JPH02213847A - Photosensitive composition - Google Patents

Abstract

PURPOSE:To obtain a photosensitive compsn. giving a planographic printing plate having superior wear resistance and high printing resistance by incorporating a high molecular compd. contg. -SO2-NH- bonds in the side or principal chain and insoluble in water but soluble in an alkaline aq. soln. and an org. acid having <=3 pKa. CONSTITUTION:A high molecular compd. having sulfonamide groups, insoluble in water but soluble in an alkaline aq. soln. and contg. -SO2-NH- bonds in the side or principal chain and an org. acid having <=3 pKa are incorporated to obtain a photosensitive compsn. The high molecular compd. is obtd. by polymerizing a low molecular compd. having one or more sulfonamide groups in which H atoms bond on an N atom and a polymerizable unsatd. bond in one molecule with a polymn. initiator in a proper solvent. The photosensitive compsn. has superior appliability and also has superior developability when the exposed part is developed with an aq. alkali developing soln. A wear resistant relief image having high adhesion to the support and high resistance to treating chemicals is formed and fine printed matter is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of the Invention] The present invention relates to a photosensitive composition suitable for manufacturing lithographic printing plates, IC circuits and photomasks.

More specifically, the present invention relates to a photosensitive composition comprising a positive-acting photosensitive compound and a polymer compound having excellent abrasion resistance and chemical resistance.

[Conventional technology]

A photosensitive composition composed of an 0-naphthoquinone diazide compound and a novolak type phenol resin has been used industrially as an extremely excellent photosensitive composition in the production of lithographic printing plates and as a photoresist.

However, due to the nature of the novolac type phenolic resin used as the main material, it has poor adhesion to the substrate, brittle film, poor coating properties, poor abrasion resistance, and insufficient printing durability when used in lithographic printing plates. Furthermore, there are problems that need to be improved, such as poor chemical resistance and particularly insufficient printing durability when UV ink is used. Burning treatment (heat treatment after exposure and development) is generally used as a method for improving these various properties. However, when the burning process is performed, there is a problem in that low-molecular compounds in the photosensitive layer adhere to non-image areas rather than image areas, making it easier to cause stains during printing.

In order to solve this problem, various polymer compounds have been investigated as binders. For example, special public relations
Although the polyhydroxystyrene or hydroxystyrene copolymer described in No. 10SO did have improved film properties, it had the disadvantage of poor abrasion resistance and chemical resistance. Furthermore, in JP-A-51-34711, it is proposed to use a polymer compound having a structural unit of an acrylic acid derivative in its molecular structure as a binder; There were problems such as a narrow range and insufficient wear resistance.

In addition, in the case of lithographic printing plates, if unnecessary images occur, there is a process of removing them using a chemical commonly called erasing liquid (erasing work).
However, if a binder with excellent chemical resistance is used, this erasing operation takes time and there is a problem in that the efficiency of the operation deteriorates.

[Purpose of the invention]

Accordingly, an object of the present invention is to provide a photosensitive composition that has excellent abrasion resistance, can be developed with an aqueous alkaline developer, and provides a lithographic printing plate with high printing durability.

Another object of the present invention is to provide a photosensitive composition that provides a lithographic printing plate that has excellent chemical resistance and has high printing durability even when printed using UV ink without performing a burning process. .

A further object of the present invention is to provide a photosensitive composition that has good adhesion to a substrate and provides a flexible film.

Yet another object of the present invention is to provide a photosensitive composition that provides a lithographic printing plate with excellent erasing efficiency.

[Structure of the invention]

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 photosensitive composition of the present invention comprises (a) a photosensitive compound that acts in a positive tone, and (b) a water-insoluble and alkaline aqueous solution containing -SO□ to N H- bonds in the side chain or main chain. It is characterized by containing a soluble polymer compound and (c) an organic acid having a pKa value of 3 or less.

By using a water-insoluble and alkaline aqueous-soluble polymer compound containing ~5Q2-NH- bonds in the side chain or main chain, the photosensitive composition has excellent abrasion resistance and
We were able to provide a flexible film with excellent chemical resistance and good adhesion to the substrate. However, it has been found that when used as a photosensitive layer of a lithographic printing plate, the polymer compound has a problem in that it takes longer to erase than the conventionally used novolac type phenolic resin.

As a result of extensive research, it was surprisingly possible to solve this problem by incorporating an organic acid with a pKa of 3 or less into the photosensitive composition, leading to the present invention.

The polymer compound having a sulfonamide group and being insoluble in water and soluble in an alkaline aqueous solution used in the present invention is preferably a polymer compound containing a -5Q2-NH bond in the side chain or main chain, More preferably, -SO in the side chain
It is a polymer compound containing a □-N I-]- bond.

The polymer compound used in the present invention that has a sulfonamide group and is insoluble in water and soluble in an alkaline aqueous solution has one sulfonamide group in which at least one H atom is bonded to one or more N atoms in one molecule. It can be obtained by polymerizing the above-mentioned low molecular weight compound having a polymerizable unsaturated bond in an appropriate solvent using a known polymerization initiator.

In the present invention, such low-molecular compounds that are more preferably used include those of general formulas (1), (II), and (I).
There is also a compound represented by (TV).

In the formula, XI, X2, and x:l each represent 1○- or -N R+ 2-. R1, , R4, R7 and RQ each do not represent =I] or -CH3. R2, R5RI
O represents a C0 to C1□ alkylene group, cycloalkylene group, arylene group, or aralkylene group, each of which may have a substituent. R3 b-) (, 01-c1□ alkyl group, cycloalkyl group, oryl group, or aralkyl group that may have a substituent is not shown. Also, R6, R
[l, R11 is C1-C which may have a substituent
I 2 alkyl group, cycloalkyl group, oryl group,
Aralkyl group not shown. R+2 represents a hydrogen atom or a C1-C1□ alkyl group, cycloalkyl group, aryl group, or aral 4-l group which may have a substituent.

Among the low molecular weight compounds represented by the general formula (r), (II), (III) or (TV), those particularly preferably used in the present invention have R2, R5 and RIG each having C2
~C6 alkylene group, cycloalkylene group, or phenylene group or naphthylene group which may have a substituent, and R3 is H or has a C1 to C6 alkyl group, cycloalkyl group, or substituent; phenyl group, naphthyl group, R6, R11SR are C, -C6
is an alkyl group, a cycloalkyl group, or a phenyl group or naphthyl group which may have a substituent, and R12 is a hydrogen atom.

Examples of the low molecular weight compounds represented by general formulas (I) and (n) include N-(o-aminosulfonylphenyl)methacrylamide, N(m-aminosulfonylphenyl)methacrylamide, N-(p -aminosulfonylphenyl)methacrylamide, N-(o-methylaminosulfonylphenyl)methacrylamide, N-(
m-methylaminosulfonylphenyl)methacrylamide, N-(p-methylaminosulfonylphenyl)methacrylamide, N-(0-ethylaminosulfonylphenyl)methacrylamide, N(m-ethylaminosulfonylphenyl)tuccrylamide, N-(p-ethylaminosulfonylphenyl)methacrylamide, N-(o
-n-propylaminosulfonylphenyl)methacrylamide, N-(m-n-propylaminosulfonylphenyl)methacrylamide, N-(p-n-propylaminosulfonylphenyl)methacrylamide, N-(o-
i-propylaminosulfonylphenyl)methacrylamide, N-(m-i-propylaminosulfonylphenyl)methacrylamide, N-(p-4-propylaminosulfonylphenyl)methacrylamide, N-(0-n
-butylaminosulfonylphenyl) methacrylamide, N-(m-n-butylaminosulfonylphenyl)methacrylamide, N-(p-n-butylaminosulfonylphenyl)methacrylamide, N-(o-4-butylaminosulfonylphenyl) ) methacrylamide, N-(
m-i-butylaminosulfonylphenyl) methacrylamide, N(p-i-butylaminosulfonylphenyl) methacrylamide, pJ-'(o-sec-butylaminosulfonylphenyl) methacrylamide, N(m-
sec-butylaminosulfonylphenyl) tuccrylamide, N-(p-sec-butylaminosulfonylphenyl)methacrylamide, N(ot-butylaminosulfonylphenyl)methacrylamide, N-(m-
t-butylaminosulfonylphenyl) methacrylamide, N-(p-t-butylaminosulfonylphenyl) methacrylamide, N-(0-phenylaminosulfonylphenyl) methacrylamide, N-(mphenylaminosulfonylphenyl) methacrylamide, N-(p-
phenylaminesulfonylphenyl)tuccrylamide, N-(o-(α-naphthylaminosulfonyl)phenyl)methacrylamide, N-(m-(α-naphthylaminosulfonyl)phenyl)methacrylamide, N-(p
(α-naphthylaminosulfonyl)phenyl)methacrylamide, N-(o-(β-naphthylaminosulfonyl)phenyl)methacrylamide, N(m-(β-naphthylaminosulfonyl)phenyl)methacrylamide, N
-(p-β-naphthylaminosulfonyl)phenyl)
Methacrylamide, N-(1-(3-aminosulfonyl)naphthyl)tuccrylamide, 11- (1-<3-
Methylaminosulfonyl)naphthyl)methacrylamide, N-(1-(3-ethylaminosulfonyl)naphthyl)tuccrylamide, N-(0-methylsulfonylaminophenyl)methacrylamide, N(m-methylsulfonylaminophenyl)methacryl Amide, N-(p-methylsulfonylaminophenyl)methacrylamide, N
-(o-ethylsulfonylaminophenyl)methacrylamide, N-(m-ethylsulfonylaminophenyl)
Methacrylamide, N-(p-ethylsulfonylaminophenyl)methacrylamide, N-(0-phenylsulfonylaminophenyl)methacrylamide, N-(m-
Phenylsulfonylaminophenyl)methacrylamide, N-(p-phenylsulfonylaminophenyl)methacrylamide, N(o-(p-methylphenylsulfonylamino)phenyl)methacrylamide, N-(m-
(p-methylphenylsulfonylamino)phenyl)methacrylamide, N-(p-Cp-methylphenylsulfonylamino)phenyl)methacrylic 7mide, 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-(2α-naphthylsulfonylaminoethyl)methacrylamide, N-(2-β-
Methacrylamides such as (naphthylsulfonylamino)ethylmethacrylamide, acrylamides having the same substituents as above, 0-aminosulfonylphenyl methacrylate, m-aminosulfonylphenyl methacrylate, p-aminosulfonylphenyl methacrylate, O-methylamino Sulfonylphenyl methacrylate, m-methylaminosulfonylphenyl methacrylate, p-methylaminosulfonylphenyl methacrylate, 0-ethylaminosulfonylphenyl methacrylate, m-ethylaminosulfonylphenyl methacrylate, p-ethylaminosulfonylphenyl methacrylate,
o-n-propylaminosulfonylphenyl methacrylate, m-n-propylaminosulfonylphenyl methacrylate, p-n-propylaminosulfonylphenyl methacrylate, Ol-propylaminosulfonylphenyl methacrylate, m-1-propylaminosulfonylphenyl methacrylate, o- n-butylaminosulfonylphenyl methacrylate, m-n-butylaminosulfonylphenyl methacrylate, pn-butylaminosulfonylphenyl methacrylate, m-1-butylaminosulfonylphenyl methacrylate, p-1-
Butylaminosulfonylphenyl methacrylate, m-
5eC-butylaminosulfonylphenyl methacrylate, psec-butylaminosulfonylphenyl methacrylate, m-t-butylaminosulfonylphenyl methacrylate, pt-butylaminosulfonylphenyl methacrylate, 0-phenylaminosulfonylphenyl methacrylate, m-phenylaminesulfonylphenyl Methacrylate, p-phenylaminosulfonylphenyl methacrylate, m-(α-naphthylaminosulfonylphenyl) methacrylate, p-(α-naphthylaminosulfonylphenyl) methacrylate, m(β
-naphthylaminosulfonylphenyl) methacrylate, p-<β-naphthylaminosulfonyl)phenyl mechacrylate, ■-(3-aminosulfonyl)naphthyl methacrylate, 1-(3methylaminosulfonyl)naphthyl methacrylate, 1-(3-ethyl (aminosulfonyl) naphthyl methacrylate, O-methylsulfonylaminophenyl methacrylate, m-methylsulfonylaminophenyl methacrylate, p-methylsulfonylaminophenyl methacrylate, 0-ethylsulfonylaminophenyl methacrylate, m-ethylsulfonylaminophenyl methacrylate, p-ethyl Sulfonylaminophenyl methacrylate, O-phenylsulfonylaminophenyl methacrylate, m-phenylsulfonylamine phenyl methacrylate, p-phenylsulfonylaminophenyl methacrylate, o-(pmethylphenylsulfonylamino)phenyl methacrylate, m
-(p-methylphenylsulfonylamino)phenyl methacrylate, p-(pmethylphenylsulfonylamino)phenyl methacrylate, p-(α-naphthylsulfonylamino)phenyl methacrylate, p-(β-naphthylsulfonylamino)phenyl methacrylate, 2
-methylsulfonylaminoethyl methacrylate, 2-
Ethylsulfonylaminoethyl methacrylate, 2-phenylsulfonylaminoethyl methacrylate, 2-p
- Methacrylic esters such as methylphenylsulfonylamine ethyl meccrylate, 2-α-naphthylsulfonylaminoethyl methacrylate, 2β-naphthylsulfonylaminoethyl meccrylate, acrylic esters having the same substituents as above, etc. Can be mentioned.

As the low molecular weight compound represented by general formula (III),
For example, N-methacrylylhenzensulfonamide, N
-methacrylyl p-)luenesulfonamide, N-methacrylyl p-)luenesulfonamide, N-methacrylyl p-methoxyphenylsulfonamide, N-methacrylyl p-butoxyphenylsulfonamide, N-methacrylyl p-methoxyphenylsulfonamide, N- Methacryglu α-naphthylsulfonamide, N-meccrylyl 0-butoxyphenylsulfonamide, N-acrylylhenzensulfonamide, N-acrylyl p-toluenesulfonamide, N-acrylyl 0-toluenesulfonamide, N-acrylyl 0-methoxy Phenylsulfonamide, N-acrylyl p-1-amyl phenylsulfonamide, N-acrylyl 0-methoxyphenylsulfonamide, N-acrylyl α-naphthylsulfonamide,
Examples include N-acrylyl m-buty-xyphenylsulfonamide.

Examples of the low molecular weight compound represented by the general formula (TV) include N-(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-naphthylsulfonylamine)sulfonylphenyl) methacrylamide, N
-(p-(β-naphthylsulfonylamino)sulfonylphenyl)methacrylamides such as methacrylamide, acrylamides having the same substituents as above, and p-(p-methylphenylsulfonylamino)sulfonylphenyl methacrylate , m-(phenylsulfonylamino)sulfonylphenyl acrylate, p-(p-methoxyphenylsulfonylamino)sulfonylphenyl methacrylate, p-(α-naphthylsulfonylamine)sulfonylphenyl methacrylate, 0-(p-methylphenylsulfonylamino) ) sulfonylphenyl methacrylate, p-(m-i-butylphenylsulfonylamino)sulfonylphenyl) methacrylate, p-(β-naphthylsulfonylamino)sulfonylphenyl methacrylate, and other methacrylic acid esters, having the same substituents as above. Examples include acrylic esters.

Further, other examples of low molecular weight compounds having an unsaturated bond polymerizable with a sulfonamide group and preferably used in the present invention include compounds represented by the following general formulas (V) to (■). .

(Vl) R'' (■) R13, RIS, and R19 each represent a hydrogen atom, a halogen atom, or a methyl group, and preferably a hydrogen atom.

R14 is optionally substituted C, -CI. represents an alkylene group, cycloalkylene group, arylene group, or aralkylene group, and preferably represents an optionally substituted methylene group, phenylene group, or naphthylene group.

RI6 and R2° each represent a single bond or an optionally substituted C1 to C12 alkylene group, cycloalkylene group, arylene group, or aralkylene group, and preferably a single bond or a methylene group.

RI7 and R21 are each optionally substituted 01-
C1□ alkylene group, cycloalkylene group, arylene group, aralkylene group, preferably C2 to C6
represents an alkylene group, an optionally substituted phenylene group, or a naphthylene group.

RIB is a hydrogen atom, optionally substituted C to C1□
represents an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group, preferably a hydrogen atom or an alkyl group of ClNC6, a cycloalkyl group, an optionally substituted phenyl group, or a naphthyl group.

R22 represents an optionally substituted C6 to C1 alkyl group, cycloalkyl group, aryl group, or aralkyl group, preferably a C6 to C6 alkyl group, a cycloalkyl group, an optionally substituted phenyl group, Indicates naphthyl group. Moreover, Y l and Y 2 each represent a single bond or -C-.

Specific examples of the compounds represented by the above general formulas (V) to (■) include p-aminosulfonylstyrene, p-
Aminosulfonyl-α-methylstyrene, p-aminosulfonylphenyl allyl ether, p-(N-methylaminosulfonyl) phenyl allyl ether, methylsulfonylaminoacetic acid vinyl ester, phenylsulfonylaminoacetic acid vinyl ester, methylsulfonylamine acetic allyl ester, Examples include phenylsulfonylaminoacetic allyl ester and p-methylsulfonylaminophenyl allyl ether.

The polymer compound having a sulfonic acid group that is preferably used in the present invention has at least one
(Although it may be a homopolymer or a copolymer of two or more types of low-molecular compounds having a sulfonamide group to which atoms are bonded and a polymerizable unsaturated bond, preferably one or more polymerizable unsaturated bonds. It is a copolymer with one or more compounds containing a bond and not containing a sulfonamide group.

Examples of compounds containing such a polymerizable unsaturated bond and not containing a sulfonamide group include acrylic acid, methacrylic acid, acrylic esters, acrylamides, methacrylic esters, methacrylamide, allyl It is a compound having a polymerizable unsaturated bond selected from compounds such as vinyl ethers, vinyl esters, styrenes, and croton esters. in particular,
For example, acrylic esters, such as alkyl (preferably the number of carbon atoms in the alkyl group is 1 to 10), acrylates (such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, acrylic acid) Ethylhexyl, octyl acrylate, t-octyl acrylate, chloroethyl acrylate, 22-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, glycidyl acrylate, hensyl acrylate, methoxyhensyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, etc.), aryl acrylate-1 (e.g. phenyl acrylate, etc.): methacrylic acid esters, e.g.
Alkyl (the alkyl group preferably has 1 to 10 carbon atoms) methacrylate (e.g. methyl methacrylate, ethyl meccrylate, propyl methacrylate, isopropyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate-1, Hensyl methacrylate, chlorobenzyl methacrylate-1, octyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxybutyl methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, trimethylolpropane monomethacrylate, penquerythritol monomethacrylate, glycidyl methacrylate, furfuryl methacrylate,
(e.g., tetrahydrofurfuryl methacrylate), aryl methacrylate (e.g., phenyl methacrylate,
cresyl methacrylate, naphthyl methacrylate, etc.) Niacrylamides, such as acrylamide, N-alkylacrylamide (the alkyl group has 1 to 10 carbon atoms, such as methyl group, ethyl group, propyl group, butyl group, L-butyl group) ), N-arylacrylamide (such as phenyl, tolyl, nitrophenyl, naphthyl, hydroxy), heptyl, octyl, cyclohexyl, benzyl, hydroxyethyl, etc. phenyl group, etc.), N,N-dialkyl acrylamide (the alkyl group includes those having 1 to 10 carbon atoms, such as methyl group, ethyl group, butyl group, isobutyl group, ethylhexyl group, cyclohexyl group, etc.) ), N,
N-arylacrylamide (as a nucleol group,
For example, there is a phenyl group. ), 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,
Examples include methyl group, ethyl group, t-butyl group, ethylhexyl group, hydroxyethyl group, and cyclohexyl group. ), N-arylmethacrylamide (the aryl group includes a phenyl group, etc.), N,N-diarylmethacrylamide (the alkyl group includes an ethyl group, a propyl group, a butyl group, etc.), N, N-
Diarylmethacrylamide (as the nucleol group,
There are phenyl groups. ), N-hydroxyethyl-N-
Methyl methacrylamide, N-methyl-N-phenyl methacrylamide, N-ethyl-N-phenyl methacrylamide: Allyl compounds, such as allyl esters (e.g. allyl acetate, allyl caproate, allyl caprylate, allyl laurate, valmitin) Allyl acid, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, etc.), oryloxyethanol, etc. Vinyl ethers, such as alkyl vinyl ethers (such as hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxy Ethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2゜2
- dimethylpropyl vinyl ether, 2-ethyl butyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, etc.), vinyl aryl ethers (e.g. vinyl phenyl ether) , vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2,4-dichlorophenyl ether, vinyl naphthyl ether, vinyl anthrani ether, etc.): vinyl esters, such as vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate-1, vinyl barate,
Vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxy acetate, vinyl butoxy acetate, vinyl phenylacetate, vinyl acetoacetate, vinyl lactate, vinyl-β
- Phenylbutyrate, vinylcyclohexylcarboxylate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate, etc., such as styrene, alkylstyrene (
For example, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene,
cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethylstyrene, trifluoromethylstyrene, ethoxymethylstyrene, acetoxymethylstyrene, etc.), alkoxystyrene (such as methoxystyrene, 4methoxy-3-methylstyrene, dimethoxystyrene, etc.), halogenstyrene (For example, chlorstyrene, dichlorostyrene, trichlorostyrene, tetrachlorstyrene, pentachlorstyrene, bromstyrene, dibromstyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, 4 -fluoro-3 to trifluoromethylstyrene, etc.): Crotonate esters, for example, alkyl crotonate (for example, butyl crotonate, hexyl crotonate, glycerin monocrotonate, etc.)
: Dialkyl itaconates (e.g. dimethyl itaconate, diethyl itaconate, dibutyl itaconate, etc.): Dialkyls of maleic acid or fumarate (e.g. dimethyl maleate, dibutyl fumarate, etc.); Acronitrile, methacrylonitrile, etc. .

Among these compounds having polymerizable unsaturated bonds, those preferably used are methacrylic esters, acrylic esters, methacrylamides, acrylamides,
Acrylotrile, methacrylonitrile, methacrylic acid,
It is acrylic acid.

The co-electric body of one or more of these compounds having a polymerizable unsaturated bond and one or more of the compounds containing a sulfonamide group and having a polymerizable unsaturated bond may be a flock body, a random body, or a graft body. Both can be used.

In these copolymers, the structural unit containing a sulfonamide group is preferably contained in an amount of 5 mol% or more, and preferably 10 to 90 mol%, based on all the structural units constituting the copolymer. Things are even better.

Examples of solvents used when synthesizing such polymeric compounds include ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, - Methoxy 2-proper tool, 1-
Examples include methoxy 2-propyl acetate, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, toluene, ethyl acetate, methyl lactate, and ethyl lactate.

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

In addition to the above-mentioned copolymers, polyurethane resins having a sulfonamide group and being insoluble in water and soluble in an alkaline aqueous solution are preferably used in the present invention.

The polyurethane resin suitably used in the present invention is preferably a polyurethane resin whose basic skeleton is a reaction product of a diisocyanate compound and a diol compound containing a sulfonamide group to which at least one H atom is bonded to N. It is.

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

That is, 2,4-tolylene diisocyanate, a dimer of 24-tolylene diisocyanate, 2.6-tolylene diisocyanate, p-xylylene diisocyanate, m-xylylene diisocyanate, 4,4'-diphenylmethane. Aromatic diisocyanate compounds such as diisocyanate, 1,5-naphthylene diisocyanate, 3,3'dimethylbiphenyl-4,4'-diisocyanate, etc.: hexamethylene diisocyanate, trimethylhexamethylene diisocyanate aliphatic diisocyanate compounds such as ester, lysine diisocyanate, dimer acid diisocyanate, etc.; isoborone diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), methylcyclohexane 2.4 (or 2.6) diisocyana
Alicyclic diisocyanate compounds such as 1,1゜3-(isocyanatomethyl)cyclohexane; diols and diisocyanates such as adducts of 1 mole of 1,3 butylene glycoyl and 2 moles of tolylene diisocyanate; Examples include diisocyanate compounds that are reactants with isocyanates.

Further, the diol compounds containing a sulfonamide group having at least one [■] atom bonded to N include those shown below.

That is, p-(1,1-dihydroxymethylethylcarbonylamino)benzenesulfonamide, p-(1,1
~N-ethyl form of dihydroxymethylethylcarbonylamino)benzenesulfonamide, N-(m-methylsulfonylaminophenyl)-2,2-dihydroxymethylpropanamide, N-(p-methylsulfonylaminophenyl)2.2- Dihydroxymethylpropanamide, N-(m-ethylsulfonylaminophenyl)2
．． 2-dihydroxymethylpropanamide, N(p-ethylsulfonylaminophenyl l-2゜2-dihydroxymethylpropanamide, N(2,2-(dihydroxyethylaminocarbonyl)ethyl)methanesulfonamide, N-(2゜2) -(dihydroxyethylaminocarbonyl)ethylbenzenesulfonamide, N-(2,2(
dihydroxyethylaminocarbonyl)ethyl p-1-
Examples include luenesulfonamide, and the like.

These diol compounds containing a sulfonamide group 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.

Namely, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, neopentyl glycol, 13-butylene glycol, 1,6
-hexanediol, 2-butene-1,4-diol,
2゜2.4-trimethyl-1,3-bentanediol,
■, 4-bis-β-hydroxyethoxycyclohexane, cyclohexane dimetatool, tricyclodecane dimetatool, hydrogenated bisphenol A1 hydrogenated bisphenol F, ethylene oxide adduct to bisphenol, propylene oxide adduct of bisphenol A, bisphenol Ethylene oxide adduct of F, propylene oxide adduct of bisphenol F, ethylene oxide adduct of hydrogenated hisphenol A, propylene oxide adduct of hydrogenated bisphenol A, hydroquinone dihydroxyethyl ether, p-xylylene glycol, dihydroxyethyl sulfone , bis(2-hydroxyethyl)-2,4-)lylene dicarbamate, 2,4-tolylene-bis(2hydroxyethylcarbamide), 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) ) acetic acid, bis(4hydroxyphenyl)acetic acid, 4,4-bis(4hydroxyphenyl)pentanoic acid, tartaric acid, and the like.

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 in the polymer, it can be treated with alcohols or amines, etc. Finally, it is synthesized in a form in which no isocyanate groups remain.

The molecular weight of the polymer compound of the present invention is preferably 2,000 or more in weight average and 1000 or more in number average. More preferably, the weight average is in the range of 5.000 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 1o.

Furthermore, the polymer compound of the present invention may contain unreacted monomers. In this case, the proportion of the monomer in the polymer compound is preferably 15% by weight or less.

The polymer compounds of the present invention may be used alone or in combination. The content of these polymer compounds contained in the photosensitive composition is about 5 to 95%, preferably about 10%.
~85%.

On the other hand, the positive-acting photosensitive compounds used in the present invention are specifically: -There are naphthoquinone diazide compounds.

Used in the present invention. - As the naphthoquinonediazide compound, an ester of 1,2-diazonaphthoquinonesulfonic acid chloride and pyrogallol-acetone resin described in Japanese Patent Publication No. 41-28403 is preferred. Other suitable orthoquinonediazide compounds include 1, 2, and 2, as described in U.S. Pat.
There are esters of diazonaphthoquinone sulfonic acid chloride and phenol-formaldehyde resins. Other useful 0-naphthoquinone diazide compounds are known and reported in numerous patents. For example, JP-A-47-5303, JP-A-48-63802, JP-A-48
-63803, Kaikai No. 48-96575, Kaikai No. 49-
No. 38701, Kaikai No. 48-13354, Special Publication No. 371
No. 8015, No. 41-11222, No. 45-96
No. 10, Japanese Patent Publication No. 49-174.81, U.S. Patent No. 2
, No. 797.213, No. 3,454.400, No. 3,544,323, No. 3.573,917, No. 3.674. ．． 495, British Patent No. 3,785,825, British Patent No. 1227.602, British Patent No. 1.251,3
No. 45, No. 1.267.005, No. L 329
．． Examples include those described in various specifications such as German Patent No. 888, German Patent No. 1,330,932, and German Patent No. 854.890.

A particularly preferred 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 are disclosed in JP-A-51-139402 and JP-A-58-1.
SO948, SO58-203434, SO59-16
SO53, SO60-121445, SO60-134
No. 235, No. 60-163043, No. 61-1187
No. 44, No. 62-10645, No. 62-10646, No. 62-1539SO, No. 62178562, Japanese Patent Application No. 62-233292, U.S. Patent No. 3,102.8
No. 09, No. 3,126.281, No. 3.130,
No. 047, No. 3.148.983, No. 3,184
, No. 310, No. 3,188.210, No. 4,63
Examples include those described in various publications or specifications such as No. 9°406.

When synthesizing these 0-naphthoquinone diazide compounds, 1
．． 0.2 of 2-diazonaphthoquinone sulfonic acid chloride
It is preferable to react by 1.2 equivalents, and more preferably 0.3 to 1.2 equivalents.
It is preferable to react 1.0 equivalent.

The obtained 0-naphthoquinonediazide compound is 1,
The result is a mixture of compounds with different positions and amounts of 2-diazonaphthoquinone sulfonic acid ester groups, but the proportion of compounds in which all hydroxyl groups have been converted with 1,2-diazonaphthoquinone sulfonic acid ester (esterification The ratio) is preferably 5 mol% or more, more preferably 20 to 99 mol%.

In addition, as a photosensitive compound that acts positively without using an 0-naphthoquinone diazide compound, for example,
Polymeric compounds having orthonitrocarbinol ester groups as described in No. 696 can also be used in the present invention.

Furthermore, a combination system of a compound that generates an acid in the light field and a compound having one C-O-C group or a -C-0-3i group that dissociates with an acid can also be used in the present invention.

For example, a compound that generates an acid upon photolysis and an acetal or 0. Combination with N-acetal compound (Japanese Patent Application Laid-open No. 1973-
89003), a combination with an orthoester or amide acetal compound (JP-A-51-120714), a combination with a polymer having an acetal or kecoul group in the main chain (JP-A-53-133429), and an enol ether compound. combination (JP-A-55-12995), N
Combination with acylimino carbon compound (JP-A-55-12
6236), a combination with a polymer having an orthoester group in the main chain (JP-A-56-17345), a combination with a silyl ester compound (JP-A-60-10247)
and a combination with a silyl ether compound (JP-A-60-3
No. 7549, JP-A No. 6L-121446), etc.

These positive-acting photosensitive compounds that occupy the photosensitive composition of the present invention (including the combinations described above, such as diphenyl phosphite and ethyl sulfate; others include trifluoroacetic acid, l-dichloroacetic acid, . Carboxylic acids with a small pKa such as 6-dichlorobenzoic acid and picric acid, and phenols can also be used.

The organic acid used in the present invention may have two or more acidic functional groups as long as it has at least one functional group with a pKa of 3 or less in the molecule. Examples of this include the following:

OH P○, N2 1100C: (CH2)2 N11CC11(OH)
The amount of C(C1b)zctlzOP031h)j) is from 10 to SO wt%, more preferably 1
It is 5 to 40% by weight.

The organic acid used in the present invention has a pKa in water at 25°C.
is preferably 3.0 or less, more preferably,
It is 1.0 or less. Examples of such organic acids include sulfonic acids, sulfinic acids, alkyl sulfuric acids, bosphonic acids, and phosphinic acids, and sulfonic acids and sulfinic acids can be particularly effectively used. Specific examples include naphthalene-2-sulfonic acid, naphthalene-2-sulfonic acid, and naphthalene-2-sulfonic acid.
1 sulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, mesitylenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, Hensensulfonic acid, m-Hensendisulfonic acid, cyclohexylsulfamic acid,
p-Toluidine-2-sulfonic acid, pyridine-3-sulfonic acid, phenyl J acid, p-toluenesulfinic acid, hensylsulfinic acid, methanesulfinic acid, phenylphosphonic acid, methylphosphonic acid, chloromethylphosphonic acid, dimethylphosphinic acid, When adding diphenyl phosphate and the organic acid of the present invention, even if it is not an organic acid, it can be added quickly (specifically for 24 hours) in a photosensitive solution (a solution in which a photosensitive composition is dissolved in an organic solvent). It also includes those that decompose (within SO% or more) and become organic acids. Examples of such sulfonyl halides and sulfonic acid esters include the following.

The above-mentioned sulfonyl halides can be coated using aprotic polar solvents such as N,N-dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, and N,N-dimethylacetamide as part of the coating solvent. The decomposition is accelerated and it becomes sulfonic acid, which is essentially equivalent to using sulfonic acid in many cases.

Such organic 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. If the speaking power of the organic acid used in the present invention is too small, the effect of the present invention cannot be obtained, and on the other hand, if the amount added is too large, the visible image after exposure may become difficult to see, or the developed image area may be easily damaged. or

In the composition of the present invention, in addition to the sulfonamide group-containing polymer compound, phenol formaldehyde resin,
m-cresol formaldehyde resin, p-cresol formaldehyde resin, m/p-mixed cresol formaldehyde resin, phenol/cresol (m~, p-
Cresol formaldehyde resins such as mixed formaldehyde resins, phenol-modified xylene resins, polyhydroxystyrene,
Known alkali-soluble polymer compounds such as polyhalogenated hydroxystyrene can be contained. These alkali-soluble polymer compounds have a weight average molecular weight of SO0 to 20,000, a number average molecular weight of 200 to 60,
000 is preferred.

This alkaline water-soluble polymer compound accounts for 7% of the total composition.
It is used in an amount of 0 weight or less.

Furthermore, as described in U.S. Pat. No. 4,123,279, phenol and formaldehyde 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 condensate with the above compound in combination to improve the oil sensitivity of the image.

The composition of the present invention may contain a cyclic acid anhydride to increase sensitivity, a printout agent to obtain a visible image immediately after exposure, a dye as an image coloring agent, and other fillers. As a cyclic acid anhydride, US Pat. No. 4,115.
128, phthalic anhydride,
Tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 36-nindooxy-Δ4-tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, maleic anhydride, chloromaleic anhydride, α-phenylmaleic anhydride, succinic anhydride, pyromellitic anhydride etc. By containing these cyclic acid anhydrides in an amount of 1 to 15% by weight based on the total composition, the sensitivity can be increased up to about 3 times.

A typical printing agent for obtaining a visible image immediately after exposure is a combination of a photosensitive compound that releases an acid upon exposure and an organic dye that can form a salt.

Specifically, Japanese Patent Application Laid-open No. 1-36209,
The combination of 0-naphthoquinonediazide-4-sulfonic acid halide and salt-forming organic dye described in JP-A No. 3-8128 and JP-A-53-36223 and JP-A-54-74
No. 728, No. 6 (No. 1-3626, No. 61-14374)
Examples include combinations of trihalomethyl compounds and salt-forming organic dyes described in Japanese Patent No. 8, No. 61-151644, and No. 63-58440. In addition to the above-mentioned salt-forming organic dyes, other dyes can also be used as image coloring agents. Suitable dyes include oil-soluble dyes and basic dyes, including salt-forming organic dyes.

Specifically, oil yellow #10 L oil yellow #130, oil pink #312, oil green BG
, Oil Blue-BO3, Oil Blue #603, Oil Black BY, Oil Black BS, Oil Black T
SO5 or more, manufactured by Orient Chemical Industry Co., Ltd.), Victoria Pure Blue, Crystal Violet) (CI
A2555), methyl iolet (C14253)
5), Rhodamine B (CI45170B), Malachite Green (CI42000>, Methylene Blue (CI5)
2015). Also, JP-A-6
The dyes described in Japanese Patent No. 2-293247 are particularly preferred.

The composition of the present invention is applied onto a support after being dissolved in a solvent that dissolves each of the above components. Use it here? Vehicles include ethylene dichloride, cyclohexanone, methyl alequinone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyedyl acetate, 1-methoxy-2-propanol, -methoxy-2-propyl Acetate, toluene, ethyl acetate, methyl lactate, ethyl lactate, dimethyl sulfoxide, dimethylacetamide, dimethylformamide, water, N-methylpyrrolidone, tetrahydrofurfuryl alcohol, acetone, diacetone alcohol, methanol, ethanol, isopropanol, diethylene glycol dimethyl ether These solvents can be used alone or in combination. The concentration (solid content) in the above components is 2 to 2% by weight of SO. 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.
/% is preferred. As the coating amount becomes thinner, the photosensitivity increases, but the physical properties of the photosensitive film deteriorate.

In the composition of the present invention, a surfactant for improving the coating properties, such as a fluorine-containing surfactant as described in JP-A-62-1709SO, can be added. A preferable addition amount is 0.01 to 0.01 of the total photosensitive composition.
1% by weight, more preferably 0.005 to 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 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 U.S. Pat. No. 2,714,066, an aluminum plate grained and then immersed in an aqueous sodium silicate solution, U.S. Pat. No. 3,181
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 can be carried out using, for example, an electrolytic solution containing an aqueous or non-aqueous solution of inorganic acids such as phosphoric acid, chromic acid, sulfuric acid, boric acid, etc., or organic acids such as oxalic acid, sulfamic acid, or their salts, either alone or in combination of two or more. This is carried out by passing an electric current through the aluminum plate as an anode.

Also effective is silicate electrodeposition as described in US Pat. No. 3,658,662.

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. It is done to improve the.

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, a surfactant or the like is used in a solvent such as trichlene.

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 ball polishing method, blast polishing method,
There is a brush polishing method in which a water-dispersed slurry of an abrasive such as pumice is rubbed with a nylon brush, and a chemical method is the polishing method using aluminum salts of mineral acids as described in Japanese Patent Application Laid-open No. 5.131187. A method of immersion in a saturated aqueous solution is suitable, and a preferred electrochemical method is alternating current electrolysis in an acidic electrolyte such as hydrochloric acid, nitric acid or a combination thereof. Among these surface roughening methods, a surface roughening method that combines mechanical roughening and electrochemical roughening as described in Japanese Patent Application Laid-open No. 55-137993 is particularly suitable for oil-sensitive images. It is preferable because it has strong adhesive strength to the support.

Graining by the method described above is preferably 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 μ.

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 components is formed on the etched surface. Examples of preferred etching agents include basic substances such as sthorium hydroxide, potassium hydroxide, tristrium phosphate, distrium phosphate, tripotassium phosphate, and dipotassium phosphate; acidic substances such as sulfuric acid. , persulfuric acid, phosphoric acid, hydrochloric acid, and their salts, but salts of metals that have 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 etching surface. .

It is most preferable to use these etching agents at concentrations and temperatures so that the rate of dissolution of the aluminum or alloy used is from 0.3 to 40 g/d per minute of immersion time. There is no problem even if it is higher or lower 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 Log/m.
It is preferable that the treatment be carried out so that it falls within the range of .

As the above-mentioned etching agent, it is preferable to use an aqueous solution of a base because of its high etching rate. In this case, since smut is generated, desmut processing is usually performed. Acids used for desmutting include nitric acid,
Sulfuric acid, phosphoric acid, chromic acid, butic acid, hydrofluoric acid, etc. are used.

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, sulfuric acid, phosphoric acid, chromic acid, oxalic acid, sulfamic acid,
When a direct or alternating current is passed through aluminum in an aqueous or non-aqueous solution containing benzenesulfonic acid or the like or a combination of two or more thereof, an anodic oxide film can be formed on the surface of the aluminum 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.
．． A range of 5 to 60 amperes/dm, voltage of 1 to 100 μm, and electrolysis time of 30 seconds to SO minutes is suitable.

Among these anodizing treatments, the British patent No. 1,
412,768, a method of anodizing at high current density in sulfuric acid, U.S. Pat. No. 4,211,6
19 and U.S. Pat. No. 3,511.661.
The method of anodic oxidation using phosphoric acid as an electrolytic bath, which is described in the above specification, is preferred.

The aluminum plate roughened and further anodized as described above may be subjected to a hydrophilic treatment if necessary. Preferred examples thereof include U.S. Pat. Alkali metal silicates, such as aqueous sodium silicate solutions, as disclosed in Japanese Patent Publication No. 3,622,063, and potassium fluorozirconate, as disclosed in U.S. Pat.
There is a method of treatment with polyvinylsulfonic 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 (for example, zinc chloride and carboxymethyl cellulose, magnesium chloride and hydroxyethyl cellulose, etc.) disclosed in U.S. Patent No. 3,511.661, Acrylamide, Special Publication No. 4635685
Amino acids and their salts (alkali metal salts such as Na salts and K salts, ammonium salts, hydrochlorides, oxalic acid), as disclosed in JP-A-60-1494.91; salt, acetate, phosphate, etc.)
, hydroxyl group-containing amines and their salts (hydrochloride, oxalate,
(phosphoric acid salts, etc.), among which amino acids and their salts, and hydroxyl group-containing amines and their salts are particularly preferred.

The undercoat layer of such a water-soluble compound has a solid content of 1 mg.
/ m to 80 nv/n (preferably).

The developing solution for the photosensitive composition of the present invention includes sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, glL triphosphate,
Sodium diphosphate, ammonium triphosphate, ammonium diphosphate, sodium metasilicate, sulfur bicarbonate
- An aqueous solution of an inorganic alkaline agent such as lithium or aqueous ammonia is suitable, and is added at a concentration of 0.1 to 10% by weight, preferably 0.5 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.

[Effects of the Invention] The photosensitive composition of the present invention has excellent coating properties when coated on a support, and has excellent developability when using an aqueous alkaline developer in the exposed area after coating, drying, and image exposure. Excellent. The relief image obtained has good abrasion resistance, adhesion to the support, and resistance to processing chemicals, 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.

Furthermore, even if erasing is performed using a commercially available erasing liquid, unnecessary images can be quickly erased, resulting in excellent erasing efficiency.

"Examples" 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.

Okuisupa-1 170, 2 g of p-aminohenzenesulfonamide in a 1a three-way flask equipped with a stirrer, cooling tube, and dropping funnel.
(1,0 moffe) and tetrahydrofuran 700
mβ was added, and the mixture was stirred under an ice water tower. To this mixture, 52.3 g (0°5 moAe) of methacrylic acid chloride was added dropwise through a dropping funnel over about 1 hour. After the dropwise addition was completed, the ice water bath was removed, and the mixture was stirred at room temperature for 30 minutes, and further stirred for 1 hour while heating to 60° C. using an oil bath. After the reaction was completed, the reaction mixture was poured into 3β of water with stirring, and the mixture was stirred for 30
After stirring for a minute, the mixture was 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).

9.72 g of N-(p-aminosulfonylphenyl) methacrylamide thus obtained (0°0408 mo
7! e) and methyl methacrylate 7.9'3g (0,
0792moAe), N,N-dimethylbormamide SOmn was placed in a 200 nl three-way flask equipped with a stirrer and a cooling tube, and stirred while heating to 64°C in a hot water bath. Add 0.246 g of αα′αchibisisobutyronitrile to this mixture, and add 0.246 g of αα′αchibis isobutyronitrile to the mixture.
Stir for hours. After the reaction was completed, the reaction mixture was stirred into 2N water, stirred for 30 minutes, filtered and dried to obtain 16 g of white solid. The weight average molecular weight (polystyrene standard) of this polymer compound was measured using Gel Permeation Chroma 1-Graphie and found to be 4900.
It was 0. (Polymer compound (a) of the present invention) 31.0 g of methacrylic acid (0.36 m
le), ethyl chloroformate 39.1g (0.36mo
/e) and 200 m7I of acetonitrile were added, and the mixture was stirred under an ice water tower. Add 36.4 g of triethylamine to this mixture.
(0.36moβe) was added dropwise using a dropping funnel over about 1 hour. After the dropwise addition was completed, the ice-water bath was removed, the mixture was stirred at room temperature for 30 minutes, and an oil bath was attached.

51.7 g (0.30 moAe) of p-aminebenzenesulfonamide 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, the mixture was stirred into 1 ρ of water and stirred for 30 minutes. The solid was collected by filtration, further reslurried in 0 ml of water SO, filtered and dried to obtain a white solid of N-(p-aminosulfonylphenyl)methacrylamide.

(Yield: 46.9 g) Next, 4.61 g of N-(p-aminosulfonylphenyl)methacrylamide (0,0192 moj!) was placed in a 200 ml three-tube flask equipped with a stirrer, condenser, and dropping funnel.
e) 2.94 g of ethyl methacrylate (0.02
58mo[e), acrylonitrile 0.80g (0
. V-65 (manufactured by Wako Pure Chemical Industries, Ltd.) 0.1
5 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, and 0.80 g of acrylonitrile.
, N,N-dimethylacetamide and V-6SO,15
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 and the mixture was cooled, poured into 2 ρ of water with stirring, stirred for 30 minutes, and then overdried to obtain 15 g of a white solid. The weight average molecular weight (polystyrene standard) of this polymer compound was measured by gel permeation chromatography and found to be 53,000.

(Polymer compound (b) of the present invention) Polymer compounds (C) and (d) shown in Table 1 were synthesized in the same manner as in Synthesis Example 1 or 2. The weight average molecules M (polystyrene standard) of these polymer compounds were all 9,000 to 80,000.

Synthesis example 5 N-methacrylylhenzensulfonamide 10゜0g
(0,044 mol), methyl methacrylate 4°46 g
(0,044 mol), 22 m of 2-methoxyethanol
Copolymerization was carried out in .rho. using 0.0213 g of V-65C2,2'-azobis-(2,4-dimethylhaleo)nitrile as an initiator.

After stirring at 60°C for 7 hours, 2-methoxyethanol 5 Qmj! was added and reprecipitated into 2A of water.

The resulting polymer was dissolved in 100 ml of tetrahydrofuran and reprecipitated in 1.5 ml of methanol to obtain 10.2 g of the polymer compound (e) shown in Table 1. (1
w=200.000, yield 70%) The constituent molar ratio is 'H-
Determined by NMR.

Examples 1 to 9 and Comparative Examples 1 to 10 After graining the surface of an aluminum plate with a thickness of 0.241 m using a nylon brush and 400 mesh of bumstone-water suspension, the substrate CI) was thoroughly washed with water. Prepared. The substrate [1] was etched by immersing it in 10% sodium hydroxide at 70°C for 20 seconds, then washing with running water, and etching it for 20 seconds.
Neutralization cleaning with %HNO3, washing with water, and electrolytic surface roughening treatment with an electricity amount of 400 coulombs/d% in a 0.7% nitric acid aqueous solution using a sinusoidal alternating waveform current under the condition of 12.7V. The substrate (11) was prepared by washing with water.

This substrate [11] was treated in a 10% aqueous sodium hydroxide solution so that the amount dissolved on the surface was 0.9 g/n.

After washing with water, neutralize in 20% nitric acid solution, wash and desmut, and then wash in 18% sulfuric acid aqueous solution to reduce the amount of oxide film to 3.
Anodized to g/rl.

Next, nine types of photosensitive liquids (A) were prepared in which the type of polymer compound of the present invention and the type of organic acid of the present invention were changed in the following photosensitive liquid (A).
)-1 to (A:l-9) were prepared.

For comparison, photosensitive liquid (A) was used as an organic acid, and pK
Using a compound with a larger than 3 (or without adding an organic acid), seven types of photosensitive solutions (A)-10 to (A:1-16) were prepared with different polymeric compounds of the present invention. .

Furthermore, as a comparative example, the following photosensitive solution CB) which does not use the polymer compound of the present invention was used, the type of organic acid of the present invention was changed, and (
or not added) 3 types of photosensitive liquids CB)-1 to CB
)-3 was prepared.

These photosensitive solutions were applied to the substrate (CHI) and heated at 100°C for 2
After drying for a minute, each photosensitive planographic printing plate (A)-1~
(A)-16 and CB)-1 to CB)-3 were produced. The coating amount at this time was 2.3 g/r+ (dry weight).

The polymer compound of the present invention used in the photosensitive liquid, the organic acid of the present invention, or the organic acid used as a comparative example was
Shown in the table.

Photosensitive liquid CA) 02.3. Esterified product of 4-trihydroxyhensiphenone and naphthoquinone-1,2-diazide-5-sulfonyl chloride (esterification rate: 90 mo 12%) O Polymer compound of the present invention 0 Wood invention organic acid 0-cresol (60% meta, 40% ortho)-formaldehyde resin (weight average molecular weight: 4,000) 02-(p-meI xyphenyl) 46-bis(trichloromethyl) S-triazine 0 Naphthoquinone-1,2-diazidosulfonyl chloride 0 Victoria Pure Blue BOH (dye manufactured by Hodogaya Chemical ■) 0 Megafac F-177 (manufactured by Dainippon Ink Chemical Co., Ltd.) Fluorine surfactant) Q Dimethylformamide 01 -Methoxy-2-propatol 0 Methyl ethyl ketone 0.45g 0.77g 0.007g 0.33g 0.02g 0.01g 0.015g 0.004g Photosensitive solution CB) In the photosensitive solution (A), the polymer compound of the present invention Cresol (60% meta form, 40% ortho form)-formaldehyde resin (average molecular weight: 4.000) without using
g Photosensitive liquid used.

Photosensitive lithographic printing plates (A)-1 to (A)-16 and (B)
Positive transparent originals of line drawings and halftone dot images were brought into close contact with the photosensitive layers of -1 to CB)-3, and exposure was performed from a distance of 1 m using a 2 kW metal halide lamp. D the exposed printing plate
The film was immersed and developed in an 8-fold diluted aqueous solution of P-4 (trade name: manufactured by Fuji Photo Film ■) at 25° C. for 60 seconds.

Erasing speed of the obtained lithographic printing plate (see notes to Table 2)
was measured to examine the efficiency of the erasure task. In addition, the printing durability is
A comparison was made by examining the number of normal prints printed using UV ink and oil-based ink.

Chemical resistance was evaluated by immersing it in chemicals and examining the erosion properties of the image area.

In addition, in order to examine the developability, exposed photosensitive planographic printing plates (A)-1 to (A)-16 and CB)1 to CB)-3 were
was treated with a fatigued developer with reduced activity, and the lithographic printing plate was printed to examine the occurrence of stains.

These results are shown in Table 2.

As is clear from Table 2, the photosensitive composition of the present invention is
This is an epoch-making product that satisfies all of the requirements of erasing speed, rigidity when using UV ink, printing durability when using oil-based ink, processing chemical resistance, and developability, which shows how superior the present invention is. .

Procedural amendment

Claims (1)

[Scope of Claims] (a) A photosensitive compound that acts in a positive manner; (b) A polymer compound that is insoluble in water and soluble in an alkaline aqueous solution, containing an -SO_2-NH- bond in its side chain or main chain. , and (c) a photosensitive composition containing an organic acid having a pKa value of 3 or less.