JPH0296756A - Photosensitive composition - Google Patents

Abstract

PURPOSE:To obtain a photosensitive compsn. having high sensitivity and superior under developability by incorporating 1,2-naphthoquinone-2-diazide-4-sulfonic ester compd., an acid anhydride and/or org. acid into the compsn. CONSTITUTION:The title photosensitive compsn. contains 1,2-naphthoquinone-2- diazide-4-sulfonic ester compd., the acid anhydride, and/or the org. acid. Esterified compds. of 1,2-naphthoquinone-2-diazide-4-sulfonic acid with a polycondensation resin of a phenol homologue with an aldehyde or ketone are particulary preferred as 1,2-naphthoquinine-2-diazide-4-sulfonic ester compd. Preferred org. acid is one having >=2 pKa, more pref. 3.0-9.0 pKa, most pref. 3.5-8.0 pKa. Thus, a photosensitive planographic printing plate having superior under developability and high sensitivity is obtd.

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 particularly, to a photosensitive composition containing a naphthoquinone diazide compound as a photosensitive component. .

Background of the Invention] A positive-working photosensitive lithographic printing plate generally has an ink-receptive photosensitive layer formed on a hydrophilic support, which becomes solubilized by exposure to actinic rays such as ultraviolet rays. When this photosensitive layer is subjected to imagewise exposure and development, the non-image area is removed leaving the image area, and an image is formed. In planographic printing, the difference in properties is utilized in that the image area is lipophilic and the non-image area is hydrophilic.

Usually, the photosensitive layer of a positive photosensitive lithographic printing plate contains an 0-quinonediazide compound as a photosensitive component.
Among the above 0-quinonediazide compounds, 1,2-naphthoquinone-2-diazide-5 is particularly preferred from the viewpoint of sensitivity and cost.
- Sulfonic acid ester compounds are generally used as useful compounds.

Conventionally, the development of such positive-working photosensitive lithographic printing plates is usually carried out in a developer consisting of an alkaline aqueous solution, but the developing ability of the developer tends to fluctuate depending on various conditions.
For example, the developing ability may be reduced due to fatigue due to multi-layer processing or deterioration due to air oxidation, and the photosensitive layer in the non-image area of the printing plate may not be completely dissolved even after processing. Therefore, it is desired that a photosensitive lithographic printing plate has a wide range of development tolerance, showing the same developability as when processed with a standard developer even with a developer having a reduced processing ability as described above. (Hereinafter, the allowable interval of decrease in development ability that allows for proper development results to be obtained is referred to as under-development.) On the other hand, photosensitive lithographic printing plates with high sensitivity are needed to improve workability, etc. The sensitivity of the photosensitive lithographic printing plate is still insufficient, and therefore, the amount of the photosensitive component added is usually reduced. However, although this method increases the sensitivity slightly, it does not reduce the under-developability. The disadvantage was that it further deteriorated. That is, a photosensitive lithographic printing plate having excellent under-developability and low sensitivity has been desired.

[Object of the Invention] An object of the present invention is to provide a photosensitive lithographic printing plate having high sensitivity and excellent under-developability, and a photosensitive composition suitable for the printing plate.

[Structure of the Invention] As a result of research by the present inventors, the above object of the present invention is to obtain at least (a) a 1,2-nattoquinone 2-diazide-4-sulfonic acid ester compound and (b) an acid anhydride. and/or an organic acid.

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

1,2-naphthoquinone-2-diazide in the present invention
Various known compounds can be used as the 4-sulfonic acid ester compound (hereinafter referred to as Compound J of the present invention), but in particular 1,2-nano-1-quinone-2-diazide-4-
Ester compounds of sulfonic acid and polycondensation resins of phenols and aldehydes or ketones are preferably used.

Examples of the phenols include phenol, 0-
Cresol, m-cresol, p-cresol, 3.5
~ Monohydric phenols such as xylenol, carvacrol, and thymol; dihydric phenols such as catechol, resorcinol, and hydroquinone; 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, cresol/formaldehyde resin, p-cresol/formaldehyde resin, and l-cresol/formaldehyde resin.
, p-mixed cresol/formaldehyde resin, resorcinol/benzaldehyde resin, pyrogallol/acetone resin, and the like.

1 for the OH group of the phenol of the compound of the present invention
, the condensation rate (reaction rate for one OH group) of 2-naphthoquinone-2-diazide-4-sulfonic acid is 15 to 80%.
is preferable, and more preferably 20 to 60%.

Furthermore, as the compound of the present invention, one of the polyhydroxy compounds is
．． Examples of such compounds include 2-naphthoquinone-2-diazide-4-sulfonic acid ester compounds.
For example, 1,2-naphthoquinonediazide-4-sulfonic acid cyclohexyl ester, 1-(1,2-naphthoquinonediazide-4-sulfonyl)-3,5-dimethylpyrazole, 1,2-naphthoquinonediazide-4-sulfone Acid-4''-hydroxydiphenyl-4''-azo-β-naphthol ester, 2'-(1,2-naphthoquinonediazide-4-sulfonyloxy)-1-hydroxy-anthraquinone, 1,2-naphthoquinonediazide-4- Sulfone F! -2,4-dihydroxybenzophenone ester, 1,2-naphthoquinonediazide-4-sulfone! −
2,3,4-trihydroxybenzophenone ester,
1,2-naphthoquinonediazide-4-sulfonic acid-2°3.4', 4'-tetrahydroxybenzophenone ester, 2 moles of 1,2-naphthoquinonediazide-4-sulfonic acid chloride and 4,4'-dihydroxy-1 ,1
Examples include a condensate of 1 mole of '-diphenylsulfone, a condensate of 1 mole of 1,2-naphthoquinonediazide-4-sulfonic acid chloride and 1 mole of purbrogalin, and the like.

In addition, 1.2 of polyurethane resin as shown below
-Naphthoquinone-2-diazide-4-sulfonic acid ester compounds may also be used.

In the following margin (where n represents an integer from 2 to 300), the compound of the present invention is a combination of a vinyl polymer having phenolic water HB and 1,2-naphthoquinone-2-diazide-4-sulfonic acid. Ester compounds 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 is preferably a phenolic water W1 used as the alkali-soluble resin described later. A vinyl polymer having a structural unit having a group in its molecular structure can be used.

As the compound of the present invention, each of the above compounds may be used alone or in combination of two or more. The proportion of the compound of the present invention in the photosensitive composition of the present invention is preferably 5 to 60% by weight, particularly preferably 10 to 60% by weight.
It is 50% by weight.

All known various organic acids can be used as the RFlt used in the present invention, but organic acids with a pKa value of 2 or more are preferred, and more preferably 3.0-9.
0, particularly preferably from 3.5 to 8.0. However, the 1lKa value used in the present invention is 25
The value is in °C.

Examples of such organic acids include, for example, Chemistry Handbook Basic Edition■
Among the organic acids described in Maruzen (111966, pp. 1054-1058), all compounds that exhibit the pKa of the present invention can be mentioned. Such compounds include, for example, benzoic acid, adipic acid, azelaic acid,
Isophthalic acid, o-toluic acid, q-toluic acid, β-
Ethylglutaric acid, button-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-dimethylglutaric acid, dimethylmalonic acid, α-tartaric acid, sperine Acid, terephthalic acid, pimelic acid, phthalic acid, fumaric acid, β-butylglutaric acid, butylmalonic acid, mandelic acid, mesotartaric acid, β-methylglutaric acid, 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 Examples include -1,2-dicarboxylic acid, erucic acid, undecenoic acid, lauric acid, rhocapric acid, pelargonic acid, and rhoundecanoic acid. 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 parts by weight.
% is appropriate, preferably 0.1 to 5%.

Further, as the acid anhydride used in the present invention, all known various acid anhydrides can be used, but cyclic acid anhydrides 'C' are preferred, such as phthalic anhydride,
Tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3,6-nindooxy-Δ4-detrahydrophthalic anhydride, tetrahydrophthalic anhydride, glutaric anhydride, maleic anhydride, chlormaleic anhydride, α-phenylmaleic anhydride, succinic anhydride acid, biomellitic acid, etc. These acid anhydrides have a concentration of 0.05-10 in photosensitive P3.
It is preferably contained in an amount of n% by weight, particularly 0.1 to 5 a% by weight.

The photosensitive composition of the present invention includes, as an alkali-soluble resin,
Although various resins known in the art can be used, novolak resins and vinyl-based polymers having a structural center having a phenolic hydroxyl group in the molecular structure are particularly preferred.

Novolac resins preferably used in the present invention include:
Resins obtained by condensing phenols and formaldehyde in the presence of an acid catalyst are mentioned, and examples of the phenols include phenol, O-cresol, --cresol, p-cresol, 3,5-xylenol, 2. 4
-xylenol, 2,5-xylenol, carvacrol mole, catechol, resorcinol, didroquinone, pyrogallol, phloroglucin, and the like.

The above-mentioned phenolic compounds can be used alone or in combination with formaldehyde to obtain a resin. Among these, preferred novolak resins are resins obtained by copolycondensing formaldehyde with at least one selected from phenol, san-cresol (or 〇-cresol), and leak-cresol; for example, phenol-formaldehyde resin, -Cresol/formaldehyde resin, 0-cresol/formaldehyde resin, phenol/low cresol/formaldehyde copolymer resin, -Cresol/p-cresol/formaldehyde copolymer resin, 0-cresol/p-cresol/formaldehyde copolymer Examples include condensate resins, phenol/m-cresol/p-cresol/formaldehyde copolycondensate resins, and phenol/O-cresol/p-cresol/formaldehyde copolycondensate resins. Furthermore, among the above novolak resins, phenol
-Cresol/leak Cresol/formaldehyde resins are preferred.

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

The molecule W of the above novolak resin (polystyrene standard) is 1, and the weight average molecule ff4 M W is 2.0 x 103
~2. OX i○1 has a number average molecular weight.

7.OXlQ2~5. The value is preferably within the range of OX103, and more preferably, the MW is 3. Ox10
3-6. Ox103, Mn is 7.7X 102”
'-1, a value within the range of 2x1Q3. The molecular weight of the novolac resin in the present invention is measured by GPC (gel permeation chromatography).

In addition, as the vinyl polymer having a phenolic water S group in its molecular structure, which is preferably used in the present invention, a polymer formed by polymerization by cleavage of a carbon-carbon double bond is used. A polymer containing at least one structural unit of the following formats [I] to [VI] is preferably used.

-Format CI] -f CR+ R2-CR3 0-Go-8-○H General formula [I[] + CRs R2-CR3+ CON R46A'zB ○H General formula [I[[] % formula% General formula [IV] +CR+ R2-CR3+- B-01-1 General formula [V] Sn H H 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. R4 represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, preferably a hydrogen atom. A is a nitrogen atom or an oxygen atom and an aromatic 7j
5IrA represents an alkylene group that may have a substituent that connects with the elementary atom, ml represents an integer from to to 10, and B1
Represents a phenylene group which may have a substitution group or a naphthylene group which may have a substituent. In the present invention, among these, a copolymer containing at least one structural unit represented by form [1] is preferred.

The vinyl polymer preferably has a copolymer-type structure, and in such a copolymer, at least one type of structural unit shown in each of the above-mentioned formats [1] to [VI] Examples of monomer units that can be used in combination with are ethylenically unsaturated olefins such as ethylene, propylene, isobutylene, bucdiene, and isoprene, 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, 0-butyl acrylate, isobutyl acrylate, dodecyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, methyl α-chloroacrylate, methyl methacrylate, ethyl methacrylate,
■ Esters of α-methylene aliphatic monocarboxylic acids such as ethyl taacrylate, nitriles such as acrylonitrile and methacryloni-1-lyl, amides such as acrylamide, such as acrylanilide, p-O-roacrylanilide, ■ - Anilides such as ditroacrylanilide and I-methoxyacrylanilide, vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate, and vinyl acetate, such as methyl glycol ether, ethyl glycol ether, isobutyl vinyl ether, etc. vinyl ethers such as ester, β-chloroethyl vinyl ether, vinyl chloride, vinylidene chloride, vinylidene cyanide, such as 1-methyl-1-methoxyethylene, 1,1-dimethoxyethylene, 1,2-dimethoxyethylene, 1.1- Dimethoxycarbonylethylene, 1-
Ethylene derivatives such as methyl-1-nitroethylene, such as N-vinylvirol, N-vinylcarbazole, N
- Vinyl compounds such as vinyl indole, N-vinylvirolone, N-vinylpyrrolidone, etc.
There is an ffi body. These vinyl-based suspended bodies exist in polymer compounds with a structure in which unsaturated double bonds are cleaved.

Among the above-mentioned monomers, those used in combination with at least one structural unit represented by the formats [I] to [VN include (meth)acrylic acids, esters of aliphatic monocarboxylic acids, Rils are preferable because they exhibit excellent overall performance. More preferred are methacrylic acid, methyl methacrylate, acrylonitrile, ethyl acrylate, and the like.

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

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

The above-mentioned polymers may be used alone, or two or more kinds thereof may be included in the photosensitive composition.

Typical specific examples of vinyl polymers used in this Bonmei are listed below. In addition, in the compound exemplified below, J5 and M
W is 1Iuffi average molecular surface, Mn is number average molecular weight, s
, fL, o, m and n each represent mol% of the structural unit.

Exemplary compound Margin below CH.

The proportion of the alkali-soluble resin in the photosensitive composition of the present invention is preferably 50 to 95% by weight, more preferably 60 to 90% by weight.

The photosensitive composition of the present invention has acid or free fA when exposed to light.
It is possible to contain a printout material consisting of a group-forming compound and a color change agent that changes its color tone by interacting with it.

As the compound which generates a Ti leaving group upon exposure to light for use in the present invention, trihaloalkyl compounds or diazonium salt compounds shown in the following symbols [VI] and [■] are preferably used.

- Clothing cost [Vl] 11 formed by a total bending atomic group may serve as the above-mentioned Xa. ) General formula [■] Ar -N2 Examples of the compound include the following - Kokudai [IXl, [X] or [
XI].

-Fukudai[IXl (in the formula,) (a represents a trihaloalkyl group having 1 to 3 carbon atoms, represents each atom of Wl, tN, S, Se, P, and C, and Z represents O, N, Indicates each atom of S, Se, and P,
Y has a chromophore group and represents a nonmetallic atomic group necessary for cyclizing W and 7. However, non-Fukudai [X] -Fukudai [XI] (wherein is a trihalo alkyl group having 1 to 3 carbon atoms, L is a hydrogen atom or a methyl group, and J 1. is a substituted or unsubstituted aryl group) One group or complex is represented by nl, tO.

1 and 1, li2.

Specifically, the compounds represented by the general formula [IX] include oxadiazole compounds having a benzofuran ring such as
2- described in Japanese Patent Application Laid-Open No. 54-747=28
Trichloromethyl-5-(p-methoxystyryl)-1
, 3,4-oxadiazole compound, or 41111 Publication No. 15iJly of 1986-241049)
TF compound*: The following compound described in JP-A No. 60-3828: The following compound described in JP-A-54-74728: The following compound described in JP-A-60-177340: JP-A-61- The following compound described in Publication No. 143748:
The following compound described in JP-A No. 55-77742: -
In addition, specific examples of the compound represented by [X] or [XI] include 4-(2,4-dimethoxy- 4-styryl)-6-dolichloromethyl-2-pyrone compound, 2,4-bis-(trichloromethylphosphorus-6-p-methoxystyryl-5-t described in JP-A-48-36281) -riazine compound, 2°4-bis-(trichloromethyl)-6-p-dimethylaminostyryl-s-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 a free compound is recommended as the counter ion moiety. 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, and preferably bala diazophenylamine salts.

The amount of 1 contained in the total photosensitive layer composition of the compound that produces T11111 groups upon exposure is preferably 0.01 to 20% by weight, more preferably 0.1 to 20% by weight, particularly preferably 02 to 10% by weight. It is.

In the photosensitive composition of the present invention, the color changing agent that changes the color tone by interacting with the acid or the photodecomposition product of the compound that generates T1111 group upon exposure to light includes those that develop color and those that fade or change color. There are two types. As the color-changing agent that causes fading or discoloration, various dyes such as diphenylmethane, triphenylmethane-based thiazine, oxazine-based, xanthine-based, anthraquinone-based, iminonapht-quinone-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, baraxin, Victoria Pure Blue BOH (Odugaya Chemical (IIV) , Oil Blue #603 [Orient Chemical Co., Ltd. l!l], Oil Pink #312 [manufactured by Orient Chemical Co., Ltd.], Oil Red 5B [manufactured by Orient Chemical Co., Ltd. (2)], Oil Blue Let #308 [Orient Chemical Co., Ltd.] Made by ■], Oil Red OG [Orient Chemical Industry i!1kl], Oil Red RR [made by Orient Chemical Industry], Oil Green #502 [made by Orient Chemical Industry ■], Subiron Red BEH Special [made by Hodogaya Chemical Industry ■] , l-cresol bubble, cresol red, rhodamine 810-damin 6G, firs i~
Acid Violet R, Sulforhodamine B, Auramine, 4-0-diethylaminophenylimino-naphthoginone, 2-carboxyanilino-4-p-diethylrea minophenylimino-naphthoquinone bostearylamino-4-D-dihydroxyethylamino- Phenylimino naphthoquinone, p-methoxybenzoyl-p'-diethylamine-〇'-methylphenyliminoacetanilide, cyano-p-diethylaminophenyliminoacetanilide, 1-phenyl-3-methyl-4-〇-diethylaminophenylimino-5-pyrazolone , 1-β-naphthyl-4-D-diethylaminophenylimino-5-
Pyrazolone.

Moreover, arylamines can be mentioned as color-changing agents that develop color. Arylamines suitable for this purpose include primary arylamines such as primary and secondary aromatic amines, as well as so-called roy dyes, examples of which include: It will be done.

Diphenylamine, dibenzylaniline, triphenylamine, diethylaniline, diphenyl-p-phenylenediamine, p-toluidine, 4゜41-biphenyldiamine, 0-chloroaniline, O-bromoaniline, 4
-chloro-O-phenylenediamine, 0-bromo-N,
N-dimethylaniline, 1,2,3-1-liphenylguanidine, naphthylamine, diaminodiphenylmethane, anilino, 2,5-dichloroaniline, N-methyldiphenylamine, 〇-toluidine, p,p'-tetramethyldiaminodiphenylmethane, N,N-dimethyl-
p-phenylenediamine, 1,2-dianilinoethylene, D, p', D''-hexamethyltriaminotriphenylmethane, p, p' -tetramethyldiamino i-liphenylmethane, p.

p'-tetramethyldiaminodiphenylmethylimine, p, p', p"-triamino-O-methyltriphenylmethane, p, p', p"-triaminotriphenylcarbinol methylaminodiphenyl-4-anilinonaphthyl Methane, p. 1. p”-triaminotriphenylmethane, p.
p'. p''-hexapropyltriaminotriphenylmethane.

The proportion of the above color changing agent in the photosensitive composition is 0,0
It is preferably used in an amount of 1 to 10%, more preferably 0.402 to 5%.

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

Structural unit [A] +CH2CH20 size structural unit [B] CH3 +C H2 0 H - ot- (In the formula, n represents an integer from 2 to 500G) The above structural units [A] and [B] used in the present invention The compound having at least one of the above structural units ['A] and [B] may be any compound having 10,000 or both of the structural units ['A] and [B]. and a boiling point of 2AO°C or higher, more preferably a compound where n is an integer in the range of 2 to 500 and a boiling point of 280°C or higher, and most preferred is a compound where n is 3AO°C or higher. -100.

This J: compound is, for example, polyethylene glycol (HO(CH2CH.O)-rrH) polyoxy 1 tyrene alkyl ether (R O (C
1] t C H - 0 ) n H )・Polyoxyethylene alkylphenyl ether (including block polymers and random polymers) ・Polyoxyethylene-polyoxybrobylene alkyl ether (terminals form an alkyl ether) )(however,
・Polyoxyethylene polystyrylphenyl ether ・Ethylene oxide derivative of alkylphenol formalin condensate ・PolyA21 ethylene polyoxyethylene glycol ・Polyoxyethylene polyhydric alcohol Fatty acid partial ester For example, CHO (CHz CHt O ) n HCHO(CH2
CHzO)nH CHO(CH,CH,0)nH CH=O(CHy CH20)nH, polyoxyethylene fatty acid ester (for example, RCOO(CH2CHsO)nH), polyol, and diethylenealkylamine.

Specifically, for example, the following are preferable.

In other words, polyoxyethylene lauryl ether, polyoxyethylene cetyl needle, 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 trioleate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate, tetra Polyoxyethylene sorbitol oleate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol monooleate, polyethylene glycol distearate, polyoxyethylene nonylphenyl ether formaldehyde condensate, oxyethylene oxybrobylene block copolymer, These include polyethylene glycol and tetraethylene glycol.

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

The photosensitive composition of the present invention may further contain a sensitizing agent such as a condensation resin of an alkyl-substituted phenol and formaldehyde.

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, a photosensitive layer can be provided by dissolving each of these components in the following solvents and coating and drying the solution on the surface of a suitable support 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,
Examples include dimethyl sulfoxide, dioxane, 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 when applying the photosensitive composition of the present invention to the surface of the support includes conventionally known methods such as spin coating, wire bar coating, dip coating, air knife coating, roll coating, blade coating, and Curtain coating etc. are possible. At this time, the coating amount varies depending on the application, but for example, the solid content is preferably 0.5 to 5.0 (J/f).

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 gold plate, paper, plastic film, glass plate, paper coated with resin, paper covered with metal foil such as aluminum, and plastic film treated to make it 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 the method using electric @Jdging.

Electrolytic etching is carried out in a bath containing inorganic acids such as phosphoric acid, sulfuric acid, hydrochloric acid, nitric acid, etc. alone or mixed for 2 seconds or more. After the graining treatment, if necessary, the despine is treated with an aqueous alkali or acid solution to neutralize it and washed 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 formed anodized skin yA5 is 1 to 50! l1g
/df is appropriate, preferably 10 to 401g/d
It is 12. fi81i oxide film, for example, coats an aluminum plate with phosphorous chromic acid solution (') N M 85%
Wit: 35v (1, oxide oxide (VN:20
(prepared by dissolving the board in water for one night) to dissolve the oxide film, and it is determined by measuring changes in the mold structure of the board before and after the film is dissolved.

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 aqueous solutions of alkali gold f1 salts such as sodium hydroxide, potassium hydroxide, 752M sodium, potassium carbonate, sodium metasilicate, potassium metasilicate, sodium diphosphate, and sodium triphosphate. Can be mentioned. The concentration of the alkali metal salt is preferably 0.1 to 10% by weight. 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) Aluminum plate with a thickness of 024 mm (material: 1050, heat treatment: 1
-116 > in a 5% sodium hydroxide aqueous solution at 60°C for 1 minute, and then in a 0.5 molar hydrochloric acid aqueous solution of 1 at a temperature of 25°C and a current density of 60A.
Electrolytic etching treatment was performed under the conditions of /df and treatment time: 30 seconds. Next, after desmutting for 10 seconds at 60°C in a 5% ω% sodium hydroxide aqueous solution,
0%! ll! iA polar acid oxidation treatment was performed in an acid solution at a temperature of 20° C., a current density of 3 A/df, and a treatment time of 1 minute.

Furthermore, a hot water sealing treatment was performed for 20 seconds using hot water at 30° C. to prepare an aluminum plate as a support for a lithographic printing plate material.

A photosensitive composition coating solution having the following composition was applied to the aluminum plate prepared as above using a rotary coater, and dried at 90°C for 4 minutes.
I got it.

(Photosensitive composition coating liquid composition) ・Novolac resin (1) $1 6.8 (]・
Compound of the present invention (QD-1) 1.50.tetrahydrophthalanhydride 11 0.25Q.1
．． 2-naphthoquinone-2-diazide-4-sulfonyl chloride 0. ogg Victoria Pure Blue BOHO, 06tJ (manufactured by Hodogaya Chemical) Methyl cellosolve 1001fl
Furthermore, in the composition of the photosensitive composition coating solution, as shown in Table 1, the compound of the present invention and tetrahydrophthalic anhydride were changed, and the period of addition of the additives was changed as appropriate to prepare a photosensitive lithographic printing plate. Samples NO2-10 were obtained.

Photosensitive lithographic printing plate samples No. 1 to 10 thus obtained
Step tablets for sensitivity measurement (Eastman Kodak's INO, 2, 21 with a concentration difference of 0.15 each)
4KW metal halide lamp (Iwa #I Denkisha Idolfin 2000)
) was used as a light source and exposed from a distance of 1 m. Next, add 80% of this sample to DP-4 (Fuji Photo Film Co., Ltd.) developer with water.
It was developed for 20 seconds at 25° C. using a developer diluted twice as much. Sensitivity was expressed as the exposure time required to completely clear the 5.0 step of step tablet i.

Furthermore, in order to examine under-developability, the developability was evaluated using a developer whose alkaline concentration was further diluted, that is, a developer whose developing ability was lowered.

The above developability is determined by diluting the Or”/Il developer by 12 times.
13 times and 14 times, respectively, at 25°C for 20
Mark Five Red Ink (Toyo Ink (Toyo Ink)...
A printing test was carried out using a printing press (manufactured by J.D. Co., Ltd.), and the degree of coloring of some halftone dots in the shadow was visually evaluated.

The results obtained above are shown in Table 2.

Below are the margins in Table 2. 3 Underprint & Gender Q: No smudges (no stains) on some halftone dots in the shadows Δ: Some smudges on some halftone dots in the shadows (slightly smudged) ×: Some halftone dots in the shadows Dirt (stains present) As is clear from the margin Table 2 below, all of the photosensitive lithographic printing plate samples HNO1 to HNO8 prepared using the photosensitive composition of the present invention had 1,2-naphthoquinone-2- Compared to springs No. 9 and 10 made from photosensitive compositions other than the present invention that do not use a diazide-4-sulfonic acid ester compound, they are superior in both sensitivity and under-developability.

Umbrella 1 Novolak 81 fat (1) Co-condensation resin of phenol, m-cresol, p-cresol, and formaldehyde (molar ratio of each of phenol, I-cresol, and p-cresol is 2.0:
4.8: 3.2. Mw = 7,500゜Mw
/Mn -5,0) *2 Compound of the present invention QD-1 (X/V=1/I MW of the resin before reacting with Q = ・Q 1]-2 (MW of the resin before reacting with Q MW = 1,700)
・QD-5 (x/y -3/I MW of resin before reacting with Q = ・QD-3 ・QD-6 QD-1 except for changing J5 to Q' below)
Same as -1.

1.000) (x/y -2/MY of the resin before reacting with Q -1,500) QD-
4. QD-7 Same as QD-3 except Q in QD-3 is changed to Q'.

[Effects of the Invention] As explained in detail above, the photosensitive composition of the present invention provides a photosensitive lithographic printing plate having wet under-developability and high sensitivity.

Claims (1)

[Scope of Claims] Photosensitivity characterized by containing at least (a) a 1,2-naphthoquinone-2-diazide-4-sulfonic acid ester compound and (b) an acid anhydride and/or an organic acid. Composition.