JPH02146042A - Photosensitive composition - Google Patents

Abstract

PURPOSE:To obtain a photosensitive compsn. having superior developability for an aq. alkali developing soln. and providing a relief image having high sear resistance by incorporating a specified polyurethane resin and a photosensitive compd. having a negative effect into a photosensitive compsn. CONSTITUTION:A polyurethane resin having sulfonamide groups and being insoluble in water but soluble in aq. alkali, pref. a polyurethane resin having sulfonamide groups in the side chain and/or principal chain, and a photosensitive compd. having a negative effect are incorporated into a photosensitive compsn. Preferred polyurethane resin having the sulfonamide groups is a polyurethane resin constituted of a fundamental skeleton comprising a reaction product of a polyol compd. having >=1 sulfonamide group in a molecule with a polyisocyanate compd. Thus, a photosensitive compsn. which can be developed with an aq. alkali developing soln., and provides a planographic printing having high durability in printing, is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a photosensitive composition suitable for manufacturing lithographic printing plates, IC circuits, photomasks, and the like. More specifically, the present invention relates to a photosensitive composition comprising a negative photosensitive compound and a polymer compound having excellent abrasion resistance and solubility in an alkaline aqueous solution.

(Prior Art) The majority of materials used as photosensitive substances in negative-acting photosensitive compositions are diazonium compounds, and the most commonly used ones include formaldehyde condensates of p-diazodiphenylamine. There are diazo resins that can be used.

The composition of the photosensitive layer of a photosensitive lithographic printing plate using a diazo resin is disclosed in, for example, US Pat. 4, diazo resin alone, that is, without a binder, as described in JP-A No. 50-3066,
As described in Publication No. 4, it can be classified as a mixture of binder and diazo resin, but in recent years, many photosensitive lithographic printing plates using diazonium compounds have a high printing durability. It is made of a diazonium compound and a polymer that acts as a binder.

As described in JP-A No. 50-30604, such a photosensitive layer is of the so-called alkaline development type, in which the unexposed area is removed (developed) with an aqueous alkaline developer, and the so-called alkaline development type, in which the unexposed area is removed (developed) with an aqueous alkaline developer, and the photosensitive layer is developed with an organic solvent developer. Although the so-called solvent-developed type is known, from the viewpoint of occupational safety and health, the alkaline-developed type is attracting attention, and this is mainly determined by the properties of the binder. A method for imparting alkali developability to the binder is to copolymerize a carboxylic acid-containing monomer as described in JP-A-50-30604, or as described in U.S. Pat. No. 2,861.058. As described in , there is a method of introducing a carboxylic acid into a polymer by reacting the hydroxyl group of polyvinyl alcohol with a cyclic acid dihydrogen such as phthalic anhydride, but the resulting polymer has a structurally Abrasion resistance is poor, and from photosensitive lithographic printing plates containing such a binder in the photosensitive layer, only lithographic printing plates with low stiffness resistance can be obtained. On the other hand, polyvinyl acetal forms a tough film and is abrasion resistant, but it has the disadvantage that only organic solvent-developable photosensitive lithographic printing plates can be obtained.

Furthermore, a photosensitive composition containing a polyurethane resin having a carboxyl group, which is described in JP-A No. 62-123452, solves these problems and has excellent developability in aqueous alkaline developers and abrasion resistance. It exhibits relatively high printing durability when used as a lithographic printing plate. However, sufficient stiffness resistance has not yet been obtained, and furthermore, there are problems that should be improved, such as poor chemical resistance and insufficient stiffness resistance especially in printing using UV ink.

In addition, there have been many attempts to use photopolymerizable compositions as photosensitive image forming layers of negative-working photosensitive lithographic printing plates.
A basic composition consisting of a polymer as a binder, a monomer and a photopolymerization initiator as disclosed in Japanese Patent Publication No. 32714, a polymer as a binder as disclosed in Japanese Patent Publication No. 34041/1983, Composition with improved curing efficiency by introducing bonds, Japanese Patent Publication No. 483
Compositions using new photopolymerization initiators are known, such as those disclosed in Patent Publications No. 8403 and Japanese Patent Publication No. 5127605, and British Patent No. 1,388,492, etc. However, the sensitivity of all photosensitive compositions is greatly affected by the surface temperature of the photosensitive lithographic printing plate during image exposure, and the disadvantage is that polymerization is strongly inhibited by oxygen during image exposure. was there.

[Problem to be solved by the invention]

Therefore, an object of the present invention is to provide a photosensitive composition in which a polymer compound used as a binder has excellent solubility in an alkaline aqueous solution and abrasion resistance, can be developed with an aqueous alkaline developer, and provides a lithographic printing plate with high stiffness resistance. The goal is to provide the following.

Another object of the present invention is to provide a photosensitive composition in which a polymer compound used as a binder has excellent chemical resistance and provides a lithographic printing plate with high rigidity even when printed using UV ink. .

[Means to solve the problem]

As a result of intensive study by the present inventors to achieve the above object,
It has been discovered that these objects can be achieved by using a novel photosensitive composition, and the present invention has been achieved.

That is, the present invention provides a photosensitive composition characterized by containing a polyurethane resin that has a sulfonamide group, is insoluble in water and soluble in an alkaline aqueous solution, and a photosensitive compound that acts in a negative tone. .

As the photosensitive compound contained in the photosensitive composition of the present invention, a photosensitive compound selected from the following (1), (ii) or (iii) can be used.

Hereinafter, the polyurethane resin having a sulfonamide group and other components used in the present invention, and the method for producing and using the photosensitive composition of the invention will be explained in detail.

(A) Polyurethane resin containing a sulfonamide group The polyurethane resin having a sulfonamide group and being insoluble in water and soluble in an alkaline aqueous solution used in the present invention preferably has a sulfonamide group in its side chain and/or main chain. It is a polyurethane resin containing.

The polyurethane resin having a sulfonamide group preferably used in the present invention is a polyurethane resin whose basic skeleton is a reaction product of a polyol compound having one or more sulfonamide groups in the molecule and a polyisocyanate compound. .

The polyurethane resin having a sulfonamide group that is more preferably used in the present invention is the following format 01 to (I
It is a polyurethane resin whose basic skeleton is a reaction product of a diol compound having a sulfonamide group and a diisocyanate compound represented by V).

HO-R'-A'-R'-OH I SO7 NH ・・・・・・・ <1) HO-R'-A'-R'-OH NH Deprived H low fR9-8O□-NH+i-'- R”fNH-S
O2R"Chi Kano!...(III) )10eR"-NH-3O2srR"(-3Q,-NH
-R"srOH-・-(■) In the formula, R1, R2, R3 and R5, R6, R7 may be the same or different, respectively (, single bond or Wt substituent, etc.) It represents a divalent aliphatic or aromatic hydrocarbon group which may be a divalent aliphatic or aromatic hydrocarbon group. Preferably it represents an alkylene group of CI to C2° or an arylene group of 016 to CI5. Also, if necessary, R', R', R3
Further, R5, R6, and R1 may contain other functional groups that do not react with isocyanate groups, such as ester, urethane, amide, ureido, and ether groups.

Incidentally, two or three of R', R2, R' and R5, Rg, and R1 may form a ring.

R4 is a hydrogen atom, an optionally substituted alkino-
, aryl, aralkyl group, preferably hydrogen atom, C1-C6 alkyl, C6-CI3 aryl, aralkyl group.

R8 is alkyl, aryl, which may have a substituent,
It represents an aralkyl group, preferably a C2-C6 alkinope C6-C,,1, aryl, aralkyl group.

AI and A2 each represent a C3 to C20 trivalent aliphatic or aromatic group which may have a nitrogen atom and a substituent.・□・ Also, x'Sx' is a single bond or C1H, N
, OSS represents a divalent linking group consisting of one or more atoms selected from OSS.

R9,' R16, RII, R1m, R13, RI
'' indicates a divalent hydrocarbon group which may be the same or different and may have a substituent. Preferably C
Indicates an alkylene, aralkylene, and arylene group of 5 to c2=. Further, if necessary, it may have other functional groups that do not react with isocyanate groups, such as ester, urethane, amide, ureido, and ether groups.

k, lSm, n are each O or l, and k+1≠
0, m+n≠0.

As a compound represented by the general formula (ri or (If)),
For example, p-(1,1-bis(hydroxymethyl)ethylcarbonylamino)benzenesulfonamide, p-
, N-ethyl form of (1,1,-bis(hydroxymethyl)ethylcarbonylamino)benzenesulfonamide,
N-(m-methylsulfonylaminophenyl)-2,2
-bis(hydroxymethyl)propanamide, N-(p
-methylsulfonylaminophenyl)-2,2-bis(
hydroxymethyl)propanamide, N-(m-ethylsulfonylaminophenyl)-2,2-bis(hydroxymethyl)propanamide, N-(p-ethylsulfonylaminophenyl)-2゜2-bis(hydroxymethyl)propane Amide, N-(N',N'-bis(hydroxyethyl)aminocarbonylethyl)methanesulfonamide, N-(N',N'-bis(hydroxyethyl)
Examples include aminocarbonylethyl)benzenesulfonamide.

Further, examples of the compound represented by -Monden (I[I) or (IV) include compounds represented by the following structural formulas.

These diol compounds having a sulfonamide group are
They can be used alone or in combination of two or more.

Furthermore, a diol compound that does not have a sulfonamide group and may have other substituents that do not react with isocyanate can also be used in combination.

Specifically, such diol compounds include those shown below.

That is, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, neopentyl glycol, 1, 3-butylene glycol,
, 6-hexanediol, 2-butene-1,4-diol, 2゜2.4-)rifthyl-1,3-bentanediol, 1,4-bis-β-hydroxyethoxycyclohexane, cyclohexane dimetatool , tricyclodecane dimetatool, hydrogenated bisphenol A, hydrogenated bisphenol F1 ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, ethylene oxide adduct of bisphenol F, propylene oxide adduct of bisphenol F , ethylene oxide adduct of hydrogenated bisphenol A, propylene oxide adduct of hydrogenated bisphenol A, hydroquinone dihydroxyethyl ether, p-xylylene glycol, dihydroxyethyl sulfone, bis(2-hydroxyethyl)-2,4-1- lylene dicarbamate, 2
．． 4-) Rylene-bis(2-hydroxyethylcarbamide), bis(2-hydroxyethyl)-m-xylylene dicarbamate, bis(2-hydroxyethyl)isophthalate 3.5-dihydroxybenzoic acid, 2. 2-bis(hydroxymethyl)propionic acid, 2,2-bis(
2-hydroxyethyl)propionic acid, 2゜2-bis(
3-hydroxypropyl) propionic acid, bis(hydroxymethyl) vinegar M, bis(4-hydroxyphenyl)
Acetic acid, 4. Examples include 4-bis(4-hydroxyphenyl)pentanoic acid and tartaric acid.

Furthermore, the diisocyanate compounds preferably used in the present invention include those shown below.

That is, 2,4-tolylene diisocyanate, a dimer of 2°4-tolylene diisocyanate, 2,6-tolylene diisocyanate, p-xylylene diisocyanate, m
-xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, 3゜3'-dimethylbiphenyl-4,4'-
Aromatic diisocyanate compounds such as diisocyanate; aliphatic diisocyanate compounds such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, dimer acid diisocyanate, etc.; isophorone diisocyanate Nat, 4.4
′-methylenebis(cyclohexyl isocyanate),
Alicyclic diisocyanate compounds such as methylcyclohexane-2,4 (or 2.6) diisocyanate, 1°3-(isocyanatomethyl)cyclohexane, etc., 1.3
Examples include diisocyanate compounds which are reaction products of diols and diisocyanates, such as adducts of 1 mol of -butylene glycol and 2 mols of tolylene diisocyanate.

The polyurethane resin of the present invention is synthesized by heating the above diisocyanate compound and diol compound in an aprotic solvent, adding a known catalyst having an activity corresponding to the reactivity of each compound.

The molar ratio of the diisocyanate and diol compound used is preferably 0.8:1 to 1.2:1, and if the isocyanate group remains at the end of the polymer, it can be treated with alcohols or amines. , it is finally synthesized in a form in which no isocyanate groups remain.

The polyurethane resin of the present invention preferably has a weight average molecular weight of 2. OO0 or more, and the number average is t,ooo or more. More preferably, the weight average is in the range of s,ooo to 300,000, and the number average is in the range of 2,000 to 250,000. Further, the polydispersity (weight average molecular weight/number average molecular weight) is preferably 1 or more, and more preferably in the range of 1.1 to 10.0 The polyurethane resin of the present invention may be used singly or in a mixture. The content of these polyurethane resins in the photosensitive composition is preferably about 5 to 95% by weight, preferably about 10 to 85% by weight.

(B) Negative-acting diazonium compounds Examples of the negative-acting diazonium compounds used in the present invention include the diazonium compounds described in U.S. Pat. Among these, diazo resins represented by condensates of aromatic diazonium salts and, for example, active carbonyl-containing compounds (for example, formaldehyde) are particularly useful. Preferred diazo resins include, for example, hexafluorophosphates, tetrafluorophosphates, and phosphates of condensates of p-diazodiphenylamine and formaldehyde or acetaldehyde. Also, sulfonates of condensates of p-diazodiphenylamine and formaldehyde (e.g., p-)luenesulfonates, dodecylbenzenesulfonates, 2 -methoxy-4
-Hydroxy-5-bency, rubene sulfonate, etc.), phosphinates (e.g., benzenephosphinate, etc.), hydroxy group-containing compound salts (e.g., 2,4-
(dihydroxyhenzophenone salt, etc.), organic carboxylic acid salts, etc. are also preferable.

Furthermore, 3-methoxy-4-diazo-diphenylamine as shown in JP-A No. 58-27141 is added to 4.4
Mesitylene sulfonate obtained by condensation with '-bis-methoxy-methyl-diphenyl ether is also suitable.

The content of these diazonium compounds in the photosensitive composition is 1 to 50% by weight, preferably 3 to 20% by weight.

Moreover, two or more types of diazonium compounds may be used in combination, if necessary.

(C) Polymerizable monomer/photopolymerization initiator The monomer that can be added to the photosensitive composition of the present invention has a boiling point of 100°C or higher at normal pressure, and is preferably at least one per molecule. It is a monomer or oligomer having a molecular weight of 10.000 or less and having two or more addition-polymerizable ethylenically unsaturated groups. Such monomers or oligomers include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth)acrylate, polypropylene glycol mono (meth)acrylate, and phenoxyethyl (meth)acrylate; polyprolene glycol di(meth)acrylate, and polyethylene glycol di(meth)acrylate; Glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neobentyl glycol di(meth)acrylate, pentaerythritol tri(
meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, hexanediol di(meth)acrylate, tri(acryloyloxyethyl)isocyanate, polyhydric alcohols such as glycerin and trimethylolethane, and ethylene. (meth)acrylates after adding oxide or propylene oxide; Polyester acrylate-1-9 described in Japanese Patent Publication No. 48-64183, Japanese Patent Publication No. 49-43191, and Japanese Patent Publication No. 52-30490, epoxy acrylates obtained by reacting epoxy resin with (meth)acrylic acid Examples include polyfunctional acrylates and methacrylates such as. In addition, Japan Adhesive Association Magazine Vol.
．． 20, Floor 7. Those introduced as photocurable polymers and oligomers on pages 300 to 308 can also be used.

The composition ratio of these monomers or oligomers to the polyurethane resin having sulfonamide groups of the present invention is 5 by weight.
:95 to 70:30 is preferable, and a more preferable range is 10:90 to 50:50.

Photoinitiators that can be added to the photosensitive composition of the present invention include vicinal polyketaldonyl compounds disclosed in U.S. Pat. No. 2,367.660, U.S. Pat. No. 2,367.661 No. and No. 2, 367, 670
α-carbonyl compounds disclosed in U.S. Pat. No. 2,448,828, α-carbonyl compounds disclosed in U.S. Pat. Aromatic acyloin compound substituted with hydrocarbon at -position, U.S. Patent No. 3,046.127
and polynuclear quinone compounds disclosed in U.S. Pat. Patent No. 3
, 870,524; acridine and phenazine compounds disclosed in U.S. Pat. No. 3,751.259; U.S. Pat. No. 4,212,970; Included are the disclosed oxadiazole compounds and the like.

Preferred examples include trihalomethyl-8-triazine compounds and trihalomethyloxadiazole compounds represented by the following symbols (V) or (Vl).

Here, in the formula, R111 represents a substituted or unsubstituted aryl or alkenyl group, and RIS represents R''-CY s or a substituted or unsubstituted alkyl group. Y represents a chlorine atom or a bromine atom.

-a Compounds represented by formula (V) include, for example, Kuhai et al., Bull, Chem, Soc, Japan;
Compounds described in Volume 42, Page 2924 (1969), British Patent No. 1.388.492, West German Patent No. 2.7
No. 18.259, and West German Patent No. 3.337.024
Examples include the compounds described in the specification of No. Specifically, the following compounds are included.

That is, 2-phenyl-4,6-bis(trichloromethyl)-3-triazine, 2-(p-chlorophenyl)-4
, 6-bis(trichloromethyl)-8-triazine, 2
-(p-)lyl)-4,6-bis(trichloromethyl)
-S-triazine, 2-(p-methoxyphenyl)-4
,6-bis(trichloromethyl)-S-)riazine, 2
-(2',4'-dichlorophenyl)-4,6-bis(
trichloromethyl)-3-)riazine, 24.6-)lis(trichloromethyl)-3-triazine, 2-methyl-4,6-bis(trichloromethyl)-S-triazine, 2-n-nonyl-4° 6-bis(trichloromethyl)
-3-) riazine, 2-(α,α,β-trichloroethyl)-4,6-bis(trichloromethyl)-S-triazine, 2-styryl-4,6-bis(trichloromethyl)-8-triazine , 2-(p-methylstyryl)-4
, 6-bis(trichloromethyl)-3-triazine, 2
-(p-methoxystyryl)-4,6-bis(trichloromethyl)-3-)riazine, 2-(4-methoxy-naphth-1-yl)-46-bis(trichloromethyl)-
3-1-Ryazine, 2-(4-ethoxy-naphtho-1-
yl)-4゜6-bis(trichloromethyl)'-3-1
-Riazine, 2-(4-(2-ethoxyethyl)-naphth-1-yl)-4,6-bis(trichloromethyl)
-3-triazine, 2- <4.1-dimethoxy-naphth-1-yl)-4,6-bis(trichloromethyl)-
3-) riazine, 2-(acenaphth-5-yl)-4,
6-bis(trichloromethyl)-S-1-riazine, 2
- (4-styrylphenyl)-4,6-bis(trichloromethyl)-3-)riazine, etc. are included.

In addition, examples of the compound represented by Monna (Vl) include JP-A-54-74728 and JP-A-55-7114.
Examples thereof include compounds described in Publication No. 2 and JP-A-59-148784.

Specifically, the following compounds are included.

That is, 2-styryl-5-trichloromethyl-1,3,
4-Oxadiazole, 2-(4-chlorostyryl)-
5-Trichloromethyl-1,3゜4-oxadiazole, 2-(4-methylstyryl)-5-)dichloromethyl-1.3.4-oxadiazole, 2-(4-methoxystyryl)-5 -Trichloromethyl-1,3,4-oxadiazole, 2-(4-butoxystyryl)-5-
) dichloromethyl-1.3.4-oxadiazole, 2
-(4-styrylstyryl)-5-)dichloromethyl-1.3.4-oxadiazole, 2-phenyl-5-
Trichloromethyl-1,3,4-oxadiazole, 2
- (4-methoxyphenyl)-5-trichloromethyl-1,3,4-oxadiazole, 2-(3,4-dimethoxyphenyl)-5-trichloromethyl-1,3,4
-Oxadiazole, 2-(4-styrylphenyl)-
5-trichloromethyl-1,3,4-oxadiazole,
2-(l-naphthyl)-5-)dichloromethyl-1,3
, 4-oxadiazole and the like.

A sensitizer can be added to the photosensitive composition of the present invention if necessary. Specifically, aromatic thiazole compounds shown in Japanese Patent Publication No. 59-28328, Japanese Patent Publication No. 54-1
Merocyanine dyes shown in JP-A No. 51024, aromatic thiopyrylium salts and aromatic biryllium salts shown in JP-A-58-40302, and other light absorbers such as 9-phenylacridine, 5-nitroacenaphthene, ketochlorins, etc. Can be mentioned. Furthermore, systems in which these are combined with hydrogen donors such as N-phenylglycine, 2-mercaptohendithiazole, and ethyl N,N'-dimethylaminobenzoate are also effectively used in the present invention.

The amount of the photopolymerization initiator and/or aggravating agent in the present invention is
It is sufficient in the range of 0.01% to 20% by weight, more preferably 0.5% by weight, based on the total of the photopolymerizable ethylenically unsaturated compound and the polyurethane resin having sulfonamide groups of the present invention. Good results are obtained with 10% by weight.

When a diazonium compound is further added to these photosensitive compositions, the diazonium compound is preferably used in an amount of 1 to 50% by weight, more preferably 2 to 35% by weight of the total composition.

(D) Other components In addition to the polyurethane resin having a sulfonamide group, the composition of the present invention contains phenol formaldehyde resin, cresol formaldehyde resin, phenol-modified xylene resin, polyhydroxystyrene, polyhalogenated hydroxystyrene, and carboxyl resin. Known alkali-soluble polymer compounds such as group-containing epoxy resins, polyacetal resins, acrylic resins, methacrylic resins, and carboxyl group-containing polyurethane resins can be included. Such alkali-soluble polymer compound is used in an amount of 70% by weight or less of the total composition.

The composition of the present invention contains a printing-out agent for obtaining a visible image immediately after exposure, a dye as an image coloring agent, a pigment, a stabilizer,
Additives such as surfactants, plasticizers and other fillers can be added.

Typical print-out agents for obtaining a visible image immediately after exposure include a combination of a photosensitive compound that releases an acid upon exposure and an organic dye that can form a salt. Specifically, JP-A-50-36209, JP-A-53-8
The combination of 0-naphthoquinonediazide-4-sulfonic acid halide and salt-forming organic dye described in JP-A No. 128, JP-A-5136223, JP-A-54-74
The combination of a trihalomethyl compound and a salt-forming organic dye described in Japanese Patent No. 728 can be mentioned. Dyes other than the above-mentioned salt-forming organic dyes can also be used as image colorants.

Suitable dyes include oil-soluble dyes and basic dyes, including salt-forming organic dyes. Specifically, oil yellow #101, oil yellow #130, oil pink #312, oil green BG, oil blue BO3, oil blue #603, oil black BY,
Oil Black BS, Oil Black T-505C or higher, manufactured by Orient Chemical Industry Co., Ltd.), Victoria Pure Flue, Crystal Bioleft (CI 42555)
, Methyl Violet (CI42535), Rhodamine B (CI45170B), Malachite Green (C
I42000), methylene blue (C152015), etc.

When combined with a diazonium compound, stabilizers such as phosphoric acid, phosphorous acid, pyrophosphoric acid, oxalic acid, boric acid, p
-1-luenesulfonic acid, benzenesulfonic acid, p-hydroxybenzenesulfonic acid, 2-methoxy-4-hydroxy-5-benzoyl-benzenesulfonic acid, malic acid, tartaric acid, dipicolinic acid, polyacrylic acid and copolymers thereof , polyvinylphosphonic acid and its copolymers, polyvinylsulfonic acid and its copolymers, 5-nitronaphthalene-1-phosphonic acid, 4-chlorophenoxymethylphosphonic acid, sodium phenyl-methyl-pyrazolone sulfonate, 2-phosphonobutane tricarboxylic acid acid-1,
2,4,l-phosphonoethanetricarboxylic acid-1,2,
Examples include 2,1-hydroxyethane-1,1-disulfonic acid.

In addition, when using a combination of a polymerizable monomer and a photopolymerization initiator, a small amount of It is desirable to add a thermal polymerization inhibitor. Suitable thermal polymerization inhibitors include hydroquinone, p-methoxyphenol, di-t-butyl-p-talezol, pyrogallol, [-butylcatechol, benzoquinone, 4,4'-thiobis(3-methyl-6-t −
butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), 2-mercaptobenzimidazole, N-nitrosophenylhydroxyamine cerous salt, and the like.

In addition, alkyl ethers (e.g. ethyl cellulose, methyl cellulose), surfactants (e.g. fluorine surfactants), film flexibility,
Plasticizers (for example, tricresyl phosphate, dimethyl phthalate, dibutyl phthalate, trioctyl phosphate, tributyl phosphate, tributyl citrate, polyethylene glycol, polypropylene glycol, etc.) can be added to impart wear resistance. The amount of these additives added varies depending on the purpose for which they are used, but
Generally 0.5 to 30% by weight based on the total solid content of the photosensitive layer
It is.

The photosensitive composition of the present invention is applied onto a support after being dissolved in a solvent that dissolves each of the above components. Solvents used here include methanol, ethanol, isopropanol, n
-butanol, t-butanol, ethylene dichloride, cyclohexanone, acetone, methyl ethyl ketone,
Ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-
Methoxyethyl acetate, l-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N,
Examples include N-dimethylformamide, N,N-dimethylacetamide, tetrahydrofuran, dioxane, dimethyl sulfoxide, ethyl acetate, methyl lactate, and ethyl lactate, and these solvents may be used alone or in combination.

Also suitable are mixed solvents in which a small amount of water or a solvent such as toluene that does not dissolve the diazo resin or polymer compound is added to these solvents or mixed solvents. The concentration (solid content) of the above components is 1 to 50% by weight.

When applying and drying a photosensitive liquid dissolved in these solvents, it is desirable to dry at 50°C to 120°C. The drying method may be performed by starting at a low temperature and drying at a high temperature after preliminary drying, or by selecting an appropriate solvent and concentration, it may be directly dried at a high temperature.

The coating amount varies depending on the application, but for example, for photosensitive planographic printing plates, the solid content is generally 0.5 to 3.
．． 0 g/m" is preferable. As the coating amount decreases, the photosensitivity increases, but the physical properties of the photosensitive film deteriorate.

Supports to which the photosensitive composition of the present invention is applied include, for example, paper, plastics (such as polyethylene,
Paper laminated with polypropylene, polystyrene, etc., such as aluminum (including aluminum alloys)
), zinc, copper, etc., such as cellulose diacetate, cellulose triacetate, cellulose propionate,
Plastic films, such as cellulose acetate, cellulose acetate butyrate, cellulose butyrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc.
Examples include plastic films laminated or vapor-deposited with the metals listed above. Among these supports, aluminum plates are particularly preferred because they are extremely dimensionally stable and inexpensive. Furthermore, a composite sheet in which an aluminum sheet is bonded to a polyethylene terephthalate film as described in Japanese Patent Publication No. 48-18327 is also preferred.

Further, in the case of a support having a surface of metal, particularly aluminum, it is desirable to perform an appropriate hydrophilic treatment.

Such hydrophilic treatment includes, for example, mechanical methods such as wire brush graining, brush graining, which roughens the aluminum surface with a nylon brush while pouring slurry of abrasive particles, boulder graining, etc., HF and A
After the surface is grained by chemical graining using lCl3, HCl as an etchant, electrolytic graining using nitric acid or hydrochloric acid as an electrolyte, or composite graining performed by combining these roughening methods, acid treatment is performed as necessary. Or etched with alkali, followed by anodization in sulfuric acid, phosphoric acid, oxalic acid, boric acid, chromic acid, sulfamic acid, or a mixed acid of these using DC or AC power to form a strong passive film on the aluminum surface. Preferably. Such a passive film itself makes the aluminum surface hydrophilic, but if necessary,
．． No. 714.066 and U.S. Patent Box 3.18L46
1, potassium fluorozirconate treatment (sodium silicate, potassium silicate) as described in US Pat. No. 2,946.638, potassium fluorozirconate treatment as described in US Pat. Phoshomolybdate treatment as described in No. 247, UK Patent Box 1,108
．． Alkyl titanate treatment as described in No. 559;
Polyacrylic acid treatment as described in German Patent No. 1,091,433, German Patent No. 1,134,093
The polyvinylphosphonic acid treatment described in the patent specification and the specification of British Patent Box 1,230.447,
Phosphonic acid treatment described in No. 6409, phytic acid treatment described in U.S. Pat.
Composite treatment consisting of a hydrophilic organic polymer compound and a divalent metal described in each publication of No. 18291, JP-A-59
Particularly preferred are those which have been subjected to a hydrophilic treatment by undercoating with a water-soluble polymer having a sulfonic acid group as described in Japanese Patent No. 101651. Other hydrophilic treatment methods include silicate electrodeposition as described in US Pat. No. 3,658,662.

The photosensitive composition of the present invention coated on a support can form a line image,
Exposure through a transparent original having a halftone image or the like, followed by development with an aqueous alkaline developer, provides a negative relief image on the original.

Light sources used for exposure include carbon arc lamps, mercury lamps, xenon lamps, metal halide lamps, strobes, ultraviolet rays, and laser beams.

〔Effect of the invention〕

The photosensitive composition of the present invention has excellent coating properties when applied onto a support, and also excellent developability when developing exposed areas with an aqueous alkaline developer after coating, drying, and image exposure. The relief image obtained has good abrasion resistance and good adhesion to the support, and when used as a printing plate, many good prints can be obtained.

Furthermore, even when printing is performed using UV ink, a large number of good printed materials can be obtained.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Synthesis Examples and Examples, but the content of the present invention is not limited thereto.

Synthesis Example 1 soomi! equipped with a stirrer, cooling tube, and dropping funnel. 40 g (0,298 moIle) of 2,2-bis(hydroxymethyl)propionic acid and 100 m# of anhydrous vinegar were placed in a Mitsuro flask and stirred in an ice-water bath. 100m of pyridine in this mixture! ! was added dropwise using a dropping funnel over a period of about 30 minutes. After the addition was completed, the ice-water bath was removed, and the mixture was stirred for 2 hours while being heated to 60° C. in an oil bath. After the reaction was completed, hydrochloric acid was added to make the mixture acidic, and the mixture was extracted with chloroform using a separating funnel. After washing the chloroform layer with water, it was dehydrated with anhydrous sodium sulfate.

The solvent was distilled off from this chloroform solution under reduced pressure to obtain 57 g of a white solid of 2,2-bis(acetoxymethyl)propionic acid.

Next, 30 g (0,137 moAe) of 2,2-bis(acetoxymethyl)propionic acid and 20 ml of thionyl chloride were added to a 30 g tube equipped with a stirrer, a cooling tube, and a dropping funnel.
0IIIi! The mixture was placed in a Mitsuro flask and stirred for 2 hours while heating to 80°C.

After the reaction was completed, unreacted thionyl chloride and the like were sufficiently removed by distillation under reduced pressure, and then an ice water bath was placed to sufficiently cool the reaction product. 46.6 g of p-aminobenzenesulfonamide (0,274 mo Ite
) and tetrahydrofuran 15Qn+I! The mixture was added dropwise using a dropping funnel over a period of about 1 hour.

After dropping, heat to 60℃ in an oil bath for 2 hours.
Stir for hours. After the reaction, the reaction mixture was stirred into 2N water, stirred for 30 minutes, and filtered to obtain a white solid of p-(1,1-bis(acetoxymethyl)ethylcarbonylamino)benzenesulfonamide. Obtained. This white solid can be purified by recrystallization from ethanol.

(Yield: 26 g) Next, 22 g of p-(1,1-bis(acetoxymethyl)ethylcarbonylamino)benzenesulfonamide
(0.06 mo/e) and 4.8 g of sodium hydroxide
(0.12 mole), ethanol 50ml, water 5
Qnl! The mixture was placed in a 300 ml three-tube flask equipped with a stirrer and a condenser, and heated under reflux for 2 hours.

This reaction mixture was poured into 1N water with stirring, stirred for 30 minutes, and then filtered to obtain a white solid of p-(1,1 bis(hydroxymethyl)ethylcarbonylamino)benzenesulfonamide.

This white solid can be purified by recrystallization from ethanol. (Yield 11g).

Next, 3.44 g of p-(1,1-bis(hydroxymethyl)ethylcarbonylamino)benzenesulfonamide
(0,012 moj2e) and 1.07 g of 2,2-dihydroxymethylpropionic acid (0,008 mo
l e), 4.4'-diphenylmethane diisocyanate 5.26 g (0,021 moj!e), N, N
- 18g of dimethylacetamide in a 100mj equipped with a stirrer and cooling tube! Put it in a Mitsuro flask and add l 00'C.
The mixture was stirred for 4 hours while heating to . This reaction mixture was cooled, 5 liters of methanol was added thereto, and the mixture was stirred for a while, then poured into 500 mf of water with stirring, and stirred for 30 minutes.

The precipitate was filtered and dried to obtain 9 g of white solid. The weight average molecular weight (polystyrene standard) of this polyurethane resin was measured by gel permeation chromatography and found to be 64,000. (Polyurethane resin (a) of the present invention).

Synthesis Examples 2 to 5 The diisocyanate compounds and diol compounds shown in Table 1 below were reacted to produce the corresponding polyurethane resins (bl~
synthesized tel. All molecular weights are weight average molecules M
(polystyrene standard) was 25,000 to 70,000.

Synthesis Example 6 98.5 g of 0-aminobenzyl alcohol (
0.8n+o Ae) and acetone 500mf,
NaC! ! - Stirred under water bath. In this flask, 27.5 g of m-benzenedisulfonyl chloride (0.1 mOβ
A solution of e) in 200 ml of acetone was added dropwise through a dropping funnel over about 1 hour. After completion of dripping, NaCβ-
The water bath was removed and the mixture was stirred at room temperature for 2 hours. After the reaction was completed, most of the acetone was distilled off under reduced pressure, and the mixture was poured into water 11 with a stirring bar, and further acidified with hydrochloric acid. The precipitate was collected by filtration and dissolved in an aqueous sodium hydroxide solution. After filtering off insoluble materials, the filtrate was placed in a separating funnel and washed twice with ethyl acetate. The aqueous layer was made acidic by adding hydrochloric acid, and the precipitate was collected by filtration. By thoroughly washing with water and drying,
A solid of N,N'-bis(0-hydroxymethylphenyl)benzene-m-disulfonamide was obtained (yield: 30.
6g).

Next, 6.28 g of N,N'-bis(0-hydroxymethylphenyl)benzene-m-disulfonamide (
0,014moI! e), 2,2-dihydroxymethylpropionic acid 0.80 g (0,OO6moJe), 4
．． 4'-diphenylmethane diisocyanate 5.26
g (0,021mo/!e) and 18g of N,N-dimethylacetamide, and heated to 100°C for 3 hours.
Stir for hours. After the reaction was completed, 1 g of methanol was added and stirred for a while, and then the mixture was poured into 500 ml of water with stirring and stirred for 30 minutes. The precipitate was filtered and dried to obtain 12 g of white solid. When the weight average molecular weight (polystyrene standard) of this polymer compound was measured by gel permeation chromatography, it was found to be 55,00.
It was 0. (Polymer compound (f) of the present invention).

The corresponding polyurethane resin (g) by reacting diisocyanate compounds and diol compounds as shown in Table 1 below
The weight average molecular weight (polystyrene standard) was 32,000 to 88.00 in all cases.

Examples 1 to 9 A JIS 1050A aluminum plate with a thickness of 0.24 mm was grained using a nylon brush and an aqueous suspension of 400 mst of bumiston, and then thoroughly washed with water. This was etched by immersing it in a 10% sodium hydroxide aqueous solution at 70°C for 60 seconds, and then washed with running water for 20 minutes.
After neutralizing and cleaning with 1% nitric acid, an anode of 160 corons/dm" was prepared in a 1% nitric acid aqueous solution using the electrochemical surface roughening method described in JP-A-53-67507, that is, using a sinusoidal alternating current waveform. Electrolytic surface roughening treatment was performed using electricity at a rate of 30%.
After being immersed in a sulfuric acid aqueous solution and desmutted for 2 minutes at 55°C, the coating amount of aluminum oxide was 2.5% in a 7% sulfuric acid aqueous solution.
Anodization treatment was performed so that the concentration was 0 g/m. then 7
0″C JIS No. 3 sodium silicate 3% water) 1 to 8 liquids
It was immersed for a minute, washed with water and dried.

Photosensitive solutions (A)-1 to (A)-9 shown below were applied to the aluminum plate obtained as described above using a wheeler, and dried at 80° C. for 2 minutes. Dry weight is 2.0 g/
It was m.

The polyurethane resins used in the present invention for photosensitive liquids CA)-1 to (A'l-9) are shown in Table 2.

Photosensitive liquid (A) Next, as a comparative example, a polyurethane resin (4,4'-diphenylmethane diisocyanate) described in Synthesis Example (J) of JP-A-62123452 was used instead of the polyurethane resin used in the present invention in the photosensitive liquid. photosensitive FE (polyurethane resin synthesized from 2,2-bis(hydroxymethyl)propionic acid and 1,3-propanediol)
B] was applied in the same manner and dried. Dry weight is 2.0 g
/ %Met.

Angry photosensitive lithographic printing plates (A)-1 to (A)-9 and C obtained using photosensitive solutions (A)-1 to [A]-9 and (B)
B) Each image was exposed for 1 minute from a distance of 1 m using a PS light manufactured by Fuji Photo Film aTI, and after immersing it in the following developer for 1 minute at room temperature, the surface was lightly rubbed with absorbent cotton to remove the unexposed area. Lithographic printing plates (A)-1 to (A)-9 and C84 were obtained.

developer Printed on high quality paper using ink and UV ink.

The final number of printed sheets of the lithographic printing plates [A)-1 to (A)-9 and (B] was examined and was as shown in Table 2.

As shown in Table 2, lithographic printing plates [A)-1 to (A)-9 (Examples 1 to 9) using the photosensitive composition of the present invention
Compared to Comparative Example CB), the number of prints was larger regardless of whether normal ink or UV ink was used, and the rigidity resistance was extremely excellent.

Each of the printing plates thus obtained was attached to a GTO type printing machine manufactured by Heidelherg, and the following photosensitive solution C
Apply C')-1 to CC'l-2 using a wheeler,
It was dried at 80°C for 2 minutes. Dry soot weight is 2.0g/rn'
Met.

The polyurethane resins used in the present invention for photosensitive liquids I:C)-1 to [C)-2 are shown in Table 3.

Photosensitive liquid [C] Next, as a comparative example, in place of the polyurethane resin used in the present invention in the photosensitive liquid, the above-mentioned JP-A-62-123 was used.
Photosensitive liquid CD) using the polyurethane resin described in Synthesis Example (J) of No. 452 was applied and dried in the same manner. The dry weight is 2.
It was 0 g/g.

Each photosensitive lithographic printing plate (C)-1 to (C)-2 and C obtained using photosensitive liquids [C)-1 to [C]-2 and [D]
D] Fuji photo film for each (1 piece of barrel PS light)
After imagewise exposure for 1 minute from a distance of m, and immersing each in the developer shown above for 1 minute at room temperature, the surface was lightly rubbed with absorbent cotton to remove the unexposed area, and the planographic printing plates (C)-1 to ( C
)-2 and (D) were obtained.

Each of the printing plates thus obtained was attached to a GTO type marking machine manufactured by Heidelherg, and printed on high-quality paper using a commercially available regular ink. The final number of printed sheets of lithographic printing plates (C) 1 to (C)-2 and (D) was examined and was as shown in Table 3.

As shown in Table 3, lithographic printing plates (C)-1 to [C)-2 (Examples 6 to 7) using the photosensitive composition of the present invention
Compared to the comparative example (D), the number of prints was larger and the rigidity resistance was very excellent.

Claims (1)

[Claims] A photosensitive composition comprising a polyurethane resin having a sulfonamide group, which is insoluble in water and soluble in an alkaline aqueous solution, and a photosensitive compound that acts in a negative tone.