JPH087438B2 - Photosensitive composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a photosensitive composition suitable for producing a lithographic printing plate, an IC circuit, a photomask and the like. More specifically, it relates to a photosensitive composition comprising a negative-working photosensitive compound and a polymer compound having excellent abrasion resistance and solubility in an alkaline aqueous solution.

[Conventional technology]

The majority of what is used as a photosensitive substance in a negative type photosensitive composition is a diazonium compound, and the most commonly used one is a diazo resin represented by a formaldehyde condensation product of p-diazodiphenylamine. is there.

The composition of the photosensitive layer of the photosensitive lithographic printing plate using a diazo resin, for example, as described in U.S. Pat.No. 2,714,066, the diazo resin alone, that is, without a binder, for example, As described in JP-A-50-30604, it can be classified into a mixture of a binder and a diazo resin, but in recent years, most of photosensitive lithographic printing plates using a diazonium compound have It is composed of a diazonium compound and a polymer that serves as a binder to provide high printing durability.

As such a photosensitive layer, as described in JP-A-50-30604, a so-called alkali developing type in which an unexposed portion is removed (developed) by an aqueous alkaline developer, and an organic solvent-based developer are used. The so-called solvent-developable type that can be removed is known, but the alkali-developable type is drawing attention from the viewpoint of occupational safety and health, and this is mainly determined by the properties of the binder. As a method of imparting alkali developability to the binder, a carboxylic acid-containing monomer is copolymerized as described in JP-A-50-30604, or U.S. Pat.
There is a method of introducing a carboxylic acid into a polymer by reacting a hydroxyl group of polyvinyl alcohol with a cyclic acid anhydride such as phthalic anhydride as described in No. 8, but the obtained polymer is Due to its structure, abrasion resistance was poor, and only a lithographic printing plate having a low printing durability could be obtained from the photosensitive lithographic printing plate containing such a binder in the photosensitive layer. On the other hand, polyvinyl acetal has a drawback that it forms a tough film and has abrasion resistance, but only an organic solvent-developing photosensitive lithographic printing plate can be obtained.

Further, many attempts have been made to use a photopolymerizable composition as a photosensitive image-forming layer of a negative-working photosensitive lithographic printing plate.
-32714 discloses a basic composition comprising a polymer as a binder, a monomer and a photopolymerization initiator as disclosed in JP-A-32714, and an unsaturated double bond as a binder as disclosed in JP-B-49-34041. Compositions having improved curing efficiency by introducing a bond, Japanese Patent Publication Nos. 48-38403 and 53-27605, and British Patent 1,388,492
Compositions using a novel photopolymerization initiator as disclosed in the specification and the like are known, and some of them are put to practical use. Sensitivity is greatly affected by the surface temperature of the photosensitive lithographic printing plate of
In addition, there is a drawback in that polymerization is strongly inhibited by oxygen during image exposure.

On the other hand, when the negative photosensitive lithographic printing plate is subjected to post-exposure development, examples of the aqueous alkaline developer composition used include, for example, benzyl alcohol and anionic interface described in JP-A-51-77401. A developer composition comprising an activator, an alkali agent and water, a developer composition comprising an aqueous solution containing benzyl alcohol, an anionic surfactant, and a water-soluble sulfite described in JP-A-53-44202. JP-A-55-155355, a developer composition containing an organic solvent having a solubility in water of 10% by weight or less at room temperature, an alkaline agent and water, and the like.

Each of these contains an organic substance such as an organic solvent and a surfactant in the developer composition. However, the organic solvent generally has toxicity and odor, has a risk of fire, and has many drawbacks such as being subject to BOD regulation even in the waste liquid, and the cost becomes high. Further, the surfactant has a problem that bubbles are generated during the developing operation, and it is desirable to use a developer composition which does not substantially contain these organic substances.

On the other hand, as a developer composition containing substantially no such organic substances, there is a developer composition described in JP-A-59-84241. However, these developer compositions are used when developing a positive-working photosensitive lithographic printing plate containing an o-naphthoquinonediazide compound as a photosensitive compound, and these developer compositions containing substantially no organic substance are used. make use of,
When the negative photosensitive lithographic printing plate described above was developed, it could not be developed without producing a residual film, and there was a problem that proper developability such as yellowing of the unexposed area could not be obtained. .

In the present invention, "substantially free of organic matter" means that the proportion of the substance in the composition is 3% by weight or less from the viewpoint of safety, but preferably 1% by weight. % Or less.

[Problems to be Solved by the Invention]

Therefore, an object of the present invention is to provide a photosensitive composition which gives a lithographic printing plate having high abrasion resistance of a polymer compound used as a binder and high printing durability.

Still another object of the present invention is to obtain a proper development when the polymer compound used as a binder is excellent in solubility in an alkaline aqueous solution and is developed after exposure by an aqueous alkaline developer containing an organic solvent and / or an organic substance such as a surfactant. Property is obtained, and with an aqueous alkaline developer that does not substantially contain these organic substances, even when developed after exposure,
It is an object of the present invention to provide a photosensitive composition which gives a lithographic printing plate capable of obtaining proper developability.

[Means for solving the problem]

As a result of intensive studies to achieve the above objects, the present inventors have found that these objects can be achieved by using a novel photosensitive composition, and have reached the present invention.

That is, the present invention provides a photosensitive composition characterized by containing a polymer compound having a —SO ₂ NH— group, which is insoluble in water and soluble in an alkaline aqueous solution, and a photosensitive compound which acts negatively. To do.

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

The —SO ₂ NH— group-containing polymer compound and other components used in the present invention, and the method for producing and using the photosensitive composition of the present invention will be described in detail below.

(1) Polymer Compound Containing —SO ₂ NH— Group The polymer compound having the —SO ₂ NH— group used in the present invention, which is insoluble in water and soluble in an alkaline aqueous solution, is preferably a side chain or a main chain. a polymer compound containing a -SO ₂ NH- group in the chain, more preferably a polymer compound containing a -SO ₂ NH- group in the side chain.

Incidentally, in the present invention, the —SO ₂ NH— group has only one group on N.
A sulfonylamino group having two hydrogen atoms bonded to each other, N
It does not include a sulfonylamino group having two hydrogen atoms bonded to it.

A polymer compound having a —SO ₂ NH— group, which is preferably used in the present invention, and which is insoluble in water and soluble in an alkaline aqueous solution, is one or more —SO ₂ NH— groups and one or more —SO ₂ NH— groups in a molecule. It can be obtained by polymerizing a low molecular weight compound having a polymerizable unsaturated bond in a suitable solvent using a known polymerization initiator.

In the present invention, such a low molecular weight compound preferably used is a compound represented by the general formula (I) or (II).

In the formula, X represents O or NH. R ¹ and R ⁴ are H or
Indicates CH ₃ . R ² and R ⁵ each represent an optionally substituted C _{1 to} C ₁₂ alkylene group, cycloalkylene group, arylene group, or aralkylene group, and R ³ and R ⁶ each have a substituent. And optionally a C _{1 to} C ₁₂ alkyl group, cycloalkyl group, aryl group, or aralkyl group.

Among the low molecular weight compounds represented by the general formula (I) or (II), those particularly preferably used in the present invention are R ² and R ⁵
There alkylene C ₂ -C ₆ respectively, a cycloalkylene group or a phenylene group which may have a substituent, a naphthylene group, R ^3, an alkyl group of R ⁶ is C ₁ -C ₆ respectively, cyclo It is a compound which is a phenyl group or a naphthyl group which may have an alkyl group or a substituent.

Examples of such a low molecular weight compound include N- (o
-Methylaminosulfonylphenyl) methacrylamide, N- (m-methylaminosulfonylphenyl) methacrylamide, N- (p-methylaminosulfonylphenyl) methacrylamide, N- (o-ethylaminosulfonylphenyl) methacrylamide, N- (M-Ethylaminosulfonylphenyl) methacrylamide, N-
(P-Ethylaminosulfonylphenyl) methacrylamide, N- (on-propylaminosulfonylphenyl) methacrylamide, N- (mn-propylaminosulfonylphenyl) methacrylamide, N- (pn)
-Propylaminosulfonylphenyl) methacrylamide, N- (o-i-propylaminosulfonylphenyl) methacrylamide, N- (m-i-propylaminosulfonylphenyl) methacrylamide, N- (p-i
-Propylaminosulfonylphenyl) methacrylamide, N- (on-butylaminosulfonylphenyl)
Methacrylamide, N- (mn-butylaminosulfonylphenyl) methacrylamide, N- (pn-butylaminosulfonylphenyl) methacrylamide, N-
(O-i-butylaminosulfonylphenyl) methacrylamide, N- (m-butylaminosulfonylphenyl) methacrylamide, N- (p-i-butylaminosulfonylphenyl) methacrylamide, N- (o-se
c-Butylaminosulfonylphenyl) methacrylamide, N- (m-sec-butylaminosulfonylphenyl) methacrylamide, N- (p-sec-butylaminosulfonylphenyl) methacrylamide, N- (ot
-Butylaminosulfonylphenyl) methacrylamide, N- (mt-butylaminosulfonylphenyl)
Methacrylamide, N- (pt-butylaminosulfonylphenyl) methacrylamide, N- (p-hydroxyethylaminosulfonylphenyl) methacrylamide, N- (o-phenylaminosulfonylphenyl) methacrylamide, N- (m- Phenylaminosulfonylphenyl) methacrylamide, N- (p-phenylaminosulfonylphenyl) methacrylamide, 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-methylaminosulfonyl) naphthyl) methacrylamide, N- (1- (3-
Ethylaminosulfonyl) naphthyl) methacrylamide, N- (o-methylsulfonylaminophenyl) methacrylamide, N- (m-methylsulfonylaminophenyl) methacrylamide, N- (p-methylsulfonylaminophenyl) methacrylamide, N- (O-Ethylsulfonylaminophenyl) methacrylamide, N-
(M-ethylsulfonylaminophenyl) methacrylamide, N- (p-ethylsulfonylaminophenyl) methacrylamide, N- (o-phenylsulfonylaminophenyl) methacrylamide, N- (m-phenylsulfonylaminophenyl) methacrylamide, N- (p-
Phenylsulfonylaminophenyl) methacrylamide, N- (o- (p-methylphenylsulfonylamino) phenyl) methacrylamide, N- (m- (p-methylphenylsulfonylamino) phenyl) methacrylamide, N- (p- ( p-methylphenylsulfonylamino) phenyl) methacrylamide, N- (p- (α-
Naphthylsulfonylamino) phenyl) methacrylamide, N- (p- (β-naphthylsulfonylamino) phenyl) methacrylamide, N- (2-methylsulfonylaminoethyl) methacrylamide, N- (2-ethylsulfonylaminoethyl) methacryl Amide, N- (2-
Phenylsulfonylaminoethyl) methacrylamide,
N- (2-p-methylphenylsulfonylaminoethyl) methacrylamide, N- (2-α-naphthylsulfonylaminoethyl) methacrylamide, N- (2-β-
Methacrylamides such as naphthylsulfonylamino) ethylmethacrylamide, acrylamides having the same substituents as described above, o-methylaminosulfonylphenyl methacrylate, m-methylaminosulfonylphenyl methacrylate, p-methylaminosulfonylphenyl methacrylate, o. -Ethylaminosulfonylphenyl methacrylate, m-ethylaminosulfonylphenyl methacrylate, p-ethylaminosulfonylphenyl methacrylate, on-propylaminosulfonylphenyl methacrylate, m-n-propylaminosulfonylphenyl methacrylate, pn-propylaminosulfonyl Phenyl methacrylate, o-i-propylaminosulfonylphenyl methacrylate, m-i
-Propylaminosulfonylphenyl methacrylate,
p-i-propylaminosulfonylphenyl methacrylate, o-n-butylaminosulfonylphenyl methacrylate, m-n-butylaminosulfonylphenyl methacrylate, p-n-butylaminosulfonylphenyl methacrylate, m-i-butylaminosulfonylphenyl methacrylate, p-i-butylaminosulfonylphenyl methacrylate, m-sec-butylaminosulfonylphenyl methacrylate, p-sec-butylaminosulfonylphenyl methacrylate, m-t-butylaminosulfonylphenyl methacrylate, p-t-
Butylaminosulfonylphenyl methacrylate, o-
Phenylaminosulfonyl phenyl methacrylate, m
-Phenylaminosulfonylphenyl methacrylate,
p-Phenylaminosulfonylphenyl methacrylate, m- (α-naphthylaminosulfonyl) phenyl methacrylate, p- (α-naphthylaminosulfonyl)
Phenyl methacrylate, m- (β-naphthylaminosulfonyl) phenyl methacrylate, p- (β-naphthylaminosulfonyl) phenyl methacrylate, 1-
(3-Methylaminosulfonyl) naphthyl methacrylate, 1- (3-ethylaminosulfonyl) naphthyl methacrylate, o-methylsulfonylaminophenyl methacrylate, m-methylsulfonylaminophenyl methacrylate, p-methylsulfonylaminophenyl methacrylate, o-ethylsulfonyl Aminophenyl methacrylate, m-ethylsulfonylaminophenyl methacrylate, p-ethylsulfonylaminophenyl methacrylate, o-phenylsulfonylaminophenyl methacrylate, m-phenylsulfonylaminophenyl methacrylate, p-phenylsulfonylaminophenyl methacrylate, o- (p-methyl Phenylsulfonylamino) phenyl methacrylate, m- (p-methylphenylsulfoni) Amino) phenyl methacrylate,
p- (p-methylphenylsulfonylamino) phenyl methacrylate, p- (α-naphthylsulfonylamino) phenyl methacrylate, p- (β-naphthylsulfonylamino) phenyl methacrylate, 2-methylsulfonylaminoethyl methacrylate, 2-ethylsulfonylamino Ethyl methacrylate, 2-phenylsulfonylaminoethyl methacrylate, 2-p-methylphenylsulfonylaminoethyl methacrylate, 2-α
-Naphthylsulfonylaminoethyl methacrylate, 2
Methacrylic acid esters such as -β-naphthylsulfonylaminoethyl methacrylate, acrylic acid esters having the same substituents as described above, and the like can be mentioned.

The polymer compound having a —SO ₂ NH— group, which is preferably used in the present invention, contains one or more —SO ₂ NH— groups and 1 in the above molecule.
It may be a homopolymer or a copolymer of two or more low molecular weight compounds having one or more polymerizable unsaturated bonds, but preferably contains one or more polymerizable unsaturated bonds,
And a copolymer of one or more low molecular weight compound that does not contain -SO ₂ NH- group.

Contains such a polymerizable unsaturated bond, and -SO
₂ NH-group-free compounds include, for example, acrylic acid, methacrylic acid, acrylic acid esters, acrylamides, methacrylic acid esters, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, crotonic acid. Examples thereof include compounds having a polymerizable unsaturated bond selected from esters and the like. Specifically, for example, acrylates, for example, alkyl (the alkyl group preferably has 1 to 10 carbon atoms) acrylate (for example, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, acrylic Amyl acid, ethylhexyl acrylate, octyl acrylate, tert-octyl acrylate, chloroethyl acrylate, allyl acrylate, 2-hydroxyethyl acrylate, 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate,
Trimethylolpropane monoacrylate, pentaerythritol monoacrylate, glycidyl acrylate, benzyl acrylate, methoxybenzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, etc.), aryl acrylate (eg, phenyl acrylate): methacrylic esters, eg, alkyl (The alkyl group has 1 carbon atom.
Methacrylate (e.g., methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, allyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, glycidyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, etc.), arylmethyl Acrylate (e.g., phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, etc.): acrylamides such as acrylamide, as the N- alkyl acrylamide (the alkyl group, those having 1 to 10 carbon atoms, such as methyl group,
Examples thereof include an ethyl group, a propyl group, a butyl group, a t-butyl group, a heptyl group, an octyl group, a cyclohexyl group, a hydroxyethyl group and a benzyl group. ) N-arylacrylamide (as the aryl group, for example, a phenyl group,
Examples include tolyl group, nitrophenyl group, naphthyl group and hydroxyphenyl group. ), N, N-dialkylacrylamide (the alkyl group has 1 to 10 carbon atoms, for example, methyl group, ethyl group, butyl group, isobutyl group, ethylhexyl group, cyclohexyl group, etc.), N, N-arylacrylamide (the aryl group includes, for example, a phenyl group), N-methyl-N-phenylacrylamide, N-hydroxyethyl-N-methylacrylamide, N-2-acetamidoethyl-N-acetylacrylamide. , N- (phenylsulfonyl) acrylamide, N- (p-methylphenylsulfonyl) acrylamide, etc .: methacrylamides such as methacrylamide, N-alkylmethacrylamide (wherein the alkyl group is one having 1 to 10 carbon atoms) , For example, methyl group, ethyl group, t-butyl group, A tylhexyl group, a hydroxyethyl group, a cyclohexyl group and the like), N-arylmethacrylamide (the aryl group includes a phenyl group and the like), N, N-
Dialkyl acrylamide (the alkyl group includes ethyl group, propyl group, butyl group, etc.), N, N-
Diarylmethacrylamide (as the aryl group,
There is a phenyl group. ), N-hydroxyethyl-N
-Methylmethacrylamide, N-methyl-N-phenylmethacrylamide, N-ethyl-N-phenylmethacrylamide, N- (phenylsulfonyl) methacrylamide, N- (p-methylphenylsulfonyl) methacrylamide: allyl compound, for example Allyl esters (eg, allyl acetate, allyl caproate, allyl caprylate,
Allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, etc.), allyloxyethanol, etc .; vinyl ethers such as alkyl vinyl ethers (eg hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, etc.) Methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-
Dimethylpropyl vinyl ether, 2-ethylbutyl 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 (for example, vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2,4-dichlorophenyl ether, vinyl naphthyl ether, vinyl anthranyl ether, etc.): vinyl esters such as vinyl butyrate, vinyl isoether Butyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl barrate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, vinylphenyl acetate, vinyl acetoacetate, vinyl lactate, vinyl-β. -Phenylbutyrate, vinylcyclohexylcarboxylate,
Vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate, etc .: Styrenes such as styrene, alkylstyrenes (eg methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, isopropylstyrene, Butyl styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, benzyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxymethyl styrene, acetoxymethyl styrene, etc.), alkoxy styrene (eg methoxy styrene, 4-methoxy-3-methyl styrene, Dimethoxystyrene etc.), halogenostyrene (eg chlorostyrene, dichlorostyrene, trichlorostyrene,
Tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-
Trifluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene, etc.): Crotonic acid esters, for example, alkyl crotonic acid (eg, butyl crotonic acid, hexyl crotonic acid, glycerin monocrotonate, etc.): Dialkyl itaconic acid ( For example, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, etc.): dialkyls of maleic acid or fumaric acid (eg, dimethyl maleate, dibutyl fumarate, etc.): acrylonitrile, methacrylonitrile, etc.

Of these compounds having a polymerizable unsaturated bond, preferably used are methacrylic acid esters, acrylic acid esters, methacrylamides, acrylamides, acrylonitrile, methacrylonitrile, methacrylic acid, acrylic acid. is there.

One or more of these compounds having a polymerizable unsaturated bond and one or more copolymers containing a —SO ₂ NH— group and having a polymerizable unsaturated bond may be a block, random or graft. Any body or the like can be used.

In these copolymers, the constitutional unit containing a —SO ₂ NH— group is 5 relative to all the constitutional units constituting the copolymer.
It is preferably contained in an amount of not less than mol%, more preferably 10 to 90 mol%.

As a solvent used when synthesizing such a polymer compound, for example, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, 1- Methoxy-2-propanol, 1
-Methoxy-2-propyl acetate, N, N-dimethylformamide, toluene, ethyl acetate, methyl lactate, ethyl lactate and the like.

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

The weight average molecular weight of the polymer compound of the present invention is preferably 2,000 or more, more preferably 5,000 to 300,000. The polymer compound of the present invention may be used alone or in combination. The content of these high molecular compounds in the photosensitive composition is about 5 to 95% by weight, preferably about 10 to 85% by weight.

(2) Negative-acting diazonium compound Examples of the negative-acting diazonium compound used in the present invention include diazonium compounds described in U.S. Pat. No. 3,867,147, diazonium compounds described in U.S. Pat. No. 2,632,703, etc., but particularly aromatic diazonium salts. Useful are diazo resins represented by, for example, condensation products of an active carbonyl-containing compound (eg formaldehyde). Preferred diazo resins include, for example, hexafluorophosphate, tetrafluoroborate and phosphate of a condensate of p-diazodiphenylamine and formaldehyde or acetaldehyde. Also, U.S. Pat.
Sulfonates of condensates of p-diazodiphenylamine and formaldehyde as described in No. 309 (eg p-toluenesulfonate, dodecylbenzenesulfonate, 2-methoxy-4-hydroxy-5-benzoyl). Benzene sulfonate, etc.), phosphinate (eg, benzene phosphinate), hydroxy group-containing compound salt (eg, 2,4-dihydroxybenzophenone salt), organic carboxylate and the like are also preferable.

Furthermore, as shown in JP-A-58-27141, 3-
Also suitable is a mesitylene sulfonate formed by condensing methoxy-4-diazodiphenylamine with 4,4'-bis-methoxy-methyl-diphenyl ether.

The content of these diazonium compounds in the photosensitive composition is 1 to 50% by weight, preferably 3 to 20% by weight. If necessary, two or more diazonium compounds may be used in combination.

(3) Polymerizable Monomer / Photopolymerization Initiator In the present invention, the monomer that can be added to the photosensitive composition has a boiling point of 100 ° C. or higher at atmospheric pressure, at least one in one molecule, and more preferably two. The above-mentioned addition-polymerizable ethylenically unsaturated group-containing monomer or oligomer having a molecular weight of 10,000 or less. Examples of such monomers or oligomers include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; polyethylene glycol di ((meth) acrylate, polypropylene Glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, Hexanediol di (meth) acrylate, tri (acryloyloxyethyl) isocyanate, glycerin and trimethylolethane Those polyhydric alcohol after adding ethylene oxide or propylene oxide (meth) acrylated etc., JP-B-48-41708, JP-B-50-6034, JP 51
-37193, urethane acrylates as described in each publication, JP-A-48-64183, JP-B-49-43191,
Polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates obtained by reacting an epoxy resin with (meth) acrylic acid, which are described in JP-B No. 52-30490, can be mentioned. Further, those introduced as photocurable monomers and oligomers in Japan Adhesive Association Magazine Vol. 20, No. 7, pages 300 to 308 can also be used.

These monomers or oligomers and --SO ₂ N of the present invention
The composition ratio of the polymer compound having an H-group is 5:95 to 70: by weight.
A range of 30 is preferable, and a more preferable range is 10:90 to 50:50.
Is.

Photoinitiators that can be added to the photosensitive composition of the present invention are vicinal polyketaldonyl compounds disclosed in U.S. Pat.No. 2,367,660, U.S. Pat.
Α-disclosed in 7,661 and 2,367,670
Carbonyl compounds, acyloin ethers disclosed in US Pat. No. 2,448,828, US Pat.
Aromatic acyloin compounds substituted in the α-position with a hydrocarbon disclosed in No. 2, U.S. Pat.Nos. 3,046,127 and 2,951,758, divergent quinone compounds, U.S. Pat.No. 3,549,367 Triarylimidazole dimer / p-aminophenyl ketone combinations disclosed in U.S. Pat.No. 3,870,524, benzothiazole-based compounds disclosed in U.S. Pat.
Examples include acridine and phenazine compounds disclosed in 751,259, oxadiazole compounds disclosed in US Pat. No. 4,212,970, and the like.

Preferably, a trihalomethyl-S-triazine compound or a trihalomethyloxadiazole compound represented by the following general formula (III) or (IV) is exemplified.

In the formula, R ⁸ represents a substituted or unsubstituted aryl or alkenyl group, and R ⁷ represents R ⁸ , —CY ₃ or a substituted or unsubstituted alkyl group. Y represents a chlorine atom or a bromine atom.

Examples of the compound represented by the general formula (III) include Wakabayashi et al., Bull. Chem. Soc. Japan, Volume 42, 2924 (1969).
), The compounds described in British Patent No. 1,388,492, West German Patent No. 2,718,259, and West German Patent No. 3,337,024. Specifically, the following compounds are included.

That is, 2-phenyl-4,6-bis (trichloromethyl) -S-triazine, 2- (p-chlorophenyl)-
4,6-bis (trichloromethyl) -S-triazine, 2
-(P-Tolyl) -4,6-bis (trichloromethyl)-
S-triazine, 2- (p-methoxyphenyl) -4,6
-Bis (trichloromethyl) -S-triazine, 2-
(2 ', 4'-Dichlorophenyl) -4,6-bis (trichloromethyl) -S-triazine, 2,4,6-tris (trichloromethyl) -S-triazine, 2-methyl-4,6-
Bis (trichloromethyl) -S-triazine, 2-n-
Nonyl-4,6-bis (trichloromethyl) -S-triazine, 2- (α, α, β-trichloroethyl) -4,6-
Bis (trichloromethyl) -S-triazine, 2-styryl-4,6-bis (trichloromethyl) -S-triazine, 2- (p-methylstyryl) -4,6-bis (trichloromethyl) -S-triazine , 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -S-triazine, 2- (4-methoxy-naphth-1-yl) -4,
6-bis (trichloromethyl) -S-triazine, 2-
(4-Ethoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -S-triazine, 2- [4- (2-
Ethoxyethyl) -naphth-1-yl] -4,6-bis (trichloromethyl) -S-triazine, 2- (4,7-
Dimethoxy-naphth-1-yl] -4,6-bis (trichloromethyl) -S-triazine, 2- (acenaphtho-5
-Yl) -4,6-bis (trichloromethyl) -S-triazine, 2- (4-styrylphenyl) -4,6-bis (trichloromethyl) -S-triazine and the like are included.

Examples of the compound represented by the general formula (IV) include compounds described in JP-A-54-74728, JP-A-55-77742, and JP-A-59-148784. Specifically, the following compounds are included.

That is, 2-styryl-5-trichloromethyl-1,3,4
-Oxadiazole, 2- (4-chlorostyryl) -5
-Trichloromethyl-1,3,4-oxadiazole, 2-
(4-methylstyryl) -5-trichloromethyl-1,3,
4-oxadiazole, 2- (4-methoxystyryl)
-5-trichloromethyl-1,3,4-oxadiazole,
2- (4-butoxystyryl) -5-trichloromethyl-1,3,4-oxadiazole, 2- (4-styrylstyryl) -5-trichloromethyl-1,3,4-oxadiazole, 2- Phenyl-5-trichloromethyl-1,3,4-
Oxadiazole, 2- (4-methoxyphenyl) -5
-Trichloromethyl-1,3,4-oxadiazole, 2-
(3,4-Dimethoxyphenyl) -5-trichloromethyl-1,3,4-oxadiazole, 2- (4-styrylphenyl) -5-trichloromethyl-1,3,4-oxadiazole, 2- (1-naphthyl) -5-trichloromethyl-
1,3,4-oxadiazole and the like are included.

If necessary, a sensitizer can be added to the photosensitive composition of the present invention. Specifically, an aromatic thiazole compound shown in JP-B-59-28328, a merocyanine dye shown in JP-A-54-151024, an aromatic thiopyrylium salt shown in JP-A-58-40302, and Examples thereof include light absorbing agents such as aromatic pyrylium salts, 9-phenylacridine, 5-nitroacenaphthene, and ketochlorins. Further, a system in which a hydrogen donor such as N-phenylglycidin, 2-mercaptobenzothiazole, ethyl N, N'-dimethylaminobenzoate, or the like is combined is also effectively used in the present invention.

In the present invention, the amount of the photopolymerization initiator and / or the sensitizer is determined by the amount of the photopolymerizable ethylenically unsaturated compound and the amount of-of the present invention.
0.01 with respect to the total of SO ₂ NH-group-containing polymer compounds
A range of from 20% to 20% by weight is sufficient, more preferably from 0.5% to 10% by weight gives good results.

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

(4) Other components In the composition of the present invention, in addition to the polymer compound having the —SO ₂ NH— group, phenol formaldehyde resin, cresol formaldehyde resin, phenol modified xylene resin, polyhydroxystyrene, polyhalogenated compound. Hydroxystyrene and carboxyl group-containing epoxy resin,
Polyacetal resin, acrylic resin, methacrylic resin,
A known alkali-soluble polymer compound such as a carboxyl group-containing polyurethane resin can be contained. Such an alkali-soluble polymer compound is used in an amount of 70% by weight or less based on the total composition.

In the composition of the present invention, additives such as a printout agent for obtaining a visible image immediately after exposure, a dye as an image colorant, a pigment, a stabilizer, a surfactant, a plasticizer and other fillers are added. Can be added.

As a printing-out agent for obtaining a visible image immediately after exposure, a combination of a photosensitive compound that releases an acid upon exposure and an organic dye capable of forming a salt can be exemplified. Specifically, a combination of o-naphthoquinonediazide-4-sulfonic acid halogenide and a salt-forming organic dye described in JP-A-50-36209 and JP-A-53-8128, And combinations of trihalomethyl compounds and salt-forming organic dyes described in JP-A-36223 and JP-A-54-74728. As the image colorant, dyes other than the above-mentioned salt-forming organic dyes can be used.
Suitable dyes including salt-forming organic dyes include oil-soluble dyes and basic dyes. Specifically, Oil Yellow # 101, Oil Yellow # 130, Oil Pink # 312, Oil Green BG, Oil Blue BOS, Oil Blue # 603, Oil Black BY, Oil Black BS, Oil Black T-505 (above, Orient Chemical Industry Co., Ltd.), Victoria Pure Blue, Crystal Violet (CI42555), Methyl Violet (CI42535),
Rhodamine B (CI45170B), Malachite green (CI42
000) and methylene blue CI52015).

When combined with a diazonium compound, as the stabilizer, phosphoric acid, phosphorous acid, pyrophosphoric acid, oxalic acid, boric acid,
p-toluenesulfonic acid, benzenesulfonic acid, p-hydroxybenzenesulfonic acid, 2-methoxy-4-hydroxy-5-benzoyl-benzenesulfonic acid, malic acid, tartaric acid, dipicolinic acid, polyacrylic acid and copolymers thereof, Polyvinylphosphonic acid and its copolymer, polyvinylsulfonic acid and its copolymer, 5-nitronaphthalene-1-phosphonic acid, 4-chlorophenoxymethylphosphonic acid, sodium phenyl-methyl-pyrazolone sulfonate, 2-phosphonobutane tricarboxylic acid -1,2,
4,1-phosphonoethanetricarboxylic acid-1,2,2,1-hydroxyethane-1,1-disulfonic acid and the like.

In addition, when a combination of a polymerizable monomer and a photopolymerization initiator is used, a small amount of the polymerizable ethylenically unsaturated compound is prevented during production or storage of the photosensitive composition to prevent unnecessary thermal polymerization. It is desirable to add a thermal polymerization inhibitor. Suitable thermal polymerization inhibitors include hydroquinone, p-methoxyphenol, di-t-butyl-p-
Cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-
Butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2-mercaptobenzimidazole, N-nitrosophenylhydroxyamine primary cerium salt and the like.

Further, alkyl ethers (eg, ethyl cellulose, methyl cellulose) for improving coating properties, surfactants (eg, fluorine-based surfactants), plasticizers for imparting film flexibility and abrasion resistance (eg, triacetate). Cresyl phosphate, dimethyl phthalate, dibutyl phthalate, trioctyl phosphate, tributyl phosphate, tributyl citrate, polyethylene glycol, polypropylene glycol, etc.) can be added. The amount of these additives added varies depending on the intended purpose, but generally 0.5 to 30% by weight based on the total solid content of the photosensitive layer.
Is.

The photosensitive composition of the present invention is dissolved in a solvent that dissolves each of the above components and applied onto a support. As the solvent used here, methanol, ethanol, isopropanol,
n-butanol, t-butanol, ethylene dichloride, cyclohexanone, acetone, methyl ethyl ketone, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether,
2-methoxyethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate,
There are N, N-dimethylformamide, tetrahydrofuran, dioxane, dimethylsulfoxide, ethyl acetate, methyl lactate, ethyl lactate and the like, and these solvents are used alone or as a mixture.

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

When the photosensitive solution dissolved in these solvents is applied and dried, it is desirable to dry at 50 ° C to 120 ° C. As a drying method, the temperature may be lowered at the beginning and pre-dried and then dried at a high temperature, or may be directly dried at a high temperature by selecting an appropriate solvent and concentration.

Further, the coating amount varies depending on the use, but in the case of a photosensitive lithographic printing plate, for example, the solid content is generally 0.5 to 3.0.
g / m ² is preferred. Although the photosensitivity increases as the coating amount decreases, the physical properties of the photosensitive film deteriorate.

The support to which the photosensitive composition of the present invention is applied is, for example, paper, paper laminated with plastics (for example, polyethylene, polypropylene, polystyrene, etc.), for example, aluminum (including aluminum alloy), zinc, and the like. Metal plates such as copper, for example, plastics such as cellulose diacetate, cellulose triacetate, cellulose pyropionate, cellulose acetate, cellulose acetate butyrate, cellulose butyrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc. Film, a paper or plastic film on which the above metal is laminated, or vapor-deposited. Among these supports, the aluminum plate is particularly preferable because it is dimensionally remarkably stable and inexpensive. Furthermore,
A composite sheet in which an aluminum sheet is bonded onto a polyethylene terephthalate film as described in JP-B-48-18327 is also preferable.

Further, in the case of a support having a surface of metal, especially aluminum, it is desirable to carry out a suitable hydrophilic treatment.

Examples of such hydrophilic treatment include a mechanical method such as wire brush graining, brush graining in which a nylon brush is roughened while pouring a slurry of abrasive particles, a mechanical method such as ball graining, HF or Al.
Chemical graining with Cl ₃ and HCl as etchants,
After graining the surface by electrolytic graining using nitric acid or hydrochloric acid as an electrolytic solution or composite graining performed by combining these surface roughening methods, etching is performed with an acid or alkali as necessary, followed by sulfuric acid and phosphorus. It is preferable to provide a strong passivation film on the aluminum surface by performing anodic oxidation with a DC or AC power supply in an acid, oxalic acid, boric acid, chromic acid, sulfamic acid or a mixed acid thereof.
Although the aluminum surface is hydrophilized by such a passivation film itself, furthermore, if necessary, US Pat. No. 2,714,066
No. 3,181,461, sodium silicate, potassium silicate, U.S. Pat. No. 2,946,638, potassium fluorozirconate, US Pat. No. 3,201,247 No. 1,108,559, alkyl titanate treatment, German Patent 1,091,433, polyacrylic acid treatment, German Patent 1,134,093 No. 3,230,447, phosphono acid treatment described in JP-B-44-6409, and phytin described in U.S. Pat. Acid treatment, a composite treatment comprising a hydrophilic organic polymer compound and a divalent metal described in JP-A-58-16893 and JP-A-58-18291,
Particularly preferred are those subjected to a hydrophilization treatment with an undercoat of a water-soluble polymer having a sulfonic acid group described in JP-A-59-101611. Other hydrophilic treatment methods include silicate electrodeposition described in US Pat. No. 3,658,662.

The photosensitive composition of the present invention coated on a support is exposed through a transparent original image having a line image, a halftone image and the like, and then developed with an aqueous alkaline developer to give a negative relief image to the original image. give.

The light source used for the exposure includes a carbon arc lamp, a mercury lamp, a xenon lamp, a metal halide lamp, a strobe, an ultraviolet laser beam, and the like.

〔The invention's effect〕

The photosensitive composition of the present invention has excellent coatability when coated on a support. It also has excellent developability when developed with an aqueous alkaline developer after coating, drying, and imagewise exposure, and proper developability when developed with an aqueous alkaline developer containing an organic solvent and / or an organic substance such as a surfactant. And an appropriate developability can be obtained even when developed with an aqueous alkaline developer which does not substantially contain these organic substances. Further, the obtained relief image has good abrasion resistance and good adhesion to a support, and when used as a printing plate, many good printed matters can be obtained.

〔Example〕

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

Synthesis Example 1 p-nitrobenzenesulfonyl chloride 88.6 g in a one-necked three-necked flask equipped with a cooling tube, a stirrer, and a dropping funnel.
(0.4 mole) and 300 ml of acetone were added, and the mixture was stirred in an ice water bath. 52.3 g (about 0.81 mole) of monoethylamine aqueous solution (containing 70% by weight) was added to this mixture with a dropping funnel for about 2 hours 3
It was added dropwise over 0 minutes. After completion of the dropping, the ice-water bath was removed, an oil bath was attached, and the mixture was stirred for 1 hour while heating at 60 ° C. After completion of the reaction, this mixture was poured into 2 liters of water with stirring and stirred for 30 minutes,
Filtered. The obtained solid was air-dried for a while, redissolved in 200 ml of acetone, and poured again into 2 l of water with stirring. After stirring for 30 minutes, filtering and drying, N-ethyl-p
A solid of nitrobenzenesulfonamide is obtained. This solid can be purified by recrystallization from a mixed solvent of ethanol-water (yield 65.4 g).

Next, 46.0 g (0.2 mole) of N-ethyl-p-nitrobenzenesulfonamide and 500 ml of ethanol were placed in a 1-necked flask equipped with a stirrer, a condenser and a dropping funnel,
It stirred, heating at 50 degreeC. To this mixture was added 4 g of palladium-carbon (5% palladium) after wetting with water. Furthermore, hydrazine monohydrate 30.0g (0.6mole)
Was dropped by a dropping funnel over about 1 hour. After the dropping was completed, the mixture was stirred under reflux for 2 hours.

After the reaction was completed, the insoluble matter was filtered off, the filtrate was sufficiently concentrated, and then poured into water 1 with stirring. The precipitate was filtered and dried to obtain a solid of N-ethyl-p-aminobenzenesulfonamide. This solid can be purified by recrystallization from a mixed solvent of ethanol-water (yield 31
g) Then N-ethyl-p-aminobenzenesulfonamide
20.0 g (0.1 mole) and 100 ml of pyridine were placed in a 300 ml three-necked flask equipped with a stirrer, a condenser and a dropping funnel,
The mixture was stirred under an ice water bath. To this mixture, 10.5 g (0.1 mole) of methacrylic acid chloride was added dropwise with a dropping funnel over about 1 hour. After the dropping, remove the ice-water bath and put an oil bath,
The mixture was stirred at 60 ° C for 2 hours.

After completion of the reaction, this mixture was poured into water 1 with stirring, acidified by adding hydrochloric acid, stirred for 30 minutes, filtered, and dried to obtain a solid N- (p-ethylaminosulfonylphenyl) methacrylamide. Was obtained. This solid can be purified by recrystallization from a mixed solvent of ethanol-water (yield 19g). N- (p-ethylaminosulfonylphenyl) methacrylamide 15.53g (0.058mole) and 2-hydroxyethyl methacrylate 8.33g. (0.064mole), acrylonitrile 3.40g (0.064mole), methacrylic acid 1.21g (0.0
14mole), α, α'-azobisisobutyronitrile 0.41
80 ml of g, N, N-dimethylformamide was placed in a 200 ml three-necked flask equipped with a stirrer and a condenser, and the mixture was stirred for 5 hours while warming to 64 ° C. The reaction mixture was poured into 2 liters of water with stirring, stirred for 30 minutes, filtered and dried to obtain 26 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 42,000.
(Polymer compound (a) of the present invention).

Synthesis Examples 2 to 7 The polymer compounds (b) to (g) shown in Table 1 were synthesized in the same manner as in Synthesis Example 1. The weight average molecular weight (polystyrene standard) of each of these polymer compounds is 15,000.
~ 100,000.

Examples 1 to 5 A JIS 1050A aluminum plate having a thickness of 0.24 mm was grained on its surface using a nylon brush and an aqueous suspension of 400 mesh pumice, and then thoroughly washed with water. 10% of this
After being immersed in an aqueous solution of sodium hydroxide at 70 ° C. for 60 seconds for etching, washed with running water and neutralized with 20% nitric acid, the electrochemical surface roughening method described in JP-A-53-67507, that is, sine Electrolytic surface roughening treatment was performed in a 1% aqueous solution of nitric acid using an alternating current waveform with an amount of electricity of 160 clones / dm ^{2 at} the anode time.
Subsequently, it was immersed in a 30% sulfuric acid aqueous solution, desmutted at 55 ° C. for 2 minutes, and then anodized in a 7% sulfuric acid aqueous solution so that the coating amount of aluminum oxide was 2.0 g / m ² .
Then, it was immersed in a 3% aqueous solution of JIS No. 3 sodium silicate at 70 ° C for 1 minute, washed with water and dried. On the aluminum plate obtained as described above, the following photosensitive liquids [A] -1 to [A]
-5 was applied using a wheeler and dried at 80 ° C for 2 minutes. The dry weight was 2.0 g / m ² .

The polymer compounds used in the present invention used in the photosensitive solutions [A] -1 to [A] -5 are shown in Table 2.

Photosensitive solution [A] Next, as a comparative example, a photosensitive solution [B] using the following polymer compound in place of the polymer compound used in the present invention in the above photosensitive solution was coated and dried in the same manner. The dry weight was 2.0 g / m ² .

(Polymer compound used in Comparative Example) It is a polymer compound with a composition of a / b / c / d in a molar ratio of 9
/ 24/58/9.

The molecular weight is 55,0 on the weight average (polystyrene standard).
It was 00.

Each of the photosensitive lithographic printing plates [A] -1 to 5 and [B] obtained by using the photosensitizing liquids [A] -1 to 5 and [B] was treated with a PS light manufactured by Fuji Photo Film Co., Ltd. Image exposure was carried out for 1 minute from a distance, and each of the following developing solutions [S] and [T] was immersed for 1 minute at room temperature, and then the surface was lightly rubbed with absorbent cotton.

Developer [S] Developer [T] When the developer [S] containing an organic substance was used, all of the photosensitive lithographic printing plates [A] -1 to [5] and [B] could be developed without leaving a film on unexposed portions. However, when a developing solution [T] containing substantially no organic substance was used, the planographic printing plates [A] -1 to 5 (Examples 1 to 5) using the photosensitive composition of the present invention remained in the unexposed areas. The film could be developed without forming a film, but in the planographic printing plate [B] of Comparative Example, a residual film was confirmed in the unexposed area.

Further, each printing plate thus obtained was attached to a GTO type printing machine manufactured by Heidelberg Co., and printed on high-quality paper using a commercially available ink. When the final number of printed sheets of the planographic printing plates [A] -1 to [5] and [B] was examined, it was as shown in Table 2.

As can be seen from Table 2, the planographic printing plates [A] -1 to 5 (Examples 1 to 5) using the photosensitive composition of the present invention have a larger number of printed sheets than the comparative example [B]. It has excellent printing durability.

Examples 6 to 7 The following photosensitive solutions [C] -1 to [C] -2 were applied to the aluminum plates obtained in Examples 1 to 5 using a wheeler.
It was dried at 0 ° C for 2 minutes. The dry weight was 2.0 g / m ² .

The polymer compounds used in the present invention used in the photosensitive liquids [C] -1 to [C] -2 are shown in Table 3.

Photosensitive liquid [C] Next, as a comparative example, a photosensitive solution [D] using the following polymer compound instead of the polymer compound used in the present invention in the above photosensitive solution was similarly applied and dried. The dry weight was 2.0 g / m ² .

(Polymer compound used in Comparative Example) A / b / c / is a high molecular compound with a composition of
It was / 45/15. The molecular weight was 52,000 in weight average (polystyrene standard).

Each of the photosensitive lithographic printing plates [C] -1 to 2 and [D] obtained by using the photosensitizing liquids [C] -1 to 2 and [D] was adjusted to 1 m with a PS light manufactured by Fuji Photo Film Co., Ltd. Image exposure was carried out for 1 minute from a distance, and each of the above-mentioned developers [S] and [T] was immersed for 1 minute at room temperature, and then the surface was lightly rubbed with absorbent cotton.

When the developer [S] containing an organic substance was used, all the photosensitive lithographic printing plates [C] -1 and [D] were developable without leaving a film on the unexposed area. However, when the developing solution [T] containing substantially no organic substance was used, the lithographic printing plates [C] -1 and 2 (Examples 6 to 7) using the photosensitive composition of the present invention remained in the unexposed area. The film could be developed without forming a film, but in the planographic printing plate [D] of Comparative Example, a residual film was confirmed in the unexposed area.

Further, each printing plate thus obtained was attached to a GTO type printing machine manufactured by Heidelberg and printed on high-quality paper with a commercially available ink. The final number of printed sheets of the planographic printing plates [C] -1 and 2 and [D] was examined and the results are shown in Table 3.

As can be seen from Table 3, the planographic printing plates [C] -1 and 2 (Examples 6 to 7) using the photosensitive composition of the present invention have a larger number of printed sheets than the comparative example [D]. It has excellent printing durability.

Claims (1)

[Claims] 1. A compound represented by the following formula (I) or (II): CH ₂ ═C (R ¹ ) CO—X—R ² —SO ₂ NH—R ³ ... (I) CH ₂ ═C (R ⁴ ) CO—X—R ⁵ —NHSO ₂ —R ⁶ (II) (In the formula, X represents O or NH, and R ¹ and R ⁴ are each H or
CH ₃ is shown, R ² and R ⁵ are each an optionally substituted C _{1 to} C ₁₂ alkylene group, cycloalkylene group, arylene group, or aralkylene group, and R ³ and R ⁶ are each which may have a substituent C ₁ -C ₁₂ alkyl group, a cycloalkyl group, an aryl group, an aralkyl group. ) A negative photosensitive lithographic printing plate composition comprising a polymer compound which is insoluble in water and soluble in an alkaline aqueous solution, and a photosensitive compound which acts on a negative type.