JPH03225341A - Photosensitive composition - Google Patents

Abstract

PURPOSE:To obtain a photosensitive material for a plano-graphic plate high in printing resistance by incorporating a novolak resin containing an o- naphthoquinonediazido compound and <= 5 wt.% phenols and an organic acid or acid anhydride. CONSTITUTION:The novolak resin is synthesized by condensing one of phenols with formaldehyde in the presence of an acid catalyst and the content of the excess phenols is reduced to <= 5 wt.% after the synthesis by heating under reduced pressure or the like. It is preferred that the novolak resin has a weight average molecular weight Mw of 2.0X10<3> - 2.0X10<4>, and a number average molecular weight Mn of 7.0X10<2> - 5.0X10<3>, and the novolak resin containing the <= 5 wt.% phenols in an amount of 50 - 90 wt.% of the photosensitive composition, thus permitting high sensitivity and superior underdeveloability to be obtained.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a photosensitive composition used in a photosensitive lithographic printing plate, and more particularly to a photosensitive composition containing a novolac resin as an alkali-soluble resin. be.

[Prior Art] Usually, the photosensitive layer of a positive photosensitive lithographic printing plate contains a quinonediazide compound as a photosensitive substance and an alkali-soluble resin as a component for increasing film strength and alkali solubility. . In particular, as the alkali-soluble resin, novolac resin is generally used from the viewpoint of strength of the image area, oil sensitivity, abrasion resistance, etc.

[Problems to be Solved by the Invention] However, since novolac resins are usually obtained by condensing phenols and formaldehyde in the presence of an acid catalyst, residual components of phenols such as cresol are inevitably present in the resin. As a result, environmental problems have arisen due to odors caused by residual components during processes such as coating liquid preparation, coating, drying, or plate making of photosensitive lithographic printing plates.

In order to solve this problem, attempts have been made to remove the phenols remaining in the novolac resin, but although this improves the odor problem, it reduces the sensitivity of the resulting photosensitive lithographic printing plate. In addition, development tolerance, particularly under-development properties, deteriorated, resulting in a problem of poor printing durability. Here, under-developability refers to a situation in which the photosensitive layer in the non-image area of the printing plate is not completely dissolved when processed with a developer whose developing ability has decreased due to fatigue due to multilayer processing or deterioration due to air oxidation. This refers to the acceptable range of reduction in developing ability within which results can be obtained.

Therefore, an object of the present invention is to improve the odor caused by the novolak resin in a photosensitive composition using a novolak resin as an alkali-soluble resin without reducing the sensitivity and under-developability of the resulting photosensitive lithographic printing plate. The purpose of the present invention is to provide a photosensitive composition that can be used as a photosensitive composition.

Another object of the present invention is to provide a photosensitive composition suitable for a photosensitive lithographic printing plate having excellent printing durability.

[Means for Solving Problem 1] In view of the above-mentioned problems, the present inventors have conducted intensive research and found that the above-mentioned object of the present invention is to obtain (a) an ortho-naphthoquinone diazide compound, (b) a 51% by weight unvortexed It has been found that this can be achieved by providing a photosensitive composition characterized by containing a novolak resin containing phenols and (c) an organic acid and/or an acid anhydride.

The present invention will be explained in more detail below.

The novolak resin used in the present invention is a resin obtained by condensing phenols and formaldehyde in the presence of an acid catalyst. Examples of the phenols include phenol, 0-cresol, -1-cresol, p-cresol, , 3,5-xylenol, 2,4-xylenol, 2
, 5-xylenol, carvacrol, resorcinol, hydroquinone, pyrogallol, phloroglucin, and the like. The above phenols can be used alone or in combination with formaldehyde to obtain a resin. Among these, preferred novolac resins are resins obtained by copolycondensing formaldehyde with at least one selected from phenol, -cresol (or 0-cresol), and p-cresol, such as phenol-formaldehyde resin, -Cresol/formaldehyde resin, 0-cresol/formaldehyde resin, phenol/p-cresol/formaldehyde copolymer resin, -monocresol/p-cresol/formaldehyde copolycondensate resin, O-cresol/p-cresol/formaldehyde copolymer resin Polycondensate resin, phenol, -cresol, p-cresol,
Examples include formaldehyde copolycondensate resins and phenol/〇-cresol/p-cresol/formaldehyde copolycondensate resins. Furthermore, among the above-mentioned novolak resins, phenol-mono-cresol-p-cresol-formaldehyde resin is preferred.

The novolac resin used in the present invention contains less than 5% by weight of phenols used for synthesis, preferably 3.5% by weight.
Although it contains no more than 3% by weight, more preferably no more than 3% by weight, such a novolak resin can be prepared by, for example, heating under reduced pressure after synthesis.

In the present invention, the above novolac resins may be used alone or in combination of two or more.

The molecular weight (polystyrene standard) of the novolac resin is a weight average molecular weight MW of 2. 0X1 03 ~2
．． Ox 104, number average molecular weight Mn is 7, OX10
2-5. The value is preferably within the range of OX103, and more preferably, the MW is 3.0×103 to 6,0×
103, Mn is 7.7X 1 02 ~ 1, 2X 1
The value is within the range of 03. The molecular weight of the novolak resin in the present invention is measured by GPC (gel permeation chromatography).

The novolac resin containing less than 5% by weight of phenols is preferably contained in the photosensitive composition of the present invention in an amount of 30 to 95% by weight, preferably 50 to 90% by weight.

In the present invention, various alkali-soluble resins other than the above-mentioned novolac resins can be contained within a range that does not impair the purpose of the present invention. Examples of the resins used include vinyl polymers having phenolic hydroxyl groups and/or carboxyl groups, and urethane resins having carboxyl groups.

As vinyl polymers having phenolic hydroxyl groups,
Preferably used are polymers formed by polymerization by cleavage of carbon-carbon double bonds and containing at least one structural unit of the following general formulas [I] to [VI].

General formula [I] 1+CR+ R2-CRs + 0-Go-B-OH General formula [I[] +CRI R2-CRa ← C0NR+-+A+rB-OH General formula [1[[] % formula% (General formula [IV] +CR+R2 CRs- -0H General formula [V] OH General formula [VI] OH In the formula, R1 and R2 each represent a hydrogen atom, an alkyl group, or a carboxyl group, preferably a hydrogen atom. R3 is a hydrogen atom, Represents a halogen atom or an alkyl group, preferably a hydrogen atom or an alkyl group such as a methyl group or an ethyl group.R+ is a hydrogen atom, an alkyl group,
Represents an aryl group or an aralkyl group, preferably a hydrogen atom. A represents an alkylene group that may have a substituent that connects a nitrogen atom or an oxygen atom and an aromatic carbon atom, - represents an integer from 0 to 10, and B represents a phenylene group that may have a substituent. Represents a naphthylene group which may have a group or a substituent. In the present invention, among these, a copolymer containing at least one structural unit represented by the general formula [II] is preferred.

The vinyl polymer preferably has a copolymer-type structure, and in such a copolymer, at least one structural unit represented by each of the general formulas [I] to [VI] Monomeric units that can be used in combination with, for example, ethylenically unsaturated olefins such as ethylene, propylene, isobutylene, butadiene, isoprene, etc., such as styrene, α-methylstyrene,
Styrenes such as p-methylstyrene and p-chlorostyrene, acrylic acids such as acrylic acid and methacrylic acid, unsaturated aliphatic dicarboxylic acids such as itaconic acid, maleic acid, and maleic anhydride, such as methyl acrylate, acrylic Ethyl acrylate, 1ln-butyl acrylate, isobutyl acrylate, dodecyl acrylate, 2-acrylic acid
Esters of α-methylene aliphatic monocarboxylic acids such as chloroethyl, phenyl acrylate, α-methyl chloroacrylate, methyl methacrylate, ethyl methacrylate, and ethyl taacrylate; Nitriles such as acrylonitrile and methacrylonitrile; e.g. Amides such as acrylamide, for example, anilides such as acrylanilide, p-chloroacrylanilide, -12-O acrylanilide, -1methoxyacrylanilide, such as vinyl acetate, vinyl propionate, vinyl benzoate, vinyl butyrate, etc. Vinyl esters, such as methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, β-chloroethyl vinyl ether, vinyl chloride, vinylidene chloride, vinylidene cyanide, such as 1-methyl-1-methoxyethylene,
Ethylene derivatives such as 1.1-dimethoxyethylene, 1.2-dimethoxyethylene, 1.1-dimethoxycarbonylethylene, 1-methyl-1-nitroethylene, such as N-vinylpyrol, N-vinylcarbazole, N-vinylindole There are vinyl monomers such as N-vinyl compounds such as , N-vinylvirolone, and N-vinylpyrrolidone. These vinyl monomers exist in polymer compounds with a structure in which unsaturated double bonds are cleaved.

Among the above monomers, (meth)acrylic acids, esters of aliphatic monocarboxylic acids, and nitriles are used in combination with at least one of the structural units represented by general formulas [I] to [VI]. shows excellent overall performance and is preferable. More preferred are methacrylic acid, methyl methacrylate, acrylonitrile, ethyl acrylate, and the like.

These monomers may be bonded to the vinyl polymer in either a block or random manner.

In the vinyl polymer, general formulas [I] to [VI
] The content of the structural units shown in each is 5 to 70
It is preferably mol %, particularly preferably 10 to 40 mol %.

Typical examples of vinyl polymers used in the present invention are listed below. In addition, in the compounds exemplified below, MW
is the weight average molecular weight, Mn is the number average molecular weight, s, j!
, o, m and n each represent mol% of the structural unit.

Exemplary compound CH.

(i) (j) CfJ,.

(k) CH.

Examples of vinyl copolymers having a carboxyl group include acrylic acids such as acrylic acid and methacrylic acid; unsaturated aliphatic dicarboxylic acids such as itaconic acid, maleic acid, and maleic anhydride; Examples include vinyl copolymers synthesized using polymer components as essential components. In the copolymer, monomer components having carboxyl groups include, for example, ethylene,
Ethylenically unsaturated olefins such as propylene, isobutylene, butadiene, isoprene; e.g. styrene, α
- Styrenes such as methylstyrene, p-methylstyrene, p-chlorostyrene: for example, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, dodecyl acrylate, 112-chloroethyl acrylate, phenyl acrylate, Esters of α-methylene aliphatic monocarboxylic acids such as α-methyl chloroacrylate, methyl methacrylate, ethyl methacrylate, and ethyl ethacrylate: Nitriles such as acrylonitrile and methacrylonitrile; Amides such as acrylamide: e.g. Imides such as N-7 enylmaleimide:
For example, anilides such as acrylanilide, p-chloroacrylanilide, -m:troacrylanilide, -methoxyacrylanilide; vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate, vinyl butyrate; for example, methyl vinyl ether , ethyl vinyl ether, isobutyl vinyl ether, β-chloroethyl vinyl ether and other vinyl ethers: vinyl chloride: vinylidene chloride; vinylidene cyanide: for example 1-methyl-1-methoxyethylene, 1.1-dimethoxyethylene, 1.2-dimethoxyethylene , 1.1-
Ethylene derivatives such as dimethoxycarbonylethylene and 1-methyl-1-nitroethylene; for example, N-vinyl compounds such as N-vinylpyrrole, N-vinylcarbazole, N-vinylindole, N-vinylvirolone, and N-vinylpyrrolidone; Preferable examples include vinyl monomers such as . These vinyl monomers exist in polymer compounds with a structure in which unsaturated double bonds are cleaved.

In the present invention, among the above monomers, esters of aliphatic monocarboxylic acids and nitriles are particularly preferably used.

These monomers may be bound in the above-mentioned polymer compound in either a block or random manner.

In addition, as a urethane resin having a carboxyl group,
Preferred examples include polyurethane resins whose basic skeleton is a reaction product of a diisocyanate compound represented by the following general formula (A) and a diol compound having a carboxyl group represented by the general formula (B) or (c).

0CN-R1-NGO(A) HO-Rs -Ar -R4-OHRs
(c) oOH In the formula, R1 represents a divalent aliphatic or aromatic hydrocarbon which may have a substituent. If necessary, other functional groups that do not react with isocyanate groups in R1, such as esters,
It may have a urethane, amide, or ureido group.

R2 is a hydrogen atom, alkyl which may have a substituent,
It represents a multigroup such as aralkyl, aryl, alkoxy, and aryloxy, preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group having 6 to 15 carbon atoms. R3,
'R4 and R5 may be the same or different, and represent a single bond, a divalent aliphatic group which may have a substituent, or an aromatic hydrocarbon group. Preferably carbon number 1-20
alkylene group, arylene group having 6 to 15 carbon atoms,
More preferably, it represents an alkylene group having 1 to 811 carbon atoms. If necessary, R3, R4, and R5 may contain other functional groups that do not react with isocyanate groups, such as ester, urethane, amide, ureido, and ether.

In addition, two or three of R2, R3, R4 and R5
may form a ring.

A" represents a trivalent aromatic hydrocarbon group which may have a substituent, preferably an aromatic group having 6 to 15 carbon atoms.

Specifically, the diisocyanate compound represented by the general formula (A) includes 2,4-tolylene diisocyanate, 2
．． Dimer of 4-tolylene diisocyanate, 2.6-tolylene diisocyanate, p-xylylene diisocyanate, metaxylylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, 3.3'- Aromatic diisocyanate compounds such as dimethyl-biphenyl-4,4' diisocyanate, etc.Aliphatic diisocyanate compounds such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, dimer acid diisocyanate, etc.: inphorone diisocyanate, 4,4 '-Methylenebis(cyclohexyl isocyanate), methylcyclohexane-2,4(or 2.6
) diisocyanate, alicyclic diisocyanate compounds such as 1j3-(isocyanatomethyl)cyclohexane, etc.: diisocyanates which are reaction products of diols and diisocyanates, such as adducts of 1 mol of 1,3-butylene glycol and 2 mols of tolylene diisocyanate; Examples include compounds.

Further, specifically, the diol compound having a carboxyl group represented by the general formula (B) or (c) is 3.5-
Dihydroxybenzoic acid, 2,2-bis(hydroxymethyl)propionic acid, 2,2-bis(hydroxyethyl)
Propionic acid, 2゜2-bis(3-hydroxypropyl)propionic acid, 2.2-bis(hydroxymethyl)acetic acid, bis-(4-hydroxyphenyl)acetic acid 1.4.4-
Examples include bis-(4-hydroxyphenyl)pentanoic acid and tartaric acid.

The polyurethane resin may be formed from a diisocyanate compound represented by the general formula (A) and two or more diol compounds having a carboxyl group represented by the general formula (B) or (c).

In the present invention, an alkali-soluble resin other than the novolac resin of the present invention is contained in the photosensitive composition, for example, at a concentration of 2 to 80%.
Contains % by weight.

As the O-naphthoquinonediazide compound in the present invention, for example, an ester compound of O-naphthoquinonediazide sulfonic acid and a polycondensation resin of phenols and aldehydes or ketones is preferably used.

Examples of the phenols include phenol, 0-
Cresol, ■-cresol, p-cresol, 3,5
- Monohydric phenols such as xylenol, carvacrol, and thymol, dihydric phenols such as catechol, resorcinol, and human 0quinone, and trihydric phenols such as pyrogallol and phloroglucin. Examples of the aldehyde include formaldehyde, benzaldehyde, acetaldehyde, crotonaldehyde, and furfural. Preferred among these are formaldehyde and benzaldehyde. Further, examples of the ketone include acetone, methyl ethyl ketone, and the like.

Specific examples of the polycondensation resin include phenol formaldehyde resin, p-cresol formaldehyde resin, -1-cresol formaldehyde resin, and l-cresol formaldehyde resin.
Examples include 2D-mixed cresol/formaldehyde resin, resorcinol/benzaldehyde resin, and pyrogallol/acetone resin.

The condensation rate of 0-naphthoquinonediazide sulfonic acid with respect to the OH group of the phenol of the 0-naphthoquinonediazide compound (reaction rate with respect to one OH group) is 15 to 80%.
is preferable, and more preferably 20 to 60%.

Further, as the O-naphthoquinonediazide compound used in the present invention, the following compounds described in JP-A-58-43451 can also be used. For example, 1.
2-naphthoquinonediazide sulfonic acid ester, 1.2
- Known 1,2-quinonediazide compounds such as naphthoquinonediazide sulfonamide, and more specifically from the book "Light-5sensitive Systems" by J. Kosar (J. Kosar).
e Systems”) pages 339-352 (196
5 years), Jijin Willy 7 Tosan 1 (John
Wiley & 5ons (New York) and W Varnish Day.

Written by De Forest (W. S. De Forest) “
Photoresist J ("photoresist") Volume 50.

(1975), McGray-H
1, 2-
Naphthoquinonediazide-5-sulfonic acid cyclohexyl ester, 1-(1,2-naphthoquinonediazide-5-
sulfonyl)-3,5-dimethylpyrazole, 1,2-
naphthoquinone diazide-5-sulfonic acid-4"-hydroxydiphenyl-4" azo-β-naphthol ester,
N,N-di(1,2-naphthoquinonediazide-5-sulfonyl)-aniline, 2'-(1,2-naphthoquinonediazide-5-sulfonyloxy)-1-hydroxy-
Anthraquinone, 1,2-naphthoquinone diazide-5-
Sulfonic acid-2,4-dihydroxybenzophenone ester, 1,2-naphthoquinonediazide-5-sulfonic acid-2,3,4-trihydroxybenzophenone ester, 1,2-naphthoquinonediazide-5-sulfonic acid ester O
A condensate of 2 moles of hydride and 1 mole of 4,4'-diaminobenzophenone, 2 moles of 1,2-naphthoquinonediazide-5-sulfonic acid chloride and 4,4'-dihydroxy-1,1
'-Diphenylsulfone 1 mol condensate, 1,2-naphthoquinonediazide-5-sulfonic acid chloride 1 mol condensate and purbrogalin 1 mol, 1,2-naphthoquinonediazide-5-(N-dihydroabiethyl)-sulfone Examples include 1,2-quinonediazide compounds such as amides. Also, Special Publication No. 37-1953, No. 37-3
No. 627, No. 37-13109, No. 4G-26126
No. 40-3801, No. 45-5604, No. 45
No.-27345, No. 51-13013, JP-A No. 4Jl
-96575, 48-63802, 48-63
1,2-quinonediazide compounds described in each publication No. 803 can also be mentioned.

Furthermore, as the 0-naphthoquinonediazide compound used in the present invention, for example, 1,2-naphthoquinonediazide-4
-sulfonic acid cyclohexyl ester, 1-(1,2-
naphthoquinonediazide-4-sulfonyl)-3,5-dimethylpyrazole, 1,2-naphthoquinonediazide-4
-Sulfonic acid-4#-hydroxydiphenyl-4''-azo-β-naphthol ester, 2'-(1,2-naphthoquinonediazide-4-sulfonyloxy)-1-human 0
xy-anthraquinone, 1,2-naphthoquinonediazide-4-sulfone i! -2,4-dihydroxybenzophenone ester, 1,2-naphthoquinonediazide-4-sulfonic acid-2,3,4-trihydroxybenzophenone ester, 1.2=naphthoquinonediazide-4-sulfonic acid-2°3.4' , 4'-tetrahydroxybenzophenone ester, 1,2-naphthoquinone diazide-
A combination of 2 moles of 4-sulfonic acid chloride and 1 mole of 4,4'-dihydroxy-1,1'-diphenylsulfone, 1
．． 1,2-naphthoquinone-2-diazide-4 of a polyhydroxy compound such as a sulfonate of 1 mole of 2-naphthoquinonediazide-4-sulfonic acid chloride and 1 mole of purbrogalin
-sulfonic acid ester compounds.

Furthermore, an 0-naphthoquinonediazide sulfonic acid ester compound of a polyurethane resin as shown below (wherein represents an integer from 2 to 300).

) Furthermore, in the present invention, an ester compound of a vinyl polymer having a phenolic hydroxyl group and 0-naphthoquinonediazide sulfonic acid can also be used. The vinyl polymer having a phenolic hydroxyl group that forms such an ester compound is a polymer having a unit having a phenolic hydroxyl group in its molecular structure, and preferably a vinyl polymer having a phenolic hydroxyl group that is used as the alkali-soluble resin described below. Polymers similar to those of vinyl polymers having structural units in their molecular structure can be used.

As the O-naphthoquinone diazide compound used in the present invention, each of the above compounds may be used alone, or two or more thereof may be used in combination. The proportion of the 0-naphthoquinone diazide compound used in the present invention in the photosensitive composition is preferably 5 to 60% by weight, particularly preferably 1
It is 0 to 50% by weight.

As the organic acid used in the present invention, all known various organic acids can be used, but organic acids having a pKa value of 2 or more are preferred, more preferably those having a pKa value of 3.0 to 9.0, and particularly preferred. An organic acid having a molecular weight of 3.5 to 8.0 is used. However, the pKa value used in the present invention is a value at 25°C.

Such organic acids include, for example, the Basics of Chemistry Handbook ■ (
Among the organic acids described in Maruzen (1966, pp. 1054-1058), all compounds that can exhibit the pKa value of the present invention can be mentioned. Examples of such compounds include benzoic acid, adipic acid, azelaic acid, isophthalic acid, p-toluic acid, qt-ruic acid, β-ethylglutaric acid, m-oxybenzoic acid, p-oxybenzoic acid, 3.5-dimethylbenzoic acid, 3,4-dimethoxybenzoic acid, glyceric acid, glutaconic acid, glutaric acid,
p-anisic acid, succinic acid, sebacic acid, β, β-diethylglutaric acid, 1.1-cyclobutanedicarboxylic acid, 1.
3-cyclobutanedicarboxylic acid, 1゜1-cyclopentanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, β,β-dimethylglutardimethylmalonic acid, α-tartaric acid, superric acid, Terephthalic acid, pimelic acid, phthalic acid, fumaric acid,
β-propylglutaric acid, propylmalonic acid, mandelic acid, mesotartaric acid, β-methylglutaric acid, β,β-methylpropylglutaric acid, methylmalonic acid, malic acid, 1
．． 1-Cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, cis-4
-cyclohexene-1,2-dicarboxylic acid, erucic acid,
Examples include undecenoic acid, lauric acid, nτ capric acid, pelargonic acid, n-undecanoic acid, and the like. Other organic acids having an enol structure such as Meldrum's acid and ascorbic acid can also be preferably used. The proportion of the organic acid in the photosensitive layer is suitably 0.05 to 10% by weight, preferably 0.1 to 5% by weight.

Further, as the acid anhydride used in the present invention, all known various acid anhydrides can be used, but cyclic acid anhydrides are preferable, such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc. phthalic acid,
Examples include 3,6-nindooxy-tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, glutaric anhydride, maleic anhydride, chloromaleic anhydride, α-phenylmaleic anhydride, succinic anhydride, and pyromellitic acid. These acid anhydrides are preferably contained in the photosensitive layer in an amount of 0.05 to 10 weight percent, particularly 0.1 to 5 weight percent.

The photosensitive composition of the present invention may preferably contain a compound that generates an acid or a free radical upon exposure to light. Trihaloalkyl compounds or diazonium salt compounds are preferably used.

General formula [■] Mu (wherein, Xa represents a trihaloalkyl group having 1 to 3 carbon atoms, W represents each atom of N, SSSe, P, and C, and Z represents 0, N, S, Se , represents each atom of P.Y has a chromophore group and represents a nonmetallic atom group necessary to cyclize W and 7.However, if the ring formed by the nonmetallic atom group ) General formula [■] Ar -N2 ] As the trihaloalkyl compound, the following - bottom [IX], [X] or [XI
] Includes compounds represented by.

- Bottom [■ General formula [X] General formula [XI] (wherein, Xa is a trihaloalkyl group having 1 to 3 carbon atoms, a hydrogen atom or a methyl group, J is a substituted or unsubstituted aryl group, or Represents a heterocyclic group, and n is 0.1 or 2.) Specifically, the compound represented by the general formula [IX] includes an oxadiazole compound having a benzofuran ring such as;
2-triclomethyl-5-(p-methoxystyryl)-1, which is described in JP-A-54-74728,
3,4-oxadiazole compound or the following compound described in JP-A No. 60-241049: The following compound described in JP-A-54-74728: #fl
The following compound described in Publication No. 55-77742: JP-A-6
0-: The following compound described in Publication No. 11826 *: Japanese Patent Application Laid-open No. 1983
-The following compound described in Publication No. 177340: JP-A-81-
The following compound* described in No. 143748 is exemplified.

Moreover, as a compound represented by -bottom [X] or [XI], specifically, 4-(2,4-dimethoxy-4-styryl)-6 described in JP-A No. 53-36223 -Dolichloromethyl-2-pyrone compound, 2,4-bis-(trichloromethyl)-6-1)-methoxystyryl-8-triazine compound described in JP-A-48-36281, 2゜4 -bis-(trichloromethyl)-6-1)-dimethylaminostyryl-8-triazine compound and the like.

On the other hand, the diazonium salt compound is preferably a diazonium salt that generates a strong Lewis acid upon exposure to light, and a counter ion of an inorganic compound is recommended as the counter ion part. As a specific example of such a compound, the anion moiety of the diazonium salt is at least one of a fluoride ion, an arsenic fluoride ion, an antimony fluoride ion, an antimony chloride ion, a tin chloride ion, a bismuth chloride ion, and a zinc chloride ion. Examples include aromatic diazonium salts, preferably paradiazophenylamine salts.

The amount of the compound that generates acid or free radicals upon exposure in the total photosensitive layer composition is preferably 0.01 to 20% by weight, more preferably 0.1 to 20% by weight, particularly preferably 0.2% by weight. ~10% by weight.

The photosensitive composition of the present invention preferably contains a color-changing agent that changes the color tone by interacting with the photodecomposition product, together with the above-mentioned compound that generates an acid or a free radical upon exposure to light. . There are two types of such color changing agents: those that develop color and those that fade or change color. As the color-changing agent that causes fading or discoloration, various dyes such as diphenylmethane, triphenylmethane-based thiazine, oxazine-based, xanthine-based, anthraquinone-based, iminonaphthoquinone-based, and azomethine-based dyes are effectively used.

Specific examples of these include the following: Brilliant Green, Eosin, Ethyl Violet, Erythrosin B1 Methyl Green, Crystal Violet, Pesic Tsuksin, Phenolphthalein, 1,3-Diphenyltriazine, Alizarin Red S1 Thymolphthalein, Methyl Violet 2B,
Quinaldine Red, Rose Bengal, Metanyl Yellow Thymol Sulfophthalein, Xylenol Blue Methyl Orange, Orange ■, Diphenylthiocarbazone, 2
, 7-dichlorofluorescein, rose methyl red, Congo red, benzobrulin 4B, α-naphthyl red, Nile blue 2B, Nile blue A1 phenacetaline, methyl violet, malachite green, rose tuxin, Victoria Pure Blue BOH (manufactured by Hodogaya Chemical W) , Oil Blue #603 [Orient Chemical Industry ■], Oil Pink #312 [Orient Chemical Industry ■]
[manufactured by Orient Chemical Industry ■], Oil Red 5B [manufactured by Orient Chemical Industry ■],
Oil Blue Let #308 [manufactured by Orient Chemical Industry ■], Oil Red OG [manufactured by Orient Chemical Industry ■], Oil Red RR [manufactured by Orient Chemical Industry ■], Oil Green #502 [manufactured by Orient Chemical Industry ■], Subiron Red BEH Special [Manufactured by Hodogaya Chemical Industry ■],
Cresol purple, cresol red, rhodamine B
10-Damin 6G1 Fast Assist Violette R
1 sulforhodamine B1 auramine, 4-o-diethylaminophenylimino naphthoquinone, 2-carboxyanilino-4-1)-diethylaminophenylimino naphthoquinone, 2-carbostearylamino-4-p-dihydroxyethylamino-phenylimino naphthoquinone, p-methoxybenzoyl-p'-diethylamino-O
'-Methylphenyliminoacetanilide, cyano-p
-diethylaminophenyliminoacetanilide, 1-
Phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone, 1-β-naphthyl-4-1
)-diethylaminophenylimino-5-pyrazolone.

Moreover, arylamines can be mentioned as color-changing agents that develop color. Arylamines suitable for this purpose include not only simple arylamines such as primary and secondary aromatic aminos but also so-called leuco dyes, examples of which include the following.

Diphenylamine, dibenzylaniline, triphenylamine, diethylaniline, diphenyl-p-phenylenediamine, p-toluidine, 4゜4'-biphenyldiamine, 0-chloroaniline, 0-bromoaniline, 4
-chloro-〇-phenylenediamine, 0-bromo-N,
N-dimethylaniline, 1.2.3-triphenylguanidine, naphthylamine, diaminodiphenylmethane,
Aniline, 2,5-dichloroaniline, N-methyldiphenylamine, 0-toluidine, p,p'-tetramethyldiaminodiphenylmethane, N,N-dimethyl-p
-phenylenediamine, 1,2-dianilinoethylene,
p, l, p"-hexamethyltriaminotriphenylmethane, p, p' -tetramethyldiaminotriphenylmethane, p.

p'-tetramethyldiaminodiphenylmethylimine,
p, p', p''-triamino-0-methyltriphenylmethane, p, p', p''-triaminotriphenylcarbinol, p, p'-tetramethylaminodiphenyl-4-anilinonaphthylmethane, p , p
', p"-triaminotriphenylmethane, p, p',
p''-hexapropyltriaminotriphenylmethane.

In the present invention, among the above-mentioned color change agents, dyes that can change color in a pH range of 1 to 5 are preferred.

The proportion of the above color change agent in the photosensitive composition is 0.0
It is preferably used in an amount of 1 to 10% by weight, more preferably 0.02 to 5% by weight.

The photosensitive composition of the present invention preferably has the following general formula [XI]
It includes a condensation resin of substituted phenols and aldehydes represented by and/or an 0-naphthoquinonediazide sulfonic acid ester compound of the resin.

General formula [XI] (In the formula, R5 and R6 each represent a hydrogen atom, an alkyl group, or a halogen atom, and R7 represents an alkyl group or cycloalkyl group having 2 or more carbon atoms.) In the substituted phenols represented, R5 and R6 are a hydrogen atom, an alkyl group (1
It includes those containing from 3 to 3 carbon atoms. C1 -C2 alkyl groups are particularly useful. ) or a halogen atom (among fluorine, chlorine, bromine and iodine atoms, chlorine and bromine atoms are particularly preferred), and R7 represents an alkyl group having 2 or more carbon atoms (preferably 15 or less carbon atoms). , C 3 -C 8 alkyl groups are particularly useful) or C cycloalkyl groups (including those containing 3 to 15 carbon atoms), C 3 -C 8 alkyl groups are particularly useful. ).

Examples of the substituted phenols include isopropylphenol, tert-butylphenol, tert-amylphenol, hexylphenol, tert-octylphenol, cyclohexylphenol, 3-methyl-4-chloro-5-tert-butylphenol, isopropylcresol, tert- butyl cresol, t
ert-7 milk cresol, hexyl cresol, te
Examples thereof include rt-octyl cresol and cyclohexyl cresol, among which tert-octylphenol and tert-butylphenol are particularly preferred.

Examples of the aldehydes include aliphatic and aromatic aldehydes such as formaldehyde, benzaldehyde, acetaldehyde, acrolein, crotonaldehyde, and furfural, including those having 1 to 6 carbon atoms. Among them, formaldehyde and benzaldehyde are preferred.

The resin obtained by condensing the substituted phenol and aldehyde in the present invention is synthesized by polycondensing the substituted phenol represented by the general formula [XI] and the aldehyde in the presence of an acidic catalyst. Inorganic acids and organic acids such as hydrochloric acid, oxalic acid, sulfuric acid, and phosphoric acid are used as acidic catalysts, and the blending ratio of substituted phenols and aldehydes is as follows:
0.7 aldehydes per 1 mole part of substituted phenols
~1.0 mole part is used. Alcohols, acetone, water, tetrahydrofuran, etc. are used as the reaction solvent.

After reaction at a predetermined temperature (-5 to 120°C) for a predetermined time (3 to 48 hours), heat under reduced pressure, wash with water, and dehydrate.
Alternatively, the reactant can be obtained by precipitating water.

The O-naphthoquinonediazide sulfonic acid ester compound of the polymerized resin of substituted phenols and aldehydes of the present invention can be prepared by dissolving the condensation resin in a suitable solvent such as dioxane, and adding O-naphthoquinonediazide sulfonic acid chloride to the solution. is added, and an alkali such as an alkali carbonate is added dropwise to the equivalence point while heating and stirring to esterify the product.

In the esterified product, the condensation rate of 0-naphthoquinonediazide sulfonic acid chloride with respect to the hydroxyl group of the phenol (reaction rate % with respect to one hydroxyl group) is 5 to 80%.
is preferable, more preferably 20 to 70%, still more preferably 30 to 60%. The condensation rate is calculated by determining the content of sulfur atoms in the sulfonyl group by elemental analysis.

The amount of the resin obtained by condensing the substituted phenol and aldehyde represented by -bottom [XI] and the 0-naphthoquinonediazide sulfonic acid ester compound of the resin in the photosensitive composition of the present invention is 0.05 -15% by weight is preferred, particularly preferably 1-10% by weight, and the weight average molecular weight MW is better.C.5. Ox 102~5. Qx
l Q3 range, more preferably 7.0X10
It is in the range of 2 to 3.0 x 103. Its number average molecular weight M
n is preferably in the range of 3, oxlQ12 to 2.5X103, more preferably 4.0XiQ2 to 2.0
The range is ×103.

The above molecular weight is measured by GPC method.

Calculation of the number average molecular weight Mn and weight average molecular weight MW is described in "Journal of the Chemical Society of Japan" by Morio Tsuge, Tatsuya Miyabayashi, and Masayuki Tanaka.
By the method described on pages oo to 805 (1972),
The test shall be performed by leveling the peaks of the oligomer region (connecting the centers of the peaks and valleys of the peaks).

The photosensitive composition of the present invention can also contain a compound having at least one of the following structural units [D] and [E] in its molecular structure.

Structural unit [D] 1+CH2CH20 amount structural unit [E] H3 fCH2CH-0k- (In the formula, n represents an integer from 2 to 5000.) At least the structural unit [0] and [E] used in the present invention As a compound having one kind, any compound having one or both of the above structural units [D] and [E] may be used, but in particular, n is an integer within the range of 2 to 5000, and Preferably, the compound has a boiling point of 240°C or higher, more preferably a compound where n is an integer in the range of 2 to 500, and the boiling point is 280°C or higher, and most preferably, n is in the range of 3 to 100. It is a compound within.

Examples of such compounds include: ・Polyethylene glycol (HO-(cH2CH20
WH)・Polyoxyethylene alkyl ether (RO(
cH2CH20)nH) ・Polyoxyethylene alkylphenyl ether ・Polyoxyethylene polystyrylphenyl ether ・Polyoxyethylene-polyoxybrobylene glycol (including block polymers and random polymers) ・Polyoxyethylene-polyoxybrobylene alkyl Ethers (terminals forming alkyl ethers) (including random polymers) Ethylene oxide derivatives of alkylphenol formalin condensates Polyoxyethylene polyhydric alcohol fatty acid partial esters For example: Polyoxyethylene fatty acid esters (for example, RCOO (cH , CH, 0)nH).polyoxyethylenealkylamine, and the like.

Specifically, for example, the following are preferable.

Namely, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene higher alcohol ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate, polyoxyethylene tetraoleate Sorbit, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol monooleate, polyethylene glycol distearate, polyoxyethylene nonylphenyl ether formaldehyde condensate, oxyethylene oxybrobylene block copolymer, polyethylene glycol, tetraethylene Glycol etc.

The proportion of the compound having at least one of the structural units [D] and [E] in the photosensitive composition is preferably 0.1 to 20% by weight, more preferably 0.1 to 20% by weight based on the total composition.
．． It is 2 to 10% by weight.

Moreover, the above-mentioned compounds may be used alone or in combination of two or more types, as long as the content is within the above-mentioned range.

In addition to the above-mentioned materials, the photosensitive composition of the present invention may further contain pigments such as dyes and pigments, sensitizers, plasticizers, surfactants, etc., if necessary.

Furthermore, by dissolving each of these components in the following solvent and further applying and drying this on the surface of a suitable support,
A photosensitive layer can be provided to form a photosensitive lithographic printing plate.

Solvents that can be used to dissolve each component of the photosensitive composition of the present invention include cellosolves such as methyl cellosolve, methyl cellosolve acetate, ethyl cellosolve, and ethyl cellosolve acetate, dimethyl formamide, dimethyl sulfoxide, dioxane, acetone, Examples include cyclohexanone, trichloroethylene, and methyl ethyl ketone. These solvents can be used alone or in combination of two or more.

The coating method used for coating the surface of the support with the photosensitive composition of the present invention includes conventionally known methods, such as spin coating, wire bar coating, dip coating, air knife coating, roll coating, blade coating, and curtain coating. Coating etc. are possible. At this time, the coating amount varies depending on the application, but for example, the solid content is 0.5 to 5. OQ/f is preferred.

The support on which the photosensitive layer using the photosensitive composition of the present invention is provided may be a metal plate made of aluminum, zinc, steel, copper, etc., or a plate plated or vapor-deposited with chromium, zinc, copper, nickel, aluminum, iron, etc. Examples include metal plates, paper, plastic films, glass plates, paper coated with resin, paper covered with metal foil such as aluminum, and plastic films treated to make them hydrophilic. Among these, aluminum plates are preferred. As a support for a photosensitive lithographic printing plate using the photosensitive composition of the present invention, it is preferable to use an aluminum plate that has been subjected to surface treatments such as graining, anodizing, and, if necessary, sealing. preferable.

Known methods can be applied to these treatments.

Examples of the graining treatment include a mechanical method and an electrolytic etching method. Examples of mechanical methods include ball polishing, brush polishing, liquid honing, and puff polishing.

The various methods described above can be used alone or in combination depending on the composition of the aluminum material. Preferred is a method using electrolytic etching.

Electrolytic etching is carried out in a bath containing one or a mixture of two or more inorganic acids such as phosphoric acid, sulfuric acid, hydrochloric acid, and nitric acid. After the graining process, desmutting is performed using an alkali or acid aqueous solution as necessary to neutralize the material, followed by washing with water.

The anodic oxidation treatment is performed by electrolyzing using an aluminum plate as an anode using a solution containing one or more of sulfuric acid, chromic acid, oxalic acid, phosphoric acid, malonic acid, etc. as an electrolytic solution. The amount of the anodic oxide film formed is suitably 1 to 50 iMdf, preferably 10 to 40 mg/df.

The amount of anodized film can be determined, for example, by immersing an aluminum plate in a phosphoric acid chromic acid solution (85% phosphoric acid solution: 35 mL of chromium chloride = 20 (prepared by dissolving J in 11 of water) to remove the oxide film. It is determined by measuring the change in weight before and after dissolving the film on the plate.

Specific examples of the sealing treatment include boiling water treatment, steam treatment, sodium silicate treatment, and dichromate aqueous solution treatment. In addition, the aluminum plate support may be subjected to subbing treatment using an aqueous solution of a water-soluble polymer compound or a metal salt such as fluorinated zirconate.

The photosensitive lithographic printing plate to which the photosensitive composition of the present invention is applied is:
It can be developed using a conventional method.

For example, the transparent positive film is exposed to light from a light source such as an ultra-high pressure mercury lamp, metal halide lamp, xenon lamp, or tungsten lamp, and then developed with various alkaline developers. As a result, only the unexposed portion remains on the surface of the support, forming a positive-positive relief image.

Examples of the alkaline developer include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate,
Examples include aqueous solutions of alkali metal salts such as sodium metasilicate, potassium metasilicate, sodium diphosphate, and sodium triphosphate. The concentration of alkali metal salt is 0.
1 to 10% by weight is preferred. Furthermore, an anionic surfactant, an amphoteric surfactant, and an organic solvent such as alcohol can be added to the developer as required.

[Example] (Preparation of aluminum plate) An aluminum plate with a thickness of 0.2411 (material 105G, tempered H16) was heated in a 5% by weight sodium hydroxide aqueous solution.
After degreasing for 1 minute at 0°C, the temperature was 25°C and the current density was 60A in a 0.5 molar aqueous hydrochloric acid solution of 111.
Electrolytic etching treatment was performed under the conditions of /df and treatment time = 30 seconds. Next, after desmutting in a 5% by weight aqueous sodium hydroxide solution at 60°C for 10 seconds,
In 0 wt% sulfuric acid solution, temperature = 20°C, current density: 3A/
df.

Treatment time: Anodization treatment was performed under conditions of 1 minute.

Furthermore, hot water sealing treatment was performed with hot water at 30°C for 20 seconds.
An aluminum plate as a support for lithographic printing plate material was produced.

Each photosensitive composition coating solution having the composition shown in Table 1 was applied to the aluminum plate prepared above using a spin coater, dried at 90°C for 4 minutes, and positive photosensitive lithographic printing plate sample No. I got ~10.

Photosensitive lithographic printing plate samples N011 to 10 thus obtained
A step tablet for sensitivity measurement (No. 2 manufactured by Eastman Kodak Co., gray scale of 21 steps with a density difference of 0.15) was attached to each of the lamps, and a 2KW metal halide lamp (Idol Fin 2000 manufactured by Iwasaki Electric Co., Ltd.) was attached. Exposure was performed from a distance of 90c+e as a light source. Next, this sample was developed at 27 DEG C. for 20 seconds using a developer prepared by diluting 5DR-1 (manufactured by Konica ■) six times with water. Sensitivity was expressed as the exposure time required to completely clear 5.0 steps of the step tablet.

Furthermore, in order to examine under-developability, the developability was evaluated using a developer with a diluted alkali concentration, that is, a developer with reduced developing ability. The above developability is 5DR-
1 The dilution rate of the developer was changed to 9 times, 10 times, and 11 times, and the planographic printing plate samples were developed at 27°C for 20 seconds. ) to perform a printing test,
The degree of shading in some halftone dots of the shadow was visually evaluated.

In addition, in order to evaluate the printing durability, we used Ultra Plate Cleaner (LJPC: A, B, C, manufactured by Chemical Co., Ltd.) as a cleaning liquid during printing to wipe the plate surface every 1,000 sheets. Examined.

We also evaluated the odor generated when aligning the film during the printing process.

Table 2 Umbrella 4 2nd under development ○: No smearing on some shadow dots (no stains) Δ: Slight smearing on some shading dots (slight staining) X: Some smearing on some shadow dots (Stained) $5: Odor ○: Almost no odor Δ: Very slight odor △: Slight odor ×: Significant odor Book 1; Novolac resin/Novolac resin A: Mixed with phenol Copolycondensation resin of cresol and formaldehyde [molar ratio of phenol and m, p-mixed cresol is 2.0:8.0, weight average molecular weight Mw -6, Go01 dispersity MW /Mn = 5, unreacted free phenol (phenol, Peng-cresol, p-
Cresol) 4.5% by weight] Novolak Resin B: Same as Novolak Resin A, but unreacted free phenols 3.
5% by weight - Novolac resin C: Same as novolac resin A, but unreacted free phenols 3.
0% by weight - Novolak resin D: Same as novolak resin A, but unreacted free phenols 2.
0% by weight ・Novolac resin E: ■-Copolycondensation resin of cresol, p-cresol, and formaldehyde (--molar ratio of cresol and p-cresol 6:4, Mw = 5,500. MW/M
n = 4.5 unreacted free phenols 3.5% by weight) - Novolac resin F: Same as novolak resin E, unreacted free phenols 2.
0 precious% ・Novolac resin (a): Same as novolac resin A, unreacted free phenols 10
Weight% novolac resin/novolac resin (b): Same as novolac m fat A, unreacted free phenols 20
Weight % of novolac resin/novolac resin (c): Same as novolac resin E, but unreacted free phenol. Photosensitive lithographic printing plate samples No. 1 to 6 prepared using the photosensitive composition of the present invention are all sample No. 09 prepared using a photosensitive composition other than the present invention.
Compared to 7 to 10, it has excellent sensitivity and under-developability,
As a result, excellent printing durability was obtained. Furthermore, there was almost no odor during production, and the product was environmentally friendly.

[Effects of the Invention] As explained in detail above, the photosensitive composition of the present invention provides a photosensitive lithographic printing plate that has high sensitivity and excellent under-developability and provides excellent printing durability. be able to. Furthermore, the odor during production is also improved.

Claims (1)

[Scope of Claims] A product characterized by containing (a) an o-naphthoquinone diazide compound, (b) a novolac resin containing less than 5% by weight of phenols, and (c) an organic acid and/or acid anhydride. Photosensitive composition.