JPH02210354A - Photosensitive composition - Google Patents

Abstract

PURPOSE:To improve stain by traces of erasion at the time of printing and to prevent a dyestuff from remaining after development by incorporating an o-naphthoquinonediazido compd. as a photosensitive component, the dyestuff and aliphat. monocarboxylic acid having at least five carbon atoms. CONSTITUTION:This photosensitive compsn. contains at least an o- naphthoquinonediazido compd. as a photosensitive component, a dyestuff and aliphat. monocarboxylic acid having at least five carbon atoms. The o- naphthoquinonediazido compd. may be a compd. obtd. by esterifying o- naphthoquinonediazidosulfonic acid with a polycondensation resin of phenols and aldehyde or ketone. The aliphat. monocarboxylic acid having at least five carbon atoms means aliphat. monocarboxylic acid having >=5 carbon atoms besides carbon atoms in substituents and aliphat. monocarboxylic acid having 7-30, especially 10-25 carbon atoms is preferably used. Stains by traces of erasion at the time of printing is improved and the dyestuff is prevented from remaining after development.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to a photosensitive composition applied to a photosensitive lithographic printing plate, and more specifically, a photosensitive composition containing an 0-naphthoquinone diazide compound as a photosensitive component. Regarding.

[Background of the Invention] A positive-working photosensitive lithographic printing plate is generally one in which an ink-receptive photosensitive layer containing an alkali-soluble resin and solubilized by exposure to ultraviolet rays or the like is formed on a hydrophilic support. When this photosensitive layer is subjected to imagewise exposure and development, the non-image area is removed leaving the image area, forming an I area. In planographic printing, the difference in properties is utilized in that the image area is lipophilic and the non-image area is hydrophilic.

The planographic printing plate formed as described above is usually subjected to plate surface correction such as deletion or correction before printing if unnecessary lines are included. In particular, deletion correction (hereinafter referred to as "erasure") is performed with a special correction agent that dissolves the photosensitive layer in the image area after development on positive-working photosensitive lithographic printing plates. There has been a problem in that stains (hereinafter referred to as "erasure trace stains") occur in non-image areas around the erased areas.

Generally, as a means to improve background smudges that occur during printing,
For example, a method is used in which the grained surface of the support is treated with a hydrophilic compound, but such a method has almost no effect on the erasure trace stains and also has the disadvantage of decreasing printing durability. There is.

Furthermore, Japanese Patent Application Laid-Open No. 60-88942 discloses a method of adding an organic acid with a low pKa value, but even if this method is used, it is not effective against the above-mentioned erasure trace stains, and furthermore, This was not preferable because it caused a phenomenon called "dye residue" in which the dye remained in the non-image area except for the image area.

Therefore, there has been a need for a photosensitive lithographic printing plate and a photosensitive composition for use in the printing plate, which are free from the above-mentioned drawbacks.

[Object of the Invention] An object of the present invention is to provide a photosensitive lithographic printing plate that improves moisture trace staining during printing and leaves almost no dye residue after development, and a photosensitive composition suitable for the printing plate. It is in.

[Structure of the Invention] As a result of intensive research, the present inventors have found that the above-mentioned object of the present invention is to provide a compound containing at least an O-naphthoquinonediazide compound, a dye, and a small amount (both containing an aliphatic monocarboxylic acid having 5 carbon atoms). It has been found that this can be achieved by providing a photosensitive composition.

[Specific structure of the invention] The present invention will be explained in more detail below.

As the 0-naphthoquinonediazide compound in the present invention, for example, an ester compound of 0-naphthoquinonediazide sulfonic acid and a polycondensation resin of phenols and aldehydes or ketones is preferably used.

Examples of the phenols include phenol, O-
Cresol, l-cresol, p-cresol, 3.5
Examples include monohydric phenols such as -xylenol, carbac 0-/-, thymol, dihydric phenols such as catechol, resorcinol, and human O-quinone, 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, o-cresol/formaldehyde resin, -1,p-mixed cresol/formaldehyde resin, resorcinol/benzaldehyde resin, and pyrogallol/acetone. Examples include 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 11 OH) 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-58-43451-1111 can also be used. That is, for example, 1,2-naphthoquinonediazide sulfonic acid ester, 1
．． Known 1,2-quinonediazide compounds such as 2-naphthoquinonediazide sulfonic acid amide, and more specifically, "Light-Sensitive Systems" by J. Kosar (J. Kosar).
tive Systems”), pp. 339-352 (1965), John Wiley and Sons (J
ohn Wiley & 5ons) (New York) and W. Varnish Day Forest (W.
, S. De Forest), "Photoresists;st", Vol. 50.

(1975), McGraw-H
1, 2 listed in ) (New York)
-naphthoquinonediazide-5-sulfonic acid cyclohexyl ester, 1-(1,2-naphthoquinonediazide-5
-sulfonyl)-3,5-dimethylpyrazole, 1.2
-naphthoquinonediazide-5-sulfonic acid-4#-H,
Droxydiphenyl-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-naphthoquinonediazide-
5-sulfonic acid-2,4-dihydroxybenzophenone ester, 1,2-naphthoquinonediazide-5-sulfonic acid-2,3,4-trihydroxybenzophenone ester, 1,2-naphthoquinonediazide-5-sulfonic acid chloride 2 moles and 4,41-diaminobenzophenone 1
mol of condensate, 2 mol of 1,2-naphthoquinonediazide-5-sulfonic acid chloride and 4,4'-dihydroxy-1
, condensate of 1 mole of 1'-diphenylsulfone, 1.2-
Examples of 1,2-quinonediazide compounds include a condensate of 1 mole of naphthoquinonediazide-5-sulfonate and 1 mole of purbrogarin, and 1,2-naphthoquinonediazide-5-(N-dihydroa and ethyl)-sulfonamide. be able to. Also, Special Publication No. 37-1953, No. 37
-3627, 37-13109, 40-261
No. 26, No. 40-3801, No. 45-5604, No. 45-27345, No. 51-130134, JP-A No. 4
No. 8-96575, No. 48-63802, No. 48-6
3803@1,2-quinonediazide compounds described in various publications 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-hydroxy-anthraquinone, 1,2-naphthoquinonediazide- 4-sulfonic acid-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-4
- sulfonic acid chloride 2 moles and 4,4'-dihydroxy-1,1'-diphenylsulfone 1 mole, 1.
2-naphthoquinonediazide-4-sulfonic acid hydride 1
1,2-naphthoquinone-2-diazide-4- of a polyhydroxy compound such as a condensate of 1 mole of purprogalin
Examples include sulfonic acid ester compounds.

Furthermore, the following O-naphthoquinonediazide sulfonic acid ester compounds of polyurethane resins Also, as the compounds of the present invention, ester compounds of a vinyl polymer having a phenolic hydroxyl group and O-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 0-naphthoquinonediazide 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%, particularly preferably 1%.
It is 0 to 50% by weight.

The aliphatic monocarboxylic acids having at least 5 carbon atoms used in the present invention (hereinafter referred to as "compounds of the present invention") are those having 5 or more carbon atoms excluding the carbon atoms of substituents. Preferably, an aliphatic monocarboxylic acid having 7 to 30 carbon atoms is used, more preferably an aliphatic monocarboxylic acid having 10 to 25 carbon atoms.

In the compound of the present invention, as the aliphatic group substituted with a carboxyl group, an alkyl group, an alkenyl group, an alkynyl group, etc. are used, and each of these groups may have no substituent, or alkyl , alkenyl, alkynyl, alkoxy, nitrile or nitro, or a substituent such as a halogen atom.

Specifically, the compounds of the present invention include CH, +
cH Tsuji-COOH (n=3-24) (CHs) r-C
-CHI CHCHHz-COOHCH.

CsH1tCHtCHtCOOHI CH3(CHz)sCH=CHCOOH.

CH3(CHt)<CH=CHCH*C00H-nCs
Ht-CsHr* C00Httrans-CHs(
CHI)scH=cHcOOH+CH3(CHz)sC
H=CHCHzCOOH-CH3(CH2)tCH=C
HCOOH.

CHz=CH(CH2)sCOOH- CH=C(CH,)ICOOH.

trans-ncsH++ CsH+5-C0OH.

trans CHi(CHz)sCH=CHCOOH
-CH5(CHI)*CH=CHC0OH.

CH, (CHt). CH=CHC0OH.

cis-CH3(CHz)sCH= CH(CHz)y
COOH.

CHs (CH!) lx CH= CHCOOH.

CH3(CHzl+CmiCCEiCCCOOH.

c i B −CHs (CHi ) la CH=
CH(CHx) 4 COOH1trans-CH3
(CHz)sCH=CH(CHz)sco OHtci
s CHs(CHzhCH=CH(CHz)yCOO
Hltrans CHs(CHz)tCH=CH(C
HI)tCOOH1CH3(CH2))(CH2CH=
CH)2(CHz)tcOOH.

CH, (CH, CH=CH), (CH,), COOH.

CHs (CH*) 13 C=CCEC-C0OH
.

CH5(CH,)4(CH=CHC)(2), (CHI
)2COOH.

CHs (CHt) + s C=C-CEC-C0
Oh.

c+s CHp(CHzhCH=CH(CH2)+t
COOH.

trans, CH3(CH2)7CH=C)I(CH2
)llCoOH9CH2=CH(CHi)t-COOH
-CHs(CH2)sCCECQ=C(GHz)sC
OOH-CH3(CH2)IICmiC-CEC(CH2
), C0OH.

CHs(CHz)tscMiC-CEC(CHI)scO
Oh.

The compound of the present invention is preferably present in the photosensitive composition at 0.01
It is contained in a proportion of ~10% by weight, more preferably 0.5~7% by weight, and may be used alone or in combination of two or more types within the above range.

The photosensitive composition of the present invention contains a dye, and various known dyes can be used, but it is preferable that the photosensitive composition interacts with photodecomposition products of compounds that generate free radicals upon exposure. A color change agent is used which changes its color tone by acting on it. There are two types of such color changing agents: those that develop color and those that fade or change color.

Examples of color-changing agents that cause fading or discoloration include diphenylmethane, triphenylmethane-based thiazine, oxazine-based,
Various dyes such as 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 Fumethane, Phenolphthalein, 1,3-Diphenyl Triazine, 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, rosexine, Victoria Pure Blue BOH (manufactured by Odogaya Chemical) , 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 [Orient Chemical Industry fill]
, Oil Red RR [Orient Chemical Industry ■], Oil Green #502 [Orient Chemical Industry ■IJ], Subiron Red BEH Special [Hodogaya Chemical Industry HfJ]
], I-Cresol Purple, Cresol Red, Rhodamine B10-Damine 6G, Fast Acid Violet R1 Sulforhodamine B1 Auramine, 4-J-
Diethylaminophenylimino naphthoquinone, 2-carboxyanilino-41-diethylaminophenylimino naphthoquinone, 2-carbostearylamino-4-El
-dihydroxyethylamino-phenylimino naphthoquinone, p-methoxybenzoyl-p'-diethylamino-〇'-methylphenyliminoacetanilide, cyano-p-diethylaminophenyliminoacetanilide, 1-phenyl-3-methyl-4-p-diethylamino Phenylimino-5-pyrazolone, 1-β-naphthyl-
4-D-diethylaminophenylimino-5-pyrazolone.

Further, as the color-changing agent that develops color, arylamines can be mentioned in particular. Arylamines suitable for this purpose include not only simple arylamines such as primary and secondary aromatic amines, but also so-called leuco dyes, examples of which include the following.

Diphenylamine, dibenzylaniline, triphenylamine, diethylaniline, diphenyl-〇-phenylenediamine, p-toluidine, 4゜4'-biphenyldiamine, O-chloroaniline, 0-bromoaniline, 4
-chloro-0-phenylenediamine, O-bromo-N,
N-dimethylaniline, 1.2.3-4-liphenylguanidine, naphthylamine, diaminodiphenylmethane, aniline, 2.5-dichloroaniline, N-methyldiphenylamine, 0-toluidine, p,l-tetramethyldiaminodiphenylmethane, N , N-dimethyl-p
-phenylenediamine, 1,2-dianilinoethylene,
p,p',p'-hexamethyltriaminotriphenylmethane, p,p'-tetramethyldiaminotriphenylmethane, p.

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

Compounds that generate a free I11 group upon exposure that interacts with the above-mentioned color change agent include the following formulas [I] and [II].
A trihaloalkyl compound or a diazonium salt compound represented by these formulas is preferably used.

General formula [I] (wherein, Xa represents a triheroalkyl group having 1 to 3 carbon atoms, W represents each atom of N, S, Se, P, and C, and 2 represents O, N, S , Se, and P.Y has a chromophore group and represents a nonmetallic atom group necessary to cyclize W and 2.However, if the ring formed by the nonmetallic atom group is xa) General formula []I] Ar -N2X- (In the formula, Ar represents an aryl group and X represents a counter ion of an inorganic compound.) Specifically, for example, - As the trihaloalkyl compound of formula [I], the following formula [I[], [rV] or [V
] Includes compounds represented by.

- Formula [111] (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 a heterocyclic group, n is 0, 1 or 2) - Specifically, the compound represented by the formula [111] is an oxadiazole having a benzofuran ring such as General formula [IV] General formula [V] ■\c-1f'r'L Compound,
2-tric00methyl-5-(p-methoxystyryl)-1, which is described in JP-A-54-74728,
3,4-oxadiazole compound or the following compound described in JP-A-60-241049: The following compound described in JP-A-54-74728: The following compound described in JP-A-55-77742; 1986
The following compound described in Publication No.-3626: JP-A-60-17
The following compound described in Publication No. 7340: JP-A-61-143
The following compound described in No. 748: Also, - formula [IV]
Or, specifically, as a compound represented by [V], 4-(2
,4-dimethoxy-4-styryl)-6-dolichloromethyl-2-pyrone compound, 2,4-bis-(triclomethyl)-6-fl- described in JP-A-48-38281 Methoxystyryl-8-) riazine compound, 2゜4-bis-(trichloromethyl)-6-El-
Examples include dimethylaminostyryl-8-triazine compounds.

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. Specific examples of such compounds include at least one type of fluoride ion, arsenic fluoride ion, antimony fluoride ion, antimony chloride ion, tin chloride ion, bismuth chloride ion, and zinc chloride ion in the 7-ion moiety of the diazonium salt. Mention may be made of certain aromatic diazonium salts, preferably paradiazophenylamine salts.

The amount of the compound that generates free radicals upon exposure to light contained in the total photosensitive layer composition is preferably 0.01 to 20% by weight,
More preferably 0.1 to 20%, particularly preferably 0
．． It is 2 to 10% by weight.

The photosensitive composition of the present invention preferably contains an alkali-soluble resin, and various resins known in the art can be used as the alkali-soluble resin. , can be done. Particularly preferred are novolac resins and vinyl polymers having a structural unit having a phenolic hydroxyl group in their molecular structures.

Novolac resins preferably used in the present invention include:
Examples include resins obtained by condensing phenols and formaldehyde in the presence of an acid catalyst, and examples of the phenols include phenol, 0-crezofur, ■-cresol, p-cresol, 3.5-xylenol, 2. 4-
Xylenol, 2.5-xylenol, carvacrol, thymol, catechol, resorcinol, human 0quinone,
Examples include pyrogallol and phloroglucin.

The above-mentioned phenolic compounds 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 〇-cresol), and p-cresol, such as phenol-formaldehyde resin. , Sono-cresol/formaldehyde resin, O-cresol/formaldehyde resin, phenol/p-cresol/formaldehyde copolymer resin, Teng-cresol/p-cresol/formaldehyde copolycondensate resin, 0-cresol/p-cresol/formaldehyde copolymer resin Examples include formaldehyde copolycondensate resin, phenol/■-cresol/p-cresol/formaldehyde copolycondensate resin, and phenol/0-cresol/p-cresol/formaldehyde copolycondensate resin. Furthermore, among the above novolak resins, phenol
-Cresol/p-cresol/formaldehyde resins are preferred.

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

The molecule It (polystyrene standard) of the above novolac resin has a weight average molecule IMw of 2.0 x 103 to 2.0
X10+, number average molecular weight Mn is 7.0X102 to 5.
Preferably, the value is within the range of 0x103, and further,
Preferably, the MW is 3.0×103 to 6.0×103,
Mn is a value within the range of 1.7×10 2 to 1.2×10 3 . The molecular weight of the novolak resin in the present invention is measured by GPC (gel permeation chromatography).

In addition, phenol preferably used in the present invention, water injection R
A vinyl polymer having a structural unit having a group in its molecular structure is a polymer obtained by polymerization by cleavage of a carbon-carbon double bond, and has at least one of the following formulas [Vl] to [x1]. Polymers containing one structural unit are preferably used.

-Formula [VI] 1+CRt R2-CRs+ 0-Co-B-OH General formula [Vl] +CRI R2-CRa+ C0NR4→A-)tB-OH General formula [VI] +CRI R2CR3+- C00-+A-B-OH General Formula [IX] +CRI R2-CR3+ -0H General formula [X] OH OH In the formula, R1 and R2 each represent a hydrogen atom, an alkyl group, or a carboxyl group, preferably a hydrogen atom. R3 represents a hydrogen atom, 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, and represents an integer from O 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, the above-
A copolymer containing at least one structural unit represented by the formula [■] 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 formulas [VI] to [XI] Monomer 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, p-methylstyrene, p-chlorostyrene Styrenes such as acrylic acid, acrylic acids such as methacrylic acid, unsaturated aliphatic dicarboxylic acids such as itaconic acid, maleic acid, maleic anhydride, such as methyl acrylate, ethyl acrylate, isobutyl acrylate, acrylic acid Isobutyl, dodecyl acrylate, acrylic acid 2-
Esters of α-methylene aliphatic monocarboxylic acids such as chloroethyl, phenyl acrylate, methyl α-chloroacrylate, methyl methacrylate, ethyl methacrylate, and ethyl ethacrylate; nitrites such as acrylonitrile and methacrylonitrile; e.g. acrylamide; Amides such as acrylanilide, p-chloroacrylanilide, -12troacrylanilide, -1methoxyacrylanilide, etc., vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate, vinyl butyrate, etc. vinyl ethers 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-ditroethylene, such as N-vinylvirol, N-vinylcarbazole, N-
There are vinyl monomers such as N-vinyl compounds such as vinyl indole, 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, those used in combination with at least one of the structural units represented by formulas [VI] to [XI] include (meth)acrylic acids, esters of aliphatic monocarboxylic acids, and nitriles. 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, - formulas [VI] to [X
The content of the structural units indicated by [] is 5 to 7.
0 mol% is preferable, and 10 to 40 mol% is particularly preferable.

The above-mentioned polymer particles may be used alone, or two or more types may be used in combination in the photosensitive composition.

Typical examples of vinyl polymers used in the present invention are listed below. In addition, in the compounds exemplified below, IV
LW is weight average molecular weight, Mn is number average molecular weight 1. s, to,
1. o, m and n are each exemplary compound CH.

The proportion of the alkali-soluble resin in the photosensitive composition of the present invention is preferably 50 to 90% by weight, more preferably 60 to 90% by weight.

The photosensitive composition of the present invention preferably further contains an organic acid and an acid anhydride other than the compound of the present invention.

The above-mentioned organic acids include all known various RM-containing organic acids, but organic acids with a pKa value of 2 or more are preferred, more preferably 1) a Ka value of 3.0 to 9.0, particularly preferably 3. Organic acids of .5 to 8.0 are used. however,
The pKa value used in the present invention is the 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, compounds that can exhibit the above 1) Ka value can be mentioned. Examples of such compounds include benzoic acid, adipic acid, azelaic acid, isophthalic acid, p-toluic acid, q-toluic acid, β-ethylglutaric acid, l-oxybenzoic acid, p-oxybenzoic acid, 3,
5-dimedylbenzoic 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-cyclopentane Dicarboxylic acid, 1.2-cyclopentanedicarboxylic acid, 1.3
-cyclopentanedicarboxylic acid, β, β-dimethylglutaric acid, dimethylmalonic acid, α-tartaric acid, speric acid,
Terephthalic acid, pimelic acid, phthalic acid, fumaric acid, β-
Abu Ovir glutarate propylmalonic acid, mandelic acid,
Mesotartaric acid, β-methylglutaric acid, β, β-methylbutyrglutaric acid, methylmalonic acid, malic acid, 1,1
-cyclohexanedicarboxylic acid, 1°2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, cis-4-cyclohexene1°2-dicarboxylic 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 0.05 to 10
Weight % is suitable, preferably 0.1 to 5 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, pyromellitic acid, and the like. These acid anhydrides are preferably contained in the photosensitive layer in an amount of 0.05 to 10% by weight, particularly 0.1 to 5% by weight.

The photosensitive composition of the present invention preferably has the following general formula [XI]
It includes a synthetic 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 (of fluorine, chlorine, bromine and iodine, 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 inpropylphenol, tert-butylphenol, tert-amylphenol, hexylphenol, tert-octylphenol, cyclohexylphenol, 3-methyl-4-tert-5-tert-butylphenol, isopropylcresol. , tert-butylcresol,
tert-amyl cresol, hexyl cresol, t
Examples include ert-octyl cresol and cyclohexyl cresol, and among these, 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 formula [X] and aldehyde in the presence of an acidic catalyst. Ru. 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), it can be obtained by heating under reduced pressure, washing with water, and perfusing with water.
Alternatively, the reactant can be obtained by precipitating water.

The 0-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 0-naphthoquinonediazide sulfonic acid to it. It is obtained by esterifying the mixture by adding O-lide and adding an alkali such as alkali carbonate dropwise to the equivalence point while heating and stirring.

In the esterified product, water of phenols! The condensation rate of 0-naphthoquinonediazide sulfone chloride per group (reaction rate % per hydroxyl group) is 5 to 80.
%, 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 represented by formula [XI] with aldehyde and the O-naphthoquinonediazide sulfonic acid ester compound of the resin in the photosensitive composition of the present invention is 0.05 -1511% by weight is preferred, particularly preferably 1-10% by weight, and the weight average molecular weight Mill is preferably 5. OX 102~5
．． 0X1Q3, more preferably 7. OX
It is in the range of 102 to 3.0×103. The number average molecule IMn is preferably in the range of 3.0X102 to 2.5X103, more preferably 4. OX 1Q 2~
The range is 2.0×103.

The above molecular weight is measured by GPC (gel permeation chromatography). Number average molecular weight Mn
The calculation of the average molecule IMw of the multilayer is described in Morio Tsuge, Tatsuya Miyabayashi, and Masayuki Tanaka, “Journal of the Chemical Society of Japan,” pp. 800-805 (
(1972) in which the peaks of the oligomer region are leveled (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 [A] and [81] in its molecular structure.

Structural unit [A] +CH2CH20+v- Structural unit [81 Ha ÷CH2CH-0+- (wherein, n represents an integer from 2 to 5ooo) At least one of the structural units [A] and [B] used in the present invention The seed-containing compound may be any compound having one or both of the above structural units [A] and [81, but in particular n is an integer within the range of 2 to 5000 and the boiling point is A compound in which n is an integer in the range of 2 to 500 is preferred, and a boiling point is in the range of 280 °C or higher, and most preferred is a compound in which n is an integer in the range of 2 to 500. It is a compound.

Examples of such compounds include ``Ho!J ethylene glycol (HO-+CH*CH
,0)'vH)・Polyoxyethylene alkyl ether (RO(CH=CHtO)nH)・Polyoxyethylene alkylphenyl ether・Polyoxyethylene polystyrylphenyl ether・Polyoxyethylene-polyoxypropylene glycol (However, (including block polymers and random polymers) Polyoxyethylene-polyoxybrobylene alkyl ether (terminally forming an alkyl ether) (However,
(including random polymers) ・Alkylphenol formalin, condensate ethylene oxide derivative CH,0(CH*CH,0)nH ・Polyoxyethylene fatty acid ester (e.g. RCOO(CH=CH*O)nH)・
Examples include polyoxyethylene alkylamine and polyoxyethylene polyhydric alcohol fatty acid partial ester.

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 trislate,
Polyoxyethylene sorbitol tetraoleate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol monooleate, polyethylene glycol distearate,
These include polyoxyethylene nonylphenyl ether formaldehyde condensate, oxyethylene oxybrobylene block copolymer, polyethylene glycol, tetraethylene glycol, and the like.

The proportion of the compound having at least one of the structural units [A] and [B] 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 1011%.

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.

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 0.402 to 5% by weight.

The photosensitive composition of the present invention combines the above materials,
In particular, by containing the compound of the present invention, the object of the present invention can be achieved, but in addition to these materials, pigments such as dyes and pigments, sensitizers, and plasticizers may be added as necessary. Agents, surfactants, etc. can be added.

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 acetate, dimethyl formamide, dimethyl sulfoxide, dioxane, Examples include acetone, cyclohexanone, trichloroethylene, methyl ethyl ketone, and the like. 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 is preferably 0.5 to 5.0 g/f in terms of solid content, for example.

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. Been formed! 1-polar oxidized skin sji is 1-50mg/
df is appropriate, preferably 10 to 40113/df
It is. @The amount of polar oxide skin a can be determined, for example, by immersing an aluminum plate in a phosphoric acid 0IA-solution (85% phosphorus R solution: 351 ml, prepared by dissolving chromium oxide (■) = 20 o in 11 water) and oxidizing it. Dissolve the film and fil before and after dissolving the film on the board
It can be obtained from l change measurements, etc.

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% is preferable. 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) A 0.24 m-thick aluminum plate (material 1050, 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, the current density was 60A/
Electrolytic etching treatment was performed under the conditions of df and treatment time: 30 seconds. The specimen was then desmutted for 10 seconds at 60°C in a 5% by weight aqueous sodium hydroxide solution.
Temperature: 20°C, current density: 3A/d in wt% sulfuric acid solution
f. Treatment time; anodization treatment was performed for 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.

Coating solutions 1 to 18 of photosensitive compositions having the following compositions were applied to the aluminum plate prepared as above using a rotary coater, and dried at 90°C for 4 minutes. 1 to 18 were obtained.

(Photosensitive composition coating liquid composition-1) ・Novolak resin-A 6.5a・
0-quinonediazide compound 1.7g (QD
-1) Compound of the present invention (a) 0.33
g・Free radical generating compound (1) 0607g ・Victoria Pure Blue 80 H0.06゜ (manufactured by Hodogaya Chemical 1lII) ・Methyl cellosolve 100- (Photosensitive composition coating liquid composition-2) ・Novolac resin-A 6.7a・O
-Quinonediazide compound 1.50 (QD-2
) ・Compound of the present invention (b) o, 3s
g・Free radical generating compound (2) 0.07
a. Victoria Pure Blue B OH0,060 (manufactured by Hodogaya Chemical@) - Esterified product of polycondensation resin of p-n-octylphenol and formaldehyde and 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride (esterified rate 50%) o, oag
・Methyl cellosolve 1 (lomf
fi (Photosensitive composition coating liquid composition-3) ・Novolac resin-B 6.50・
O-quinonediazide compound 1.79 (QD
-1) -Compound of the present invention (c) 0.4
a. Free radical generating compound (3) o, ol
g. Victoria Pure Blue BOH 0.06 g (manufactured by Hodokugaya Chemical ■) - Polycondensation resin of p-tert butylphenol and formaldehyde 0.08 (tomethyl cellosolve 100112 (photosensitive composition coating liquid composition - 4) - Novolac Resin - 86.7g ・θ-quinonediazide compound 1.5g (Q
D-2) Compound of the present invention (d) 0.40
・Rheodor TW-0120 (manufactured by Kako 1111i) 0.
1g・Free radical generating compound (4) 0.0
7 (Victoria Pureful-8080,069 (Hodogaya Kagaku Kan Seibu) Methyl Seo Solv 100i1 (
Photosensitive composition coating liquid composition-5) - Novolak resin - 8,0-quinonediazide compound (QD-3) - Compound of the present invention <a) - 3,4-dimethoxybenzoic acid - Free radical generating compound (2) - Victoria Pure Blue BOH (manufactured by Hodogaya Kagaku) ・Polyethylene glycol #2000 (manufactured by Kanto Kagaku) ・Methyl cellosolve (photosensitive composition coating liquid composition-6) ・Novolac resin-B ・0-quinonediazide compound (QD-1> ・Book) Compound of the invention (e) - Tetrahydrophthalic anhydride - Free radical generating compound (1) - Victoria Pure Blue 808 (manufactured by Hodogaya Chemical) 7, Og 1.3g 0.317 0.4g 0, 0711 0, 06Q o, 1g 100[ 6,5g 1.1g 0.4Q o,3g O,ozg O,06g ・Methyl cellosolve (photosensitive composition coating liquid composition-7) ・Novolac resin-A ・0-quinonediazide compound (QD -1) ・Compound (f) of the present invention ・Free radical generating compound (4) ・Victoria Pure Blue BOH (manufactured by Hodogaya Chemical 9M) ・Methyl cellosolve (photosensitive composition coating liquid composition-8) ・Novolac resin-C ・O-quinonediazide compound (QD-4) ・Compound of the present invention (IJ) ・Free radical generating compound <1) ・3,5-dimethoxybenzoic acid ・Rheodol 460 (manufactured by Kako AI) ・Victoria Pure Blue BO) Tsuchigaya Chemical ■) 00mN 6゜5゜1.7g 0.5 (1 0,080 o, oeg 100, .12 6.7 (1 1,5g 0, 35g 0.07Q Q, 20Q o, 1og o, oeg ・Esterified product of polycondensation resin of p-n-octylphenol and formaldehyde and 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride (esterification rate 50%) ・Methyl cellosolve (photosensitive composition coating liquid) Composition-9) ・Novolak resin-C ・Acrylic resin-A ・O-quinonediazide compound (QD-5) ・Compound (h) of the present invention ・Free radical generating compound (2) ・p-anisic acid・HCO-30 ( Nikko Chemicals ■〉 Victoria Pure Blue BOH (manufactured by Odugaya Chemical ■) ・Polycondensation resin of p-n-octylphenol and formaldehyde and 1,2-naphthoquinone-2-diazide-5-o, oaa 1001ρ 5.4 g 1 .4g 1.4 g 0,25!11 0.08(1 0,25(1 0,08(] 0,061;1 Esterified product with sulfonyl chloride (esterification rate 50%) o, ogg
・Methyl cellosolve 1001β (
Photosensitive composition coating liquid composition-10) - Novolac tree 11! -84.8g ・Acrylic resin -〇 2. Oa・
0-quinonediazide compound 1.4g (QD
-6) Compound (i) of the present invention 0.20
g・Free radical generating compound (3) 0.10
゜・Tetrahydrophthalic anhydride 0.309・
Rheodor TW-0120 (Chemical (11) 0.1
2g Victoria Pure Blue BOH0,060 (manufactured by Hodogaya Kagaku n) Esterified product of polycondensation resin of p-n-octylphenol and formaldehyde and 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride (esterification rate 50%) o, oag・
Methyl cellosolve 1001ρ (photosensitive composition coating liquid composition-11) - Novolak resin - C - Acrylic resin -8 - 0-quinonediazide compound (QD-3) - Compound of the present invention (e) - 12 leaving group forming compound (2 ) ・3.4-Dimethoxybenzoic acid・Go-430 (Nikko Chemicals■) ・Victoria Pure Blue BOH (manufactured by Hodogaya Chemical! 1) ・Polycondensation resin of p-n-octylphenol and formaldehyde and 1.2-naphthoquinone- Esterified product with 2-diazide-5-sulfonyl chloride (esterification rate 50%) - Methyl cellosolve (photosensitive composition coating liquid composition - 12) - Novolak resin - 8 - Acrylic resin - B 6.0 a 1.1 g 1.10 0, 16! J O, 050 0, 25111 o, oa.

O,06(1 0,08g 100 *(1 5,60 1,5g ・O-quinonediazide compound 1.1g(Q
D-2) Compound (C) of the present invention 0.400
・Free radical generating compound (2') 0.08
g・Cyclohexanedicarboxylic acid 0.12g・
PEG #2000
G, 050・Victoria Pure Blue BOH0,06t
J (manufactured by Odugaya Chemical) - Esterified product of polycondensation resin of p-n-octylphenol and formaldehyde and 1,2-nafdoquinone-2-diazide-5-sulfonyl chloride (esterification rate 50%) o , oag・
Methyl cellosolve 100mR (photosensitive composition coating liquid composition -13) ・Novolak resin = A 5.79・
Acrylic resin-A 1. IQ・
0-quinonediazide compound 1.4g (QD
-6) Compound of the present invention (j) 0.30
g・Free radical generating compound (1)・Benzoic acid・TMGO-15 (Nikko Chemicals ■)・Victoria Pure Blue BOH (manufactured by Hodogaya Chemical 8I)・Polycondensation resin of p-n-octylphenol and formaldehyde and 1,2- Esterified product with naphdoquinone-2-diazide-5-sulfonyl chloride (esterification rate 50%) ・Methyl cellosolve (photosensitive composition coating liquid composition-14) ・Novolac resin-C ・Acrylic resin-8 ・0-quinonediazide compound (QD-5) - Compound of the present invention (1) - Free radical generating compound (3) - Tetrahydrophthalic acid - Q Q -430 0,039 G, 459 O,1G (1 o, oeg o, osg G0i 5. 4g 1.3 g 1.5Q 0, osg O,081; 1 G, 25g 0. oag ・Victoria Pure Blue B OH0,061J (manufactured by Hodogaya Chemical ■) ・The weight of p-n-octylphenol and formaldehyde Esterified product of condensation resin and 1.2-naphthoquinone-2-diazide-5-sulfonyl chloride (esterification rate 50%) 0.089.
Methyl cellosolve 100t12 (
Photosensitive composition coating liquid composition-15) - Novolac resin-B7. OQ ・O-quinonediazide compound 1.30 (Q
D-3) ・Butyric acid (C3H7C00H) 0.4 g
・Free radical generating compound (2) 0゜08Q ・Victoria Pure Blue BOH0,06Q (manufactured by Odogaya Chemical Co., Ltd.) ・Methyl cellosolve 100d (photosensitive composition coating liquid composition-16) ・Novolac resin-B 6.70・
0-quinonediazide compound 1.5Q (QD
-2) - Malonic acid 0.4g (H
OOC-CH2-COOH) ・Free 11 group producing compound (1) 0.08
g. Victoria Pure Blue B OH0,06<1 (manufactured by Odugaya Kagaku III) ・Methyl Serotsuru 7 100 Review (Photosensitive composition coating liquid composition-17) Compound (d) of the present invention was removed from coating liquid composition-4 Other than that, the coating liquid composition is the same as 4.

Photosensitive composition coating liquid composition-18) Same as coating liquid composition-6 except that the compound (e) of the present invention was removed from coating liquid composition-6.

Photosensitive lithographic printing plate samples No. 001 to 18 thus obtained
A step tablet for sensitivity measurement (Eastman Kodak i!jj No-2, 21 gray scale levels with a density difference of 0.15) was placed on top, and a 2KW metal halide lamp (Idol Fin 200 manufactured by Iwasaki Electric Co., Ltd.) was attached.
0) as a light source under conditions of 8.0 mW/cv. Next, this sample was developed at 27° C. for 20 seconds using a developer prepared by diluting SDR-1 (manufactured by Konica ■) six times with water to obtain a lithographic printing plate.

The remaining dye in the non-image areas of each of the obtained lithographic printing plates was visually evaluated.

Furthermore, in order to evaluate the erasure trace stain, a part of the image of each lithographic printing plate obtained above was erased with erasing liquid 5IR-15 (manufactured by Konica ■), and then Mark Five Red Ink (made by Heidel GTO) was erased with Heidel GTO. A printing test was conducted using Toyo Ink (manufactured by Toyo Ink ■). Evaluate whether or not ink adheres to the erased trace during printing (Seito 1 table *1 Erased trace stain: ○ No stain, no ink adheres) X Stain (ink ink adheres) $2 Dye residue; 0 None × Yes Δ Slightly present As is clear from Table 1, samples Nos. 1 to 14 of the present invention containing the compound of the present invention were samples with almost no erased stains or dye residues. Ta.

・Compound of the present invention (a): nC1-Ha, C00H (b): nc++HiscOOH (6): cis-CH3(CH mountain CH=CH(CH2
)tcOOH(d): cis CH3(CHs)+
aCH=CH(CHzLCOOH(e): cis
CHs(CHs)tcH=cH(CH-)1. C00H
(f): nC4H; COOH (g): trans CH3(CHs)tcH=c
H(CHs)ncOOH(h): ncHs(CHs)
+5COOH(i): nCHa(CHs)t<C00
H(j): nCHa(CHs)+5COOH・Novolac all A; Copolycondensation resin of phenol, mist-cresol, p-cresol, and formaldehyde (the molar ratio of each of phenol, --cresol, and p-cresol is 2 .0
: 4.8:3゜2. My -7゜Goo, Mw
/Mn -5,0) B: ■ Copolycondensation resin of -cresol, p-cresol, and formaldehyde (--molar ratio of each of cresol and p-cresol is 6:4
, My −8,000, Mw /Mn = 6.0)
C: Copolycondensation resin of phenol, l-cresol, p-cresol, and formaldehyde (molar ratio of each of phenol, easy-cresol, and p-cresol is 3.0
: 4.2:・Acrylic OI visit A; B; C; D-4 (m: n=6:4 Mw of goza before reacting with Q'=800) υ D-6 (reacting with Q' Mw=2,600) 0-quinone diacid compound υ D-3 ・11 leaving group forming compound (2) in the previous 84; [Effect of the invention] As explained in detail above, the photosensitive composite acid of the present invention By using this, it is possible to obtain a photosensitive lithographic printing plate in which erasure trace stains during printing are improved and almost no dye remains after development.

Claims (1)

[Claims] A photosensitive composition containing at least an o-naphthoquinone diazide compound, a dye, and an aliphatic monocarboxylic acid having at least 5 carbon atoms.