JPH0358049A - Photosensitive composition - Google Patents

Abstract

PURPOSE:To enhance abrasion resistance, chemical resistance, and development latitude of a planographic printing plate by incorporating a photosensitive compound made of a specified condensation reaction product in the composition. CONSTITUTION:This composition contains the photosensitive compound (C) made of the condensation reaction product of a compound (A) having an SO2-NH and/or CO-NH-CO bond, and a quinonediazosulfonylhalide (B). For example, the compound (C) made of the condensation reaction product of the compound of (A), obtained by polymerizing N-(p-aminosulfonylphenyl)- methacrylamide of formula I with methyl methacrylate, with the compound (B) of 1,2-naphthoquinone-2-diazido-5-sulfonylchloride can be used. The known o-naphthoquinonediazide compound can be used in combination.

Description

Detailed Description of the Invention [Industrial field] The present invention relates to a photosensitive material suitable for manufacturing lithographic printing plates, IC circuits, and photomasks, and in particular has properties such as abrasion resistance and resistance that act on the body type. This invention relates to a photosensitive composition with excellent chemical properties and development latitude.

[Purpose of the invention]

Accordingly, an object of the present invention is to provide a photosensitive composition that provides a lithographic printing plate that has excellent abrasion resistance, can be developed with an aqueous alkaline developer, and has excellent printing durability. Another object of the present invention is to provide a photosensitive material that provides a lithographic printing plate with excellent chemical resistance and high stiffness even when printed with UV ink without the need for burning treatment. be.

Yet another object is to provide a photosensitive composite with excellent development latitude.

[Means to solve the problem]

As a result of intensive study to achieve the above purpose, the inventors of the present invention found that
It has been found that the above object can be achieved by incorporating a -SOiI-NH bond and a condensation product with diazidesulfonyl halide in a photosensitive composition, and the present invention has been achieved.

The present invention will be explained in detail below.

-SOa-NH bond and/or ? used in the present invention? or -SQ2-NH- bond and/or -CO-N in the main chain
It is a polymer containing one H-CO bond.

-SD2-NH bond and/or -CD in the present invention
Preferred examples of compounds having -NH-CO bond include one or more -SO■-NH bond and/or -C
It can be obtained by polymerizing a compound having one D--NH--CO bond and one or more polymerizable unsaturated bonds using a known polymerization initiator in an appropriate solvent.

Compounds having such unsaturated bonds that are preferably used in the present invention include the following general formulas (I) to (XI
) are listed.

1. SLhN口-1<” ＼Z − CONF[ 1CO − R” 'H? Medium, x+. x! , X3 each represents 101 or NR26-. R'+ R'l R'+ R
9+ R”RIA Rl6 Rllll, R!
O, R22, R24, R2J, i sore-H
Or it represents -CH3. R"l R'l R" each may have a substituent. -C, ■ represents an alkylene group, cycloalkylene group, arylene group, or aralkylene group. R3 and RIS represent a hydrogen atom, a C, to C, alkyl group, a cycloalkyl group, or an aromatic group which may have a substituent. Rml R'l R"l
RI! , R′? , Rl″l R″R22 represents an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group of C, to CtZ, which may have a substituent. Z is
Indicates an alkylene group of 01 to C1 which may have a substituent, a cycloalkylene group, and an aromatic ring group which may be substituted. Yl? 2 indicates -C1 or -SO■1. Y3 represents a single bond or 101. RZ& represents a hydrogen atom or an alkyl group of 01 to C12 which may have a substituent, a cycloalkyl group, an aryl group, or an aralkyl group.

Among the compounds represented by general formulas (1) to (XI), those particularly preferably used in the present invention are R2, R%RI
O is an alkylene group, a cycloalkylene group, or a phenylene group which may have a substituent, each of which is 02 to C,
is a naphthylene group, Rco and Rls are hydrogen atoms or C,
-C, an alkyl group, Z is a phenylene group or naphthylene group which may have a substituent, and Rtb is a hydrogen atom or an alkyl group of 01 to C4 which may have a substituent.

Examples of the compounds represented by the general formulas (1) and (II) include N-(o-aminosulfonylphenyl)methacrylate a. ．． N-(m-aminosulfonylphenyl>methacrylamide, N-(p-anosulfonylphenyl)methacrylic acid, N-(o
-Methylaminosulfonylphenyl) methacrylamide, N-(m-methylacinosulfonylphenyl)methacrylate, N<p-methylaminosulfonylphenyl)methacrylate, N-(o-ethylaminosulfonyl) Phenyl〉Methacrylamide, N-(m-ethylanosulfonylphenyl) methacrylamide, N-(
p-ethylaminosulfonylphenyl) methacrylamide, N-(on-probyla ξnosulfonylphenyl) methacrylamide, N-(m-n-7'robilanosulfonylphenyl>methacrylate, N-(p -n
-Propylaminosulfonylphenyl>methacrylamide, N-(o-i-propylaminosulfonylphenyl)methacrylamide, N-(m-i-propylaminosulfonylphenyl)methacrylamide, N-(p-i
-7” ropylaminosulfonylphenyl>methacrylamide, N-(on-butylaminosulfonylphenyl)methacrylamide, N-(m-n-butylaminosulfonylphenyl)methacrylamide, N-(p-n-butyl aminosulfonylphenyl) methacrylamide, N
-(o-i-butylaminosulfonylphenyl)
Meccrylamide, N-(m-i-butylaξnosulfonylphenyl)methacrylamide, N-(p-i-butylaξnosulfonylphenyl)methacrylamide, pJ
-(o-sec-butylaminosulfonylphenyl)methacrylamide, N-(m-sec-butylaminosulfonylphenyl)methacrylamide/N-(p-s
ec-butynoleaminosnorefonylphenyl) methacrylamide, N-(0-t-butylaminosulfonylphenyl>methacrylamide, N-(m-t-butylaminosulfonylphenyl)methacrylamide, N-(p- t
-butylaminosulfonylphenyl)methacrylate ξ-do, N-(0-phenylaminosulfonylphenyl)methacrylate ξ-do, N-(m-fuynylaminosulfonylphenyl)methacrylate ξ-do, N- (p one phenyla ξ
nosulfonylphenyl) methacrylamide, N-(o-
(α-naphthylaminosulfonyl)phenyl)methacrylamide, N-(m-(α-naphthylaminosulfonyl)phenyl)methacrylate, N-(p-
(α-naphthylaminosulfonyl)phenyl)methacrylamide, N-(o-(β-naphthylaminosulfonyl>phenyl)methacrylamide, N-(m
- (β-naphthyl-nosulfonyl)phenyl)methac. Rylamide, N-(p-(β-naphthylaminosulfonyl)phenyl)methacrylamide, N-
(1-(3-Acnosulfonyl)naphthyl)methacrylate, N-(1-(3-methylaminosulfonyl)naphthyl)methacrylamide, N-(1-(3-ethylaminosulfonyl)naphthyl)methacrylate ADD, N
- (o-methylsulfonylaminophenyl)methacrylate ξ-do, N-(m-methylsulfonylaminophenyl)methacrylate ξ-do, N-(p-methylsulfonylaminophenyl)methacrylamide, N-(0-ethylsulfonyl Aminophenylbu methacrylamide, N
(m-ethylsulfonylaminophenyl) methacrylamide, N- (p-ethylsulfonylaminophenyl)
Methacrylamide. ．． N-(o-phenylsulfonylaminophenyl)methacryl ado, N-(m-phenylsulfonylaminophenyl)methacrylamide, N-
(p-phenylsulfonylaminophenyl) methacrylamide, N-(o-(p-methylphenylsulfonylamino)phenyl)methacrylamide, N-(m-(p-
Methylphenylsulfonylaξ・no)phenyl)methacrylamide, N-(P-(p-methylphenylsulfonylamino)phenyl>methacrylamide, N-
(p-(α-naphthylsulfonylamino)phenylmethacrylamide, N-(p-(β-naphthylsulfonylamino)phenyl)methacrylamide, N-(2-methylsulfonylaminoethyl)methacrylamide, N-
(2-ethylsulfonylaminoethyl)methacrylamide, N-(2-phenylsulfonylaminoethyl)methacrylamide, N-<2-p-methylphenylsulfonylaminoethyl)methacrylamide, N-(2-
α-Naphthylsulfonylaξnoethyl)methacrylaξ
methacrylic acid ξ-dos such as N-(2-β-naphthylsulfonylamino)ethyl methacrylate ξ-do, acrylamide ξ-dos having the same substituents as above, and O-azu nosulfonylphenyl methacrylate, m -Aizumi nosulfonylphenyl methacrylate, p-Aξnosulfonylphenyl methacrylate, 0-methylaminosulfonylphenyl methacrylate, m-methylaminosulfonylphenyl methacrylate, p-methylaminosulfonylphenyl methacrylate, 〇1ethylaminosulfonylphenyl methacrylate, m-ethylaminosulfonylphenyl methacrylate, p-ethylaminosulfonylphenyl methacrylate, on-propylaminosulfonylphenyl methacrylate}, m-n-propylaminosulfonylphenyl methacrylate, p-n-propylamino Sulfonylphenyl methacrylate, O-i-propylaminosulfonylphenyl methacrylate-1, m-
i-propylaminosulfonylphenyl methacrylate, o-n-butylaminosulfonylphenyl methacrylate}, m-n-butylaminosulfonylphenyl methacrylate, p-n-7'thylaminosulfonylphenyl methacrylate, m-i 1-butylaminosulfonylphenyl methacrylate, p-i-butylaminosulfonylphenyl methacrylate, m-sec-butylaminosulfonylphenyl methacrylate, p-se
c-butylaminosulfonylphenyl methacrylate,
m-t-butylaminosulfonylphenyl methacrylate}, p-t-butylaminosulfonylphenyl methacrylate, 0-, phenylaminosulfonylphenyl methacrylate, m-phenylaminosulfonylphenyl methacrylate, p-phenylaminosulfonylphenyl methacrylate} , m-(α-naphthylaminosulfonylphenyl) methacryly}, p-(α-naphthyla ξnosulfonylphenyl) methacrylate, m-(β-naphthyla ξnosulfonyl) phenyl methacrylate, p-
(β-Naphthylaminosulfonyl) phenyl methacrylate, 1-(3-aminosulfonyl) naphthyl methacrylate, 1-(3-methylaminosulfonyl) naphthyl methacrylate, 1-(3-ethylaminosulfonyl)
Naphthyl methacrylate, 0-methylsulfonylaminophenyl methacrylate, m-methylsulfonylaminophenyl methacrylate, p-methylsulfonylaminophenyl methacrylate, 0-ethylsulfonylaminophenyl methacrylate, m-ethylsulfonylaminophenyl methacrylate, p-ethylsulfonylaminophenyl methacrylate fruit phenyl methacrylate, 0-phenylsulfonylaminophenyl methacrylate, m-phenylsulfonylaminophenyl methacrylate, p-phenylsulfonylaminophenyl methacrylate, o-(p-methylphenylsulfonylamino) phenyl methacrylate, m-
(p-methylphenylsulfonylamino) phenyl methacrylate, p-(p-methylphenylsulfonylamino) phenyl methacrylate, p-(α-naphthylsulfonylamino) phenyl methacrylate, p-(β-naphthylsulfonylamino) phenyl methacrylate ,2
-Methylsulfonylaminoethyl methacrylate, 2-
Ethylsulfonylaminoethyl methacrylate, 2-phenylsulfonylaminoethyl methacrylate, 2-p
Examples include methacrylic acid esters such as -methylphenylsulfonylaminoethyl methacrylate, 2-α-naphthylsulfonylaminoethyl methacrylate, and 2-β-naphthylsulfonylaminoethyl methacrylate, and acrylic acid esters having the same substituents as above. .

Examples of the compound represented by general formula (I) include N
-methacryloylbenzenesulfonamide, N-methacryloyl-p-}luenesulfonamide, N-methacryloyl-m-toluenesulfonamide, N-methacryloyl-p-methoxyphenylsulfonamide, N-methacryloyl-p-butoxyphenylsulfonamide, N
-methacryloyl p-methoxyphenylsulfonamide, N-methacryloyl α-naphthylsulfonamide, N-methacryloyl 10-butoxyphenylsulfonamide, N-acryloyl benzenesulfonamide,
N-acryloyl-p-toluenesulfonamide, N-
Acryloyl 10-toluenesulfonamide, N-acryloyl 10-methoxyphenylsulfonamide, N-
Examples include acryloyl-p-i-amyl phenylsulfonamide, N-acryloyl-0-methoxyphenylsulfonamide, N-acryloyl-α-naphthylsulfonamide, and N-acryloyl-m-butoxyphenylsulfonamide.

Examples of the compound represented by the general formula (TV) include
- (p-(p-methylphenylsulfonylamino)sulfonylphenyl)methacrylamide, N-(p-
= (phenylsulfonylamino)sulfonylphenyl)
Methacrylamide, N-(m-(p-methoxyphenylsulfonylamino)sulfonylphenyl>methacrylamide, N-(o-(o-methoxyphenylsulfonylamino)sulfonylphenyl)methacrylamide, N-(p-(p- i-butylphenylsulfonylamino)sulfonylphenyl)methacrylamide, N-(p-
(α-naphthylsulfonylamino)sulfonylphenyl)methacrylamide, N-(p-(β-naphthylsulfonylamino)sulfonylphenyl)meccrylamide,
methacrylamides such as, acrylamides having both the above substituents, p-(p-methylphenylsulfonylamino)sulfonylphenylmethacryry}, m-(
7enylsulfonylamino)sulfonylphenyl methacrylate-1-, p-(p-methoxyphenylsulfonylamino)sulfonylphenyl methacrylate, p-(α
-naphthylsulfonylamino)sulfonylphenyl methacrylate}, o-(p-methylphenylsulfonylamino)sulfonylphenyl methacrylate, p-(m-i
-Methacrylic acid esters such as -butylphenylsulfonylamino)sulfonylphenyl) methacrylate, p-(β-naphthylsulfonylamino)sulfonylphenyl methacrylate, etc., having the same substituents as above? Examples include acrylic acid esters.

Examples of the compounds represented by formulas (V) to (XI) of 1a include p-aminosulfonylstyrene, p-aminosulfonyl-α-methylstyrene, p-aminosulfonylphenyl allyl ether, p-(N-methylamino sulfonyl) phenyl allyl ether, methylsulfonylamino acetic acid vinyl ester, phenylsulfonylamino acetic acid vinyl ester, methylsulfonylamino acetic acid allyl ester, phenylsulfonylamino acetic acid allyl ester, p-methylsulfonylamino phenyl allyl ether, I) (N-acetyl (aminosulfonyl) styrene, p-styrylmethylsulfonylamide, p-ethylsulfonylaminostyrene, p-styrylphenylimide, p-styrylethylimide, maleimide, methylmaleimide, and the like.

A compound having one -SO--NH bond and/or -C-NH-['O bond that is preferably used in the present invention has one or more -S--NH bond and/or -C-NH-['O bond in one molecule.
/ or the above general formula CI) having one -CO-NH-CO bond and one or more polymerizable unsaturated bonds
It is a homopolymer of a compound as shown in (XI) or a copolymer of two or more thereof, preferably having one or more polymerizable unsaturated bonds, and - SO NH
It is a copolymer with one or more compounds that do not contain one bond and/or -GO-NH-CO bond.

Examples of compounds containing such a polymerizable unsaturated bond and not containing a sulfonamide or -Co-NH-CO bond include acrylic acid, methacrylic acid, acrylic esters, acrylamides, and methacrylic acid. Acid esters, methacrylamides, allyl compounds,
It is a compound having a polymerizable unsaturated bond selected from vinyl ethers, vinyl esters, styrenes, crotonic acid esters, etc. Specifically, for example, acrylic esters, such as alkyl (the alkyl group preferably has 1 to 10 carbon atoms) acrylates (such as methyl acrylate, ethyl acrylate, probyl acrylate, butyl acrylate, Acrylic acid, ethylhexyl acrylate, octyl acrylate, t-octyl acrylate, chloroethyl acrylate, 2,2-
Dimethylhydroxyprobyl acrylate, 5-hydroxybentyl acrylate, trimethylolbroban monoacrylate, pentaerythritol monoacrylate, glycidyl acrylate, pendyl acrylate,
Methoxybenzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, etc.), aryl acrylate (e.g. phenyl acrylate, etc.): Methacrylic acid esters, e.g. alkyl (alkyl group preferably has 1 to 10 carbon atoms) ) methacrylates (e.g. methyl methacrylate, ethyl methacrylate, proyl methacrylate I, isobrobyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, pendyl methacrylate 1, chlorbenzyl methacrylate, octyl methacrylate, 4- Hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate,
2.2-dimethyl-3-hydroxypropane monomethacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, glycidyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, etc.), ryoryl methacrylate (e.g. phenyl methacrylate) , talesyl methacrylate, naphthyl methacrylate, etc.): Acrylamides, such as acrylamide, N-alkyl acrylamide (alkyl group has 1 to 10 carbon atoms)
Examples include methyl group, ethyl group, probyl group, butyl group, t-butyl group, heptyl group, octyl group, cyclohexyl group, benzyl group, hydroxyethyl group, and the like. ), N-arylacrylamide (Aryl groups include, for example, phenyl group, tolyl group, nitrophenyl group, naphthyl group, hydroxyphenyl group, etc.)
, N,N-dialkyl acrylamide (the alkyl group has 1 to 10 carbon atoms, such as methyl group, ethyl group, butyl group, isobutyl group, ethylhexyl group,
Examples include cyclohexyl group. ), N,N-diarylacrylamide (aryl groups include, for example, phenyl groups), N-methyl-N-phenylacrylamide, N-hydroxyethyl-N-methylacrylamide, N-2-acetamidoethyl-N- Acetylacrylamide, etc.: Methacrylamides, such as methacrylamide, N-alkyl methacrylamide (the alkyl group has 1 to 10 carbon atoms, such as methyl group, ethyl group, t-butyl group, ethylhexyl group, hydroxyethyl group) , cyclohexyl group, etc.〉, N-
Arylmethacrylamide (aryl groups include phenyl groups, etc.), N,N-dialkylmethacrylamide (alkyl groups include ethyl group, proyl group, butyl group, etc.), N,N-diarylmethacrylamide Examples of the amide aryl group include a phenyl group. 〉, N-hydroxyethyl-N-methylmethacrylamide, N-methyl-N-phenylmethacrylamide,
N-ethyl-N-phenylmethacrylamide, etc.: Allyl compounds, such as allyl esters (e.g., allyl acetate, allyl cabroate, allyl cabrylate, allyl laurate, allyl balmitate, allyl stearate, allyl benzoate, allyl acetoacetate) , allyl lactate),
Allyloxyethanol, etc.: Vinyl ethers, such as alkyl vinyl ethers (e.g., hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2.2-dimethylpropylene vinyl ether) , 2-ethyl butyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, penzyl vinyl ether, tetrahydrofurfuryl vinyl ether, etc.), vinyl aryl ethers (e.g., vinyl phenyl ether, Vinyl esters, such as vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl Acetate, vinyl parate, vinyl cabroate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxy acetate, vinyl butoxy acetate, vinyl phenyl acetate, vinyl acetoacetate, vinyl lactate, vinyl β-phenyl butyrate, vinyl cyclohexyl carboxylate ,
Vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate, etc.: Styrenes, such as styrene, alkylstyrenes (such as methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, Isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, decylstyrene, penzylstyrene, chloromethylstyrene, trifluoromethylstyrene, ethoxymethylstyrene, acetoxymethylstyrene, p-(p-hydroxybenzoyloxymethyl>styrene, etc.) , hydroxystyrene, alkoxystyrene (e.g., methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene, etc.), halogenated styrene (e.g., chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, Promstyrene, dibromstyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene, etc.>: Crotonate esters, e.g., alkyl crotonate (e.g., butyl crotonate, hexinobeglycerin crotonate, monocrotonate, etc.); dialkyl itaconates (e.g., dimethyl itaconate, diethyl itaconate, dibutyl itaconate, etc.); dialkyl maleates or fumarates (e.g., dimethyl maleate, dibutyl fumarate, etc.): Acronitrile,
Examples include methacrylonitrile.

Among these low molecular weight compounds having polymerizable unsaturated bonds, those preferably used are methacrylic esters, acrylic esters, methacrylates, acrylamides, acrylotrile, methacrylonitrile, methacrylic acid, It is acrylic acid. A copolymer of one or more of these compounds having a polymerizable unsaturated bond and one or more compounds containing a sulfonamide group and having a polymerizable unsaturated bond is a block body,
Random bodies, graft bodies, etc. can all be used.

In these copolymers, sulfonamide or Co-
Compound containing one Nil-Co bond (structural unit)
is preferably contained in an amount of 5 mol% or more based on all the compounds (structural units) constituting the copolymer. , 10-9
It is more preferable to contain 0 mol%.

Examples of solvents used when synthesizing such copolymers include ethylene dichloride, cyclohexanone,
Methyl ethyl ketone, acetone, methanol, ethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, 1-methoxy-2-probanol, 1-methoxy-2-propylacetate, N. Examples include N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, toluene, ethyl acetate, methyl lactate, and ethyl lactate.

These solvents may be used alone or in combination of two or more.

In addition, -SO■-NH1 or 100-N in the present invention
Polyurethane resins and polystyrene resins are preferably used as compounds containing H-CO- bonds.

Such a polyurethane resin preferably has as a basic skeleton a reaction product of a diisocyanate compound and a sulfonic acid compound having at least one H atom bonded to N or a diol compound containing a -〇〇NHCO- bond. It is a polyurethane resin.

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

That is, 2.4-1-tolylene diisocyanate, a dimer of 2,4-tolylene diisocyanate, 2.6-1-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-1, etc.; isophorone diisocyanate; Isocyanate, 4.
4'-methylenebis(cyclohexyl isocyanate)
, methylcyclohexane-2.4 (or 2.6) diisocynate, 1.3-(isocyanatomethyl)cyclohexane, etc.; 1
, 3-butylene glycol and 2 moles of tolylene diisocyanate.

On the other hand, the sulfonamide in which at least one H atom is bonded to N or the diol compound containing one 100 NHCO bond specifically includes those shown below.

That is, p-(1.1-dihydroxymethylethylcarbonylaξno)benzenesulfonamide, p-(1.1
-N-ethyl form of benzenesulfonamide (dihydroxymethylethylcarbonylamino), N-(m-methylsulfonylaminophenyl)-2,2-dihydroxymethylbropanamide, N-(p-methylsulfonylaminophenyl) )=2,2-dihydroxymethylbrobanamide, N-(m-ethylsulfonylaminophenyl)-2
, 2-dihydroxymethylpropanamide, N-(p-ethylsulfonylaminophenyl)-22-dihydrothymethylpropanamide, N-(2.2-(dihydroxyethylaminocarbonyl)ethyl)methane wintersulfonamide, N- (2.2-(dihydroxyethylaminocarbonyl)ethylbenzenesulfonamide, N- (2
．． 2-(dihydroxyethylaminocarbonyl)ethyl-p-}luenesulfonamide, and the like.

These diol compounds containing a sulfonamide or -CONHCO bond can be used alone or in combination of two or more.

Furthermore, a diol compound that does not have a sulfonamide or -CONHCO- bond and may have other substituents that do not react with incyanate can also be used in combination.

Specifically, such diol compounds include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, brobylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, neobentyl glycol, 1.3- Butylene glycol, 1,6-hexanediol, 2-butene-1,4-diol, 2,2
．． 4-trimethyl-1,3-pencunediol, 1,4
- bis-β-hydroxyethoxycyclohexane, cyclohexanedimethanol, tricyclodecane dimethanol, hydrogenated bisphenol A1 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-Tolylene dilubamate, 2,4-Tolylene bis(2-hydroxyethylcarbamate), Bis(2-
hydroxyethyl)-m-xylylene dilubamate,
Bis(2-hydroxyethyl)isophthalate, 3.5
-dihydroxybenzoic acid, 2,2-bis(hydroxymethyl)probionic acid, 2,2-bis(2-hydroxyethyl)probionic acid, 2,2-bis(3-hydroxybutopyl)propionic acid, bis(hydroxy Examples include methyl)acetic acid, bis(4-hydroxyphenyl)acetic acid, 4,4-bis(4-hydroxyphenyl)pentanoic acid, and tartaric acid.

The polyurethane resin is prepared by mixing the diisocyanate compound and the diol compound in an aprotic solvent, adding a known catalyst having an activity corresponding to the reactivity of each compound, and heating the mixture. The molar ratio of diisocyanate and diol compound used is preferably O. a:X~1.
If the ratio is 2:1 and isocyanate groups remain at the ends of the polymer, by treatment with alcohols or amines, they are finally combined in a form in which no isocyanate groups remain.

-S (h-NH one bond and/or preferably has a weight average of 1,000 or more and a number average of 5
00 or more. Preferably a weight average of 2,000 to 3
00,000, and the number average ranges from 1,000 to 250,000. The polydispersity (weight average molecular weight/number average molecular weight) is preferably 1 or more, particularly preferably 1.1 to 10.
is within the range of

Moreover, -SQ. -NH bond and/or may contain unreacted monomers,
In this case, the proportion of the monomer in the polymer compound is 15
It is desirable that the amount is less than % by weight.

The quinodiazide sulfonyl halide used in the present invention is preferably 1,2-naphthoquinone-2-diazide-5
-(or -4-)sulfonyl chloride, can be prepared by condensation reaction with quinonediazide sulfonyl chloride to form photosensitive composition Ii.
A child is born to be offered as a portion of the goods.

Such a condensation reaction can be carried out by carrying out a dehydrochlorination condensation reaction in the presence of a dehydrochlorination agent. This reaction proceeds in either an aqueous solvent or an organic solvent as long as it is in the coexistence of a dehydrochlorinating agent. When in an aqueous solvent, suitable dehydrochlorination agents include lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and the like. When the reaction is carried out in an organic solvent, examples of organic solvents that do not have an OH group include diethyl ether, diisopropyl ether, acetone, dichloromethane, chloroform, carbon tetrachloride, tetrahydrofuran, dioxane, ethyl acetate, Benzene, toluene, acetonitrile, etc. are preferred.

As the dehydrochlorination agent, pyridine, diethylamine, triethylamine, N,N-dimethylaniline, N,N-
Diethylaniline, p-(N,N-dimethylano)pyridine, etc. are preferred. The condensation reaction is -SO! -0.05 to 1.05 equivalents of quinonediazide sulfonic acid chloride per equivalent of one -NEI bond and/or group to be synthesized.
5 equivalents, dehydrochlorination agent 0. It is preferable to use 2 to 3 equivalents, and the reaction temperature is preferably 10 to 40°C. In addition, when the -Sow-NO= bond and/or the didosulfonic acid chloride in the present invention undergo a condensation reaction, for example, in the former compound If there is a phenolic hydroxyl group, 61
The compound of the present invention may be synthesized by a condensation reaction between g and quinonediazide sulfonic acid chloride. Further, it is preferable that the resulting quinonediazide compound has a quinonediazide group introduction rate (condensation rate of quinonediazide sulfonic acid chloride with respect to -SO2-NH-, group) of 3 mol% or more, and particularly preferably, It is 15 mol% to 99 mol%.

Further, the condensation reaction compound (quinonediazide compound) of the present invention may be used alone or as a mixture. The content of these quinonediazide compounds contained in the photosensitive compound is about 5 to 95% by weight, preferably about 10 to 95% by weight.
85% by weight, particularly preferably 30-60% by weight.

In addition to the compound of the present invention, a known 0-naphthoquinonediazide compound can be used in the photosensitive compound of the present invention as a photosensitive compound that acts in a positive manner.

As the known O-naphthoquinone diazide compound used in the present invention, the ester of 1,2-diazonaphthoquinone sulfonic acid chloride and birogallol-acetone resin described in Japanese Patent Publication No. 43-28403 is preferred. Other suitable O-quinonediazide compounds include U.S. Pat. Nos. 3,046,120 and 3.1.
There are esters of 1,2-diazonaphthoquinone sulfonic acid chloride and phenol-formaldehyde resins described in No. 88,210. Other useful 0-naphthoquinone diazide compounds are known and reported in numerous patents. For example, JP-A-47-53
No. 03, No. 1972-63802, No. 6380 No. 1973
No. 3, No. 48-96575, No. 38701, No. 49-1973
No. 1972-13354, Special Publication No. 37-18015
No. 1-11222, No. 45-9610
No. 49-17481, U.S. Patent No. 2,79
No. 7,213, No. 3,454,400, No. 3,5
No. 44,323, No. 3.573, 917, No. 3
, 674,495, British Patent No. 3,785,825, British Patent No. 1,227.602, British Patent No. 1,251,345
No. 1,267.005, No. 1,329,88
No. 8, German Patent No. 1,330,932, German Patent No. 854
, No. 890, etc. can be mentioned.

A particularly preferred known 0-naphthoquinone diazide compound in the present invention is a compound obtained by reacting a polyhydroxy compound having a molecular weight of 1.000 or less with 1,2-diazonaphthoquinone sulfonic acid chloride. Specific examples of such compounds include JP-A-51-139402, JP-A-58-150948, JP-A-58-203434,
No. 59-165053, No. 60-121445, No. 60-134235, No. 60-163043,
No. 61-118744, No. 62-10645, No. 6
No. 2-10646, No. 62-153950, No. 6 2
-178562, Japanese Patent Application No. 62-233292, U.S. Patent No. 3,102.809, U.S. Patent No. 3. 126,
No. 281, No. 3,130,047, No. 3.148
．． No. 983, No. 3,184.310, No. 3, 1
88. Examples include those described in publications or specifications such as No. 210 and No. 4,639.406.

When preparing these 0-naphthoquinone diazide compounds, it is important to
．． 0.2-diazonaphthoquinone sulfonic acid chloride.
It is preferable to react in an amount of 2 to 1.2 equivalents, and more preferably 0.2 to 1.2 equivalents.
It is preferable to react 3 to 1.0 equivalents.

The obtained 0-naphthoquinonediazide compound has 1.2-
Although it is a mixture of diazonaphthoquinone sulfonic acid ester groups with various positions and amounts of introduction, the proportion of compounds in which all hydroxyl groups have been converted with 1,2-diazonaphthoquinone sulfonic acid ester (
esterification rate) is preferably 5 mol% or more,
More preferred is 20 to 99 mol%.

As a photosensitive compound that acts on the outer positive type, for example, a polymer having an ortho-nitro-carbinol ester group, which is described in the specification of Japanese Patent Publication No. 56-2696, can also be used in the present invention.

Furthermore, a combination of a compound that generates an acid upon photolysis and a compound having a -C-O-C group or a 10-0-St group that dissociates with an acid can also be used in the present invention.

For example, a combination of a compound that generates an acid through photolysis and an acetal or ○,N-acetal compound (Japanese Patent Application Laid-open No. 48
-89003), combination with orthoester or amide acetal compound JP-A-51-12071
No. 4>, combination with a polymer having an acetal or ketal group as the main group (JP-A-53-133429), combination with an enol ether compound (JP-A-55-1299)
No. 5), combination with N-acylimino carbon compound (JP-A-55-126236), combination with polymer having orthoester group in the main chain (JP-A-56-17345), combination with silyl ester compound Unexamined Japanese Patent Publication No. 6 (1-
1 (No. 124T) and a combination with a silyl ether compound (Unexamined Japanese Patent Publication No. 60-37549)
No. 6), etc.

The photosensitive component that acts on the positive type occupied in the photosensitive composite of the present invention is the combination of the above-mentioned condensation reaction product of the present invention and the above-mentioned known positive-type photosensitive compounds (combinations such as those described above). 5 to 95% by weight, preferably 1O to 85% by weight (including systems)
% by weight, particularly preferably from 30 to 60% by weight, but the amount of the condensation reaction raw material of the present invention based on the total amount of this positive type photosensitive material is from 10 to 90% by weight, preferably from 30 to 7% by weight.
It is assumed to be 0% by weight.

The composition of the present invention may contain the compound itself. In particular, this compound
A polymer having a weight average molecular weight of 1,000 or more is preferable, and a polymer having a weight average molecular weight of 3,000 or more is more preferable.

In the photosensitive composite bottom of the present invention, other polymeric compounds include phenol formaldehyde resin, m-cresol formaldehyde resin, p-cresol formaldehyde resin, m-/p-a combination';y resol formaldehyde resin, and phenol/cresol formaldehyde resin. (m-Jp-, or m-
/p- mixture may be used> It is possible to contain known alkali-soluble polymer compounds such as cresol formaldehyde resins such as mixed formaldehyde resins, phenol-modified xylene resins, polyhydroxystyrene, polyhalogenated hydroxystyrene, etc. can.

These alkali-soluble polymer compounds have a weight average molecular weight of 500 to 20,000 and a number average molecular weight of 200 to 5.
A value of 0.000 is preferred.

Such alkaline water-soluble polymer compounds make up 7 of the total compositions.
It is used in an amount of 0% by weight or less.

Furthermore, as described in U.S. Pat. No. 4,123,279, phenol having an alkyl group having 3 to 8 carbon atoms as a substituent, such as t-butylphenol formaldehyde resin and octylphenol formaldehyde resin, It is preferable to use a metal shrinkage product of formaldehyde and formaldehyde in combination in order to improve the oil sensitivity of the image.

The photosensitive composition of the present invention contains a cyclic acid anhydride to increase sensitivity, a print-out agent to obtain a visible image immediately after exposure,
Dyes and other fillers can be added as image colorants. As the cyclic acid anhydride, U.S. Patent No. 4,
115. Phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3,6-endoxy-Δ4-tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, maleic anhydride, chloranhydride as described in No. 128 Examples include maleic acid, α-phenylmaleic anhydride, succinic anhydride, biromellitic anhydride, and the like. 1 to 15 of these cyclic acid anhydrides in the total set
By including it in weight%, the sensitivity can be increased up to about 3 times.

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
The combination of Q-naphthoquinonediazide-4-sulfonic acid halide and a salt-form organic dye described in Japanese Patent Application Laid-open No. 53-36223, Japanese Patent Application Laid-open No. 54-74728, 6 0-3 6 2 6, 61-143748, 6 1-1 5 1 6 4
A combination of a trihalomethyl compound and a salt-form or organic dye described in No. 4 and No. 63-58440 can be mentioned.

The above-mentioned salt-form or organic dye is used as a coloring agent for images. Other dyes can also be used. Suitable dyes include oil-soluble dyes and basic dyes, including salt-form organic dyes. Specifically, Oil Yellow #101, Oil Yellow #130, Oil Bink #312, Oil Green BG, Oil Blue BOS, Oil Blue #6.
03, Oil Black BY, Oil Black BS, Oil Black T-505 (manufactured by Orient Chemical Industry Co., Ltd.), Victoria Viewer Blue, Crystal Violet (C Engineering 42555), Methyl Violet (
CI42535), rhodamine B (CI45170B)
, malachite green (CI42000), methylene blue (CI52015), and the like. Moreover, the dyes described in JP-A-62-293247 are particularly preferred.

The photosensitive composition of the present invention contains acids having a pKa of 3.0 or less, such as sulfonic acids, to improve developability and to prevent additives such as dyes in the photosensitive composition from remaining in exposed areas after development. , sulfinic acids, alkyl sulfates, phosphonic acids, and phosphinic acids can be added.

Specific examples include naphthalene-2-sulfonic acid, naphthalene-1-sulfonic acid, p-toluenesulfonic acid,
dodecylbenzenesulfonic acid, mesitylenesulfonic acid,
Methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, m-benzenedisulfonic acid, cyclohexylsulfamic acid, p-}luidine-2-sulfonic acid, pyridine-3-sulfonic acid, phenyl J acid, p-}luenesulfine acid, penzylsulfinic acid, methanesulfinic acid, phenylphosphonic acid, methylphosphonic acid, chloromethylphosphonic acid, dimethylphosphinic acid, diphenyl phosphate, diphenyl phosphite, ethyl sulfate, and the like. Others: trifluoroacetic acid, trichloroacetic acid, 2,
Carboxylic acids with a small pKa such as 6-dichlorobenzoic acid and bicric acid, and phenols can also be used. These acids may be used alone or in combination of two or more, and are used in an amount of 0.05 to 5% by weight, preferably 0.2 to 2% by weight, based on the total photosensitive composition.

The photosensitive composition of the present invention is dissolved in a solvent that dissolves each of the above components to form a coating solution, which is then coated onto a support. The solvents used here include ethylene dichloride, cyclohexanone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, 1-methoxy-
2-Propanonope 1-methoxy-2-probyl acetate, toluene, ethyl acetate, methyl lactate, ethyl lactate, dimethyl sulfoxide, dimethyl acetamide, dimethyl formamide, water, N-methylpyrrolidone, tetrahydrofurfuryl alcohol, acetone, diacetone alcohol , methanol, ethanol, inbrobanol, diethylene glycol dimethyl ether, etc., and these solvents are used alone or as a mixture.

The concentration of the photosensitive composition in the coating solution is 2 to 50% by weight. The coating amount varies depending on the application, but for example, for photosensitive planographic printing plates, the solid content is generally 0.5
~3.0 g/m' is preferred. As the coating amount becomes thinner, the photosensitivity increases, but the physical properties of the photosensitive film deteriorate.

A surfactant, for example a fluorine surfactant as described in JP-A-62-170950, can be added to the composition of the present invention to improve coating properties. A preferable addition amount is 0.01 to 0.01 of the total photosensitive composition.
1% by weight, more preferably 0.05-0.5% by weight.

When producing a lithographic printing plate using the photosensitive composition of the present invention, an aluminum plate is preferable as the support.

Aluminum plates include pure aluminum plates and aluminum alloy plates. Various aluminum alloys can be used; for example, alloys of aluminum and metals such as silicon, copper, manganese, magnesium, chromium, zinc, lead, bismuth, and nickel are used. These compositions contain some iron and titanium as well as other negligible impurities.

The aluminum plate is surface-treated as necessary. For example, surface treatment such as graining treatment, immersion treatment in an aqueous solution of sodium silicate, potassium fluorozirconate, phosphate, etc., or anodization treatment is preferably performed. Also, as described in British Patent No. 851,819, an aluminum plate grained and then immersed in an aqueous sodium silicate solution;
181. As described in the specification of No. 461, an aluminum plate which is anodized and then immersed in an aqueous solution of an alkali metal silicate is also preferably used.

The above-mentioned anodizing treatment may be carried out using, for example, an aqueous or non-aqueous solution of an inorganic acid such as phosphoric acid, chromic acid, sulfuric acid, or boric acid, or an organic acid such as oxalic acid or sulfamic acid, or a salt thereof, either alone or in combination of two or more. The method is carried out by passing a current through an aluminum plate as an anode in an electrolytic solution.

Also, U.S. Patent No. 3. 658. Silicate electrodeposition as described in '662 is also effective.

These hydrophilic treatments are performed not only to make the surface of the support hydrophilic, but also to prevent harmful reactions with the photosensitive composition provided thereon, and to improve the adhesion with the photosensitive layer. This is done to improve the quality of life.

Prior to graining the aluminum plate, if necessary, the surface may be pretreated to remove rolling oil from the surface and expose a clean aluminum surface. For the former, solvents such as trichlorethylene, surfactants, etc. are used. For the latter, a method using an alkaline etching agent such as sodium hydroxide or potassium hydroxide is widely used.

Mechanical, chemical, and electrochemical methods are all effective as the graining method. Mechanical methods include the ball polishing method, plastic polishing method, and brush polishing method in which a water-dispersed slurry of an abrasive such as pumice is rubbed with a nylon brush.
A method of immersion in a saturated aqueous solution of an aluminum salt of a mineral acid as described in Publication No. 31187 is suitable.
As the electrochemical method, a method of alternating current electrolysis in an acidic electrolyte such as hydrochloric acid, nitric acid, or a combination thereof is preferred.

Among these surface roughening methods, especially Japanese Patent Application Laid-Open No. 55-1379
A surface roughening method that combines mechanical roughening and electrochemical roughening as described in No. 93 is preferred because it provides strong adhesion of the oil-sensitive image to the support.

It is preferable that the graining by the method described above is carried out in such a range that the centerline surface roughness (Ha) of the surface of the aluminum plate is 0.3 to 1.0 μm.

The thus grained aluminum plate is washed with water and chemically etched as required.

The etching solution is usually selected from aqueous base or acid solutions that dissolve aluminum. In this case, it is necessary that no film different from aluminum derived from the etching solution is formed on the etched surface. Examples of preferred etching agents include basic substances such as sodium hydroxide, potassium hydroxide, trisodium phosphate, disodium phosphate, tripotassium phosphate, and dipotassium phosphate; acidic substances such as sulfuric acid and persulfuric acid. , phosphoric acid, hydrochloric acid, and their salts, but salts of metals having a lower ionization tendency than aluminum, such as zinc, chromium, cobalt, nickel, copper, etc., are not preferred because they form an unnecessary film on the etched surface.

These etching agents have a dissolution rate of 0.00% per minute of immersion time for the aluminum or alloy used, depending on the concentration and temperature settings. Most preferably, it is carried out at an amount of 3 to 40 g/m', but it may be more or less than this.

Etching is performed by immersing the aluminum plate in the above etching solution or applying the etching solution to the aluminum plate, and the etching amount is 0.5 to 10 g/m.
' is preferably processed.

As the etching agent, it is preferable to use an aqueous base solution because of its high etching rate. In this case, since smut occurs, a desmut process is usually performed. The acids used in the desmutting treatment include nitric acid, sulfuric acid, phosphoric acid, chromic acid, hydrofluoric acid, and hydrofluoroboric acid.

The etched aluminum plate is washed with water and anodized if necessary. Anodic oxidation can be performed by methods conventionally practiced in this field. Specifically, when a direct or alternating current is passed through aluminum in an aqueous or non-aqueous solution containing sulfuric acid, phosphoric acid, chromic acid, oxalic acid, sulfamic acid, benzenesulfonic acid, etc. or a combination of two or more of these, aluminum An anodic oxide film can be formed on the surface of the support.

The processing conditions for anodic oxidation vary depending on the electrolyte used and cannot be determined unconditionally, but generally the electrolyte concentration is 1 to 80% by weight, the solution temperature is 5 to 70°C, and the current density is 0. .5~60 ampere/clm2, voltage l~IOOV,
An appropriate electrolysis time range is from 30 seconds to 50 minutes.

Among these anodizing treatments, especially British patent No. 1,
412,768, a method of anodizing at high current densities in sulfuric acid, as described in U.S. Pat. 211
, 619, and the method of anodizing in low concentrations of sulfuric acid, as described in U.S. Pat. 511.
The method of anodizing using phosphoric acid as an electrolytic bath, which is described in the specification of No. 661, is preferred.

The aluminum plate roughened as described above and further anodized may be subjected to hydrophilic treatment if necessary, and preferred examples thereof include those described in U.S. Pat. No. 2,714,066 and U.S. Pat. No. 3,181. ．． Alkali metal silicates, such as aqueous sodium silicate solutions as disclosed in US Pat. 153. There is a method of treatment with polyvinylphosphonic acid as disclosed in US Pat.

Further, an undercoat layer made of a water-soluble compound can be provided on the aluminum plate which has been roughened as described above, anodized, and further subjected to a hydrophilic treatment if necessary. Examples of such water-soluble compounds include Japanese Patent Publication No. 57-16349.
Combinations of water-soluble metal salts and hydrophilic cellulose (e.g., zinc chloride and carboxymethyl cellulose, magnesium chloride and hydroxyethyl cellulose, etc.) are disclosed in U.S. Patent No. 3,511,661. Polyacrylamide, Special Publication Showa 46-3
Polyvinylphosphonic acid disclosed in Japanese Patent Application No. 5685, amino acids and their salts (alkali metal salts such as Na salts and K salts, ammonium salts, hydrochlorides, oxalates) disclosed in JP-A-60-149491. , acetate, phosphate, etc.), amines having a hydroxyl group and their salts (hydrochloride, oxalate, phosphate, etc.) disclosed in JP-A-60-232998, among which amino acids and its salts, and hydroxyl group-containing amines and their salts are particularly preferred.The undercoat layer of such water-soluble compounds is preferably provided in a solids content in the range of 1 .mu./m' to 80 .mu./m'.

Developers for the photosensitive composition of the present invention include sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, tribasic sodium phosphate,
Aqueous solutions of inorganic alkaline agents such as dibasic sodium phosphate, dibasic ammonium phosphate, dibasic ammonium phosphate, sodium metasilicate, sodium bicarbonate, aqueous ammonia, etc. are suitable, and their concentrations are 0. 1-10% by weight, preferably 0. It is added in an amount of 5 to 5% by weight.

Moreover, a surfactant and an organic solvent such as alcohol can be added to the alkaline aqueous solution as required.

Light sources used for exposure include carbon arc lamps, mercury lamps, xenon lamps, tungsten lamps, and metal halide lamps.

〔Effect of the invention〕

The photosensitive composite material of the present invention has excellent developability when using an aqueous alkaline developer in the exposed area after coating, drying, and image exposure.
Has a wide range of latitude. The obtained relief image has good abrasion resistance, adhesion to the support, and processing chemical resistance, and when used as a printing plate, a large number of 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 examples and examples, but the content of the present invention is not limited thereto.

Example 1: 170.2 g of p-aminobenzenesulfonamide (
1.0 mol) and 700 ml of tetrahydrofuran were added thereto, and the mixture was stirred in an ice-water bath. 52.3 g (0.5 mol) of methacrylic acid chloride was added dropwise to this mixture using a dropping funnel over about 1 hour. After dropping, remove the ice water bath and
Stir for 30 minutes at room temperature, and then stir for 60 minutes using an oil bath.
The mixture was stirred for 1 hour while heating to ℃. After the reaction was completed, the reaction mixture was poured into 3 liters of water with stirring, stirred for 30 minutes, and then filtered to obtain a white solid of N-(p-aminosulfonylphenyl) methacrylamide. This white solid could be purified by recrystallization from a mixed solvent of water and acetone (yield: 39.3 g).

N-(p-aminosulfonylphenyl)methacrylamide thus obtained9. 7 2 g (0.040
8 mol) and methyl methacrylate7. 9 3 g (
0.0792 mol), N,N-dimethylformamide 5
0 ml was placed in a 200 mil three-necked flask equipped with a stirrer and condenser, and stirred while heating to 64"C using a vortex water bath. To this mixture was added 0.2 4 6 α, α'-azobisisobutyronitrile. g and stirred for 5 hours under a nitrogen stream while maintaining the temperature at 64°C. After the reaction was completed, the reaction mixture was poured into 2 liters of water with stirring, and stirred for 30 minutes.
By filtering and drying, 16 g of white solid was obtained.

The weight average molecular weight (polystyrene standard) of this polymer compound was measured by gel permeation chromatography and found to be 49,000 (polymer compound (a) in Table 1 below).

High molecular compound (a) 1 3. 7 g and 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride 9
．． Add 100mf of N,N-dimethylacetamide to 1g, and while stirring and cooling the reaction solution so that it does not rise above 30°C, a solution of 4.0g of triethylamine dissolved in 2M of N,N-dimethylacetamide is heated for 30 minutes. It was dripped. After reacting for an additional hour at 20-30°C, the reaction solution was poured into 300 mN of water, and the precipitate was collected by filtration and dried to obtain 16 g of condensation product (A).

Combination Example 2 3 L O g (0.36
mole), ethyl chloroformate 3 9. 1 g (0.36
mole> and 200mj of acetonitrile! and stirred in an ice water bath. Add 36.4 g of triethylamine to this mixture.
(0.36 mol) was added dropwise through the dropping funnel over about 1 hour. After dropping, remove the ice water bath and leave at room temperature for 30 minutes.
Stir for a minute and attach an oil bath.

51.7 g (0.30 mol) of p-aminobenzenesulfonamide was added to this reaction mixture, and the mixture was stirred for 1 hour while warming to 70° C. in an oil bath. After the reaction was completed, this mixture was poured into 1 liter of water with stirring and stirred for 30 minutes. The solid was collected by filtration, further slurried in 500 ml of water, filtered and dried to obtain a white solid of N-(p-aminosulfonylphenyl) methacrylamide (yield: 46.9 g).

Next, add N-(p-aminosulfonylphenyl) to a 200 mm three-necked flask equipped with a stirrer, condenser, and dropping funnel.
Methacrylamide 4. 6 1 g (0.0192 mol), ethyl methacrylate 2.94 g (0.0258
mol), acrylonitrile 0.80 g (0.0
15 mol> and N. 20g N-dimethylacetamide
was added and stirred while heating to 65°C using a whirlpool water bath.

V-65 C2.2'-Azobis-(2.
4-dimethylvalero)nitrile] (manufactured by Wako Pure Condiments) 0.
15 g was added and stirred for 2 hours under a nitrogen stream while maintaining the temperature at 65°C. This reaction mixture was further added with 4.61 g of N-(p-aminosulfonylphenyl)methacrylamide, 2.94 g of ethyl methacrylate, 0.80 g of acrylonitrile,
N,N-dimethylacetamide and V-65 0.1
5 g of the mixture was added dropwise through the dropping funnel over a period of 2 hours. After the dropwise addition was completed, the mixture was further stirred at 65°C for 2 hours. After the reaction was completed, 40 g of methanol was added, cooled, poured into 2 liters of water with stirring, stirred for 30 minutes, and filtered and dried.
g of white solid was obtained. The weight average molecular weight (polystyrene standard) of this polymer compound was measured by gel permeation chromatography and found to be 53,000 (for the polymer compounds in Table 1).

Next, the polymer compound 1) was combined in the same manner as in Example 1.
A condensation product (B) was obtained by reacting with 2-naphthoquinone-2-diazide-5-sulfonyl chloride.

Synthesis Examples 3 and 4 Synthesis The polymer compounds (C) and (d) shown in Table 1 were combined in the same manner as in Example 1 or 2, respectively. The weight average molecular weight (boristyrene standard) of these polymer compounds is 9. It was OO~80,000.

Using these polymer compounds (C) and (d), they were reacted with 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride in the same manner as in Synthesis Example 1 to form the condensation products (C) and (d), respectively. C), (D> were obtained.

Synthesis Example 5 N-methacrylbenzenesulfonamide 10.0g (0
．． 044 mol), 4.46 g (0.044 mol), methyl methacrylate
044 mol) in 22 2-methoxyethanol,
V-65 [2,2'-azobis-(2,4-dimethylvalero)nitrile 1 0. Copolymerization was carried out using 0213g as an initiator. After stirring at 60°C for 7 hours, 2-
After adding 60 parts of methoxyethanol, the mixture was reprecipitated into 2 liters of water. The obtained polymer was added to 100 ml of tetrahydrofuran.
The polymer compound (e) shown in the IT table was obtained by re-precipitation in 1.52 methanol. 2
(Mw=200,000, yield 70%). The structural molar ratio was determined by 'H NMR.

Next, using this polymer compound (e), 1,2-naphthoquinone-2-diazide-5-
The condensed proboscis (E) was obtained by reaction with sulfonyl chloride.

In addition, the condensed raw materials (A) to (E) shown in Examples 1 to 5
As measured by a spectrophotometer, the introduction rate of naphthoquinonediazide groups is determined by the amount of reactable -SO2NL groups or -C
All values were in the range of 40% to 80% based on one group of ONH-So2.

Examples 1 to 5 and Comparative Examples 1 to 4 Thickness 0. The surface of a 24 mm aluminum plate was grained using a nylon brush and 400 mesh pumice stone-water suspension, and then thoroughly washed with water to prepare a CIE substrate. Substrate [I] was dissolved in 10% sodium hydroxide for 70 minutes.
After etching by immersion at ℃ for 20 seconds, washing with running water, 20% HNO. Neutralize and wash with water, 1 2.
using a sinusoidal alternating waveform current under conditions of 7 V.

Electrolytic surface roughening treatment was performed in a 7% nitric acid aqueous solution with an electric charge of 400 coulombs/dm2, followed by washing with water to prepare a substrate (n).

The substrate [■] was treated in a 10% aqueous sodium hydroxide solution so that the amount of surface dissolution was 0.9 g/m''. After washing with water, it was neutralized and washed in a 20% nitric acid solution to remove the desmut 1. After that, the amount of oxide film was reduced to 3g/in 18% sulfuric acid aqueous solution.
It was anodized to become lTl2.

Next, in the photosensitive liquid [A] of the following set, five types of photosensitive liquids (A)-1 to 5 were used in which the type of quinonediazide compound (condensation product) of the present invention was changed as shown in Table 2 below. l:A
]-5 was prepared. As a comparative example, in the photosensitive liquid [A], 2,3.4-
Trihydroxybenzophenone and naphthoquinone-1,2
-Photosensitive liquid CA using esterified product with diazide-5-sulfonyl chloride (esterification rate: 60 mol%)]-
6; Photosensitive liquid (A)-7 and photosensitive liquid (A:]-8; in which polymer compound (a) and polymer compound (e) in Table 1 were respectively used instead of the quinonediazide compound of the present invention; Instead of the quinonediazide compound of the invention, m-cresol-formaldehyde resin (weight average molecular weight 4,000)
A photosensitive solution [A]-9 was prepared using the following.

These photosensitive solutions were applied to the substrate (II) and heated at 100°C for 2
After drying for a minute, the photosensitive planographic printing plate (AE-1~(A)
-9 was produced. The coating amount was 2.3 g/dry weight.

Photosensitive liquid [A] - Esterified product of 2,3.4-}lyhydroxybenzophenone and naphthoquinone-1,2-diazide-5-sulfonyl chloride (esterification rate: 60 mol) 0.45 g - Quinonediazide compound of the present invention (Condensed biomaterials: Table 2) 0. 60g
・m-cresol-formaldehyde resin (weight average molecular weight: 4,000) 0.40 g ・Naphthalene-1-sulfone M O. 01g・2-(
p-methoxyphenyl)-4,6-bistrichloromethyl)-1S-triazine 0. 0 2 g・
Naphthoquinone-1,2-diazido-4-sulfonyl chloride 0.01 g・Victoria Via Blue BOH (dye manufactured by Hodogaya Chemical@) 0.015 g・
Megafac F-177 (Dainippon Ink Chemical Industry @ I!! Fluorine surfactant) 0.004 g・Dimethylacetamide 4g・L-methoxy-2-probanol 9g・Methyl ethyl ketone 7g Photosensitive lithographic printing plate CA]-1 ~
(A:] A positive transparent original of the line drawing and halftone image was brought into close contact with the photosensitive layer of -9, and a 1 m
Exposure was carried out from a distance of . The exposed printing plate was immersion developed in developer A of the following set at 25° C. for 60 seconds.

Composition: In order to determine the printing durability, a comparison was made by printing using UV ink and examining the number of normal prints that could be printed. Chemical resistance was evaluated by immersing it in chemicals and examining the erosion properties of the image area.

In addition, in order to investigate the development latitude, development was carried out by changing the temperature of the developer, and the ease with which the number of solid stages of the step wedge changed was investigated. These results are shown in Table 2.

As is clear from Table 2, the photosensitive lithographic printing plate using the photosensitive composition of the present invention had extremely good UV ink printing durability, chemical resistance, and development latitude.

Claims (1)

[Claims] A photosensitive composition characterized by containing a condensation reaction product of a compound having -SO_2-NH- bond and/or ▲ mathematical formula, chemical formula, table, etc. ▼ bond and quinonediazide sulfonyl halide.