JP2006251356A - Photosensitive negative image forming material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive negative image forming material having high sensitivity, excellent in work efficiency, economical efficiency, printing durability, fouling resistance and storage stability, and useful as a photosensitive lithographic printing original plate for scanning exposure adaptable to a CTP system. <P>SOLUTION: The photosensitive negative image forming material has, on a support, a photosensitive layer containing a compound having an acid group and a -SH group, a photopolymerization or thermal polymerization initiator and a compound having at least one addition polymerizable ethylenically unsaturated bond. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention is a photosensitivity that can be used for image forming materials such as three-dimensional stereolithography, holography, planographic printing plates, color proofs, photoresists, and color filters, and photocurable resin materials such as inks, paints, and adhesives. Relates to the composition. More particularly, the present invention relates to a photosensitive composition that can be directly made from a digital signal of a computer or the like using various lasers, and is suitably used as a so-called lithographic printing plate material capable of direct plate making.

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 a printing plate precursor adapted to this 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. A lithographic printing plate precursor (photosensitive lithographic printing plate) having such a constitution has a desirable printing plate and printing performance that are easy to develop and further excellent in resolution, thickness, printing durability, and stain resistance. .

The photosensitive composition basically contains a polymerizable compound having an ethylenically unsaturated bond, a photopolymerization initiation system, and optionally a binder resin, and the photoinitiation system absorbs light by scanning exposure and is active. An active species such as a radical is generated to cause and advance a polymerization reaction of a polymerizable compound, thereby curing an exposed area to form an image.
In such a photosensitive composition capable of scanning exposure, various photoinitiating systems excellent in 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, a semiconductor laser using an InGaN-based material and capable of continuous oscillation in a 350 nm to 450 nm region has 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, a photosensitive composition containing a sensitizing dye, a hexaarylbiimidazole compound, and a mercapto compound that are highly sensitive in this short wavelength region has been proposed (see, for example, Patent Documents 1 and 2).

  In addition, as a common problem to all image forming materials containing these photosensitive compositions, the problem of how to enlarge the ON / OFF of the image in the laser light irradiated portion and the unirradiated portion, that is, the image forming material There is a problem of achieving both high sensitivity and storage stability. Usually, the radical photopolymerization system is highly sensitive, but the sensitivity is greatly lowered due to polymerization inhibition by oxygen in the air. Therefore, means for providing an oxygen barrier layer on the image forming layer is taken. However, when an oxygen-blocking layer is provided, fogging due to dark polymerization or the like occurs, and storage stability deteriorates. Also, when the photoinitiating material in the photosensitive layer decomposes and disappears under storage conditions, the amount of active radicals generated by light irradiation is reduced, which is one of the causes of storage stability deterioration. Accordingly, it is difficult to achieve both high sensitivity and storage stability, and a photosensitive composition containing the above-mentioned high sensitivity sensitizing dye, hexaarylbiimidazole compound, and mercapto compound (see, for example, Patent Documents 1 and 2). Thus, it cannot be said that both high sensitivity and storage stability are sufficiently achieved. As described above, a sufficiently satisfactory result has not been obtained with the conventional technique, and a new technique that has not been conventionally required has been demanded.

Further, solid lasers and semiconductor lasers (hereinafter sometimes referred to as “infrared lasers”) that emit infrared rays having a wavelength of 760 nm to 1200 nm can be easily obtained with high output and small size. If a CTP system using these infrared light sources can be constructed, a light-sensitive material that can be handled under a bright room (yellow light or white light) can be used.
In particular, in the field of lithographic printing, these infrared lasers are very useful as a recording light source for making a printing plate directly from digital data such as a computer. Along with this, various researches have been made on image recording materials sensitive to these various laser beams. Acid-catalyst-crosslinked negative recording materials compatible with infrared lasers having a photosensitive wavelength of 760 nm or more (for example, see Patent Document 3), radicals A polymerization type negative recording material (see, for example, Patent Document 4) is known.
Therefore, it is suitable for CTP systems using relatively short-wavelength semiconductor lasers of 350 to 450 nm, or CTP systems using solid-state lasers and semiconductor lasers that emit infrared light with a wavelength of 760 to 1200 nm. Therefore, it is strongly desired in the industrial field to obtain a lithographic printing plate precursor suitable for the former CTP system.
JP 2004-191938 A JP 2004-295058 A JP-A-8-276558 JP 2000-89455 A Bruce M. Monroe et al., Chemical Review, 1993, volume 93, p. 435-448 RS Davidson, Journal of Photochemistry and Biology A: Chemistry, 1993, Vol. 73, p. 81-96

  The object of the present invention in consideration of the above problems is high sensitivity and excellent workability, economy, printing durability, stain resistance and storage stability, for example, photosensitivity for scanning exposure suitable for CTP system. It is an object of the present invention to provide a photosensitive negative image forming material useful as a lithographic printing plate.

As a result of intensive studies to achieve the above object, the inventors of the present invention contain a compound having an acid group and an —SH group, a polymerization initiator, and a compound having an ethylenically unsaturated bond capable of addition polymerization. The present inventors have found that a photosensitive negative type image forming material using a photosensitive composition gives high photosensitivity and is excellent in stability over time, thereby completing the present invention.
That is, the present invention is as follows.
(1) a support, and (A) a compound having an acid group and an —SH group, (B) a polymerization initiator, and (C) a compound having at least one ethylenically unsaturated bond capable of addition polymerization. Photosensitive negative image forming material having a photosensitive layer.
(2) The photosensitive negative image-forming material as described in (1) above, wherein the compound (A) having an acid group and an —SH group is a compound represented by the following formula (1).

In formula (1),
A represents a group having an acid group selected from carboxylic acid, sulfonic acid, and phosphoric acid.
X represents a heterocyclic group.
m represents an integer of 1 to 6, and when two or more, a plurality of A may be the same or different.
n represents an integer of 1 to 6.
(3) The photosensitivity as described in (2) above, wherein the total number of nitrogen atoms, sulfur atoms and oxygen atoms contained in the heterocyclic ring represented by X in formula (1) is 2 or more Negative type image forming material.
(4) The photosensitive negative image-forming material as described in (2) above, wherein the number of nitrogen atoms contained in the heterocyclic group represented by X in formula (1) is 2 or more.
(5) The photosensitive negative image-forming material as described in any one of (1) to (4) above, wherein the polymerization initiator (B) is a hexaarylbiimidazole compound.

  In the photosensitive material, the distribution of radicals generated by exposure is smaller in the vicinity of the support than the surface of the photosensitive layer due to the light absorption distribution. Therefore, the curing in the vicinity of the support is low, the adhesiveness with the support is weak, and is easily damaged by development. In particular, the small dot portion of the halftone dot is greatly affected, and halftone dot skipping occurs during printing, which tends to cause printing failure.

  Acid groups such as a carboxyl group and a phosphoric acid group are excellent in adhesion to a metal support such as aluminum, particularly an anodized aluminum support. In addition, the —SH group quickly draws out hydrogen by radicals generated from the polymerization initiator, becomes —S ·, and starts polymerization. This -S. Is quickly added to the ethylenically unsaturated bond in the photosensitive layer to cause a polymerization reaction. Therefore, when a compound having an acid group and a —SH group is used, a cured product having excellent adhesion to the support is generated with the initiation of polymerization by —S ·, and an image having excellent image strength can be obtained. .

  By using the compound of the present invention as a photosensitive layer component, a photosensitive lithographic printing plate having excellent sensitivity and stability over time, and particularly excellent printing durability at a small dot portion (highlight) can be provided. .

Hereinafter, the present invention will be described in detail.
The photosensitive layer of the photosensitive negative image forming material of the present invention includes, for example, (A) a compound having an acid group and —SH group, (B) a polymerization initiator, and (C) an ethylenically unsaturated compound capable of addition polymerization. A compound having at least one bond is applied using a photosensitive composition dissolved in a solvent.
Below, each compound is demonstrated one by one.

(A) Compound having an acid group and —SH group (A) The compound having an acid group and —SH group used in the present invention is not limited as long as it satisfies these conditions.
Preferably, it is a compound represented by following formula (1).

In formula (1),
A represents a group having an acid group selected from carboxylic acid, sulfonic acid, and phosphoric acid.
X represents a heterocyclic group.
m represents an integer of 1 to 6, and when two or more, a plurality of A may be the same or different.
n represents an integer of 1 to 6.

  Examples of the heterocycle of X include the following. Thiophene, thiathrene, furan, pyran, isobenzofuran, chromene, xanthene, phenoxazine, pyrrole, pyrazole, isothiazole, isoxazole, pyridine, pyrazine, pyrimidine, pyridazine, 1,2,4-triazine, 1,3,5- Triazine, imidazole, oxazole, thiazole, 1,2,3-triazole, 1,3,4-triazole, 1,2,4-triazole, 1,3,4-oxadiazole, quinoline, phenanthridine, quinoxaline, 1,8-naphthyridine, acridine, tetrazole, oxadiazole, thiadiazole, benzimidazole, benzoxazole, benzothiazole, indolizine, isoindolizine, indole, indazole, purine, quinolidine, isoquinoline, phthala , Naphthyridine, quinazoline, cynoline, pteridine, carbazole, carboline, phenanthrine, acridine, perimidine, phenanthroline, phthalazine, phenazazine, phenoxazine, furazane, phenoxazine, and the like. It may also have a substituent.

   Examples of the substituent include halogen atom, amino group, substituted amino group, substituted carbonyl tomb, hydroxyl group, substituted oxy group, silyl group, nitro group, cyano group, alkyl group, alkenyl group, aryl group, heterocyclic group, sulfo group. Group, substituted sulfonyl group, sulfonate group, substituted sulfinyl group, phosphono group, substituted phosphono group, phosphonate group, substituted phosphonate group, and the like, and when it can be introduced, it may further have a substituent.

  Examples of the alkyl group include linear, branched or cyclic alkyl groups having 1 to 20 carbon atoms. Among these, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 5 to 20 carbon atoms, and a cyclic alkyl group having 5 to 20 carbon atoms are more preferable. Specific examples thereof include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, hexadecyl group, octadecyl group. , Eicosyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group , 2-norbornyl group, and adamantyl group.

  When the alkyl group has a substituent (ie, when it is a substituted alkyl group), the alkyl part of the substituted alkyl group includes any one of the hydrogen atoms on the alkyl group having 1 to 20 carbon atoms described above. In addition, a divalent organic residue can be exemplified, and a preferable range of the number of carbon atoms is the same as that of the alkyl group.

  Preferred examples of the substituted alkyl group include a chloromethyl group, a bromomethyl group, a 2-chloroethyl group, a trifluoromethyl group, a methoxymethyl group, a methoxycarbonylmethyl group, an isopropoxymethyl group, a butoxymethyl group, s -Butoxybutyl, methoxyethoxyethyl, allyloxymethyl, phenoxymethyl, acetyloxymethyl, methylthiomethyl, tolylthiomethyl, pyridylmethyl, tetramethylpiperidinylmethyl, N-acetyltetramethyl Piperidinylmethyl group, trimethylsilylmethyl group, methoxyethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyloxymethyl group, benzoyloxymethyl group, N-cyclohexylcarbamoyloxy Til group, N-phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxoethyl group, 2-oxopropyl group, carboxypropyl group, methoxycarbonylethyl group, allyloxycarbonylbutyl group, Chlorophenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl group, N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, N-methyl-N- (sulfophenyl) carbamoylmethyl group , Sulfobutyl group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N-dipropylsulfamoylpropyl group, N-tolylsulfamoylpropyl group, N-methyl-N- (phospho Phenyl) sulfamoyloctyl, phosphonobutyl, phosphonatohexyl, diethylphosphonobutyl, diphenylphosphonopropyl, methylphosphonobutyl, methylphosphonatobutyl, tolylphosphonohexyl, tolylphosphonatohexyl Group, phosphonooxypropyl group, phosphonatoxybutyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-methyl-1-phenylethyl group, p-methylbenzyl group, cinnamyl group, allyl group, 1- Examples thereof include a propenylmethyl group, a 2-butenyl group, a 2-methylallyl group, a 2-methylpropenylmethyl group, a 2-propynyl group, a 2-butynyl group, and a 3-butynyl group. Among these, a phenethyl group, a 1-methyl-1-phenylethyl group, a p-methylbenzyl group, and a cinnamyl group are particularly preferable.

Examples of the substituent that can be introduced into the alkyl group include monovalent substituents composed of the nonmetallic atoms exemplified below in addition to the substituents described in the description of the substituted alkyl group. Preferred examples including the above-described substituent include a halogen atom (—F, —Br, —Cl, —I), hydroxyl group, alkoxy group, aryloxy group, mercapto group, alkylthio group, arylthio group, alkyldithio group, aryl. Dithio group, amino group, N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N-arylcarbamoyloxy group, alkylsulfoxy group, aryl Sulfoxy group, acylthio group, acylamino group, -Alkylacylamino group, N-arylacylamino group, ureido group, N'-alkylureido group, N ', N'-dialkylureido group, N'-arylureido group, N', N'-diarylureido group, N′-alkyl-N′-arylureido group, N-alkylureido group, N-arylureido group, N′-alkyl-N-alkylureido group, N′-alkyl-N-arylureido group, N ′, N '-Dialkyl-N-alkylureido group, N', N'-dialkyl-N-arylureido group, N'-aryl-N-alkylureido group, N'-aryl-N-arylureido group, N ', N '-Diaryl-N-alkylureido group, N', N'-diaryl-N-arylureido group, N'-
Alkyl-N′-aryl-N-alkylureido group, N′-alkyl-N′-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryl Roxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, alkylsulfinyl group, arylsulfuryl group Iniru group, an alkylsulfonyl group, an arylsulfonyl group, (referred to as a sulfonato group) sulfo group (-SO ₃ H) and its conjugated base group, alkoxy sulfonyl group, aryloxy sulfonyl group, sulfinamoyl group, N- alkylsulfinamoyl group N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkylsulfamoyl group Group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, phosphono group (—PO ₃ H ₂ ) And its conjugate base group (referred to as phosphonato group), dialkylphosphono group (- O ₃ (alkyl) ₂₎ "alkyl = alkyl group, hereinafter the" diarylphosphono group (-PO ₃ (aryl) ₂₎ "aryl = aryl group, hereinafter the" alkylaryl phosphono group (-PO ₃ ( alkyl) (aryl)), monoalkylphosphono group (—PO ₃ (alkyl)) and its conjugate base group (referred to as alkylphosphonato group), monoarylphosphono group (—PO ₃ H (aryl)) and Its conjugate base group (referred to as arylphosphonate group), phosphonooxy group (—OPO ₃ H ₂ ) and its conjugate base group (referred to as phosphonatoxy group), dialkylphosphonooxy group (—OPO ₃ H (alkyl) ₂ ) , diarylphosphono group _{(-OPO 3 (aryl) 2)} , alkylaryl phosphono group (-OPO ₃ (alkyl) ( aryl)), a monoalkylphosphonooxy group (—OPO ₃ H (alkyl)) and its conjugate base group (alkylphosphonatoxy group). ), Monoarylphosphonooxy group (—OPO ₃ H (aryl)) and its conjugate base group (referred to as arylphosphonatoxy group), cyano group, nitro group, aryl group, alkenyl group, alkynyl group, heterocyclic ring Group, silyl group, and the like.

Specific examples of the alkyl moiety in the substituent that can be introduced into the alkyl group are the same as in the case where the monovalent substituent described above is a substituted alkyl group, and the preferred range is also the same.
Specific examples of the aryl moiety in the substituent that can be introduced into the alkyl group represented by the monovalent substituent include phenyl, biphenyl, naphthyl, tolyl, xylyl, mesityl, cumenyl, and chlorophenyl. Group, bromophenyl group, chloromethylphenyl group, hydroxyphenyl group, methoxyphenyl group, ethoxyphenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group, methylaminophenyl group Dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, ethoxyphenylcarbonyl group, phenoxycarbonylphenyl group, N-phenylcarbamoylphenyl group, cyanophenyl group, sulfo Eniru group, a sulfophenyl group, phosphono phenyl group, phosphonium Hona preparative phenyl group, and the like.

Examples of the alkenyl group include alkenyl groups having 2 to 20 carbon atoms. Among these, an alkenyl group having 2 to 10 carbon atoms is preferable, and an alkenyl group having 2 to 8 carbon atoms is more preferable. The alkenyl group may further have a substituent. Examples of the substituent that can be introduced include a halogen atom, an alkyl group, a substituted alkyl group, an aryl group, and a substituted aryl group. The halogen atom is a linear or branched chain having 1 to 10 carbon atoms. A cyclic alkyl group is preferred. Specific examples of the alkenyl group include, for example, vinyl group, 1-propenyl group, 1-butenyl group, cinnamyl group, 1-pentenyl group, 1-hexenyl group, 1-octenyl group, 1-methyl-1-propenyl group, A 2-methyl-1-propenyl group, a 2-methyl-1-butenyl group, a 2-phenyl-1-ethenyl group, a 2-chloro-1-ethenyl group, and the like can be given.

  Examples of the alkynyl group include alkynyl groups having 2 to 20 carbon atoms. Among these, an alkynyl group having 2 to 10 carbon atoms is preferable, and an alkynyl group having 2 to 8 carbon atoms is more preferable. Specific examples thereof include ethynyl group, 1-propynyl group, 1-butynyl group, phenylethynyl group, trimethylsilylethynyl group and the like.

  Examples of the aryl group include a benzene ring, a group in which 2 to 3 benzene rings form a condensed ring, and a group in which a benzene ring and a 5-membered unsaturated ring form a condensed ring. Specific examples thereof include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenaphthenyl group, and a fluorenyl group. Among these, a phenyl group and a naphthyl group are more preferable.

  When the aryl group has a substituent (that is, when it is a substituted aryl group), the substituted alkyl group has a monovalent substituent composed of a nonmetallic atom as a substituent on the ring-forming carbon atom. Is mentioned. Preferable examples of the substituent to be introduced include those described above in the description of the alkyl group, the substituted alkyl group, and the substituent in the substituted alkyl group.

  Preferred examples of the substituted aryl group include a biphenyl group, a tolyl group, a xylyl group, a mesityl group, a cumenyl group, a chlorophenyl group, a bromophenyl group, a fluorophenyl group, a chloromethylphenyl group, a trifluoromethylphenyl group, Hydroxyphenyl group, methoxyphenyl group, methoxyethoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, methylthiophenyl group, tolylthiophenyl group, ethylaminophenyl group, diethylaminophenyl group, morpholinophenyl group, acetyloxyphenyl group, benzoyl Oxyphenyl group, N-cyclohexylcarbamoyloxyphenyl group, N-phenylcarbamoyloxyphenyl group, acetylaminophenyl group, N-methylbenzoylaminophenyl group, carbo Cyphenyl group, methoxycarbonylphenyl group, allyloxycarbonylphenyl group, chlorophenoxycarbonylphenyl group, carbamoylphenyl group, N-methylcarbamoylphenyl group, N, N-dipropylcarbamoylphenyl group, N- (methoxyphenyl) carbamoylphenyl group N-methyl-N- (sulfophenyl) carbamoylphenyl group, sulfophenyl group, sulfonatophenyl group, sulfamoylphenyl group, N-ethylsulfamoylphenyl group, N, N-dipropylsulfamoylphenyl group, N-tolylsulfamoylphenyl group, N-methyl-N- (phosphonophenyl) sulfamoylphenyl group, phosphonophenyl group, phosphonatophenyl group, diethylphosphonophenyl group, diphenylphosphonophenyl group Methylphosphonophenyl group, methylphosphonatophenyl group, tolylphosphonophenyl group, tolylphosphonophenyl group, allylphenyl group, 1-propenylmethylphenyl group, 2-butenylphenyl group, 2-methylallylphenyl group, 2 -Methylpropenylphenyl group, 2-propynylphenyl group, 2-butynylphenyl group, 3-butynylphenyl group and the like can be mentioned. Among these, a biphenyl group, a tolyl group, a xylyl group, a mesityl group, a chlorophenyl group and the like are preferable.

The heterocyclic group is preferably a 3- to 8-membered heterocyclic group, more preferably a 3- to 6-membered heterocyclic group containing a nitrogen atom, an oxygen atom or a sulfur atom, a nitrogen atom, an oxygen atom or sulfur. A 5- to 6-membered heterocyclic group containing an atom is more preferable. Specific examples thereof include a pyridyl group and a piperidinyl group.

  The silyl group may have a substituent, is preferably a silyl group having 0 to 30 carbon atoms, more preferably a silyl group having 3 to 20 carbon atoms, and further preferably a silyl group having 3 to 10 carbon atoms. Specific examples thereof include a trimethylsilyl group, a triethylsilyl group, a tripropylsilyl group, a triisopropylsilyl group, a cyclohexyldimethylsilyl group, and a dimethylvinylsilyl group.

  Examples of the halogen atom include a fluorine atom, a bromine atom, a chlorine atom, and an iodine atom. Among these, a chlorine atom and a bromine atom are preferable.

The substituted oxy group (R ⁰⁶ O-), can be used a group R ⁰⁶ is a monovalent nonmetallic atom group exclusive of a hydrogen atom. Preferred substituted oxy groups include alkoxy groups, aryloxy groups, acyloxy groups, carbamoyloxy groups, 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 ⁰⁷ CO—) in the acyloxy group include those in which R ⁰⁷ is the alkyl group, substituted alkyl group, aryl group, and substituted aryl group mentioned above. 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, ethoxy, propyloxy, isopropyloxy, butyloxy, pentyloxy, hexyloxy, dodecyloxy, benzyloxy, allyloxy, phenethyloxy, 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 group, and the like.

The amino group may be a substituted amino group including an amide group. The substituted amino group (R ⁰⁸ NH—, (R ⁰⁹ ) (R ⁰¹⁰ ) N—) including an amide group is a group in which R ⁰⁸ , R ⁰⁹ , and R ⁰¹⁰ are monovalent nonmetallic atomic groups excluding hydrogen atoms Can be used. R ⁰⁹ and R ⁰¹⁰ may be bonded to form a ring. 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 group, N′-alkylureido group, N ′, N′-dialkylureido group, N′-arylureido group, N ′, N′-diarylureido group N′-alkyl-N′-arylureido group, N-alkylureido group, N-arylureido group, N′-alkyl-N-alkylureido group, N′-alkyl-N-arylureido group, N ′, N′-dialkyl-N-alkylureido group, N′-alkyl-N′-arylureido group, N ′, N′-dialkyl-N-alkylureido group, N ′, '-Dialkyl-N'-arylureido group, N'-aryl-N-alkylureido group, N'-aryl-N-arylureido group, N', N'-diaryl-N-alkylureido group, N ', N′-diaryl-N-arylureido group, N′-alkyl-N′-aryl-N-alkylureido group, N ′
-Alkyl-N'-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N- Examples include an aryl-N-alkoxycarbonylamino group and an N-aryl-N-aryloxycarbonylamino group. 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 ⁰⁷ of the acyl group (R ⁰⁷ CO-) in the group is as previously described. Of these, more preferred are an N-alkylamino group, an N, N-dialkylamino group, an N-arylamino group, and an 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 sulfonyl group (R ⁰¹¹ —SO ₂ —), those in which R ⁰¹¹ is a group composed of a monovalent nonmetallic atomic group can be used. More preferable examples include an alkylsulfonyl group, an arylsulfonyl group, and a substituted or unsubstituted sulfamoyl 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 butylsulfonyl group, phenylsulfonyl group, chlorophenylsulfonyl group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfuryl group. A famoyl group, an N-alkyl-N-arylsulfamoyl group, and the like.

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, that is, various oniums (ammonium, sulfonium, phosphonium, iodonium, azinium, etc.) and metal ions (Na ⁺ , K +, Ca ^{2). +} , Zn ^2+, etc.).

As the substituted carbonyl group (R ⁰¹³ —CO—), those in which R ⁰¹³ is a group composed of 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 can be mentioned, 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, ethoxycarbonyl group, allyloxycarbonyl group, dimethylaminophenylethenylcarbonyl group, methoxycarbonylmethoxycarbonyl group, N -Methylcarbamoyl group, N-phenylcarbamoyl group, N, N-diethylcarbamoyl group, morpholinocarbonyl group and the like.

As the substituted sulfinyl group (R ⁰¹⁴ —SO—), a group in which R ⁰¹⁴ is a monovalent nonmetallic atomic group can be used. Preferable 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.

  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.

Phosphonato group _{(-PO 3 H 2 -, -} PO 3 H-) and the meaning of a phosphono group (-PO ₃ H _2), first dissociation or acid, a conjugated base anion group derived from the second dissociation acid To do. 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.).

The substituted phosphonato group is a conjugated base anion group obtained by substituting one organic oxo group in the above-described substituted phosphono group. 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)).

  As the heterocyclic ring for X, those having a total number of nitrogen atoms, sulfur atoms and oxygen atoms forming the heterocyclic ring of 2 or more are preferable from the viewpoint of sensitivity. Examples include imidazole, 1,2,4-triazole, 1,3,4-triazole, tetrazole, oxazole, oxadiazole, thiadiazole, benzimidazole, benzoxazole, benzothiazole, triazine, and pyrimidine.

  Further, as the heterocyclic ring of X, those having 2 or more nitrogen atoms forming the heterocyclic ring are preferable in terms of sensitivity and stability over time. Examples thereof include imidazole, 1,2,4-triazole, 1,3,4-triazole, tetrazole, oxazole, oxadiazole, thiadiazole, benzimidazole, triazine, and pyrimidine.

As the acid group of A, a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group are preferable from the viewpoint of adhesion of the support, and among them, the carboxylic acid group and the phosphoric acid group are excellent in adhesion to the metal support. Preferably, a carboxyl group is most preferable from the viewpoint of coexistence of developability (dirtability) of the non-image area.
Further, these acid groups may be neutralized to form a salt (carboxylate group, sulfonate group, phosphate group). When two or more acid groups are present in the molecule, some of them may be in the form of neutralized salts, or all may be in the form of neutralized salts.

  The acid group of A may be connected to the heterocyclic ring (X) through the linking group (L) as in the partial structure represented by the formula (2), or may be directly bonded without using the linking group. good.

In the formula (2), specific examples of the divalent linking group represented by L include a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms, a linear chain having 2 to 20 carbon atoms, A branched or cyclic alkenylene group, an alkynylene group having 2 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms (monocyclic or heterocyclic ring), -OC (= O)-, -OC (= O) Ar-, -OC (= O) O -, - OC (= O) OAr -, - C (= O) NR -, - C (= O) NAr -, - SO 2 NR -, - SO 2 NAr -, - O -(Alkyleneoxy, polyalkyleneoxy), -OAr- (aryleneoxy, polyaryleneoxy), -C (= O) O-, -C (= O) O-Ar-, -C (= O) Ar- , -C (= O) -, - SO 2 O -, - SO 2 OAr -, - OSO 2 -, - OSO 2 Ar -, - N _{SO 2 -, - NArSO 2 -} , - NRC (= O) -, - NArC (= O) -, - NRC (= O) O -, - NArC (= O) O -, - OC (= O) NR -, - OC (= O) NAr -, - NAr -, - NR -, - N + RR '-, - N + RAr -, - N + ArAr' -, - S -, - SAr -, - ArS- A heterocyclic group (for example, a heteroatom having at least one nitrogen, oxygen, sulfur, etc., a monocyclic or condensed ring having 3 to 12 carbon atoms,) -OC (= S)-, -OC ( = S) Ar-, -C (= S) O-, -C (= S) OAr-, -C (= S) OAr-, -C (= O) S-, -C (= O) SAr- , -ArC (= O)-, -ArC (= O) NR-, -ArC (= O) NAr-, -ArC (= O) O-, -ArC (= O) O-, -ArC (= O ) S—, —ArC (═S) O—, —ArO—, —ArNR— and the like can be mentioned. Here, R and R ′ each independently represents a hydrogen atom or a linear, branched, or cyclic alkyl group, alkenyl group, or alkynyl group. Ar and Ar ′ each independently represents an aryl group.

Among such linking groups, arylene groups having 6 to 20 carbon atoms (monocyclic, heterocyclic), -C (= O) NR-, -C (= O) NAr-, -O- (alkyleneoxy, poly Alkyleneoxy), -OAr- (aryleneoxy, polyaryleneoxy), -C (= O) O-, -C (= O) O-Ar-, -C (= O)-, -C (= O) Ar-, -S-, -SAr-, -ArS-, -ArC (= O)-, -ArC (= O) O-, -ArC (= O) O-, -ArO-, -ArNR-, etc. Preferably, an arylene group having 6 to 20 carbon atoms (monocyclic, heterocyclic), -C (= O) NR-, -C (= O) NAr-, -O- (alkyleneoxy, polyalkyleneoxy), -OAr -(Aryleneoxy, polyaryleneoxy), -C (= O) O-, -C (= O) O-Ar-,- Ar -, - ArS -, - ArC (= O) -, - ArC (= O) O -, - ArC (= O) O -, - ArO -, - ArNR- are more preferable.
The linking group represented by L may be a combination of two or more of the linking groups listed here.

In Formula (1), m represents an integer of 1 to 6, and when m is 2 or more, a plurality of A may be the same or different. m is preferably 1 to 4 and more preferably 1 to 2 in terms of adhesion.
Although n represents the integer of 1-6, 1-3 are preferable and 1 is especially preferable at the point of stability with time.

  Specific examples of the compound (A) having an acid group and an —SH group are shown below, but the present invention is not limited to these specific examples.

  These compounds may be used alone or in combination of two or more. For example, by combining two or more kinds, physical properties such as mechanical strength of the cured product, sensitivity, and the like can be changed according to the purpose.

Moreover, you may use it combining the compound containing another -SH group as needed.
In particular, when used in combination with a long-chain alkyl group and / or a compound having a fluoroalkyl group having 3 or more fluorine atoms and a —SH group, it has an excellent degree of curing of the surface layer of the photosensitive layer due to its functional action, and a curing reaction. The influence of oxygen on the surface can be reduced, and an image excellent in adhesion to the support can be provided, and a printing plate with high printing durability can be provided.
Furthermore, the compound having an acid group and —SH group of the present invention, a compound having a long-chain alkyl group and / or a fluoroalkyl group having 3 or more fluorine atoms and an —SH group, and other —SH groups When the compound is used in combination, an image excellent in adhesion to the support, the degree of cure of the surface layer of the photosensitive layer, and the degree of cure of the intermediate layer can be obtained, so that a printing plate with higher printing durability can be provided.

  The content of the compound (A) in the present invention is 0 in the total solid content contained in the photosensitive composition when applied to the recording layer of an image recording material such as a photosensitive lithographic printing plate. 0.01 to 50% by mass is preferable, more preferably 0.01 to 30% by mass, and still more preferably 0.1 to 20% by mass.

(B) Polymerization initiator The polymerization initiator contained in the photosensitive layer in the invention is a radical generated by light and / or heat energy, and (C) at least one ethylenically unsaturated bond capable of addition polymerization. It refers to a compound that initiates and accelerates the polymerization reaction of the compound it has.

Specific initiator compounds known to those skilled in the art can be used without limitation. Specifically, for example, Bruce M. Monroe et al., Chemical Review, 93, 435 (1993) and RS Davidson, Journal of Photochemistry and Biology A: Chemistry, 73.81 (1993); JP Faussier, Photoinitiated Polymerization-Theory and Applications ": Rapra Review vol.9, Report, RapraTechnology (1998); M. Tsunooka et al., Prog. Polym. Sci., 21, 1 (1996), etc. 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
A group of compounds that cause oxidative or reductive bond cleavage as described in et al, JACS, 102, 3298 (1980) and the like is also known.

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

(A) Compound which is reduced to generate bond by cleaving bond. Compound having carbon-halogen bond: It is considered that carbon-halogen bond is reductively cleaved to generate active species (for example, 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 them by the synthesis methods described in MP Hutt, EF Elslager and LM Merbel, Journal of Heterocyclic Chemistry, 7,511 (1970). Halomethyloxadiazoles and compounds described in the specifications of German Patent Nos. 2641100, 3333450, 3021590, and 3021599 can be preferably used.

  Compound having nitrogen-nitrogen bond or nitrogen-containing heterocycle-nitrogen-containing heterocycle bond: reductive bond cleavage (for example, described in J. Pys. Chem., 96, 207 (1992)) . Specifically, hexaarylbiimidazoles and the like are preferably used. The active species to be generated are lophine radicals, which together with a hydrogen donor if necessary, initiate radical chain reactions, and image formation using oxidation reactions with lophine radicals is also known (J. Imaging Sci., 30, 215 (1986)).

  Compound having 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)). ) Specifically, for example, iodonium salts described in European Patent No. 104143, US Pat. No. 4,837,124, JP-A-2-150848, JP-A-2-96514, European Patents 370693 and 233567. Sulfonium salts described in U.S. Pat. Nos. 297443, 297442, 279210, 422570, U.S. Pat.Nos. 3,902,144, 4,933,377, 4760013, 4,734,444 and 2,833,827, Diazonium salts (such as benzenediazonium which may have a substituent), diazonium salt resins (formaldehyde resin of diazodiphenylamine), N-alkoxypyridinium salts and the like (for example, US Pat. No. 4,743,528, Kaisho 63-13834 No. 63-142345, JP-A 63-142346, JP-B 46-42363, etc., specifically 1-methoxy-4-phenylpyridinium tetrafluoroborate, etc. Further, compounds described in JP-B Nos. 52-147277, 52-14278, and 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, 156153, 271851, 0388343, U.S. Pat. Nos. 3,901,710 and 4,181,531, 60-198538, Japanese Patent Laid-Open No. 53-133022, nitrobenzester compounds, European Patent No. 099672, No. 84515, No. 199672, No. 0441115, No. 0101122, US Pat. No. 4,618,564, Nos. 4371605, 4431774, JP-A 64-18143, JP-A-2-245756, JP-A-4-365048, iminosulfonate compounds, JP-B-62-2223, Kosho 63-14340, JP 59-17483 Issue JP-like compounds described are listed, further, it includes, for example, compounds as shown 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 aliphatic group or an aromatic group which may be substituted.
Disulfones: Reducing S—S bond reductively and generating an acid. For example, diphenyl disulfones as described in JP-A No. 61-166544 are known.

(B) Oxidation causing bond cleavage to generate active species Alkylate complex: It is considered that a carbon-hetero bond is oxidatively cleaved to generate an active radical (for example, 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 the carbon adjacent to nitrogen is cleaved by oxidation to generate an active radical (see, for example, J. Am. Chem. Soc., 116, 4211 (1994)). be written). 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) Others Although the sensitization mechanism is not clear, many of them can function as initiator compounds. Examples thereof include organometallic compounds such as titanocene and ferrocene, aromatic ketones, acylphosphine, bisacylphosphine and the like, and active species can generate radicals and acids.

  Hereinafter, among the initiator compounds used in the present invention, preferred compounds particularly excellent in sensitivity and stability are specifically exemplified.

(1) Halomethyltriazines Examples include compounds represented by the following formula [II]. Excellent 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 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, Wakabayashi et al., Bull. Chem. Soc. Japan, 4
2,2924 (1969), for example, 2-phenyl-4,6-bis (trichloromethyl) -S-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl) -S -Triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -S-triazine, 2- (2 ′, 4′-dichlorophenyl) -4,6-bis (trichloromethyl) -S-triazine, 2,4,6-tris (trichloromethyl) -S-triazine, 2-methyl-4,6- Bis (trichloromethyl) -S-triazine, 2-n-nonyl-4,6-bis (trichloromethyl) -S-triazine, 2- (α, α, β-trichloroethyl) -4,6-bis (trichloro Methyl) -S- triazine. 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- Naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2- [4- (2-ethoxyethyl) -naphth-1-yl] -4,6-bis-tri Lormethyl-S-triazine, 2- (4,7-dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2- (acenaphtho-5-yl) -4,6-bis Examples include compounds described in German Patent No. 3333724, such as -trichloromethyl-S-triazine, and the like.

  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.

(2) Titanocenes Any titanocene compound that is particularly preferably used as an initiator compound may be any titanocene compound that can generate an active species when irradiated with light in the presence of the sensitizing dye. Well, for example, JP-A-59-152396, JP-A-61-151197, JP-A-63-41483, JP-A-63-41484, JP-A-2-249, JP-A-2-291, Known compounds described in JP-A-3-27393, JP-A-3-12403, and JP-A-6-41170 can be appropriately selected and used.

More specifically, di-cyclopentadienyl-Ti-di-chloride, 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-bis-2,6-difluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,4 -Difluorophenyl-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophen-1-yl, di-methylcyclopentadienyl-Ti- Bis-2, 3, , 6-tetrafluorophenyl-1-yl, di-methylcyclopentadienyl-Ti-bis-2,4-difluorophen-1-yl, bis (cyclopentadienyl) -bis (2,6- And difluoro-3- (pyr-1-yl) phenyl) titanium.

(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 represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkenyl. A 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 bonded to form a cyclic structure. Also good. 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, an alkyl group having 1 to 14 carbon atoms, or an aryl group), —COOR ⁵⁸ or —OR ⁵⁹ (where R ⁵⁸ represents an alkyl group having 1 to 14 carbon atoms). Or an aryl group) is included as a substituent.

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 substituents of the substituted alkyl group. included.

In addition, examples of the heterocyclic group of R ^{51 to} R ⁵⁴ include a 5-membered or more, preferably 5 to 7-membered heterocyclic group containing at least one of N, S, and O. May contain a condensed ring. Furthermore, you may have what was mentioned as a substituent of the above-mentioned substituted aryl group as a substituent.

  Specific examples of the compound represented by the formula [III] include compounds described in the specifications of U.S. Pat. Nos. 3,567,453 and 4,434,891, European Patent Nos. 109772 and 109773, and those shown below. Can be mentioned.

(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-trifluoromethyl Eniru) -4,4 ', 5,5'-tetraphenyl biimidazole.

(5) Onium Salt Compound Examples of the preferred (5) onium salt compound as the radical initiator used in the present invention include compounds represented by the following general formulas (1) to (3).

In general formula (1), Ar ¹ and Ar ² each independently represent an aryl group having 20 or less carbon atoms, which may have a substituent. Preferred substituents when this aryl group has a substituent include a halogen atom, a nitro group, an alkyl group having 12 or less carbon atoms, an alkoxy group having 12 or less carbon atoms, or a carbon atom having 12 or less carbon atoms. An aryloxy group is mentioned. (Z ² ) ⁻ represents a counter ion selected from the group consisting of halogen ion, perchlorate ion, carboxylate ion, tetrafluoroborate ion, hexafluorophosphate ion, and sulfonate ion, preferably perchloric acid Ions, hexafluorophosphate ions, and aryl sulfonate ions.

In General Formula (2), Ar ³ represents an aryl group having 20 or less carbon atoms, which may have a substituent. Preferred examples of the substituent include a halogen atom, a nitro group, an alkyl group having 12 or less carbon atoms, an alkoxy group having 12 or less carbon atoms, an aryloxy group having 12 or less carbon atoms, and 12 or less carbon atoms. Examples thereof include an alkylamino group, a dialkylamino group having 12 or less carbon atoms, an arylamino group having 12 or less carbon atoms, or a diarylamino group having 12 or less carbon atoms. (Z ³ ) ⁻ represents a counter ion having the same meaning as (Z ² ) ⁻ .

In general formula (3), R ²³ , R ²⁴ and R ²⁵ may be the same or different and each represents a hydrocarbon group having 20 or less carbon atoms which may have a substituent. Preferable substituents include a halogen atom, a nitro group, an alkyl group having 12 or less carbon atoms, an alkoxy group having 12 or less carbon atoms, or an aryloxy group having 12 or less carbon atoms. (Z ⁴ ) ⁻ represents a counter ion having the same meaning as (Z ² ) ⁻ .

  Specific examples of onium salts that can be suitably used in the present invention include those described in paragraphs [0030] to [0033] of Japanese Patent Application No. 11-310623 previously proposed by the present applicant. And those described in paragraphs [0015] to [0046] of Japanese Patent Application No. 2000-160323, Japanese Patent Application No. 2000-266797, Japanese Patent Application No. 2001-177150, Japanese Patent Application No. 2000-160323, Specific aromatic sulfonium salt compounds described in Japanese Patent Application No. 2000-184603, Japanese Patent Application No. 2000-310808, Japanese Patent Application No. 2002-265467, and Japanese Patent Application No. 2002-366539 may be mentioned.

  The onium salt used in the present invention preferably has a maximum absorption wavelength of 400 nm or less, and more preferably 360 nm or less. Thus, the photosensitive lithographic printing plate can be handled under white light by setting the absorption wavelength in the ultraviolet region.

(6) Organic peroxide When an organic peroxide type initiator compound is used, radicals can be generated as active species with very high sensitivity.

  The organic peroxide used in the present invention includes almost all organic compounds having one or more oxygen-oxygen bonds in the molecule. Examples thereof include 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-butylperoxide Oxy) cyclohexane, 2,2-bis (t-butylperoxy) butane, t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, paraffin hydroperoxide, 2,5-dimethylhexane 2,5-dihydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, bis (t-butylperoxide Oxyisopropyl) 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, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, Meta-toluoyl peroxide, diisopropyl par Xydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, dimethoxyisopropyl peroxycarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, t-butyl Peroxyacetate, 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 maleate, t -Butyl peroxyisopropyl carbonate, 3 , 3 ′, 4,4′-tetra- (t-butylperoxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra- (t-amylperoxycarbonyl) benzophenone, 3,3 ′, 4, 4′-tetra (t-hexylperoxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra (t-octylperoxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra (cumylperoxy) Carbonyl) benzophenone, 3,3 ′, 4,4′-tetra (p-isopropylcumylperoxycarbonyl) benzophenone, carbonyldi (t-butylperoxydihydrogendiphthalate), carbonyldi (t-hexylperoxydihydrogen) Diphthalate).

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 ′ Peroxide esters such as tetra (cumylperoxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra (p-isopropylcumylperoxycarbonyl) benzophenone, di-t-butyldiperoxyisophthalate are preferred. .
Preferable examples of the initiator compound include titanocene compounds, triazine compounds, and hexaarylbiimidazole compounds, and particularly preferable initiator compounds include hexaarylbiimidazole compounds.

  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, the compatibility with the photosensitive layer can be enhanced by using two or more kinds in combination.
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.

  Still more preferable examples of the radical initiator in the present invention include the above-mentioned aromatic ketones, onium salt compounds, organic peroxides, hexaarylbiimidazole compounds, metallocene compounds, and compounds having a carbon halogen bond. More preferable examples include aromatic iodonium salts, aromatic sulfonium salts, titanocene compounds, and hexaarylbiimidazole compounds.

These radical initiators are 0.1-50 mass% with respect to the total solid of a photosensitive layer, Preferably, it is 0.5-30 mass%, Most preferably, it is a photosensitive composition in the ratio of 5-20 mass%. Can be added inside.
The radical initiator in the present invention is preferably used alone or in combination of two or more.

(C) Polymerizable compound The third essential component “(C) a compound having at least one ethylenically unsaturated bond capable of addition polymerization” in the photosensitive composition of the present invention is obtained by the above-described photoinitiated photoreaction. It is a compound that causes irreversible changes in its physical or chemical properties due to the action of the active species, and causes a curing reaction, color development, decoloring reaction, etc. Especially if it has such properties Any compound can be used without limitation. For example, the compounds listed in the above-mentioned starting system often have such properties.
As the characteristics of the polymerizable compound (C) that changes depending on radicals, acids, and / or bases generated from the photoinitiating system, for example, molecular properties such as absorption spectrum (color), chemical structure, polarizability, It includes changes in material properties such as solubility, 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 the polymerizable compound (C), it is possible to form an image by causing oxidation or reduction by radicals generated from the initiation system. . Such examples include, for example, J. Am. Chem. Soc., 108, 128 (1986), J. Imaging. Soc., 30, 215 (1986), Israel. J. Chem., 25, 264. (1986).

  Among these, a photocurable resin or a negative photopolymer can be formed by using a compound capable of addition polymerization or polycondensation as the polymerizable compound (C) and combining it with an initiation system. Such a composition is also useful as a negative photosensitive layer of a photosensitive lithographic printing plate.

  Examples of such polymerizable compound (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), and anionic polymerizable compounds (such as epoxy). Examples of such compounds are described in, for example, Photopolymer Social Association, Photopolymer Handbook, Kogyo Kenkyukai (1989), Polymer, Vol. 45, 786 (1996), etc. . In addition, a composition in which a thiol compound is used as the polymerizable compound (C) and combined with a photoradical generation system is also well known.

  (C) It is also useful to use an acid-decomposable compound as the polymerizable compound 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. Specific examples thereof include, 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.

  For the purpose of obtaining a highly sensitive photosensitive lithographic printing plate, which is one of the main uses of the photosensitive composition of the present invention, an addition polymerizable compound (C) that is a polymerizable compound is used below. Take this case as an example and describe it in more detail.

(C-1) Addition polymerizable compound An addition polymerizable compound having at least one ethylenically unsaturated double bond, which is a preferred polymerizable compound (C) used in the present invention, has a terminal ethylenically unsaturated bond. It is selected from compounds having at least 1, preferably 2 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,
Those having an aromatic skeleton described in JP-A-59-5240, JP-A-59-5241, JP-A-2-226149, those containing an amino group described in JP-A-1-165613, etc. 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. )

  Further, urethane acrylates such as those described in JP-A-51-37193, JP-B-2-32293, 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, JP-A-1-105238 Can obtain a photosensitive composition having a very high photosensitive speed.

  Other examples include reacting polyester acrylates, epoxy resins and (meth) acrylic acid as described in JP-A-48-64183, JP-B-49-43191 and JP-B-52-30490. And polyfunctional acrylates and methacrylates such as epoxy acrylates. Further, specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337, JP-B-1-40336, and vinylphosphonic acid compounds described in JP-A-2-25493 are also included. be able to. 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 photosensitive lithographic printing plate. 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 area, that is, the cured film, those having three or more functionalities are preferable. Further, 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. With regard to the compounding ratio of the addition polymerizable compound in the photosensitive layer, a larger amount is advantageous in terms of sensitivity, but if it is too much, 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, 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 property, refractive index change, surface adhesiveness, etc. Depending on the case, a layer configuration and coating method such as undercoating and overcoating can be performed.

  (C) The content in the case of using a compound other than the (C-1) addition polymerizable compound as the polymerizable compound can be appropriately selected as appropriate depending on the intended property change or the compound used. Specifically, 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 the photosensitive lithographic printing plate which is a preferred embodiment of the photosensitive composition of the present invention, a binder polymer is further added to the photosensitive composition from the viewpoint of improving film properties. It is preferable to use it.
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 to enable 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 59-44615, JP-B 54-34327, JP-B 58-12777, and JP-B. 54-25957, JP-A-54-92723, JP-A-59-53836, JP-A-59-71048, ie, methacrylic acid copolymer, acrylic acid copolymer , Itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, and partially esterified maleic acid copolymer. 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.

  The binder polymer is preferably a compound having an ethylenically unsaturated bond represented by the following general formulas (a) to (c) in the side chain from the viewpoint of sensitivity. Among these, compounds having an ethylenically unsaturated bond represented by the following general formulas (a) and (b) are most preferable in terms of sensitivity and storage stability.

In the general formulas (a) to (c), R ^{1 to} R ¹¹ each independently represents a monovalent organic group. X and Y each independently represent an oxygen atom, a sulfur atom, or —N—R ¹² . Z represents an oxygen atom, a sulfur atom, —N—R ¹² or a phenylene group. R ¹² represents a hydrogen atom or a monovalent organic group.

In the general formula (a), R ^{1 to} R ³ each independently represents a monovalent organic group, and as R ^l , a hydrogen atom or an alkyl group is preferable, and among them, a hydrogen atom A methyl group is preferred because of high radical reactivity. R ² and R ³ are each independently a hydrogen atom, halogen atom, amino group, carboxyl group, alkoxycarbonyl group, sulfo group, nitro group, cyano group, alkyl group, aryl group, alkoxy group, aryloxy group , Alkylamino group, arylamino group, alkylsulfonyl group, arylsulfonyl group, and the like. Among them, a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, an alkyl group, and an aryl group are preferable because of high radical reactivity.
X represents an oxygen atom, a sulfur atom, or —NR ¹² —, and R ¹² represents a hydrogen atom or a monovalent organic group. Here, examples of R ¹² include an alkyl group which may have a substituent. Among them, a hydrogen atom, a methyl group, an ethyl group, and an isopropyl group are preferable because of high radical reactivity.
Each of the above groups may have a substituent, and examples of the substituent that can be introduced include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, a halogen atom, an amino group, an alkylamino group, and an aryl group. Amino group, carboxyl group, alkoxycarbonyl group, sulfo group, nitro group, cyano group, amide group, alkylsulfonyl group, arylsulfonyl group and the like can be mentioned.

In the general formula (b), R ^{4 to} R ⁸ each independently represents a monovalent organic group, and R ^{4 to} R ⁸ are, for example, a hydrogen atom, a halogen atom, an amino group, a dialkylamino group, Carboxyl group, alkoxycarbonyl group, sulfo group, nitro group, cyano group, alkyl group, aryl group, alkoxy group, aryloxy group, alkylamino group, arylamino group, alkylsulfonyl group, arylsulfonyl group, etc. , A hydrogen atom, a carboxyl group, an alkoxycarbonyl group, an alkyl group, and an aryl group are preferable. Each of these groups may have a substituent, and examples of the substituent that can be introduced include those listed in the general formula (a).
Y represents an oxygen atom, a sulfur atom, or —N—R ¹² . Examples of R ¹² include the same as those in general formula (a).

In the general formula (c), R ^{9 to} R ¹¹ each independently represents a monovalent organic group, and R ⁹ is preferably a hydrogen atom or an alkyl group, among which a hydrogen atom A methyl group is preferred because of high radical reactivity. R ¹⁰ and R ¹¹ are each independently a hydrogen atom, halogen atom, amino group, dialkylamino group, carboxyl group, alkoxycarbonyl group, sulfo group, nitro group, cyano group, alkyl group, aryl group, alkoxy group, aryl Examples thereof include an oxy group, an alkylamino group, an arylamino group, an alkylsulfonyl group, and an arylsulfonyl group. Among them, a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, an alkyl group, and an aryl group are preferable because of high radical reactivity. Each of these groups may have a substituent, and examples of the substituent that can be introduced include those listed in the general formula (a).
Z represents an oxygen atom, a sulfur atom, —NR ¹² —, or a phenylene group which may have a substituent. Examples of R ¹² include an alkyl group which may have a substituent. Among them, a hydrogen atom, a methyl group, an ethyl group, and an isopropyl group are preferable because of high radical reactivity.

  In addition, as the binder polymer in the present invention, those having a carboxyl group in the side chain are preferable from the viewpoint of excellent development removability of the non-image area, and among them, excellent developability and adhesion to the protective layer of the present invention. Therefore, a side chain carboxyl group-containing polymer represented by the following general formula (d) is preferable. Hereinafter, the side chain carboxyl group-containing polymer will be described in detail.

In General Formula (d), R ¹ represents a hydrogen atom or a methyl group, and R ² includes two or more atoms selected from the group consisting of a carbon atom, a hydrogen atom, an oxygen atom, a nitrogen atom, and a sulfur atom. And represents a linking group having 2 to 82 atoms. A represents an oxygen atom or —NR ³ —, and R ³ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms. n represents an integer of 1 to 5.
First, R ¹ in the general formula (d) represents a hydrogen atom or a methyl group, and a methyl group is particularly preferable.

The linking group represented by R ² in the general formula (d) includes two or more atoms selected from the group consisting of a carbon atom, a hydrogen atom, an oxygen atom, a nitrogen atom, and a sulfur atom. Is from 2 to 82, preferably from 2 to 50, and more preferably from 2 to 30. The number of atoms shown here refers to the number of atoms including the substituent when the linking group has a substituent.
More specifically, the number of atoms constituting the main skeleton of the linking group represented by R ² is preferably 1-30, more preferably 3-25, and 4-20. More preferred is 5-10. The “main skeleton of the linking group” in the present invention refers to an atom or an atomic group used only for linking A and the terminal COOH in the general formula (d), and particularly when there are a plurality of linking paths. Refers to an atom or atomic group that constitutes a path with the least number of atoms used. Therefore, when a linking group has a ring structure, the number of atoms to be included differs depending on the linking site (for example, o-, m-, p-, etc.).

More specifically, examples of the linking group represented by R ² in the general formula (d) include alkylene, substituted alkylene, arylene, substituted arylene, and the like, and these divalent groups include a plurality of amide bonds or ester bonds. You may have the structure connected.
Examples of the linking group having a chain structure include ethylene and propylene. A structure in which these alkylenes are linked via an ester bond can also be exemplified as a preferable example.

Among these, the linking group represented by R ² in the general formula (d) is preferably an (n + 1) -valent hydrocarbon group having an aliphatic cyclic structure having 3 to 30 carbon atoms. More specifically, a compound having an aliphatic cyclic structure such as cyclopropane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclodecane, dicyclohexyl, tercyclohexyl, norbornane and the like, which may be substituted by one or more arbitrary substituents And (n + 1) valent hydrocarbon groups by removing (n + 1) hydrogen atoms on an arbitrary carbon atom constituting. R ² preferably has 3 to 30 carbon atoms including a substituent.

One or more arbitrary carbon atoms of the compound constituting the aliphatic cyclic structure may be replaced with a heteroatom selected from a nitrogen atom, an oxygen atom, or a sulfur atom. In terms of printing durability, R ² is a condensed polycyclic aliphatic hydrocarbon, a bridged cyclic aliphatic hydrocarbon, a spiro aliphatic hydrocarbon, an aliphatic hydrocarbon ring assembly (a plurality of rings are connected by a bond or a linking group). And (n + 1) valent hydrocarbon group having an aliphatic cyclic structure which may have a substituent having 5 to 30 carbon atoms and containing two or more rings. preferable. Also in this case, the carbon number includes the carbon atom of the substituent.

Most preferably, the linking group represented by R ² is one having 5 to 10 atoms constituting the main skeleton of the linking group, and is structurally a chain structure having an ester bond in the structure. And those having a cyclic structure as described above are preferred.

  Although depending on the design of the photosensitive layer, a substituent having a hydrogen atom capable of hydrogen bonding, particularly a substituent having an acid dissociation constant (pKa) smaller than that of carboxylic acid tends to lower the printing durability. Therefore, it is not preferable. On the other hand, hydrophobic substituents such as halogen atoms, hydrocarbon groups (alkyl groups, aryl groups, alkenyl groups, alkynyl groups), alkoxy groups, aryloxy groups and the like are more preferable because they tend to improve printing durability. When the cyclic structure is a monocyclic aliphatic hydrocarbon having 6 or less members such as cyclopentane or cyclohexane, it preferably has such a hydrophobic substituent. If possible, these substituents may be bonded to each other or with a substituted hydrocarbon group to form a ring, and the substituent may be further substituted.

R ³ in the case where A in the general formula (d) is NR ³ — represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms. Examples of the monovalent hydrocarbon group having 1 to 10 carbon atoms represented by R ³ include an alkyl group, an aryl group, an alkenyl group, and an alkynyl group.
Specific examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, isopropyl group, isobutyl group, sec-butyl group, 1 carbon number such as tert-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclopentyl group, cyclohexyl group, 1-adamantyl group, 2-norbornyl group Up to 10 linear, branched or cyclic alkyl groups.
Specific examples of the aryl group include carbon having one heteroatom selected from the group consisting of an aryl group having 1 to 10 carbon atoms such as a phenyl group, a naphthyl group, and an indenyl group, a nitrogen atom, an oxygen atom, and a sulfur atom. Examples include heteroaryl groups of 1 to 10, such as furyl, thienyl, pyrrolyl, pyridyl, and quinolyl groups.
Specific examples of the alkenyl group include those having 1 to 10 carbon atoms such as vinyl group, 1-propenyl group, 1-butenyl group, 1-methyl-1-propenyl group, 1-cyclopentenyl group, 1-cyclohexenyl group and the like. A linear, branched, or cyclic alkenyl group is mentioned.
Specific examples of the alkynyl group include alkynyl groups having 1 to 10 carbon atoms such as ethynyl group, 1-propynyl group, 1-butynyl group, and 1-octynyl group. The substituent that R ³ may have is the same as those exemplified as the substituent that R ² can introduce. However, the carbon number of R < ³ > is 1-10 including the carbon number of a substituent.

A in the general formula (d) is preferably an oxygen atom or —NH— because synthesis is easy.
Further, n in the general formula (d) represents an integer of 1 to 5, and is preferably 1 in terms of printing durability.

  Furthermore, as the binder polymer of the present invention, those having an amide group in the side chain are preferred from the viewpoint of excellent developability, storage stability, and adhesiveness to the protective layer. A polymer having an amide group represented by e) is more preferable.

In general formula (e), Z represents —CO— or —SO ₂ —, and R represents a hydrogen atom or a monovalent organic group. Z is particularly preferably —CO—, and R is preferably a hydrogen atom, an alkyl group which may have a substituent, an aryl group, an alicyclic group, or a heterocyclic group.

  Moreover, a linear organic polymer can also be used as a binder polymer in this invention. As such a “linear organic polymer”, a known one can be arbitrarily used. Preferably, a linear organic polymer that is soluble or swellable in water or weak alkaline water is selected in order to enable water development or weak alkaline water development. The linear organic polymer is selected and used not only as a film-forming agent for the photosensitive layer but also according to the use as water, weak alkaline water or organic solvent developer. For example, when a water-soluble organic polymer is used, water development becomes possible. Examples of such linear organic polymers include radical 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-54-25957. Disclosed in JP-A-54-92723, JP-A-59-53836, and JP-A-59-71048, that is, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer. Examples thereof include a polymer, a crotonic acid copolymer, a maleic acid copolymer, and a partially esterified maleic acid copolymer. 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 a polymer having a hydroxyl group are useful.

  Among these, in particular, (meth) acrylic resins having a benzyl group or an allyl group and a carboxyl group in the side chain, and Japanese Patent Application Laid-Open Nos. 2000-187322, 2002-62648, 2001-253217, and Japanese Patent Application Alkali-soluble resins having a double bond in the side chain described in JP-A-2002-287920, JP-A-2002-62648 and the like are excellent in balance of film strength, sensitivity, and developability, and are preferable.

  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-based 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.

  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.

  The glass transition point (Tg) of such a binder polymer is preferably in the range of 60 to 300 ° C, more preferably 80 to 250 ° C, and most preferably 90 to 200 ° C, from the viewpoint of storage stability and sensitivity.

  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) is appropriately selected from the viewpoint of image strength and developability. The acid value is preferably 0.4 to 3.0 meq / g, more preferably the acid value is in the range of 0.6 to 1.3 meq / g.

The weight average molecular weight of the binder polymer used in the present invention is preferably 1,000 or more, more preferably 10,000 to 200,000, and the number average molecular weight is preferably 1,500 or more. More preferably, it is the range of 2000-250,000. The polydispersity (weight average molecular weight / number average molecular weight) is preferably 1 or more, and more preferably 1.1 to 10.
These binder polymers may be random polymers, block polymers, graft polymers or the like, but are preferably random polymers.

The binder polymer used in the present invention can be synthesized by a conventionally known method. Solvents used in the synthesis include, for example, tetrahydrofuran, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, diethylene glycol dimethyl ether, 1-methoxy. Examples include 2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, toluene, ethyl acetate, methyl lactate, ethyl lactate, dimethyl sulfoxide, and water. These solvents are used alone or in combination of two or more.
As the radical polymerization initiator used for synthesizing the polymer used in the present invention, known compounds such as azo initiators and peroxide initiators can be used.

  The binder polymer used in the present invention may be used alone or in combination. The amount of these binder polymers added to the photosensitive layer in the present invention is 20 to 95% by mass, preferably 30 to 90% by mass, based on the total solid content. By making the addition amount 20% by mass or more, the effect of improving the strength of the image portion can be obtained when an image is formed. Further, when the addition amount is 95% by mass or less, image formation becomes possible. The content ratio of (C) addition polymerizable compound and (D) binder polymer is preferably in the range of 1/3 to 7/3 by mass ratio.

(E) Sensitizing dye The photosensitive layer according to the invention preferably further contains a sensitizing dye from the viewpoint of improving sensitivity. The sensitizing dye is used for the purpose of improving the exposure sensitivity according to the absorption wavelength. For this reason, a dye suitable for the exposure wavelength may be selected according to the image forming mechanism. As the sensitizing dye, (1) those having absorption in the 350 nm to 450 nm region, (2) those having absorption in the infrared region, and the like are appropriately used. The exposure of the wavelength that can be absorbed by the sensitizing dye promotes the radical generation reaction of the polymerization initiator (B) and the polymerization reaction of the addition polymerizable compound (C).

(1) Sensitizing dye having absorption in the region of 350 to 450 nm Examples of such a sensitizing dye include compounds represented by the following general formulas (XIV) to (XVIII).

In formula (XIV), A ¹ represents a sulfur atom or NR ⁵⁰ , R ⁵⁰ represents an alkyl group or an aryl group, and L ² forms a basic nucleus of the dye together with adjacent A ¹ and an adjacent carbon atom. R ⁵¹ and R ⁵² each independently represent a hydrogen atom or a monovalent nonmetallic atomic group, and R ⁵¹ and R ⁵² may be bonded to each other to form an acidic nucleus of the dye. Good. W represents an oxygen atom or a sulfur atom.

  Preferred specific examples of the compound represented by the general formula (XIV) are shown below.

In formula (XV), Ar ¹ and Ar ² each independently represent an aryl group, and are linked via a bond with —L ³ —. Here, L ³ represents —O— or —S—. W is synonymous with that shown in the general formula (XIV).

  Preferable examples of the compound represented by the general formula (XV) include the following.

In the formula (XVI), A ² represents a sulfur atom or NR ⁵⁹ , L ⁴ represents a nonmetallic atomic group that forms a basic nucleus of the dye together with adjacent A ² and a carbon atom, R ⁵³ , R ⁵⁴ , R ⁵⁵ , R ⁵⁶ , R ⁵⁷ and R ⁵⁸ each independently represent a monovalent nonmetallic atomic group, and R ⁵⁹ represents an alkyl group or an aryl group.

  Preferable examples of the compound represented by the general formula (XVI) include the following.

In formula (XVII), A ³ and A ⁴ each independently represent —S— or —NR ⁶³ — or —NR ⁶⁴ —, wherein R ⁶³ and R ⁶⁴ each independently represent a substituted or unsubstituted alkyl group, substituted or Represents an unsubstituted aryl group, and L ⁵ and L ⁶ each independently represent a nonmetallic atomic group that forms a basic nucleus of a dye in combination with adjacent A ³ , A ^4, and adjacent carbon atoms; R ⁶¹ and R ⁶² are each independently a monovalent nonmetallic atomic group, or can be bonded to each other to form an aliphatic or aromatic ring.

  Preferable examples of the compound represented by the general formula (XVII) include the following.

In formula (XVIII), R ⁶⁶ represents an aromatic ring or a hetero ring which may have a substituent, and A ⁵ represents an oxygen atom, a sulfur atom or —NR ⁶⁷ —. R ⁶⁴ , R ⁶⁵ and R ⁶⁷ each independently represent a hydrogen atom or a monovalent nonmetallic atomic group, and R ⁶⁷ and R ⁶⁴ , and R ⁶⁵ and R ⁶⁷ each represent an aliphatic or aromatic ring. Can be combined to form.

  Preferable specific examples of the compound represented by the general formula (XVIII) include those shown below.

Examples of the sensitizing dye also include compounds represented by the following general formula (I). As the sensitizing dye having absorption in the region of 350 to 450 nm, the compound represented by formula (I) is most preferable from the viewpoint of sensitivity.

  In the general formula (I), A represents an aromatic ring or a hetero ring which may have a substituent, and X represents an oxygen atom, a sulfur atom or —NR 1 —. R1, R2, R3, and R6 each independently represent a hydrogen atom or a monovalent nonmetallic atomic group, and R4 and R5 each independently represent a monovalent nonmetallic atomic group. A, R3, R4, R5, and R6 can be bonded to each other to form an aliphatic or aromatic ring.

Here, when R 1, R 2, R 3, R 4, R 5 and R 6 represent a monovalent nonmetallic atomic group, they preferably represent a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.
Next, preferred examples of R1, R2, R3, R4, R5, and R6 will be specifically described. Examples of preferable alkyl groups include linear, branched, and cyclic alkyl groups having 1 to 20 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, a propyl group, Butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, octadecyl, eicosyl, isopropyl, isobutyl, s-butyl, Examples thereof include t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group and 2-norbornyl group. Of these, linear alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, and cyclic alkyl groups having 5 to 10 carbon atoms are more preferable.

  Specific examples of preferable aryl groups as R1, R2, R3, R4, R5, and R6 include those in which 1 to 3 benzene rings form a condensed ring, and a benzene ring and a 5-membered unsaturated ring form a condensed ring. Specific examples include phenyl group, naphthyl group, anthryl group, phenanthryl group, indenyl group, acenaphthenyl group, fluorenyl group, and among these, phenyl group, naphthyl group Is more preferable.

A more preferred example of R1 includes a substituted or unsubstituted aryl group, and a more preferred example of R2 and R6 includes a substituted or unsubstituted alkyl group. Particularly preferred examples of R2 include an alicyclic alkyl group, and specific examples include a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Preferred examples of R3, R4, and R5 include a substituted or unsubstituted aryl group or a substituted or unsubstituted alkyl group. Particularly preferred examples include R3 and R4, or R4 and R5, or R3. This is a case where R5 is bonded with a divalent linking group. Specifically, it is preferable that a cycloalkyl structure is formed between R3, R4 and R5. Preferable cycloalkyl structures include a cyclohexyl structure, a cycloheptyl structure, a cyclooctyl structure, and an adamantane structure. The reason why these substituents are suitable is not clear, but by having such substituents, the interaction between the electronically excited state caused by light absorption and the initiator compound becomes particularly large, and the radical of the initiator compound The efficiency of generating an acid or base is improved (sensitivity improving effect), and a bulky structure is introduced adjacent to the imine structure, so that hydrolysis, oxidative decomposition, etc. from the photosensitive film due to decomposition of the imine structure It is conceivable that disappearance is suppressed (storage stability improving effect).

Next, A in the general formula (I) will be described. A represents an aromatic ring or a hetero ring which may have a substituent, and specific examples of the aromatic ring or hetero ring which may have a substituent include R1, R2, R3 in the general formula (I) , R4, R5 and R6 are the same as those exemplified in the description.
Among them, preferable A includes an alkoxy group, a thioalkyl group, and an aryl group having an amino group, and more preferable A includes an aryl group having an amino group. Particularly preferred aryl groups having an amino group include a dialkylaminoaryl group and a diarylaminoaryl group. Specifically, a dimethylaminophenyl group, a diethylaminophenyl group, a piperidinophenyl group, a morpholinophenyl group, and a julolidine group. And a diphenylaminophenyl group.

  Although the preferable specific example (Exemplary compound D1-Exemplary compound D9) of the sensitizing dye represented by general formula (I) based on this invention is shown below, this invention is not limited to these.

  These sensitizing dyes can be subjected to various chemical modifications for improving the characteristics of the photosensitive layer. For example, by combining a sensitizing dye and an addition polymerizable compound structure (for example, acryloyl group or methacryloyl group) by a method such as covalent bond, ionic bond, hydrogen bond, etc. It is possible to suppress unnecessary precipitation of the dye from the film.

Furthermore, for the purpose of enhancing the processability of the photosensitive layer to an (alkali) aqueous developer, a hydrophilic moiety (carboxyl group and its ester, sulfonic acid group and its ester, ethylene oxide) is used for these sensitizing dyes. It is effective to introduce an acid group or polar group). In particular, ester-type hydrophilic groups have a relatively hydrophobic structure in the photosensitive layer and are therefore excellent in compatibility. In the developer, acid groups are generated by hydrolysis, and hydrophilicity is increased. Has characteristics.
In addition, for example, a substituent can be appropriately introduced into the sensitizing dye in order to improve compatibility in the photosensitive layer and suppress crystallization. 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 into the sensitizing dye, adhesion to an inorganic substance such as a metal or a metal oxide can be improved. In addition, a method such as polymerization of a sensitizing dye can be used depending on the purpose.

  Details of the usage, such as which structure of these sensitizing dyes are used, whether they are used alone or in combination of two or more, and how much is added, can be appropriately set in accordance with the performance design of the final photosensitive material . For example, the compatibility with the photosensitive composition layer can be enhanced 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 physical properties of the photosensitive layer when used for a lithographic printing plate precursor. It is. The photosensitivity of the photosensitive layer, the resolution, and the physical properties of the exposed film are greatly affected by the absorbance at the light source wavelength. Therefore, the addition amount of the sensitizing dye is appropriately selected in consideration of these factors. 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 are cases 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, the substrate adhesion Will be insufficient. When used as a lithographic printing plate used in a relatively thin film thickness, (1) the addition amount of the sensitizing dye having absorption in the region of 350 to 450 nm is such that the absorbance of the photosensitive layer is 0.1 to 1.5. Is preferably set to be in the range of 0.25 to 1. When used as a photosensitive lithographic printing plate, this is generally 0.05 to 30 parts by weight, preferably 0.1 to 20 parts by weight, more preferably 0.2 to 100 parts by weight of the photosensitive layer component. It is the range of -10 mass parts.

(2) Sensitizing dye having absorption in the infrared region In the present invention, as a sensitizing dye having absorption in the infrared region (specifically, a wavelength of about 680 nm to 1200 nm), infrared light is absorbed and thermal energy is absorbed. It is preferable to contain an infrared absorbing agent that converts it into the following. Examples of such an infrared absorber include a known spectral sensitizing dye, or a dye or pigment that absorbs light and interacts with a photo radical initiator. By using such (2) sensitizing dye, the photosensitive layer of the present invention has infrared sensitivity.

<Spectral sensitizing dye or dye>
Spectral sensitizing dyes or dyes preferred as infrared absorbers used in the present invention are polynuclear aromatics (for example, pyrene, perylene, triphenylene), xanthenes (for example, fluorescein, eosin, erythrosine, rhodamine B, rose bengal). ), Cyanines (eg, thiacarbocyanine, oxacarbocyanine), merocyanines (eg, merocyanine, carbomerocyanine), thiazines (eg, thionine, methylene blue, toluidine blue), acridines (eg, acridine orange, chloroflavin) , Acriflavine), phthalocyanines (eg, phthalocyanine, metal phthalocyanine), porphyrins (eg, tetraphenylporphyrin, central metal-substituted porphyrin), chlorophylls (eg, chlorophyll) Le, chlorophyllin, center metal-substituted chlorophyll), metal complexes (for example, the following compound), anthraquinones (e.g., anthraquinone), squaryliums (e.g., squarylium), and the like.

More preferable spectral sensitizing dyes or dyes include compounds described in the following publications.
The pyrylium salts described in Japanese Patent Publication No. 40-28499, for example, the following compounds may be mentioned.

  Examples of the cyanines described in JP-B No. 46-42363 include the following compounds.

  Examples of the benzofuran dye described in JP-A-2-63053 include the following compounds.

  Examples of the conjugated ketone dyes disclosed in JP-A-2-85858 and JP-A-2-216154 include the following compounds.

  Examples thereof include dyes described in JP-A-57-10605 and azocinnamylidene derivatives described in JP-B-2-30321, such as the following compounds.

  Examples of the cyanine dyes described in JP-A-1-287105 include the following compounds.

  Examples of the xanthene dyes described in JP-A Nos. 62-31844, 62-31848, and 62-143043 include the following compounds.

  Aminostyryl ketone described in JP-B-59-28325, for example, the following compounds may be mentioned.

  Further, in particular, the following infrared absorbing dyes or pigments are also preferably used as the sensitizing dye. Preferred examples of the dye include cyanine dyes described in JP-A-58-125246, JP-A-59-84356, JP-A-59-202829, JP-A-60-78787, and the like. Examples include cyanine dyes described in Japanese Patent No. 434,875.

Other cyanine dyes that can be suitably used in the present invention include those disclosed in JP-A-200200.
Described in paragraph numbers [0017] to [0019] of Japanese Patent Application Laid-Open No. 1-133969, paragraph numbers [0012] to [0038] of Japanese Patent Application Laid-Open No. 2002-40638, and paragraph numbers [0012] to [0023] of Japanese Patent Application Laid-Open No. 2002-23360. Can be mentioned. Specific examples include those exemplified below.

Further, as a sensitizing dye, a near infrared absorption sensitizer described in US Pat. No. 5,156,938 is also preferably used, and further described in US Pat. No. 3,881,924. Substituted arylbenzo (thio) pyrylium salts, trimethine thiapyrylium salts described in JP-A-57-142645 (US Pat. No. 4,327,169), JP-A-58-1810
No. 51, No. 58-220143, No. 59-41363, No. 59-84248, No. 59-84249, No. 59-146063, No. 59-146061, JP-A 59 -216146, the cyanine dye described in US Pat. No. 4,283,475, the pentamethine thiopyrylium salt and the like, and Japanese Patent Publication Nos. 5-13514 and 5-19702 A pyrylium compound is also preferably used.

  In addition, near infrared absorbing dyes described as formulas (I) and (II) in US Pat. No. 4,756,993 and phthalocyanine dyes described in EP 916513A2 are also preferable dyes. Can do.

Furthermore, the anionic infrared absorber described in Japanese Patent Application No. 10-79912 can also be suitably used. An anionic infrared absorbing agent refers to an anionic infrared absorbing agent having an anionic structure without a cationic structure in the mother nucleus of a dye that substantially absorbs infrared rays. For example, (b) anionic metal complex, (b) anionic carbon black, (c) anionic phthalocyanine, and (d) a compound represented by the following general formula (i). The counter cation of these anionic infrared absorbers is a monovalent cation containing a proton or a polyvalent cation.
As the sensitizing dye having absorption in the infrared region, the compound represented by the general formula (i) is most preferable in terms of sensitivity.

  Here, (a) an anionic metal complex refers to an anion formed by the central metal of the complex part that substantially absorbs light and the entire ligand.

  (B) Examples of the anionic carbon black include carbon black to which anionic groups such as sulfonic acid, carboxylic acid, and phosphonic acid groups are bonded as substituents. In order to introduce these groups into carbon black, as described in Carbon Black Handbook 3rd Edition (Edited by Carbon Black Association, April 5, 1995, published by Carbon Black Association), page 12, What is necessary is just to take means, such as oxidizing carbon black.

  (C) Anionic phthalocyanine refers to a phthalocyanine skeleton having the anion group previously mentioned in the description of (b) as a substituent bonded to form an anion as a whole.

Next, (d) the compound represented by the general formula (i) will be described in detail. In the general formula (i), G ⁹ represents an anionic substituent, and G ¹⁰ represents a neutral substituent. (X ¹⁰ ) ⁺ represents a 1 to m-valent cation containing a proton, and m represents an integer of 1 to 6. M ⁵ represents a conjugated chain, and this conjugated chain M ⁵ may have a substituent or a ring structure. The conjugated chain M ⁵ can be represented by the following formula.

In the formula, R ⁸⁰ , R ⁸¹ and R ⁸² are each independently a hydrogen atom, halogen atom, cyano group, alkyl group, aryl group, alkenyl group, alkynyl group, carbonyl group, thio group, sulfonyl group, sulfinyl group, oxy A group and an amino group, which may be linked to each other to form a ring structure. n represents an integer of 1 to 8.

  Of the anionic infrared absorbers represented by the general formula (i), those of the following IRA-1 to IRA-5 are preferably used.

  Moreover, the cationic infrared absorber shown to the following IRC-1-IRC-44 can also be used preferably.

In the structural formula, T ⁻ represents a monovalent counter anion, preferably a halogen anion (F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ ), a Lewis acid anion (BF ₄ ⁻ , PF ₆ ⁻ , SbCl _6). ⁻ , ClO ₄ ⁻ ), an alkyl sulfonate anion, and an aryl sulfonate anion.

  The alkyl of the alkyl sulfonic acid means a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, a butyl group. , Pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, octadecyl, eicosyl, isopropyl, isobutyl, s-butyl, t- A butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group, and 2-norbornyl group can be exemplified. 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.

  The aryl of the aryl sulfonic acid includes one consisting of one benzene ring, two or three benzene rings forming a condensed ring, and benzene ring and five-membered unsaturated ring forming 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, and among these, a phenyl group and a naphthyl group are more preferable.

  Moreover, the nonionic infrared absorber shown to the following IRN-1-IRN-9 can also be used preferably.

  Among the exemplified compounds, IRA-1 is a particularly preferred anionic infrared absorber, and IRC-7, IRC-30, IRC-40, and IRC-42 are nonionic infrared absorbers as cationic infrared absorbers. As IRN-9.

<Pigment>
Examples of infrared absorbing pigments used in the present invention include commercially available pigments and color index (CI) manual, “Latest Pigment Handbook” (edited by Japan Pigment Technical Association, published in 1977), “Latest Pigment Application Technology” (CMC). Publication, 1986), “Printing Ink Technology” CMC Publishing, 1984) can be used.

  Examples of the pigment include black pigments, yellow pigments, orange pigments, brown pigments, red pigments, purple pigments, blue pigments, green pigments, fluorescent pigments, metal powder pigments, and other polymer-bonded dyes. Specifically, insoluble azo pigments, azo lake pigments, condensed azo pigments, chelate azo pigments, phthalocyanine pigments, anthraquinone pigments, perylene and perinone pigments, thioindigo pigments, quinacridone pigments, dioxazine pigments, isoindolinone pigments , Quinophthalone pigments, dyed lake pigments, azine pigments, nitroso pigments, nitro pigments, natural pigments, fluorescent pigments, inorganic pigments, carbon black, and the like. Among these pigments, carbon black is preferable.

  These pigments may be used without surface treatment, or may be used after surface treatment. The surface treatment method includes a method of surface coating with a resin or wax, a method of attaching a surfactant, a method of bonding a reactive substance (eg, silane coupling agent, epoxy compound, polyisocyanate, etc.) to the pigment surface, etc. Can be considered. The above-mentioned surface treatment methods are described in “Characteristics and Applications of Metal Soap” (Yokoshobo), “Printing Ink Technology” (CMC Publishing, 1984) and “Latest Pigment Application Technology” (CMC Publishing, 1986). Yes.

  The particle diameter of the pigment is preferably in the range of 0.01 μm to 10 μm, preferably in the range of 0.05 μm to 1 μm, from the viewpoint of the stability of the dispersion in the photosensitive layer coating solution and the uniformity of the photosensitive layer. More preferably, it is particularly preferably in the range of 0.1 μm to 1 μm.

  As a method for dispersing the pigment, a known dispersion technique used in ink production, toner production, or the like can be used. Examples of the disperser include an ultrasonic disperser, a sand mill, an attritor, a pearl mill, a super mill, a ball mill, an impeller, a disperser, a KD mill, a colloid mill, a dynatron, a three-roll mill, and a pressure kneader. Details are described in "Latest Pigment Applied Technology" (CMC Publishing, 1986).

The sensitizing dye added to accelerate the polymerization reaction (curing reaction) may be directly added together with other components in the photosensitive layer. However, another layer adjacent to the sensitizing dye may be provided to the photosensitive layer. Even if it is added, the same effect can be obtained.
In particular, when the photosensitive layer in the present invention is used as a material for a negative photosensitive layer of a photosensitive lithographic printing plate described later, it may be added to the same layer as the photosensitive layer, or another layer is provided there. Although it may be added, when a negative photosensitive lithographic printing plate is prepared, the optical density at the absorption maximum in the wavelength range of 300 nm to 1200 nm of the photosensitive layer is between 0.1 and 3.0. Is preferable from the viewpoint of sensitivity. Since the optical density is determined by the addition amount of the sensitizing dye and the thickness of the photosensitive layer, the predetermined optical density can be obtained by controlling both conditions. The optical density 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 method of measuring, a method of forming a photosensitive layer on a reflective support such as aluminum, and measuring a reflection density.
The addition amount of the sensitizing dye having absorption in the infrared region to the photosensitive layer is preferably about 0.5 to 20% by mass, and more preferably 2 to 10% by mass.

(F) 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.
(F-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 co-sensitizer reacts with various intermediate active species (radicals and cations) generated in the course of the photoreaction initiated by the thermal polymerization initiator and the subsequent addition polymerization reaction to generate new active radicals. Estimated. 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 sodium arylsulfinate and the like.

(C) Compounds that react with radicals to convert into highly active radicals or act as chain transfer agents: For example, compounds having SH, PH, SiH, and 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-mercaptobenzthiazoles, 2-mercaptobenzoxazoles, 2-mercaptobenzimidazoles and the like.

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 to suppress crystal precipitation, substituents that improve 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.

(F-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-t-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 to form a photosensitive lithographic printing plate. 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.

(F-3) Colorant, etc. Furthermore, when the photosensitive composition of the present invention is used in a photosensitive lithographic printing plate, 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 a colorant, many dyes cause a decrease in the sensitivity of the 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.

(F-4) Other additives Further, when the photosensitive composition of the present invention is used for photosensitive lithographic printing plates, inorganic fillers, other plasticizers, and photosensitive layer surfaces are 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), which will be described later, a UV initiator, a thermal crosslinking agent, or the like can be added to enhance the effect of heating and exposure after development.
In addition, it is also possible to provide an additive and an intermediate layer for improving the adhesion between the photosensitive layer and the support and improving the development and removal 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 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 photosensitive lithographic printing plate, when a photosensitive layer is formed by coating on a support, the components of the photosensitive layer are appropriately used as a coating composition in which a photosensitive composition is dissolved in a solvent. To be served. 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 organic solvents such as ethyl. 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 the photosensitive layer of the photosensitive lithographic printing plate for scanning exposure which is a preferred embodiment of the photosensitive composition of the present invention is generally about 0.1 g / m ² to about 10 g in terms of the mass after drying. A range of / m ² is suitable. More preferably from 0.5 to 5 g / m ^2.

  In addition, the photosensitive layer coating solution has a nonionic interface as described in JP-A Nos. 62-251740 and 3-208514 in order to increase the processing stability of the photosensitive layer with respect to development conditions. Activators, amphoteric surfactants as described in JP-A-59-121044 and JP-A-4-13149, and fluorine-based surfactants as described in JP-A-62-170950 are added. can do.

  Specific examples of the nonionic surfactant include sorbitan tristearate, sorbitan monopalmitate, sorbitan trioleate, stearic acid monoglyceride, polyoxyethylene nonylphenyl ether and the like.

  Specific examples of amphoteric surfactants include alkyldi (aminoethyl) glycine, alkylpolyaminoethylglycine hydrochloride, 2-alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine, N-tetradecyl-N, N- Examples include betaine type (for example, trade name Amorgen K, manufactured by Dai-ichi Kogyo Co., Ltd.).

  The proportion of each surfactant in the photosensitive layer coating solution is preferably 0.05 to 15% by mass, more preferably 0.1 to 5% by mass.

(Support)
In order to obtain a photosensitive lithographic printing plate 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 (for example, 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 to 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 Patent Publication No. 47-5125, an aluminum plate is 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 support body provided with electrolytic grains as disclosed in JP-B-46-27481, JP-A-52-58602, JP-A-52-30503, and the above-mentioned anodizing treatment and sodium silicate treatment. A combined surface treatment is also useful. Further, those obtained by sequentially performing mechanical surface roughening, chemical etching, electrolytic graining, anodizing treatment and sodium silicate treatment 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 US Pat. No. 3,055,295 and JP-A-56-13168, and a hydrophilic swelling described in JP-A-9-80744. Examples thereof include sol-gel films made of titanium oxide, polyvinyl alcohol, and silicic acids described in JP-A-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 using the photosensitive composition of this invention for the photosensitive lithographic printing plate for scanning exposure, a protective layer can be provided on the photosensitive layer containing a polymeric compound as needed. Such a photosensitive lithographic printing plate is usually exposed in the air, but the protective layer is low in oxygen, basic substances, etc. present in the air that inhibit the image forming reaction caused by exposure in the photosensitive layer. It prevents the mixing of molecular compounds into the photosensitive layer and prevents the inhibition of image formation reaction due to exposure in the atmosphere. 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, and 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, the use of polyvinyl alcohol as the main component gives the best results in terms of basic characteristics 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 an oleophilic 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, 20 to 60% by mass of acrylic emulsion or water-insoluble vinylpyrrolidone-vinyl acetate copolymer is mixed in a hydrophilic polymer made of polyvinyl alcohol and laminated on the photosensitive layer, thereby providing sufficient adhesion. It is described that it is obtained. Any of these known techniques can be applied to the protective layer in the present invention. Such a coating method for 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 photosensitive lithographic printing plate using the photosensitive composition of the present invention is made into a lithographic printing plate, it is usually exposed to a developing solution after exposure processing (image exposure) described in detail below. The unexposed part of the layer is removed to form an image. As a preferred developing solution when these photosensitive compositions are used for preparing a lithographic printing plate, a developing solution 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. An inorganic alkaline agent and an aqueous solution of an organic alkaline agent such as monoethanolamine or diethanolamine are 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.

  As a particularly preferred developer used here, a nonionic compound described in JP-A No. 2002-202616 is contained, the pH is 11.5 to 12.8, and the conductivity is 3 to 30 mS / cm. And a developer having

  In the plate making process of the photosensitive lithographic printing plate 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, heat treatment is performed in the range of 200 to 500 ° C. 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 a photosensitive lithographic printing plate 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 is an internal drum system, an external drum system,
Any of a flat bed system etc. may be sufficient. 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: YAG as a solid state laser (YVO ₄ ) and SHG crystal × 2 combinations (355 nm, 5 mW to 1 W), Cr: LiSAF and SHG crystal combination (430 nm, 10 mW), KNbO ₃ ring resonator (430 nm, 30 mW) as a semiconductor laser system, Combination of waveguide type wavelength conversion element and AlGaAs, InGaAs semiconductor (380 nm to 450 nm, 5 mW to 100 mW), combination of waveguide type wavelength conversion element and AlGaInP, AlGaAs semiconductor (300 nm to 350 nm, 5 mW to 100 mW), AlGaInN (350 nm to 350 nm) 450nm, 5mW-30mW) and other pulse lasers Te N ₂ laser (337 nm, pulse 0.1~10mJ), XeF (351nm, pulse 10 to 250 mJ) and available.
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 a lithographic printing plate exposure apparatus of a 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 a 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) External drum (multi-beam) system Drum rotation speed F (radians / s), photosensitive material sub-scanning length Lx (cm), resolution Z (dots / cm), total exposure time t (s), 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 rotational speed H of the polygon mirror (radians / s), the sub-scanning length Lx (cm) of the photosensitive material, the resolution Z (dots / cm), the total exposure time t (s), Equation (eq4) is generally established between the number of beams (n).
H.Z.n.t = Lx (eq4)

The resolution (2560 dpi) required for the actual printing plate, plate size (A1 / B1, sub-scan length 42 inch), exposure conditions of about 20 sheets / hour and the photosensitive characteristics (photosensitive wavelength, By substituting (sensitivity: about 0.1 mJ / cm ² ) into the above equation, it can be understood that a combination with a multi-beam exposure method of a semiconductor laser is more preferable in the photosensitive 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.

(Back coat layer)
A back coat is provided on the back surface of the support as necessary. As such a backcoat, a coating comprising a metal oxide obtained by hydrolysis and polycondensation of an organic polymer compound described in JP-A-5-45885 and an organic or inorganic metal compound described in JP-A-6-35174 A layer is preferably used.
Among these coating layers, silicon alkoxy compounds such as Si (OCH ₃ ) ₄ , Si (OC ₂ H ₅ ) ₄ , Si (OC ₃ H ₇ ) ₄ , and Si (OC ₄ H ₉ ) ₄ are available at a low price. The coating layer of the metal oxide provided therefrom is particularly preferred because of its excellent development resistance.

(Middle layer)
The photosensitive lithographic printing plate according to the invention may be provided with an intermediate layer for the purpose of improving adhesion between the photosensitive layer and the support and soiling. Specific examples of such an intermediate layer include JP-B-50-7481, JP-A-54-72104, JP-A-59-101651, JP-A-60-149491, JP-A-60-232998, JP-A-3-56177, JP-A-4-282737, JP-A-5-16558, JP-A-5-246171, JP-A-7-159983, JP-A-7-314937, JP-A-8-202025, Special Kaihei 8-320551, JP 9-34104, JP 9-236911, JP 9-269593, JP 10-69092, JP 10-115931, JP 10-161317, JP 10-260536, JP-A-10-282682, JP-A-11-84684, Japanese Patent Application No. 8-225335, Japanese Patent Application No. 8-270098, Japanese Patent Application No. 9-195863, Japanese Patent Application No. 9-195864, Japanese Patent Application No. 9-89646, Japanese Patent Application No. 9-106068, Japanese Patent Application No. 9-183834, Japanese Patent Application No. 9-264411, Japanese Patent Application No. 9 -127232, Japanese Patent Application No. 9-245419, Japanese Patent Application No. 10-127602, Japanese Patent Application No. 10-170202, Japanese Patent Application No. 11-36377, Japanese Patent Application No. 11-165661, Japanese Patent Application No. 11-284091 No., Japanese Patent Application No. 2000-14697, and the like.

(Exposure, development and printing)
Since the photosensitive lithographic printing plate according to the present invention has the photosensitive layer in the present invention described above, exposure with an infrared laser, exposure with an ultraviolet lamp, and thermal recording with a thermal head are possible. In the present invention, image exposure is preferably performed by a solid-state laser and a semiconductor laser that emit infrared rays having a wavelength of 760 nm to 1200 nm.

  In addition, as other exposure light rays for the photosensitive composition of the present invention, ultrahigh pressure, high pressure, medium pressure, and 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 photosensitive lithographic printing plate 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 Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples.
<Synthesis Examples 1 and 2>
(Synthesis Example 1: Synthesis of Exemplary Compound (A-16))
40 g of 2,5-dimercapto-1,3,4-thiadiazole was dissolved in 200 ml of N, N-dimethylacetamide and cooled to 0 ° C. A solution of sodium hydroxide 11.3 g in methanol 80 ml was added dropwise, and after completion of the addition, the mixture was reacted for 10 minutes. 1,2.9-cyclohexyldicarboxylic acid anhydride (42.9 g) was added little by little, and after all was added, the mixture was reacted at room temperature for 6 hours. The reaction solution was poured into 900 ml of water, and the precipitated crystals were collected by filtration and dried. The obtained crude crystals were isolated and purified by silica gel column chromatography (elution solvent: ethyl acetate / methanol = 95/5 to 90/10) to obtain 18 g of compound (A-16). Identification was performed by ¹ H-NMR, infrared absorption spectrum, mass spectrometry spectrum, and elemental analysis.

(Synthesis Example 2: Synthesis of Exemplified Compound (A-25))
After dissolving 45 g of trithiocyanuric acid in 200 ml of N, N-dimethylacetamide, 36.6 g of acrylic acid was added. The temperature was raised to 100 ° C. and reacted for 8 hours. The reaction solution was poured into 800 ml of water, and the precipitated crystals were collected by filtration and dried. The obtained crude crystals were isolated and purified by silica gel column chromatography (elution solvent: ethyl acetate / methanol = 95/5 to 90/10) to obtain 10 g of compound (A-25). Identification was performed by ¹ H-NMR, infrared absorption spectrum, mass spectrometry spectrum, and elemental analysis.

<Examples 1 to 6, Comparative Example 1>
(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 indication according to JISB0601).

A back coat coating solution was applied to the back surface of the substrate thus treated with a bar coater and dried at 100 ° C. for 1 minute to prepare a support provided with a back coat layer having a coating amount after drying of 70 mg / m ² . . The backcoat coating solution was prepared by adding the following additive solution to the following sol-gel reaction solution and by the method shown below.

(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 additive solution.

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

(Coating of photosensitive layer)
On the aluminum support thus treated, a photosensitive composition having the following composition was applied in a dry coating amount of 1.0 to 2.0 g / m ² and dried at 80 ° C. for 2 minutes to form a photosensitive layer. Formed.

(Photosensitive composition)
(A) component (compound of Table 1) 0.16g
(B) The following polymerization initiator (I-1) 0.20 g
(C) The following polymerizable compound (M-1) 1.2 g
The following binder polymer (P-1) 1.2g
The following sensitizing dye (D-4) 0.12 g
Fluorine nonionic surfactant (F-780F)
0.03g
Thermal polymerization inhibitor 0.01g
(N-nitrosophenylhydroxylamine aluminum salt)
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 Methyl ethyl ketone 20 g
20g propylene glycol monomethyl ether

(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 photosensitive lithographic printing plate.

(Sensitivity evaluation)
A Fuji step guide manufactured by Fuji Photo Film Co., Ltd. (gray scale whose transmission optical density changes discontinuously at ΔD = 0.15) is adhered to the photosensitive lithographic printing plate thus obtained, Exposure was performed with a xenon lamp through an optical 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 was used as an optical filter, and exposure was performed with 400 nm monochromic 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

(Exposure of photosensitive lithographic printing plate)
The photosensitive lithographic printing plate obtained as described above was subjected to solid image exposure and 175 lines / inch by using 400 nm monochromatic light as a light source and adjusting the exposure power so that the plate surface exposure energy density was 100 μJ / cm ² . A halftone image exposure of 1 to 99% in 1% increments was performed.

(Development / plate making)
Development processing was performed using an automatic processor Stablon 900N manufactured by Fuji Photo Film Co., Ltd. As the developer, a 1: 4 water diluted solution of DV-2 manufactured by Fuji Photo Film Co., Ltd. was used for both the feed solution and the replenisher solution. The temperature of the developing bath was 30 ° C. As the finisher, a 1: 1 water dilution (pH = 10.8) of FN-6 manufactured by Fuji Photo Film Co., Ltd. was used.

(Print durability test)
R201 manufactured by Roland was used as the printing machine, and GEOS-G (N) manufactured by Dainippon Ink was used as the ink. While the printing was continued, the solid image portion and the printed matter of the 3% halftone dot portion were observed, and the printing durability was examined based on the number of images on which the image began to fade. The larger the number, the better the printing durability. The evaluation results are shown in Table 1.

  In Table 1, the structure of the compound (A-1, 2, 6, 9, 16, 27) of the component (A) of the present invention is the same as that of the exemplified compound. Moreover, the structure of the compound (PA-1) used for the comparative example is as shown below. The compound (PA-1) used in the comparative example is a compound outside the scope of the present invention.

  As is apparent from Table 1, all the photosensitive lithographic printing plates using the photosensitive negative image forming material of the present invention can form images with high sensitivity, and the solid portion printing durability and halftone dot printing durability. Excellent in properties.

<Examples 7 to 12, Comparative Examples 2 and 3>
An intermediate layer, a photosensitive layer, and a protective layer were sequentially formed on the support used in Example 1 by the following procedure to prepare a photosensitive lithographic printing plate.

(Coating intermediate layer)
Prepare the following intermediate layer coating solution on the surface of the support so that the amount of phenylphosphonic acid applied is 20 mg / m ² , apply it at 180 rpm with a wheeler, and dry at 80 ° C. for 30 seconds. To form an intermediate layer.

(Interlayer coating solution)
Phenylphosphonic acid 0.07g ~ 1.4g
Methanol 200g

(Coating of photosensitive layer)
On the support provided with the intermediate layer, a photosensitive composition having the following composition was prepared, and coated with a wheeler so that the coating amount became 1.0 to 2.0 g / m ² , and at 100 ° C. for 1 minute. A photosensitive layer was formed by drying.

(Photosensitive composition)
(A) component (compound of Table 2) 0.25g
(B) The following polymerization initiator (I-2) 0.23 g
(C) 2.1 g of the following addition polymerizable compound (M-2)
2.0 g of the binder polymer (P-1)
The following sensitizing dye (D-5) 0.18 g
Color pigment dispersion 2.0g
(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 Thermal polymerization inhibitor 0.01 g
(N-nitrosophenylhydroxylamine aluminum salt)
Fluorosurfactant 0.02g
(Dai Nippon Ink Chemical Co., Ltd., MegaFuck F-780F)
Methyl ethyl ketone 20.0g
Propylene glycol monomethyl ether 20.0g

(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 photosensitive lithographic printing plate.

(Exposure of photosensitive lithographic printing plate)
The photosensitive lithographic printing plate obtained as described above was subjected to solid image exposure and 175 lines / inch by using 400 nm monochromatic light as a light source and adjusting the exposure power so that the plate surface exposure energy density was 100 μJ / cm ² . A halftone image exposure of 1 to 99% in 1% increments was performed.
Separately, as forced aging conditions, exposure was performed after storage at 60 ° C. and 50% RH for 3 days before exposure, or at 45 ° C. and 75% RH for 3 days.

(Development / plate making)
Development processing was performed using an automatic processor Stablon 900N manufactured by Fuji Photo Film Co., Ltd. As the developer, a 1: 4 water diluted solution of DV-2 manufactured by Fuji Photo Film Co., Ltd. was used for both the feed solution and the replenisher solution. The temperature of the developing bath was 30 ° C. As the finisher, a 1: 1 water dilution (pH = 10.8) of FN-6 manufactured by Fuji Photo Film Co., Ltd. was used.

(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. The evaluation results are shown in Table 2.

(Stain resistance test)
Using R201 manufactured by Roland as a printing machine and printing using GEOS-G (S) manufactured by Dainippon Ink & Chemicals, Inc. as an ink, the obtained printed matter was observed, and the non-image area (unexposed Part) was visually evaluated for stain resistance. The evaluation results are shown in Table 2.

  In addition, the structure of the compound (A-16, 17, 19, 24, 25, 28) of the component (A) of the present invention used as an addition polymerization compound for the photosensitive layer in Table 2 is the same as that of the exemplified compound. The structures of compounds (PA-2) and (PA-3) used in Comparative Examples are shown below. Compounds (PA-2) and (PA-3) are compounds outside the scope of the present invention.

  As is apparent from Table 2, the photosensitive lithographic printing plate using the photosensitive negative image-forming material of the present invention is excellent in printing durability, and even when subjected to forced aging, non-image areas are stained. Absent.

<Examples 13 to 18, Comparative Examples 4 and 5>
(Coating of photosensitive layer)
On a support provided with an intermediate layer similar to that in Example 7, a photosensitive composition having the following composition was prepared and applied with a wheeler so that the coating amount was 1.0 to 2.0 g / m ² . A photosensitive layer was formed by drying at 100 ° C. for 1 minute.

(Photosensitive composition)
(A) component (compound of Table 3)
(B) Polymerization initiator (I-1) 0.22 g
(C) 2.0 g of the following addition polymerizable compound (M-3)
The following binder polymer (P-3) 2.0 g
The following sensitizing dye (D-6) 0.19 g
Color pigment dispersion 2.0g
(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 Thermal polymerization inhibitor 0.01 g
(N-nitrosophenylhydroxylamine aluminum salt)
Fluorosurfactant 0.02g
(Dai Nippon Ink Chemical Co., Ltd., MegaFuck F-780F)
Methyl ethyl ketone 20.0g
Propylene glycol monomethyl ether 20.0g

(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 photosensitive lithographic printing plate.

(Exposure of photosensitive lithographic printing plate)
The photosensitive lithographic printing plate obtained as described above was subjected to solid image exposure and 175 lines / inch by using 400 nm monochromatic light as a light source and adjusting the exposure power so that the plate surface exposure energy density was 100 μJ / cm ² . A halftone image exposure of 1 to 99% in 1% increments was performed.

(Development / plate making)
Development processing was performed using an automatic processor Stablon 900N manufactured by Fuji Photo Film Co., Ltd. As the developer, a 1: 4 water diluted solution of DV-2 manufactured by Fuji Photo Film Co., Ltd. was used for both the feed solution and the replenisher solution. The temperature of the developing bath was 30 ° C. As the finisher, a 1: 1 water dilution (pH = 10.8) of FN-6 manufactured by Fuji Photo Film Co., Ltd. was used.
Here, development was performed while changing the conveyance speed of the automatic developing machine, and printing plates having different developer immersion times were produced.

(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. The results are shown in Table 3.

  In Table 3, the structures of the compounds (A-16) and (A-25) of the component (A) of the present invention used as the addition polymerization compound of the photosensitive layer are the same as those of the exemplified compound. The structures of compounds (AA-1), (AA-2), (BA-1), and (BA-2) are shown below. Compounds (AA-1), (AA-2), (BA-1), and (BA-2) are compounds outside the scope of the present invention.

As is apparent from Table 3, the photosensitive lithographic printing plate using the photosensitive negative image-forming material containing the component (A) of the present invention has a solid image portion and 3% regardless of the developer immersion time. Excellent printing durability at halftone dots. As shown in Examples 14, 15, 17 and 18, in the photosensitive negative image forming material, together with the component (A) of the present invention, the compounds (AA-1), (AA-) outside the scope of the present invention Even if 2), (BA-1) and (BA-2) are contained, the effect of the present invention is not changed.

<Examples 19 to 33, Comparative Examples 6 to 10>
(Coating of photosensitive layer)
On a support provided with an intermediate layer similar to that in Example 7, a photosensitive composition having the following composition was prepared and applied with a wheeler so that the coating amount became 1.0 to 2.0 g / m ² . A photosensitive layer was formed by drying at 100 ° C. for 1 minute.

(Photosensitive composition)
(A) component (compound of Table 4) 0.60g
(B) Polymerization initiator (compound described in Table 4) 0.28 g
(C) 1.1 g of the following addition polymerizable compound (M-4)
1.1 g of the above addition polymerizable compound (M-3)
Compound (PA-2) 1.20 g
The following binder polymer (P-2) 2.0g
The following sensitizing dye (D-9) 0.20 g
Color pigment dispersion 2.0g
(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 Thermal polymerization inhibitor 0.01 g
(N-nitrosophenylhydroxylamine aluminum salt)
Fluorosurfactant 0.02g
(Dai Nippon Ink Chemical Co., Ltd., MegaFuck F-780F)
Methyl ethyl ketone 20.0g
Propylene glycol monomethyl ether 20.0g

(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 photosensitive lithographic printing plate.

(Exposure of photosensitive lithographic printing plate)
The photosensitive lithographic printing plate obtained as described above was subjected to solid image exposure and 175 lines / inch by using 400 nm monochromatic light as a light source and adjusting the exposure power so that the plate surface exposure energy density was 100 μJ / cm ² . A halftone image exposure of 1 to 99% in 1% increments was performed.
Separately, as forced aging conditions, exposure was performed after storage at 60 ° C. and 50% RH for 3 days before exposure, or at 45 ° C. and 75% RH for 3 days.

(Development / plate making)
Development processing was performed using an automatic processor Stablon 900N manufactured by Fuji Photo Film Co., Ltd. As the developer, a 1: 4 water diluted solution of DV-2 manufactured by Fuji Photo Film Co., Ltd. was used for both the feed solution and the replenisher solution. The temperature of the developing bath was 30 ° C. As the finisher, a 1: 1 water dilution (pH = 10.8) of FN-6 manufactured by Fuji Photo Film Co., Ltd. was used.

(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. The results are shown in Table 4.

(Stain resistance test)
Using R201 manufactured by Roland as a printing machine and printing using GEOS-G (S) manufactured by Dainippon Ink & Chemicals, Inc. as an ink, the obtained printed matter was observed, and the non-image area (unexposed Part) was visually evaluated for stain resistance. The evaluation results are also shown in Table 4.

  In Table 4, the structure of the compound (A-19, 23, 28) of the component (A) of the present invention used as the addition polymerization compound of the photosensitive layer is the same as that of the exemplified compound. The structures of the compounds (I-3) to (I-6) used for the polymerization initiator are shown below. Compounds (PA-2) and (I-1) are as described above.

  As is apparent from Table 4, the photosensitive lithographic printing plate using the photosensitive negative image-forming material of the present invention is excellent in printing durability and is free from non-image area staining even when subjected to forced aging.

<Examples 34 to 40, Comparative Examples 11 to 14>
(undercoat)
The following undercoat liquid was applied to the same aluminum support as in Example 1 with a wire bar, and dried at 90 ° C. for 30 seconds using a hot air dryer. The coating amount after drying was 10 mg / m ² .

(Undercoat liquid)
0.1 g of a copolymer of ethyl acrylate and 2-acrylamido-2-methyl-1-propanesulfonic acid sodium salt in a molar ratio of 75:15
2-Aminoethylphosphonic acid 0.1g
50g of methanol
Ion exchange water 50g

(Coating of photosensitive layer)
A photosensitive composition having the following composition was prepared, applied to the aluminum support obtained as described above using a wire bar, and dried at 115 ° C. for 45 seconds with a hot air dryer to form a recording layer. did. The coating amount after drying was in the range of 1.2 to 1.3 g / m ² .

(Recording layer coating solution)
(A) 0.21 g of compounds described in Table 5
(B) Polymerization initiator (compound described in Table 5) 0.28 g
(C) The following polymerizable compound (M-5) 0.60 g
The polymerizable compound (M-1) 0.60 g
The following binder polymer (P-4) 1.10 g
Infrared absorber (compound described in Table 5) 0.08 g
N-phenyliminodiacetic acid monoanilide 0.12 g
0.04g of ethyl violet chloride salt
Fluorosurfactant 0.02g
(Megafuck F-176, manufactured by Dainippon Ink & Chemicals, Inc.)
Methyl ethyl ketone 9.0g
Methanol 8.0g
1-methoxy-2-propanol 8.0g

(Formation of protective layer)
Next, the following protective layer coating solution was applied to the surface of the photosensitive layer using a slide hopper, and dried at 120 ° C. for 75 seconds with a hot air drying apparatus to provide a protective layer to obtain a photosensitive lithographic printing plate. . In addition, the film | membrane mass of the protective layer after application | coating and drying was 1.3-1.6 g / m < ² >.

(Protective layer coating solution)
Polyvinyl alcohol PVA105 (Kuraray Co., Ltd.) 2.5g
Nonionic surfactant 0.03g
(EMAREX NP-10 manufactured by Nippon Emulsion Co., Ltd.)
Ion exchange water 96.9g

(Exposure of photosensitive lithographic printing plate)
The obtained negative photosensitive lithographic printing plate was subjected to the conditions of 9 W output, 210 rpm outer drum rotation speed, 100 mJ / cm ² plate surface energy, and 2400 dpi resolution on a Trendsetter 3244VFS manufactured by Creo equipped with a water-cooled 40 W infrared semiconductor laser. Exposed.
Separately, as forced aging conditions, exposure was performed after storage at 60 ° C. and 50% RH for 3 days before exposure, or at 45 ° C. and 75% RH for 3 days.

(Development / plate making)
After the exposure, the film was developed using an automatic processor Stablon 900N manufactured by Fuji Photo Film Co., Ltd. As the developer, a 1: 4 water diluted solution of DV-2 manufactured by Fuji Photo Film Co., Ltd. was used for both the feed solution and the replenisher solution. The temperature of the developing bath was 30 ° C. As the finisher, a 1: 1 water dilution (pH = 10.8) of FN-6 manufactured by Fuji Photo Film Co., Ltd. was used.

(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. The results are shown in Table 5.

(Stain resistance test)
Using R201 manufactured by Roland as a printing machine and printing using GEOS-G (S) manufactured by Dainippon Ink & Chemicals, Inc. as an ink, the obtained printed matter was observed, and the non-image area (unexposed Part) was visually evaluated for stain resistance. The evaluation results are also shown in Table 5.

  In Table 5, the structure of the compound (A-18) of the component (A) of the present invention used as the addition polymerization compound for the photosensitive layer is the same as that of the exemplified compound. The structures of the compounds (IS-2, 4, 5, 6) and infrared absorbers (IR-1) to (IR-3) used for the polymerization initiator are shown below. Compound (PA-1) is as described above.

  As is apparent from Table 5, the photosensitive lithographic printing plate using the photosensitive negative image-forming material of the present invention is excellent in printing durability and is free from non-image area staining even when subjected to forced aging.

Claims (5)

A support, and
(A) a compound having an acid group and a —SH group,
A photosensitive negative image forming material having a photosensitive layer containing (B) a polymerization initiator and (C) a compound having at least one addition-polymerizable ethylenically unsaturated bond. The photosensitive negative image-forming material according to claim 1, wherein the compound (A) having an acid group and a -SH group is a compound represented by the following formula (1).
In formula (1),
A represents a group having an acid group selected from carboxylic acid, sulfonic acid, and phosphoric acid.
X represents a heterocyclic group.
m represents an integer of 1 to 6, and when two or more, a plurality of A may be the same or different.
n represents an integer of 1 to 6.   3. The photosensitive negative image forming according to claim 2, wherein the total number of nitrogen atoms, sulfur atoms and oxygen atoms contained in the heterocyclic ring represented by X in the formula (1) is 2 or more. material.   The photosensitive negative image-forming material according to claim 2, wherein the number of nitrogen atoms contained in the heterocyclic group represented by X in formula (1) is 2 or more.   The photosensitive negative image-forming material according to claim 1, wherein the polymerization initiator (B) is a hexaarylbiimidazole compound.