JP2007025057A - Photosensitive composition and new compound for use in the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive composition using a new photoinitiation system having high sensitivity to an oscillation wavelength of an inexpensive short-wavelength semiconductor laser and also having high sensitivity to various wavelengths of 350-450 nm, and useful as a photosensitive layer of a lithographic printing original plate for scanning exposure adapted for a computer-to-plate (CTP) system excellent in work efficiency and economical efficiency, and a new dye compound usable in the photosensitive composition having high sensitivity to the oscillation wavelength of the inexpensive short-wavelength semiconductor laser. <P>SOLUTION: The photosensitive composition contains (A) a sensitizing dye of which one-electron oxidized derivative produced by one electron oxidation of the dye is capable of releasing one or more electrons, (B) an initiator compound capable of generating a radical, an acid or a base, and (C) a compound of which physical or chemical property is irreversibly changed by at least one of a radical, an acid and a base. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a photosensitive composition that cures with high sensitivity upon exposure and a novel dye compound used therefor, and in particular, is useful as a photosensitive layer of a lithographic printing plate precursor capable of forming an image by scanning exposure based on a digital signal. The present invention relates to a photosensitive composition and a novel dye compound having excellent photothermal conversion ability.

Conventionally, as a lithographic printing plate, a PS plate having a configuration in which a lipophilic photosensitive resin layer is provided on a hydrophilic support has been widely used. As the plate making method, usually, mask exposure (surface After exposure), the desired printing plate was obtained by dissolving and removing the non-image area.
In recent years, digitization techniques for electronically processing, storing, and outputting image information using a computer have become widespread, and various new image output methods corresponding to the technology have come into practical use. As a result, computer-to-plate (CTP) technology that scans highly directional light such as laser light in accordance with digitized image information and directly manufactures a printing plate without using a lith film is desired. Obtaining an adapted printing plate precursor is an important technical issue.

  As one of methods for obtaining such a lithographic printing plate capable of scanning exposure, a method of forming an ink receptive resin layer region on a support having a hydrophilic surface is employed. This is a material in which a negative photosensitive layer that is cured by scanning exposure to form an ink receptive region is provided on a support, and has a configuration using a photopolymerization composition excellent in photosensitive speed. Some have been proposed and are already in practical use. The lithographic printing plate precursor having such a constitution has desirable printing plate and printing performance such that development processing is simple, and further excellent in resolution, inking property, printing durability, and stain resistance.

The photopolymerizable composition basically contains a polymerizable compound having an ethylenically unsaturated bond, a photopolymerization initiation system, and optionally a binder resin, and by scanning exposure, the photoinitiation system absorbs light, An active species such as an active radical is generated to cause and advance the polymerization reaction of the polymerizable compound, thereby curing the exposed area to form an image.
In such a photopolymerizable composition capable of scanning exposure, various photoinitiating systems having excellent photosensitivity have been disclosed (for example, see Non-Patent Documents 1 and 2). The photoinitiating system described in these documents is a light source when applied to a conventional CTP system using a long wavelength visible light source such as an Ar laser (488 nm) or an FD-YAG laser (532 nm) as an exposure light source. In the present situation where the output is not sufficiently high, sufficient sensitivity cannot be obtained, and a highly sensitive starting system that can be adapted to further high-speed exposure is desired.

On the other hand, in recent years, for example, semiconductor lasers that use InGaN-based materials and can continuously oscillate in the 350 nm to 450 nm region have been put into practical use. The scanning exposure system using these short-wave light sources has an advantage that an economical system can be constructed while having a sufficient output because a semiconductor laser can be manufactured at a low cost because of its structure. Furthermore, as compared with a system using a conventional FD-YAG or Ar laser, a photosensitive material having photosensitivity in a short wavelength region capable of working under a brighter safe light can be used. However, there is currently no known photoinitiating system having sufficient sensitivity for scanning exposure in such a short wavelength region of 350 nm to 450 nm.
In response to this, a photosensitive composition containing a sensitizing dye having a high sensitivity in this short wavelength region has been proposed (see Patent Document 1), but a further photoinitiating system including these sensitizing dyes and the like. Higher sensitivity is desired.

  Further, for example, as described in Non-Patent Documents 3 and 4, obtaining a highly sensitive photoinitiating system is a technique that is still widely desired in the imaging field. The photoinitiating system consisting of a sensitizing dye and an initiator compound can generate an acid and a base in addition to the above active radicals by selecting the initiator compound. For example, images such as stereolithography, holography, and color hard copy It is used in the field of manufacturing, manufacturing of electronic materials such as photoresists, and photocurable resin materials such as inks, paints, and adhesives. In these industrial fields, it is eagerly desired to find a sensitizing dye excellent in light absorption and sensitizing ability for the purpose of efficiently causing the decomposition of the initiator compound.

Bruce M. Monroe et al., Chemical Revue, 1993, volume 93, p. 435-448 R. S. Davidson, Journal of Photochemistry and Biology A: Chemistry, 1993, Vol. 73, p. 81-96 J. P. Faussier, "Photoinitiated Polymerization-Theory and Applications", Rapra Review, 1998, Vol. 9, Rapra Technology M. Tsunooka et al, Progressive Polymer Science (Prog. Polym. Sci.), 1996, 21, 21, JP 2000-258910 A

  The object of the present invention in consideration of the above-mentioned problems is high with respect to the oscillation wavelength of an inexpensive short-wave semiconductor laser useful as a photosensitive layer of a lithographic printing plate precursor for scanning exposure suitable for a CTP system excellent in workability and economy. It is an object of the present invention to provide a photosensitive composition using a novel photoinitiating system having a high sensitivity with respect to a wide wavelength range from 350 nm to 450 nm. A second object of the present invention is to provide a novel dye compound that can be used in a photosensitive composition that is highly sensitive to the oscillation wavelength of the shortwave semiconductor laser.

  As a result of intensive studies to achieve the above-mentioned object, the present inventor has given a high photosensitivity to a novel photoinitiating system comprising a sensitizing dye having a specific structure and an initiator compound, particularly in the vicinity of 350 nm to 450 nm. The present invention was completed. That is, the object of the present invention has been achieved by the following means.

(1) (A) A sensitizing dye capable of emitting one electron or more electrons from a one-electron oxidant produced by one-electron oxidation,
(B) an initiator compound capable of generating radicals, acids or bases, and
(C) a compound whose physical or chemical properties are irreversibly changed by at least one of radicals, acids and bases,
Containing the photosensitive composition.

(2) The photosensitive composition according to (1), wherein the sensitizing dye in (1) is represented by the following general formula (I) or general formula (II):

In formula (I), R ¹ and R ² independently represent a substituted or unsubstituted alkyl group, aryl group or heterocyclic group. R ³ , R ⁴ , R ⁵ and R ⁶ each independently represents a hydrogen atom or a monovalent substituent. L ¹ , L ² and L ³ independently represent a methine group which may have a substituent. m represents an integer of 0 or more. A ¹ represents a substituted or unsubstituted aromatic group or heterocyclic group.
In the formula (II), R ²¹ and R ²² independently represent a substituted or unsubstituted alkyl group, aryl group or heterocyclic group. R ²³ , R ²⁴ , R ²⁵ and R ²⁶ each independently represents a hydrogen atom or a monovalent substituent. L ²¹ and L ²² independently represent a methine group which may have a substituent. n represents an integer of 0 or more. A ²¹ represents a substituted or unsubstituted aromatic group or heterocyclic group.
However, the general formula (I) and the general formula (II) have a structure in which a one-electron oxidant produced by one-electron oxidation can emit one electron or more.

(3) In the general formula (I) and the general formula (II), a structure in which a one-electron oxidant formed by one-electron oxidation can emit one electron or more is represented by the following general formula (III) The photosensitive composition as described in (1) or (2) above.

  Ra and Rb independently represent a hydrogen atom or a substituted or unsubstituted alkyl group, aryl group or heterocyclic group. X represents a substituent capable of generating a C radical and a leaving fragment X by cleavage of the C—X bond upon oxidation.

(4) A compound represented by general formula (I) or general formula (II).

(5) The photosensitive composition as described in any one of (1) to (3) above, wherein the initiator compound is hexaarylbisimidazoles.

(6) The above (1), wherein the compound whose physical or chemical properties are irreversibly changed by at least one of radical, acid and base is an unpolymerizable compound having an ethylenically unsaturated double bond. ) To (3) or (5).

(7) A photopolymerization method comprising exposing the photosensitive composition according to the above (1), (2), (3), (5) or (6) with a laser beam having a wavelength of 450 nm or less. .

  Although the mechanism of action of the present invention is not clear, the sensitizing dye of the present invention is highly sensitive to wavelengths from 350 nm to 450 nm and highly sensitive to irradiation (exposure) of an oscillation wavelength of an inexpensive short-wave semiconductor laser. It becomes an excited state, and electron transfer, energy transfer, heat generation, etc. related to the electron excited state due to this light absorption act on the coexisting initiator compound to cause a chemical change in the initiator compound to generate radicals, acids or bases. . Furthermore, it is a compound whose physical or chemical properties are irreversibly changed by at least one of radical, acid and base by at least one of radical, acid or base generated here. Causes irreversible changes such as coloring, decoloring, and polymerization. By using an addition polymerizable compound having an ethylenically unsaturated double bond, which is preferable among such compounds, the curing reaction starts and proceeds, and the exposed region is cured. For this reason, by using the photosensitive composition of the present invention, it has sufficient sensitivity for scanning exposure with a short-wave semiconductor laser, and has no maximum absorption in the ultraviolet region, so that it is stable under white light. It has the advantage that it can be handled even under bright fluorescent lamps. Therefore, in this photosensitive composition, a lithographic printing plate precursor using an addition polymerizable compound as a photosensitive layer can be recorded with high sensitivity, excellent safelight stability, and undesired non-image area. The occurrence of smudges is suppressed, and it is considered that excellent printing performance is exhibited.

  The photosensitive composition of the present invention is a lithographic printing plate precursor having sufficient sensitivity suitable for scanning exposure with a semiconductor laser having a short wavelength such as InGaN and having excellent printing durability, stain resistance and stability. Useful as a photosensitive layer. In addition, the sensitizing dye of the present invention can generate radicals, acids, and bases with high sensitivity to the oscillation wavelength of the short-wave semiconductor laser when applied to the photoinitiating system used in the photosensitive composition. Play.

Hereinafter, the present invention will be described in detail.
The photosensitive composition of the present invention is (A) a one-electron oxidant produced by one-electron oxidation, and (B) a radical, an acid or a base. And (C) a compound whose physical or chemical properties are irreversibly changed by at least one of radicals, acids and bases. Among these, (A) This photosensitivity is obtained with a sensitizing dye capable of emitting one or more electrons from a one-electron oxidant produced by one-electron oxidation, and (B) an initiator compound capable of generating a radical, acid or base. Constitutes the photoinitiating system of the composition; In this system, the one-electron oxidant produced by one-electron oxidation produces electron transfer, energy transfer, heat generation, etc. due to the electronic excitation state caused by light absorption of a sensitizing dye capable of emitting one or more electrons. By action, the initiator compound undergoes a chemical change to generate radicals, acids or bases.

First, this photoinitiating system will be described.
One of the characteristics of the sensitizing dye having a specific structure (A) useful for the photoinitiating system of the present invention is that it has particularly excellent absorption characteristics in the 350 nm to 450 nm region. Furthermore, (A) the sensitizing dye that can be emitted by one-electron oxidant of the present invention produced by one-electron oxidation of the present invention efficiently emits one or more electrons, (B) efficiently causes decomposition of various initiator compounds, Very high photosensitivity. In general, the sensitization mechanism of a photoinitiating system comprising a sensitizing dye / initiator compound is (a) reductive decomposition of an initiator compound based on an electron transfer reaction from an electronically excited state of the sensitizing dye to the initiator compound, b) Oxidative decomposition of initiator compound based on electron transfer from initiator compound to electronically excited state of sensitizing dye, (c) Initiation based on energy transfer from electronically excited state of sensitizing dye to initiator compound Although a route such as decomposition of an agent compound from an electronically excited state is known, it was found that the sensitizing dye of the present invention causes any of these types of sensitizing reactions with excellent efficiency.

  In order to obtain high sensitivity, the present inventor is very important that the one-electron oxidant produced by one-electron oxidation of the sensitizing dye has a structure capable of emitting one electron or more. However, the 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 initiator compound. . As another possibility, the partial structure of the sensitizing dye may contribute to the efficiency of the initial stage of the sensitization reaction (electron transfer, etc.) and the subsequent reaction leading to the decomposition of the initiator compound. is there.

The sensitizing dye of the present invention is characterized in that a one-electron oxidant produced by one-electron oxidation is a compound capable of emitting one electron or more. These compounds are preferably compounds selected from the following types 1 and 2.
(Type 1)
A compound in which a one-electron oxidant formed by one-electron oxidation can further emit one or more electrons with a subsequent bond cleavage reaction.
(Type 2)
A compound capable of emitting one or more electrons after a one-electron oxidant produced by one-electron oxidation undergoes a subsequent bond formation reaction.

First, the compound of type 1 will be described.
JP-A-9-211769 (specific example: 28-) shows a compound that can be emitted from a one-electron oxidant produced by one-electron oxidation of a type 1 compound, with a subsequent bond cleavage reaction. Compounds PMT-1 to S-37 described in Table E and Table F on page 32), JP-A-9-211774, JP-A-11-95355 (specific examples: compounds INV1-36), JP-T 2001-500996 (Specific Examples: Compounds 1-74, 80-87, 92-122), US Pat. No. 5,747,235, US Pat. No. 5,747,236, European Patent 786662A1 (Specific Examples: Compounds INV1-35), "One-photon two-electron sensitizer" described in Japanese Patent Application Laid-Open No. 11-102044, European Patent No. 893732A1, US Patent No. 6,054,260, US Patent No. 5,994,051 or the like Compound called deprotonating electron donating sensitizer "and the like. The preferred ranges of these compounds are the same as the preferred ranges described in the cited patent specifications.

In addition, as a compound of type 1 that can be emitted by one-electron oxidant generated by one-electron oxidation and further releasing one electron or more with a subsequent bond cleavage reaction, a compound represented by the general formula (1) ( General formula (1) described in JP-A-2003-114487), general formula (2) (synonymous with general formula (2) described in JP-A-2003-114487), general formula (3) (JP-A-2003-114487) General formula (1) described in 2003-114488), general formula (4) (synonymous with general formula (2) described in Japanese Patent Application Laid-Open No. 2003-114488), general formula (5) (Japanese Patent Application Laid-Open No. 2003-114488). 114488 (general formula (3)), general formula (6) (synonymous with general formula (1) described in JP2003-75950), and general formula (7) (JP2003-75950). In the general formula (2)), the general formula (8) (JP-A-2) The reaction represented by the general formula (1) described in 004-239943) or the chemical reaction formula (1) (synonymous with the chemical reaction formula (1) described in JP-A-2004-245929) may occur. Among the compounds, a compound represented by the general formula (9) (synonymous with the general formula (3) described in JP-A-2004-245929) can be given. The preferred ranges of these compounds are the same as the preferred ranges described in the cited patent specifications.

In the general formulas (1) and (2), RED ₁ and RED ₂ represent a reducing group. R ₁ is a non-metallic atomic group capable of forming a cyclic structure corresponding to a tetrahydro form of a 5- or 6-membered aromatic ring (including an aromatic heterocycle) or a hexahydro form together with carbon atom (C) and RED _1. To express. R ₂ , R ₃ and R ₄ represent a hydrogen atom or a substituent. Lv ₁ and Lv ₂ represent a leaving group. ED represents an electron donating group.

In the general formulas (3), (4) and (5), Z ₁ represents an atomic group capable of forming a 6-membered ring together with the nitrogen atom and the two carbon atoms of the benzene ring. _{R 5, R 6, R 7} , R 9, R 10, R 11, R 13, R 14, R 15, R 16, R 17, R 18, R 19 represents a hydrogen atom or a substituent. R ₂₀ represents a hydrogen atom or a substituent. When R ₂₀ represents a group other than an aryl group, R ₁₆ and R ₁₇ are bonded to each other to form an aromatic ring or an aromatic heterocycle. R ₈ and R ₁₂ represent a substituent that can be substituted on the benzene ring, m1 represents an integer of 0 to 3, and m2 represents an integer of 0 to 4. Lv ₃ , Lv ₄ and Lv ₅ represent a leaving group.

In general formulas (6) and (7), RED ₃ and RED ₄ represent a reducing group. R _{21 to} R ₃₀ represent a hydrogen atom or a substituent. Z ₂ represents —C (R ₁₁₁ ) (R ₁₁₂ ) —, —NR ₁₁₃ —, or —O—. R ₁₁₁ and R ₁₁₂ each independently represents a hydrogen atom or a substituent. _R113 represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.

In the general formula (8), RED ₅ is a reducing group and represents an arylamino group or a heterocyclic amino group. R ₃₁ represents a hydrogen atom or a substituent. X represents an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylamino group, an arylamino group, or a heterocyclic amino group. Lv ₆ is a leaving group and represents a carboxy group or a salt thereof, or a hydrogen atom.

The compound represented by the general formula (9) is a compound that undergoes a bond formation reaction represented by the chemical reaction formula (1) by being further oxidized after two-electron oxidation accompanied by decarboxylation has occurred. In the chemical reaction formula (1), R ₃₂ and R ₃₃ represent a hydrogen atom or a substituent. Z ₃ represents a group which forms a 5-membered or 6-membered heterocycle with C═C. Z ₄ represents a group that forms a 5- or 6-membered aryl group or heterocyclic group with C═C. M represents a radical, a radical cation, or a cation. In the general formula (9), R ₃₂ , R ₃₃ and Z ₃ have the same meaning as in the chemical reaction formula (1). Z ₅ represents a group which forms a 5- or 6-membered cyclic aliphatic hydrocarbon group or heterocyclic group together with C—C.

Next, the type 2 compound will be described.
As a compound in which a one-electron oxidant produced by one-electron oxidation with a type 2 compound can further emit one or more electrons with a subsequent bond formation reaction, a compound represented by the general formula (10) A compound capable of causing a reaction represented by the general formula (1) described in 2003-140287) and the chemical reaction formula (1) (synonymous with the chemical reaction formula (1) described in JP-A-2004-245929) And a compound represented by the general formula (11) (synonymous with the general formula (2) described in JP-A No. 2004-245929). The preferred ranges of these compounds are the same as the preferred ranges described in the cited patent specifications.

In the general formula (10), RED ₆ represents a reducing group that is one-electron oxidized. Y reacts with a one-electron oxidant formed by one-electron oxidation of RED ₆ to form a new bond, a carbon-carbon double bond site, a carbon-carbon triple bond site, an aromatic group site, or Reactive group containing a non-aromatic heterocyclic moiety of a benzo-fused ring. Q represents a linking group linking RED ₆ and Y.

The compound represented by the general formula (11) is a compound that undergoes a bond formation reaction represented by the chemical reaction formula (1) by being oxidized. In the chemical reaction formula (1), R ₃₂ and R ₃₃ represent a hydrogen atom or a substituent. Z ₃ represents a group which forms a 5-membered or 6-membered heterocycle with C═C. Z ₄ represents a group that forms a 5- or 6-membered aryl group or heterocyclic group with C═C. Z ₅ represents a group which forms a 5- or 6-membered cyclic aliphatic hydrocarbon group or heterocyclic group together with C—C. M represents a radical, a radical cation, or a cation. In the general formula (11), R ₃₂ , R ₃₃ , Z ₃ and Z ₄ have the same meanings as in the chemical reaction formula (1).

Any dye may be used in the present invention, but the dyes listed below are preferred.
For example, cyanine dye, styryl dye, hemicyanine dye, merocyanine dye (including zero methine merocyanine (simple merocyanine)), trinuclear merocyanine dye, tetranuclear merocyanine dye, rhodacyanine dye, complex cyanine dye, complex merocyanine dye, allopolar dye, oxonol Dye, hemioxonol dye, squalium dye, croconium dye, azamethine dye, coumarin dye, arylidene dye, anthraquinone dye, triphenylmethane dye, azo dye, azomethine dye, spiro compound, metallocene dye, fluorenone dye, fulgide dye, perylene dye , Phenazine dye, phenothiazine dye, quinone dye, indigo dye, diphenylmethane dye, polyene dye, acridine dye, acridinone color , Diphenylamine dyes, quinacridone dyes, quinophthalone dyes, phenoxazine dyes, phthaloperylene dyes, porphyrin dyes, chlorophyll dyes, phthalocyanine dyes and metal complex dyes.

  For more information on these dyes, see FM Harmer, “Heterocyclic Compounds-Cyanine Dyes and Related Compounds”, (John Wiley. John Wiley & Sons (New York, London, 1964), DM Sturmer, “Heterocyclic Compounds in Heterocyclic Compounds in Heterocyclic Chemistry” -Special topics in cyclic chemistry), Chapter 18, Section 14, 482-515 (John Wiley & Sons-New York, London, 1977), "Rods Chemistry." Rodd's Chemistry of Carbon Compounds 2nd. Ed. Vol. IV, part B ", Chapter 15, pages 369-422 (Elsevier Science Publishing Company Inc., New York, 1977), etc. Has been.

The sensitizing dye of the present invention is preferably represented by general formula (I) and general formula (II). Subsequently, the compounds represented by formulas (I) and (II) of the present invention will be described in detail.
In the general formula (I), R ¹ and R ² represent a substituted or unsubstituted alkyl group, aryl group, or heterocyclic group. Examples of the alkyl group include a methyl group, an ethyl group, and a propyl group. Examples of the aryl group include a phenyl group and a naphthyl group. Examples of the heterocyclic group include a pyridyl group and a morpholino group.

These may have a substituent at any position. Examples of the substituent include monovalent substituents (hereinafter referred to as R). Examples of the monovalent substituent R include a halogen atom, an alkyl group (including a cycloalkyl group and a bicycloalkyl group), an alkenyl group (including a cycloalkenyl group and a bicycloalkenyl group), an alkynyl group, an aryl group, and a heterocyclic ring. Group, cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy, amino group (anilino) Group), acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, Telocyclic thio group, sulfamoyl group, sulfo group, alkyl and arylsulfinyl group, alkyl and arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl and heterocyclic azo group, imide group, phosphino group , A phosphinyl group, a phosphinyloxy group, a phosphinylamino group, and a silyl group.
More specifically, R represents a halogen atom (for example, a chlorine atom, a bromine atom, an iodine atom), an alkyl group [straight chain, branched, cyclic substituted or unsubstituted alkyl group. They are alkyl groups (preferably alkyl groups having 1 to 30 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl). A cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, such as cyclohexyl, cyclopentyl, 4-n-dodecylcyclohexyl), a bicycloalkyl group (preferably having 5 to 30 carbon atoms). A substituted or unsubstituted bicycloalkyl group, that is, a monovalent group obtained by removing one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms, for example, bicyclo [1,2,2] heptan-2-yl, bicyclo [2,2,2] octane-3-yl), a tricyclo structure with more ring structures Domo is intended to cover. An alkyl group (for example, an alkyl group of an alkylthio group) in the substituents described below also represents such an alkyl group. ], An alkenyl group [represents a linear, branched or cyclic substituted or unsubstituted alkenyl group. They are alkenyl groups (preferably substituted or unsubstituted alkenyl groups having 2 to 30 carbon atoms, such as vinyl, allyl, prenyl, geranyl, oleyl), cycloalkenyl groups (preferably substituted or substituted groups having 3 to 30 carbon atoms). An unsubstituted cycloalkenyl group, that is, a monovalent group obtained by removing one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms (for example, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl), Bicycloalkenyl group (a substituted or unsubstituted bicycloalkenyl group, preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom of a bicycloalkene having one double bond. For example, bicyclo [2,2,1] hept-2-en-1-yl, bicyclo 2,2,2] oct-2-en-4-yl). ], An alkynyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, such as ethynyl, propargyl, trimethylsilylethynyl group, aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms) For example, phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl), a heterocyclic group (preferably a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic compound A monovalent group in which one hydrogen atom is removed from, and more preferably a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms, such as 2-furyl, 2-thienyl, 2 -Pyrimidinyl, 2-benzothiazolyl), cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group Preferably, it is a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, such as methoxy, ethoxy, isopropoxy, t-butoxy, n-octyloxy, 2-methoxyethoxy), aryloxy group (preferably having a carbon number) 6 to 30 substituted or unsubstituted aryloxy groups such as phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoylaminophenoxy), silyloxy groups (preferably carbon 3 to 20 silyloxy groups such as trimethylsilyloxy, t-butyldimethylsilyloxy), heterocyclic oxy groups (preferably substituted or unsubstituted heterocyclic oxy groups having 2 to 30 carbon atoms, 1-phenyltetrazole 5-oxy, 2-tetrahydropyranyloxy An acyloxy group (preferably a formyloxy group, a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, such as formyloxy, acetyloxy, Pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy), a carbamoyloxy group (preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms, such as N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di-n-octylaminocarbonyloxy, Nn-octylcarbamoyloxy), an alkoxycarbonyloxy group (preferably a substitution of 2 to 30 carbon atoms) Or an unsubstituted alkoxycarbonyloxy group such as methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, n-octylcarbonyloxy), an aryloxycarbonyloxy group (preferably a substituted or unsubstituted group having 7 to 30 carbon atoms) An aryloxycarbonyloxy group such as phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyloxy), an amino group (preferably an amino group, a substituted or unsubstituted group having 1 to 30 carbon atoms) Alkylamino groups, substituted or unsubstituted anilino groups having 6 to 30 carbon atoms such as amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino), acylamino groups (preferably Or a formylamino group, a substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, such as formylamino, acetylamino, pivaloylamino, lauroyl Amino, benzoylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino), aminocarbonylamino group (preferably substituted or unsubstituted aminocarbonylamino having 1 to 30 carbon atoms, such as carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino), an alkoxycarbonylamino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, such as , Methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino), aryloxycarbonylamino group (preferably substituted or unsubstituted having 7 to 30 carbon atoms) Aryloxycarbonylamino group of, for example, phenoxycarbonylamino, p-chlorophenoxycarbonylamino, mn-octyloxyphenoxycarbonylamino), sulfamoylamino group (preferably substituted or unsubstituted having 0 to 30 carbon atoms) Sulfamoylamino groups such as sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octylaminosulfonylamino), alkyl and arylsulfonylamino groups (preferably carbon A substituted or unsubstituted alkylsulfonylamino having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonylamino having 6 to 30 carbon atoms, such as methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2,3,5-tri Chlorophenylsulfonylamino, p-methylphenylsulfonylamino), mercapto group, alkylthio group (preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, such as methylthio, ethylthio, n-hexadecylthio), arylthio group (preferably A substituted or unsubstituted arylthio having 6 to 30 carbon atoms such as phenylthio, p-chlorophenylthio, m-methoxyphenylthio), a heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio having 2 to 30 carbon atoms) A group such as 2-benzothiazolylthio, 1-phenyltetrazol-5-ylthio), a sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms such as N-ethylsulfamoyl, N -(3-dodecyloxypropyl) sulfamoyl, N, N-dimethylsulfamoyl, N-acetylsulfamoyl, N-benzoylsulfamoyl, N- (N'-phenylcarbamoyl) sulfamoyl), sulfo group, alkyl and An arylsulfinyl group (preferably a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms such as methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p-methylphenyl Sulfinyl), Alkyl and arylsulfonyl groups (preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms such as methylsulfonyl, ethylsulfonyl, phenylsulfonyl, p- Methylphenylsulfonyl), acyl group (preferably formyl group, substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, or 4 to 30 carbon atoms) Heterocyclic carbonyl groups bonded to carbonyl groups by substituted or unsubstituted carbon atoms, such as acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl, 2-pyridylcarbonyl, 2 -Furylcarbonyl), A reeloxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, such as phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, pt-butylphenoxycarbonyl), An alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl), a carbamoyl group (preferably having 1 carbon atom) To 30 substituted or unsubstituted carbamoyl such as carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methylsulfonyl) carbamo Yl), aryl and heterocyclic azo groups (preferably substituted or unsubstituted arylazo groups having 6 to 30 carbon atoms, substituted or unsubstituted heterocyclic azo groups having 3 to 30 carbon atoms, such as phenylazo, p-chlorophenylazo , 5-ethylthio-1,3,4-thiadiazol-2-ylazo), imide group (preferably N-succinimide, N-phthalimide), phosphino group (preferably substituted or unsubstituted having 2 to 30 carbon atoms) Phosphino groups such as dimethylphosphino, diphenylphosphino, methylphenoxyphosphino), phosphinyl groups (preferably substituted or unsubstituted phosphinyl groups having 2 to 30 carbon atoms such as phosphinyl, dioctyloxyphosphinyl, di Ethoxyphosphinyl), phosphinyloxy group (preferred Or a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, such as diphenoxyphosphinyloxy, dioctyloxyphosphinyloxy), a phosphinylamino group (preferably having 2 to 3 carbon atoms). 30 substituted or unsubstituted phosphinylamino groups such as dimethoxyphosphinylamino, dimethylaminophosphinylamino), silyl groups (preferably substituted or unsubstituted silyl groups having 3 to 30 carbon atoms such as , Trimethylsilyl, t-butyldimethylsilyl, phenyldimethylsilyl).
Among the above functional groups, those having a hydrogen atom may be substituted with the above groups by removing this. Examples of such functional groups include an alkylcarbonylaminosulfonyl group, an arylcarbonylaminosulfonyl group, an alkylsulfonylaminocarbonyl group, and an arylsulfonylaminocarbonyl group. Examples thereof include methylsulfonylaminocarbonyl, p-methylphenylsulfonylaminocarbonyl, acetylaminosulfonyl, and benzoylaminosulfonyl groups.
Further, the substituent may be further substituted, and when there are a plurality of substituents, they may be the same or different. Moreover, you may combine with substituents and may form a ring.

R ¹ and R ² may combine with each other to form a ring. The ring to be formed is preferably a case in which R ¹ , R ² and a nitrogen atom are combined to form a 5-, 6- or 7-membered ring. The formed ring may further have a substituent. Examples of the substituent include the monovalent substituent R described above.

R ¹ and R ² are preferably an alkyl group or an aryl group. More preferably, it is an alkyl group.

R ³ , R ⁴ , R ⁵ and R ⁶ represent a hydrogen atom or a monovalent substituent. Examples of the monovalent substituent include the above-described monovalent substituent R.

R ³ , R ⁴ , R ⁵ and R ⁶ are preferably a hydrogen atom, an alkyl group, or an aryl group. More preferably, they are a hydrogen atom and an alkyl group. More preferably, it is a hydrogen atom.

R ³ and R ⁴ , R ⁵ and R ⁶ may be bonded to each other to form a ring. The ring to be formed is preferably a case in which R ³ , R ⁴ and two carbon atoms to which they are bonded together form a 5-, 6- or 7-membered ring. The same applies to the case where R ⁵ and R ⁶ form a ring. The formed ring may further have a substituent. Examples of the substituent include the monovalent substituent R described above.

In the general formula (I), R ¹ and R ³ may be bonded to each other to form a ring. The ring to be formed is preferably a case where R ¹ , R ³ and the nitrogen atom to which they are bonded together with two carbon atoms form a 5-, 6- or 7-membered ring. The same applies to the case where R ² and R ⁵ form a ring.
The formed ring may further have a substituent. Examples of the substituent include the monovalent substituent R described above.

L ¹ , L ² and L ³ represent a methine group which may have a substituent. Examples of the substituent on L ¹ , L ² and L ³ include the monovalent substituent R described above. Preferred examples of the substituent on L ¹ , L ² and L ³ include an alkyl group, an aryl group, an alkoxy group and a halogen atom. An alkyl group is preferred. L ¹ , L ² and L ³ are preferably unsubstituted methine groups.
Different substituents on L may be bonded to form a ring. In addition, a substituent on L ¹ , L ² or L ³ and R ⁴ or R ⁶ may be bonded to form a ring. Further, a substituent on L ¹ , L ² or L ³ and A ¹ may be bonded to form a ring.

m represents an integer of 0 or more. Preferably it is 0.
When m is an integer of 2 or more, the repeated L ² and L ³ may be the same or different.

A ¹ represents a substituted or unsubstituted aromatic group or heterocyclic group. Aromatic groups include phenyl, biphenyl, naphthyl, tolyl, xylyl, mesityl, cumenyl, chlorophenyl, bromophenyl, chloromethylphenyl, hydroxyphenyl, methoxyphenyl, ethoxyphenyl , Phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group, methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, ethoxyphenyl Carbonyl group, phenoxycarbonylphenyl group, N-phenylcarbamoylphenyl group, phenyl group, cyanophenyl group, sulfophenyl group, sulfonatophenyl group, phosphonophenyl group, phosphor Such as Tofeniru group, and the like.
These may further have a substituent at an arbitrary position. Examples of the substituent include the monovalent substituent R described above.

  The heterocyclic group is a group derived from a monocyclic or polycyclic heterocyclic ring containing at least one of nitrogen, oxygen and sulfur atoms. Examples of the heterocyclic ring constituting the heterocyclic group include thiophene, thiathrene, furan, pyran, isobenzofuran, chromene, xanthene, phenoxazine, pyrrole, pyrazole, isothiazole, isoxazole, imidazole, oxazole, thiazole, triazole, oxadi Azole, thiadiazole, pyridine, pyrazine, pyrimidine, pyridazine, pyrrolidine, tetrahydrofuran, tetrahydrothiophene, pyrroline, dihydrofuran, dihydrothiophene, imidazolidine, oxazolidine, thiazolidine, imidazoline, oxazoline, thiazoline, pyrazolidine, isoxazolidine, isothiazolidine, pyrazoline, Isoxazoline, isothiazoline, tetrahydropyran, piperidine, morpholine, indolizine Isoindolizine, indoyl, indazole, purine, quinolidine, isoquinoline, phthalazine, naphthyridine, quinazoline, sinoline, pteridine, carbazole, carboline, phenanthrine, acridine, perimidine, phenanthrolin, phthalazine, phenalazine, phenoxazine, furan, phenoxazine Etc.

These may have a substituent at any position. Examples of the substituent include the above-described monovalent substituent R and divalent substituent. Examples of the divalent substituent include ═O, ═NR, ═S, and ═CR ₂ (wherein R represents a monovalent substituent, and the above-described monovalent substituent is exemplified).
These may be further bonded with substituents on the ring to form a condensed heterocycle. Examples of the condensed heterocycle include indole ring, benzofuran ring, benzothiophene ring, benzimidazole ring, benzoxazole ring, benzothiazole ring, quinoline ring, isoquinoline ring, and the like. You may have a substituent further on these condensed rings. Examples of the substituent include the aforementioned monovalent substituent R and divalent substituent.

However, in the general formula (I) and the general formula (II), a structure in which a one-electron oxidant formed by one-electron oxidation can emit one electron or more is represented by the following general formula (III) Is preferred.
In general formula (III), Ra and Rb represent a hydrogen atom or a substituted or unsubstituted alkyl group, aryl group, or heterocyclic group. Examples of the substituted or unsubstituted alkyl group, aryl group, and heterocyclic group include the above-described substituent examples.

Ra and Rb may combine with each other to form a ring. The ring to be formed is preferably a case in which Ra, Rb and a carbon atom are combined to form a 5-, 6- or 7-membered ring. The formed ring may further have a substituent. Examples of the substituent include the monovalent substituent R described above.
Ra and Rb are preferably a hydrogen atom, an alkyl group, or an aryl group. More preferred is a hydrogen atom or an alkyl group.

X represents a substituent capable of generating a C radical and a leaving fragment X by cleavage of the C—X bond upon oxidation. Examples of X include CO ₂ ⁻ M, SiR ′ ₃ , SnR ′ ₃ , GeR ′ ₃ , and B ⁻ Ar ₃ M. Here, R ′ represents a substituted or unsubstituted alkyl group, Ar represents a substituted or unsubstituted aryl group, and M represents a cation necessary for adjusting the charge of the whole molecule.
R ′ is preferably a methyl group or an ethyl group. Particularly preferred is a methyl group.
Ar is preferably a phenyl group or a naphthyl group. Particularly preferred is a phenyl group.

M is preferably a hydrogen ion, a sodium ion, a potassium ion, or an ammonium ion (N ⁺ R ″ ₄ ). Particularly preferably, it is an ammonium ion. Here, R ″ represents a hydrogen atom or a monovalent substituent. Examples of the monovalent substituent include the above-described monovalent substituent R. Four R ″ bonded to the nitrogen atom may be the same or different. R ″ is preferably a substituted or unsubstituted alkyl group. R ″ may combine with each other to form a ring. Examples of N ⁺ R ″ ₄ that form a ring include pyridinium ions, imidazolium ions, piperidinium ions, diazabicycloundecenium ions (DBU− H ⁺ ).
N ⁺ R ″ ₄ is preferably tetraethylammonium ion, tetrabutylammonium ion, triethylammonium ion, pyridinium ion, or diazabicycloundecenium ion. Particularly preferred are tetraethylammonium ion or triethylammonium ion.
The preferred X CO ₂ ^- is _{^{N + HEt 3, SiMe 3 -}} N + Et 4, CO 2.

Next, general formula (II) will be described.
R ²¹ and R ²² represent a substituted or unsubstituted alkyl group, aryl group, or heterocyclic group. Examples of R ²¹ and R ²² are the same as R ¹ and R ² in formula (I). The preferred examples are also the same.
R ²³ , R ²⁴ , R ²⁵ and R ²⁶ represent a hydrogen atom or a monovalent substituent. Examples of R ²³ , R ²⁴ , R ²⁵ and R ²⁶ are the same as R ³ , R ⁴ , R ⁵ and R ⁶ in formula (I). The preferred examples are also the same.

L ²¹ and L ²² represent a methine group which may have a substituent. Examples of substituents on L ²¹ and L ²² are in general formula (I). The same as in the case of L ¹ , L ² and L ³ . The preferred examples are also the same. Further, the substituents on L ²¹ and L ²² may be bonded to form a ring. Further, the substituent on L ²¹ or L ²² and R ²⁴ or R ²⁶ may be bonded to form a ring. Further, a substituent on L ²¹ or L ²² and A ²¹ may combine to form a ring.

  n represents an integer of 0 or more. Preferably 0 and 1. Particularly preferred is 1.

A ²¹ represents a 5- or 6-membered heterocyclic group. Examples of A ²¹ are the same as those of A ¹ in the general formula (I). The preferred examples are also the same.

In general formula (I), the bond between L ¹ and A ¹ , L ² = L ³ bond when m is 1 or more, and L ²¹ = L ²² bond when n is 1 or more in general formula (II), Since it is a double bond, a geometric isomer exists, but any structure of E-form and Z-form may be used, and a mixture of any ratio may be used.

  The compound represented by the general formula (I) or (II) may take a tautomer depending on the environment in which it is placed. Although the present invention is described in one of the representative forms, tautomers different from those described in the present invention are also included in the compounds of the present invention.

The compound of the present invention may contain isotopes (for example, ² H, ³ H, ¹³ C, ¹⁵ N, ¹⁷ O, ¹⁸ O and the like).

  Examples of the sensitizing dye of the present invention include compound examples INV 1 to INV 4 described in JP-A No. 11-101444, and examples of compounds represented by the following general formulas (I) and (II). However, the present invention is not limited to this.

The sensitizing dye of the present invention can be synthesized with reference to the methods described in the following books, patents and literature. K. Venkataraman “The Chemistry of Synthetic Dyes” Volumes 1 to 8 (Academic Press-New York, San Francisco, London, 1952-1978). FM Harmer “Heterocyclic Compounds-Cyanine Dyes and Related Compounds”, (John Wiley & Sons )-New York, London, 1964). DM Sturmer, “Heterocyclic Compounds-Special topics in cyclic chemistry” (John Wiley and Sons)
& Sons)-New York, London, 1977). "Rodd's Chemistry of Carbon Compounds 2nd. Ed. Vol. IV, part B" (Elsevier Science Publishing Company Inc., New York, 1977). Nobu Okawara et al. “Functional pigments” (Kodansha Scientific, published in 1992). The Chemical Society of Japan "Experimental Chemistry Course 4th Edition Volume 19" (Maruzen, 1992). JP 2003-221517, JP 10-204085, JP 6-192309, JP 59-28329, JP 51-7488, US Pat. No. 4,147,552, British Patent 867592, J. Chem. Soc. 1964, 5472, J. Chem. Soc. Perkin Trans. 1 1975, 568, Pharmazie 1997, 52, 739, Helv. Chim. Acta. 1971, 54, 980, Indian J. Chem. 1965, 358, J. Phys. Chem. A 1999,
103, 9626, J. Heterocycl. Chem. 1986, 23, 1347, J. Drug. Res. 1972, 4, 123, Chem. Pharm. Bull. 1973, 21, 1914, Synthesis 1997, 87, J. Am. Chem Soc. 1941, 63, 3203, Zhur. Obshchei. Khim. 1956, 26, 2891.

The sensitizing dye used in the present invention can be further subjected to various chemical modifications for improving the characteristics of the photosensitive layer. For example, sensitizing dye and addition polymerizable compound structure (for example, acryloyl group or methacryloyl group) are bonded by a method such as covalent bond, ionic bond, hydrogen bond, etc. Unnecessary precipitation suppression of the dye from the subsequent film can be performed.
In addition, partial structures having radical generating ability in sensitizing dyes and initiator compounds described later (for example, reductive decomposable sites such as alkyl halides, oniums, peroxides, biimidazoles, oniums, biimidazoles, borates, amines) , Trimethylsilylmethyl, carboxymethyl, carbonyl, imine, and other oxidatively cleavable moieties) can significantly increase the photosensitivity particularly in a low concentration of the starting system.

Further, when the photosensitive composition of the present invention is used as a photosensitive layer of a lithographic printing plate precursor which is a preferred mode of use, it is hydrophilic for the purpose of enhancing the processing suitability for an alkaline or aqueous developer. It is effective to introduce a functional site (carboxyl group and its ester, sulfonic acid group and its ester, ethylene oxide group or other acid group or polar group). In particular, ester-type hydrophilic groups have a relatively hydrophobic structure in the photosensitive layer, so that they have excellent compatibility, and in the developer, acid groups are generated by hydrolysis, resulting in increased hydrophilicity. Have.
In addition, for example, a substituent can be appropriately introduced in order to improve compatibility in the photosensitive layer and to suppress crystal precipitation. For example, in certain types of photosensitive systems, unsaturated bonds such as aryl groups and allyl groups may be very effective in improving compatibility. By introducing an obstacle, crystal precipitation can be remarkably suppressed. Further, by introducing a phosphonic acid group, an epoxy group, a trialkoxysilyl group, or the like, 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.

As the sensitizing dye used in the present invention, at least one sensitizing dye that is a feature of the present invention may be used. For example, the sensitizing dye that has been modified as described above may be used as long as it has the characteristics of the sensitizing dye of the present invention. The details of usage, such as what type of dye is used, whether it is 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, the compatibility with the photosensitive layer can be increased by using two or more sensitizing dyes in combination.
In selecting the sensitizing dye, in addition to the photosensitivity, the molar extinction coefficient at the emission wavelength of the light source used is an important factor. By using a dye having a large molar extinction coefficient, the amount of the dye added can be made relatively small, which is economical and advantageous from the viewpoint of film properties of the photosensitive layer.
In the present invention, in addition to the specific sensitizing dye (A), other general-purpose sensitizing dyes can be used in combination as long as the effects of the present invention are not impaired.

Since the photosensitivity and resolution of the photosensitive layer and the physical properties of the exposure film are greatly affected by the absorbance at the light source wavelength, the addition amount of the sensitizing dye is appropriately selected in consideration of these. For example, the sensitivity decreases in a low region where the absorbance is 0.1 or less. Also, the resolution becomes low due to the influence of halation. However, for the purpose of curing a thick film of, for example, 5 μm or more, there is a case where such a low absorbance can be increased instead. Further, in a region where the absorbance is as high as 3 or more, most of the light is absorbed on the surface of the photosensitive layer, and the internal curing is inhibited. For example, when used as a printing plate, the film strength and the substrate adhesion are poor. It will be insufficient.
For example, when the photosensitive composition of the present invention is used in the photosensitive layer of a lithographic printing plate precursor using a relatively thin film thickness, the amount of the sensitizing dye added is such that the absorbance of the photosensitive layer is 0.1 to 1. .5, preferably 0.25 to 1. Since the absorbance is determined by the addition amount of the sensitizing dye and the thickness of the photosensitive layer, the predetermined absorbance can be obtained by controlling both conditions. The absorbance of the photosensitive layer can be measured by a conventional method. As a measuring method, for example, on a transparent or white support, a photosensitive layer having a thickness appropriately determined in a range where the coating amount after drying is necessary as a lithographic printing plate is formed, and a transmission type optical densitometer is used. Examples thereof include a measuring method, a method of forming a recording layer on a reflective support such as aluminum, and measuring a reflection density.
When the photosensitive composition of the present invention is used as a photosensitive layer of a lithographic printing plate precursor, the addition amount of the sensitizing dye is usually 0.05 to 100 parts by mass with respect to 100 parts by mass of the total solid component constituting the photosensitive layer. It is 30 mass parts, Preferably it is 0.1-20 mass parts, More preferably, it is the range of 0.2-10 mass parts.

Next, (B) the initiator compound, which is the second essential component of the photoinitiating system in the photosensitive composition of the present invention, will be described.
(B) Initiator Compound The initiator compound in the present invention undergoes a chemical change due to the effects of electron transfer, energy transfer, heat generation, etc. caused by the electronic excitation state of the sensitizing dye, and consists of radicals, acids, and bases. A compound that produces at least one selected from the group.
Hereinafter, radicals, acids, and bases generated in this way are simply referred to as active species. When these compounds are not present, or when only the initiator compound is used alone, practically sufficient sensitivity cannot be obtained, but as one aspect of using the sensitizing dye and the active compound in combination, These can be used as a single compound by an appropriate chemical method (such as linking of a sensitizing dye and an initiator compound through a chemical bond).

Usually, many of these initiator compounds are considered to generate active species through the following initial chemical processes represented by (1) to (3). That is, (1) reductive decomposition of the initiator compound based on the electron transfer reaction from the electronically excited state of the sensitizing dye to the initiator compound, and (2) the electron transfer from the initiator compound to the electronically excited state of the sensitizing dye. (3) decomposition of the initiator compound from the electronically excited state based on energy transfer from the electronically excited state of the sensitizing dye to the initiator compound. Although it is often ambiguous as to which type (1) to (3) each individual initiator compound belongs, the major feature of the sensitizing dye in the present invention is any of these types of initiator compounds. Even if it is combined, it has a very high sensitizing effect.

As the initiator compound in the present invention, those known to those skilled in the art can be used without limitation, and specifically, for example, Bruce M. Monroe et al., Chemical Revue, 93, 435 (1993), RS Davidson, Journal, of Photochemistry and biology A: Chemistry, 73. 81 (1993) .JP
Faussier "Photoinitiated Polymerization-Theory and Applications": Rapra Review
vol. 9, Report, Rapra Technology (1998). M. Tsunooka et al., Prog. Polym. Sci., 21, 1 (1996). it can. Further, as other compound groups having the functions of (1) and (2), FD Saeva, Topics in Current Chemistry, 156, 59 (1990). GG Maslak, Topics in Current Chemistry, 168, 1 (1993) HB Shuster et al, JACS, 112, 6329 (1990). IDF Eaton et al., JACS, 102, 3298 (1980). The group of compounds that yields can also be used as initiator compounds.

  In the following, specific examples of preferred initiator compounds are: (a) those that are reduced to cause bond cleavage to generate active species, (b) those that can be oxidized to cause bond cleavage to generate active species, (c However, there are many cases where there is no general explanation as to which of the individual compounds belongs, and the present invention is not limited to the description of these reaction mechanisms.

(A) Those that are reduced to cause bond cleavage and generate active species.
Compound having a carbon-halogen bond: It is considered that a carbon-halogen bond is reductively cleaved to generate an active species (for example, described in Polymer Preprints, Jpn., 41 (3) 542 (1992). ) As the active species, radicals and acids can be generated. Specifically, for example, in addition to halomethyl-s-triazines, those skilled in the art can easily synthesize by the synthesis methods described in MP Hutt, EF Elslager and LM Merbel, Journal of Heterocyclic chemistry, 7, 511 (1970). Halomethyl oxadiazoles that can be used, and compounds described in German Patent Nos. 2641100, 3333450, 3021590, and 3021599 can be preferably used.

Compounds having a nitrogen-nitrogen bond or a nitrogen-containing heterocycle-nitrogen-containing heterocycle bond: reductive bond cleavage (for example, as described in J. Pys. Chem., 96, 207 (1992). ). Specifically, hexaarylbiimidazoles and the like are preferably used. The active species produced are lophine radicals, and in combination with hydrogen donors as necessary, radical chain reactions are initiated, and image formation using oxidation reactions with lophine radicals is also known (J. Imaging Sci.,
30, 215 (1986).

  Compounds having an oxygen-oxygen bond: It is considered that an oxygen-oxygen bond is reductively cleaved to generate an active radical (for example, described in Polym. Adv. Technol., 1, 287 (1990).) . Specifically, for example, organic peroxides are preferably used. A radical can be generated as an active species.

Onium compounds: It is considered that carbon-hetero bonds and oxygen-nitrogen bonds are reductively cleaved to generate active species (for example, as described in J. Photopolym. Sci. Technol., 3, 149 (1990). ing). Specifically, for example, iodonium salts described in European Patent No. 104143, U.S. Pat. No. 4,837,124, Japanese Patent Laid-Open No. 2-150848, and Japanese Patent Laid-Open No. 2-96514, European Patent Nos. 370693, 233567, 297443, 293442, 279210, 422570, U.S. Pat. Nos. 3,902,144, 4,933,377, 4,760013, 4,734,344 and 2,833,827, sulfonium salts and diazonium salts (which may have a substituent) Diazonium, etc.), diazonium salt resins (formaldehyde resin of diazodiphenylamine, etc.), N-alkoxypyridinium salts, etc. (for example, U.S. Pat. No. 4,743,528, JP-A-63-138345, JP-A-63-142345). No., JP 3-142346, JP-B-46-42363, etc., specifically 1-methoxy-4-phenylpyridinium tetrafluoroborate, etc.), and further, JP-B-52-147277, 52-14278. Nos. 52-14279 are preferably used. Generates radicals and acids as active species.

  Active esters: nitrobenzyl esters of sulfonic acid or carboxylic acid, esters of sulfonic acid or carboxylic acid with N-hydroxy compounds (N-hydroxyphthalimide, oxime, etc.), sulfonic acid esters of pyrogallol, naphthoquinone diazide-4 -Sulfonates can be reductively decomposed. As the active species, radicals and acids can be generated. Specific examples of the sulfonic acid esters include European Patent Nos. 0290750, 046083, 1156153, 271851, 0388343, U.S. Pat. Nos. 3,901,710 and 4,181,531, Japanese Patent Laid-Open No. 60-198538. Nitrobenzester compounds described in JP-A-53-133022, European Patents 0196672, 84515, 199672, 044115, 0101122, US Pat. Nos. 4,618,564, 4371605, and 4431774, The iminosulfonate compounds described in JP-A No. 64-18143, JP-A-2-245756, JP-A-4-365048, JP-B-62-2223, JP-B-63-14340, JP-A-59-174831 Compounds, etc. For example compounds may be mentioned below.

  (In the formula, Ar represents an aromatic group or an aliphatic group which may be substituted.)

Moreover, it is also possible to produce | generate a base as an active species, for example, the following compound groups are known.
Ferrocene and iron arene complexes: An active radical can be reductively generated. Specifically, for example, they are disclosed in JP-A-1-304453 and JP-A-1-152109.

(In the formula, R represents an optionally substituted aliphatic group or aromatic group.)
Disulfones: Reducing S—S bond reductively and generating an acid. For example, diphenyl disulfones as described in JP-A 61-166544 are known.

(B) Those that are oxidized to cause bond cleavage and generate active species.
Alkylate complex: It is considered that a carbon-hetero bond is oxidatively cleaved to generate an active radical (for example, as described in J. Am. Chem. Soc., 112, 6329 (1990)). Specifically, for example, triarylalkyl borates are preferably used.

  Alkylamine compound: It is considered that the C—X bond on carbon adjacent to nitrogen is cleaved by oxidation to generate an active radical (for example, J. Am. Chem. Soc., 116, 4211 (1994). As described in). X is preferably a hydrogen atom, a carboxyl group, a trimethylsilyl group, a benzyl group or the like. Specific examples include ethanolamines, N-phenylglycines, N-trimethylsilylmethylanilines, and the like.

  Sulfur-containing and tin-containing compounds: Compounds in which the nitrogen atoms of the above-described amines are replaced with sulfur atoms and tin atoms can generate active radicals by the same action. Further, a compound having an SS bond is also known to be sensitized by SS cleavage.

  α-Substituted methylcarbonyl compound: An active radical can be generated by oxidative cleavage of the carbonyl-α carbon bond. Moreover, what converted carbonyl into the oxime ether also shows the same effect | action. Specifically, 2-alkyl-1- [4- (alkylthio) phenyl] -2-morpholinopronone-1 and these and a hydroxylamine were reacted, and then N—OH was etherified. Mention may be made of oxime ethers.

  Sulfinic acid salts: An active radical can be reductively generated. Specific examples include sodium arylsulfinate.

(C) Although the sensitization mechanism is not clear, the compound can function as an initiator compound. Other sensitization mechanisms are not clear, but many of them can function as an initiator compound, and these are also the initiators in the present invention. It can be used as a compound. For example, organometallic compounds such as titanocene compounds and ferrocene compounds, aromatic ketones, acylphosphine, bisacylphosphine and the like can be mentioned, and radicals or acids can be generated as active species.

Hereinafter, among the initiator compounds used in the present invention, a preferred compound group particularly excellent in sensitivity and stability will be specifically exemplified.
(1) Halomethyltriazines Examples of halomethyltriazines include compounds represented by the following formula [II]. Particularly excellent in radical generation and acid generation ability.

In the formula [II], X represents a halogen atom. Y ¹ represents —CX ₃ , —NH ₂ , —NHR ¹ ′, —NR ¹ ′ ₂ , or —OR ¹ ′. Here, R ¹ ′ represents an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group. R ¹ represents —CX ₃ , an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, or a substituted alkenyl group.
Specific examples of such compounds 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- And triazine, 2- (α, α, β-trichloroethyl) -4,6-bis (trichloromethyl) -S-triazine, and the like. In addition, compounds described in GB 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 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-trichloromethyl S-triazine, 2- (4,7-dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2- (acenaphtho-5-yl) -4,6-bis-trichloro Examples of the compound described in DE 3337024, such as methyl-S-triazine, include the following compounds.

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 And -6-trichloromethyl-S-triazine.
Further, compounds described in JP-A No. 62-58241, for example, the following compounds can be mentioned.

  Further, compounds described in JP-A-5-281728, for example, the following compounds can be mentioned.

(3) Borate salt compounds Borate salts represented by the following formula [III] are excellent in radical generating ability.

In the formula [III], R ⁵¹ , R ⁵² , R ⁵³ and R ⁵⁴ 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. An alkenyl group, a substituted or unsubstituted alkynyl group, or a substituted or unsubstituted heterocyclic group, wherein R ⁵¹ , R ⁵² , R ⁵³ and R ⁵⁴ are combined to form a cyclic structure. May be. However, at least one of R ⁵¹ , R ⁵² , R ⁵³ and R ⁵⁴ is a substituted or unsubstituted alkyl group. Z ⁺ represents an alkali metal cation or a quaternary ammonium cation.

The alkyl groups of R ^{51 to} R ⁵⁴ include straight chain, 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, the following groups,

(Here, R ⁵⁵ and R ⁵⁶ independently represent a hydrogen atom, an alkyl group having 1 to 14 carbon atoms, or an aryl group.), —COOR ⁵⁷ (wherein R ⁵⁷ represents a hydrogen atom, having 1 to 14 carbon atoms. an alkyl group or an aryl group,), -. COOR ⁵⁸ or -OR ⁵⁹ (wherein R ⁵⁸ is included those having as a substituent a) an alkyl group or an aryl group, 1 to 14 carbon atoms..

Examples of the aryl group of R ^{51 to} R ⁵⁴ include 1 to 3 ring aryl groups such as a phenyl group and a naphthyl group, and examples of the substituted aryl group include the substitution of the above substituted alkyl group with the above aryl group. And those having an alkyl group having 1 to 14 carbon atoms.

Examples of the alkenyl group represented by R ^{51 to} R ⁵⁴ 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 ^{51 to} R ⁵⁴ 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 substituent of the substituted alkyl group. included.

In addition, examples of the heterocyclic group of R ^{51 to} R ⁵⁴ include a 5- or more-membered heterocyclic group containing at least one of N, S and O, preferably a 5- to 7-membered heterocyclic group. 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 formula [III] include compounds described in U.S. Pat. Nos. 3,567,453 and 4,434,891, European Patents 109772 and 109773, and those shown below.

(4) Hexaarylbiimidazoles Excellent in stability and capable of generating highly sensitive radicals. Specifically, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-bromophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 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′-bis (o-nitrophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-methylphenyl) -4,4 ′, 5,5 '-Tetraphenylbiimidazole, 2,2'-bis (o-tri Fluoromethylphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole and the like.

(5) Onium salt compounds 15 (5B), 16 (6B), and 17 (7B) group elements of the periodic table, specifically, N, P, As, Sb, Bi, O, S, Se, Te, I Onium compounds are sensitive initiator compounds, especially iodonium salts and sulfonium salts, especially diaryl iodonium,
Triarylsulfonium salt compounds are extremely excellent in terms of both sensitivity and storage stability. Acids and / or radicals can be generated, and these can be used properly by appropriately selecting the use conditions according to the purpose. Specific examples include the following compounds.

(6) Organic peroxide When an organic peroxide type initiator compound is used, radicals can be generated as active species with very high sensitivity.
(6) “Organic peroxide” as another example of the initiator compound (compound (B)) used in the present invention includes almost all organic compounds having one or more oxygen-oxygen bonds in the molecule. Examples thereof include, for example, methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, acetylacetone peroxide, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (t-butylperoxy) butane, t-butyl hydroperoxide, cumene hydroperoxide, Diisopropylbenzene hydroperoxide, parame Hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide , Dicumyl peroxide, bis (t-butylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t -Butylperoxy) hexyne-3, acetyl peroxide, isobutyryl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, succinic peroxide, peroxy Benzoyl oxide, 2,4-dichlorobenzoyl peroxide Meta-toluoyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, dimethoxyisopropyl peroxycarbonate, di (3-methyl-3-methoxybutyl ) Peroxydicarbonate, t-butylperoxyacetate, t-butylperoxypivalate, t-butylperoxyneodecanoate, t-butylperoxyoctanoate, t-butylperoxy-3,5 5-trimethylhexanoate, t-butyl peroxylaurate, t-butyl peroxybenzoate, di-t-butyl peroxyisophthalate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-Butyl peroxide maleate Acid, t-butylperoxyisopropyl carbonate, 3,3 ′, 4,4′-tetra- (t-butylperoxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra- (t-amylperoxy) Carbonyl) 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, carbonyldi (t-butylperoxydihydrogen diphthalate) , Carbonyldi (t-hexylperoxydihydrogen diphthalate) and the like.

  Among these, 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 ′ Peroxyesters such as tetra (cumylperoxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra (p-isopropylcumylperoxycarbonyl) benzophenone, di-t-butyldiperoxyisophthalate are preferred. .

(7) Titanocene compound As the titanocene compound suitable for the initiator compound, JP-A-59-152396, JP-A-61-151197, JP-A-63-41484, JP-A-2-249, and JP-A-2 And titanocene compounds described in each publication such as -4705.

  Specific examples of the titanocene compound include di-cyclopentadienyl-Ti-bis-phenyl, 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-methylcyclopenta Dienyl-Ti-bis-2,3,4,5,6-pentafluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1 − 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 (cyclopentadienyl) bis [2,6-difluoro-3- (N- Butylbialoyl-amino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-ethylacetylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-methylacetyl) Amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-ethylpropionylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3 -(N-ethyl- (2,2-dimethylbutanoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-butyl- (2,2-dimethylbutane) Noyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-pentyl- (2,2-dimethylbutyl) Noyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-hexyl)-(2,2-dimethylbutanoyl) phenyl] titanium, bis (cyclopentadienyl) ) Bis [2,6-difluoro-3- (N-methylbutyrylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-methylpentanoylamino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-ethylcyclohexylcarbonylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-ethyl) Isobutyrylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-ethylacetylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6- Difluoro-3- (2,2,5,5-tetramethyl-1,2,5-azadisilolidin-1-yl) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- ( Octylsulfonamido) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (4-tolylsulfonamide) Phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (4-dodecylphenyl sulfonyl) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,6-difluoro-3- (4- (1-pentylheptyl) phenylsulfonylamido) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3 -(Ethylsulfonylamido) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3-((4-bromophenyl) -sulfonylamido) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (2-naphthylsulfonylamido) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (hexadecylsulfonylamido) phenyl] titanium, bis (cyclo Pentadienyl) bis [2,6-difluoro-3- (N-methyl- (4-dodecylphenyl)] Ruhoniruamido) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-methyl-4- (1-pentylheptyl) phenyl) sulfonylamide)] titanium, bis (cyclopentadienyl) bis [2,6 -Difluoro-3- (N-hexyl- (4-tolyl) -sulfonylamido) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (pyrrolidine-2,5-dioni-1) -Yl) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (3,4-dimethyl-3-pyrrolidin-2,5-dioni-1-yl) phenyl] titanium, bis (Cyclopentadienyl) bis [2,6-difluoro-3- (phthalimido) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3 Isobutoxycarbonylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (ethoxycarbonylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro- 3-((2-chloroethoxy) -carbonylamino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,6-difluoro-3- (phenoxycarbonylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (3-phenylthioureido) Phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (3-butylthioureido) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- ( 3-phenylureido) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (3-butylureido) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro -3- (N, N-diacetylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro 3- (3,3-dimethyl-ureido) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,6-difluoro-3- (acetylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (butyrylamino) phenyl] titanium, bis (Cyclopentadienyl) bis [2,6-difluoro-3- (decanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (octadecanoylamino) phenyl] Titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (isobutyrylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (2-ethyl) Hexanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (2-methylbuta) Ylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (pivaloylamino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,6-difluoro-3- (2,2-dimethylbutanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (2 -Ethyl-2-methylheptanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (cyclohexylcarbonylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2 , 6-Difluoro-3- (2,2-dimethyl-3-chloropropanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (3-phenylpropanoylamino) Phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (2-chloromethyl-2-methyl) 3-chloro-propanoylamino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,6-difluoro-3- (3,4-xyloylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (4- Ethylbenzoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (2,4,6-mesitylcarbonylamino) phenyl] titanium, bis (cyclopentadienyl) bis [ 2,6-difluoro-3- (benzoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (3-phenylpropyl) benzoylamino) phenyl] titanium, bis (Cyclopentadienyl) bis [2,6-difluoro-3- (N- (3-ethylheptyl) -2,2-dimethylpentanoylamino ] Phenyl titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-isobutyl- (4-toluyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6- Difluoro-3- (N-isobutylbenzoylamino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-cyclohexylmethylpivaloylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N -(Oxolan-2-ylmethyl) benzoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (3-ethylheptyl) -2,2-dimethylbutanoylamino ) Phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (3-phenylpropyl- (4-toluyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (oxolani-2-ylmethyl)-(4-toluyl) amino) phenyl] titanium, bis (si Ropentajieniru) bis [2,6-difluoro -3- (N- (4- Toruirumechiru) benzoylamino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (4-toluylmethyl)-(4-toluyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6 -Difluoro-3- (N-butylbenzoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-butyl- (4-toluyl) amino) phenyl] titanium, bis (Cyclopentadienyl) bis [2,6-difluoro-3- (N-hexyl- (4-toluyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- ( N- (2,4-dimethylpentyl) -2,2-dimethylbutanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro- - (2,4-dimethylpentyl) -2,2-dimethyl pentanoylamino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,6-difluoro-3-((4-toluyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (2,2 -Dimethylpentanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (2,2-dimethyl-3-ethoxypropanoylamino) phenyl] titanium, bis (cyclopentadi) Enyl) bis [2,6-difluoro-3- (2,2-dimethyl-3-allyloxypropanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N -Allylacetylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (2-ethylbutanoylamino) Phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3-(N-cyclohexylmethyl-benzoylamino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-cyclohexylmethyl- (4-toluyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3 -(N- (2-ethylhexyl) benzoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-isopropylbenzoylamino) phenyl] titanium, bis (cyclopentadienyl) ) Bis [2,6-difluoro-3- (N- (3-phenylpropyl) -2,2-dimethylpentanoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro- 3- (N-hexylbenzoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro -3- (N-cyclohexylmethyl-2,2-dimethylpentanoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-butylbenzoylamino) phenyl] titanium ,

Bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (2-ethylhexyl) -2,2-dimethylpentanoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2 , 6-Difluoro-3- (N-hexyl-2,2-dimethylpentanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-isopropyl-2,2 -Dimethylpentanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (3-phenylpropyl) pivaloylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-butyl-2,2-dimethylpentanoylamino) phenyl] titanium, bis (cyclo Ntajieniru) bis [2,6-difluoro -3- (N- (2- methoxyethyl) benzoylamino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-benzylbenzoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-benzyl- (4-Toluyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (2-methoxyethyl)-(4-toluyl) amino) phenyl] titanium, bis (Cyclopentadienyl) bis [2,6-difluoro-3- (N- (4-methylphenylmethyl) -2,2-dimethylpentanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2 , 6-Difluoro-3- (N- (2-methoxyethyl) -2,2-dimethylpentanoylamino) phenyl] titanium, bis (cyclopentadiene) Le) bis [2,6-difluoro-3-(N-cyclohexylmethyl - (2-ethyl-2-methyl-heptanoyl) amino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-butyl- (4-chlorobenzoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3 -(N-hexyl- (2-ethyl-2-methylbutanoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-cyclohexyl-2,2-dimethyl) Pentanoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (oxolani-2-ylmethyl) -2,2-dimethylpentanoyl) amino) phenyl] titanium Bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-cyclohexyl- (4-chlorobenzoyl) amino) phenyl Titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-cyclohexyl- (2-chlorobenzoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro -3- (3,3-dimethyl-2-azetidinoni-1-yl) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,6-difluoro-3-isocyanatophenyl) titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-ethyl- (4-tolylsulfonyl) ) Amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-hexyl- (4-tolylsulfonyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [ 2,6-difluoro-3- (N-butyl- (4-tolylsulfonyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-isobutyl- (4- Tolylsulfonyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-butyl- (2,2-di) Chill -3 chloropropanoyl) amino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (3-phenylpropanoyl) -2,2-dimethyl-3-chloropropanoyl) amino) phenyl] titanium, bis (cyclopenta Dienyl) bis [2,6-difluoro-3- (N-cyclohexylmethyl- (2,2-dimethyl-3-chloropropanoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6 -Difluoro-3- (N-isobutyl- (2,2-dimethyl-3-chloropropanoyl) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-butyl- ( 2-chloromethyl-2-methyl-3-chloropropanoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3 (Butyl thiocarbonyl amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (phenylthio carbonylamino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,6-difluoro-3-isocyanatophenyl) titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-ethyl- (4-tolylsulfonyl) ) Amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-hexyl- (4-tolylsulfonyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [ 2,6-difluoro-3- (N-butyl- (4-tolylsulfonyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-isobutyl- (4- Tolylsulfonyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-butyl- (2,2-di) Til-3-chloropropanoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (3-phenylpropanoyl) -2,2-dimethyl-3- Chloropropanoyl) amino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-cyclohexylmethyl- (2,2-dimethyl-3-chloropropanoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-isobutyl- (2,2-dimethyl-3-chloropropanoyl) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N -Butyl- (2-chloromethyl-2-methyl-3-chloropropanoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (butylthiocarbonylamino) phenyl] Titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (phenylthiocarbonylamino) phenyl] titanium, bis Methylcyclopentadienyl) bis [2,6-difluoro-3-(N-hexyl-2,2-dimethyl-butanoylamino) amino) phenyl] titanium,

Bis (methylcyclopentadienyl) bis [2,6-difluoro-3- (N-hexyl-2,2-dimethylpentanoylamino) phenyl] titanium, bis (methylcyclopentadienyl) bis [2,6- Difluoro-3- (N-ethylacetylamino) phenyl] titanium, bis (methylcyclopentadienyl) bis [2,6-difluoro-3- (N-ethylpropionylamino) phenyl] titanium, bis (trimethylsilylpentadienyl) ) Bis [2,6-difluoro-3- (N-butyl-2,2-dimethylpropanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- ( 2-methoxyethyl) -trimethylsilylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6- Fluoro-3- (N-butylhexyldimethylsilylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-ethyl- (1,1,2, -trimethylpropyl) Dimethylsilylamino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,6-difluoro-3- (3-ethoxymethyl-3-methyl-2-azethiodinon-1-yl) phenyl] titanium, bis (cyclopentadienyl) bis [2, 6-difluoro-3- (3-allyloxymethyl-3-methyl-2-azetidinon-1-yl) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (3-chloro Methyl-3-methyl-2-azetidinoni-1-yl) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-benzyl-2,2-dimethylpropanoylamino) phenyl ] Titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (5,5-dimethyl-2-pyrrolidinoni-1-yl) phenyl] tita , Bis (cyclopentadienyl) bis [2,6-difluoro-3- (6,6-diphenyl-2-Piperijinoni-1-yl) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (2,3-dihydro-1,2-benzisothiazolo-3-one (1,1-dioxide) -2-yl) phenyl] Titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-hexyl- (4-chlorobenzoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro -3- (N-hexyl- (2-chlorobenzoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-isopropyl- (4-chlorobenzoyl) amino) Phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (4-methylphenylmethyl)-(4-chlorobenzoyl) a Roh) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3-(N-(4-methylphenyl methyl) - (2-chlorobenzoyl) amino) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,6-difluoro-3- (N-butyl- (4-chlorobenzoyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3 -(N-benzyl-2,2-dimethylpentanoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (2-ethylhexyl) -4-tolyl-sulfonyl] ) Amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (3-oxaheptyl) benzoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2 , 6-Difluoro-3- (N- (3,6-dioxadecyl) benzoylamino) phenyl] titanium, bis (cyclopentadienyl) bi [2,6-difluoro-3- (trifluoromethylsulfonyl) amino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (trifluoroacetyl) phenyl] titanium,

Bis (cyclopentadienyl) bis [2,6-difluoro-3- (2-chlorobenzoyl) amino] phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (4-chloro Benzoyl) amino] phenyl] titanium, bis (cyclopentadienyl) bis [2,6-difluoro-3- (N- (3,6-dioxadecyl) -2,2-dimethylpentanoylamino) phenyl] titanium, bis (Cyclopentadienyl) bis [2,6-difluoro-3- (N- (3,7-dimethyl-7-methoxyoctyl) benzoylamino) phenyl] titanium, bis (cyclopentadienyl) bis [2,6 -Difluoro-3- (N-cyclohexylbenzoylamino) phenyl] titanium and the like.

  Preferable initiator compounds include halomethyltriazines, hexaarylbiimidazoles, and titanocene compounds, and particularly preferably hexaarylbiimidazoles.

  The initiator compound described above can also be subjected to various chemical modifications for improving the characteristics of the photosensitive layer as in the case of the sensitizing dye. For example, bonding with sensitizing dyes, addition-polymerizable unsaturated compounds and other initiator compound parts, introduction of hydrophilic sites, compatibility improvement, introduction of substituents for suppressing crystal precipitation, substituents for improving adhesion Methods such as introduction and polymerization can be used.

The method of using these initiator compounds can be arbitrarily set as appropriate depending on the performance design of the light-sensitive material as in the case of the sensitizing dye described above. For example, by using two or more kinds in combination, the compatibility with the photosensitive layer can be increased.
A larger amount of the initiator compound is usually advantageous in terms of photosensitivity, and is used in a range of 0.5 to 80 parts by weight, preferably 1 to 50 parts by weight, with respect to 100 parts by weight of the photosensitive layer component. Sufficient photosensitivity can be obtained.

Third essential component in the photosensitive composition of the present invention “(C) Compound whose physical or chemical properties are irreversibly changed by at least one of radical, acid and base generated from an initiator compound” ”Is a compound that is generated by the photoreaction of the above-mentioned photoinitiating system, and its physical or chemical characteristics are irreversibly changed by the action of the active species, and a curing reaction, color development, decoloring reaction, etc. occur. Any compound having such properties can be used without particular limitation. For example, the compounds listed in the above-mentioned initiation system themselves often have such properties.
The characteristics of the compound (C) that changes depending on the radical, acid, and / or base generated from the photoinitiating system include, for example, molecular properties such as absorption spectrum (color), chemical structure, polarizability, and solubility. , Changes in material physical properties such as strength, refractive index, fluidity, and adhesiveness.

For example, if a compound whose absorption spectrum changes with pH, such as a pH indicator, is used as the component (C) polymerizable compound and an acid or base is generated from the initiation system, the color tone can be changed only in the exposed area. Such a composition is useful as an image forming material. Similarly, when a compound whose absorption spectrum is changed by oxidation / reduction or nucleophilic addition reaction is used as (C), it is possible to form an image by causing oxidation or reduction by radicals generated from the initiation system. Such examples are described, for example, in J. Am. Chem. Soc., 108, 128 (1986), J. Imaging. Soc., 30, 215 (1986), Israel. J. Chem., 25, 264. (1986).

  Among these, as the compound (C), (C-1) a polymerizable compound that reacts with a radical, an acid, and / or a base (hereinafter appropriately referred to as a polymerizable compound), specifically, addition polymerization or heavy polymerization. A photocurable resin or a negative photopolymer can be formed by using a condensable compound and combining with an initiation system. Such a composition is also useful as a negative photosensitive layer of a lithographic printing plate precursor.

  Examples of such component (C) include radical polymerizable compounds (such as compounds having an ethylenically unsaturated bond), cationic polymerizable compounds (such as epoxy compounds, vinyl ether compounds, and methylol compounds), anionic polymerizable compounds (such as epoxy compounds). Such examples are described in, for example, Photopolymer Social Society, Photopolymer Handbook, published by Industrial Research Institute (1989), Polymer, Vol. 45, 786 (1996). A composition using a thiol compound as (C) and combined with a photoradical generation system is also well known.

  It is also useful to use an acid-decomposable compound as (C) and combine it with a photoacid generator. For example, a material that uses a polymer whose side chain or main chain is decomposed by an acid and changes its solubility or hydrophilicity / hydrophobicity by light is widely used as a photodegradable photosensitive resin or a positive photopolymer. Such specific examples are, for example, ACS. Symp. Ser. 242, 11 (1984), JP-A-60-3625, U.S. Pat. Nos. 5102771, 5206317, 5212047, JP-A-4-26850, JP-A-3-1921731, JP-A-60-10247, JP-A-62-245050 and the like.

  In the following, one of the main uses of the photosensitive composition of the present invention, the case of using an addition polymerizable compound which is a compound (C) that is particularly excellent for the purpose of obtaining a highly sensitive lithographic printing plate precursor. Take an example and explain in more detail.

(C-1) Addition polymerizable compound An addition polymerizable compound having at least one ethylenically unsaturated double bond, which is a preferred compound (C) used in the present invention, has at least one terminal ethylenically unsaturated bond. It is selected from compounds having, preferably two or more. Such compound groups are widely known in the industrial field, and these can be used without any particular limitation in the present invention. These have chemical forms such as monomers, prepolymers, i.e. dimers, trimers and oligomers, or mixtures thereof and copolymers thereof. Examples of monomers and copolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), and esters and amides thereof. In this case, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound is used. In addition, unsaturated carboxylic acid ester having a nucleophilic substituent such as hydroxyl group, amino group, mercapto group, amide and monofunctional or polyfunctional isocyanate, addition reaction product of epoxy, monofunctional or polyfunctional A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. In addition, an unsaturated carboxylic acid ester having an electrophilic substituent such as an isocyanato group or an epoxy group, an addition reaction product of an amide with a monofunctional or polyfunctional alcohol, an amine or a thiol, a halogen group Also suitable are substitution reaction products of unsaturated carboxylic acid esters, amides with monofunctional or polyfunctional alcohols, amines, and thiols having a leaving substituent such as a tosyloxy group. As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid.

  Specific examples of the monomer of an ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol. Diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate , Tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate , Pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer.

  Methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, Hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacryloxy- 2-hydroxypro ) Phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane.

  Itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate And sorbitol tetritaconate.

Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate.
Examples of isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate.

Examples of maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.
Examples of other esters include aliphatic alcohol esters described in JP-B-46-27926, JP-B-51-47334, JP-A-57-196231, JP-A-59-5240, JP Those having an aromatic skeleton described in JP-A-59-5241 and JP-A-2-226149, those containing an amino group described in JP-A-1-165613, and the like are also preferably used.
The aforementioned ester monomers can also be used as a mixture.

Specific examples of amide monomers of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis. -Methacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide and the like.
Examples of other preferable amide monomers include those having a cyclohexylene structure described in JP-B No. 54-21726.

  In addition, urethane-based addition polymerizable compounds produced by using an addition reaction of isocyanate and hydroxyl group are also suitable, and specific examples thereof include, for example, one molecule described in JP-B-48-41708. A vinyl urethane containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group represented by the following general formula (V) to a polyisocyanate compound having two or more isocyanate groups. Compounds and the like.

_{CH 2 = C (R) COOCH} 2 CH (R ') OH (V)
(However, R and R ′ represent H or CH _3. )

  Also, urethane acrylates such as those described in JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765, JP-B-58-49860, JP-B-56-17654, Urethane compounds having an ethylene oxide skeleton described in JP-B-62-39417 and JP-B-62-39418 are also suitable.

  Further, by using addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238, It is possible to obtain a photosensitive composition having an extremely excellent photosensitive speed.

  Other examples include polyester acrylates, epoxy resins and (meth) acrylic acid as described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, and JP-A-52-30490. Mention may be made of polyfunctional acrylates and methacrylates such as reacted epoxy acrylates. Further, specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337 and JP-B-1-40336, vinylphosphonic acid compounds described in JP-A-2-25493, and the like can also be mentioned. . In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, Journal of Japan Adhesion Association vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photocurable monomers and oligomers, can also be used.

About these addition polymerizable compounds, the details of usage, such as the structure, single use or combination, addition amount, etc. can be arbitrarily set according to the performance design of the final lithographic printing plate precursor. For example, it is selected from the following viewpoints. From the viewpoint of photosensitive speed, a structure having a high unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. Further, in order to increase the strength of the image portion, that is, the cured film, those having three or more functionalities are preferable, and furthermore, different functional numbers and different polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrenic compound, vinyl ether type). A method of adjusting both photosensitivity and intensity by using a compound) is also effective. A compound having a large molecular weight or a compound having high hydrophobicity is excellent in photosensitive speed and film strength, but is not preferable in terms of development speed and precipitation in a developer. In addition, the selection and use method of the addition polymerization compound is also an important factor for the compatibility and dispersibility with other components in the photosensitive layer (for example, binder polymer, initiator, colorant, etc.). The compatibility may be improved by using a low-purity compound or using two or more kinds in combination. In addition, a specific structure may be selected for the purpose of improving the adhesion of the substrate and an overcoat layer described later. Regarding the compounding ratio of the addition polymerizable compound in the photosensitive layer, a larger amount is more advantageous in terms of sensitivity, but if it is too much, an undesirable phase separation occurs or a problem in the production process due to the adhesiveness of the photosensitive layer. For example, problems such as transfer of photosensitive layer components and manufacturing defects due to adhesion, and precipitation from a developer may occur. From these viewpoints, the addition polymerizable compound is preferably used in the range of 5 to 80% by mass, and more preferably 25 to 75% by mass with respect to the nonvolatile component in the photosensitive layer. These may be used alone or in combination of two or more. In addition, the use method of the addition polymerizable compound can be arbitrarily selected from the viewpoint of polymerization inhibition with respect to oxygen, resolution, fogging, refractive index change, surface adhesiveness, etc. Depending on the case, a layer configuration and coating method such as undercoating and overcoating can be performed.

  As the component (C), the content in the case of using a compound other than the polymerizable compound (C-1) can be appropriately selected as appropriate depending on the intended property change or the compound used. When a compound whose absorption spectrum is changed by oxidation / reduction or nucleophilic addition reaction is used, it is preferably about 10 to 80% by mass in the total solid content of the composition.

(D) Binder polymer In application to the photosensitive layer of a lithographic printing plate precursor which is a preferred embodiment of the photosensitive composition of the present invention, a binder polymer is further used in the photosensitive composition from the viewpoint of improving film properties. It is preferable to do.
As the binder polymer, it is preferable to contain a linear organic polymer. As such a “linear organic polymer”, any compound may be used, but preferably water or weak alkaline water soluble or swellable that enables water development or weak alkaline water development. A linear organic polymer is selected. The linear organic high molecular polymer is selected and used not only as a film-forming agent for the composition but also according to its use as water, weak alkaline water or an organic solvent developer. For example, when a water-soluble organic polymer is used, water development is possible. Examples of such linear organic high molecular polymers include addition polymers having a carboxylic acid group in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, and JP-B-sho. 54-25957, JP-A-54-92723, JP-A-59-53836, JP-A-59-71048, ie, methacrylic acid copolymer, acrylic acid copolymer, itacon Examples include acid copolymers, crotonic acid copolymers, maleic acid copolymers, and partially esterified maleic acid copolymers. Similarly, there is an acidic cellulose derivative having a carboxylic acid group in the side chain. In addition, those obtained by adding a cyclic acid anhydride to an addition polymer having a hydroxyl group are useful.

Among these, [benzyl (meth) acrylate / (meth) acrylic acid / other addition polymerizable vinyl monomers as required] copolymer and [allyl (meth) acrylate / (meth) acrylic acid / as required Other addition-polymerizable vinyl monomers] are preferred because they are excellent in the balance of film strength, sensitivity and developability.
In addition, Japanese Patent Publication No. 7-2004, Japanese Patent Publication No. 7-120041, Japanese Patent Publication No. 7-120042, Japanese Patent Publication No. 8-12424, Japanese Patent Laid-Open No. 63-287944, Japanese Patent Laid-Open No. 63-287947, Japanese Patent Laid-Open No. Urethane binder polymers containing acid groups described in Japanese Patent No. 271741 and Japanese Patent Application No. 10-116232 are very excellent in strength, and are advantageous in terms of printing durability and suitability for low exposure.
A binder having an amide group described in JP-A No. 11-171907 is suitable because it has excellent developability and film strength.

In addition, polyvinyl pyrrolidone, polyethylene oxide, and the like are useful as the water-soluble linear organic polymer. In order to increase the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are also useful. These linear organic high molecular polymers can be mixed in an arbitrary amount in the entire composition. However, when it exceeds 90% by mass, a preferable result is not given in terms of the strength of the formed image. Preferably it is 30-85 mass%. The photopolymerizable compound having an ethylenically unsaturated double bond and the linear organic polymer are preferably in the range of 1/9 to 7/3 by mass ratio. In a preferred embodiment, a binder polymer that does not require water and is soluble in alkali is used. By doing so, an organic solvent that is not environmentally preferable is not used as the developer, or the amount can be limited to a very small amount. In such a method of use, the acid value of the binder polymer (the acid content per gram of polymer expressed as a chemical equivalent number) and the molecular weight are appropriately selected from the viewpoint of image strength and developability. The preferred acid value is 0.4 to 3.0 meq / g, the preferred molecular weight is in the range of 3000 to 500,000 in terms of weight average molecular weight, more preferably the acid value is 0.6 to 2.0 meq / g, The weight average molecular weight is in the range of 10,000 to 300,000.

(E) Other components The photosensitive composition of the present invention may further contain other components suitable for its use and production method. Hereinafter, preferred additives will be exemplified.
(E-1) Co-sensitizer The sensitivity can be further improved by using a certain additive (hereinafter referred to as a co-sensitizer). These mechanisms of action are not clear, but many are thought to be based on the following chemical processes. That is, the photosensitivity initiated by the thermal polymerization initiator and the subsequent intermediate polymerization species (radicals and cations) generated in the course of the addition polymerization reaction react with the co-sensitizer to generate new active radicals. It is estimated that These can be broadly divided into (a) those that can be reduced to generate active radicals, (b) those that can be oxidized to generate active radicals, and (c) radicals that are more active by reacting with less active radicals. Can be classified into those that act as chain transfer agents, but there is often no generality as to which of these individual compounds belong.

(A) Compound that is reduced to produce an active radical Compound having a carbon-halogen bond: It is considered that the carbon-halogen bond is reductively cleaved to generate an active radical. Specifically, for example, trihalomethyl-s-triazines and trihalomethyloxadiazoles can be preferably used.
Compound having nitrogen-nitrogen bond: It is considered that the nitrogen-nitrogen bond is reductively cleaved to generate an active radical. Specifically, hexaarylbiimidazoles and the like are preferably used.
Compound having oxygen-oxygen bond: It is considered that an oxygen-oxygen bond is reductively cleaved to generate an active radical. Specifically, for example, organic peroxides are preferably used.
Onium compounds: It is considered that carbon-hetero bonds and oxygen-nitrogen bonds are reductively cleaved to generate active radicals. Specifically, for example, diaryliodonium salts, triarylsulfonium salts, N-alkoxypyridinium (azinium) salts and the like are preferably used.
Ferrocene and iron arene complexes: An active radical can be reductively generated.

(B) Compound which is oxidized to generate an active radical Alkylate complex: It is considered that a carbon-hetero bond is oxidatively cleaved to generate an active radical. Specifically, for example, triarylalkyl borates are preferably used.
Alkylamine compound: It is considered that the C—X bond on carbon adjacent to nitrogen is cleaved by oxidation to generate an active radical. X is preferably a hydrogen atom, a carboxyl group, a trimethylsilyl group, a benzyl group or the like. Specific examples include ethanolamines, N-phenylglycines, N-trimethylsilylmethylanilines, and the like.
Sulfur-containing and tin-containing compounds: Compounds in which the nitrogen atoms of the above-described amines are replaced with sulfur atoms and tin atoms can generate active radicals by the same action. Further, a compound having an SS bond is also known to be sensitized by SS cleavage.

α-Substituted methylcarbonyl compound: An active radical can be generated by oxidative cleavage of the carbonyl-α carbon bond. Moreover, what converted carbonyl into the oxime ether also shows the same effect | action. Specifically, 2-alkyl-1- [4- (alkylthio) phenyl] -2-morpholinopronone-1 and these and a hydroxylamine were reacted, and then N—OH was etherified. Oxime ethers can be listed.
Sulfinic acid salts: An active radical can be reductively generated. Specific examples include arylsulfin sodium.

(C) Compounds that react with radicals to convert to highly active radicals or act as chain transfer agents: For example, compounds having SH, PH, SiH, GeH in the molecule are used. These can generate hydrogen by donating hydrogen to a low-activity radical species to generate radicals, or after being oxidized and deprotonated. Specific examples include 2-mercaptobenzimidazoles.

  More specific examples of these co-sensitizers are described, for example, in JP-A-9-236913 as additives for the purpose of improving sensitivity, and these are also applied in the present invention. be able to. Some examples are shown below, but the present invention is not limited thereto. In the following formulae, -TMS represents a trimethylsilyl group.

These co-sensitizers can also be subjected to various chemical modifications for improving the characteristics of the photosensitive layer as in the case of the above sensitizing dye. For example, bonds with sensitizing dyes, initiator compounds, addition polymerizable unsaturated compounds and other parts, introduction of hydrophilic sites, compatibility improvement, introduction of substituents for suppressing crystal precipitation, substituents for improving adhesion Methods such as introduction and polymerization can be used.
These co-sensitizers can be used alone or in combination of two or more. The amount used is 0.05 to 100 parts by weight, preferably 1 to 80 parts by weight, and more preferably 3 to 50 parts by weight with respect to 100 parts by weight of the compound having an ethylenically unsaturated double bond.

(E-2) Polymerization inhibitor In the present invention, in addition to the above basic components, unnecessary thermal polymerization of a compound having an ethylenically unsaturated double bond that can be polymerized during production or storage of the photosensitive composition. In order to prevent this, it is desirable to add a small amount of a thermal polymerization inhibitor. Suitable thermal polymerization inhibitors include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol ), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt and the like. The addition amount of the thermal polymerization inhibitor is preferably about 0.01% by mass to about 5% by mass with respect to the mass of the entire composition. In addition, if necessary, a higher fatty acid derivative such as behenic acid or behenic acid amide is added to prevent polymerization inhibition due to oxygen, and a lithographic printing plate precursor is used. It may be unevenly distributed on the surface of the photosensitive layer in the course of drying. The amount of the higher fatty acid derivative added is preferably about 0.5% by mass to about 10% by mass of the total composition.

(E-3) Colorant, etc. Furthermore, when the photosensitive composition of the present invention is used for a lithographic printing plate precursor, a dye or pigment may be added for the purpose of coloring the photosensitive layer. Thereby, so-called plate inspection properties such as visibility after plate making and suitability for an image density measuring machine as a printing plate can be improved. As the colorant, many dyes cause a decrease in the sensitivity of the photopolymerization type photosensitive layer. Therefore, it is particularly preferable to use a pigment as the colorant. Specific examples include pigments such as phthalocyanine pigments, azo pigments, carbon black and titanium oxide, and dyes such as ethyl violet, crystal violet, azo dyes, anthraquinone dyes, and cyanine dyes. The addition amount of the dye and the pigment is preferably about 0.5% by mass to about 5% by mass of the total composition.

(E-4) Other additives Furthermore, when the photosensitive composition of the present invention is used for a lithographic printing plate precursor, an inorganic filler, other plasticizer, or photosensitive layer surface is used to improve the physical properties of the cured film. You may add well-known additives, such as a fat-sensitizing agent which can improve ink inking property.

  Examples of plasticizers include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, and triacetyl glycerin. 10 mass% or less can be added with respect to the total mass of the compound which has an ionic unsaturated double bond, and a binder.

Further, for the purpose of improving the film strength (printing durability) described later, a UV initiator, a mature crosslinking agent, or the like can be added to enhance the effect of heating and exposure after development.
In addition, it is possible to provide an additive and an intermediate layer for improving the adhesion between the photosensitive layer and the support and improving the development removability of the unexposed photosensitive layer. For example, by adding or undercoating a compound having a relatively strong interaction with the substrate, such as a compound having a diazonium structure or a phosphone compound, adhesion can be improved and printing durability can be improved. By adding or undercoating with a hydrophilic polymer such as acid or polysulfonic acid, the developability of the non-image area is improved, and the stain resistance can be improved.

In order to produce a lithographic printing plate precursor, when the photosensitive composition of the present invention is applied on a support to form a photosensitive layer, it is dissolved in various organic solvents and used. Solvents used here include acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, Acetylacetone, cyclohexanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol monomethyl ether, Ethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, methyl lactate, lactic acid There are ethyl and the like. These solvents can be used alone or in combination. The solid content in the coating solution is suitably 2 to 50% by mass.

The coating amount of the photosensitive layer on the support is preferably selected as appropriate according to the use in consideration of the sensitivity of the photosensitive layer, the developability, the strength of the exposed film and the printing durability. When the coating amount is too small, the printing durability is not sufficient. On the other hand, if the amount is too large, the sensitivity is lowered, it takes time for exposure, and a longer time is required for development processing, which is not preferable. The coating amount as a photosensitive layer of a lithographic printing plate precursor for scanning exposure, which is a preferred use mode of the photosensitive composition of the present invention, is generally about 0.00 by weight after drying. A range of lg / m ² to about 10 g / m ² is suitable. More preferably from 0.5 to 5 g / m ^2.

  When the photosensitive composition of the present invention is used as a photosensitive layer of a lithographic printing plate precursor, it is represented by the general formula (1) or the general formula (2) as a sensitizing dye from the viewpoint of sensitivity and storage stability. It is preferable to use an initiator system in which hexaarylbiimidazoles are combined as an initiator compound, and an embodiment containing an initiator system composed of these compounds and (C-1) an addition polymerizable compound is particularly preferable.

(Support)
In order to obtain a lithographic printing plate precursor using the photosensitive composition of the present invention, it is desirable to provide the photosensitive layer on a support having a hydrophilic surface. As the hydrophilic support, a conventionally known hydrophilic support used in a lithographic printing plate can be used without limitation. The support used is preferably a dimensionally stable plate, for example, paper, paper laminated with plastic (eg, polyethylene, polypropylene, polystyrene, etc.), metal plate (eg, aluminum, zinc). , Copper, etc.), plastic films (eg, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc.) It is done. These may be a single component sheet such as a resin film or a metal plate, or may be a laminate of two or more materials. For example, a paper or plastic film on which a metal as described above is laminated or vapor-deposited. And laminated sheets of different plastic films. Also, these surfaces may be subjected to appropriate known physical and chemical treatments for the purpose of imparting hydrophilicity and improving strength, if necessary.

Particularly preferred supports include paper, polyester film or aluminum plate, among which dimensional stability is good and relatively inexpensive, and a surface with excellent hydrophilicity and strength can be provided by surface treatment as required. An aluminum plate is particularly preferred. A composite sheet in which an aluminum sheet is bonded on a polyethylene terephthalate film as described in Japanese Patent Publication No. 48-18327 is also preferable.

  A suitable aluminum plate is a pure aluminum plate or an alloy plate containing aluminum as a main component and containing a trace amount of foreign elements, and may be a plastic film on which aluminum is laminated or vapor-deposited. 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 at most 10% by mass. Particularly suitable aluminum in the present invention is pure aluminum, but completely pure aluminum is difficult to produce in the refining technique, and may contain slightly different elements. Thus, the composition of the aluminum plate applied to the present invention is not specified, and an aluminum plate made of a publicly known material can be appropriately used. The thickness of the aluminum plate used in the present invention is about 0.1 mm to 0.6 mm, preferably 0.15 mm to 0.4 mm, particularly preferably 0.2 mm to 0.3 mm.

In the case of a support having a surface of metal, particularly aluminum, roughening (graining) treatment, immersion treatment in an aqueous solution of sodium silicate, potassium fluoride zirconate, phosphate, etc., or anodic oxidation treatment, etc. It is preferable that surface treatment is performed.
Prior to roughening the aluminum plate, a degreasing treatment with, for example, a surfactant, an organic solvent, or an alkaline aqueous solution 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, a method of mechanically roughening, a method of electrochemically dissolving and roughening a surface, and a method of selectively dissolving a surface chemically. This is done by the method of As the mechanical method, 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. Further, as an electrochemical surface roughening method, there is a method of performing alternating current or direct current in hydrochloric acid or nitric acid electrolyte. Further, as disclosed in JP-A-54-63902, a method in which both are combined can also be used.
The aluminum plate roughened in this way can be subjected to an anodizing treatment to enhance the water retention and wear resistance of the surface through an alkali etching treatment and a neutralization treatment, if desired. 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, phosphoric 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.

Furthermore, an aluminum plate that has been roughened and then immersed in an aqueous sodium silicate solution can be preferably used. As described in Japanese Examined Patent Publication No. 47-5125, an aluminum plate which has been anodized and then immersed in an aqueous solution of an alkali metal silicate is preferably used. The anodizing treatment is carried out in an electrolytic solution in which an inorganic acid such as phosphoric acid, chromic acid, sulfuric acid or boric acid, or an organic acid such as oxalic acid or sulfamic acid, or a salt solution thereof, or a combination of two or more thereof, is used. This is carried out by passing an electric current using the aluminum plate as an anode.
Silicate electrodeposition as described in US Pat. No. 3,658,662 is also effective as a hydrophilic treatment for the support. A surface obtained by combining a support subjected to electrolytic grain as disclosed in JP-B-46-27481, JP-A-52-58602, and JP-A-52-30503 with the above-described anodizing treatment and sodium silicate treatment. Processing is also useful. Further, those obtained by performing mechanical surface roughening, chemical etching, electrolytic graining, anodizing treatment, and sodium silicate treatment in this order as disclosed in JP-A-56-28893 are also suitable.

Furthermore, after performing these treatments, water-soluble resins such as polyvinylphosphonic acid, polymers and copolymers having sulfonic acid groups in the side chain, polyacrylic acid, water-soluble metal salts (for example, zinc borate) or Those having a primer such as a yellow dye or an amine salt are also suitable.
Further, a sol-gel treated substrate in which a functional group capable of causing an addition reaction by a radical as disclosed in JP-A-7-159983 is covalently used.
As another preferred example, a substrate provided with a water-resistant hydrophilic layer as a surface layer on an arbitrary support can be raised. Examples of such a surface layer include a layer composed of an inorganic pigment and a binder described in U.S. Pat. No. 3,055,295 and JP-A-56-13168, a hydrophilic swelling layer described in JP-A-9-80744, Examples thereof include sol-gel films made of titanium oxide, polyvinyl alcohol, and silicic acids described in 8-507727.
These hydrophilic treatments are performed to make the surface of the support hydrophilic, in order to prevent harmful reactions of the photosensitive composition provided thereon, and to improve the adhesion of the photosensitive layer, etc. It is for the purpose.

(Protective layer)
When the photosensitive composition of the present invention is used in a lithographic printing plate precursor for scanning exposure, a protective layer can be provided on the photosensitive layer containing a polymerizable compound as necessary. Such a lithographic printing plate precursor is usually exposed in the air, but the protective layer is a low molecular weight molecule such as oxygen or a basic substance present in the air that inhibits the image forming reaction caused by exposure in the photosensitive layer. This prevents the compound from being mixed into the photosensitive layer and prevents the inhibition of the image forming reaction due to exposure in the air. Therefore, the properties desired for such a protective layer are low permeability of low-molecular compounds such as oxygen, furthermore, good transparency of light used for exposure, excellent adhesion to the photosensitive layer, And it is desirable that it can be easily removed in the development process after exposure.

  Such a device for the protective layer has been conventionally devised, which is described in detail in US Pat. No. 3,458,311 and JP-A-55-49729. As a material that can be used for the protective layer, for example, a water-soluble polymer compound having relatively excellent crystallinity is preferably used. Specifically, polyvinyl alcohol, polyvinyl pyrrolidone, acidic celluloses, gelatin, gum arabic, Water-soluble polymers such as acrylic acid are known, but among these, using polyvinyl alcohol as a main component gives the best results in terms of basic properties such as oxygen barrier properties and development removability. The polyvinyl alcohol used for the protective layer may be partially substituted with an ester, an ether, and an acetal as long as it contains an unsubstituted vinyl alcohol unit for having necessary oxygen barrier properties and water solubility. Similarly, some of them may have other copolymer components. In particular, a mixture obtained by replacing polyvinyl pyrrolidone in a range of 15 to 50% by mass with respect to polyvinyl alcohol is preferable from the viewpoint of storage stability.

  Specific examples of polyvinyl alcohol include those having a hydrolysis rate of 71 to 100% and a molecular weight in the range of 300 to 2400. Specifically, PVA-105, PVA-110, PVA-117, PVA-117H, PVA-120, PVA-124, PVA-124H, PVA-CS, PVA-CST, PVA-HC, manufactured by Kuraray Co., Ltd. PVA-203, PVA-204, PVA-205, PVA-210, PVA-217, PVA-220, PVA-224, PVA-217EE, PVA-217E, PVA-220E, PVA-224E, PVA-405, PVA- 420, PVA-613, L-8 and the like.

Components of the protective layer (selection of PVA, use of additives), coating amount, and the like are selected in consideration of fogging, adhesion, and scratch resistance in addition to oxygen barrier properties and development removability. In general, the higher the hydrolysis rate of the PVA used (the higher the content of the unsubstituted vinyl alcohol unit in the protective layer), the thicker the film thickness, the higher the oxygen barrier property, which is advantageous in terms of sensitivity. However, when the oxygen barrier property is extremely increased, there arises a problem that unnecessary polymerization reaction occurs during production and raw storage, and unnecessary fogging and image line thickening occur during image exposure. In addition, adhesion to the image area and scratch resistance are extremely important in handling the plate. That is, when a hydrophilic layer made of a water-soluble polymer is laminated on a new oil-based polymer layer, film peeling due to insufficient adhesion tends to occur, and the peeled part causes defects such as poor film hardening due to inhibition of oxygen polymerization.

  On the other hand, various proposals have been made to improve the adhesion between these two layers. For example, U.S. Pat. No. 292,501 and U.S. Pat. No. 44,563 contain 20-60 of acrylic emulsion or water-insoluble vinylpyrrolidone-vinyl acetate copolymer in a hydrophilic polymer mainly composed of polyvinyl alcohol. It is described that sufficient adhesion can be obtained by mixing by mass% and laminating on a polymerized layer. Any of these known techniques can be applied to the protective layer in the present invention. Such a coating method of the protective layer is described in detail in, for example, US Pat. No. 3,458,311 and JP-A-55-49729.

  Furthermore, other functions can be imparted to the protective layer. For example, by adding a colorant (such as a water-soluble dye) that is excellent in transparency of light used for exposure (for example, a wavelength of 760 to 1200 nm for an infrared laser) and can efficiently absorb light of a wavelength that is not related to exposure. Therefore, the suitability for safelight can be further enhanced without lowering the sensitivity.

  When a lithographic printing plate precursor using the photosensitive composition of the present invention is made into a lithographic printing plate, it is usually subjected to an exposure process (image exposure) described in detail below, and then a photosensitive layer with a developer. The unexposed portion is removed to form an image. As a preferred developer when these photosensitive compositions are used for preparing a lithographic printing plate, a developer as described in JP-B-57-7427 is exemplified, and sodium silicate and potassium silicate are used. , Sodium hydroxide, potassium hydroxide, lithium hydroxide, tribasic sodium phosphate, dibasic sodium phosphate, tribasic ammonium phosphate, dibasic ammonium phosphate, sodium metasilicate, sodium bicarbonate, aqueous ammonia etc. A suitable inorganic alkaline agent or an aqueous solution of an organic alkaline agent such as monoethanolamine or diethanolamine is suitable. It is added so that the concentration of such an alkaline solution is 0.1 to 10% by mass, preferably 0.5 to 5% by mass.

Such an alkaline aqueous solution may contain a small amount of a surfactant, an organic solvent such as benzyl alcohol, 2-phenoxyethanol, and 2-butoxyethanol as necessary. Examples thereof include those described in US Pat. Nos. 3,375,171 and 3,615,480.
Further, the developers described in JP-A-50-26601, 58-54341, JP-B-56-39464, and 56-42860 are also excellent.

A particularly preferred developer used here contains a nonionic compound represented by the following general formula (VI) described in JP-A No. 2002-202616, and has a pH of 11.5 to 12.8. And a developer having a conductivity of 3 to 30 mS / cm.
A-W General Formula (VI)
(In the general formula (VI), A represents a hydrophobic organic group having a log P of AH of 1.5 or more, and W represents a nonionic hydrophilic organic group having a log P of W-H of less than 1.0. Represents.)

logP is C.I. Hansch, A.M. Leo, “Substituent Constants for Correlation Analysis in Chemistry and Biology”, J. Am. Commonly used as a hydrophobicity parameter as described in Wille & Sons, (1979) and distributed to each layer for the octanol / water bilayer system of the molecule of interest (AH and WH). Defined as the logarithm of the equilibrium concentration ratio P calculated from the ratio.
Here, it is used as an index for identifying each group of A and W in the general formula (VI), and is an AH or WH structure conveniently bonded to a hydrogen atom to each organic group of A or W. A. K. Choose, et. al. J. et al. Comput. Chem. 9, 80 (1988). Based on the described method, it is calculated from known data.

  Specifically, as the structure, the organic groups A and W are different from each other, and represent a monovalent organic residue that satisfies the above-mentioned logP. More preferably, they are the same or different from each other and may have a hydrogen atom, a halogen atom, a substituent, and may contain an unsaturated bond, a heterocyclic group, a hydroxyl group, a substituted oxy group. , Mercapto group, substituted thio group, amino group, substituted amino group, substituted carbonyl group, carboxylate group, sulfo group, sulfonate group, substituted sulfinyl group, substituted sulfonyl group, phosphono group, substituted phosphono group, phosphonato group, substituted phosphonate group Represents a cyano group or a nitro group.

  Examples of the hydrocarbon group which may have the above substituent and may contain an unsaturated bond include an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an alkenyl group, a substituted alkenyl group, and an alkynyl group. Groups, and substituted alkynyl groups.

As these alkyl groups and substituted alkyl groups, those exemplified above as preferred specific examples of R ¹ , R ² and R ³ can be similarly mentioned.
Here, in these substituents, examples of the alkyl group include a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms. Specific examples thereof include a methyl group. Ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, octadecyl, eicosyl, isopropyl, 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- Mention may be made of norbornyl groups. 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.

Specific examples of aryl groups include phenyl, biphenyl, naphthyl, tolyl, xylyl, mesityl, cumenyl, fluorophenyl, chlorophenyl, bromophenyl, chloromethylphenyl, hydroxyphenyl, methoxy Phenyl group, ethoxyphenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group, methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxy Carbonylphenyl, ethoxycarbonylphenyl, phenoxycarbonylphenyl, N-phenylcarbamoylphenyl, phenyl, etrophenyl, cyanophenyl, sulfophenyl, sulfo Natofeniru group, phosphono phenyl group, such as phosphate Hona preparative phenyl group can be exemplified.
Examples of alkenyl groups include vinyl group, 1-propenyl group, 1-butenyl group, cinnamyl group, 2-chloro-1-ethenyl group, and the like. Examples of alkynyl groups include ethynyl group, 1 -Propynyl group, 1-butynyl group, trimethylsilylethynyl group, phenylethynyl group and the like.

The above-described acyl group (R ⁴ CO-), R ⁴ can be exemplified hydrogen atom and the above alkyl group, an aryl group, an alkenyl group, an alkynyl 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 include chloromethyl, bromomethyl, 2-chloroethyl, trifluoromethyl, methoxymethyl, methoxyethoxyethyl, allyloxymethyl, phenoxymethyl, methylthiomethyl, Ruthiomethyl 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, methoxycarbonylmethyl group, methoxycarbonylbutyl group, ethoxycarbonyl Bonylmethyl group, butoxycarbonylmethyl group, allyloxycarbonylmethyl group, benzyloxycarbonylmethyl group, methoxycarbonylphenylmethyl group, trichloromethylcarbonylmethyl group, allyloxycarbonylbutyl group, chlorophenoxycarbonylmethyl group, carbamoylmethyl group, N- Methylcarbamoylethyl group, N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, N-methyl-N- (sulfophenyl) carbamoylmethyl group, sulfopropyl group, sulfobutyl group, sulfonatobutyl group, sulfur Famoylbutyl group, N-ethylsulfamoylmethyl group, N, N-dipropylsulfamoylpropyl group, N-tolylsulfamoylpropyl group, N-methyl-N- (phosphono Eniru) sulfamoyl-octyl group,

Phosphonobutyl group, phosphonatohexyl group, diethylphosphonobutyl group, diphenylphosphonopropyl group, methylphosphonobutyl group, methylphosphonatobutyl group, tolylphosphonohexyl group, tolylphosphonatohexyl group, phosphonooxypropyl group, phospho Natoxybutyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-methyl-1-phenylethyl group, p-methylbenzyl group, cinnamyl group, allyl group, 1-prohenylmethyl group, 2-butenyl group , 2-methylallyl group, 2-methylpropenylmethyl group, 2-propynyl group, 2-butynyl group, 3-butynyl group, and the following functional groups.

  Examples of the aryl group 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 can be exemplified, and among these, a phenyl group and a naphthyl group are more preferable.

As the substituted aryl group, those having a monovalent nonmetallic atomic group (other than a hydrogen atom) as a substituent on the ring-forming carbon atom of the aryl group described above 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 these substituted aryl groups include biphenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, fluorophenyl group, chloromethylphenyl group, trifluoromethylphenyl group, Hydroxyphenyl, methoxyphenyl, methoxyethoxyphenyl, allyloxyphenyl, phenoxyphenyl, methylthiophenyl, tolylthiophenyl, phenylthiophenyl, ethylaminophenyl, diethylaminophenyl, morpholinophenyl, acetyl Oxyphenyl group, benzoyloxyphenyl group, N-cyclohexylcarbamoyloxyphenyl group, N-phenylcarbamoyloxyphenyl group, acetylaminophenyl group, N-methylbenzoyl Minophenyl 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-dipropylsulfa Moylphenyl group, N-tolylsulfamoylphenyl group, N-methyl-N- (phosphonophenyl) sulfamoylphenyl group, phosphonophenyl group, phosphonatophenyl group, diethylphosphonophenyl group, diph Nylphosphonophenyl group, methylphosphonophenyl group, methylphosphonatophenyl group, tolylphosphonophenyl group, tolylphosphonophenyl 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.

  Examples of the alkenyl group include the same alkenyl groups as those described above for the substituent that can be introduced. The substituted alkenyl group is a group in which the substituent is replaced and bonded to the hydrogen atom of the alkenyl group. As the substituent, the substituent in the above-mentioned substituted alkyl group is used, while the alkenyl group uses the above-mentioned alkenyl group. be able to. Examples of preferable substituted alkenyl groups include those represented by the following structures.

  Examples of the alkynyl group include the same alkynyl groups as those described above for the substituent that can be introduced. The substituted alkynyl group is a group in which the substituent is replaced with a hydrogen atom of the alkynyl group, and as the substituent, the substituent in the above-described substituted alkyl group is used, while the alkynyl group is the above-described alkynyl group. Can be used.

The heterocyclic group is a monovalent group obtained by removing one hydrogen on the heterocyclic ring and a group formed by bonding one substituent to the above-mentioned substituted alkyl group by further removing one hydrogen from the monovalent group. It is a valent group (substituted heterocyclic group). Examples of preferred heterocycles include those represented by the following structures.

The substituted oxy group (R ⁵ O-), it can be used R ⁵ is a monovalent nonmetallic atom group exclusive of hydrogen. Preferred substituted oxy groups include alkoxy groups, aryloxy groups, acyloxy groups, carbamoyloxy tombs, N-alkylcarbamoyloxy groups, N-arylcarbamoyloxy groups, N, N-dialkylcarbamoyloxy groups, N, N-diarylcarbamoyloxy groups. Groups, N-alkyl-N-arylcarbamoyloxy groups, alkylsulfoxy groups, arylsulfoxy groups, phosphonooxy groups, and phosphonatoxy groups. Examples of the alkyl group and aryl group in these include the alkyl groups, substituted alkyl groups, aryl groups, and substituted aryl groups described above.

Examples of the acyl group (R ⁶ CO—) in the acyloxy group include those in which R ⁶ is the aforementioned alkyl group, substituted alkyl group, aryl group, and substituted aryl group. Among these substituents, an alkoxy group, an aryloxy group, an acyloxy group, and an arylsulfoxy group are more preferable. Specific examples of preferred substituted oxy groups include methoxy group, ethoxy group, propyloxy group, isopropyloxy grave, butyloxy group, pentyloxy group, hexyloxy group, dodecyloxy group, benzyloxy group, allyloxy group, phenethyloxy group, Carboxyethyloxy group, methoxycarbonylethyloxy group, ethoxycarbonylethyloxy group, methoxyethoxy group, phenoxyethoxy group, methoxyethoxyethoxy group, ethoxyethoxyethoxy group, morpholinoethoxy group, morpholinopropyloxy group, allyloxyethoxyethoxy group, Phenoxy, tolyloxy, xylyloxy, mesityloxy, cumenyloxy, methoxyphenyloxy, ethoxyphenyloxy, chlorophenyloxy, bromo Niruokishi group, acetyloxy group, benzoyloxy group, naphthyloxy group, a phenylsulfonyloxy group, a phosphonooxy group, phosphonatoxy and the like.

As the substituted thio group (R ⁷ S—), those in which R ⁷ is a monovalent nonmetallic atomic group excluding hydrogen can be used. Examples of preferred substituted thio groups include alkylthio groups, arylthio groups, alkyldithio groups, aryldithio groups, and acylthio groups. Alkyl group in these alkyl groups described above as the aryl group, a substituted alkyl group, and aryl group, those can be cited shown as substituted aryl group, R ⁶ acyl group in the acylthio group (R ⁶ CO-) in As described above. Among these, an alkylthio group and an arylthio group are more preferable. Specific examples of preferable substituted thio groups include a methylthio group, an ethylthio group, a phenylthio group, an ethoxyethylthio group, a carboxyethylthio group, and a methoxycarbonylthio group.

As the substituted amino group (R ⁸ NH—, (R ⁹ ) (R ¹⁰ ) N—), those in which R ⁸ , R ⁹ and R ¹⁰ are monovalent nonmetallic atomic groups excluding hydrogen can be used. Preferred examples of the substituted amino group include an N-alkylamino group, an N, N-dialkylamino group, an N-arylamino group, an N, N-diarylamino group, an N-alkyl-N-arylamino group, an acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido tomb, 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-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 can be mentioned.

Examples of the alkyl group and aryl group include those described above as the alkyl group, substituted alkyl group, aryl group, and substituted aryl group, such as acylamino group, N-alkylacylamino group, and N-arylacylamino. R ⁶ acyl group (R ⁶ CO-) in the group is as previously described. Among these, more preferred are N-alkylamino group, N, N-dialkylamino group, N-arylamino group, and acylamino group. Specific examples of preferred substituted amino groups include methylamino group, ethylamino group, diethylamino group, morpholino group, piperidino group, pyrrolidino group, phenylamino group, benzoylamino group, acetylamino group and the like.

As the substituted carbonyl group (R ¹¹ —CO—), those in which R ¹¹ is a monovalent nonmetallic atomic group can be used. Preferred examples of the substituted carbonyl group include 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 may be mentioned. Examples of the alkyl group and aryl group in these include those described above as the alkyl group, substituted alkyl group, aryl group, and substituted aryl group. Among these, more preferred substituted carbonyl groups include formyl, acyl, carboxyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, N-alkylcarbamoyl, N, N-dialkylcarbamoyl, N-ary. A rucarbamoyl group, and even more preferred are a formyl group, an acyl group, an alkoxycarbonyl group and an aryloxycarbonyl group. Specific examples of preferred substituted carbonyl groups include formyl group, acetyl group, benzoyl group, carboxyl group, methoxycarbonyl group, allyloxycarbonyl group, N-methylcarbamoyl group, N-phenylcarbamoyl group, N, N-diethylcarbamoyl group. And a morpholinocarbonyl group.

As the substituted sulfinyl group (R ¹² —SO—), those in which R ¹² is a monovalent nonmetallic atomic group can be used. Preferred examples include alkylsulfinyl group, arylsulfinyl group, sulfinamoyl group, N-alkylsulfinamoyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl Group, N-alkyl-N-arylsulfinamoyl group. Examples of the alkyl group and aryl group in these include those described above as the alkyl group, substituted alkyl group, aryl group, and substituted aryl group. Of these, more preferred examples include an alkylsulfinyl group and an arylsulfinyl group. Specific examples of such a substituted sulfinyl group include a hexylsulfinyl group, a benzylsulfinyl group, and a tolylsulfinyl group.

As the substituted sulfonyl group (R ¹³ —SO ₂ —), those in which R ¹³ is a monovalent nonmetallic atomic group can be used. More preferable examples include an alkylsulfonyl group and an arylsulfonyl group. Examples of the alkyl group and aryl group in these include those described above as the alkyl group, substituted alkyl group, aryl group, and substituted aryl group. Specific examples of such a substituted sulfonyl group include a butylsulfonyl group and a chlorophenylsulfonyl group.

As described above, the sulfonate group (—SO ₃ —) means a conjugate base anion group of the sulfo group (—SO ₃ H), and is usually preferably used together with a counter cation. Such counter cations include those generally known, ie, species, oniums (ammonium, sulfonium, phosphonium, iodonium, azinium, etc.) and metal ions (Na ⁺ , K ⁺ , Ca ²⁺ , Zn ²⁺ etc.).

As described above, the carboxylate group (—CO ₂ ⁻ ) means a conjugate base anion group of the carboxyl group (CO ₂ H), and is usually preferably used together with a counter cation. Examples of such counter cations include those generally known, that is, various onium salts (ammonium compounds, sulfonium compounds, phosphonium compounds, iodonium compounds, azinium compounds, etc.) and metal ions (Na ⁺ , K ⁺ , Ca). ²⁺ , Zn ^2+, etc.).

  The substituted phosphono group means a group in which one or two hydroxyl groups on the phosphono group are substituted with other organic oxo groups, and preferred examples thereof include the above-mentioned dialkylphosphono group, diarylphosphono group, alkylarylphospho group. Group, monoalkylphosphono group and monoarylphosphono group. Of these, dialkylphosphono groups and diarylphosphono groups are more preferred. Specific examples thereof include a diethyl phosphono group, a dibutyl phosphono group, a diphenyl phosphono group, and the like.

As described above, the phosphonate group (—PO ₃ ²⁻ , —PO ₃ H ⁻ ) is a conjugated base anion group derived from the acid first dissociation or acid second dissociation of the phosphono group (—PO ₃ H ₂ ). Means. Usually, it is preferable to use it with a counter cation. Examples of such counter cations include those generally known, that is, various oniums (ammonium compounds, sulfonium compounds, phosphonium compounds, iodonium compounds: azinium compounds, etc.), and metal ions (Na ⁺ , K ⁺ , Ca ²⁺ , Zn ²⁺ etc.).

The substituted phosphonato group is a conjugated base anion group obtained by substituting one organic oxo group with a hydroxyl group among the above-mentioned substituted phosphono groups. As a specific example, the above-described monoalkylphosphono group (—PO ₃ H ( alkyl)), and a conjugate base of a monoarylphosphono group (—PO ₃ H (aryl)). Usually, it is preferable to use it with a counter cation. Such counter cations include those generally known, that is, various oniums (ammonium, sulfonium, phosphonium, iodonium, azinium, etc.) and metal ions (Na ⁺ , K ⁺ , Ca ²⁺ , Zn ²⁺ etc.).

  If the preferable specific example in each structure of A and W in said Formula (I) is given, A will be the organic group containing an aromatic, and W will be the nonionic organic group containing a polyoxyalkylene group.

  In order to clarify the structures of A and W, specific examples represented by AH and WH are shown below.

  Specific examples (Y-1 to Y-22) of the nonionic compound represented by the general formula (VI) are shown below.

  More preferable examples of the nonionic compound represented by the general formula (VI) include those represented by the following formula (IA) or (IB).

In said formula, R < ¹⁰ >, R < ²⁰ > is H or a C1-C100 hydrocarbon group, n and m are integers of 0-100 (however, n and m are not 0 simultaneously). Examples of the hydrocarbon group include an alkyl group, an aryl group, an aralkyl group and the like, and further include those in which these hydrocarbon groups are bonded by an ether bond, an ester bond or an amide bond.
More preferable examples of R ¹⁰ and R ²⁰ include H or a linear or branched alkyl group having 1 to 100 carbon atoms. R ¹⁰ and R ²⁰ are groups: R ³⁰ —X— (R ³⁰ is a linear or branched alkyl group having 1 to 100 carbon atoms, and X is —O—, —OCO—, —COO—, — NHCO-
Or represents -CONH-).
More preferably, R ¹⁰ and R ²⁰ are a hydrogen atom, a linear or branched alkyl group or group having 1 to 10 carbon atoms: R ³⁰ —X— (R ³⁰ is a linear or branched alkyl group having 1 to 10 carbon atoms) And X is —O—, —OCO—, —COO—, —NHCO—, or —CONH—.

Examples of the compound represented by the general formula (IA) include polyoxyethylene phenyl ether, polyoxyethylene methyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, and the like.
Examples of the compound represented by the general formula (IB) include polyoxyethylene naphthyl ether, polyoxyethylene methyl naphthyl ether, polyoxyethylene octyl naphthyl ether, polyoxyethylene nonyl naphthyl ether and the like.

In the compounds of the general formulas (IA) and (IB), the number of repeating units of the polyoxyethylene chain is preferably 3-50, more preferably 5-30. The number of repeating units of the polyoxypropylene chain is preferably 0 to 10, more preferably 0 to 5. The polyoxyethylene part and the polyoxypropylene part may be random or block copolymers.
The nonionic aromatic ether activators represented by the general formulas (IA) and (IB) are used alone or in combination of two or more.

  In the present invention, it is effective to add the nonionic compound represented by the general formula (V) in the developing solution in an amount of 0.1 to 15% by mass, preferably 1.0 to 8.0% by mass. If the addition amount is too small, the developability and the solubility of the photosensitive layer components are lowered.

  In the plate-making process of the lithographic printing plate precursor according to the present invention, the entire surface may be heated before exposure, during exposure, and between exposure and development, if necessary. By such heating, the image forming reaction in the photosensitive layer is promoted, and advantages such as improvement in sensitivity and printing durability and stabilization of sensitivity may occur. Further, for the purpose of improving the image strength and printing durability, it is also effective to carry out whole surface post-heating or whole surface exposure on the developed image. Usually, heating before development is preferably performed under mild conditions of 150 ° C. or less. If the temperature is too high, problems such as an undesired curing reaction in the non-image area may occur. On the other hand, very strong conditions can be used for heating after development. Usually, a heat treatment in the range of 200 to 500 ° C. is performed. If the temperature is low, sufficient image strengthening action cannot be obtained. If the temperature is too high, problems such as deterioration of the support and thermal decomposition of the image area occur.

  As a method for exposing the lithographic printing plate precursor for scanning exposure according to the present invention, a known method can be used without limitation. Desirably, the wavelength of the light source is 350 nm to 450 nm, and specifically, an InGaN-based semiconductor laser is suitable. The exposure mechanism may be any of an internal drum system, an external drum system, a flat bed system, and the like. In addition, the photosensitive layer component of the present invention can be made soluble in neutral water or weak alkaline water by using a high water-soluble component. After loading on top, a system such as exposure-development can be performed on the machine.

As an available laser light source of 350 to 450 nm, the following can be used.
As a gas laser, Ar ion laser (364 nm, 351 nm, 10 mW to 1 W), Kr ion laser (356 nm, 351 nm, 10 mW to 1 W), He—Cd laser (441 nm, 325 nm, 1 mW to 100 mW), and Nd: Combination of YAG (YVO4) and SHG crystal x 2 times (355 nm, 5 mW to 1 W), combination of Cr: LiSAF and SHG crystal (430 nm, 10 mW), as a semiconductor laser system, KNbO3 ring resonator (
430 nm, 30 mW), a combination of waveguide type wavelength conversion element and AlGaAs, InGaAs semiconductor (380 nm to 450 nm, 5 mW to 100 mW), a combination of waveguide type wavelength conversion element, AlGaInP, AlGaAs semiconductor (300 nm to 350 nm, 5 mW to 100 mW) AlGaInN (350 nm to 450 nm, 5 mW to 30 mW) In addition, N2 laser (337 nm, pulse 0.1 to 10 mJ), XeF (351 nm, pulse 10 to 250 mJ), etc. can be used as the pulse laser.
In particular, an AlGaInN semiconductor laser (commercially available InGaN-based semiconductor laser 400 to 410 nm, 5 to 30 mW) is preferable in terms of wavelength characteristics and cost.

Further, as the lithographic printing plate exposure apparatus of the scanning exposure method, there are an inner drum method, an outer drum method, and a flat bed method as an exposure mechanism, and all of the light sources other than the pulse laser can be used as the light source. . Practically, the following exposure apparatus is particularly preferable in terms of the relationship between the photosensitive material sensitivity and the plate making time.
・ Single beam exposure system that uses one gas laser or solid-state laser light source with internal drum system ・ Multi-beam exposure system that uses many (10 or more) semiconductor lasers with flat bed system ・ Many semiconductor lasers with external drum system Multi-beam exposure equipment used (10 or more)

In the laser direct-drawing lithographic printing plate as described above, the photosensitive material sensitivity X (J / cm ² ), the photosensitive material exposure area S (cm ² ), the power q (W) of one laser light source, the laser Equation (eq1) is established between the number n and the total exposure time t (s).
X · S = n · q · t − (eq1)

i) In the case of the internal drum (single beam) system, the laser rotation speed f (radians / s), the sub-scanning length Lx (cm) of the photosensitive material, the resolution Z (dots / cm), and the total exposure time t (s) In general, equation (eq2) holds.
f · Z · t = Lx − (eq2)
ii) In the case of the external drum (multi-beam) system, the drum rotation speed F (radians / s), the photosensitive material sub-scanning length Lx (cm), the resolution Z (dots / cm), the total exposure time t (s), the number of beams In general, equation (eq3) is established during (n).
F · Z · n · t = Lx − (eq3)
iii) In the case of a flat bed (multi-beam) system, the rotation speed H (radian / s) of the polygon mirror, the sub-scanning length Lx (cm) of the photosensitive material, the resolution Z (dot / cm), the total exposure time t (s), Equation (eq4) is generally established between the number of beams (n).
H · Z · n · t = Lx − (eq4)

Resolution (2560 dpi) required for an actual printing plate, plate size (A1 / B1, sub-scanning length 42 inch), exposure conditions of about 20 sheets / hour and photosensitive characteristics of the photosensitive composition of the present invention (photosensitive wavelength, By substituting (sensitivity: about 0.1 mJ / cm ² ) into the above formula, it can be understood that a combination with a semiconductor laser multi-beam exposure method is more preferable in the light-sensitive material of the present invention. Further, by combining operability, cost, etc., a combination with an external drum type semiconductor laser multi-beam exposure apparatus is most preferable.

  Further, as other exposure light for the photosensitive composition of the present invention, ultrahigh pressure, high pressure, medium pressure, low pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, various visible and ultraviolet laser lamps Fluorescent lamps, tungsten lamps, sunlight, etc. can also be used.

  Applications of the photosensitive composition according to the present invention can be applied without limitation to a wide range of fields known as applications of photocurable resins in addition to the photosensitive layer of the lithographic printing plate precursor for scanning exposure described in detail above. For example, a highly sensitive optical modeling material can be obtained by applying to a liquid photosensitive composition used in combination with a cationically polymerizable compound as necessary. Further, a hologram material can be obtained by utilizing a change in refractive index accompanying photopolymerization. It can be applied to various transfer materials (peeling sensitive material, toner developing sensitive material, etc.) by utilizing the change in surface adhesiveness accompanying photopolymerization. It can also be applied to photocuring of microcapsules. It can also be applied to the production of electronic materials such as photoresists, and photocurable resin materials such as inks, paints and adhesives.

  Examples The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

<Synthesis example>
Synthesis of Exemplified Compound 25 1 g of N-methyl-N- (trimethylsilyl) methyl-p-aminobenzaldehyde and 1.19 g of 3-cyclohexyl-2-cyclohexyliminooxazolidin-4-one were dissolved in 10 ml of THF, and 0.1% of potassium t-butoxide was dissolved. 25 g was added and reacted at an external temperature of 60 ° C. for 2 hours. After completion of the reaction, the mixture was allowed to cool to room temperature, water was added, and the reaction product was extracted with ethyl acetate. The crude product was purified by column chromatography, and the resulting crystals were dried to obtain 1.3 g of Exemplified Compound 25 (yield 62%).
Mass spectrum 467 (M ⁺ ).
¹ H NMR (CDCl ₃ ) d 0.10 (s, 9H), 1.15-1.87 (m, 18H), 2.22-2.37 (m, 2H), 2.95 (s, 2H), 3.00 (s, 3H), 3.70-3.80 (br, 1H), 4.00-4.10 (m, 1H), 6.40 (s, 1H), 6.63 (d, J = 6.8Hz, 2H), 7.53 (d, J = 6.8Hz, 2H).
Other compounds used in the following examples were synthesized in the same manner.

<Examples 1-13, Comparative Examples 1-7>
(Preparation of support)
An aluminum plate having a thickness of 0.3 mm was etched by being immersed in 10% by mass sodium hydroxide at 60 ° C. for 25 seconds, washed with running water, neutralized with 20% by mass nitric acid, and then washed with water. This was subjected to an electrolytic surface roughening treatment in a 1% by mass nitric acid aqueous solution using a sinusoidal alternating waveform current at an anode time electricity of 300 coulomb / dm ² . Subsequently, after dipping in a 1% by mass aqueous sodium hydroxide solution at 40 ° C. for 5 seconds and then in a 30% by mass sulfuric acid aqueous solution and desmutting at 60 ° C. for 40 seconds, the current density in a 20% by mass sulfuric acid aqueous solution was 2A / current density. At dm ² , the anodization treatment was performed for 2 minutes so that the thickness of the anodized film was 2.7 g / m ² . When the surface roughness was measured, it was 0.3 μm (Ra display according to JIS B0601).
The following sol-gel reaction liquid was applied to the back surface of the substrate thus treated with a bar coater, dried at 100 ° C. for 1 minute, and a support provided with a backcoat layer having a coating amount after drying of 70 mg / m ^2. It was created.

(Sol-gel reaction solution)
Tetraethylsilicate 50 parts by weight Water 20 parts by weight Methanol 15 parts by weight Phosphoric acid 0.05 parts by weight

  When the above components were mixed and stirred, heat generation started in about 5 minutes. After reacting for 60 minutes, a backcoat coating solution was prepared by adding the following solution.

Pyrogallol formaldehyde condensation resin (molecular weight 2000) 4 parts by weight dimethyl phthalate 5 parts by weight fluorinated surfactant 0.7 parts by weight (N-butyl perfluorooctane / sulfonamidoethyl acrylate / polyoxyethylene acrylate copolymer: molecular weight 20,000)
50 parts by mass of methanol silica sol (manufactured by Nissan Chemical Industries, Ltd., 30% by mass of methanol)
800 parts by mass of methanol

(Preparation of photosensitive layer)
On the thus-treated aluminum support, a photosensitive composition having the following composition was applied such that the dry coating amount was 1.3 g / m ² and dried at 80 ° C. for 2 minutes to form a photosensitive layer.

(Photosensitive composition)
Pentaerythritol tetraacrylate 1.5g
Allyl methacrylate / methacrylic acid / N-isopropylamide copolymer (copolymerization molar ratio 70/12/18) 2.0 g
Photopolymerization initiation system (compounds used, contents listed in Table 1)
・ Sensitizing dye Xg
・ Initiator compound Yg
・ Co-sensitizer Zg
Fluorine nonionic surfactant (F-177P) 0.03g
Thermal polymerization inhibitor 0.01g
(N-nitrosophenylhydroxylamine aluminum salt)
20g of methyl ethyl ketone
20g propylene glycol monomethyl ether
2.0 g of pigment dispersion

(Composition of pigment dispersion)
Pigment Blue 15: 6 15 parts by mass Allyl methacrylate / methacrylic acid copolymer 10 parts by mass (copolymerization molar ratio 83/17)
-Cyclohexanone 15 parts by mass-Methoxypropyl acetate 20 parts by mass-Propylene glycol monomethyl ether 40 parts by mass

(Formation of protective layer)
On this photosensitive layer, a 3% by weight aqueous solution of polyvinyl alcohol (saponification degree 98 mol%, polymerization degree 550) was applied so that the dry coating weight was 2 g / m ^2, and dried at 100 ° C. for 2 minutes for protection. A layer was formed to obtain a lithographic printing plate precursor.

[Evaluation of sensitivity]
A Fuji step guide manufactured by Fuji Photo Film Co., Ltd. (gray scale whose transmission optical density changes discontinuously at ΔD = 0.15) was brought into close contact with the lithographic printing plate precursor thus obtained. Exposure was performed with a xenon lamp through a filter so as to obtain a known exposure energy.
Thereafter, the film was immersed in a developer having the following composition at 25 ° C. for 10 seconds, developed, the maximum number of steps at which the image was completely removed was read, the exposure energy amount was determined, and the sensitivity was calculated (unit, mJ / cm). ² ). The smaller the amount of energy, the higher the sensitivity. For the purpose of estimating the suitability of exposure to a short-wave semiconductor laser, Kenko BP-40 is used as an optical filter and 400 nm.
The exposure was performed with monochromatic light. The results are shown in Table 1.

(Developer)
PH 12.0 aqueous solution with the following composition: Potassium hydroxide 0.2g
・ 1K potassium silicate 2.4g
(SiO ₂ / K ₂ O = 1.9)
・ The following compound 5.0 g
・ Ethylenediaminetetraacetic acid ・ 4Na salt 0.1g
・ Water 91.3g

In Table 1, the structure of the sensitizing dye according to the present invention used in the photopolymerization initiation system is the same as that of the exemplified compound. In addition, initiator compounds (A-1) to (A-10) and a co-sensitizer (C-1)
The structure of (C-3) is as follows. The following sensitizing dyes (DR-1) to (DR-3) used in Comparative Examples are dye compounds outside the scope of the present invention. In the following formula, Ts represents a tosyl group.

  As is apparent from Table 1, all the lithographic printing plate precursors using the photosensitive composition of the present invention for the photosensitive layer can form an image with high sensitivity, and this photoinitiating system shows sufficient sensitivity for practical use. all right. On the other hand, Comparative Examples 1 to 3 using only the sensitizing dye and only the initiator compound do not form an image, and use a photoinitiating system in which the initiator compound and the sensitizing dye that is outside the scope of the present invention are combined. It was clear that the lithographic printing plate precursors of Comparative Examples 4 to 7 could not obtain practically sufficient sensitivity. It can be seen from Examples 1 to 13 that the photosensitive composition of the present invention can be applied in a wide range regardless of the sensitization mechanism. Further, by comparing Examples 5, 10 and 13 with Comparative Examples 4 to 7, the structural characteristics showing the high sensitivity of the sensitizing dye of the present invention are represented by the general formula (1) or the general formula (2). It is suggested to be in the structure shown.

<Examples 14 to 27 and Comparative Example 8>
An intermediate layer, a photosensitive layer, and a protective layer were sequentially formed on the support used in Examples 1 to 13 in the following procedure to prepare a lithographic printing plate precursor.
(Coating intermediate layer)
On the surface of the support, a coating solution having the following composition (A) is prepared so that the coating amount of phenylphosphonic acid is 20 mg / m ^2, and after coating at 180 rpm with a wheeler, 80 ° C. And dried for 30 seconds to form an intermediate layer.

(Intermediate layer coating solution A)
Phenylphosphonic acid 0.07g ~ 1.4g
Methanol 200g

(Coating of photosensitive layer)
A photosensitive composition having the following composition is prepared on a support provided with the above intermediate layer, coated with a wheeler so that the coating amount is 1.3 g / m ^2, and dried at 100 ° C. for 1 minute to be photosensitive. A layer was formed.

(Photosensitive composition)
Addition polymerizable compound (compound described in Table 2) 1.6 g
Binder polymer (compound described in Table 2) 2.0 g
Sensitizing dye (compound described in Table 2) 0.15 g
Initiator compound (compound described in Table 2) 0.2 g
Co-sensitizer (compound described in Table 2) 0.3 g
2.0 g of pigment dispersion
Thermal polymerization inhibitor 0.01g
(N-nitrosophenylhydroxylamine aluminum salt)
Fluorosurfactant 0.02g
(Dai Nippon Ink Chemical Co., Ltd., MegaFuck F-177)
Methyl ethyl ketone 20.0g
Propylene glycol monomethyl ether 20.0g

(Composition of pigment dispersion)
Pigment Blue 15: 6 15 parts by mass Allyl methacrylate / methacrylic acid copolymer 10 parts by mass (copolymerization molar ratio 83/17)
-Cyclohexanone 15 parts by mass-Methoxypropyl acetate 20 parts by mass-Propylene glycol monomethyl ether 40 parts by mass

(Formation of protective layer)
On this photosensitive layer, a 3% by weight aqueous solution of polyvinyl alcohol (saponification degree 98 mol%, polymerization degree 550) was applied so that the dry coating weight was 2 g / m ^2, and dried at 100 ° C. for 2 minutes for protection. A layer was formed to obtain a lithographic printing plate precursor.

(Exposure of planographic printing plate precursor)
Using the lithographic printing plate precursor obtained as described above, 400 nm monochromatic light as a light source, adjusting the exposure power so that the plate surface exposure energy density is 200 μJ / cm ² , solid image exposure and 175 lines / inch, Halftone image exposure was performed from 1 to 99% in 1% increments.

(Development / plate making)
Fuji Photo Film Co., Ltd. automatic processor LP-850 was charged with a predetermined developer (described in Table 2) and Fuji Photo Film Co., Ltd. finisher FP-2W.
The exposed plate was developed / engraved under the condition of a development time of 18 seconds to obtain a lithographic printing plate.

(Print durability test)
R201 manufactured by Roland was used as the printing machine, and GEOS-G (N) manufactured by Dainippon Ink & Chemicals, Inc. was used as the ink. While the printing was continued, the printed matter in the solid image portion was observed, and the printing durability was examined based on the number of sheets on which the image began to fade. The larger the number, the better the printing durability.

(Forced dot printing test)
R201 manufactured by Roland was used as the printing machine, and GEOS-G (N) manufactured by Dainippon Ink & Chemicals, Inc. was used as the ink. On the 5000th sheet from the start of printing, PS plate cleaner CL-2 manufactured by Fuji Photo Film Co., Ltd. was soaked in a printing sponge, the halftone dots were wiped, and the ink on the printing plate was washed. Thereafter, 10,000 sheets were printed, and the presence or absence of halftone dots in the printed matter was visually observed.

(Dirty test)
Printing is performed using R201 manufactured by Roland as a printing machine and GEOS-G (S) manufactured by Dainippon Ink and Chemicals, Inc. as an ink. Part) was evaluated visually.

(Addition polymerizable compound in Table 2)
(M-1): Pentaerythritol tetraacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd .; NK ester A-TMMT)
(M-2): Glycerin dimethacrylate hexamethylene diisocyanate urethane prepolymer (manufactured by Kyoeisha Chemical Co., Ltd .; UA101H)

(Binder polymer in Table 2)
(B-1): Allyl methacrylate / methacrylic acid / N-isopropylacrylamide
(Molar ratio of copolymerization 67/13/20)
Measured acid value obtained by NaOH titration 1.15 meq / g
Weight average molecular weight 130,000 determined from GPC measurement (B-2): Allyl methacrylate / methacrylic acid copolymer
(Copolymerization molar ratio 83/17)
Measured acid value obtained by NaOH titration 1.55 meq / g
Weight average molecular weight determined by GPC measurement: 125,000 (B-3): polyurethane resin which is a polycondensation product of the following diisocyanate and diol
・ 4,4′-diphenylmethane diisoisocyanate (MDI)
・ Hexamethylene diisocyanate (HMDI)
-Polypropylene glycol, weight average molecular weight 1000 (PPG1000)
・ 2,2-bis (hydroxymethyl) propionic acid (DMPA)
[Copolymerization molar ratio (MDI / HMDI / PPG1000 / DMPA)
40/10/15/35]
Measured acid value determined by NaOH titration 1.05 meq / g
Weight average molecular weight determined by GPC measurement: 45,000

(Developer in Table 2)
(DV-1)
Aqueous solution of pH 10 having the following composition: 0.1 parts by mass of monoethanolamine 1.5 parts by mass of triethanolamine 1.5 parts of compound of formula 1 below 4.0 parts by mass of compound of formula 2 below 2.5 parts by mass of formula below 3 compounds 0.2 parts by mass / water 91.7 parts by mass

(DV-2)
An aqueous solution of pH 10 having the following composition: 1.2 parts by mass of sodium hydrogencarbonate, 0.8 part by mass of sodium carbonate, 3.0 parts by mass of the compound of the following formula 1, 2.0 parts by mass of the compound of the following formula 2, 2.0 parts by mass of the following formula 3 0.2 parts by mass of water 92.8 parts by mass of water

(DV-3)
PH 13 aqueous solution having the following composition: 1K potassium silicate 3.0 parts by mass Potassium hydroxide 1.5 parts by mass Compound of formula 3 below 0.2 parts by mass Water 95.3 parts by mass

(DV-4)
The developer of pH 12 used in Examples 1-13

(Where R is H or C ₄ H ₉ and n is about 4 (average value).)

  As is apparent from Table 2, all of the lithographic printing plate precursors of Examples 14 to 27 using the photosensitive composition of the present invention as a photosensitive layer were capable of making a plate with high productivity by scanning exposure, that is, It was also found that an excellent lithographic printing plate can be provided even under low energy exposure conditions. On the other hand, the lithographic printing plate precursor of Comparative Example 8 that does not use the sensitizing dye according to the present invention could not obtain a practical lithographic printing plate.

(Example 28)
In the photosensitive composition used for the photosensitive layer, the photoinitiating system was changed to the following composition, and the film thickness of the photosensitive layer was changed to 1.5 g / m ^2. 28 planographic printing plate precursors were prepared.
(Light initiation system)
Sensitizing dye (Exemplary Compound 25) 0.1 g
Initiator compound (A-1) 0.08 g
Co-sensitizer (C-2) 0.2g

(Exposure / Development)
The obtained lithographic printing plate precursor was subjected to scanning exposure using a monochromatic light of 400 nm under the condition of an exposure energy density of 0.25 mJ / cm ² . Next, after the plate was heated at 100 ° C. for 10 seconds and developed under the same conditions as in Example 1, a lithographic printing plate having a blue image with excellent visibility was obtained.

(Evaluation of planographic printing plate)
Using the resulting lithographic printing plate and performing offset printing using a Heidelberg KOR-D machine, it is possible to obtain 50,000 or more prints with excellent image density and excellent image quality without smearing in non-image areas. It was.

(Example 29)
The lithographic printing plate precursor obtained in Example 28 was exposed to a yellow lamp for 1 hour before exposure, and then subjected to plate making and printing in the same manner as in Example 28. Good results exactly the same as in Example 28 were obtained.

(Example 30)
In Example 29, the lithographic printing plate precursor exposed to yellow light for 1 hour was stored for 3 days under a forced storage condition of 65% humidity and 45 ° C., and then plate-making and printing were performed in the same manner as in Example 29. Good results similar to those of Example 29 were obtained.

(Example 31)
A photosensitive layer using a photosensitive composition having the following composition was coated on a PET film so as to have a coating amount of 1.5 g / m ² .
(Photosensitive composition)
Binder resin (polymethyl methacrylate) 90% by mass
Sensitizing dye (Exemplary Compound 25) 1.5% by mass
Initiator compound A-6 5.0 mass%
Acid decoloring dye 2.0% by mass
(Victoria pure blue naphthalene sulfonate)

  The resulting blue photosensitive material was exposed for 30 seconds with a metal halide lamp. The blue color disappeared completely and changed to a pale yellow transparent film. Thus, by utilizing the acid generation function of the present initiation system, the photosensitive composition of the present invention could be applied as an image forming material utilizing the color changing function.

(Example 32)
The same operation as in Example 31 was carried out except that the initiator compound was changed to A-7. As in Example 31, photodecoloration of the dye in the exposed area was observed.

(Example 33)
The same operation as in Example 31 was performed except that the initiator compound was changed to A-8. As in Example 31, photodecoloration of the dye in the exposed area was observed.

(Example 34)
A photosensitive layer using a photosensitive composition having the following composition was coated on a PET film so as to have a coating amount of 1.5 g / m ² .
(Photosensitive composition)
Binder resin (polymethyl methacrylate) 91% by mass
Sensitizing dye (Exemplary Compound 25) 1.3% by mass
Initiator compound A-6 7.7 mass%
Oxidative coloring dye (leuco crystal violet) 2.0% by mass

  When the obtained light yellow transparent photosensitive material was exposed with a metal halide lamp for 30 seconds, it developed a bright blue color. This is considered to be oxidative coloring of the leuco dye by radical generation of the present initiation system. As described above, the photosensitive composition of the present invention could be applied as an image forming material utilizing a color changing function by utilizing the acid generating ability of the present initiation system.

Claims (4)

(A) a sensitizing dye capable of emitting one or more electrons from a one-electron oxidant produced by one-electron oxidation,
(B) an initiator compound capable of generating radicals, acids or bases, and
(C) a compound whose physical or chemical properties are irreversibly changed by at least one of radicals, acids and bases,
Containing the photosensitive composition. 2. The photosensitive composition according to claim 1, wherein the sensitizing dye is a sensitizing dye represented by the following general formula (I) or general formula (II).

In formula (I), R ¹ and R ² independently represent a substituted or unsubstituted alkyl group, aryl group or heterocyclic group. R ³ , R ⁴ , R ⁵ and R ⁶ each independently represents a hydrogen atom or a monovalent substituent. L ¹ , L ² and L ³ independently represent a methine group which may have a substituent. m represents an integer of 0 or more. A ¹ represents a substituted or unsubstituted aromatic group or heterocyclic group.
In the formula (II), R ²¹ and R ²² independently represent a substituted or unsubstituted alkyl group, aryl group or heterocyclic group. R ²³ , R ²⁴ , R ²⁵ and R ²⁶ each independently represents a hydrogen atom or a monovalent substituent. L ²¹ and L ²² independently represent a methine group which may have a substituent. n represents an integer of 0 or more. A ²¹ represents a substituted or unsubstituted aromatic group or heterocyclic group.
However, the general formula (I) and the general formula (II) have a structure in which a one-electron oxidant produced by one-electron oxidation can emit one electron or more. In the general formula (I) and the general formula (II), a structure in which a one-electron oxidant formed by one-electron oxidation can emit one electron or more is represented by the following general formula (III) The photosensitive composition according to claim 1 or 2.

Ra and Rb independently represent a hydrogen atom or a substituted or unsubstituted alkyl group, aryl group or heterocyclic group. X represents a substituent capable of generating a C radical and a leaving fragment X by cleavage of the C—X bond upon oxidation. A compound represented by general formula (I) or general formula (II).

In formula (I), R ¹ and R ² independently represent a substituted or unsubstituted alkyl group, aryl group or heterocyclic group. R ³ , R ⁴ , R ⁵ and R ⁶ each independently represents a hydrogen atom or a monovalent substituent. L ¹ , L ² and L ³ independently represent a methine group which may have a substituent. m represents an integer of 0 or more. A ¹ represents a substituted or unsubstituted aromatic group or heterocyclic group.
In the formula (II), R ²¹ and R ²² independently represent a substituted or unsubstituted alkyl group, aryl group or heterocyclic group. R ²³ , R ²⁴ , R ²⁵ and R ²⁶ each independently represents a hydrogen atom or a monovalent substituent. L ²¹ and L ²² independently represent a methine group which may have a substituent. n represents an integer of 0 or more. A ²¹ represents a substituted or unsubstituted aromatic group or heterocyclic group.
However, the general formula (I) and the general formula (II) have a structure in which a one-electron oxidant produced by one-electron oxidation can emit one electron or more.