JP2002268218A - Photosensitive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive composition giving a planographic printing plate excellent in wear and printing resistances, developable even with an exhausted developing solution in a short time and ensuring wide developing conditions. SOLUTION: In the photosensitive composition containing a vinyl polymerized high molecular compound insoluble in water and soluble in an alkaline aqueous solution and o-naphthoquinone diazide, the vinyl polymerized high molecular compound is a copolymer containing at least one monomeric unit derived from (A) a monomeric compound having an active imino group represented by a specified formula and at least one monomeric unit derived from (B) a monomeric compound having an ester chain represented by a specified formula.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photosensitive composition suitable for producing a lithographic printing plate, an IC circuit and a photomask. More specifically, it consists of a polymer compound with excellent abrasion resistance and chemical resistance, has a wide range of development conditions, is excellent in coupling performance, ballpoint pen suitability, sensitivity, storage stability, and develops after a long time after exposure. The present invention relates to a photosensitive lithographic printing plate capable of performing an efficient plate-making operation with little change in sensitivity over time.

[0002]

2. Description of the Related Art A photosensitive composition comprising an o-naphthoquinonediazide compound and a novolak-type phenol resin has been industrially used as a very excellent photosensitive composition for producing a lithographic printing plate or as a photoresist. However, due to the properties of the novolak type phenol resin used as the main component, the adhesion to the base plate is poor, the film is brittle, the abrasion resistance is poor, and the printing durability when used for lithographic printing plates is not sufficient. There was a point to be improved, and there was a limit in application. In order to solve such a problem, various polymers have been studied as binders. For example,
The polyhydroxystyrene or hydroxystyrene copolymer described in JP-A-52-41050 certainly has improved film properties, but has the disadvantage of poor abrasion resistance. On the other hand, JP-A-63-226641 describes a positive-type photosensitive composition using an alkali-soluble polymer having an active imino group as a binder.
It is disclosed that adhesion to a substrate and abrasion resistance are improved. However, the developer is generally an alkaline aqueous solution, and is not discarded after developing a printing plate having a predetermined area, but is recycled. As more areas of the printing plate are developed, the alkali content decreases and the development time becomes longer than at the beginning,
The developability of the printing plate decreases. In addition, this phenomenon often generates insolubles in the developer. Therefore, there is a need for a photosensitive composition that can provide a printing plate that can be developed with a development time as short as possible even when the developer is diluted. In addition, there is a need for a photosensitive composition suitable for a wide range of development conditions.

[0003]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a photosensitive composition which can be developed with an aqueous alkaline developer, has excellent abrasion resistance, and provides a lithographic printing plate having high printing durability. It is. It is a further object of the present invention to provide a photosensitive composition which can be developed in a short time even with a fatigue developing solution and gives a lithographic printing plate having a wide range of developing conditions.

[0004]

Means for Solving the Problems As a result of various studies on the copolymer composition of the vinyl polymer, the present inventors found that a vinyl polymer polymer compound soluble in water and soluble in an alkaline aqueous solution and o-naphthoquinonediazide were contained. In the positive-working photosensitive composition, the vinyl polymer-based compound is at least (A) a compound represented by the following formula (I) or (II):
A monomer compound having an active imino group represented by
(B) a photosensitive composition characterized by being a copolymer containing a monomer unit derived from a monomer compound having an ester chain represented by the following formula (III) or (IV):
The inventors have found that these objects are achieved, and have reached the present invention.

[0005]

Embodiments of the present invention will be described below in detail. The vinyl polymer-based polymer compound used in the present invention, which is insoluble in water and soluble in an alkaline aqueous solution, includes (A) a monomer compound having an active imino group represented by the following formula (I) or (II), and (B) The following formula (II
It is a polymer compound obtained by polymerizing at least one of the monomer compounds having an ester chain represented by I) or (IV) in a suitable solvent using a known polymerization initiator. The monomer compound (A) having an active imino group in the present invention is a compound represented by the general formula (I) or (II).

[0006]

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Wherein A represents a hydrogen atom, a halogen atom or an alkyl group. B is a single bond, an alkylene group,
Represents a phenylene group, a substituted alkylene group or a substituted phenylene group. X ¹ is,

[0008]

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[0009] X ² is,

[0010]

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Wherein R ¹ represents an optionally substituted alkyl group, cycloalkyl group, phenyl group or naphthyl group. ]

[0012]

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(Wherein, E and E ′ each independently represent a hydrogen atom, a halogen atom, an alkyl group or a phenyl group; F and F ′ each independently represent a single bond, an alkylene group or a substituted alkylene group. X ³ and X ⁴ are each independently

[0014]

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[0015] )

A in the general formula (I) is a hydrogen atom, a halogen atom or an alkyl group, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, further preferably a hydrogen atom or a methyl group. B is a single bond, an alkylene group, a phenylene group, a substituted alkylene group or a substituted phenylene group, and more preferably a single bond or a phenylene group. X ¹ is,

[0017]

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Which is more preferably

[0019]

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## EQU1 ## X ² is,

[0021]

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Which is more preferably

[0023]

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Wherein R ¹ represents an alkyl group, a cycloalkyl group, a phenyl group or a naphthyl group which may have a substituent, and is a halogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group. Is preferably a phenyl group, a naphthyl group, a cyclohexyl group or an alkyl group having 1 to 4 carbon atoms which may have a substituent.

E and E 'in the general formula (II) each independently represent a hydrogen atom, a halogen atom, an alkyl group or a phenyl group, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, further preferably Is a hydrogen atom. F and F ′ each independently represent a single bond, an alkylene group or a substituted alkylene group, more preferably a single bond or an alkylene group having 1 to 4 carbon atoms, further preferably a single bond or a methylene group. X ³ and X ⁴ are each independently

[0026]

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Wherein more preferably,

[0028]

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Is as follows.

The low molecular weight compound represented by the general formula (I) or (II) includes the following compounds.

[0031]

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The content of the monomer unit derived from the compound (A) having an alkali-soluble group which can be suitably used as a monomer compound of a vinyl polymer type polymer compound which is insoluble in water and soluble in an alkaline aqueous solution is 1 to 60 mol%. is there. Preferably it is 10-35 mol%. If it is less than 1 mol%, it causes poor development or contamination, and if it exceeds 60 mol%, it causes unfavorable development flow or deterioration of printing durability.

As the (meth) acrylate (B) having an ester chain, a compound represented by the general formula (III) or (IV) can be mentioned.

[0034]

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(Wherein, R ⁴ represents —H or —CH ₃ ; R ⁵ ,
R ⁶ represents an alkylene group. R ⁷ represents a hydrogen atom or an optionally substituted alkyl group, cycloalkyl group, aryl group or aralkyl group. n is 1 to 5
Number of 0. )

The compound represented by the general formula (III) or (IV)
Of the compounds, those particularly preferably used in the present invention
Is R^Five, R⁶Is an alkylene group having 1 to 12 carbon atoms, more preferably
Preferably an alkylene group having 2 to 6 carbon atoms, such as -CH_TwoCH
_Two-, -CH_TwoCH_TwoCH_Two−, − (CH_Two)_Four−, − (CH_Two)_Five−, − (C
H _Two)_{6 -}, -CH (CH_Three) CH_Two−, −CH (CH_Three) CH (CH_Three)-Etc.
R⁷Is a hydrogen atom or a carbon atom which may have a substituent 1
To 12 alkyl groups, more preferably 1 to 6 carbon atoms.
And particularly preferably a hydrogen atom or
It is a trahydrofurfuryl group. n is a polyester unit
Represents a number of 1 to 50, preferably 2 to 10.

The above-mentioned polyester chains may all be composed of the same ester unit, or may be different from each other.
Two or more kinds of esters may be bonded irregularly or blockwise. Specific compounds include caprolactone acrylate (ToneM-100 manufactured by UCC), caprolactone-modified 2-hydroxyethyl acrylate (Placcel FA series manufactured by Daicel), and caprolactone-modified 2-hydroxyethyl acrylate
Examples include hydroxyethyl methacrylate (Placcel FM series manufactured by Daicel) and caprolactone-modified tetrahydrofurfuryl acrylate (Kayarad TC series manufactured by Nippon Kayaku).

The content of the monomer unit derived from (meth) acrylate (B) having an ester group, which is preferably used as a monomer compound of a vinyl polymer type polymer compound which is insoluble in water and soluble in an alkaline aqueous solution, is 1 to 50 mol. %. If it is less than 1 mol%, it causes poor development or staining, and if it exceeds 50 mol%, it causes the development flow and is unsuitable.

The polymer compound used in the present invention is
(A) a compound having an active imino group and (B) a (meth) acrylate having an ester chain may each be one or more copolymers, and preferably have at least one polymerizable unsaturated bond. And having the general formula (I) or (I
It is a copolymer of the active imino group represented by I) and one or more compounds having no polyester chain represented by the general formula (III) or (IV).

It contains such a polymerizable unsaturated bond and does not contain an active imino group represented by the general formula (I) or (II) and a polyester chain represented by the general formula (III) or (IV). As the compound, for example, polymerization selected from acrylic acid, methacrylic acid, acrylic esters, acrylamides, methacrylic esters, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, croton esters and the like It is a compound having a sexually unsaturated bond. 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, 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, glycidyl acrylate , Benzyl acrylate, methoxy benzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, etc.), aryl acrylate (eg phenyl acrylate, etc.) ): Methacrylic esters, for example,
Alkyl (the alkyl group preferably has 1 to 10 carbon atoms) methacrylate (eg, methyl methacrylate, ethyl methacrylate, propyl methacrylate,
Isopropyl methacrylate, amyl methacrylate,
Hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, trimethylolpropane monomethacrylate,
Pentaerythritol monomethacrylate, glycidyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, etc., aryl methacrylate (eg, phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, etc.): acrylamides such as acrylamide, N-alkylacrylamide (the alkyl group As the number of carbon atoms is 1 to 1
There are 0, for example, methyl group, ethyl group, propyl group, butyl group, t-butyl group, heptyl group, octyl group, cyclohexyl group, hydroxyethyl group, benzyl group and the like. ), N-arylacrylamides (for example, the phenyl group, tolyl group, nitrophenyl group, naphthyl group, hydroxyphenyl group, etc.), N, N-dialkylacrylamide (the alkyl group includes carbon Those having 1 to 10 atoms, for example, methyl group, ethyl group, butyl group, isobutyl group, ethylhexyl group, cyclohexyl group, etc.), N, N-arylacrylamide (as the aryl group, for example, phenyl group etc.) ), N-methyl-N-phenylacrylamide, N-hydroxyethyl-N-methylacrylamide, N-2-acetamidoethyl-N-acetylacrylamide and the like: methacrylamides such as methacrylamide, N-alkylmethacrylamide ( The alkyl group has 1 to 10 carbon atoms. Things, such as methyl group, ethyl group, t- butyl group, ethylhexyl group,
Examples include a hydroxyethyl group and a cyclohexyl group. ), N-aryl methacrylamide (the aryl group includes a phenyl group, etc.), N, N-dialkyl methacrylamide (the alkyl group includes an ethyl group, a propyl group, a butyl group, etc.), N, N-diarylmethacrylamide (the aryl group includes a phenyl group and the like), N-hydroxyethyl-N-
Methyl methacrylamide, N-methyl-N-phenyl methacrylamide, N-ethyl-N-phenyl methacrylamide, etc .: Allyl compounds, for example, allyl esters (for example, allyl acetate, allyl caproate, allyl caprylate, allyl laurate, palmitin) Allyl acid, 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, methoxyethyl vinyl ether, ethoxy) Ethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2
-Dimethylpropyl vinyl ether, 2-ethylbutyl 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 ether (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 isobutyrate, vinyl trimethyl acetate, and vinyl Diethyl acetate, vinyl valate, vinyl caproate, vinyl Chloroacetate, vinyldichloroacetate, vinylmethoxyacetate, vinylbutoxyacetate, vinylphenylacetate, vinylacetoacetate, vinyl lactate, vinyl-β-phenylbutyrate, vinylcyclohexylcarboxylate, vinyl benzoate, vinyl salicylate, vinyl chlorbenzoate Vinyl acid, vinyl tetrachlorobenzoate, vinyl naphthoate, etc .: styrenes such as styrene, alkyl styrene (for example, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, Decyl styrene,
Benzylstyrene, chloromethylstyrene, trifluoromethylstyrene, ethoxymethylstyrene, acetoxymethylstyrene, etc.), alkoxystyrene (for example, methoxystyrene, 4-methoxy-3-methylstyrene,
Dimethoxystyrene, halogen styrene (for example, chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4)
-Trifluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene, etc.): crotonic esters, for example, alkyl crotonates (such as butyl crotonate, hexyl crotonate, glycerin monocrotonate, etc.): dialkyl itaconates (For example, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, etc.): dialkyls of maleic acid or fumaric acid (eg, dimethyl maleate, dibutyl fumarate, etc.): acronitrile, methacrylonitrile, etc.
Of these compounds having a polymerizable unsaturated bond, those preferably used are methacrylic esters, acrylic esters, methacrylamides, acrylamides,
Acrylotrile, methacrylonitrile, methacrylic acid,
Acrylic acid, particularly preferably used are acrylonitrile and methacrylonitrile.

One or more of these may be used, and the content of these copolymer components preferably used is 0%.
8080 mol%, particularly preferably 30 to 80 mol%. One or more of these compounds having a polymerizable unsaturated bond, one or more of a low molecular compound represented by the general formula (I) or (II) and one or more of a (meth) acrylate having a poly (oxyalkylene) chain. As the polymer, any of a block body, a random body, a graft body and the like can be used.

Examples of the solvent used for synthesizing such a high molecular compound include ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-glycol.
Methoxyethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-
Examples include dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, toluene, ethyl acetate, methyl lactate, and ethyl lactate. These solvents are used alone or in combination of two or more.

The molecular weight of the polymer compound of the present invention is preferably 2,000 or more by weight average and 1,000 or more by 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, more preferably in the range of 1.1 to 10. The polymer compound of the present invention may contain an unreacted monomer. In this case, the proportion of the monomer in the polymer compound is desirably 15% by mass or less. The polymer compound of the present invention may be used alone or as a mixture. The content of these high molecular compounds contained in the photosensitive composition is about 3 to 95.
%, Preferably about 5 to 85% by weight.

The o-naphthoquinonediazide compound used in the present invention is an ester of 1,2-diazonaphthoquinonesulfonic acid chloride and pyrogallol-acetone resin described in JP-B-43-28403. preferable. Other suitable orthoquinonediazide compounds include U.S. Patent Nos. 3,046,120 and 3,188,2
There are esters of 1,2-diazonaphthoquinone sulfonic acid chloride and phenol-formaldehyde resin described in US Pat. Other useful o-naphthoquinonediazide compounds have been reported in many patents and are known. For example, JP-A-47-5303,
8-63802, 48-63803, 48-96575, 49-49
No. 38701, No. 48-13354, No. 37-18015, No. 41-
No. 11222, No. 45-9610, No. 49-17481, U.S. Pat.No. 2,797,213, No. 3,454,400, No. 3,544,323
No. 3,573,917, No. 3,674,495, No. 3,785,82
No. 5, UK Patent Nos. 1,227,602, 1,251,345,
Examples thereof include those described in the specifications such as 1,267,005, 1,329,888, 1,330,932, and German Patent 854,890.

Particularly preferred o-naphthoquinonediazide compounds in the present invention are compounds obtained by reacting a polyhydroxy compound having a molecular weight of 1,000 or less with 1,2-diazonaphthoquinonesulfonic acid chloride. Specific examples of such compounds are described in JP-A-51-139402 and JP-A-58-150948.
No. 58-203434, No. 59-165053, No. 60-121445,
No. 60-134235, No. 60-163043, No. 61-118744, No. 62-
No. 10645, No. 62-10646, No. 62-153950, No. 62-178562
No., Japanese Patent Publication No. 8-14696, U.S. Pat.No. 3,102,809,
No. 3,126,281, No. 3,130,047, No. 3,148,983
No. 3,184,310, No. 3,188,210, No. 4,639,40
Examples described in each gazette or specification such as No. 6 can be cited. When synthesizing these o-naphthoquinonediazide compounds, it is preferable to react 0.2-1.2 equivalents of 1,2-diazonaphthoquinonesulfonic acid chloride with respect to the hydroxyl group of the polyhydroxy compound, and further react 0.3-1.0 equivalents. Is preferred.

The resulting o-naphthoquinonediazide compound is a mixture of various 1,2-diazonaphthoquinonesulfonate groups in which the position and the amount of 1,2-diazonaphthoquinonesulfonate ester groups are different. The ratio of the compound converted in the above (the content of the completely esterified compound) in the mixture is preferably 5 mol% or more, more preferably 20 to 99 mol%. The amount of the o-naphthoquinonediazide compound in the photosensitive composition of the present invention is 10 to 50% by mass, more preferably 15 to 40% by mass.

In the composition of the present invention, in addition to the above-mentioned polymer compound, phenol formaldehyde resin, m-cresol formaldehyde resin, p-cresol formaldehyde resin, m- / p-mixed cresol formaldehyde resin, phenol / cresol ( a known alkali-soluble polymer such as cresol formaldehyde resin such as mixed formaldehyde resin, phenol-modified xylene resin, polyhydroxystyrene, polyhalogenated hydroxystyrene, etc. Compounds can be included. These alkali-soluble polymer compounds have a weight average molecular weight of 500
Those having a number average molecular weight of 200 to 60,000 with a molecular weight of up to 20,000 are preferred. Such an alkali-soluble polymer compound is used in the total composition.
It is used in an addition amount of 70% by mass or less.

Further, as described in U.S. Pat. No. 4,123,279, phenol having a C3-8 alkyl group as a substituent, such as t-butylphenol formaldehyde resin and octylphenol formaldehyde resin, and formaldehyde are used. It is preferred to use a condensate of the above in combination in order to improve the oil sensitivity of the image. It is preferable to add a cyclic acid anhydride, a phenol, or an organic acid to the photosensitive composition of the present invention in order to increase sensitivity. U.S. Pat.No. 4,115,128 as a cyclic acid anhydride
Phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3,6
-Endoxy-Δ4-tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, maleic anhydride, chloromaleic anhydride, α-phenylmaleic anhydride, succinic anhydride, pyromellitic anhydride and the like.

As phenols, bisphenol A, p-nitrophenol, p-ethoxyphenol,
2,3,4-trihydroxybenzophenone, 4-hydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 4,4,4 "-trihydroxy-triphenylmethane, 4,4 ', 3", 4 " -Tetrahydroxy-3,5,3 ', 5'-
Tetramethyltriphenylmethane and the like can be mentioned. As organic acids, JP-A-60-88942, JP-A-2-96
No. 755, etc. There are sulfonic acids, sulfinic acids, alkyl sulfates, phosphonic acids, phosphinic acids, phosphoric esters, carboxylic acids, and the like,
Specifically, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, p-toluenesulfinic acid, ethyl sulfate, phenylphosphonic acid, phenylphosphinic acid, phenyl phosphate, diphenyl phosphate, benzoic acid, isophthalic acid, adipic acid, p-toluic acid, 3,4-dimethoxybenzoic acid, phthalic acid, terephthalic acid, 1,4-cyclohexene-2,2-dicarboxylic acid, erucic acid, lauric acid, n-
Undecanoic acid, ascorbic acid and the like.

The proportion of the cyclic acid anhydrides, phenols and organic acids in the photosensitive composition is preferably 0.05 to 15% by mass, more preferably 0.1 to 5% by mass.
Further, in the photosensitive composition of the present invention, in order to widen the development latitude, JP-A-62-251740,
Nonionic surfactants as described in JP-A-4-68355, JP-A-59-121044, registration 2639471
Amphoteric surfactants as described in the specification can be added.

Specific examples of the nonionic surfactant include:
Polyoxyethylene polyoxypropylene block polymer, sorbitan tristearate, sorbitan monopalmitate, sorbitan triolate, stearic acid monoglyceride, polyoxyethylene sorbitan monooleate, polyoxyethylene nonyl phenyl ether, and the like. Specific examples include alkyl di (aminoethyl) glycine, alkyl polyaminoethyl glycine hydrochloride, Amogen K (trade name, manufactured by Dai-ichi Kogyo Co., Ltd., N-tetradecyl-N, N-betaine type), 2
-Alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine, Levon 15 (trade name, manufactured by Sanyo Chemical Co., Ltd., alkylimidazoline system) and the like. Among them, it is particularly preferable to add a polyoxyethylene polyoxypropylene block polymer. The proportion of the nonionic surfactant and the amphoteric surfactant in the photosensitive composition is preferably 0.05 to 15% by mass,
More preferably, the content is 0.1 to 5% by mass.

In the photosensitive composition of the present invention, a printing-out agent for obtaining a visible image immediately after exposure, a dye as an image coloring agent and other fillers 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, o-naphthoquinonediazide-4- described in JP-A-50-36209 and JP-A-53-8128 are disclosed.
Combinations of sulfonic acid halides and salt-forming organic dyes and JP-A Nos. 53-36223, 54-74728, 60-3626, and 61
And combinations of trihalomethyl compounds and salt-forming organic dyes described in JP-A-143748, JP-A-61-151644 and JP-A-63-58440.

Such trihalomethyl compounds include oxadiazole-based compounds and triazine-based compounds, both of which have excellent stability over time and give clear print-out images.
In a photosensitive lithographic printing plate using an aluminum support having an oxide film amount of 1.0 g / m ² or more, the residual color after development is particularly deteriorated. The invention is particularly effective when a photosensitive composition containing such a compound is used, and a lithographic printing plate having almost no residual color can be obtained. Other dyes besides the above-mentioned salt-forming organic dyes can be used as image coloring agents. 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 (orientation above) Chemical Industry Co., Ltd.), Victoria Pure Blue, Crystal Violet (CI42555), Ethyl Violet (CI42600), Methyl Violet (CI42535), Rhodamine B (CI45170B), Malachite Green (C
I42000), methylene blue (CI52015) and the like. Dyes described in JP-A-62-293247 are particularly preferred.

The photosensitive composition of the present invention is dissolved in a solvent in which each of the above components is dissolved, and coated on a support. As the solvent used here, γ-butyrolactone, ethylene dichloride, cyclohexanone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2- Propyl acetate, toluene, ethyl acetate,
Methyl lactate, ethyl lactate, dimethylsulfoxide, dimethylacetamide, dimethylformamide, water, N-methylpyrrolidone, tetrahydrofurfuryl alcohol,
There are acetone, diacetone alcohol, methanol, ethanol, isopropanol, diethylene glycol dimethyl ether and the like, and these solvents are used alone or as a mixture. And the concentration (solid content) in the above components
Is 2 to 50% by mass. The coating amount varies depending on the application, but, for example, in the case of a photosensitive lithographic printing plate, generally, a solid content of 0.5 to 3.0 g / m ² is preferable. As the amount of coating decreases, the photosensitivity increases, but the physical properties of the photosensitive film deteriorate.

In the photosensitive composition of the present invention, a surfactant for improving coating properties, for example, JP-A-62-1709.
A fluorine-based surfactant as described in JP-B-50 can be added. A preferable addition amount is 0.01 to 1% by mass, more preferably 0.05 to 0.5% by mass of the whole photosensitive composition.

When a lithographic printing plate is produced using the photosensitive composition of the present invention, an aluminum plate is preferred as the support. Aluminum plates include pure aluminum and aluminum alloy plates. Various aluminum alloys can be used, and for example, an alloy of aluminum with a metal such as silicon, copper, manganese, magnesium, chromium, zinc, lead, bismuth, or nickel is used. These compositions also contain some negligible amount of impurities in addition to some iron and titanium.

The aluminum plate is subjected to a surface treatment as required. For example, surface treatment such as graining treatment, immersion treatment in an aqueous solution of sodium silicate, potassium fluorozirconate, phosphate, or the like, or anodic oxidation 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 solution of sodium silicate, U.S. Pat.
As described in the specification of Japanese Patent No. 1,461, an aluminum plate subjected to an anodizing treatment and then immersed in an aqueous solution of an alkali metal silicate is also preferably used. The anodizing treatment may be, for example, an electrolytic solution of an inorganic acid such as phosphoric acid, chromic acid, sulfuric acid, or boric acid, or an organic acid such as oxalic acid or sulfamic acid, or an aqueous solution or a non-aqueous solution of a salt thereof alone or in combination of two or more. It is carried out by passing a current through an aluminum plate as an anode. U.S. Patent No.
Electrodeposition of silicate as described in 3,658,662 is also effective. These hydrophilic treatments are performed not only to make the surface of the support hydrophilic, but also to prevent harmful reactions with the photosensitive composition provided thereon and to improve the adhesion with the photosensitive layer. It is done to improve.

Prior to graining the aluminum plate, if necessary, the surface may be subjected to a pretreatment to remove rolling oil on the surface and to expose a clean aluminum surface. For the former, solvents such as trichlene, surfactants and the like are used. For the latter, a method using an alkali etching agent such as sodium hydroxide or potassium hydroxide is widely used. As the graining method, any of mechanical, chemical and electrochemical methods is effective. Examples of the mechanical method include a ball polishing method, a blast polishing method, and a brush polishing method in which an aqueous dispersion slurry of an abrasive such as pumice is rubbed with a nylon brush, and the chemical method is disclosed in JP-A-54-31187. A method of immersing in a saturated aqueous solution of an aluminum salt of a mineral acid as described in the official gazette is suitable, and as an electrochemical method, a method of alternating current electrolysis in an acidic electrolyte such as hydrochloric acid, nitric acid or a combination thereof is used. Is preferred. Among such surface roughening methods, particularly, a surface roughening method combining mechanical surface roughening and electrochemical surface roughening as described in JP-A-55-137793 discloses oil-sensitive images. Is preferred because of its strong adhesion to the support. Graining by the above-mentioned method has a center line surface roughness (Ha) of 0.3 to 1.
It is preferable that the application is performed within a range of 0 μ.

The aluminum plate thus grained is washed with water and chemically etched as required. The etching solution is usually selected from aqueous solutions of bases or acids that dissolve aluminum. In this case, a film different from aluminum derived from the etchant component must not be formed on the etched surface. Preferred examples of the etching agent include sodium hydroxide, potassium hydroxide, trisodium phosphate, disodium phosphate, tripotassium phosphate, and dipotassium phosphate as basic substances; and sulfuric acid and persulfuric acid as acidic substances. , Phosphoric acid, hydrochloric acid, and salts thereof. Metals having a lower ionization tendency than aluminum, such as salts of zinc, chromium, cobalt, nickel, and copper, are not preferable because they form unnecessary films on the etched surface.

Most preferably, these etching agents are used so that the dissolution rate of the aluminum or alloy used is from 0.3 g / m ² to 40 g / m ² per minute of immersion time, when the concentration and temperature are set. However, it may be higher or lower. The etching is performed by immersing the aluminum plate in the above-mentioned etching solution or by applying the etching solution to the aluminum plate, and is preferably processed so that the etching amount is in the range of 0.5 to 10 g / m ² . As the etching agent, it is preferable to use an aqueous solution of a base because of its high etching rate. In this case, since a smut is generated, a normal desmutting process is performed. The acids used for desmutting are nitric acid, sulfuric acid, phosphoric acid,
Chromic acid, hydrofluoric acid, hydrofluoric acid and the like are used.

The etched aluminum plate is:
Washed and anodized as needed. The anodic oxidation can be performed by a method conventionally used in this field. Specifically, when a direct current or an alternating current is applied to aluminum in an aqueous solution or a non-aqueous solution of sulfuric acid, phosphoric acid, chromic acid, oxalic acid, sulfamic acid, benzenesulfonic acid, or the like or a combination of two or more of them, aluminum is supported. An anodized film can be formed on the body surface.
The anodizing treatment conditions vary depending on the electrolytic solution used, and thus cannot be unconditionally determined. Generally, however, the concentration of the electrolytic solution is 1 to 80% by mass, the liquid temperature is 5 to 70 ° C, and the current density is 0.5 to 0.5%. 60
Amps / dm ² , a voltage of 1 to 100 V, and an electrolysis time of 30 seconds to 50 minutes are appropriate. Among these anodizing treatments, in particular, the method of anodizing at a high current density in sulfuric acid described in British Patent No. 1,412,768, U.S. Pat.
The method of anodizing in a low concentration of sulfuric acid as described in 1,619 and the method of anodizing phosphoric acid as an electrolytic bath described in U.S. Pat. No. 3,511,661 are preferred.

The aluminum plate which has been roughened and anodized as described above may be subjected to a hydrophilic treatment, if necessary. A preferred example is US Pat. No. 2,714,066.
And alkali metal silicates such as those disclosed in U.S. Pat.No. 3,181,461, such as aqueous sodium silicate or potassium fluoride zirconate disclosed in JP-B-36-22063 and U.S. Pat. There is a method of treating with polyvinyl sulfonic acid as described above.

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 if necessary, hydrophilized. Examples of such water-soluble compounds include Japanese Patent Publication No. Sho 57-1
No. 6349 discloses a combination of a water-soluble metal salt and hydrophilic cellulose (for example, zinc chloride and carboxymethyl cellulose, magnesium chloride and hydroxyethyl cellulose), and polyacrylamide disclosed in U.S. Pat. No. 3,511,661. Polyvinyl phosphonic acid disclosed in JP-B-46-35685, JP-A-60-149491
And amino acids and salts thereof (Na
Salts, alkali metal salts such as K salts, ammonium salts, hydrochlorides, oxalates, acetates, phosphates, etc.), JP-A-60-232998
Amines having a hydroxyl group and their salts (hydrochloride, oxalate, phosphate, etc.) disclosed in
63-165183 discloses a compound having an amino group and a phosphonic acid group or a salt thereof, and JP-A-3-261592 discloses (a) an amino group and (b) a phosphonic acid group, and a phosphinic acid. Compounds having one group or one phosphate group or salts thereof, and aliphatic or aromatic phosphonic acids or phosphinic acids disclosed in JP-A-5-246171 or salts thereof, and the like. Above all, Japanese patent application
The compounds disclosed in JP-A-2-59592 and JP-A-5-246171 are particularly preferred. Such water-soluble primer layer compounds preferably provided in the range of 1mg / m ² ~80mg / m ² in solid content.

The surface of the photosensitive layer provided as described above is preferably matted in order to reduce the time for evacuation and prevent blurring during close contact exposure using a vacuum printing frame. Specifically, JP-A-50-125805, JP-B-57-65
No. 82, a method of providing a mat layer as described in each of JP-A-61-28986, a method of heat-fusing a solid powder as described in JP-B-62-62337, and the like. .

The developer for the photosensitive composition of the present invention comprises
Alkaline aqueous solutions substantially free of organic solvents are preferred, specifically sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, tribasic sodium phosphate, dibasic sodium phosphate, Aqueous solutions such as ammonium phosphate, dibasic ammonium phosphate, sodium metasilicate, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, aqueous ammonia and the like are suitable, and their concentration is 0.1 to 10% by mass, Preferably, it is added so as to be 0.5 to 5% by mass.

Of these, a developer containing an alkali silicate such as potassium silicate, lithium silicate, sodium silicate and the like is preferable since stains during printing hardly occur.
When the composition of the alkali silicate is [SiO ₂ ] / [M] = 0.
5 to 2.5 (where [SiO ₂ ] and [M] indicate the molar concentration of SiO _{2 and} the molar concentration of the total alkali metal, respectively),
And developer containing SiO ₂ 0.8 to 8 wt% is preferably used. In addition, water-soluble sulfites such as sodium sulfite, potassium sulfite, and magnesium sulfite, resorcin, methylresorcin, hydroquinone, and thiosalicylic acid can be added to the developer.
The preferred content of these compounds in the developer is 0.
It is 002 to 4% by mass, preferably 0.01 to 1% by mass.

An alkaline aqueous solution having a pH of 12.5 or less can be used as a developer for the photosensitive lithographic printing plate of the present invention.
More preferably, an alkaline aqueous solution having a pH of 8 to 11 is used. Examples of the basic compound used to adjust the pH value include sodium tribasic phosphate, potassium tribasic phosphate, ammonium tribasic phosphate, dibasic sodium phosphate,
Phosphates such as potassium diphosphate and dibasic ammonium phosphate, carbonates such as ammonium bicarbonate, sodium carbonate, potassium carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate, sodium borate, potassium borate, and borate Borates such as ammonium acid, and alkali metal hydroxides such as potassium hydroxide, sodium hydroxide and lithium hydroxide, and ammonium hydroxide. Particularly preferred are combinations of carbonate and bicarbonate. These may be used alone or as a mixture.

As another basic compound, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, n-butylamine, monoetalamine, diethanolamine, triethanolamine, monoisopropanolamine And water-soluble organic amine compounds such as diisopropanolamine, ethyleneimine, ethylenediamine, pyridine and the like. Among them, monoethanolamine, diethanolamine, triethanolamine and the like are particularly preferable, and may be used in combination with an inorganic alkali metal salt or the like. The concentration of these basic compounds in the aqueous solution is used in the range of pH 12.5 or less, more preferably pH 8 to 11, as described above, but is generally in the range of 0.05 to 10% by mass. You can choose.

In the developer, anionic surfactants and amphoteric surfactants described in JP-A-50-51324 and JP-A-59-84241 are disclosed. JP-A-60-111246 and JP-A-55-959 by including at least one of nonionic surfactants as described in JP-A-60-213943 and the like.
No. 46, No. 50-142528, by including a polymer electrolyte, the wettability to the photosensitive composition is increased, and the development stability (development latitude) is increased. And it is preferably used.
The addition amount of such a surfactant is preferably 0.001 to 2% by mass, particularly preferably 0.003 to 0.5% by mass.

Further, as the alkali metal of the alkali silicate, it is preferred that potassium is contained in an amount of 20 mol% or more of all alkali metals, because generation of insolubles in the developer is small, more preferably 90 mol% or more, and most preferably. 100 mol%
Is the case. Further, in the developer used in the present invention, some organic solvents such as alcohols and chelating agents described in JP-A-58-190952, as described in JP-B-1-30139. An antifoaming agent such as a metal salt or an organic silane compound can be added. Light sources used for exposure include carbon arc lamps, mercury lamps, xenon lamps,
There are a tungsten lamp, a metal halide lamp, and the like.

The photosensitive lithographic printing plate using the photosensitive composition of the present invention is disclosed in JP-A-54-8002, JP-A-55-115045, and JP-A-59-15045.
It goes without saying that the plate-making process may be carried out by the method described in each publication of -58431. That is, after the development processing, washing with water and then desensitization processing, or desensitization processing as it is,
Alternatively, treatment with an aqueous solution containing an acid or treatment with an aqueous solution containing an acid may be followed by desensitization treatment. Furthermore, in the development process of this type of photosensitive lithographic printing plate, the alkali aqueous solution is consumed depending on the processing amount, and the alkali concentration is reduced, or the alkali concentration is reduced by air due to long-time operation of the automatic developing solution. Although the processing capacity is reduced, the processing capacity may be restored by using a replenisher as described in JP-A-54-62004. In this case, U.S. Patent No.
It is preferred to replenish by the method described in 4,882,246. Further, the plate making process described above is disclosed in Japanese Patent Application Laid-Open No. 2-7054.
It is preferably carried out with an automatic developing machine as described in JP-A Nos. 2-332357.

When the photosensitive lithographic printing plate using the photosensitive composition of the present invention is subjected to image exposure, development, washing or rinsing, and then unnecessary image portions are erased,
It is preferable to use an erasing liquid as described in Japanese Patent Publication No. 2-13293. Further, as a desensitized gum applied as desired in the final step of the plate making process, Japanese Patent Publication No. Sho 62-168
No. 34, No. 62-25118, No. 63-52600, JP-A-62-7595
And those described in JP-A-62-11693 and JP-A-62-83194 are preferred.

Further, when the photosensitive lithographic printing plate using the photosensitive composition of the present invention is image-exposed, developed, rinsed or rinsed, optionally erased, washed with water and burned, , Before burning
No. 55-28062, JP-A-62-31859 and JP-A-61-159655.

[0074]

EXAMPLES The present invention will be described in more detail with reference to Synthesis Examples and Examples, which should not be construed as limiting the scope of the present invention. [Synthesis Example 1] 500 m equipped with a stirrer, a cooling pipe, and a dropping funnel
l In a three-necked flask, add N- (p-toluenesulfonyl)
9.58 g (0.040 mole) of methacrylamide, 2.93 g (0.005 mole) of Praxel FM-4 (caprolactone-modified 2-hydroxyethyl methacrylate) manufactured by Daicel, 2.65 g (0.050 mole) of acrylonitrile, benzyl acrylate
0.81 g (0.005 mole) and N, N-dimethylacetamide 3
0 g was added, and the mixture was stirred while being heated to 65 ° C. by a hot water bath. 0.25 g of V-65 (manufactured by Wako Pure Chemical Industries, Ltd.) was added to the mixture, and the mixture was stirred for 30 minutes under a nitrogen stream while maintaining the temperature at 65 ° C. The reaction mixture was further added with 38.32 g of N- (p-toluenesulfonyl) methacrylamide and Praxel FM-4 manufactured by Daicel.
(Caprolactone-modified 2-hydroxyethyl methacrylate) 11.72 g, acrylonitrile 10.61 g, benzyl acrylate 3.24 g, V-65 (manufactured by Wako Pure Chemical Industries, Ltd.) 1.00 g
And a mixture of N, N-dimethylacetamide (120 g) was added dropwise over 2 hours using a dropping funnel. 65 after addition
Stirred at C for 4 hours. After completion of the reaction, 100 g of methanol was added and the mixture was cooled, poured into 2 L of water with stirring, stirred for 30 minutes, and then filtered and dried to obtain 65 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 65,000. (Polymer compound (a) of the present invention)

[Synthesis Examples 2 to 6] Polymer compounds (b) to (f) shown in Table 1 were synthesized in the same manner as in Synthesis Example 1.

[0076]

[Table 1]

[Examples 1 to 9 and Comparative Examples 1 to 3] Thickness 0.24
mm JIS A 1050 aluminum plate
While supplying the suspension of miston and water to the aluminum surface
Brush brush with the following rotating nylon brush
Inning process was performed. The first brush has a hair length of 100 mm and a hair diameter of 0.95 m
m, flocking density 70 / cm^TwoThe second brush has a hair length of 80 mm,
Hair diameter 0.295mm, flocking density 670 / cm ^TwoMet. Brasserie
The rotation of each tool was 250 rpm. Brush grini
After washing well with water, 10% sodium hydroxide
Immerse in an aqueous solution at 60 ° C for 25 seconds to etch,
After washing with water, neutralization washing with 20% nitric acid and washing with water were performed. these,
Using a sinusoidal alternating current under the condition of VA = 12.7V
And 160 coulomb / dm in 1% nitric acid aqueous solution^Two The anode when electricity
The electrolytic surface roughening treatment was performed by the amount. The surface roughness was measured
However, it was 0.79 μ (Ra display). Followed by 1
30% for 30 seconds in 40% aqueous sodium hydroxide solution
Immersion in sulfuric acid aqueous solution at 60 ° C for 40 seconds
After that, in 20% sulfuric acid aqueous solution, current density 2A / dm^TwoAt
1.6g / m^TwoAnodic oxidation with direct current to achieve the weight of the oxide film
Then, the substrate was adjusted. Surface of substrate treated in this way
Apply undercoat liquid (A) with the following composition and dry at 80 ° C for 30 seconds
did. 10mg / m coating amount after drying^TwoMet.

[Undercoat liquid (A)] Aminoethylphosphonic acid 0.10 g Phenylphosphonic acid 0.15 g Triethanolamine 0.05 g β-alanine 0.10 g Methanol 40 g Pure water 60 g Thus, the substrate (I) was prepared. Next, on this substrate (I), the following photosensitive solution was
1 / m ^{2 was applied and} dried at 100 ° C. for 1 minute to obtain a positive photosensitive lithographic printing plate. The coating amount after drying was 1.15 g / m ² . In order to further shorten the vacuum adhesion time,
A mat layer was formed as described in JP-A-28986.

[Photosensitive Solution] Esterified product of 1,2-diazonaphthoquinone-5-sulfonyl chloride and pyrogallol-acetone resin (as described in Example 1 of US Pat. No. 3,635,709) 0.8 g Polymer compound of the invention (or comparative polymer compound) 0.4 g Cresol-formaldehyde novolak resin (meta / para ratio; 6: 4, weight average molecular weight 8,000) 1.5 g Phenol-formaldehyde novolak resin (weight average molecular weight 15,000) 0.2 g p -Normal octylphenol-formaldehyde resin (described in U.S. Pat. No. 4,123,279) 0.02 g naphthoquinone-1,2-diazide-4-sulfonic acid chloride 0.01 g tetrahydrophthalic anhydride 0.02 g benzoic acid 0.02 g Pyrogallol 0.05 g 4- [pN, N-bis (ethoxycarbonylmethyl) aminophen Nyl] -2,6-bis (trichloromethyl) -S-triazine (hereinafter abbreviated as triazine A) 0.07 g The counter anion of Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.) is converted to 1-naphthalenesulfonic acid. Changed dye 0.045 g F176PF (fluorinated surfactant) (manufactured by Dainippon Ink and Chemicals, Inc.) 0.01 g MEK / (1-methoxy-2-propanol) = 15 g / 10 g

Through a step wedge manufactured by Fuji Photo Film Co., Ltd. (density difference of each step is 0.15), a distance of 1 m to 3 k
After exposure for 1 minute with a metal halide lamp w, Fuji Photo Film Co., Ltd. PS processor 900U
At 30 ° C. for 12 seconds with a molar ratio of SiO ₂ / K ₂ O of 1.
16. Development was performed with an aqueous solution having a SiO ₂ concentration of 1.4%.

The development tolerance was evaluated by using a solution in which the pH was increased or decreased by 0.2 with respect to the above-described developer, and the change in the number of solid plates due to the pH was evaluated. The smaller this value is,
It shows that the development tolerance is good. Printing durability depends on exposure,
After the development, whether or not printing was normally performed was checked using a printing machine Sprint manufactured by Komori Printing Machine Co., Ltd., and evaluation was made based on the number of printed sheets until the printing was not performed normally. The greater the number of printed sheets, the better the printing durability. Developing resistance to fatigue developer is entirely exposed positive photosensitive lithographic printing plate [Fuji Photo Film Co., Ltd. VS] was repeatedly developed with a developer of the mother liquor per liter, and 4.0 m ² treated, fatigue A developer was used. The printing plate was developed at 25 ° C. with a fresh untreated developer and the fatigue developer at 25 ° C., and the difference in development time (seconds) was determined. The difference was evaluated as fatigue developability. The smaller the difference, the better. Table 2 shows the results.

[0082]

[Table 2]

As can be seen from Table 2, the lithographic printing plates using the polymer compound of the present invention (Examples 1 to 6) all exhibited excellent results in terms of development tolerance, fatigue liquid developability, and printing durability. Indicated. On the other hand, the lithographic printing plates containing no polymer compound of the present invention (Comparative Examples 1 to 3) were inferior in fatigue developability, development tolerance or printing durability.

The photosensitive lithographic printing plate produced using the photosensitive composition containing the specific polymer compound of the present invention has excellent printing durability, development tolerance and fatigue developability. A lithographic printing plate can be obtained.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03F 7/022 G03F 7/022 H01L 21/027 H01L 21/30 502R F-term (Reference) 2H025 AA00 AA01 AA06 AA07 AA08 AA12 AB03 AB08 AB16 AC01 AD03 BE01 CB06 CB14 CB15 CB41 CB47 CB52 FA03 FA17 4J002 BC11X BC12W BC12X BE04W BF01W BG01W BG02W BG04W BG05W BABG07W BG10W BG13W BH02A CC03X03 CC03X CC03X CC03X CC03X CC03X CC03X CC3X CB09 CC02 CD10 4J100 AB02R AB04R AB07P AB07R AB08R AB09R AB10R AE02R AE05R AE06R AE09R AG02R AG06R AG08R AG10R AG12R AG15R AJ02R AL03R AL04R AL08Q AL08R AL09R AL10R AL11R AL14R AL16R AL34R AL49R AM02R AM10R AM17R AM21P AM21R AM43P BA03Q BA03R BA04Q BA04R BA05R BA06R BA07Q BA08R BA14R BA21Q BA30R BA31R BA39P BA41R BA58P BA59P BB 01R BB03R BB05R BB07R BB18R BC04R BC43R BC48R BC49R BC53R CA05 CA06 DA01 DA38 DA39 DA61 EA05 JA37

Claims (1)

[Claims] 1. A photosensitive composition comprising a vinyl polymer-based polymer compound insoluble in water and soluble in an alkaline aqueous solution, and o-naphthoquinonediazide, wherein the vinyl polymer-based polymer compound is represented by the following (A): A photosensitive composition comprising a copolymer containing at least one monomer unit derived from the monomer compound represented by (B). (A) A monomer compound having an active imino group represented by the following general formula (I) or (II). Embedded image Wherein A represents a hydrogen atom, a halogen atom or an alkyl group. B represents a single bond, an alkylene group, a phenylene group, a substituted alkylene group or a substituted phenylene group.
X ¹ is Represents X ² is (Wherein, R ¹ represents an optionally substituted alkyl group, a cycloalkyl group, a phenyl group, or a naphthyl group). [Formula 4] (Where E and E ′ each independently represent a hydrogen atom, a halogen atom, an alkyl group or a phenyl group; F and F ′ each independently represent a single bond, an alkylene group or a substituted alkylene group; X ³ and X ⁴ is each independently Represents (B) A monomer compound having an ester chain represented by the following general formula (III) or (IV). Embedded image (In the formula, R ⁴ represents —H or —CH _3. R ⁵ and R ⁶ each represent an alkylene group. R ⁷ represents a hydrogen atom or an optionally substituted alkyl group, cycloalkyl group, aryl Represents a group or an aralkyl group, wherein n is a number from 1 to 50.)