, 3-butynyl group and the like.

  Specific examples of the aryl group in these substituents include those in which 1 to 3 benzene rings form a condensed ring, and those in which a benzene ring and a 5-membered unsaturated ring form a condensed ring. Specific examples thereof include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenaphthenyl group, and a fluorenyl group. Among these, a phenyl group and a naphthyl group are more preferable.

  Specific examples of the substituted aryl group include those having a monovalent nonmetallic atomic group excluding hydrogen as a substituent on the ring-forming carbon atom of the aryl group. Preferred specific examples of the substituted aryl group include a biphenyl group, a tolyl group, a xylyl group, a mesityl group, a cumenyl group, a chlorophenyl group, a bromophenyl group, a fluorophenyl group, a chloromethylphenyl group, a trifluoromethylphenyl group, and a hydroxyphenyl group. , Methoxyphenyl group, methoxyethoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, methylthiophenyl group, tolylthiophenyl group, ethylaminophenyl group, diethylaminophenyl group, morpholinophenyl group, acetyloxyphenyl group, benzoyloxyphenyl group N-cyclohexylcarbamoyloxyphenyl group, N-phenylcarbamoyloxyphenyl group, acetylaminophenyl group, N-methylbenzoylaminophenyl group, carboxypheny Group, methoxycarbonylphenyl group, allyloxycarbonylphenyl group, chlorophenoxycarbonylphenyl group, carbamoylphenyl group, N-methylcarbamoylphenyl group, N, N-dipropylcarbamoylphenyl group, N- (methoxyphenyl) carbamoylphenyl group, N-methyl-N- (sulfophenyl) carbamoylphenyl group, sulfophenyl group, sulfonatophenyl group, sulfamoylphenyl group, N-ethylsulfamoylphenyl group, N, N-dipropylsulfamoylphenyl group, N -Tolylsulfamoylphenyl group, N-methyl-N- (phosphonophenyl) sulfamoylphenyl group, phosphonophenyl group, phosphonatophenyl group, diethylphosphonophenyl group, diphenylphosphonophenyl group Methylphosphonophenyl group, methylphosphonatophenyl group, tolylphosphonophenyl group, tolylphosphonatophenyl group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2-methylallylphenyl group, 2-methylpropenylphenyl Group, 2-propynylphenyl group, 2-butynylphenyl group, 3-butynylphenyl group and the like.

  As the heteroaryl group, a monocyclic or polycyclic aromatic ring containing at least one of nitrogen, oxygen, and sulfur atoms is used, and preferably a 5-membered or 6-membered aromatic such as furan, pyrrole, or pyridine. Substituents can be used. Examples of the alkenyl group include vinyl group, 1-propenyl group, 1-butenyl group, cinnamyl group, 2-chloro-1-ethenyl group and the like. Examples of alkynyl group include ethynyl group, 1- A propynyl group, a 1-butynyl group, a trimethylsilylethynyl group, etc. are mentioned.

Examples of G ¹ in the acyl group (G ¹ CO—) include hydrogen and the above alkyl groups and aryl groups. Among these substituents, even more preferred are halogen atoms (—F, —Br, —Cl, —I), alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, N-alkylamino groups, N, N— Dialkylamino group, acyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, acylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, sulfo group, sulfonate group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group Group, N-arylsulfa Yl group, N-alkyl-N-arylsulfamoyl group, phosphono group, phosphonate group, dialkyl phosphono group, diaryl phosphono group, monoalkyl phosphono group, alkyl phosphonate group, monoaryl phosphono group, aryl phosphine group Examples include an onato group, a phosphonooxy group, a phosphonateoxy group, an aryl group, and an alkenyl group.

  In the general formula (XXVI) described above, Y is a structure represented by the following partial structural formula (A-1) among examples of nitrogen-containing heterocycles formed in cooperation with adjacent N and adjacent carbon atoms. Is particularly preferable because it provides a photoinitiating system having high sensitizing ability and very excellent storage stability.

（式（Ａ−１）中、Ｘ₁ 、Ｘ₂ はそれぞれ独立に、置換もしくは非置換のアルキル基、アリール基、ヘテロアリール基を表し、Ｘ₁ 、Ｘ₂ が互いに結合して５、６もしくは７員の脂肪族または芳香族環を形成してもよい。）
Ｘ₁ 、Ｘ₂ の具体例としては、先に挙げた置換もしくは非置換のアルキル基、アリール基、ヘテロアリール基の例が挙げられる。

(In formula (A-1), X ₁ and X ₂ each independently represents a substituted or unsubstituted alkyl group, aryl group or heteroaryl group, and X ₁ and X ₂ are bonded to each other to form 5, 6 or A 7-membered aliphatic or aromatic ring may be formed.)
Specific examples of X ₁ and X ₂ include the examples of the substituted or unsubstituted alkyl group, aryl group and heteroaryl group mentioned above.

  Next, X in the general formula (XXVI) will be described. X represents a monovalent non-metallic atomic group, for example, substitution in which Y in general formula (XXVI) may replace a hydrogen atom of a nitrogen-containing heterocycle formed in cooperation with adjacent N and adjacent carbon atoms Any of those listed as examples of groups, hydrogen atoms, and the like can be suitably used. Among these substituents, when an alkyl group that may be substituted, an aryl group that may be substituted, a heteroaryl group that may be substituted, or an alkenyl group that may be substituted is used, Since an inexpensive raw material can be synthesized in a short process, it is economical. In particular, Y is an aryl group which may be substituted, a heteroaryl group which may be substituted, or an alkenyl group which may be substituted, which is advantageous in terms of absorption wavelength and very excellent in storage stability. Give the pigment.

  Specific examples of the aryl group and substituted aryl group that are particularly preferable as Y include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenaphthenyl group, and a fluorenyl group. Specific examples of the substituted aryl group include biphenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, fluorophenyl group, chloromethylphenyl group, trifluoromethylphenyl group, hydroxyphenyl group, Methoxyphenyl group, methoxyethoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, methylthiophenyl group, tolylthiophenyl group, ethylaminophenyl group, diethylaminophenyl group, morpholinophenyl group, acetyloxyphenyl group, benzoyloxyphenyl group, N-cyclohexylcarbamoyloxyphenyl group, N-phenylcarbamoyloxyphenyl group, acetylaminophenyl group, N-methylbenzoylaminophenyl group, carboxyphenyl group, Alkoxycarbonyl phenyl group, allyloxycarbonyl phenyl group, chlorophenoxy carbonyl phenyl group, carbamoyl phenyl group, N- methylcarbamoyl-phenyl group, N, N- dipropylcarbamoylphenyl group,

N- (methoxyphenyl) carbamoylphenyl group, N-methyl-N- (sulfophenyl) carbamoylphenyl group, sulfophenyl group, sulfonatophenyl group, sulfamoylphenyl group, N-ethylsulfamoylphenyl group, N, N-dipropylsulfamoylphenyl group, N-tolylsulfamoylphenyl group, N-methyl-N- (phosphonophenyl) sulfamoylphenyl group, phosphonophenyl group, phosphonatophenyl group, diethylphosphonophenyl group , Diphenylphosphonophenyl group, methylphosphonophenyl group, methylphosphonatophenyl group, tolylphosphonophenyl group, tolylphosphonatophenyl group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2-methylallylphenyl Group, 2-methyl group Penirufeniru group, 2-propynyl phenyl group, 2-butynyl phenyl group, 3-butynyl phenyl group, and the like.

  Particularly preferred examples of the heteroaryl group include, for example, any of the nitrogen-containing heterocycles formed by Y in the general formula (XXVI) in cooperation with the adjacent N and adjacent carbon atoms. Can be used. Others, thiophene, thiathrene, furan, pyran, isobenzofuran, chromene, xanthene, phenoxazine, pyrrole, pyrazole, isothiazole, isoxazole, pyrazine, pyrimidine, pyridazine, indolizine, isoindolizine, indoir, indazole, purine, Quinolidine, isoquinoline, phthalazine, naphthyridine, quinazoline, cinazoline, pteridine, carbazole, carboline, phenanthrine, acridine, perimidine, phenanthrolin, phthalazine, phenalazine, phenoxazine, furazane, phenoxazine, etc. It may be condensed or may have a substituent.

Preferred examples of the alkenyl group as Y include those represented by the following partial structure (A-2) in addition to the examples of the alkenyl group described above.

（部分構造式（Ａ−２）中、Ｍ₁ 、Ｍ₂ はそれぞれ独立に、置換されてもよいメチン炭素を表し、Ｘ₃ は置換もしくは非置換のアリール基もしくは、ヘテロアリール基を表し、ｎは１以上の整数である。）
Ｍ₁ 、Ｍ₂が独立にＣＨ、ＣＣＨ₃である場合、特に色素の製造が容易であり、ｎが１、２の場合、吸収特性と安定性の両方に優れた色素が得られる。Ｘ₃は置換もしくは非置換のアリール基もしくは、ヘテロアリール基は既に例示したものが何れも好適に使用できる。

(In the partial structural formula (A-2), M ₁ and M ₂ each independently represents an optionally substituted methine carbon, X ₃ represents a substituted or unsubstituted aryl group or heteroaryl group, n Is an integer of 1 or more.)
When M ₁ and M ₂ are independently CH and CCH ₃ , the production of the dye is particularly easy, and when n is 1 or 2, a dye excellent in both absorption characteristics and stability can be obtained. As X _{3, any} of substituted or unsubstituted aryl groups or heteroaryl groups already exemplified can be preferably used.

In the following, examples of the general formula (XXVI) of the present invention are shown as chemical structural formulas (D1) to (D54) as more specific descriptions. The general formula (XXVI) of the present invention is the structural requirement described above. Any of those satisfying the above conditions can be suitably used, and the present invention is not limited by the following chemical structural formula.

上記一般式(XIV)〜(XXVI)で表される増感色素の中でも、光吸収特性に基づく高感度化の観点で、一般式（XIV）、(XVI)、（XVIII）、（XXVI）、（XXIII）が好ましく、一般式（XVIII）が最も好ましい。

Among the sensitizing dyes represented by the general formulas (XIV) to (XXVI), from the viewpoint of high sensitivity based on the light absorption characteristics, the general formulas (XIV), (XVI), (XVIII), (XXVI), (XXIII) is preferred, and general formula (XVIII) is most preferred.

(1-1-2) Chemical Modification of Sensitizing Dye Regarding these sensitizing dyes, when a lithographic printing plate is prepared using the polymerization initiation system of the present invention, an ink for inkjet recording containing this sensitizing dye Various chemical modifications can also be made to improve the properties of the image formed by. For example, by combining a sensitizing dye and an addition polymerizable compound structure (for example, an acryloyl group or a methacryloyl group) by a method such as a covalent bond, an ionic bond, or a hydrogen bond, the exposure film can be increased in strength or exposed. Unnecessary precipitation suppression of the dye from the subsequent film can be performed.

  Furthermore, when a lithographic printing plate is prepared using the polymerization initiation system of the present invention, the adhesion to an aluminum support, which is a preferred mode of use of an image formed by an ink jet recording ink containing this sensitizing dye, is increased. For the purpose, it is effective to introduce a hydrophilic moiety (carboxyl group and its ester, sulfonic acid group and its ester, acid group or polar group such as ethylene oxide group). In addition, for example, a substituent can be appropriately introduced in order to improve the compatibility in the ink for inkjet recording and to suppress crystal precipitation. For example, in a certain polymerization initiation system, an unsaturated bond such as an aryl group or an allyl group may be very effective in improving the compatibility, and a method such as introduction of a branched alkyl structure may be used. By introducing steric hindrance, crystal precipitation can be remarkably suppressed. In addition, by introducing a phosphonic acid group, an epoxy group, a trialkoxysilyl group, etc., adhesion to an inorganic substance such as a metal or a metal oxide can be improved. In addition, a method such as polymerization of a sensitizing dye can be used depending on the purpose.

Details of the usage such as which structure of these sensitizing dyes are used, whether they are used alone or in combination of two or more, and how much is added, can be appropriately set according to the performance design of the final photosensitive material. . For example, by using two or more sensitizing dyes in combination, the compatibility in the ink for ink jet recording can be increased. In selecting the sensitizing dye, in addition to the photosensitivity, the molar extinction coefficient at the emission wavelength of the radiation source to be used is an important factor. By using a sensitizing dye having a large molar extinction coefficient, the addition amount of the sensitizing dye can be made relatively small, so that it is economical, and when used in a lithographic printing plate, from the viewpoint of film physical properties of the image layer Is also advantageous. The photosensitivity and resolution of the image and the physical properties of the image are greatly affected by the absorbance at the radiation source wavelength. Therefore, the addition amount of the sensitizing dye is appropriately selected in consideration of these factors. When used as a lithographic printing plate used in a relatively thin film thickness, for example, the addition amount of the sensitizing dye is such that the absorbance of the image formed by the ink jet recording ink containing this sensitizing dye is 0.1 to 1. .5, preferably 0.25 to 1. When the absorbance is 0.1 or more, the sensitivity does not decrease and the resolution is not lowered due to the influence of halation. Even if the absorbance is less than 0.1, the degree of cure may be increased for the purpose of curing a thick film of 5 μm or more. If the absorbance is 3 or less, most of the radiation is absorbed in the vicinity of the image surface, and the internal curing is not hindered. For example, even when used as a printing plate, sufficient film strength and substrate adhesion can be obtained.
When used as a lithographic printing plate, the addition amount of the sensitizing dye is usually 0.05 to 30 parts by mass, preferably 0.1 to 20 parts by mass, more preferably 100 parts by mass of the ink for ink jet recording. It is the range of 0.2-10 mass parts.

(1-2) Polymerization initiator As the polymerization initiator of the present invention, a radical polymerization initiator and a cationic polymerization initiator can be used.
(1-2-1) Radical polymerization initiator Preferred radical polymerization initiators that can be used in the present invention include (a) aromatic ketones, (b) aromatic onium salt compounds, (c) organic peroxides, ( d) thio compound, (e) hexaarylbiimidazole compound, (f) ketoxime ester compound, (g) borate compound, (h) azinium compound, (i) metallocene compound, (j) active ester compound, (k) Examples thereof include compounds having a carbon halogen bond, and (l) alkylamine compounds. These radical polymerization initiators may be used alone or in combination with the above compounds (a) to (l).

(A) Preferred examples of aromatic ketones include compounds having a benzophenone skeleton or a thioxanthone skeleton described in “RADIATION CURING IN POLYMER SCIENCE AND TECHNOLOGY” JPFOUASSIER JFRABEK (1993), p77-117, for example,

Etc. More preferable examples of (a) aromatic ketones include α-thiobenzophenone compounds described in JP-B-47-6416, benzoin ether compounds described in JP-B-47-3981, and α-substituted benzoin compounds described in JP-B-47-22326. Benzoin derivatives described in JP-B-47-23664, aroylphosphonic acid esters described in JP-A-57-30704, dialkoxybenzophenones described in JP-B-60-26483, JP-B-60-26403, Benzoin ethers described in JP-A-62-81345, α-aminobenzophenones described in US Pat. No. 4,318,791, European Patent 0284561A1, for example,

P-di (dimethylaminobenzoyl) benzene described in JP-A-2-21152, thio-substituted aromatic ketone described in JP-A-61-194062, acylphosphine sulfide described in JP-B-2-9597, No. 2-9596, for example,

Examples thereof include thioxanthones described in JP-B 63-61950, and coumarins described in JP-B 59-42864.

Another example of the (b) aromatic onium salt is a group V, VI or VII element of the periodic table, specifically N, P, As, Sb, Bi, O, S, Se. , Te, or I aromatic onium salts. Examples of such aromatic onium salts include compounds disclosed in Japanese Patent Publication No. 52-14277, Japanese Patent Publication No. 52-14278, and Japanese Patent Publication No. 52-14279. In particular,

Can be mentioned.
Furthermore, the following diazonium salts can also be mentioned.

  Another example of the radical polymerization initiator used in the present invention (c) “organic peroxide” includes almost all organic compounds having one or more oxygen-oxygen bonds in the molecule. Examples include 3,3'4,4'-tetra- (t-butylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra- (t-amylperoxycarbonyl) benzophenone, 3,3 ' 4,4'-tetra- (t-hexylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra- (t-octylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra- ( Cumylperoxycarbonyl) benzophenone, 3,3'4,4'-tetra- (p-isopropylcumylperoxycarbonyl) benzophenone, di-t-butyldiperoxy Peroxide ester such Sofutareto are preferred.

The (d) thio compound as a radical polymerization initiator used in the present invention is represented by the following general formula [II].

(In the general formula [II], R ²⁰ represents an alkyl group, an aryl group or a substituted aryl group, R ²¹ represents a hydrogen atom or an alkyl group, and R ²⁰ and R ²¹ are bonded to each other to form oxygen, sulfur, And a group of nonmetallic atoms necessary to form a 5- to 7-membered ring which may contain a heteroatom selected from nitrogen atoms.)
The alkyl group in the general formula [II] is preferably an alkyl group having 1 to 4 carbon atoms. As the aryl group, those having 6 to 10 carbon atoms such as phenyl and naphthyl are preferable, and as the substituted aryl group, a halogen atom such as a chlorine atom and an alkyl such as a methyl group as described above. And those substituted with an alkoxy group such as a group, a methoxy group, and an ethoxy group. R ²¹ is preferably an alkyl group having 1 to 4 carbon atoms.

  Examples of the radical polymerization initiator (e) hexaarylbiimidazole used in the present invention include lophine dimers described in JP-B Nos. 45-37377 and 44-86516, such as 2, 2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-bromophenyl) -4,4', 5,5'-tetraphenyl Biimidazole, 2,2'-bis (o, p-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-chlorophenyl) -4,4', 5 , 5'-tetra (m-methoxyphenyl) biimidazole, 2,2'-bis (o, o'-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bi (O-nitrophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-methylphenyl) -4,4', 5,5'-tetraphenylbiimidazole, Examples include 2,2′-bis (o-trifluorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole.

Other examples of radical polymerization initiators used in the present invention include (f) ketoxime esters such as 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, and 3-propionyloxy. Iminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-p -Toluenesulfonyloxyiminobutan-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one and the like can be mentioned.
As an example of the (g) borate salt which is another example of the radical polymerization initiator in the present invention, a compound represented by the following general formula [III] can be mentioned.

(In the general formula [III], R ²² , R ²³ , R ²⁴ and R ²⁵ may be the same or different from each other, and each is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted group. Represents an alkenyl group, a substituted or unsubstituted alkynyl group, or a substituted or unsubstituted heterocyclic group, and R ²² , R ²³ , R ²⁴ and R ²⁵ are bonded to form a cyclic structure. Provided that at least one of R ²² , R ²³ , R ²⁴ and R ²⁵ is a substituted or unsubstituted alkyl group, Z ⁺ represents an alkali metal cation or a quaternary ammonium cation) . Examples of the alkyl group for R ^{22 to} R ²⁵ include linear, branched, and cyclic groups, and those having 1 to 18 carbon atoms are preferable. Specifically, methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, octyl, stearyl, cyclobutyl, cyclopentyl, cyclohexyl and the like are included. Examples of the substituted alkyl group include the above alkyl groups, halogen atoms (for example, —Cl, —Br, etc.), cyano groups, nitro groups, aryl groups (preferably phenyl groups), hydroxy groups,

(Wherein R ²⁶ and R ^{27 each} independently represents a hydrogen atom, an alkyl group having 1 to 14 carbon atoms, or an aryl group), —COOR ²⁸ (where R ²⁸ is a hydrogen atom, having 1 to 14 carbon atoms) An alkyl group or an aryl group), -OCOR ²⁹ or -OR ³⁰ (wherein R ²⁹ and R ³⁰ represent an alkyl group having 1 to 14 carbon atoms or an aryl group) as a substituent. included. The aryl groups of R ^{22 to} R ²⁵ include 1 to 3 ring aryl groups such as a phenyl group and a naphthyl group, and the substituted aryl group is a substitution of the above substituted alkyl group with the above aryl group. Those having a group or an alkyl group having 1 to 14 carbon atoms are included. Examples of the alkenyl group of R ^{22 to} R ²⁵ include linear, branched, and cyclic groups having 2 to 18 carbon atoms, and examples of the substituent of the substituted alkenyl group include the substituents of the substituted alkyl group. Is included. Examples of the alkynyl group of R ^{22 to} R ²⁵ include linear or branched groups having 2 to 28 carbon atoms, and examples of the substituent of the substituted alkynyl group include those listed as the substituents of the substituted alkyl group. included. In addition, examples of the heterocyclic group of R ^{22 to} R ²⁵ include a 5-membered or more, preferably 5 to 7-membered heterocyclic group containing at least one of N, S, and O. May contain a condensed ring. Furthermore, you may have what was mentioned as a substituent of the above-mentioned substituted aryl group as a substituent. Specific examples of the compound represented by the general formula [III] are described in U.S. Pat. Nos. 3,567,453 and 4,343,891 and European Patents 109,772 and 109,773. Examples include compounds and those shown below.

  Examples of the (h) azinium salt compound which is another example of the radical polymerization initiator of the present invention include JP-A 63-138345, JP-A 63-142345, JP-A 63-142346, and JP-A 63-142346. Examples thereof include compounds having an N—O bond described in JP-A-63-143537 and JP-B-46-42363.

  Examples of (i) metallocene compounds which are other examples of radical polymerization initiators include JP-A 59-152396, JP-A 61-151197, JP-A 63-41484, and JP-A 2-249. And titanocene compounds described in JP-A-2-4705 and iron-arene complexes described in JP-A-1-304453 and JP-A-1-152109.

  Specific examples of the titanocene compound include di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, and di-cyclopentadienyl-Ti-bis-2,3. 4,5,6-pentafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-cyclopentadienyl-Ti- Bis-2,4,6-trifluorophen-1-yl, di-cyclopentadienyl-Ti-2,6-difluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,4 -Difluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophen-1-yl, di-methylcyclopentadienyl-Ti- -2,3,5,6-tetrafluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,4-difluorophen-1-yl, bis (cyclopentadienyl) -bis (2,6-difluoro-3- (pyridin-1-yl) phenyl) titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (methylsulfonamido) phenyl] titanium, bis (cyclopenta And dienyl) bis [2,6-difluoro-3- (N-butylbialoyl-amino) phenyl] titanium.

  Examples of (j) active ester compounds which are other examples of radical polymerization initiators include imide sulfonate compounds described in JP-B-62-2223, JP-B-63-14340, and JP-A-59-174831. The active sulfonates can be mentioned.

  Preferred examples of the compound (k) having a carbon halogen bond, which is an example of a radical polymerization initiator, include those represented by the following general formulas [IV] to [X].

(In the formula [IV], X ² represents a halogen atom. Y ² represents —C (X ² ) ₃ , —NH ₂ , —NHR ³² , —NR ³² , —OR ³² , where R ³² is alkyl. R ³¹ represents a group, a substituted alkyl group, an aryl group, or a substituted aryl group, and R ³¹ represents —C (X ² ) ₃ , an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, or a substituted alkenyl group. Compound.

(In the general formula [V], R ³³ represents an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aryl group, a substituted aryl group, a halogen atom, an alkoxy group, a substituted alkoxyl group, a nitro group, or a cyano group. , X ³ is a halogen atom, and n is an integer of 1 to ^3. )

(In the general formula [VI], R ³⁴ represents an aryl group or a substituted aryl group, and R ³⁵ represents

Or Z ² is —C (═O) —, —C (═S) — or —SO ₂ —, and R ³⁶ and R ³⁷ are alkyl groups, substituted alkyl groups, alkenyl groups, substituted alkenyl groups. , An aryl group or a substituted aryl group, R ³⁸ is the same as R ³² in the general formula [IV], X ³ is a halogen atom, and m is 1 or 2. ) A compound represented by

In the general formula [VII], R ³⁹ is an optionally substituted aryl group or heterocyclic group, R ⁴⁰ is a trihaloalkyl group or trihaloalkenyl group having 1 to 3 carbon atoms, and p is 1 2 or 3.

(In the general formula [VIII], L is a hydrogen atom or a substituent of the formula: CO- (R ⁴¹ ) _q (C (X ⁴ ) ₃ ) _r , Q is a sulfur, selenium or oxygen atom, a dialkylmethylene group, An alkene-1,2-ylene group, a 1,2-phenylene group or an N—R group, and M is a substituted or unsubstituted alkylene group or alkenylene group, or a 1,2-arylene group, R ⁴² is an alkyl group, an aralkyl group or an alkoxyalkyl group, R ⁴¹ is a carbocyclic or heterocyclic divalent aromatic group, X ⁴ is a chlorine, bromine or iodine atom, q = 0 and a carbonylmethylene heterocyclic compound having a trihalogenomethyl group represented by: r = 1 or q = 1 and r = 1 or 2.

(In the general formula [IX], X ⁵ is a halogen atom, t is an integer of 1 to 3, s is an integer of 1 to 4, and R ⁴³ is a hydrogen atom or a CH _{3 -t} X ⁵ _t group. And R ⁴⁴ is an s-valent optionally substituted unsaturated organic group), 4-halogeno-5- (halogenomethyl-phenyl) -oxazole derivative.

(In the general formula [X], X ⁶ is a halogen atom, v is an integer of 1 to 3, u is an integer of 1 to 4, and R ⁴⁵ is a hydrogen atom or a CH _{3 -v} X ⁶ _v group. 2- (halogenomethyl-phenyl) -4-halogeno-oxazole derivative represented by: wherein R ⁴⁶ is an u-valent unsaturated organic group which may be substituted.

  Specific examples of such a compound having a carbon-halogen bond include, for example, compounds described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), such as 2-phenyl 4,6-bis. (Trichloromethyl) -S-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl) -S-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl)- S-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -S-triazine, 2- (2 ', 4'-dichlorophenyl) -4,6-bis (trichloromethyl) -S-triazine, 2,4,6-tris (trichloromethyl) -S-triazine, 2-methyl-4,6-bis (trichloromethyl) -S-triazine, 2-n-nonyl-4,6- Bis (trichloromethyl) -S-triazine, 2- (α, α, β-trichloroethyl) -4,6-bis (trichloromethyl) -S-triazine and the like can be mentioned. In addition, compounds described in British Patent 1388492, for example, 2-styryl-4,6-bis (trichloromethyl) -S-triazine, 2- (p-methylstyryl) -4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxystyryl) -4-amino-6-trichloromethyl-S-triazine, etc. And compounds described in JP-A-53-133428, such as 2- (4-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2- (4-ethoxy-naphtho). -1-yl) -4,6-bis-trichloromethyl-S-triazine, 2- [4- (2-ethoxyethyl) -naphth-1-yl] -4,6-bis-to Chloromethyl-S-triazine, 2- (4,7-dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine), 2- (acenaphtho-5-yl) -4,6- Examples thereof include bis-trichloromethyl-S-triazine and the compounds described in German Patent 3333724.

Further, compounds described in J. Org. Chem. 29, 1527 (1964) by FC Schaefer et al., For example, 2-methyl-4,6-bis (tribromomethyl) -S-triazine, 2,4,6-tris ( Tribromomethyl) -S-triazine, 2,4,6-tris (dibromomethyl) -S-triazine, 2-amino-4-methyl-6-tribromomethyl-S-triazine, 2-methoxy-4-methyl- Examples include 6-trichloromethyl-S-triazine. Further, compounds described in JP-A-62-258241 can be exemplified. Furthermore, compounds described in JP-A-5-281728, for example,

Etc. Alternatively, those skilled in the art can easily synthesize them according to the synthesis methods described in MP Hutt, EF Elslager and LM Herbel, “Journal of Heterocyclic chemistry”, Volume 7 (No. 3), pages 511 and after (1970). The following compound groups that can

Alternatively, compounds such as those described in German Patent 2,641,100, such as 4- (4-methoxy-styryl) -6- (3,3,3-trichloropropenyl) -2-pyrone and 4- (3 4,5-trimethoxy-styryl) -6-trichloromethyl-2-pyrone, compounds described in German Patent No. 3333450, compounds described in German Patent No. 3021590, or described in German Patent No. 3021599 A compound group, etc. can be mentioned.

(L) Examples of alkylamine compounds include alkyl compounds described in JP-A-56-4604, JP-A-5-132507, JP-A-2001-324806, JP-T-9-503871, and JP-A-8-254821. Mention may be made of amine compounds.

  As an even more preferable example of the radical polymerization initiator in the present invention, the above-mentioned (a) aromatic ketones, (b) aromatic onium salt, (c) organic peroxide, (e) hexaarylbiimidazole, ( i) a metallocene compound, (k) a compound having a carbon halogen bond, and most preferred examples include an aromatic iodonium salt, an aromatic diazonium salt, a titanocene compound, and a trihalomethyl represented by the general formula [IV]. -S-triazine compounds can be mentioned.

(1-2-2) Cationic Polymerization Initiator As a preferable cationic polymerization initiator (photoacid generator) that can be used in the present invention, for example, a chemically amplified photoresist or a compound used for photocationic polymerization is used. (See Organic Electronics Materials Study Group, “Organic Materials for Imaging”, Bunshin Publishing (1993), pages 187-192). Examples of the cationic polymerization initiator suitable for the present invention are listed below.

First, B (C ₆ F ₅ ) ₄ —, PF ₆ —, AsF ₆ —, SbF ₆ —, CF ₃ SO ₃ — salts of aromatic onium compounds such as diazonium, ammonium, iodonium, sulfonium, and phosphonium are listed. be able to.
Specific examples of onium compounds that can be used in the present invention are shown below.

Secondly, sulfonated substances that generate sulfonic acid can be mentioned, and specific compounds thereof are exemplified below.

Thirdly, halides that generate hydrogen halide can also be used, and specific compounds thereof are exemplified below.

Fourthly, an iron allene complex can be mentioned.

  The polymerization initiator in the present invention is suitably used alone or in combination of two or more. These polymerization initiators are contained in an amount of 0.01 to 20 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the polymerizable compound of the present invention. Further, the polymerization initiator of the present invention is 200: 1 to 1: 200, preferably 50: 1 to 1:50, more preferably, in a mass ratio of polymerization initiator: sensitizing dye to the above sensitizing dye. Is suitably included in the polymerization initiation system in an amount of 20: 1 to 1: 5.

(1-3) Other Additives Other additives such as co-sensitizers and chain transfer agents may be added to the polymerization initiation system of the present invention.
The co-sensitizer has functions such as further improving the sensitivity of the sensitizing dye to radiation or suppressing the inhibition of polymerization of the polymerizable compound by oxygen.
Examples of such co-sensitizers include amines such as MR Sander et al., “Journal of Polymer Society”, Vol. 10, page 3173 (1972), Japanese Examined Patent Publication No. 44-20189, Japanese Patent Laid-Open No. 51-82102. Publication, JP 52-134692, JP 59-138205, JP 60-84305, JP 62-18537, JP 64-33104, Research Disclosure 33825 Specifically, triethanolamine, p-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, p-methylthiodimethylaniline and the like can be mentioned.

  Other examples of co-sensitizers include thiols and sulfides, for example, thiol compounds described in JP-A-53-702, JP-B-55-500806, JP-A-5-142772, and JP-A-56 And the like. Specific examples include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, 2-mercapto-4 (3H) -quinazoline, β-mercaptonaphthalene. Etc.

Other examples include amino acid compounds (eg, N-phenylglycine), organometallic compounds described in Japanese Patent Publication No. 48-42965 (eg, tributyltin acetate), and hydrogen described in Japanese Patent Publication No. 55-34414. Donors, sulfur compounds described in JP-A-6-308727 (eg, trithiane), phosphorus compounds described in JP-A-6-250387 (diethylphosphite, etc.), Si-- described in Japanese Patent Application No. 6-191605 H, Ge-H compound, etc. are mentioned.
Such a co-sensitizer is suitably contained in an amount of, for example, 0.01 to 20% by mass, preferably 0.1 to 10% by mass with respect to the polymerization initiation system.

(1-4) Effect of Polymerization Initiating System The sensitizing dye can absorb specific radiation and promote decomposition of the polymerization initiator. A sensitizing dye absorbs specific radiation and enters an electronically excited state. The sensitizing dye in an electronically excited state comes into contact with the polymerization initiator, and effects such as electron transfer, energy transfer, and heat generation occur. As a result, the polymerization initiator undergoes a chemical change and decomposes to generate radicals, acids or bases.
For example, the sensitizing dye of the present invention has excellent absorption characteristics having a maximum absorption value (λmax) in the range of 300 to 500 nm, preferably 350 to 450 nm, more preferably 360 to 420 nm. A sensitizing dye that absorbs radiation in a specific region and further becomes an electronically excited state, and efficiently causes decomposition of the polymerization initiator. Therefore, in the polymerization initiating system of the present invention, the sensitizing dye plays a role as a catalyst to promote the photodecomposition of the polymerization initiator, and thus exhibits extremely high photosensitivity.
In general, the sensitization mechanism of a polymerization initiation system comprising a sensitizing dye / polymerization initiator is:
(A) reductive decomposition of the polymerization initiator based on an electron transfer reaction from the electronically excited state of the sensitizing dye to the polymerization initiator,
(B) oxidative degradation of the polymerization initiator based on electron transfer from the polymerization initiator to the electronically excited state of the sensitizing dye,
(C) decomposition of the polymerization initiator from the electronically excited state based on energy transfer from the electronically excited state of the sensitizing dye to the polymerization initiator;
Such a route is known. The sensitizing dye of the present invention causes any of these types of sensitizing reactions with excellent efficiency. The present inventors have found that in order to obtain high sensitivity, it is very important that the sensitizing dye has a chemical structure represented by the above general formulas (XIV) to (XXVI). The specific mechanism of action is not clear. The sensitizing dye of the present invention exhibits a high-intensity emission (fluorescence and / or phosphorescence) spectrum. From this, one possibility is that the sensitizing dye of the present invention having the above partial structure has a relatively long lifetime in the excited state, and therefore it is considered that it acts on the efficiency of the reaction with the polymerization initiator. It is done. As other possibilities, the chemical structures represented by the general formulas (XIV) to (XXVI) can be used to improve the efficiency of the initial stage of the sensitization reaction (electron transfer, etc.) and further the subsequent reaction leading to the decomposition of the polymerization initiator. It may also contribute to efficiency.

(2) Ink for ink jet recording The ink for ink jet recording of the present invention contains the polymerization initiation system, a polymerizable compound, a color material, and other components.
(2-1) Polymerizable Compound The polymerizable compound of the present invention is a radical polymerizable compound such as JP-A-7-159983, JP-B-7-31399, JP-A-8-224982, JP-A-10-863, A photocurable material using a photopolymerizable composition described in Japanese Patent Application No. 7-231444, etc. and Japanese Patent Application No. 7-231444, and a cationic polymerizable compound, for example, a cationic polymerization type light A curable resin is known, and a photo-cationic polymerization type photocurable resin sensitized to a long wavelength region longer than visible light is also disclosed in, for example, JP-A-6-43633 and JP-A-8-324137. It has been published.
(2-1-1) Radical polymerizable compound A radical polymerizable compound is a compound having an ethylenically unsaturated bond capable of radical polymerization, and having at least one ethylenically unsaturated bond capable of radical polymerization in the molecule. Any material may be used as long as it has a chemical form such as a monomer, oligomer or polymer. Only one kind of radically polymerizable compound may be used, or two or more kinds thereof may be used in combination at an arbitrary ratio in order to improve desired properties. A polyfunctional compound having two or more functional groups is more preferable than a monofunctional compound. More preferably, two or more polyfunctional compounds are used in combination for controlling performance such as reactivity and physical properties.

  Examples of the polymerizable compound having an ethylenically unsaturated bond capable of radical polymerization include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid and maleic acid, and salts, esters and urethanes thereof. And radical polymerizable compounds such as amides, anhydrides, acrylonitrile, styrene, various unsaturated polyesters, unsaturated polyethers, unsaturated polyamides, and unsaturated urethanes. Specifically, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, butoxyethyl acrylate, carbitol acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, benzyl acrylate, bis (4-acryloxypolyethoxyphenyl) propane, neopentyl glycol Diacrylate, 1,6-hexanediol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, pentaerythritol triacrylate, pentaerythritol Tetraacrylate, dipentaery Acrylic acid derivatives such as lithol tetraacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, oligoester acrylate, N-methylol acrylamide, diacetone acrylamide, epoxy acrylate, methyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate , Lauryl methacrylate, allyl methacrylate, glycidyl methacrylate, benzyl methacrylate, dimethylaminomethyl methacrylate, 1,6-hexanediol dimethacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, trimethylol Methacryl derivatives such as tan trimethacrylate, trimethylolpropane trimethacrylate, 2,2-bis (4-methacryloxypolyethoxyphenyl) propane, and other derivatives of allyl compounds such as allyl glycidyl ether, diallyl phthalate, triallyl trimellitate More specifically, Shinzo Yamashita, “Cross-linking agent handbook”, (1981 Taiseisha); Kato Kiyomi, “UV / EB curing handbook (raw material)” (1985, Polymer publication) ); Rad-Tech Study Group, “Application and Market of UV / EB Curing Technology”, p. 79, (1989, CMC); Eiichiro Takiyama, “Polyester Resin Handbook”, (1988, Nikkan Kogyo Shimbun) Commercially available products described in the above, or radically polymerizable or crosslinkable monomers known in the industry, Ligomers and polymers can be used.

(2-1-2) Cationic Polymerizable Compound As the cationic polymerizable compound, various known cationic polymerizable compounds (monomers) can be used. Examples thereof include JP-A-6-9714, JP-A-2001-31892, JP-A-2001-40068, JP-A-2001-55507, JP-A-2001-310938, JP-A-2001-310937, and JP-A-2001-220526. An epoxy compound, a vinyl ether compound, an oxetane compound, etc. are mentioned. Examples of the cationically polymerizable compound of the present invention include oxetane compounds, epoxy compounds, vinyl ether compounds, or combinations thereof.

一般式（１）において、Ｒ₁〜Ｒ₆は、各々水素原子または置換基を表す。ただし、Ｒ₃〜Ｒ₆で表される基の少なくとも一つは置換基である。 The (a) oxetane compound is a compound having an oxetane ring, and examples thereof include all known oxetane compounds as introduced in JP-A Nos. 2001-220526 and 2001-310937. In particular, a compound containing an oxetane ring represented by the following general formula (1) is preferable.

In General formula (1), R < ₁ > -R < ₆ > represents a hydrogen atom or a substituent respectively. However, at least one of the groups represented by R _{3 to} R ₆ is a substituent.

In the general formula (1), examples of the substituent represented by R _{1 to} R ₆ include a fluorine atom and an alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group). Etc.), a C1-C6 fluoroalkyl group, an allyl group, an aryl group (for example, a phenyl group, a naphthyl group, etc.), a furyl group, or a thienyl group. Moreover, these groups may further have a substituent.

  Examples of the compound having one oxetane ring in the molecule include compounds represented by the following general formulas (2) to (5).

In the above general formulas (2) to (5), R _{1 to} R ₆ each represent a group having the same meaning as in the general formula (1), Z is independent, oxygen or sulfur atom, or oxygen or sulfur atom in the main chain Represents a divalent hydrocarbon group which may contain
In the above general formulas (2) to (5), the substituents represented by R ₇ and R ₈ are each an alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, or a butyl group). Etc.), an alkenyl group having 1 to 6 carbon atoms (for example, 1-propenyl group, 2-propenyl group, 2-methyl-1-propenyl group, 2-methyl-2-propenyl group, 1-butenyl group, 2- Butenyl group, 3-butenyl group, etc.), aryl group (eg, phenyl group, naphthyl group, etc.), aralkyl group (eg, benzyl group, fluorobenzyl group, methoxybenzyl group, etc.), acyl group having 1 to 6 carbon atoms (For example, propylcarbonyl group, butylcarbonyl group, pentylcarbonyl group, etc.), C1-C6 alkoxycarbonyl group (for example, ethoxycarbonyl group, propoxycarbonyl group) Butoxycarbonyl group), represents the number 1-6 alkylcarbamoyl group having a carbon (e.g., propylcarbamoyl group, butyl pentylcarbamoyl group), alkoxy carbamoyl group (e.g., ethoxy carbamoyl group).

  In the general formulas (2) to (5), an oxygen or sulfur atom represented by Z or a divalent hydrocarbon group which may contain an oxygen or sulfur atom in the main chain is an alkylene group (for example, Ethylene group, trimethylene group, tetramethylene group, propylene group, ethylethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, etc.), alkenylene group (for example, vinylene group, propenylene) Group), alkynylene group (for example, ethynylene group, 3-pentynylene group, etc.), and the carbon atom of the aforementioned alkylene group, alkenylene group, alkynylene group may be replaced by an oxygen atom or a sulfur atom. .

As the oxetane ring-containing compound used in the present invention, in the above general formulas (2) to (5), R ₁ is a lower alkyl group, particularly an ethyl group, and R ₇ and R ₈ are a propyl group, a butyl group, and a phenyl group. Or a benzyl group, wherein Z is a hydrocarbon group containing no oxygen or sulfur atom (an alkylene group, an alkenylene group, an alkynylene group, etc.). At this time, at least one group represented by R _{3 to} R ₆ is a substituent.
Examples of the compound having two or more oxetane rings in the molecule include compounds represented by the following general formulas (6) and (7).

In the general formulas (6) and (7), m represents 2, 3 or 4, and Z has the same meaning as Z represented by the general formulas (2) to (5).
R _{1 to} R ₆ each represent a group having the same meaning as in the general formula (1). However, in General formula (6), at least 1 of R < ₃ > -R < ₆ > is a substituent.
R ₉ is selected from the group consisting of linear or branched alkylene groups having 1 to 12 carbon atoms, linear or branched poly (alkyleneoxy) groups, or the following general formulas (9), (10) and (11). Represents a divalent group. The linear or branched alkylene group having 1 to 12 carbon atoms is preferably a group represented by the following general formula (8).

In the general formula (8), R ₁₀ represents a lower alkyl group such as a methyl group, an ethyl group, or a propyl group.

In the general formula (9), n is 0 or an integer of 1 to 2000, R ₁₁ is an alkyl group having 1 to 10 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group). , A heptyl group, an octyl group, a nonyl group, or the like) or a group selected from the following general formula (12). R ₁₂ represents an alkyl group having 1 to 10 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, etc.).

In the general formula (12), j is 0 or an integer of 1 to 100, R ₁₃ is an alkyl group having 1 to 10 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, Hexyl group, heptyl group, octyl group, nonyl group, etc.).

In the general formula (10), R ₁₄ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, Nonyl group, etc.), an alkoxy group having 1 to 10 carbon atoms (eg, methoxy group, ethoxy group, propoxy group, butoxy group, pentoxy group, etc.), halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom) Etc.), a nitro group, a cyano group, a mercapto group, an alkoxycarbonyl group (for example, a methyloxycarbonyl group, an ethyloxycarbonyl group, a butyloxycarbonyl group, etc.) or a carboxyl group.

In the general formula (11), R ₁₅ represents an oxygen atom, a sulfur atom, NH, SO, SO ₂ , CH ₂ , C (CH ₃ ) ₂ or C (CF ₃ ) ₂ .

Preferred embodiments of the partial structure of the oxetane ring-containing compound used in the present invention include, for example, in the above general formulas (6) and (7), R ₁ is a lower alkyl group (for example, a methyl group, an ethyl group, a propyl group). And the like, particularly preferably an ethyl group. As R ₉ , a hexamethylene group or one in which R ₁₄ is a hydrogen atom in the general formula (10) is preferably used.

In the general formula (8), R ₁₀ is preferably an ethyl group, and in general formulas (9) and (12), R ₁₂ and R ₁₃ are each preferably a methyl group. However, in General Formula (6), at least one of the groups represented by R _{3 to} R ₆ is a substituent.

  Furthermore, examples of the compound having two or more oxetane rings in the molecule include compounds represented by the following general formula (13).

In the general formula (13), r is an integer of 25 to 200, R ₁₆ is an alkyl group or a trialkylsilyl group having 1 to 4 carbon atoms. R ₁ and R _{4 to} R ₆ have the same meanings as those in the general formula (1), and at least one of the groups represented by R _{3 to} R ₆ is a substituent.
Although the specific example of the compound containing the oxetane ring represented by General formula (1) based on this invention is shown in Table 1, this invention is not limited to these.

In addition, each of the above compounds can be easily synthesized mainly by the following scheme by referring to the following literature, including the method described in item 4 of "Catchball between polymer science and organic chemistry". The synthesis method is not limited to this.

1) Hu Xianming, Richard M. et al. Kellogg, Synthesis, 533-538, May (1995)
2) A. O. Fitton, J .; Hill, D.C. Ejane, R.A. Miller, Synth. , 12, 1140 (1987)
3) Toshiro Imai and Shinya Nishida, Can. J. et al. Chem. Vol. 59, 2503-2509 (1981)
4) Nobujiro Shimizu, Shintaro Yamaoka, and Yuho Tsuno, Bull. Chem. Soc. Jpn. 56, 3853-3854 (1983)
5) Walter Fisher and Cyril A. Grob, Helv. Chim. Acta. , 61, 2336 (1978)
6) Chem. Ber. 101, 1850 (1968)
7) “Heterocyclic Compounds with Three- and Four-membered Rings”, Part Two, Chapter IX, Interscience Publishers, John Wiley & Sons, N
8) H.M. A. J. et al. Curless, “Synthetic Organic Photochemistry”, Plenum, New York (1984).
9) M.M. Braun, Nachr. Chem. Tech. Lab. 33, 213 (1985)
10) S.M. H. Schroeter, J.A. Org. Chem. , 34, 5, 1181 (1969)
11) D. R. Arnold, Adv. Photochem. 6,301 (1968)

Examples of the (b) epoxy compound include aromatic epoxides, alicyclic epoxides, and aliphatic epoxides.
A preferable aromatic epoxide is a di- or polyglycidyl ether produced by the reaction of a polyhydric phenol having at least one aromatic nucleus or an alkylene oxide adduct thereof and epichlorohydrin, such as bisphenol A or an alkylene oxide thereof. Examples thereof include di- or polyglycidyl ethers of adducts, di- or polyglycidyl ethers of hydrogenated bisphenol A or its alkylene oxide adducts, and novolak-type epoxy resins. Here, examples of the alkylene oxide include ethylene oxide and propylene oxide.

As the alicyclic epoxide, cyclohexene oxide obtained by epoxidizing a compound having at least one cycloalkane ring such as cyclohexene or cyclopentene ring with a suitable oxidizing agent such as hydrogen peroxide or peracid. Or a cyclopentene oxide containing compound is preferable.
Preferred aliphatic epoxides include di- or polyglycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof, and typical examples thereof include diglycidyl ether of ethylene glycol, diglycidyl ether of propylene glycol or Diglycidyl ether of alkylene glycol such as diglycidyl ether of 1,6-hexanediol, polyglycidyl ether of polyhydric alcohol such as di- or triglycidyl ether of glycerin or its alkylene oxide adduct, polyethylene glycol or its alkylene oxide adduct Diglycidyl ethers of polyalkylene glycols such as diglycidyl ethers, polypropylene glycols or diglycidyl ethers of adducts thereof Tel and the like. Here, examples of the alkylene oxide include ethylene oxide and propylene oxide.

  Among these epoxides, in view of fast curability, aromatic epoxides and alicyclic epoxides are preferable, and alicyclic epoxides are particularly preferable. In the present invention, one of the epoxides may be used alone, or two or more may be used in appropriate combination.

In the present invention, from the viewpoint of mutagenicity test (AMES), sensitization test, etc., particularly from the viewpoint of safety to the human body, epoxy compounds having an oxirane group include epoxidized fatty acid esters, epoxidized fatty acid glycerides. Particularly preferred is at least one of the following.
The epoxidized fatty acid ester and the epoxidized fatty acid glyceride are not particularly limited as long as an epoxy group is introduced into the fatty acid ester or fatty acid glyceride.
The epoxidized fatty acid ester is produced by epoxidizing an oleic acid ester, and examples thereof include methyl epoxy stearate, butyl epoxy stearate, octyl epoxy stearate and the like. Similarly, the epoxidized fatty acid glyceride is produced by epoxidizing soybean oil, linseed oil, castor oil and the like, and epoxidized soybean oil, epoxidized linseed oil, epoxidized castor oil and the like are used.

(c) Examples of vinyl ether compounds include ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, butanediol divinyl ether, hexanediol divinyl ether, cyclohexanedimethanol divinyl ether. , Di- or trivinyl ether compounds such as trimethylolpropane trivinyl ether, ethyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, octadecyl vinyl ether, cyclohexyl vinyl ether, hydroxybutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexane dimethanol monovinyl ether, n-propyl Pills vinyl ether, isopropyl vinyl ether, isopropenyl ether -O- propylene carbonate, dodecyl vinyl ether, diethylene glycol monovinyl ether, and octadecyl vinyl ether.

  Among these vinyl ether compounds, in consideration of curability, adhesion, and surface hardness, di- or trivinyl ether compounds are preferable, and divinyl ether compounds are particularly preferable. In the present invention, one of the above vinyl ether compounds may be used alone, or two or more thereof may be used in appropriate combination.

(2-1-3) Preferred polymerizable compound As the polymerizable compound of the present invention, (meth) acrylic monomers or prepolymers, epoxy monomers or prepolymers, urethane monomers or prepolymers are preferably used. More preferably, they are the following compounds.

  2-ethylhexyl-diglycol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxybutyl acrylate, hydroxypivalate neopentyl glycol diacrylate, 2-acryloyloxyethyl phthalate, methoxy-polyethylene glycol acrylate, tetramethylol Methane triacrylate, 2-acryloyloxyethyl-2-hydroxyethylphthalic acid, dimethylol tricyclodecane diacrylate, ethoxylated phenyl acrylate, 2-acryloyloxyethyl succinic acid, nonylphenol EO adduct acrylate, modified glycerin triacrylate Bisphenol A diglycidyl ether acrylic acid adduct, modified bisphenol A diacrylate, phenoxy-polyethylene Glycol acrylate, 2-acryloyloxyethyl hexahydrophthalic acid, bisphenol A PO adduct diacrylate, bisphenol A EO adduct diacrylate, dipentaerythritol hexaacrylate, pentaerythritol triacrylate tolylene diisocyanate urethane prepolymer, lactone Modified flexible acrylate, butoxyethyl acrylate, propylene glycol diglycidyl ether acrylic acid adduct, pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer, 2-hydroxyethyl acrylate, methoxydipropylene glycol acrylate, ditrimethylolpropane tetraacrylate, penta Erythritol triacrylate hexamethylene di Socia sulfonates urethane prepolymer, stearyl acrylate, isoamyl acrylate, isomyristyl acrylate, isostearyl acrylate.

  These acrylate compounds have lower skin irritation and sensitization (rash) than the polymerizable compounds conventionally used in UV curable inks, can relatively reduce viscosity, and provide stable ink ejection properties. Further, the polymerization sensitivity and the adhesion to the recording medium are also good. In the present invention, when the acrylate compound is used as the polymerizable compound, the content of the acrylate compound is, for example, 20 to 95% by mass, preferably 50%, based on the total mass of the ink for inkjet recording of the present invention. It is suitable to set it to -95 mass%, More preferably, it is 70-95 mass%.

In the present invention, the monomers listed as the polymerizable compounds described above are low in sensitization even with a low molecular weight, have high reactivity, low viscosity, and adhesion to a recording medium. Excellent.
In order to further improve sensitivity, bleeding, and adhesion to the recording medium, it is preferable to use the above monoacrylate in combination with a polyfunctional acrylate monomer or polyfunctional acrylate oligomer having a molecular weight of 400 or more, preferably 500 or more. It is preferable in terms of improving the performance. Furthermore, it is particularly preferable to use a monofunctional, bifunctional, or trifunctional or higher polyfunctional monomer in combination. While maintaining safety, the sensitivity, bleeding, and adhesion to the recording medium can be further improved. As the oligomer, an epoxy acrylate oligomer and a urethane acrylate oligomer are particularly preferable.

When recording on a flexible recording medium such as a PET film or PP film, the combination of a monoacrylate selected from the above compound group and a polyfunctional acrylate monomer or polyfunctional acrylate oligomer gives the film flexibility and adhesion. It is preferable because the film strength can be increased while improving the properties. As monoacrylate, stearyl acrylate, isoamyl acrylate, isomystil acrylate, and isostearyl acrylate have high sensitivity and low shrinkage to prevent curling, and are preferable in terms of prevention of bleeding, odor of printed matter, and cost reduction of irradiation device. .
Incidentally, methacrylates, skin mildness is better than acrylate.
Of the above-mentioned compounds, when alkoxy acrylate is used in an amount of less than 70% by mass and the balance is acrylate, it is preferable because it has good sensitivity, bleeding characteristics and odor characteristics.

(2-1-4) Addition amount of polymerizable compound The addition amount of the polymerizable compound of the present invention is, for example, 1 to 97% by mass with respect to the total mass of the ink jet recording ink of the present invention, and more preferably. Is 30-95 mass%.

(2-2) Color Material The color material of the present invention is not particularly limited, but a pigment excellent in weather resistance is preferable, and any known color material such as a soluble dye and an oily dye can be used. Conventionally, a general dye could not be used as a coloring material that can be used in ink jet recording ink. This is because the dye functions as a polymerization inhibitor in the polymerization reaction, so that there is a problem that the sensitivity of radiation is lowered. However, since the amount of active species generated in the polymerization initiation system of the present invention increases, such a coloring material can also be used.
Although it does not necessarily limit as a coloring material of this invention, For example, the organic or inorganic pigment of the following number described in a color index can be used.

  That is, as red or magenta pigment, Pigment Red 3, 5, 19, 22, 31, 38, 43, 48: 1, 48: 2, 48: 3, 48: 4, 48: 5, 49: 1, 53 : 1, 57: 1, 57: 2, 58: 4, 63: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 88, 104, 108, 112, 122, 123, 144 146, 149, 166, 168, 169, 170, 177, 178, 179, 184, 185, 208, 216, 226, 257, Pigment Violet 3, 19, 23, 29, 30, 37, 50, 88, Pigment Orange 13, 16, 20, 36, blue or cyan pigments include Pigment Blue 1, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16 17-1, 22, 27, 28, 29, 36, 60, as green pigment, Pigment Green 7, 26, 36, 50, as yellow pigment, Pigment Yellow 1, 3, 12, 13, 14, 17, 34, 35, 37, 55, 74, 81, 83, 93, 94, 95, 97, 108, 109, 110, 137, 138, 139, 153, 154, 155, 157, 166, 167, 168, 180, 185, 193, Pigment Black 7, 28, 26 as the black pigment, and Pigment White 6, 18, 21, etc. as the white pigment can be used according to the purpose.

The color material of the present invention needs to be appropriately dispersed in the ink after being added to the ink for inkjet recording of the present invention. For dispersion of the color material, for example, a dispersion device such as a ball mill, a sand mill, an attritor, a roll mill, an agitator, a Henschel mixer, a colloid mill, an ultrasonic homogenizer, a pearl mill, a wet jet mill, or a paint shaker can be used.
It is also possible to add a dispersant when dispersing the color material. The type of the dispersant is not particularly limited, but a polymer dispersant is preferably used, and examples of the polymer dispersant include Solsperse series manufactured by Zeneca. Moreover, it is also possible to use a synergist according to various pigments as a dispersion aid. These dispersants and dispersion aids are preferably added in an amount of 1 to 50 parts by mass with respect to 100 parts by mass of the coloring material of the present invention.
The coloring material may be added directly to the ink jet recording ink of the present invention, but may be added in advance to a dispersion medium such as a solvent or a polymerizable compound according to the present invention in order to improve dispersibility. In order to avoid the deterioration of the solvent resistance when the solvent remains in the cured image and the problem of VOC (Volatile Organic Compound) of the remaining solvent, the coloring material is added to the polymerizable compound of the present invention. It is preferable to do. Further, as the polymerizable compound to be used, it is preferable in view of dispersion suitability to select a monomer having the lowest viscosity.

The average particle diameter of the color material particles of the present invention is, for example, 0.08 to 0.5 μm, preferably 0.1 to 0.45 μm, and more preferably 0.15 to 0.4 μm. . The maximum particle size of the color material is, for example, 0.3 to 10 μm, preferably 0.3 to 3 μm. It is appropriate to select the pigment, the dispersant, the dispersion medium, the dispersion conditions, and the filtration conditions so that the maximum particle size is obtained. By controlling the particle size, clogging of the head nozzle can be suppressed, and ink storage stability, ink transparency, and curing sensitivity can be maintained.
The color material of the present invention is contained in an amount of, for example, 1 to 10% by mass, preferably 2 to 8% by mass, based on the total ink mass.

(2-3) Other components Other components can be added to the ink for ink jet recording of the present invention, if necessary. Examples of other components include a polymerization inhibitor, a solvent, and a cationic polymerizable monomer.
A polymerization inhibitor may be added from the viewpoint of enhancing the storage stability. In addition, the ink for inkjet recording of the present invention is preferably ejected by heating and lowering the viscosity in the range of 40 to 80 ° C., and a polymerization inhibitor is preferably added to prevent clogging of the head due to thermal polymerization. The polymerization inhibitor is preferably added in an amount of 200 to 20000 ppm based on the total amount of the ink for inkjet recording of the present invention. Examples of the polymerization inhibitor include hydroquinone, benzoquinone, p-methoxyphenol, TEMPO, TEMPOL, and cuperon Al.

In view of the fact that the ink for ink jet recording used in the present invention is a radiation curable ink, it is preferable not to contain a solvent so that it can react quickly and be cured immediately after ink landing. However, a predetermined solvent can be included as long as it does not affect the curing speed of the ink. In the present invention, an organic solvent or water can be used as the solvent. In particular, an organic solvent can be added in order to improve the adhesion to a recording medium (support such as paper). The addition of an organic solvent is effective because the VOC problem can be avoided. The amount of the organic solvent is, for example, in the range of 0.1 to 5% by mass, preferably 0.1 to 3% by mass, with respect to the total mass of the ink for inkjet recording of the present invention.
As a means for preventing sensitivity deterioration due to the light-shielding effect of the ink coloring material, in addition to the combination of a cationic polymerizable compound and a cationic polymerization initiator, and a combination of a radical polymerizable compound and a radical polymerization initiator, these polymerizable compounds and A radical-cation hybrid type curable ink may be used in combination with a polymerization initiator.

  In addition, a known compound can be added to the ink for ink jet recording of the present invention as necessary. For example, surfactants, leveling additives, matting agents, polyester resins for adjusting film properties, polyurethane resins, vinyl resins, acrylic resins, rubber resins, waxes and the like are appropriately selected and added. be able to. In order to improve the adhesion to a recording medium such as polyolefin or PET, it is also preferable to contain a tackifier that does not inhibit the polymerization. Specifically, a high molecular weight adhesive polymer described in JP-A-2001-49200, pages 5 to 6 (for example, (meth) acrylic acid and an alcohol having an alkyl group having 1 to 20 carbon atoms). An ester, a copolymer of (meth) acrylic acid and an alicyclic alcohol having 3 to 14 carbon atoms, a copolymer of an ester of (meth) acrylic acid and an aromatic alcohol having 6 to 14 carbon atoms), and polymerizability. Examples thereof include a low molecular weight tackifying resin having an unsaturated bond.

(2-4) Properties of Inkjet Recording Ink As described above, the inkjet recording ink of the present invention contains a colorant, a polymerizable compound, and a polymerization initiation system. These components are 1 to 10% by mass, preferably 2 to 8% by mass, and 1 to 97% by mass of the polymerizable compound, preferably 3 to 3% by mass with respect to the total mass of the inkjet recording ink. 95% by mass and the polymerization initiation system is contained in an amount of 0.01 to 20% by mass, preferably 0.1 to 20% by mass, and the total mass% of each component is 100% by mass. Is appropriate.
The obtained ink for inkjet recording has a viscosity of, for example, 7 to 30 mPa · s, preferably 7 at a temperature at the time of ejection (for example, 40 to 80 ° C., preferably 25 to 30 ° C.) in consideration of ejection properties. It is preferably ˜20 mPa · s. For example, the viscosity of the ink for inkjet recording of the present invention at room temperature (25 to 30 ° C.) is 35 to 500 mPa · s, preferably 35 to 200 mPa · s. The composition ratio of the ink for inkjet recording of the present invention is preferably adjusted as appropriate so that the viscosity is in the above range. By setting the viscosity at room temperature high, even when a porous recording medium is used, ink penetration into the recording medium can be avoided, and uncured monomers and odors can be reduced. Furthermore, ink bleeding at the time of ink droplet landing can be suppressed, and as a result, the image quality is improved.

  The surface tension of the ink for inkjet recording of the present invention is, for example, 20 to 30 mN / m, preferably 23 to 28 mN / m. When recording on various recording media such as polyolefin, PET, coated paper, and non-coated paper, 20 mN / m or more is preferable from the viewpoint of bleeding and penetration, and the wettability is preferably 30 mN / m or less.

(3) Inkjet recording method and apparatus An inkjet recording method and an inkjet recording apparatus that can be suitably employed in the present invention will be described below.
(3-1) Inkjet recording method The present invention is a method in which the ink jet recording ink is jetted onto a support (recording material), the ink landed on the support is irradiated with radiation, and the ink is cured to form an image. Provide a method of forming. That is, the present invention
(a) applying the ink jet recording ink onto a support;
(b) Radiation having a peak wavelength of 200 to 600 nm, preferably 300 to 450 nm, more preferably 350 to 420 nm in the ink jet recording ink, 2000 mJ / cm ² or less, preferably 10 to 2000 mJ / cm ² , more preferably, 20~1000mJ / cm ² and even more preferably, a step of curing the inkjet ink by irradiating at an output of 50 to 800 mJ / cm ^2; and
(c) a step in which the cured ink for ink jet recording forms an image on a support,
Relates to a method comprising:

Furthermore, the ink jet recording method of the present invention will be described by taking as an example a method for preparing a lithographic printing plate including injecting an ink jet recording ink onto the lithographic printing plate to form an image.
The lithographic printing plate of the present invention has a hydrophilic support and a hydrophobic image formed on the hydrophilic support. This lithographic printing plate production method comprises the following steps:
(1) a step of ejecting the inkjet recording ink of the present invention onto the hydrophilic support; and
(2) a step of irradiating the surface of the hydrophilic support on which the ink has been ejected to cure the ink, thereby forming a hydrophobic image formed by curing the ink on the hydrophilic support;
And have.

(3-1-1) Lithographic printing plate Here, the lithographic printing plate has a support and an image formed on the support.
Conventionally, so-called PS plates having a configuration in which a lipophilic photosensitive resin layer is provided on a hydrophilic support have been widely used as lithographic printing plates. As a method for producing the PS plate, a desired printing plate is usually obtained by performing mask exposure (surface exposure) through a lith film and then dissolving and removing the non-exposed portion. However, in recent years, digitization techniques for electronically processing, storing, and outputting image information using a computer have become widespread, and a new image output method corresponding to the technique has been demanded. In particular, Computer-to-Plate (CTP) technology has been developed that scans highly-preferred light such as laser light according to digitized image information without using a lithographic film, and directly produces printing plates. Yes.
As a method for obtaining a lithographic printing plate that enables such scanning exposure, a method of directly producing a lithographic printing plate with an ink jet recording ink can be mentioned. This is because the ink is ejected onto a support, preferably a hydrophilic support by an ink jet method or the like, and this is exposed to radiation, whereby the ink jet recording ink portion is exposed to form a desired image (preferably, A printing plate having a hydrophobic image) is obtained. An ink jet recording ink suitable for such a method is the ink jet recording ink of the present invention.
The support (recording medium) on which the ink jet recording ink of the present invention is ejected is not particularly limited as long as it is a dimensionally stable plate-like support. The support is preferably a hydrophilic support. For example, paper, paper laminated with plastic (eg, polyethylene, polypropylene, polystyrene, etc.), metal plate (eg, aluminum, zinc, copper, etc.), plastic film (eg, cellulose diacetate, cellulose triacetate, cellulose propionate) Cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc.), and paper or plastic films on which the above-mentioned metals are laminated or deposited. Preferable supports include a polyester film and an aluminum plate. Among these, an aluminum plate that has good dimensional stability and is relatively inexpensive is preferable.

  The aluminum plate is a pure aluminum plate, an alloy plate containing aluminum as a main component and containing a trace amount of foreign elements, or a plastic laminated on a thin film of aluminum or an aluminum alloy. Examples of foreign elements contained in the aluminum alloy include silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel, and titanium. The content of foreign elements in the alloy is preferably 10% by mass or less. In the present invention, a pure aluminum plate is preferable, but completely pure aluminum is difficult to manufacture in terms of refining technology, and therefore may contain a slightly different element. The composition of the aluminum plate is not specified, and a known material can be used as appropriate.

The thickness of the support is preferably from 0.1 to 0.6 mm, more preferably from 0.15 to 0.4 mm.
Prior to using the aluminum plate, it is preferable to perform a surface treatment such as roughening treatment or anodizing treatment. By the surface treatment, it is easy to improve hydrophilicity and secure adhesion between the image recording layer and the support. Prior to roughening the aluminum plate, a degreasing treatment with a surfactant, an organic solvent, an alkaline aqueous solution or the like for removing rolling oil on the surface is performed as desired.

The surface roughening treatment of the aluminum plate is performed by various methods. For example, mechanical surface roughening treatment, electrochemical surface roughening treatment (surface roughening treatment for dissolving the surface electrochemically), chemical treatment, etc. Surface roughening treatment (roughening treatment that chemically selectively dissolves the surface).
As a method for the mechanical surface roughening treatment, a known method such as a ball polishing method, a brush polishing method, a blast polishing method, or a buff polishing method can be used. Also, a transfer method in which the uneven shape is transferred with a roll provided with unevenness in the aluminum rolling step may be used.
Examples of the electrochemical surface roughening treatment include a method in which an alternating current or a direct current is used in an electrolytic solution containing an acid such as hydrochloric acid or nitric acid. Another example is a method using a mixed acid as described in JP-A-54-63902.
The surface-roughened aluminum plate is subjected to an alkali etching treatment using an aqueous solution of potassium hydroxide, sodium hydroxide or the like, if necessary, further neutralized, and if desired, wear resistant. In order to increase the anodic oxidation treatment.

As the electrolyte used for the anodizing treatment of the aluminum plate, various electrolytes that form a porous oxide film can be used. In general, sulfuric acid, hydrochloric acid, oxalic acid, chromic acid or a mixed acid thereof is used. The concentration of these electrolytes is appropriately determined depending on the type of electrolyte.
The conditions for anodizing treatment vary depending on the electrolyte used and cannot be specified in general. In general, however, the electrolyte concentration is 1 to 80% by mass solution, the liquid temperature is 5 to 70 ° C., and the current density is 5 to 60 A / day. dm ² , voltage 1 to 100 V, and electrolysis time 10 seconds to 5 minutes are preferable. The amount of the anodized film formed is preferably from 1.0 to 5.0 g / m ^2, and more preferably 1.5 to 4.0 g / m ^2. Within this range, good printing durability and good scratch resistance of the non-image area of the lithographic printing plate can be obtained.

  As the support used in the present invention, the substrate having the above-mentioned surface treatment and having an anodized film may be used as it is, but for further improvement in adhesion to the upper layer, hydrophilicity, resistance to contamination, heat insulation and the like. If necessary, the surface of the anodized film described in JP-A-2001-253181 and JP-A-2001-322365 may be enlarged or sealed, and immersed in an aqueous solution containing a hydrophilic compound. A hydrophilic treatment or the like can be appropriately selected and performed. Of course, these enlargement processing and sealing processing are not limited to those described above, and any conventionally known method can be performed.

[Sealing treatment]
Sealing treatment includes vapor sealing, single treatment with zirconic fluoride, treatment with an aqueous solution containing an inorganic fluorine compound such as treatment with sodium fluoride, vapor sealing with addition of lithium chloride, sealing with hot water. Hole processing is also possible.
Of these, sealing treatment with an aqueous solution containing an inorganic fluorine compound, sealing treatment with water vapor, and sealing treatment with hot water are preferable. Each will be described below.

<Sealing treatment with an aqueous solution containing an inorganic fluorine compound>
As the inorganic fluorine compound used for the sealing treatment with an aqueous solution containing an inorganic fluorine compound, a metal fluoride is preferably exemplified.
Specifically, for example, sodium fluoride, potassium fluoride, calcium fluoride, magnesium fluoride, sodium fluoride zirconate, potassium fluoride zirconate, sodium fluoride titanate, potassium fluoride titanate, zircon fluoride Ammonium acid, ammonium fluoride titanate, potassium fluoride titanate, fluorinated zirconate, fluorinated titanate, hexafluorosilicic acid, nickel fluoride, iron fluoride, phosphor fluoride, ammonium fluoride phosphate It is done. Of these, sodium fluorinated zirconate, sodium fluorinated titanate, fluorinated zirconic acid, and fluorinated titanic acid are preferable.

The concentration of the inorganic fluorine compound in the aqueous solution is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, from the viewpoint of sufficiently sealing the micropores of the anodized film. Further, in terms of stain resistance, it is preferably 1% by mass or less, and more preferably 0.5% by mass or less.
It is preferable that the aqueous solution containing an inorganic fluorine compound further contains a phosphate compound. When the phosphate compound is contained, the hydrophilicity of the surface of the anodized film is improved, so that on-machine developability and stain resistance can be improved.

Suitable examples of the phosphate compound include phosphates of metals such as alkali metals and alkaline earth metals.
Specifically, for example, zinc phosphate, aluminum phosphate, ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, monoammonium phosphate, monopotassium phosphate, monosodium phosphate, dihydrogen phosphate Potassium, dipotassium hydrogen phosphate, calcium phosphate, sodium ammonium hydrogen phosphate, magnesium hydrogen phosphate, magnesium phosphate, ferrous phosphate, ferric phosphate, sodium dihydrogen phosphate, sodium phosphate, hydrogen phosphate Disodium, lead phosphate, diammonium phosphate, calcium dihydrogen phosphate, lithium phosphate, phosphotungstic acid, ammonium phosphotungstate, sodium phosphotungstate, ammonium phosphomolybdate, sodium phosphomolybdate, sodium phosphite , Tripolyphosphate Potassium, and sodium pyrophosphate. Of these, sodium dihydrogen phosphate, disodium hydrogen phosphate, potassium dihydrogen phosphate, and dipotassium hydrogen phosphate are preferable.
The combination of the inorganic fluorine compound and the phosphate compound is not particularly limited, but the aqueous solution contains at least sodium zirconate fluoride as the inorganic fluorine compound and contains at least sodium dihydrogen phosphate as the phosphate compound. Is preferred.
The concentration of the phosphate compound in the aqueous solution is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, from the viewpoint of improving on-press developability and stain resistance. Further, in terms of solubility, it is preferably 20% by mass or less, and more preferably 5% by mass or less.
The ratio of each compound in the aqueous solution is not particularly limited, but the mass ratio of the inorganic fluorine compound and the phosphate compound is preferably 1/200 to 10/1, and preferably 1/30 to 2/1. Is more preferable.
The temperature of the aqueous solution is preferably 20 ° C. or higher, more preferably 40 ° C. or higher, preferably 100 ° C. or lower, more preferably 80 ° C. or lower.
The aqueous solution preferably has a pH of 1 or more, more preferably has a pH of 2 or more, preferably has a pH of 11 or less, and more preferably has a pH of 5 or less.
The method for sealing with an aqueous solution containing an inorganic fluorine compound is not particularly limited, and examples thereof include an immersion method and a spray method. These may be used alone or in combination, or may be used in combination of two or more.
Of these, the dipping method is preferred. When the treatment is performed using the dipping method, the treatment time is preferably 1 second or longer, more preferably 3 seconds or longer, and preferably 100 seconds or shorter, and 20 seconds or shorter. More preferred.

<Sealing treatment with water vapor>
Examples of the sealing treatment with water vapor include a method of bringing pressurized or normal pressure water vapor into contact with the anodized film continuously or discontinuously.
The temperature of the water vapor is preferably 80 ° C. or higher, more preferably 95 ° C. or higher, and preferably 105 ° C. or lower.
The water vapor pressure is preferably in the range (1.008 × 10 ^{5 to} 1.043 × 10 ⁵ Pa) from (atmospheric pressure−50 mmAq) to (atmospheric pressure + 300 mmAq).
Further, the time for which the water vapor is contacted is preferably 1 second or longer, more preferably 3 seconds or longer, 100 seconds or shorter, more preferably 20 seconds or shorter.

<Sealing treatment with hot water>
Examples of the sealing treatment with water vapor include a method in which an aluminum plate on which an anodized film is formed is immersed in hot water.
The hot water may contain an inorganic salt (for example, phosphate) or an organic salt.
The temperature of the hot water is preferably 80 ° C. or higher, more preferably 95 ° C. or higher, and preferably 100 ° C. or lower.
Further, the time of immersion in hot water is preferably 1 second or longer, more preferably 3 seconds or longer, more preferably 100 seconds or shorter, and even more preferably 20 seconds or shorter.
Examples of the hydrophilization treatment used in the present invention include US Pat. Nos. 2,714,066, 3,181,461, 3,280,734 and 3,902,734. There is an alkali metal silicate method as described in the book. In this method, the support is immersed in an aqueous solution such as sodium silicate or electrolytically treated. In addition, the treatment with potassium zirconate fluoride described in JP-B 36-22063, U.S. Pat. Nos. 3,276,868, 4,153,461 and 4,689, And a method of treating with polyvinyl phosphonic acid as described in each specification of No. 272.
The support of the present invention preferably has a center line average roughness of 0.10 to 1.2 μm. Within this range, good adhesion to the image recording layer, good printing durability and good stain resistance can be obtained.

(3-1-2) Step of Injecting Inkjet Recording Ink onto the Hydrophilic Support When the inkjet recording ink of the present invention is ejected onto the surface of the hydrophilic support, the inkjet recording ink is 40 to The ink composition is preferably ejected after being heated to 80 ° C., preferably 25 to 30 ° C., to lower the viscosity of the ink composition to 7 to 30 mPa · s, preferably 7 to 20 mPa · s. In particular, when an ink composition having an ink viscosity of 35 to 500 MP · s at 25 ° C. is used, a great effect can be obtained. By using this method, high injection stability can be realized. A radiation curable ink jet recording ink such as the ink of the present invention generally has a higher viscosity than a water-based ink generally used in ink jet recording inks, and therefore has a large viscosity fluctuation due to temperature fluctuations during printing. The ink viscosity fluctuation has a great influence on the change in the droplet size and the change in the ejection speed of the droplets, thereby causing deterioration of the image quality. Therefore, it is necessary to keep the temperature of ink at the time of printing as constant as possible. Therefore, it is appropriate that the control range of the temperature of the present invention is the set temperature ± 5 ° C., preferably the set temperature ± 2 ° C., more preferably the set temperature ± 1 ° C.

(3-1-3) Step of curing the ink by irradiating the hydrophilic support on which the ink has been ejected The ink ejected on the surface of the hydrophilic support is cured by irradiating the radiation. To do. This is because the sensitizing dye in the polymerization initiation system contained in the ink for ink jet recording of the present invention absorbs radiation to be in an excited state, and the polymerization initiator is decomposed by contact with the polymerization initiator in the polymerization initiation system. This is because the polymerizable compound is cured by radical polymerization.
Here, α-rays, γ-rays, electron beams, X-rays, ultraviolet rays, visible light, infrared light, or the like can be used as the radiation used. The peak wavelength of the radiation is, for example, 200 to 600 nm, preferably 300 to 450 nm, more preferably 350 to 450 nm, depending on the absorption characteristics of the sensitizing dye. In addition, the polymerization initiation system of the present invention has sufficient sensitivity even with low output radiation. Thus, the output of radiation, for example, 2000 mJ / cm ² or less, preferably, 10 to 2000 mJ / cm ^2, more preferably, 20~1000mJ / cm ^2, more preferably, irradiation energy of 50 to 800 mJ / cm ² It is appropriate to be. Moreover, it is appropriate that the radiation is irradiated at an exposure surface illuminance of, for example, 10 to 2000 mW / cm ² , preferably 20 to 1000 mW / cm ² .

The ink for ink jet recording of the present invention is appropriately irradiated with such radiation for, for example, 0.01 to 120 seconds, preferably 0.1 to 90 seconds.
Radiation irradiation conditions and a basic irradiation method are disclosed in JP-A-60-132767. Specifically, the light source is provided on both sides of the head unit including the ink ejection device, and the head unit and the light source are scanned by a so-called shuttle method. Irradiation of radiation takes a certain time (for example, 0.01 to 0.5 seconds, preferably 0.01 to 0.3 seconds, more preferably 0.01 to 0.15 seconds) after ink landing. Will be done. In this way, by controlling the time from ink landing to irradiation to an extremely short time, it is possible to prevent the ink that has landed on the recording medium from spreading before curing. Further, since the ink can be exposed to a porous recording medium before the ink penetrates to a deep part where the light source does not reach, residual unreacted monomer can be suppressed, and as a result, odor can be reduced. .
Further, the curing may be completed by another light source that is not driven. In WO99 / 54415, as an irradiation method, a method using an optical fiber or a method in which a collimated light source is applied to a mirror surface provided on the side surface of the head unit to irradiate the recording unit with UV light is disclosed.

By adopting the ink jet recording method as described above, the dot diameter of the landed ink can be kept constant even on various recording media having different surface wettability, and the image quality is improved. In addition, in order to obtain a color image, it is preferable to superimpose in order from the color with the lowest brightness. By superimposing the inks in the order of low lightness, the irradiation line can easily reach the lower ink, and good curing sensitivity, reduction of residual monomers, reduction of odor, and improvement of adhesion can be expected. Irradiation can be performed by injecting all colors and exposing them together, but exposure for each color is preferable from the viewpoint of curing acceleration.
In this way, the ink for inkjet recording of the present invention is cured by irradiation with radiation, and forms a hydrophobic image on the surface of the hydrophilic support.

(3-2) Inkjet recording apparatus The inkjet recording apparatus used in the present invention is not particularly limited, and a commercially available inkjet recording apparatus can be used. That is, in the present invention, recording can be performed on a recording medium using a commercially available inkjet recording apparatus.
The ink jet recording apparatus of the present invention includes, for example, an ink supply system, a temperature sensor, and a radiation source.
The ink supply system includes, for example, an original tank containing the ink jet recording ink of the present invention, a supply pipe, an ink supply tank immediately before the ink jet head, a filter, and a piezo ink jet head. The piezo-type inkjet head has a multi-size dot of 1 to 100 pl, preferably 8 to 30 pl, for example, 320 × 320 to 4000 × 4000 dpi, preferably 400 × 400 to 1600 × 1600 dpi, and more preferably 720 × 720 dpi. It can drive so that it can inject with the resolution of. In the present invention, dpi represents the number of dots per 2.54 cm.

As described above, since it is desirable that the radiation curable ink has a constant temperature for the ejected ink, heat insulation and heating can be performed from the ink supply tank to the inkjet head portion. The temperature control method is not particularly limited, but for example, it is preferable to provide a plurality of temperature sensors at each piping site and perform heating control according to the ink flow rate and the environmental temperature. The temperature sensor can be provided in the vicinity of the ink supply tank and the nozzle of the inkjet head. Moreover, it is preferable that the head unit to be heated is thermally shielded or insulated so that the apparatus main body is not affected by the temperature from the outside air. In order to shorten the printer start-up time required for heating or to reduce the loss of thermal energy, it is preferable to insulate from other parts and reduce the heat capacity of the entire heating unit.

As a radiation source, a mercury lamp, a gas / solid laser or the like is mainly used, and a mercury lamp and a metal halide lamp are widely known as ultraviolet light curable ink jets. However, from the viewpoint of environmental protection, mercury-free is strongly desired, and replacement with a GaN-based semiconductor ultraviolet light-emitting device is very useful industrially and environmentally. Furthermore, LED (UV-LED) and LD (UV-LD) are small, have a long life, have high efficiency, and are low in cost, and are expected as light sources for photocurable ink jets.
In addition, a light emitting diode (LED) and a laser diode (LD) can be used as a radiation source. In particular, when an ultraviolet light source is required, an ultraviolet LED and an ultraviolet LD can be used. For example, Nichia Corporation has launched a purple LED whose main emission spectrum has a wavelength between 365 nm and 420 nm. When even shorter wavelengths are required, US Pat. No. 6,084,250 discloses an LED that can emit radiation centered between 300 nm and 370 nm. Other ultraviolet LEDs are also available and can emit radiation in different ultraviolet bands. Particularly preferred radiation sources in the present invention are UV-LEDs, and particularly preferred are UV-LEDs having a peak wavelength in the range of 350 to 420 nm.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the embodiments in these examples.

<Preparation of colorant dispersion>
According to the method described below, each colorant dispersion was prepared using yellow, magenta, cyan, and black pigments. Each pigment was dispersed using a polymer dispersant to obtain a pigment dispersion. In addition, the dispersion conditions are performed by appropriately adjusting the dispersion conditions using a known dispersion device (pain shaker) so that the average particle diameter of each pigment particle is in the range of 0.2 to 0.3 μm. Subsequently, after heating, it filtered and filtered and prepared.

（マゼンタ色材分散物１）

(Yellow color material dispersion 1)

(Magenta colorant dispersion 1)

（シアン色材分散物１）

（ブラック色材分散物１）

(Magenta colorant dispersion 2)

(Cyan colorant dispersion 1)

(Black color material dispersion 1)

[Example 1]
<Preparation of ink for ink jet recording>
Using each color material dispersion 1 prepared as described above, inks for ink-jet recording of each color were prepared according to the method described below.

(Yellow ink 1: Example 1-1)

Here, bifunctional aromatic urethane acrylate A (molecular weight 1500):

Hexafunctional aliphatic urethane acrylate B (molecular weight 1000):

である。

It is.

(Magenta ink 1: Example 1-2)

Here, sensitizing dye B:

である。

It is.

(Cyan ink 1: Example 1-3)

である。 Here, sensitizing dye C:

It is.

(Black ink 1: Example 1-4)

である。 Here, sensitizing dye D:

It is.

  The crude ink 1 of each color prepared as described above was filtered through a filter having an absolute filtration accuracy of 2 μm to obtain ink 1 of each color.

[Examples 2 to 5]
<Preparation of ink>
Using magenta color material dispersions 1 and 2, magenta inks 2 to 5 were prepared according to the method described below.

(Magenta ink 2: Example 2)

(Magenta ink 3: Example 3)

である。 Here, lactone-modified acrylate A (molecular weight 458):

It is.

(Magenta ink 4: Example 4)

である。 Here, polymerization initiator B:

It is.

(Magenta ink 5: Example 5)

である。 Here, sensitizing dye E:

It is.

[Comparative Examples 1-2]
<Preparation of ink>
Magenta inks 6-7 were prepared according to the method described below.





(Magenta ink 6: Comparative example 1)

(Magenta ink 7: Comparative example 2)

  In the ink compositions prepared in the above examples and comparative examples, the ink viscosity at the ejection temperature is 7 to 20 mPa.s. It was within the range of s.

<Inkjet image recording>
Image printing was performed using the inks of Examples and Comparative Examples prepared as described above.
Image printing was performed by recording on a support (recording medium) using a commercially available inkjet recording apparatus having a piezoelectric inkjet nozzle.
As the support (recording medium) used, a grained aluminum support, a surface-treated transparent biaxially oriented polypropylene film with printability, a soft vinyl chloride sheet, cast coated paper, and commercially available recycled paper were used. used.
The ink supply system of the ink jet recording apparatus includes an original tank, a supply pipe, an ink supply tank immediately before the ink jet head, a filter, and a piezo ink jet head, and heat insulation and heating are performed from the ink supply tank to the ink jet head portion. Temperature sensors were provided near the ink supply tank and the nozzles of the ink jet head, respectively, and temperature control was performed so that the nozzle portions were always 70 ° C. ± 2 ° C. The piezo-type inkjet head was driven so that 8 to 30 pl multi-size dots could be ejected at a resolution of 720 × 720 dpi. After landing, UV-LED light with a peak wavelength of 395 nm is condensed to an exposure surface illuminance of 100 mW / cm ² , and the exposure system, main scanning speed, and emission are set so that irradiation starts 0.1 seconds after ink landing on the recording medium. The frequency was adjusted. Further, the exposure time was variable, and exposure energy was irradiated. In the present invention, dpi represents the number of dots per 2.54 cm.

Using each ink of the example and the comparative example, the ink was ejected at an environmental temperature of 25 ° C. and irradiated with the UV-LED light. In Examples 1-1 to 1-4, the light was emitted in the order of black → cyan → magenta → yellow and irradiated with UV-LED light for each color (collectively referred to as Example 1). In order to eliminate tackiness by palpation, the exposure was performed with a total exposure energy per color of 300 mJ / cm ² as the energy for complete curing.

<Evaluation of inkjet image>
For each formed image, the sensitivity required for curing, penetrability in commercially available recycled paper, ink bleeding on a grained aluminum support, adhesion, printing durability, storage stability, in accordance with the method described below Was evaluated.

(Measurement of curing sensitivity)
The amount of exposure energy (mJ / cm ² ) at which the sticky feeling disappears on the image surface after ultraviolet irradiation was defined as the curing sensitivity. The smaller the value, the higher the sensitivity.

(Permeability evaluation for commercial recycled paper)
For images printed on commercially available recycled paper, permeability was evaluated according to the following criteria.
○: Almost no penetration and no residual monomer odor △: Slight penetration and slight residual monomer odor X: Clearly the ink penetrates the back side and the residual monomer odor is strong

(Evaluation of ink bleeding on grained aluminum support)
For images printed on a grained aluminum support, ink bleeding was evaluated according to the following criteria.
○: No blur between adjacent dots Δ: Slightly blur dots ×: Dot blurs and the image is clearly blurred

(Evaluation of adhesion in grained aluminum support)
With respect to the print image created above, a sample that does not scratch the print surface at all, and in accordance with JISK 5400, 11 cuts are made on the print surface at 1 mm intervals vertically and horizontally, and a 1 mm square grid is 100. Samples made individually are prepared, cellotape (registered trademark) is pasted on each printing surface, peeled off quickly at an angle of 90 degrees, and the remaining printed images or grids were evaluated according to the following criteria. did.
○: No peeling of the printed image is observed even in the cross cut test. Δ: Some peeling of the ink is recognized in the cross cut test, but almost no peeling is observed unless the ink surface is scratched. Easy to peel off with cello tape (registered trademark)

(Evaluation of printing durability)
The image printed on the grained aluminum support prepared above was used as a printing plate, and after printing with a Heidel KOR-D machine, the number of finished sheets was relatively compared as an index of printing durability (Example 1 was set to 100). ). A larger numerical value is preferable because it has a higher printing durability.

(Evaluation of storage stability)
The prepared ink was stored at 75% RH and 60 ° C. for 3 days, and then the ink viscosity at the injection temperature was measured. The increase in the ink viscosity was expressed as the viscosity ratio after storage / before storage. It was judged that the storage stability was good when the viscosity did not change and was close to 1.0, and when it was less than 1.5, the storage stability was determined.
These evaluation results are shown in Table A.

Table A

From Table A, the ink composition using the specific sensitizing dye in the present invention is highly sensitive to radiation irradiation, can form a high-quality image even in image-forming properties on paper, and is preserved. It can be seen that the stability is also good, and even when used for the production of a printing plate, it is possible to form images with high printing durability and high image quality.
In particular, in Example 1 in which the inks of Examples 1-1 to 1-4 were combined, a high-resolution image without dot bleeding was obtained for any color. Furthermore, even on high-quality paper, the ink was sufficiently cured without causing the ink to turn around, and there was almost no odor due to unreacted monomers. Further, the ink recorded on the film had sufficient flexibility, and the ink was not cracked even when it was bent, and there was no problem in the adhesion test by peeling the cello tape (registered trademark).

Claims (4)

An ink for inkjet recording, which contains a coloring material, a polymerizable compound, and a polymerization initiation system and is curable by irradiation with radiation, wherein the polymerization initiation system comprises the following general formulas (XIV) and (XVI) An ink for inkjet recording, comprising a sensitizing dye containing at least one compound selected from the group consisting of compounds represented by (XXVI) and a polymerization initiator.

(In the general formula (XIV), A ¹ represents S or NR ⁵⁰ , wherein R ⁵⁰ represents an alkyl group or an aryl group, and L ² represents the sensitization in cooperation with the adjacent A ¹ and the adjacent carbon atom. Represents a non-metallic atomic group that forms a basic nucleus of the dye, and R ⁵¹ and R ⁵² each independently represent a monovalent non-metallic atomic group, or are bonded to each other to form an acidic nucleus of the sensitizing dye. And W represents O or S).

(In the general formula (XVI), A ² represents S or NR ⁵⁹ , wherein R ⁵⁹ represents an alkyl group or an aryl group, and L ⁴ represents the sensitization in combination with the adjacent A ² and the adjacent carbon atom. Represents a non-metallic atomic group forming a basic nucleus of the dye, and R ⁵³ , R ⁵⁴ , R ⁵⁵ , R ⁵⁶ , R ⁵⁷ and R ⁵⁸ each independently represents a monovalent non-metallic atomic group).

(In General Formula (XVII), A ³ and A ⁴ each independently represent S, NR ⁶⁰ or NR ⁶³ , wherein R ⁶⁰ and R ⁶³ each independently represent an alkyl group or an aryl group, and L ⁵ and L ⁶ independently represents a nonmetallic atomic group that forms a basic nucleus of the sensitizing dye in combination with adjacent A ³ , A ⁴ and adjacent carbon atoms, and R ⁶¹ and R ⁶² each independently Represents a non-valent metal valence group, or is bonded to each other to form an aliphatic ring or an aromatic ring.)

(In the general formula (XVIII), R ⁶⁶ represents an aromatic ring or a hetero ring, A ⁵ represents O, S or NR ⁶⁷ , and R ⁶⁴ , R ⁶⁵ and R ⁶⁷ each independently represents a monovalent nonmetallic atom. Or R ⁶⁴ and R ⁶⁷ and R ⁶⁵ and R ⁶⁷ are bonded to each other to form an aliphatic ring or an aromatic ring.)

(In the general formula (XIX), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ each independently represents a monovalent nonmetallic atomic group, provided that , R ¹ and R ³ are each represented by a monovalent organic residue represented by the following partial structural formula (XIX-1), or R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently bonded to form an aliphatic ring or an aromatic ring.
Partial structural formula (XIX-1)

(In the partial structural formula (XIX-1), R ¹⁰ represents a monovalent nonmetallic atomic group, or R ¹ , R ² , R ³ , R ⁴ , R ^{5 in the} general formula (XIX). , R ⁶ , R ⁷ , R ⁸ or R ⁹ are bonded to form an aliphatic ring or an aromatic ring, and Z is divalent necessary to form a 5-membered acidic nucleus together with adjacent atoms. Represents a nonmetallic atomic group of

(In the general formula (XX), R is a monovalent nonmetallic atomic group, X is a monovalent nonmetallic atomic group, and each can be bonded to each other, and Y is a 5-membered or 6-membered ring. To express.)

(In the general formula (XXI), Ar represents an aromatic ring, A represents —NR ³ R ⁴ , —SR ⁵ or —OR ⁶ , R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ^6. Each independently represents a monovalent non-metallic atomic group, and Z ⁻ represents a counter ion necessary for charge neutralization.)

(In General Formula (XXII), Y independently represents an oxygen atom or a sulfur atom, R ₁ and R ₂ each independently represent a monovalent nonmetallic atomic group other than a hydrogen atom, and R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ and R ₁₂ each independently represents a monovalent nonmetallic atomic group.)

(In the general formula (XXIII), X represents an oxygen atom or a sulfur atom, and R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are each independently monovalent. Represents a nonmetallic atomic group, and A represents an aryl group or heteroaryl group having 20 or less carbon atoms.)

(In the general formula (XXIV), X represents an oxygen atom or a sulfur atom, and R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are each independently monovalent. Represents a non-metallic atomic group.)

(In the general formula (XXV), X _{1 to} X ₅ each independently represents a monovalent nonmetallic atomic group, and Z represents an aryl group or a heteroaryl group.)

(In general formula (XXVI), Y represents a nonmetallic atomic group that forms a nitrogen-containing heterocycle in cooperation with adjacent N and carbon atoms, and X represents a monovalent nonmetallic atomic group.) A method of forming an image on a support, comprising:
(a) applying the inkjet recording ink according to claim 1 on the support;
(b) curing the inkjet recording ink by irradiating the inkjet recording ink with radiation having a peak wavelength of 350 to 420 nm with an irradiation energy of 2000 mJ / cm ² or less; and
(c) the cured ink jet recording ink forms an image on the support,
Including methods.   The method according to claim 2, wherein the sensitizing dye contained in the ink jet recording ink has a maximum value of absorption at 350 to 420 nm. A method for producing a lithographic printing plate having a support and an image formed on the support,
(1) a step of ejecting the inkjet recording ink according to claim 1 onto the support; and
(2) A step of irradiating the support on which the ink is ejected to cure the ink and forming an image formed by curing the ink on the support;
And a method comprising: