JP2010018688A - Light absorbing composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an infrared ray-absorbing composition which absorbs light in a near-infrared region, does not absorb light in a region of 400-700 nm, and has excellent invisibility and high fastness, and to provide materials coated with the same (information recording materials, filters or the like). <P>SOLUTION: A light absorbing composition contains a compound represented by general formula (1) and a dithiol metal complex compound. In the formula (1), R<SP>1</SP>represents an alkyl group, an aryl group or a heteroaryl group; R<SP>2</SP>and R<SP>3</SP>each independently represents a hydrogen atom or a substituent, wherein at least one of R<SP>2</SP>and R<SP>3</SP>is an electron-withdrawing group and R<SP>2</SP>and R<SP>3</SP>may be linked to form a ring; and R<SP>4</SP>represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, substituted boron and a metal atom, and may be covalently or coordinately bonded to R<SP>1</SP>and/or R<SP>3</SP>. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a light-absorbing composition, and particularly relates to an infrared-absorbing composition that has absorption in the near-infrared region and has no absorption in the visible region.

  Near-infrared absorbing dyes are used as optical filters for plasma display panels (PDP) and infrared cut films for CCDs and heat ray shielding films, and for photothermal conversion materials as write-once optical discs (CD-R) and flash fusion fixing materials. It is used as an information display material as security ink and invisible barcode ink, and is invisible in addition to having strong absorption in the near infrared region, particularly as a characteristic characteristic of near infrared pigments There is a high demand for invisibility. At the same time, high fastness is required as a performance required for all dyes.

Examples of dyes with excellent invisibility that hardly absorb in the region of 400 nm to 700 nm include cyanine methine dyes and J-aggregates thereof, but long methine conjugated chains are flexible and have absorption forms accompanying isomerization. It is easy to decompose due to changes in heat and reaction with heat, oxygen, and nucleophiles, and has low robustness.
Highly robust near-infrared absorbing dyes with a rigid skeleton include vanadyl naphthalocyanine dyes marketed by Nippon Shokubai Co., Ltd. and quartertalylene dyes marketed by BASF Corporation, but vanadyl phthalocyanine is invisible. Insufficient sex. On the other hand, although quarterrylene has good invisibility in a molecular dispersion state such as a solution, when the concentration is increased, absorption occurs in the visible region due to association, the invisibility is lost, and the usage form is limited.
As a dye that has excellent invisibility and covers the infrared region widely, there are diimonium dyes marketed by Nippon Kayaku Co., Ltd., etc., but they are easy to be reduced, their fastness is insufficient, and their usage is limited. It will be.
Thus, currently, no near-infrared dye that achieves both invisibility and fastness has been put on the market, and the development of a near-infrared dye that satisfies these performances is desired.

Further, pyrrolopyrrole dyes are known as novel infrared dyes (see, for example, Non-Patent Document 1). Non-Patent Document 1 describes the results of studies aimed at infrared fluorescent dyes, and describes that a high fluorescence quantum yield is achieved by increasing the molecular rigidity by boron complexation. Moreover, the application to an organic electroluminescent element is known as an example which applied the fluorescent dye characteristic to this skeleton group (for example, refer patent documents 1-3).
In general, in order to emit strong fluorescence, a fluorescent dye is used in a dilute state that does not cause concentration quenching, and a host material is co-deposited and used in a molecular dispersion state. Such fluorescent dyes are generally known to have low light resistance.

  In order to achieve near-infrared dye compositions that achieve both invisibility and fastness with pyrrolopyrrole dyes, improvement of fastness (especially light fastness) is an important issue, especially molecularly dispersed dispersions It has been desired to improve the light resistance of the coated material and the amorphous coated film (amorphous film). Further, pyrrolopyrrole dyes are known to have improved light resistance when used as fine particles, but further improvement in light resistance has been desired.

Japanese Patent No. 3704748 JP 2003-027049 A International Publication WO2003 / 048268 Pamphlet “Angewante Chemie International Edition of English”, Volume 46, pages 3750-3753 (2007)

  An object of the present invention is to provide a highly robust infrared-absorbing composition having absorption in the near-infrared region and excellent in invisibility that has no absorption in the 400-700 nm region. (Information recording records, filters, etc.).

（式中、Ｒ¹はアルキル基、アリール基またはヘテロアリール基を表す。Ｒ²及びＲ³は各々独立に水素原子または置換基を表し、少なくとも一方は電子吸引性基であり、Ｒ²及びＲ³は結合して環を形成しても良い。Ｒ⁴は水素原子、アルキル基、アリール基、ヘテロアリール基、置換ホウ素、金属原子を表し、Ｒ¹及び／又はＲ³と共有結合もしくは配位結合しても良い。） The problems of the present invention have been solved by the following means.
[1] A light-absorbing composition comprising a compound represented by the following general formula (1) and a dithiol metal complex compound.

(In the formula, R ¹ represents an alkyl group, an aryl group or a heteroaryl group .R ² and R ³ each independently represent a hydrogen atom or a substituent, at least one of an electron withdrawing group, R ² and R ³ may be bonded to form a ring, and R ⁴ represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, a substituted boron or a metal atom, and is covalently bonded or coordinated with R ¹ and / or R ^3. May be combined.)

（式中、Ｒ^a1及びＲ^a2は、各々独立にアルキル基、アリール基、ヘテロアリール基、チオ基、又はシアノ基を表し、Ｒ^a1とＲ^a2とが連結して環構造を形成しても良く、形成された環は、飽和環もしくは不飽和環のいずれであっても良い。ｎは２又は３の整数を表す。Ｍは金属原子を表す。Ｚａは０、１−、２−を表す。また、Ｚａが１−、２−を表すとき、ＹはＺａの電荷を中和するカチオン化合物を表す。） [2] The light-absorbing composition according to item [1], wherein the dithiol metal complex compound is a compound represented by the following general formula (A).

(Wherein R ^a1 and R ^a2 each independently represents an alkyl group, an aryl group, a heteroaryl group, a thio group, or a cyano group, and R ^a1 and R ^a2 may be linked to form a ring structure. The ring formed may be either a saturated ring or an unsaturated ring, n represents an integer of 2 or 3, M represents a metal atom, Za represents 0, 1-, 2-. In addition, when Za represents 1- or 2-, Y represents a cationic compound that neutralizes the charge of Za.)

（式中、Ｒ^a1、Ｒ^a2、Ｒ^a3、Ｒ^a4は、各々独立にアルキル基、アリール基、ヘテロアリール基、チオ基、又はシアノ基を表し、Ｒ^a1とＲ^a2ないしＲ^a3とＲ^a4が連結して環構造を形成しても良く、形成された環は、飽和環もしくは不飽和環のいずれであっても良い。Ｍは金属原子を表す。Ｚａは０、１−、２−を表す。また、Ｚａが１−、２−を表すとき、ＹはＺａの電荷を中和するカチオン化合物を表す。） [3] The light-absorbing composition according to item [2], wherein the compound represented by the general formula (A) is a compound represented by the following general formula (A1).

(Wherein R ^a1 , R ^a2 , R ^a3 and R ^a4 each independently represents an alkyl group, an aryl group, a heteroaryl group, a thio group, or a cyano group, and R ^a1 and R ^a2 or R ^a3 and R ^a4 May be linked to form a ring structure, and the formed ring may be either a saturated ring or an unsaturated ring, M represents a metal atom, Za represents 0, 1 or 2; In addition, when Za represents 1- or 2-, Y represents a cationic compound that neutralizes the charge of Za.)

（前記一般式（Ａ２）〜（Ａ５）中、Ｒ^１１は置換基を表し、ｍは１〜４の整数を表す。複数のＲ^１１は同一でも異なっていても良い。ＥＷＧは電子吸引性基を表す。Ａｒはアリール基またはヘテロアリール基を表す。Ｒ^１２及びＲ^１３は各々独立にアリール基、ヘテロアリール基、又はアルキル基を表す。ｎは２又は３の整数を表す。Ｍは金属原子を表す。Ｚａは０、１−、２−を表す。また、Ｚａが１−、２−を表すとき、ＹはＺａの電荷を中和するカチオン化合物を表す。） [4] The light-absorbing composition according to item [2], wherein the compound represented by the general formula (A) is a compound represented by any one of the following general formulas (A2) to (A5).

(In the general formulas (A2) to (A5), R ¹¹ represents a substituent, m represents an integer of 1 to 4. A plurality of R ¹¹ may be the same or different. EWG represents an electron-withdrawing group. Ar represents an aryl group or a heteroaryl group, R ¹² and R ¹³ each independently represents an aryl group, a heteroaryl group, or an alkyl group, n represents an integer of 2 or 3, and M represents a metal atom. Za represents 0, 1-, 2-. When Za represents 1-, 2-, Y represents a cationic compound that neutralizes the charge of Za.)

[5] The light-absorbing composition according to any one of [1] to [4], wherein R ³ in the general formula (1) is a heterocycle.
[6] The light-absorbing composition according to any one of [1] to [5], wherein the compound represented by the general formula (1) is molecularly dispersed.
[7] The light-absorbing composition according to item [6], which is in an amorphous state.
[8] The light-absorbing composition according to any one of [1] to [5], including fine particles composed of the compound represented by the general formula (1).

（式中、Ｚ¹はアリール環もしくはヘテロアリール環を形成する原子団を表す。Ｒ⁵は炭素数６〜２０のアリール基、炭素数４〜２０のヘテロアリール基、炭素数１〜２０のアルキル基、炭素数１〜２０のアルコキシ基、炭素数１〜２０のアルコキシカルボニル基、カルボキシル基、炭素数１〜２０のカルバモイル基、ハロゲン原子、又はシアノ基のいずれか１つを表し、Ｒ⁵とＺ¹とが結合して縮合環を形成しても良い。Ｒ²²及びＲ²³は各々独立にシアノ基、炭素数１〜６のアシル基、炭素数１〜６のアルコキシカルボニル基、炭素数１〜１０のアルキルもしくはアリールスルフィニル基、又は炭素数３〜２０の含窒素ヘテロアリール基を表し、又はＲ²²及びＲ²³が結合して環状酸性核を表す。Ｒ⁴は水素原子、炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基、炭素数４〜２０ヘテロアリール基、金属原子、又は置換基としてハロゲン原子、炭素数１〜１０のアルキル基、炭素数６〜２０のアリール基、もしくは炭素数４〜２０のヘテロアリール基を有する置換ホウ素を表し、Ｒ²³と共有結合もしくは配位結合を有しても良い。また、当該化合物は更に置換基を有しても良い。） [9] The light-absorbing composition according to any one of [1] to [8], which absorbs infrared rays of 700 nm to 1000 nm.
[10] The infrared absorbing compound according to item [9], wherein the compound represented by the general formula (1) is a compound represented by the following general formula (2).

(In the formula, Z ¹ represents an atomic group forming an aryl ring or a heteroaryl ring. R ⁵ is an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 4 to 20 carbon atoms, or an alkyl having 1 to 20 carbon atoms. A group, an alkoxy group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 20 carbon atoms, a carboxyl group, a carbamoyl group having 1 to 20 carbon atoms, a halogen atom, or a cyano group, and R ⁵ and Z ¹ may be bonded to form a condensed ring, and R ²² and R ²³ are each independently a cyano group, an acyl group having 1 to 6 carbon atoms, an alkoxycarbonyl group having 1 to 6 carbon atoms, or 1 carbon atom. Represents an alkyl or arylsulfinyl group having from 10 to 10 carbon atoms, or a nitrogen-containing heteroaryl group having from 3 to 20 carbon atoms, or R ²² and R ²³ are bonded to each other to represent a cyclic acidic nucleus, wherein R ⁴ represents a hydrogen atom, 1 to carbon atoms 20 alkyl groups, C6-C20 aryl group, C4-C20 heteroaryl group, metal atom, or halogen atom as a substituent, C1-C10 alkyl group, C6-C20 aryl group, or C4-C4 Represents a substituted boron having ˜20 heteroaryl groups, and may have a covalent bond or a coordinate bond with R ^{23. In} addition, the compound may further have a substituent.

（式中、Ｒ³¹は炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基または炭素数３〜２０のヘテロアリール基を表す。Ｒ³²はシアノ基、炭素数１〜６のアシル基、炭素数１〜６のアルコキシカルボニル基、炭素数１〜１０のアルキルもしくはアリールスルフィニル基、又は炭素数３〜１０の含窒素ヘテロアリール基を表す。Ｒ⁶及びＲ⁷は各々独立に水素原子、炭素数１〜１０のアルキル基は炭素数６〜１０のアリール基、又は炭素数４〜１０のヘテロアリール基を表し、Ｒ⁶及びＲ⁷は結合して環を形成してよく、形成する環としては炭素数５〜１０の脂環、炭素数６〜１０のアリール環、又は炭素数３〜１０のヘテロアリール環である。Ｒ⁸及びＲ⁹は各々独立に炭素数１〜１０のアルキル基、炭素数１〜１０のアルコキシ基、炭素数６〜２０のアリール基、又は炭素数３〜１０のヘテロアリール基を表す。Ｘは酸素原子、イオウ原子、−ＮＲ−、−ＣＲＲ’−を表し、Ｒ及びＲ’は水素原子、炭素数１〜１０のアルキル基、又は炭素数６〜１０のアリール基を表す。）
［１２］［１］〜［１１］のいずれか１項に記載の組成物を含む塗布物。 [11] The infrared absorbing compound according to item [9], wherein the compound represented by the general formula (1) is a compound represented by the following general formula (3).

(In the formula, R ³¹ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a heteroaryl group having 3 to 20 carbon atoms. R ³² represents a cyano group or an acyl having 1 to 6 carbon atoms. Group, an alkoxycarbonyl group having 1 to 6 carbon atoms, an alkyl or arylsulfinyl group having 1 to 10 carbon atoms, or a nitrogen-containing heteroaryl group having 3 to 10 carbon atoms, wherein R ⁶ and R ⁷ are each independently a hydrogen atom. The alkyl group having 1 to 10 carbon atoms represents an aryl group having 6 to 10 carbon atoms or a heteroaryl group having 4 to 10 carbon atoms, and R ⁶ and R ⁷ may be bonded to form a ring. The ring is an alicyclic ring having 5 to 10 carbon atoms, an aryl ring having 6 to 10 carbon atoms, or a heteroaryl ring having 3 to 10 carbon atoms, and R ⁸ and R ⁹ are each independently alkyl having 1 to 10 carbon atoms. Group, C1-C10 alkoxy group, carbon Represents an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 3 to 10 carbon atoms, X represents an oxygen atom, a sulfur atom, -NR-, or -CRR'-, R and R 'represent a hydrogen atom or a carbon number of 1 Represents an alkyl group having 10 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms.)
[12] A coated product comprising the composition according to any one of [1] to [11].

The light-absorbing composition of the present invention has performance that satisfies all of excellent light-absorbing properties and high fastness (particularly high light resistance). In particular, the composition in which R ³ in the general formula (1) is a heterocycle exhibits good performance. Moreover, the light absorptive composition whose compound represented by the said General formula (1) is a compound represented by the said General formula (2) has the especially outstanding invisibility. Moreover, the light-absorbing composition in which the compound represented by the general formula (1) is the compound represented by the general formula (3) can achieve both higher fastness and higher invisibility. . Furthermore, the light-absorbing composition of the present invention exhibits higher fastness by including fine particles composed of the compound represented by any one of the general formulas (1) to (3).
Moreover, the light absorbing composition of the present invention has an excellent infrared absorbing ability, and can selectively absorb infrared rays of 700 nm to 1000 nm.
In addition, the light-absorbing composition and the coated material of the present invention (ink, toner, infrared information recording material, photothermal converter, filter, etc.) have excellent infrared absorption ability, excellent invisibility and excellent Balances durability.

Hereinafter, the present invention will be described in detail.
The light absorbing composition of the present invention contains a compound represented by the following general formula (1) and a dithiol metal complex compound. The light-absorbing composition of the present invention has performance that satisfies all of excellent infrared absorption characteristics, invisibility and fastness.

[Compound represented by the general formula (1)]
First, the compound represented by the following general formula (1) will be described.

(In the formula, R ¹ represents an alkyl group, an aryl group or a heteroaryl group .R ² and R ³ each independently represent a hydrogen atom or a substituent, at least one of an electron withdrawing group, R ² and R ³ may be bonded to form a ring, and R ⁴ represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, a substituted boron or a metal atom, and is covalently bonded or coordinated with R ¹ and / or R ^3. May be combined.)

In the general formula (1), the alkyl group represented by R ¹ preferably has 1 to 30 carbon atoms (in the present invention, “A to B” is used to mean “A or more and B or less”). More preferably an alkyl group having 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms, such as methyl, ethyl, iso-propyl, tert-butyl, n-octyl, n-decyl, n-hexadecyl, cyclo And propyl, cyclopentyl, cyclohexyl and the like.
The aryl group represented by R ¹ is preferably an aryl group having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 12 carbon atoms, such as phenyl or o-methyl. Examples include phenyl, p-methylphenyl, biphenyl, naphthyl, anthranyl, phenanthryl and the like.
The heteroaryl group represented by R ¹ is preferably a heteroaryl group having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms. Examples of the hetero atom include a nitrogen atom, an oxygen atom, a sulfur atom, Specific examples include imidazolyl, pyridyl, quinolyl, furyl, thienyl, benzoxazolyl, benzimidazolyl, benzthiazolyl, naphthothiazolyl, benzoxazolyl, m-carbazolyl group, azepinyl group and the like.
Two R ¹ in the general formula (1) may be the same as or different from each other.

R ² and R ³ each independently represent a hydrogen atom or a substituent, at least one of which is an electron-withdrawing group, and R ² and R ³ may combine to form a ring. Examples of the substituent include an alkyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms such as methyl, ethyl, iso-propyl, tert-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, etc.), an alkenyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably carbon number). 2-10, for example, vinyl, allyl, 2-butenyl, 3-pentenyl, etc.), alkynyl group (preferably having 2-30 carbon atoms, more preferably 2-20 carbon atoms, particularly preferably carbon number). 2-10, for example, propargyl, 3-pentynyl, etc.), aryl group (preferably having 6 carbon atoms) 30, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenyl, p-methylphenyl, biphenyl, naphthyl, anthranyl, phenanthryl, etc.), amino group (preferably carbon Number 0 to 30, more preferably 0 to 20 carbon atoms, particularly preferably 0 to 10 carbon atoms, including alkylamino group, arylamino group and heterocyclic amino group, such as amino, methylamino, dimethylamino, diethylamino , Dibenzylamino, diphenylamino, ditolylamino, etc.), an alkoxy group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms such as methoxy, Ethoxy, butoxy, 2-ethylhexyloxy, etc.), ants Ruoxy group (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 12 carbon atoms, such as phenyloxy, 1-naphthyloxy, 2-naphthyloxy, etc.) An aromatic heterocyclic oxy group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include pyridyloxy, pyrazyloxy, pyrimidyloxy, quinolyloxy and the like. ),

An acyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as acetyl, benzoyl, formyl, pivaloyl, etc.), an alkoxycarbonyl group ( Preferably it has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms, and examples thereof include methoxycarbonyl, ethoxycarbonyl and the like, and an aryloxycarbonyl group (preferably having a carbon number). 7 to 30, more preferably 7 to 20 carbon atoms, particularly preferably 7 to 12 carbon atoms, such as phenyloxycarbonyl, and acyloxy groups (preferably 2 to 30 carbon atoms, more preferably carbon atoms). 2 to 20, particularly preferably 2 to 10 carbon atoms, for example, acetoxy, benzoyloxy An acylamino group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, and examples thereof include acetylamino and benzoylamino). An alkoxycarbonylamino group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms such as methoxycarbonylamino), aryloxycarbonylamino group (Preferably 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, particularly preferably 7 to 12 carbon atoms, such as phenyloxycarbonylamino), sulfonylamino group (preferably 1 carbon atom) To 30, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, Methanesulfonylamino, benzenesulfonylamino, etc.), sulfamoyl groups (preferably having 0 to 30 carbon atoms, more preferably 0 to 20 carbon atoms, particularly preferably 0 to 12 carbon atoms, such as sulfamoyl, methyl And carbamoyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms). For example, carbamoyl, methylcarbamoyl, diethylcarbamoyl, phenylcarbamoyl, etc.), alkylthio group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, Methylthio, ethylthio, etc.), ants Ruthio group (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 12 carbon atoms, and examples thereof include phenylthio and the like. ),

Aromatic heterocyclic thio group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as pyridylthio, 2-benzimidazolylthio, 2-benzoxazolyl And sulfonyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, such as mesyl and tosyl). ), Sulfinyl groups (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methanesulfinyl, benzenesulfinyl, etc.) A ureido group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, Ureido, methylureido, phenylureido, etc.), phosphoric acid amide group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, for example diethyl phosphorus Acid amide, phenylphosphoric acid amide, etc.), hydroxy group, mercapto group, halogen atom (eg fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxyl group, nitro group, hydroxam An acid group, a sulfino group, a hydrazino group, an imino group, a heterocyclic group (preferably having a carbon number of 1 to 30, more preferably a carbon number of 1 to 12, and examples of the hetero atom include a nitrogen atom, an oxygen atom, a sulfur atom, Specifically, for example, imidazolyl, pyridyl, quinolyl, furyl, thienyl, piperidyl, morpholino, ben Oxazolyl, benzimidazolyl, benzthiazolyl, carbazolyl group, azepinyl group, etc.), silyl group (preferably having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms, Examples thereof include trimethylsilyl and triphenylsilyl). These substituents may be further substituted.

The electron-withdrawing group represented by R ² or R ³ is preferably an electron-withdrawing group having a Hammett σm value or σp value (sigma para value) of 0.2 or more, such as a cyano group, an acyl group, and an alkyl group. Examples thereof include an oxycarbonyl group, an aryloxycarbonyl group, a sulfamoyl group, a sulfinyl group, and a heterocyclic group. These electron withdrawing groups may be further substituted.

  Hammett's substituent constant σ value will be described. Hammett's rule is a method described in 1935 by L. E. in order to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives. P. A rule of thumb proposed by Hammett, which is widely accepted today. Substituent constants determined by Hammett's rule include σp value and σm value, and these values can be found in many general books. For example, J. et al. A. Dean, “Lange's Handbook of Chemistry”, 12th edition, 1979 (Mc Graw-Hill) and “Areas of Chemistry”, No. 122, 96-103, 1979 (Nankodo), Chem. Rev. 1991, 91, 165-195. In the present invention, a substituent having a Hammett's substituent constant σm value or σp value of 0.2 or more indicates an electron-attracting group. The σm value or σp value is preferably 0.25 or more, more preferably 0.3 or more, and particularly preferably 0.35 or more.

Specific examples include cyano group (σp = 0.66), carboxyl group (—COOH: σp = 0.45), alkoxycarbonyl group (—COOMe: σp = 0.45), aryloxycarbonyl group (—COOPh: σp = 0.44), carbamoyl. Group (—CONH ₂ : σp = 0.36), alkylcarbonyl group (—COMe: σp = 0.50), arylcarbonyl group (—COPh: σp = 0.43), alkylsulfonyl group (—SO ₂ Me: σp = 0.72), aryl A sulfonyl group (—SO ₂ Ph: σp = 0.68), a 2-pyridyl group (σm = 0.33), a 3-pyridyl group (σp = 0.25), a 4-pyridyl group (σp = 0.44), or 2-benzothiazolyl (σp = 0.29), 2-benzoxazolyl (σp = 0.33), and the like. In the present specification, Me represents a methyl group, and Ph represents a phenyl group. The values in parentheses are the σ values of typical substituents in Chem. Rev. 1991, Vol. 91, pp. 165-195.

Further, when R ² and R ³ are combined to form a ring, a 5- to 7-membered ring (preferably a 5- to 6-membered ring) is formed, and the formed ring is usually a merocyanine dye and an acidic nucleus. Are preferably used, and specific examples thereof include the following.
(A) 1,3-dicarbonyl nucleus: For example, 1,3-indandione nucleus, 1,3-cyclohexanedione, 5,5-dimethyl-1,3-cyclohexanedione, 1,3-dioxane-4,6- Zeon etc.
(B) pyrazolinone nucleus: for example 1-phenyl-2-pyrazolin-5-one, 3-methyl-1-phenyl-2-pyrazolin-5-one, 1- (2-benzothiazoyl) -3-methyl-2 -Pyrazolin-5-one and the like.
(C) Isoxazolinone nucleus: For example, 3-phenyl-2-isoxazolin-5-one, 3-methyl-2-isoxazolin-5-one and the like.
(D) Oxindole nucleus: For example, 1-alkyl-2,3-dihydro-2-oxindole and the like.
(E) 2,4,6-triketohexahydropyrimidine nucleus: for example, barbituric acid or 2-thiobarbituric acid and its derivatives. Examples of the derivatives include 1-alkyl compounds such as 1-methyl and 1-ethyl, 1,3-dialkyl compounds such as 1,3-dimethyl, 1,3-diethyl and 1,3-dibutyl, 1,3-diphenyl, 1,3-diaryl compounds such as 1,3-di (p-chlorophenyl) and 1,3-di (p-ethoxycarbonylphenyl), 1-alkyl-1-aryl compounds such as 1-ethyl-3-phenyl, Examples include 1,3-di (2-pyridyl) 1,3-diheterocyclic substituents and the like.
(F) 2-thio-2,4-thiazolidinedione nucleus: for example, rhodanine and its derivatives. Examples of the derivatives include 3-alkylrhodanine such as 3-methylrhodanine, 3-ethylrhodanine and 3-allylrhodanine, 3-arylrhodanine such as 3-phenylrhodanine, and 3- (2-pyridyl) rhodanine. And the like.
(G) 2-thio-2,4-oxazolidinedione (2-thio-2,4- (3H, 5H) -oxazoledione nucleus: for example, 3-ethyl-2-thio-2,4-oxazolidinedione and the like.
(H) Tianaphthenone nucleus: For example, 3 (2H) -thianaphthenone-1,1-dioxide and the like.
(I) 2-thio-2,5-thiozolidinedione nucleus: For example, 3-ethyl-2-thio-2,5-thiazolidinedione and the like.
(J) 2,4-thiozolidinedione nucleus: For example, 2,4-thiazolidinedione, 3-ethyl-2,4-thiazolidinedione, 3-phenyl-2,4-thiazolidinedione and the like.
(K) Thiazolin-4-one nucleus: For example, 4-thiazolinone, 2-ethyl-4-thiazolinone and the like.
(L) 4-thiazolidinone nucleus: for example, 2-ethylmercapto-5-thiazoline-4-one, 2-alkylphenylamino-5-thiazoline-4-one, and the like.
(M) 2,4-imidazolidinedione (hydantoin) nucleus: for example, 2,4-imidazolidinedione, 3-ethyl-2,4-imidazolidinedione, etc.
(N) 2-thio-2,4-imidazolidinedione (2-thiohydantoin) nucleus: for example, 2-thio-2,4-imidazolidinedione, 3-ethyl-2-thio-2,4-imidazolidinedione Such.
(O) Imidazolin-5-one nucleus: For example, 2-propylmercapto-2-imidazolin-5-one and the like.
(P) 3,5-pyrazolidinedione nucleus: for example, 1,2-diphenyl-3,5-pyrazolidinedione, 1,2-dimethyl-3,5-pyrazolidinedione, and the like.
(Q) Benzothiophen-3-one nucleus: for example, benzothiophen-3-one, oxobenzothiophen-3-one, dioxobenzothiophen-3-one and the like.
(R) Indanone nucleus: For example, 1-indanone, 3-phenyl-1-indanone, 3-methyl-1-indanone, 3,3-diphenyl-1-indanone, 3,3-dimethyl-1-indanone, and the like.

In addition, although the σ value of R ² and R ^{3 in} the case of forming a ring cannot be defined, in the present invention, it is considered that R ² and R ³ are each substituted with a partial structure of the ring. In this case, the σ value is defined. For example, when a 1,3-indandione ring is formed, it is considered that R ² and R ³ are each substituted with a benzoyl group.

The ring formed by combining R ² and R ³ is preferably a 1,3-dicarbonyl nucleus, a pyrazolinone nucleus, a 2,4,6-triketohexahydropyrimidine nucleus (including a thioketone body), 2- Thio-2,4-thiazolidinedione nucleus, 2-thio-2,4-oxazolidinedione nucleus, 2-thio-2,5-thiazolidinedione nucleus, 2,4-thiazolidinedione nucleus, 2,4-imidazolidinedione nucleus 2-thio-2,4-imidazolidinedione nucleus, 2-imidazolin-5-one nucleus, 3,5-pyrazolidinedione nucleus, benzothiophen-3-one nucleus, or indanone nucleus, more preferably 1,3-dicarbonyl nucleus, 2,4,6-triketohexahydropyrimidine nucleus (including thioketone body), 3,5-pyrazolidinedione nucleus, benzothiophen-3-one nucleus Or the Indanone nucleus.

R ³ is particularly preferably a heterocycle.
Two R ² in the general formula (1) may be the same as or different from each other, and two R ³ may be the same as or different from each other.

The alkyl group, aryl group, and heteroaryl group represented by R ^{4 have the same} meaning as the substituent described for R ¹ , and the preferred range is also the same. The substituent of the substituted boron represented by R ⁴ has the same meaning as the substituent described above for R ² and R ³ , and is preferably an alkyl group, an aryl group, or a heteroaryl group. The metal atom represented by R ⁴ is preferably a transition metal, magnesium, aluminum, calcium, barium, zinc, or tin, and more preferably aluminum, zinc, tin, vanadium, iron, cobalt, nickel, copper Palladium, iridium, or platinum, particularly preferably aluminum, zinc, vanadium, iron, copper, palladium, iridium, or platinum.
R ⁴ may be covalently or coordinated with R ¹ and / or R ³ .
Two R ⁴ in the general formula (1) may be the same as or different from each other.

  The compound represented by the general formula (1) is preferably a compound represented by the following general formula (2) or (3).

(In the formula, Z ¹ represents an atomic group forming an aryl ring or a heteroaryl ring. R ⁵ is an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 4 to 20 carbon atoms, or an alkyl having 1 to 20 carbon atoms. A group, an alkoxy group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 20 carbon atoms, a carboxyl group, a carbamoyl group having 1 to 20 carbon atoms, a halogen atom, or a cyano group, and R ⁵ and Z ¹ may be bonded to form a condensed ring, and R ²² and R ²³ are each independently a cyano group, an acyl group having 1 to 6 carbon atoms, an alkoxycarbonyl group having 1 to 6 carbon atoms, or 1 carbon atom. Represents an alkyl or arylsulfinyl group having from 10 to 10 carbon atoms, or a nitrogen-containing heteroaryl group having from 3 to 20 carbon atoms, or R ²² and R ²³ are bonded to each other to represent a cyclic acidic nucleus, wherein R ⁴ represents a hydrogen atom, 1 to carbon atoms 20 alkyl groups, C6-C20 aryl group, C4-C20 heteroaryl group, metal atom, or halogen atom as a substituent, C1-C10 alkyl group, C6-C20 aryl group, or C4-C4 Represents a substituted boron having ˜20 heteroaryl groups, and may have a covalent bond or a coordinate bond with R ^{23. In} addition, the compound may further have a substituent.

(In the formula, R ³¹ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a heteroaryl group having 3 to 20 carbon atoms. R ³² represents a cyano group or an acyl having 1 to 6 carbon atoms. Group, an alkoxycarbonyl group having 1 to 6 carbon atoms, an alkyl or arylsulfinyl group having 1 to 10 carbon atoms, or a nitrogen-containing heteroaryl group having 3 to 10 carbon atoms, wherein R ⁶ and R ⁷ are each independently a hydrogen atom. Represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a heteroaryl group having 4 to 10 carbon atoms, and R ⁶ and R ⁷ may be bonded to form a ring. The ring is an alicyclic ring having 5 to 10 carbon atoms, an aryl ring having 6 to 10 carbon atoms, or a heteroaryl ring having 3 to 10 carbon atoms, and R ⁸ and R ⁹ are each independently alkyl having 1 to 10 carbon atoms. Group, C1-C10 alkoxy group, carbon Represents an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 3 to 10 carbon atoms, X represents an oxygen atom, a sulfur atom, -NR-, or -CRR'-, R and R 'represent a hydrogen atom or a carbon number of 1 Represents an alkyl group having 10 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms.)

The general formula (2) will be described.
In the general formula (2), Z ¹ represents an atomic group forming an aryl ring or a heteroaryl ring. The aryl ring and heteroaryl ring formed are synonymous with the aryl group and heteroaryl group described as the substituents for R ² and R ³ in the general formula (1), and the preferred ranges are also the same.
R ⁵ is an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 4 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 20 carbon atoms, It represents any one of a carboxyl group, a carbamoyl group having 1 to 20 carbon atoms, a halogen atom, or a cyano group. Specifically, it has the same meaning as in the example described in R ² and R ³ in formula (1), and preferred ranges are also the same.
R ⁵ and Z ¹ may combine to form a condensed ring, and examples of the condensed ring include a naphthyl ring and a quinoline ring.
By introducing a group represented by R ⁵ into the aryl ring or heteroaryl ring formed by Z ¹ , invisibility can be greatly improved.

R ²² and R ²³ are each independently a cyano group, an acyl group having 1 to 6 carbon atoms, an alkoxycarbonyl group having 1 to 6 carbon atoms, alkylsulfinyl or arylsulfinyl group having 1 to 10 carbon atoms, or the number of 3 to 20 carbon Represents a nitrogen-containing heteroaryl group or a cyclic acidic nucleus in which R ²² and R ²³ are bonded. Specifically, it is synonymous with the example demonstrated by R < ² > and R < ³ > in the said General formula (1), and its preferable range is also the same. R ⁴ has the same meaning as R ⁴ in the general formula (1), and the preferred range is also the same. R ⁴ may have a covalent bond or a coordinate bond with R ²³ .

The compound represented by the general formula (2) may further have a substituent, and the substituent is synonymous with the substituents of R ² and R ³ , and the preferred range is also the same.

As a preferable combination in the general formula (2), Z ¹ forms a benzene ring or a pyridine ring, R ⁵ is an alkyl group, an alkoxy group, a halogen atom, or a cyano group, and R ²² and R ²³ are each independently A heterocyclic group, a cyano group, an acyl group, an alkoxycarbonyl group, or a cyclic acidic nucleus in which R ²² and R ²³ are bonded, and R ⁴ is a hydrogen atom, a substituted boron atom, a transition metal atom, magnesium, aluminum, calcium, barium, This is the case of zinc and tin. As a particularly preferred combination, Z ¹ forms a benzene ring, R ⁵ is an alkyl group, a halogen atom or a cyano group, and R ²² and R ²³ are each independently a nitrogen-containing heterocyclic group and a cyano group or an alkoxycarbonyl group. Or a cyclic acidic nucleus in which R ²² and R ²³ are bonded, and R ⁴ is a hydrogen atom, substituted boron, aluminum, zinc, vanadium, iron, copper, palladium, iridium, or platinum.

The general formula (3) will be described.
In the general formula (3), R ³¹ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a heteroaryl group having 3 to 20 carbon atoms. 1) has the same meaning as the example described in R ¹ in the preferred range is also the same.
R ³² is a cyano group, an alkoxycarbonyl group having 1 to 6 carbon atoms, an alkyl or arylsulfinyl group having 1 to 10 carbon atoms, or a nitrogen-containing heteroaryl group having 3 to 10 carbon atoms. it is the same as examples of R ² in the formula (1), and preferred ranges are also the same.

R ⁶ and R ⁷ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a heteroaryl group having 4 to 10 carbon atoms. are the same as examples of the substituents R ² and R ³ in formula (1), and preferred ranges are also the same. R ⁶ and R ⁷ may combine to form a ring, and the ring formed is an alicyclic ring having 5 to 10 carbon atoms, an aryl ring having 6 to 10 carbon atoms, or a heteroaryl ring having 3 to 10 carbon atoms. Preferred examples include a benzene ring, naphthalene ring, and pyridine ring.
By introducing a 5-membered nitrogen-containing heterocycle substituted with R ⁶ and R ⁷ and further forming a boron complex, an infrared absorbing dye that achieves both high fastness and high invisibility can be realized.

R ⁸ and R ⁹ each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a heteroaryl group having 3 to 10 carbon atoms; Specifically, it is synonymous with the example of the substituent of R < ² >, R < ³ > in the said General formula (1), A preferable range is also the same.
X represents an oxygen atom, a sulfur atom, -NR-, or -CRR'-. R and R ′ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group. .

As a preferable combination in the general formula (3), R ³¹ is an alkyl group having 1 to 10 carbon atoms, a benzene ring or a pyridine ring, R ³² is a cyano group or an alkoxycarbonyl group, R ⁶ and R ⁷ Are bonded to form a benzene ring, a pyridine ring, a pyrazine ring, or a pyrimidine ring, R ⁸ and R ⁹ are each independently an alkyl group having 1 to 6 carbon atoms, a phenyl group, or a naphthyl group, and X is oxygen It is an atom, a sulfur atom, —NR—, or —CRR′—, and R and R ′ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group. As a particularly preferred combination, R ³¹ is an alkyl group having 1 to 10 carbon atoms or a benzene ring, R ³² is a cyano group, R ⁶ and R ⁷ are combined to form a benzene ring or a pyridine ring, ⁸ and R ⁹ are each independently an alkyl group having 1 to 6 carbon atoms, a phenyl group or a naphthyl group, and X is an oxygen atom or a sulfur atom.

  Specific examples of the compound (pigment compound) represented by any one of the general formulas (1) to (3) are shown below, but the present invention is not limited to the following specific examples.

Next, a method for synthesizing the compound represented by any one of the general formulas (1) to (3) will be described.
The compound represented by any one of the general formulas (1) to (3) can be obtained by condensing an active methylene compound with a corresponding diketopyrrolopyrrole compound and, in some cases, further reacting with boron or a metal. Can be synthesized. Diketopyrrolopyrrole can be synthesized by the method described in “High Performance Pigments”, Wiley-VCH, 2002, pages 160 to 163. More specific examples include US Pat. No. 5,969, It can be synthesized by the methods described in the specification of No. 154 and JP-A-9-323993. The condensation reaction between diketopyrrolopyrrole and an active methylene compound and the subsequent boronation can be synthesized according to Non-Patent Document 1 described above.

The compound represented by any one of the general formulas (1) to (3) is not particularly limited, but preferably has an absorption maximum at 700 to 1050 nm, more preferably 700 to 1000 nm. It is preferable that the compound represented by any one of the general formulas (1) to (3) selectively absorbs infrared rays having a wavelength of 700 nm to 1000 nm.
In addition, the compound represented by any one of the general formulas (1) to (3) has a molar extinction coefficient ε not particularly limited, but is preferably 50,000 to 300,000, more preferably 100,000. ~ 250,000.

  The compound represented by any one of the general formulas (1) to (3) can be preferably used as an IR dye. Since it is invisible, the color of the compound is preferably transparent, but may be slightly colored green or gray.

When the light-absorbing composition of the present invention is applied to a filter or the like, the compound represented by any one of the general formulas (1) to (3) is generally in a molecularly dispersed state in order to reduce the influence of scattering. Or in an amorphous state. Further, it may be used as fine particles. The light-absorbing composition of the present invention exhibits higher fastness by including fine particles composed of the compound represented by any one of the general formulas (1) to (3).
Below, the preparation method of the microparticles | fine-particles which consist of a compound represented by either of said general formula (1)-(3) is demonstrated.

(Preparation method of fine particles)
The compound represented by any one of the general formulas (1) to (3) is obtained as a crude crystal by the above-described compound synthesis method. However, when used as fine particles, post-treatment is preferably performed. Examples of post-treatment methods include fine particle control processes such as solvent salt milling, salt milling, dry milling, solvent milling, and acid pasting, solvent heat treatment, resin, surfactant and dispersant, etc. The surface treatment process by.

  The compound represented by any one of the general formulas (1) to (3) may be subjected to a solvent heat treatment as a post-treatment. Examples of the solvent used in the solvent heat treatment include water, aromatic hydrocarbon solvents such as toluene and xylene, halogenated hydrocarbon solvents such as chlorobenzene and o-dichlorobenzene, and alcohols such as isopropanol and isobutanol. Examples thereof include solvents, polar aprotic organic solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, and N-methyl-2-pyrrolidone, glacial acetic acid, pyridine, and mixtures thereof. It is preferable to adjust the average particle size of the compound (pigment) represented by any one of the general formulas (1) to (3) to 0.01 μm to 1 μm by these post-treatments.

[Dithiol metal complex]
Next, the dithiol metal complex will be described.
Since pyrrolopyrrole dyes are known to have improved light resistance when used as fine particles, those skilled in the art usually did not think of further improving light resistance. In addition, the use of dithiol complexes also caused concerns (technical demerits) such as a decrease in invisibility due to changes in absorption and deterioration of the film surface due to the deposition of dithiol complexes with low solubility. The vendor did not recall the adoption of dithiol complexes.
The dithiol metal complex used in the present invention is a metal complex having at least one dithiol compound as a ligand, and may be a metal complex consisting of only a dithiol ligand, or may contain other ligands simultaneously. You may go out. Preferable examples of other ligands include those in which the ligand is bidentately coordinated via two nitrogen atoms (N, N-bidentate ligand).

  The dithiol metal complex used in the present invention is preferably a metal complex consisting only of a dithiol ligand, and particularly preferably a dithiol metal complex represented by the following general formula (A).

(Wherein R ^a1 and R ^a2 each independently represents an alkyl group, an aryl group, a heteroaryl group, a thio group, or a cyano group, and R ^a1 and R ^a2 may be linked to form a ring structure. The ring formed may be either a saturated ring or an unsaturated ring, n represents an integer of 2 or 3, M represents a metal atom, Za represents 0, 1-, 2-. In addition, when Za represents 1- or 2-, Y represents a cationic compound that neutralizes the charge of Za.)

Description In formula (A), the alkyl group represented by R ^a1 and R ^a2, aryl group, examples of heteroaryl groups include substituents represented by R ² and R ³ in formula (1) And the preferred range is also the same.
The “thio group” in the present invention means a monovalent substituent bonded with a sulfur atom, and specifically represents an alkylthio group, an arylthio group, an aromatic heterocyclic thio group or a thioester group.
In the general formula (A), M is preferably a transition metal, more preferably Cr, Mn, Fe, Co, Ni, Cu, Mo, Pd, or Pt. Preferred examples of the cation compound represented by Y include an ammonium cation, a pyridinium cation, a phosphonium cation, an oxonium cation, a sulfonium cation, a selenonium cation, and a metal cation, and a quaternary ammonium cation and a pyridinium cation are particularly preferable.

  The compound represented by the general formula (A) is preferably a compound represented by the following general formula (A1).

^{R a1, R a2, R a3} , R a4 in Formula (A1) each independently represent an alkyl group, an aryl group, a heteroaryl group, thio group, or a cyano radical, R in the general formula (A) It has the same meaning as ^a1 and R ^a2, and preferred ranges are also the same. R ^a1 and R ^a2 or R ^a3 and R ^a4 may be linked to form a ring structure, and the formed ring may be either a saturated ring or an unsaturated ring. M, Za and Y in the general formula (A1) have the same meanings as M, Za and Y in the general formula (A), and preferred ranges thereof are also the same.

  Moreover, it is preferable that the compound represented by the said general formula (A) is a compound represented by either of the following general formula (A2)-(A5).

In the general formulas (A2) to (A5), R ¹¹ represents a substituent, which is synonymous with the examples of the substituent represented by R ² or R ³ in the general formula (1), and the preferred range is also the same. is there. m represents an integer of 1 to 4, and a plurality of R may be substituted. EWG represents an electron-withdrawing group and is synonymous with the electron-withdrawing group represented by R ² or R ³ in the general formula (1), and the preferred range is also the same. Preferable specific examples of EWG include a cyano group and a fluoroalkyl group (such as a trifluoromethyl group). Ar represents an aryl group or a heteroaryl group, and is synonymous with the aryl group or heteroaryl group described as an example of the substituent represented by R ² or R ³ in the general formula (1), and the preferred range is also the same. It is. R ¹² and R ¹³ each independently represents an aryl group, a heteroaryl group, or an alkyl group, and an aryl group, a hetero group described as an example of the substituent represented by R ² or R ³ in the general formula (1) It is synonymous with an aryl group and an alkyl group, and its preferable range is also the same. N, M, Za and Y in the general formulas (A2) to (A5) have the same meanings as n, M, Za and Y in the general formula (A), and preferred ranges thereof are also the same.

  Specific examples of the dithiol metal complex represented by the general formula (A) are shown below, but the present invention is not limited to the following specific examples.

  Further, specific examples of the dithiol metal complex that can be used in the present invention include JP-A 1-1114801, JP-A 64-74272, JP-A 62-39682, and JP-A 61-80106. Examples thereof include compounds described in JP-A 61-42585 and JP-A 61-32003.

  Examples of the dithiol metal complex used in the present invention include “Journal of the American Chemical Society” Vol. 95, pp. 6970-6969 (1973), and JP-A 61- Refer to the descriptions in each of Japanese Patent Nos. 32003, 61-42585, 61-57674, 61-71503, 61-80106, 64-75568, etc. Can be prepared. Moreover, exemplary compound A-21-A-26 is marketed from the reagent maker, and this can also be obtained.

〔Composition〕
Next, the light absorbing composition of the present invention will be described.
The light absorbing composition of the present invention may be aqueous or non-aqueous.
(Aqueous composition)
When the light-absorbing composition of the present invention is an aqueous composition, the aqueous liquid in which the compound represented by the general formula (1) and the dithiol metal complex compound are dispersed is mainly composed of water, and if desired. A mixture to which a hydrophilic organic solvent is added can be used.

  Examples of the hydrophilic organic solvent include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, t-butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol and other alcohols, ethylene glycol, diethylene glycol Polyhydric alcohols such as triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol, ethylene glycol monomethyl ether, ethylene glycol mono Ethyl ether, ethylene glycol butyl ether, diethylene glycol mono Chill ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, ethylene glycol diacetate, ethylene glycol monomethyl ether acetate triethylene glycol monoethyl ether, ethylene glycol monophenyl ether Glycol derivatives such as ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenetriamine, triethylenetetramine, polyethyleneimine, tetramethylpropylenediamine Such as amine, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, sulfolane, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, 2-oxazolidone, 1 , 3-dimethyl-2-imidazolidinone, acetonitrile, acetone and the like.

  Furthermore, the light-absorbing composition of the present invention may contain an aqueous resin. Examples of the aqueous resin include a water-soluble resin that dissolves in water, a water-dispersible resin that disperses in water, a colloidal dispersion resin, or a mixture thereof. Specific examples of the aqueous resin include acrylic, styrene-acrylic, polyester, polyamide, polyurethane, and fluorine resins.

The water-dispersible resin used in the present invention is a dispersion in which a hydrophobic synthetic resin is dispersed in a dispersion medium whose main component is water (sometimes referred to as a solvent in this specification).
The content of water contained in the solvent is preferably 30% to 100%, more preferably 50% to 100%. As the solvent other than water, a solvent having solubility in water such as alcohols such as methanol, ethanol and isopropyl alcohol, ketones such as acetone and methyl ethyl ketone, tetrahydrofuran and butyl cellosolve is preferably used.
As the synthetic resin (polymer), various polymers such as an acrylic resin, a styrene-acrylic resin, a vinyl resin, a polyurethane resin, a polyester resin, a polyamide resin, and a fluorine resin can be used. Examples of the water-soluble resin include gelatin, polyvinyl alcohol, and carboxymethyl cellulose.

  Acrylic resins include acrylic acid esters such as acrylic acid and alkyl acrylate, acrylamide, acrylonitrile, methacrylic acid esters such as methacrylic acid and alkyl methacrylate, and homopolymers of any monomer of methacrylamide and methacrylonitrile. Or the copolymer obtained by superposition | polymerization of 2 or more types of these monomers can be mentioned. Among these, homopolymers of monomers of acrylic acid esters such as alkyl acrylates and methacrylic acid esters such as alkyl methacrylates, or copolymers obtained by polymerization of two or more of these monomers preferable. For example, mention may be made of homopolymers of monomers of acrylic acid esters and methacrylic acid esters having an alkyl group having 1 to 6 carbon atoms, or copolymers obtained by polymerization of two or more of these monomers. it can. The acrylic resin has the above composition as a main component and, for example, partially uses a monomer having any group of a methylol group, a hydroxyl group, a carboxyl group, and an amino group so that a crosslinking reaction with a carbodiimide compound is possible. The resulting polymer.

  Examples of the vinyl resin include polyvinyl alcohol, acid-modified polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, polyvinyl methyl ether, polyolefin, ethylene / butadiene copolymer, polyvinyl acetate, vinyl chloride / vinyl acetate copolymer, vinyl chloride / ( A meth) acrylic acid ester copolymer and an ethylene / vinyl acetate copolymer (preferably ethylene / vinyl acetate / (meth) acrylic acid ester copolymer) can be mentioned. Among these, polyvinyl alcohol, acid-modified polyvinyl alcohol, polyvinyl polymer, polyolefin, ethylene / butadiene copolymer and ethylene / vinyl acetate copolymer (preferably ethylene / vinyl acetate / acrylic acid ester copolymer). Is preferred. The vinyl resin can be crosslinked with a carbodiimide compound so that, for example, polyvinyl alcohol, acid-modified polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, polyvinyl methyl ether, and polyvinyl acetate leave a vinyl alcohol unit in the polymer. Thus, the polymer having a hydroxyl group is used, and the other polymer is, for example, a crosslinkable polymer by partially using a monomer having any of a methylol group, a hydroxyl group, a carboxyl group, and an amino group.

  Examples of the polyurethane resin include polyhydroxy compounds (eg, ethylene glycol, propylene glycol, glycerin, trimethylolpropane), aliphatic polyester polyols obtained by reaction of polyhydroxy compounds and polybasic acids, polyether polyols (eg, Polyurethane derived from poly (oxypropylene ether) polyol, poly (oxyethylene-propylene ether) polyol), polycarbonate-based polyol, and polyethylene terephthalate polyol, or a mixture thereof and polyisocyanate can be given. In the polyurethane resin, for example, the hydroxyl group remaining unreacted after the reaction between polyol and polyisocyanate can be used as a functional group capable of crosslinking reaction with a carbodiimide compound.

  As the polyester resin, generally used is a polymer obtained by reacting a polyhydroxy compound (eg, ethylene glycol, propylene glycol, glycerin, trimethylolpropane) with a polybasic acid. In the above-mentioned polyester resin, for example, the hydroxyl group and carboxyl group remaining unreacted after the reaction between the polyol and the polybasic acid can be used as a functional group capable of crosslinking reaction with the carbodiimide compound. Of course, a third component having a functional group such as a hydroxyl group may be added.

  The dispersion state of the aqueous dispersion of the polymer may be one in which the polymer is emulsified in a dispersion medium, emulsion polymerized, micelle-dispersed, or partially hydrophilic in the polymer molecule. Any of them may be used. For aqueous dispersions of polymers (or simply referred to as aqueous dispersions), “Synthetic resin emulsions (Hiraku Okuda, Hiroshi Inagaki, published by Kobunshi Shuppankai (1978)),“ Application of synthetic latex (Takaaki Sugimura, Kataoka, Y., Suzuki, K., Kasahara, K., published by Kobunshi Kagaku Kai (1993)), “Synthetic Latex Chemistry (Muroichi Soichi, published by Kobunshi Kagaku Kai (1970))”, etc. The average particle size is preferably in the range of about 1 to 50000 nm, more preferably about 5 to 1000 nm, and the particle size distribution of the dispersed particles is not particularly limited, and even those having a wide particle size distribution have a monodispersed particle size distribution. It may be a thing.

In addition, you may use the following commercially available polymers as an aqueous dispersion.
Superflex 830, 460, 870, 420, 420NS (Polyurethane made by Daiichi Kogyo Seiyaku), Bondick 1370NS, 1320NS, Hydran Hw140SF, WLS201, WLS202, WLS213 (Polyurethane made by Dainippon Ink & Chemicals), Olester UD350, UD500, UD600 (Mitsui Chemicals Polyurethane), Neoletz R972, R966, R9660 (Enomoto Kasei Polyurethane), Finetex Es650, Es2200 (Dainippon Ink Chemicals Polyester), Vironal MD1100, MD1400, MD1480 (Toyobo Polyester), Julimer ET325 ET410, AT-613, SEK301 (Nippon Pure Chemicals Acrylic), Boncoat AN117, AN226 (Dai Nippon Ink Industrial acrylic), Luckstar DS616, DS807 (Styrene-butadiene rubber manufactured by Dainippon Ink and Chemicals), Nippon LX110, LX206, LX426, LX433 (Nippon Zeon styrene-butadiene rubber), Nippon LX513, LX1551, LX550, LX1571 ( Nippon Zeon acrylonitrile-butadiene rubber).

  As the polymer used as the binder of the composition of the present invention, one kind may be used alone, or two or more kinds may be mixed and used as necessary.

  Although there is no restriction | limiting in particular in the molecular weight of the polymer used as a binder of a near-infrared absorption layer, Usually, the thing of about 3,000-1,000,000 is preferable at a weight average molecular weight. When the weight average molecular weight is less than 3,000, the strength of the coating layer may be insufficient, and when it exceeds 1,000,000, the coated surface may be poor.

  Further, a surfactant and a dispersant may be used in order to improve fine particle dispersion and image quality. Examples of the surfactant include anionic, nonionic, cationic, and amphoteric surfactants. Any surfactant may be used, but an anionic or nonionic surfactant is used. Is preferred. Examples of anionic surfactants include fatty acid salts, alkyl sulfate esters, alkylbenzene sulfonates, alkyl naphthalene sulfonates, dialkyl sulfosuccinates, alkyl diaryl ether disulfonates, alkyl phosphates, and polyoxyethylene alkyls. Examples thereof include ether sulfate, polyoxyethylene alkylaryl ether sulfate, naphthalene sulfonic acid formalin condensate, polyoxyethylene alkyl phosphate ester salt, glycerol borate fatty acid ester, polyoxyethylene glycerol fatty acid ester and the like.

  Nonionic surfactants include, for example, polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene oxypropylene block copolymer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin Examples include fatty acid esters, polyoxyethylene fatty acid esters, polyoxyethylene alkylamines, fluorine-based resins, and silicon-based materials.

(Non-aqueous composition)
When the light-absorbing composition of the present invention is a non-aqueous composition, the composition contains a compound represented by any one of the general formulas (1) to (3) and a dithiol metal complex compound in a non-aqueous vehicle. Dispersed.
Resins used in non-aqueous vehicles are, for example, petroleum resins, casein, shellac, rosin modified maleic resin, rosin modified phenolic resin, nitrocellulose, cellulose acetate butyrate, cyclized rubber, chlorinated rubber, oxidized rubber, hydrochloric acid rubber , Phenolic resin, alkyd resin, polyester resin, unsaturated polyester resin, amino resin, epoxy resin, vinyl resin, vinyl chloride, vinyl chloride-vinyl acetate copolymer, acrylic resin, methacrylic resin, polyurethane resin, silicone resin, fluorine resin , Drying oil, synthetic drying oil, styrene / maleic resin, styrene / acrylic resin, polyamide resin, polyimide resin, polyester resin, benzoguanamine resin, melamine resin, urea resin chlorinated polypropylene, butyral resin, vinylidene chloride resin, etc. It is below. A photocurable resin or a thermosetting resin may be used as the non-aqueous vehicle.

  Examples of the solvent used in the non-aqueous vehicle include aromatic solvents such as toluene, xylene, and methoxybenzene, and acetates such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. Solvents, propionate solvents such as ethoxyethyl propionate, alcohol solvents such as methanol and ethanol, ether solvents such as butyl cellosolve, propylene glycol monomethyl ether, diethylene glycol ethyl ether, diethylene glycol dimethyl ether, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc. Ketone solvents, aliphatic hydrocarbon solvents such as hexane, N, N-dimethylformamide, γ-butyrolactam, N Methyl-2-pyrrolidone, aniline, nitrogen compound-based solvent such as pyridine, a lactone-based solvents such as γ- butyrolactone, carbamic acid esters such as a mixture of 48:52 of methyl carbamate and ethyl carbamate acid.

  When the compound represented by any one of the general formulas (1) to (3) is used as fine particles, the composition of the present invention is obtained from the compound represented by any one of the general formulas (1) to (3). The obtained fine particles, the dithiol metal complex compound, and the aqueous or non-aqueous medium are dispersed by using a dispersing device. Examples of the dispersing device that can be used include a ball mill, a sand mill, a bead mill, a roll mill, a jet mill, a paint shaker, an attritor, an ultrasonic disperser, and a disper.

  In the present invention, when using fine particles comprising the compound represented by any one of the general formulas (1) to (3), the volume average particle size of the fine particles is preferably 10 nm or more and 250 nm or less. The volume average particle diameter of the fine particles refers to the particle diameter of the fine particles themselves or, in the case where an additive such as a dispersant is attached to the fine particles, the particle diameter to which the additive is attached. In the present invention, a nanotrac UPA particle size analyzer (UPA-EX150, trade name, manufactured by Nikkiso Co., Ltd.) can be used as a device for measuring the volume average particle diameter of fine particles. The measurement is performed according to a predetermined measurement method by placing 3 ml of the fine particle dispersion in a measurement cell. As parameters input at the time of measurement, the ink viscosity is used as the viscosity, and the pigment density is used as the density of the dispersed particles.

  A more preferable volume average particle diameter is 20 nm or more and 250 nm or less, and further preferably 30 nm or more and 230 nm or less. When the number average particle size of the particles in the pigment dispersion is less than 10 nm, there are cases where the storage stability cannot be ensured, whereas when it exceeds 250 nm, the optical density may be lowered.

The content of the compound represented by any one of the general formulas (1) to (3) in the light-absorbing composition of the present invention is preferably in the range of 0.1 to 35% by mass, More preferably, it is in the range of ˜25 mass%. If the density is less than 0.1% by mass, sufficient color density may not be obtained. If the concentration exceeds 35% by mass, the dispersion stability may decrease.
Moreover, content of the said dithiol metal complex compound in the light absorptive composition of this invention is 1-100 mass% with respect to the compound represented by either of the said General formula (1)-(3). Is preferable, and it is more preferable that it is 5-50 mass%.

  Applications of the composition of the present invention include image recording materials and filter applications for forming images, particularly invisible images, and photothermal conversion material applications. Specific examples include infrared cut filters and inkjet recording materials. As heat-sensitive recording materials, pressure-sensitive recording materials, recording materials using electrophotography, transfer-type silver halide photosensitive materials, printing inks, recording pens, photothermal conversion materials for flash fixing, light irradiation melting adhesives, etc. Is a recording material using a filter, an ink jet recording material, a heat sensitive recording material, and an electrophotographic method.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to these.

Synthesis example 1
[Preparation of Exemplified Compound (D-1)]
Exemplified compound (D-1) was prepared according to the following scheme.

  First, diketopyrrolopyrrole (DPP) was synthesized according to the method described in US Pat. No. 5,969,154 using 4- (2-ethylhexyloxy) benzonitrile as a raw material.

3 grams (1 molar equivalent) of diketopyrrolopyrrole and 1.6 grams (2.5 molar equivalent) of pyridine acetonitrile are stirred in 60 mL of toluene, and 6.5 grams (8 molar equivalents) of phosphorus oxychloride are added for 4 hours. Heated to reflux. After cooling to room temperature, 50 mL of chloroform and 20 mL of water were added, and the mixture was further stirred for 30 minutes. The organic layer was taken out by a liquid separation operation and washed with an aqueous sodium hydrogen carbonate solution, and then the solvent was distilled off under reduced pressure. The obtained crude product was purified by silica gel column chromatography (solvent chloroform), and further recrystallized using a chloroform / acetonitrile solvent to obtain 3 g of the target compound (D-1) in a yield of 77%.
¹ H-NMR (CDCl ₃ ): δ 0.9-1.0 (m, 12H), 1.3-1.6 (m, 16H), 1.8 (m, 2H), 3.95 (d, 4H), 7.0 (t, 2H), 7.1 (d, 4H), 7.6 (m, 4H), 7.7 (d, 4H), 8.45 (d, 2H)

Synthesis example 2
(Preparation of exemplary compound (D-25))
Exemplified compound (D-25) was prepared according to the above scheme.
0.75 gram (1 molar equivalent) of exemplary compound (D-1) and 0.5 gram (2.5 molar equivalent) of chlorodiphenyl boron were heated to reflux in 20 mL of orthodichlorobenzene for 3 hours. After cooling to room temperature and adding 10 mL of water, the organic layer was taken out by a liquid separation operation, washed with an aqueous sodium bicarbonate solution, and then the solvent was distilled off under reduced pressure. The obtained crude product was purified by silica gel column chromatography (chloroform solvent) and recrystallized using chloroform / methanol solvent to obtain 0.58 g of the target compound (D-25) in a yield of 53%. It was.
¹ H-NMR (CDCl ₃ ): δ 0.9-1.0 (m, 12H), 1.3-1.6 (m, 16H), 1.8 (m, 2H), 3.75 (d, 4H), 6.35 (d, 4H), 6.65 (d, 4H), 6.7 (t, 2H), 7.1-7.2 (m, 20H), 7.35 (d, 2H) ), 7.45 (t, 2H), 7.8 (d, 2H)

Example 1
(Production of membrane sample (S-1))
Referring to the method described in “Journal of the American Chemical Society” Vol. 87, pages 1483 to 1489 (1965), a dithiol metal complex compound (exemplary compound ( A-10)) was synthesized.
10 mg of the exemplary compound (D-25) and 1 mg of the exemplary compound (A-10) were dissolved in 1 mL of chloroform, and filtered to prepare a composition sample (S1). The produced composition sample (S1) was spin-coated (500 ppm, 10 seconds--1000 ppm, 20 seconds) on a glass substrate to produce a film sample (S-1). In addition, the glass substrate used what was cleaned with acetone after ultrasonically cleaning with pure water. The film sample (S-1) is an amorphous film made of the exemplified compound (D-25).

(Production of membrane sample (S-0))
A comparative composition sample (S0) was prepared in the same manner as above except that only 10 mg of the exemplary compound (D-25) was dissolved in chloroform, and a comparative film sample (S-0) was prepared. The film sample (S-0) is an amorphous film made of the exemplified compound (D-25).

(Evaluation)
About the said film | membrane sample (S-1) and (S-0), the film | membrane absorption spectrum was measured using the spectrophotometer (The Shimadzu Corporation make, brand name, UVPC-3100). The measurement results are normalized by the maximum absorption wavelength λmax, and are shown in FIG. In FIG. 1, the horizontal axis represents wavelength, and the vertical axis represents normalized absorption intensity.
As is clear from the results of FIG. 1, the maximum absorption wavelengths of the film samples (S-1) and (S-0) are almost the same wavelength, and both absorption spectra are almost in the visible region of wavelength 400 to 700 nm. It did not change. From this, it was found that both of them had good invisibility and there was no influence on the invisibility by the dithiol metal complex compound.

Next, on the membrane samples (S-1) and (S-0), a merry-go-round type light resistance tester (manufactured by Eagle Engineering Co., Ltd., cell test machine type III (trade name); with Schott WG320 filter (trade name)) The sample was irradiated with xenon light having an illuminance of 170,000 lx, and the residual ratio of the exemplary compound (D-25) was calculated according to the following formula.
Residual rate% = 100 × (absorption intensity after irradiation) / (absorption intensity before irradiation)
The absorption intensity is a value measured at the maximum absorption wavelength of the ultraviolet absorption spectrum of the compound represented by the general formula (1). The results are shown in FIG. In FIG. 2, the horizontal axis represents the Xe light irradiation time (hour), and the vertical axis represents the remaining rate (%).
As is clear from the results of FIG. 2, in the film sample (S-0) of the comparative example, the residual rate was about 20% after 18 hours of irradiation, whereas in the film sample (S-1) of the present invention, Even after 48 hours of irradiation, the residual rate was about 40%. From this, it was found that the film sample (S-1) of the present invention was excellent in light resistance.

  From the above results, the light-absorbing composition of the present invention and the coating film thereof have absorption in the near-infrared region, no absorption in the visible region (400 to 700 nm), excellent invisibility, and light resistance. It turns out that it is excellent.

Example 2
(Production of membrane samples (S-2) to (S-7))
The kind of compound (Exemplary Compound (D-25)) represented by General Formula (1) in Example 1 and the kind of Compound (Exemplary Compound (A-10)) represented by General Formula (2) in Example 1 Membrane samples (S-2) to (S-7) were produced in the same manner as in Example 1 except that the content was changed as shown in Table 1 below. The film samples (S-2) to (S-7) are amorphous films made of the compound represented by the general formula (1). The compound represented by the general formula (1) used in this example was prepared in the same manner as in Synthesis Example 1. In addition, the compound represented by the general formula (2) includes “Journal of the American Chemical Society” Vol. 95, pages 6970-6969 (1973), and the like. JP-A 61-32003, JP-A 61-42585, JP-A 61-57674, JP-A 61-71503, JP-A 61-80106, JP-A 64-75568, etc. Was synthesized with reference to the method described in 1.

(Production of membrane samples (S-8) and (S-9))
1. Preparation of Fine Particle Dispersion Water was added to 10 parts by mass of the exemplary compound (D-25) and 2 parts by mass of dodecylbenzenesulfonic acid (DBS) as a dispersant to give 500 parts by mass. To this was further added 500 parts by mass of 0.1 mmφ zirconia beads, followed by treatment with a planetary ball mill at 300 rpm for 5 hours to prepare an aqueous dispersion of fine particles.
Thereafter, the beads are separated from the aqueous dispersion by filtration, and the particle size of the fine particles comprising the exemplified compound (D-25) is measured using a Nanotrac UPA particle size analyzer (UPA-EX150, trade name, manufactured by Nikkiso Co., Ltd.). As a result, the average particle size was 0.06 μm.

2. Preparation of Fine Particle Dispersion Film An aqueous gelatin solution was added to the obtained aqueous dispersion and applied to a polyethylene terephthalate (PET) plate coated with gelatin to prepare a gelatin dispersion film of fine particles of the exemplified compound (D-25) (film sample ( S-8)). The absorption spectrum of the obtained gelatin film was measured, and the aqueous dispersion concentration was adjusted so that the λmax optical density of absorption of the exemplary compound (D-25) was 1.5. A membrane sample (S-9) was produced in the same manner except that the exemplified compound (D-25) was replaced with the exemplified compound (D-10).

(Evaluation)
The film samples (S-0) to (S-9) were evaluated for light resistance and invisibility.
Irradiate Xe light with an illuminance of 170,000 lx using a merry-go-round type light resistance tester (manufactured by Eagle Engineering, cell test machine type III (trade name); with Schott WG320 filter (trade name)), and irradiated with Xe light for 14 hours The transmittance was measured at the maximum absorption wavelength of the later infrared absorption spectrum, and the residual rate was calculated in the same manner as in Example 1. The results are shown in Table 1.
The invisibility is evaluated by visual inspection. The case where coloring is observed as compared with the membrane sample (S-0) is ×, the case where the coloring degree is equivalent to that of the membrane sample (S-0) is ○, and the membrane sample ( A case where the degree of coloring was low and the transparency was high compared to S-0) was evaluated as ◎.

As is clear from the results in Table 1, the film rate of the comparative example (S-0) was as low as 30%. On the other hand, the membrane samples (S-1) to (S-9) of the present invention have the same degree of coloring as the membrane sample (S-0), good invisibility, and a residual rate of 75%. It was found that the light resistance was high and excellent in light resistance. From this, it was found that the amorphous film using the light absorbing composition of the present invention was excellent in light resistance.
Further, when the film sample (S-1) and the film sample (S-2) are compared, the film sample (S-2) in which the content of the dithiol metal complex compound is increased, while maintaining the invisibility, the light resistance It was found that the property was further improved. Further, the dispersion film samples (S-9) and (S-10) using fine particles of the exemplified compound (D-25) or (D-10) are further invisible, and the residual ratio is 95% and 98%. %, Which was very high, and was particularly excellent in light resistance.

  The light-absorbing composition of the present invention containing the compound represented by the general formula (1) and the dithiol metal complex compound and the coating material using the same have good infrared absorption and invisibility, and high Light resistance. The light absorbing composition of the present invention can be applied as a marker such as a filter or an ink, or an industrial photothermal conversion material.

FIG. 1 shows membrane absorption spectra of the membrane sample (S-1) and the membrane sample (S-0). FIG. 2 is a graph showing the results of light resistance evaluation of the film sample (S-1) and the film sample (S-0).

Claims (12)

The light absorptive composition containing the compound represented by following General formula (1), and a dithiol metal complex compound.

(In the formula, R ¹ represents an alkyl group, an aryl group or a heteroaryl group .R ² and R ³ each independently represent a hydrogen atom or a substituent, at least one of an electron withdrawing group, R ² and R ³ may be bonded to form a ring, and R ⁴ represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, a substituted boron or a metal atom, and is covalently bonded or coordinated with R ¹ and / or R ^3. May be combined.) The light absorptive composition of Claim 1 whose said dithiol metal complex compound is a compound represented by the following general formula (A).

(Wherein R ^a1 and R ^a2 each independently represents an alkyl group, an aryl group, a heteroaryl group, a thio group, or a cyano group, and R ^a1 and R ^a2 may be linked to form a ring structure. The ring formed may be either a saturated ring or an unsaturated ring, n represents an integer of 2 or 3, M represents a metal atom, Za represents 0, 1-, 2-. In addition, when Za represents 1- or 2-, Y represents a cationic compound that neutralizes the charge of Za.) The light-absorbing composition according to claim 2, wherein the compound represented by the general formula (A) is a compound represented by the following general formula (A1).

(Wherein R ^a1 , R ^a2 , R ^a3 and R ^a4 each independently represents an alkyl group, an aryl group, a heteroaryl group, a thio group, or a cyano group, and R ^a1 and R ^a2 or R ^a3 and R ^a4 May be linked to form a ring structure, and the formed ring may be either a saturated ring or an unsaturated ring, M represents a metal atom, Za represents 0, 1 or 2; In addition, when Za represents 1- or 2-, Y represents a cationic compound that neutralizes the charge of Za.) The light-absorbing composition according to claim 2, wherein the compound represented by the general formula (A) is a compound represented by any one of the following general formulas (A2) to (A5).

(In the general formulas (A2) to (A5), R ¹¹ represents a substituent, m represents an integer of 1 to 4. A plurality of R ¹¹ may be the same or different. EWG represents an electron-withdrawing group. Ar represents an aryl group or a heteroaryl group, R ¹² and R ¹³ each independently represents an aryl group, a heteroaryl group, or an alkyl group, n represents an integer of 2 or 3, and M represents a metal atom. Za represents 0, 1-, 2-. When Za represents 1-, 2-, Y represents a cationic compound that neutralizes the charge of Za.) The light absorptive composition of any one of Claims 1-4 whose R < ³ > in the said General formula (1) is a heterocyclic ring.   The light-absorbing composition according to claim 1, wherein the compound represented by the general formula (1) is molecularly dispersed.   The light-absorbing composition according to claim 6, which is in an amorphous state.   The light absorptive composition of any one of Claims 1-5 containing the microparticles | fine-particles which consist of a compound represented by the said General formula (1).   It is a light absorptive composition given in any 1 paragraph of Claims 1-8, Comprising: An infrared absorptive composition which absorbs 700 nm or more and 1000 nm or less infrared rays. The infrared absorbing compound according to claim 9, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (2).

(In the formula, Z ¹ represents an atomic group forming an aryl ring or a heteroaryl ring. R ⁵ is an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 4 to 20 carbon atoms, or an alkyl having 1 to 20 carbon atoms. A group, an alkoxy group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 20 carbon atoms, a carboxyl group, a carbamoyl group having 1 to 20 carbon atoms, a halogen atom, or a cyano group, and R ⁵ and Z ¹ may be bonded to form a condensed ring, and R ²² and R ²³ are each independently a cyano group, an acyl group having 1 to 6 carbon atoms, an alkoxycarbonyl group having 1 to 6 carbon atoms, or 1 carbon atom. Represents an alkyl or arylsulfinyl group having from 10 to 10 carbon atoms, or a nitrogen-containing heteroaryl group having from 3 to 20 carbon atoms, or R ²² and R ²³ are bonded to each other to represent a cyclic acidic nucleus, wherein R ⁴ represents a hydrogen atom, 1 to carbon atoms 20 alkyl groups, C6-C20 aryl group, C4-C20 heteroaryl group, metal atom, or halogen atom as a substituent, C1-C10 alkyl group, C6-C20 aryl group, or C4-C4 Represents a substituted boron having ˜20 heteroaryl groups, and may have a covalent bond or a coordinate bond with R ^{23. In} addition, the compound may further have a substituent. The infrared absorbing compound according to claim 9, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (3).

(In the formula, R ³¹ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a heteroaryl group having 3 to 20 carbon atoms. R ³² represents a cyano group or an acyl having 1 to 6 carbon atoms. Group, an alkoxycarbonyl group having 1 to 6 carbon atoms, an alkyl or arylsulfinyl group having 1 to 10 carbon atoms, or a nitrogen-containing heteroaryl group having 3 to 10 carbon atoms, wherein R ⁶ and R ⁷ are each independently a hydrogen atom. The alkyl group having 1 to 10 carbon atoms represents an aryl group having 6 to 10 carbon atoms or a heteroaryl group having 4 to 10 carbon atoms, and R ⁶ and R ⁷ may be bonded to form a ring. The ring is an alicyclic ring having 5 to 10 carbon atoms, an aryl ring having 6 to 10 carbon atoms, or a heteroaryl ring having 3 to 10 carbon atoms, and R ⁸ and R ⁹ are each independently alkyl having 1 to 10 carbon atoms. Group, C1-C10 alkoxy group, carbon Represents an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 3 to 10 carbon atoms, X represents an oxygen atom, a sulfur atom, -NR-, or -CRR'-, R and R 'represent a hydrogen atom or a carbon number of 1 Represents an alkyl group having 10 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms.)   The coating material containing the composition of any one of Claims 1-11.

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