JP2759387B2 - Photosensitive composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive composition suitably used in the production of lithographic printing plates, IC circuits and photomasks. More specifically, the present invention relates to a negative photosensitive composition containing a photocrosslinkable polymer compound having excellent abrasion resistance.

[0002]

2. Description of the Related Art Photocrosslinkable materials which are crosslinked by a cycloaddition reaction are well known, and they are widely used as main components of a photosensitive composition used for producing a photosensitive lithographic printing plate or the like. ing. As these photocrosslinkable polymer compounds, a polymer compound having a maleimide group in a side chain, a cinnamyl group having a photodimerizable unsaturated double bond adjacent to an aromatic nucleus, a cinnamylidene group or a chalcone group in a side chain. High molecular compounds are useful.

[0003] Negative-working photosensitive lithographic printing plates and the like using these photocrosslinkable polymer compounds include an alkali developing type in which unexposed portions are removed (developed) with an aqueous alkali developing solution;
Although a solvent development type which is removed by an organic solvent-based developer is known, an alkali development type is preferable in terms of occupational safety and health, and this is determined mainly by the properties of the photocrosslinkable polymer compound. As a method for imparting alkali developability to the photocrosslinkable polymer compound, for example, as described in JP-A-52-988 and JP-B-49-28122, a photocrosslinkable group and a polymerizable polymer are used. A method in which a low-molecular compound having a saturated bond is copolymerized with methacrylic acid or acrylic acid to synthesize a low-molecular compound having a photocrosslinkable group and a polymerizable unsaturated bond, as described in JP-B-57-56485. As described in JP-A-59-218440 and the like, a method in which a molecular compound and maleic anhydride are copolymerized and then hydrolyzed to synthesize a polymer compound containing a carboxylic anhydride unit, A method in which a carboxylic acid is formed while a crosslinkable group is introduced by a polymer reaction, as described in JP-A-48-74594, etc., wherein a photocrosslinkable group is introduced into polyacrylic acid by a polymer reaction. It is possible to improve the method and the like.

[0004] However, photosensitive compositions using these photocrosslinkable polymer compounds have low abrasion resistance and, when used as a lithographic printing plate, have the drawback of insufficient press life. .

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a negative photosensitive composition containing a photo-crosslinkable polymer compound having excellent abrasion resistance when used as a lithographic printing plate. Another object of the present invention is to provide a photosensitive composition which gives a printing plate having high printing durability.

[0006]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that these objects can be achieved by using a novel photosensitive composition, and have reached the present invention. did. That is, the present invention provides a photosensitive composition containing a photocrosslinkable polymer compound, wherein the photocrosslinkable polymer compound is a structural unit represented by the following general formula (I) and a structure represented by the following general formula (IV) The present invention relates to a photosensitive composition, which is a copolymer having units.

[0007] ^{_{- [CH 2 -C (R 1}} ) (- R 2 -A)] - ------ (I) { wherein, R ¹ represents a hydrogen atom or a methyl group, R ² is a single It represents a bond or a divalent linking group consisting of two or more atoms selected from C, H, N, O, and S, and A represents a functional group represented by the following general formula (II) or (III).

[0008]

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Wherein R ³ and R ⁴ are each a hydrogen atom,
A halogen atom or a C ₁₂ or less alkyl group, R ³
And R ⁴ may together form a 5- or 6-membered ring. R ⁵ and R ⁶ each represent a hydrogen atom, a halogen atom,
A cyano group, a nitro group or a C ₁₂ or less alkyl group, R ⁷ denotes which may have a substituent C ₁₂ or less aromatic group, a heteroaromatic group. )｝-[CH ₂ -C (R ⁸ ) (-X-R ⁹ -Y)]------- (IV) wherein R ⁸ represents a hydrogen atom or a methyl group; R ⁹ represents a single bond or a divalent linking group consisting of two or more atoms selected from C, H, N, O, and S; and Y represents the following general formula ( V), having a weight average molecular weight of 5
Shows a polymer component of 00 or more.

[0010] ^{_{- [CH 2 -C (R 10}} ) (-R 11 -Z)] - ------ (V) ( wherein, R ¹⁰ represents a hydrogen atom or a methyl group, R ¹¹ is a single A bond or a divalent linking group consisting of two or more atoms selected from C, H, N, O, and S, wherein Z is -COOH, -O
^{-PO (OH) (OR 12)} , - PO (OH) (OR 13), - SO 3 H, -CONHSO 2 R
Indicates one of ¹⁴

Note that R¹², R¹³Is a hydrogen atom or
C which may have a substituent₁~ C _FifteenRepresents a hydrocarbon group of
Then R¹⁴Is an optionally substituted C₁~ C_FifteenCarbonization
Shows a hydrogen group. Hereinafter, the present invention will be described in detail. Book
Represented by the above general formula (I) used in the invention
A structural unit and a structural unit represented by the above general formula (IV)
Having a copolymer preferably represented by the following general formula (VI)
Monomer and a macromer represented by the following general formula (VII)
-(Macromonomer) by radical copolymerization
can get.

CH ₂ = C (R ¹ ) (− R ² −A) ------ (VI) CH ₂ = C (R ⁸ ) (− X −R ⁹ −Y) ------ (VII) (In the formula, R ¹ , R ² , A, R ⁸ , R ⁹ , X and Y are the same as those described above.) As the compound represented by the general formula (VI), for example, -28122, JP-B-55-12042, JP-A-50-24384, JP-B-51-37673, JP-A-62-284350, JP-A-51-125474.
And compounds described in JP-A-52-988 and the like.

Among these compounds, those preferably used in the present invention are shown below.

[0014]

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[0015]

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[0016]

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[0017] ^{(wherein, R 1, R 3, R} 4, R 5, R 6 and R ⁷ are the same meanings as defined above, preferably, R ^3,
R ⁴ is a halogen atom or a C ₁ -C ₄ alkyl group, and more preferably, R ³ and R ⁴ are each a methyl group. Further, R ⁵ and R ⁶ are each preferably a hydrogen atom, and R ⁷ is preferably a phenyl group which may have a substituent.

R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ each represent a hydrogen atom or a methyl group, and n ^{1 to} n ^{19 each} represent a natural number, preferably 1 to 12. ) The macromer of the general formula (VII) preferably used in the present invention is
It can be produced by a conventionally known synthesis method. Specifically, radical polymerization is performed using a polymerization initiator and / or a chain transfer agent containing a reactive group such as a carboxyl group, an acyl halide group, a hydroxyl group, an amino group, a halogeno group, or an epoxy group in a molecule. It is synthesized by a method such as a radical polymerization method in which an oligomer having a reactive group bonded to the terminal obtained therefrom is reacted with various reagents to form a macromer.

Specifically, P. Dreyfuss & RP Quirk,
Encycl. Polym. Sci. Eng., 7 , 551 (1987),
PF Rempp, & E. Franta, Adv. Polym. Sci., 58 ,
1 (1984), Yusuke Kawakami "Chemical Industry" 38 , 56 (1
987), Yushita Yamashita “Polymer” 31 , 988 (198)
2), Shiro Kobayashi "Polymer" 30 , 625 (1981),
Ito Koichi "Polymer Processing" 35 , 262 (1986), Higashi Kishiro, Tsuda Takashi "Functional Materials" 1987 No. 10, 5, etc. and can be synthesized according to the methods described in literatures and patents cited therein. it can.

However, the macromer suitably used in the present invention has a repeating unit (the above-mentioned general formula (V))
Since it contains an acidic group, it is synthesized by the following method. As one of the methods, for example, as shown in the following reaction formula (1), the monomer is synthesized by radical polymerization according to the above method using a monomer containing a functional group in which the acidic group is protected, and the terminal reaction is performed. It introduces a functional group.

[0021]

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The introduction and deprotection of acidic groups contained in the macromer suitably used in the present invention (eg, hydrolysis, hydrogenolysis, oxidative decomposition, etc.) are known in the art. The method can be carried out by the following method. Specifically, JFW McOmie, “Protective Group
s in Organic Chemistry ”, Plenum Press (1973
), TW Greene, “Protective Groups in Organic S
ynthesis ”, John Wiley & Sons (1981), Ryohei Oda“ Polymer Fine Chemicals ”Kodansha (1976)
Year), Yoshio Iwakura, Keisuke Kurita "Reactive Polymers" Kodansha (1
977), G. Berneret al, J. Radiation Curing,
1986, No. 10, p10, JP-A-62-212266.
No. 9, JP-A-62-286064, JP-A-62-21
0475, JP-A-62-195684, JP-A-62-195684
No. 258476, JP-A-63-260439, Japanese Patent Application No. 62-220510, and Japanese Patent Application No. 62-226692.

As another method, for example, as shown in the following reaction formula (2), after synthesizing an oligomer in the same manner as described above, a “specific reactive group” bonded to one end of the oligomer is replaced with a “specific reactive group”. This is a method of synthesizing by reacting with a reagent containing a polymerized double bond group that reacts only with a “specific reactive group” by utilizing the difference in reactivity with the acidic group contained in the oligomer. .

[0024]

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Table Q shows specific examples of specific combinations of functional groups as shown in the reaction formula (2). However, the present invention is not limited to these, and it is important that macromerization can be achieved without protecting the acidic groups in the oligomer by utilizing the selectivity of the reaction in ordinary organic chemical reactions. Just do it. Table-Q 特定 Specific functional group at the end of oligomer in the reagent for introducing a polymerizable group: Q ¹ Part Functional group: Q ² part ───────────────────────────── -CO-Cl, acid anhydride, -OH, -NHR ¹⁹ -SO ₂ Cl ───────────────────────────── -COOH, -NHR ¹⁹ halogeno group ──────── ───────────────────── -OH, -NHR ¹⁹ -CO-Cl, -SO ₂ -Cl ───────────── ──────────────── R ¹⁹ is a hydrogen atom or a C _1- which may have a substituent.
It represents a C ₁₅ hydrocarbon group, and is preferably a hydrogen atom.

As still another method, as shown in the following reaction formula (3), a macromer having a functional group (for example, a hydroxyl group) capable of introducing an acidic group is synthesized by the above method, There is a method of introducing an acidic group.

[0027]

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In this method, an acidic group is introduced at the macromer stage. However, the macromer before introducing the acidic group is first converted into a polymer by radical polymerization, and then the acidic group is introduced. It may be a polymer. By the above method and the like, the copolymer used in the present invention is synthesized,
Preferred examples of the structural unit represented by the general formula (V) include the following structural units.

[0029]

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(Wherein R ¹⁰ and R ¹⁴ are the same as described above, G is O or NH, and R ²⁰ is a C ₁ -C ₁₅ hydrocarbon linking group which may have a substituent. Specific examples of these structural units include the following.

[0031]

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[0032]

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As the chain transfer agent which can be used in synthesizing the macromer suitably used in the present invention, a mercapto compound having a reactive group described above (for example, thioglycolic acid, thiomalic acid, thiosalicylic acid,
2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N- (2-mercaptopropionyl) glycine, 2-mercaptonicotinic acid, 3-mercaptonicotinic acid
[N- (2-mercaptoethyl) carbamoyl] propionic acid, 3- [N- (2-mercaptoethyl) amino]
Propionic acid, N- (3-mercaptopropionyl) alanine, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, 2-mercaptoethanol, 3-mercapto-
1,2-propanediol, 1-mercapto-2-propanol, 3-mercapto-2-butanol, mercaptophenol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercapto-3-pyridinol, etc.) Examples thereof include oxidized disulfide compounds and iodinated alkyl compounds (for example, iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, and 3-iodopropanesulfonic acid). preferable.

Examples of the polymerization initiator containing a specific reactive group that can be used include, for example, 2,2'-azobis (2-cyanopropanol) and 2,2'-azobis (2
-Cyanopentanol), 4,4'-azobis (4-cyanovaleric acid), 4,4'-azobis (4-cyanovaleric chloride), 2,2'-azobis [2- (5-methyl-2 -Imidazolin-2-yl) propane], 2,2 '
-Azobis [2- (2-imidazolin-2-yl) propane], 2,2'-azobis [2- (3,4,5,6-
Tetrahydropyrimidin-2-yl) propane], 2,
2'-azobis {2- [1- (2-hydroxyethyl)
-2-imidazolin-2-yl] propane｝, 2,2 '
-Azobis [2-methyl-N- (2-hydroxyethyl) -propionamide] and the like, and derivatives thereof.

The use amount of these chain transfer agents or polymerization initiators is 0.1 to 15% by weight, preferably 0.5 to 10% by weight, based on all monomers. The structural unit represented by the general formula (IV) of the present invention may include only the structural unit represented by the general formula (V), or may further include another structural unit. In this case, the macromer can be synthesized by simultaneously using another polymerizable monomer.

Examples of such a polymerizable monomer include acrylic esters, acrylamides, methacrylic esters, methacrylamides, allyl compounds, and the like.
It is a compound having a polymerizable unsaturated bond selected from vinyl ethers, vinyl esters, styrenes, crotonic 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, 2-ethylhexyl acrylate, octyl acrylate, t-octyl acrylate, chloroethyl 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 (for example, phenyl acrylate): methacrylic esters, for example, alkyl (the number of carbon atoms of the alkyl group) Is preferably 1 to 10) methacrylate (for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl 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 Methacrylates), aryl methacrylates (for example, phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, etc.): acrylamides, for example, acrylamide, N-alkylacrylamide (the alkyl group has 1 to 1 carbon atoms)
10 things such as methyl group, ethyl group, propyl group,
Examples include a butyl group, a t-butyl group, a heptyl group, an octyl group, a cyclohexyl group, a benzyl group, and a hydroxyethyl group. ), N-arylacrylamides (for example, the aryl groups include phenyl, tolyl, nitrophenyl, naphthyl, hydroxyphenyl, sulfamoylphenyl and the like), N, N-dialkylacrylamide ( Examples of the alkyl group include C1 to C1.
0, for example, methyl group, ethyl group, butyl group, isobutyl group, ethylhexyl group, cyclohexyl group and the like. ), N, N-diarylacrylamide (the aryl group includes, for example, a phenyl group), N-methyl-N-phenylacrylamide, N-hydroxyethyl-N-methylacrylamide, N-2-acetamidoethyl- N-acetylacrylamide and the like: methacrylamides, for example, methacrylamide, N-alkyl methacrylamide (the alkyl group has 1 to carbon atoms)
Ten compounds, for example, methyl group, ethyl group, t-butyl group, ethylhexyl group, hydroxyethyl group, cyclohexyl group and the like. ), N-arylmethacrylamide (the aryl group includes a phenyl group, a hydroxyphenyl group, a sulfamoylphenyl 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-methylmethacrylamide, N-methyl-N-phenylmethacrylamide, N-ethyl-N-phenyl Methacrylamide and the like: Allyl compounds, for example, allyl esters (for example, allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, etc.), allyl Oxyethanol and the like: vinyl ethers such as alkyl vinyl ethers (eg, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether,
Methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-
2,2-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 and the like, 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 isobutyrate, vinyl trimethyl acetate, Vinyl diethyl acetate, vinyl valate, vinyl caproe DOO, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate,
Vinyl butoxy acetate, vinyl phenyl acetate, vinyl aceto acetate, vinyl lactate, vinyl-β-phenyl butyrate, vinyl cyclohexyl carboxylate, vinyl benzoate, vinyl salicylate,
Vinyl chlorobenzoate, vinyl tetrachlorobenzoate,
Vinyl naphthoate and the like: styrenes, for example, 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, benzyl styrene, chloromethyl Styrene, trifluoromethylstyrene, ethoxymethylstyrene, acetoxymethylstyrene, etc., alkoxystyrene (eg, methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene, etc.), halogenated styrene (eg, chlorostyrene, dichlorostyrene, trichloro) Styrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene Emissions, trifluoromethyl styrene, 2-
Bromo-4-trifluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene, etc.): crotonic esters such as alkyl crotonates (eg, butyl crotonate, hexyl crotonate, glycerin monocrotonate, etc.): Dialkyl itaconates (eg, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, etc.): dialkyls of maleic acid or fumaric acid (eg, dimethyl maleate, dibutyl fumarate, etc.): acrylonitrile, methacrylonitrile, etc.

Among these polymerizable monomers, acrylates, methacrylates, acrylamides, methacrylamides, acrylonitrile and methacrylonitrile are preferably used. Further, a monomer represented by the general formula (VI) is also preferable. General formula (IV)
In Y, the proportion of the structural unit of the general formula (V) occupies 5 to 5.
It is preferably 100% by weight, more preferably 20 to 10%.
0% by weight.

The copolymer of the present invention may contain only one type of the structural unit represented by the general formula (I) and one type of the structural unit represented by the general formula (IV), but may contain two or more types of the structural units. May be. Further, the copolymer of the present invention may be composed of only the structural unit represented by the general formula (I) and the structural unit represented by the general formula (IV), or may contain other structural units. Good. In this case, when synthesizing the copolymer of the present invention, another polymerizable monomer may be used together with the monomer represented by the general formula (VI) and the macromer represented by the general formula (VII).

Examples of such a polymerizable monomer include acrylic esters, methacrylic esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, crotonic esters and the like. . Among these polymerizable monomers, the above-mentioned acrylates, methacrylates, acrylamides, methacrylamides, acrylonitrile, and methacrylonitrile are preferably used.

Further, the structural unit represented by the general formula (V) may be contained in the main chain of the copolymer of the present invention. In the copolymer of the present invention, the main chain portion and the Y portion in the general formula (IV) may be a random copolymer or a block copolymer, respectively. The copolymer of the present invention preferably contains the structural unit represented by the general formula (I) in an amount of 10% by weight or more, preferably 20 to 95% by weight, based on all the structural units constituting the copolymer. More preferably,

Further, the composition preferably contains 1% by weight or more of the structural unit represented by the general formula (IV), and 5 to 50% by weight.
More preferably, it is contained. The molecular weight of the macromer suitably used in the present invention is 500 or more in weight average, and preferably in the range of 700 to 200,000. Further, the molecular weight of the copolymer of the present invention is preferably 2,000 or more, more preferably in the range of 5,000 to 300,000, the number average molecular weight is preferably 800 or more, more preferably in the range of 1,000 to 250,000. It is. The polydispersity (weight average molecular weight / number average molecular weight) is preferably 1 or more, and more preferably 1.1 to 10.

The copolymer of the present invention may contain unreacted monomers and macromers. In this case, the proportion of these compounds in the copolymer is desirably 15% by weight or less. As a solvent used when synthesizing such a copolymer, for example, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, diethylene glycol dimethyl ether , 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, toluene, ethyl acetate, methyl lactate, ethyl lactate, dimethyl sulfoxide, water and the like. Can be

These solvents may be used alone or as a mixture of two or more. The copolymer of the present invention may be used alone or as a mixture. The content of these copolymers contained in the photosensitive composition is about 5 to 99% by weight, preferably about 10 to 95% by weight. The photosensitive composition of the present invention can contain a photosensitizer as needed.

As the photosensitizer, a triplet sensitizer having a maximum absorption which allows sufficient light absorption in the range of 300 nm or more is preferable. As sensitizers, bensophenone derivatives, benzuanthrone derivatives, quinones, aromatic nitro compounds, naphthothiazoline derivatives, benzothiazoline derivatives, thioxanthones, naphthothiazole derivatives,
Ketocoumarin compounds, benzodithiol derivatives, benzothiazole derivatives, naphthofuranone compounds, pyrylium salts, thiapyrylium salts and the like can be mentioned. Specifically, Michler's ketone, N, N-diethylaminobenzophenone, benzanthrone, (3-methyl-1,3
-Diaza-1,9-benz) anthrone picramide, 5
-Nitroacenaphthene, 2-chlorothioxanthone, 2
-Isopropylthioxanthone, dimethylthioxanthone, methylthioxanthone-1-ethylcarboxylate, 2-nitrofluorene, 2-dibenzoylmethylene-3-methylnaphthothiazoline, 3,3-carbonyl-
Bis (7-diethylaminocoumarin), 2,4,6-triphenylthiapyrylium perchlorate, 2- (p-
Chlorobenzoyl) naphthothiazole, and the like.

Further, Japanese Patent Application Laid-Open No. 3-54566 and Japanese Patent Application Laid-Open
Compounds described in JP-A-236552, JP-A-2-173646 and JP-A-2-131236 are also preferable. These sensitizers may be added in an amount of about 1 to about 20 of the total composition.
%, More preferably 3 to 10% by weight.
The photosensitive composition of the present invention may further contain a diazonium compound having a negative action, if necessary.

Examples of such a negative-acting diazonium compound include diazonium compounds described in US Pat. No. 3,867,147 and diazonium compounds described in US Pat. No. 2,632,703. Particularly, aromatic diazonium salts and, for example, active carbonyl-containing compounds are disclosed. A diazo resin represented by a condensate with a compound (for example, formaldehyde) is useful. Preferred diazo resins include 4-diazo-diphenylamine, 1-diazo-4-N, N-dimethylaminobenzene, 1-diazo-4-N, N-diethylaminobenzene, 1-diazo-4-N-ethyl-. N-hydroxyethylaminobenzene, 1-diazo-4-N-methyl-N-hydroxyethylaminobenzene, 1-diazo-2,5-diethoxy-4-benzoylaminobenzene, 1-diazo-4-N-benzylamino Benzene, 1
-Diazo-4-N, N-dimethylaminobenzene, 1-
Diazo-4-morpholinobenecene, 1-diazo-2,
5-dimethoxy-4-p-tolylmercaptobenzene,
1-diazo-2-ethoxy-4-N, N-dimethylaminobenzene, p-diazo-dimethylaniline, 1-diazo-2,5-dibutoxy-4-morpholinobenzene,
1-diazo-2,5-diethoxy-4-morpholinobenzene, 1-diazo-2,5-dimethoxy-4-morpholinobenzene, 1-diazo-2,5-diethoxy-4
-Morpholinobenzene, 1-diazo-2,5-diethoxy-4-p-tolylmercaptobenzene, 1-diazo-3-ethoxy-4-N-methyl-N-benzylaminobenzene, 1-diazo-3-chloro -4-N, N-diethylaminobenzene, 1-diazo-3-methyl-4-pyrrolidinobenzene, 1-diazo-2-chloro-4-N,
N-dimethylamino-5-methoxybenzene, 1-diazo-3-methoxy-4-pyrrolidinobenzene, 3-methoxy-4-diazodiphenylamine, 3-ethoxy-4
-Diazodiphenylamine, 3- (n-propoxy)-
4-diazophenylamine, 3-isopropoxy-4-
A diazo monomer such as diazodiphenylamine and a condensing agent such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, and benzaldehyde are each in a molar ratio of 1: 1 to 1: 1.
1: 0.5, preferably 1: 0.8 to 1: 0.6, and a reaction product of an anion with a condensate obtained by condensing this in a usual manner. Examples of anions include tetrafluoroboric acid, hexafluorophosphoric acid, triisopropylnaphthalenesulfonic acid, 5-nitro-o-toluenesulfonic acid,
Sulfosalicylic acid, 2,5-dimethylbenzenesulfonic acid, 2,4,6-trimethylbenzenesulfonic acid, 2-
Nitrobenzenesulfonic acid, 3-chlorobenzenesulfonic acid, 3-bromobenzenesulfonic acid, 2-fluorocaprylnaphthalenesulfonic acid, dodecylbenzenesulfonic acid, 1-naphthol-5-sulfonic acid, 2-methoxy-4-hydroxy-5-benzoyl -Benzenesulfonic acid and paratoluenesulfonic acid. Among them, alkyl aromatic sulfonic acids such as hexafluorophosphoric acid, triisopropylnaphthalenesulfonic acid and 2,5-dimethylbenzenesulfonic acid are particularly preferable.

Further, a reaction product of the above-mentioned diazo monomer and a condensate obtained from an aldehyde having a carboxylic acid and / or a phenol or an acetal thereof (and, if necessary, the above-mentioned condensing agent) and the above-mentioned anion, The diazo resins described in JP-A-1-102456 and JP-A-1-102457 are also preferably used in the present invention. Particularly, a diazo resin containing a carboxylic acid group is preferable.

The content of these diazonium compounds in the photosensitive composition is 0.1 to 15% by weight, preferably 0.3 to 5%.
% By weight. If necessary, the diazonium compound 2
More than one species may be used in combination. In the photosensitive composition of the present invention, the structural unit represented by the general formula (I) and the general formula (I)
In addition to the copolymer having the structural unit represented by V), phenol formaldehyde resin, cresol formaldehyde resin, phenol-modified xylene resin, polyhydroxystyrene, polyhalogenated hydroxystyrene and carboxyl group-containing epoxy resin, polyacetal resin, acrylic resin Known alkali-soluble polymer compounds such as methacrylic resin, carboxyl group-containing polyurethane resin and the like, and JP-A-52-988, JP-B-49-28
No. 122, JP-A-2-285353 and the like. Such a polymer compound is used in an amount of not more than 70% by weight of the total composition.

In the composition of the present invention, a printing-out agent for obtaining a visible image immediately after exposure, dyes, pigments, stabilizers, surfactants, plasticizers and other fillers as image coloring agents are used. Additives 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, JP-A-50-
Combinations of o-naphthoquinonediazide-4-sulfonic acid halogenide and salt-forming organic dyes described in JP-A-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. Dyes other than the salt-forming organic dyes described above can also be used as colorants for images. Suitable dyes including salt-forming organic dyes include oil-soluble dyes and basic dyes. Specifically, Oil Yellow # 101, Oil Yellow # 13
0, Oil Pink # 312, Oil Green BG, Oil Blue BOS, Oil Blue # 603, Oil Black BY, Oil Black BS, Oil Black T-50
5, Orient Chemical Co., Ltd., Victoria Pure Blue, Crystal Violet (CI425
55), methyl violet (CI42535), rhodamine B (CI45170B), malachite green (CI42000), methylene blue (CI5201)
5) and the like.

As the stabilizer for the diazonium compound, 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, polyvinyl Phosphonic acid and its copolymer, polyvinyl sulfonic acid and its copolymer, 5-nitronaphthalene-1-phosphonic acid, 4-chlorophenoxymethylphosphonic acid, sodium phenyl-methyl-pyrazolone sulfonate, 2-phosphonobutanetricarboxylic acid- 1,
2,4,1-phosphonoethanetricarboxylic acid-1,2,2
2,1-hydroxyethane-1,1-disulfonic acid and the like.

In addition to the above, it is preferable to further add a thermal polymerization inhibitor to the photosensitive composition, for example, hydroquinone, p-methoxyphenol, di-tert-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 and the like are useful. Also, 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, 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 varies depending on the purpose of use, but is generally 0.5 to 30% by weight based on the total solid content of the photosensitive layer.

The photosensitive composition of the present invention is dissolved in a solvent capable of dissolving each of the above components and applied on a support. As the solvent used here, methanol, ethanol, isopropyl alcohol, n-butyl alcohol, t-butyl alcohol, 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, N, N-dimethylformamide, tetrahydrofuran, dioxane, dimethylsulfoxide, ethyl acetate , Methyl lactate, ethyl lactate, etc., and these solvents are used alone or in combination.

A mixed solvent obtained by adding a small amount of a sensitizer such as water or toluene, a solvent that does not dissolve the diazo resin or the copolymer to these solvents or the mixed solvent is also suitable. The concentration (solid content) of the above components in the solvent is 1 to 50% by weight. When applying and drying a photosensitive solution dissolved in these solvents, it is desirable to dry at 50 ° C to 120 ° C.
The drying may be carried out at a low temperature, followed by preliminary drying, followed by drying at a high temperature. Alternatively, drying may be carried out directly at a high temperature by selecting an appropriate solvent and concentration.

The amount of coating varies depending on the application. For example, a photosensitive lithographic printing plate generally has a solid content of preferably 0.5 to 3.0 g / m ² . The photosensitivity increases as the coating amount decreases, but the physical properties of the photosensitive film deteriorate. The support on which the photosensitive composition of the present invention is applied is, for example, paper, paper laminated with plastic (for example, polyethylene, polypropylene, polystyrene, etc.), for example, aluminum (including aluminum alloy) zinc,
Plates of metals such as copper, for example, plastics such as cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose acetate, cellulose acetate butyrate, cellulose butyrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc. , Or a paper or plastic film on which a metal as described above is laminated or vapor-deposited. Among these supports, the aluminum plate is particularly preferable because it is extremely stable in dimension and inexpensive. Furthermore, Japanese Patent Publication No. 48-18327
Also, a composite sheet in which an aluminum sheet is bonded to a polyethylene terephthalate film as described in JP-A No. 5-2,086 is preferable.

In the case of a support having a metal surface, particularly an aluminum surface, it is desirable to perform an appropriate hydrophilic treatment. As such a hydrophilization treatment, for example, a mechanical method such as wire brush graining, brush graining for roughening with an nylon brush while pouring a slurry of abrasive particles, ball graining, etc.
After graining the surface by chemical graining using HF, AlCl ₃ or HCl as an etchant, electrolytic graining using nitric acid or hydrochloric acid as an electrolytic solution, or composite graining using a combination of these roughening methods, if necessary Etching with acid or alkali, followed by sulfuric acid, phosphoric acid,
It is preferable to provide a strong passivation film on the aluminum surface by anodizing with dc or ac power in 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, if necessary, U.S. Pat.
No. 3,181,461, sodium silicate, potassium silicate, U.S. Pat. No. 2,946,638, potassium fluorozirconate, U.S. 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, the phosphonic acid treatment described in JP-B-44-6409, and the phytin described in U.S. Pat. No. 3,307,951. Acid treatment, JP-A-58-1
No. 6893 and Japanese Patent Application Laid-Open No. 58-18291, undercoating treatment with a complex of a hydrophilic organic polymer compound and a divalent metal ion, described in JP-A-59-101651. Those subjected to a hydrophilic treatment with an undercoat of a water-soluble polymer having a sulfonic acid group are particularly preferable. U.S. Pat.No. 3,658,
No. 662, electrodeposition of silicate.

The photosensitive composition of the present invention coated on a support is exposed through a transparent original having a line image, a halftone dot image, and the like, and then developed with an aqueous alkaline developer so that the original is negatively exposed. Give a relief statue. Examples of the light source used for exposure include a carbon arc lamp, a mercury lamp, a xenon lamp, a metal halide lamp, a strobe, an ultraviolet ray, a laser beam, and the like.

In the development after the exposure, the aqueous alkaline developer composition to be used includes, for example, JP-A-51-7740.
No. 1, a developer composition comprising benzyl alcohol, an anionic surfactant, an alkali agent and water,
JP-A-53-44202 discloses a developer composition comprising an aqueous solution containing benzyl alcohol, an anionic surfactant and a water-soluble sulfite.
No. 5355, a developer composition containing an organic solvent having an solubility in water of 10% by weight or less at room temperature, an alkali agent and water, and the like.

These all contain an organic solvent in the developer composition. However, the organic solvent generally has toxicity and odor, has a risk of fire, and has many disadvantages such as being subject to BOD regulations even in the case of waste liquid, and the cost is high. Therefore, it is desirable to use a developer composition that contains substantially no organic solvent. still,
In the present invention, "substantially contains no organic solvent" means
From the viewpoint of safety described above, the ratio of the organic solvent in the composition is 3% by weight or less, preferably 1% by weight.
% By weight or less, more preferably 0.5% by weight or less, and desirably does not contain it at all.

On the other hand, examples of the developer composition containing substantially no organic solvent include compositions used for developing a positive photosensitive lithographic printing plate, and the like. Is extremely alkaline and may cause rash, inflammation, etc. when attached to the human body. Therefore, as the developer composition used in the present invention, a composition containing substantially no organic solvent and having a pH of 12 or less is preferable.

As the alkaline agent used in such a developer, a salt of a weak base or a weak acid and a strong base is preferable. Specifically, monoethanolamine, diethanolamine,
Organic amines such as triethanolamine, and sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, Na salt or K salt of organic carboxylic acid, Na salt or K salt of phosphoric acid (first, second, and second) 3), N of boric acid
a salt or K salt (first, second, third) and the like.
Among these alkaline agents, organic amines and carbonates are preferred. In order to prevent the deterioration of the developer, it is preferable to use two or more kinds of alkali agents in combination.

These alkali agents are used in the developer composition in an amount of 10%.
Used at weight percents or less. In addition, the developer is disclosed in
Anionic surfactants and amphoteric surfactants as described in JP-A-51324, JP-A-59-752
No. 55, and a surfactant such as a nonionic surfactant described in JP-A-60-111246 may be contained. These surfactants are used in an amount of 10% by weight or less in the developer composition, and preferably 6% by weight or less.

Further, a water-soluble sulfite such as sodium sulfite may be added to the developer. These sulphite salts are used in the developer composition at 5% by weight or less. The developer composition preferably used in the present invention has a pH of 12 or less, and more preferably has a pH in the range of 8 to 11.5. When the photosensitive composition of the present invention is developed with the developer described above, the copolymer of the present invention to be used is preferably soluble or dispersible in the developer, but may simply swell. . In this case, it is preferable that the unexposed portion of the photosensitive composition of the present invention is mechanically scraped off with a brush or the like after dipping in a developer.

[0063]

The photosensitive composition of the present invention has excellent abrasion resistance in the exposed area, and when used as a printing plate, many good printed matter can be obtained.

[0064]

The present invention will be described below in more detail with reference to Synthesis Examples and Examples, but the present invention is not limited thereto. Synthesis Example 1 of Macromer: MM-1 100 g of 2-methoxyethyl acetate was placed in a flask equipped with a stirrer and a cooling tube, and heated and stirred at 85 ° C. in a nitrogen stream.

In this flask, 95 g of dimethyl-t-butylsilyl methacrylate, 5 g of β-mercaptopropionic acid, 4,4′-azobis (4-cyanovaleric acid) were added.
A mixture of 8 g and 100 g of 2-methoxyethyl acetate was added dropwise at a constant flow rate over 2.5 hours. After dropping,
The mixture was further stirred at 85 ° C. for 3 hours. Next, 13.4 g of glycidyl methacrylate, 2 g of N, N-dimethyldodecylamine and 1.5 g of t-butylhydroquinone were added, and
Stirred at C for 8 hours.

After cooling, 5 g of p-toluenesulfonic acid and 200 ml of a 90% by weight aqueous solution of N, N-dimethylacetamide were added to the reaction mixture, heated to 40 ° C. and stirred for 1 hour. After cooling, the reaction mixture was reprecipitated in 2 liters of a mixed solution of water / acetone (volume ratio 1/5), and the precipitate was collected by decantation. The precipitate is further washed with acetone and dried to obtain a viscous substance 68.
g was obtained. The weight average molecular weight (polystyrene standard) measured by gel permeation chromatography was 3.8 × 10 ³ . Synthesis Example 2 of Macromer: MM-2 100 g of 2-methoxyethyl acetate was placed in a flask equipped with a stirrer and a condenser, and heated and stirred at 70 ° C. under a nitrogen stream.

In this flask, 50 g of a compound (a) represented by the following structural formula, 50 g of methacrylic acid, 4 g of 2-mercaptoethanol, 1.2 g of 2,2'-azobisisobutyronitrile and 2-methoxyethyl acetate 100
g of the mixture was added dropwise at a constant flow rate over 4 hours. After the addition was completed, the mixture was stirred at 70 ° C. for 4 hours. Next, the reaction mixture was cooled to room temperature, 12.1 g of pyridine was added, and 16.1 g of methacrylic acid chloride was added dropwise. After the addition, the mixture was stirred at room temperature for 1 hour, 0.5 g of t-butylhydroquinone was added, and the mixture was stirred at 60 ° C for 2 hours.

After cooling, the mixture was poured into 2 liters of water with stirring.
After stirring for 1 hour as it was and allowing it to stand, water was removed by decantation. After two additional washes with water, 1
-Dissolved in 200 ml of methoxy-2-propanol and reprecipitated in 2 l of petroleum ether. The precipitate was collected by decantation and dried under reduced pressure to obtain 55 g of a viscous substance. The weight average molecular weight (polystyrene standard) was measured by gel permeation chromatography and found to be 4.4 × 10 ³ .

[0069]

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Synthesis Example 3 of Macromer: MM-3 100 g of N, N-dimethylacetamide was placed in a flask equipped with a stirrer and a condenser, and heated and stirred at 85 ° C. under a nitrogen stream. In the flask, compound (a) 40 described above was added.
g, 2-hydroxyethyl methacrylate 60 g, 4,
0.7 g of 4'-azobis (4-cyanovaleric acid), 4 g of thioglycolic acid and 100 of N, N-dimethylacetamide
g of the mixture was added dropwise at a constant flow rate over 2.5 hours. After completion of the dropwise addition, the mixture was further stirred at 85 ° C. for 3 hours.

Next, 12 g of glycidyl methacrylate,
2 g of N, N-dimethyldodecylamine and 1.2 g of t-butylhydroquinone were added, and the mixture was stirred at 110 ° C. for 8 hours.
After cooling, 20 g of acetic acid was added, followed by reprecipitation in 2 liters of water, and the precipitate was collected by decantation. The precipitate was further washed with a mixed solution of tetrahydrofuran and hexane and dried.

The obtained viscous substance was placed in a flask together with 300 g of N, N-dimethylacetamide. 56 g of triethylamine and 55.4 g of succinic anhydride are added to this mixture.
Was added and stirred at 80 ° C. for 5 hours. 200 g of acetic acid after cooling
Was added, and the mixture was reprecipitated in 3 liters of water, and the precipitate was collected by decantation. The precipitate was further washed with water and dried to obtain 91 g of a viscous substance. The weight average molecular weight (polystyrene standard) measured by gel permeation chromatography was 5.9 × 10 ³ . Macromer Synthesis Examples 4 to 8: MM-4 to MM-8 Macromers MM-4 to MM-8 shown below were synthesized in the same manner as in Macromer Synthesis Examples 1 to 3. The weight average molecular weight (polystyrene standard) of these macromers is 1.8 × 1
0 ^{3 to} 1.1 × 10 ⁴ .

The suffix indicates the composition weight ratio.

[0074]

Embedded image

[0075]

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Synthesis Example 1 of Copolymer: In a flask equipped with a GP-1 stirrer and a condenser, 120 g of the macromer MM-200, N, N-dimethylacetamide and 200 g of water described above in the synthesis example were placed, and nitrogen was added. 75 ° C under air flow
And heated and stirred. In this flask, 80 g of the aforementioned compound (a) and dimethyl 2,2'-azobisisobutyrate 1 were added.
g and 50 g of N, N-dimethylacetamide were added dropwise at a constant flow rate over 2.5 hours. After completion of the dropwise addition, the mixture was further stirred at 75 ° C. for 3 hours and then poured into 3 liters of water with stirring.

The precipitate was collected by filtration and dried to obtain 89 g of a white solid. The weight average molecular weight (polystyrene standard) measured by gel permeation chromatography was 4.2 × 10 ⁴ . Synthesis Example 2 of Copolymer: 1-methoxy-2 was placed in a flask equipped with a GP-2 stirrer and a condenser.
-50 g of propanol was added, and the mixture was heated and stirred at 75 ° C under a nitrogen stream. In this flask, 30 g of the macromer MM-2 shown in the synthesis example above, 70 g of the aforementioned compound (a),
A mixture of 1 g of dimethyl 2,2'-azobisisobutyrate and 250 g of 1-methoxy-2-propanol was added at a constant flow rate.
It was added dropwise over 2.5 hours. 3 hours after the completion of dropping
After stirring at 5 ° C., the mixture was poured into 3 liters of water with stirring.

The precipitate was collected by filtration and dried to obtain 91 g of a white solid. The weight average molecular weight (polystyrene standard) measured by gel permeation chromatography was 4.9 × 10 ⁴ . Copolymer Synthesis Examples 3 to 10: In the same manner as in Synthesis Examples 1 to 2 of GP-3 to GP-10 copolymers, copolymers GP-3 to GP-3 were obtained using the monomers and macromers shown in Tables 1 and 2.
GP-10 was synthesized. The weight average molecular weight (polystyrene standard) of these copolymers is 3.7 × 10 ^{4 to} 1.4 × 10
^{Was in} the range of ⁵ .

[0079]

[Table 1]

[0080]

[Table 2]

Synthesis Example 1 of Comparative Copolymer for Comparative Example 1: LP-1 The same procedure as in the synthesis example of the copolymer GP-1 except that methacrylic acid was used in place of the macromer MM-1 was used.
In the same manner as in the synthesis example of P-1, a comparative copolymer LP-
Compound 1 was synthesized. The weight average molecular weight (polystyrene standard) measured by gel permeation chromatography was 3.9 × 10 ⁴ . Synthesis Example 2 of Comparative Copolymer: LP-2 In the synthesis example of copolymer GP-9 shown above, except that methacrylic acid was used instead of macromer MM-1.
In the same manner as in the synthesis example of P-9, a comparative copolymer LP-
Compound 2 was synthesized. The weight average molecular weight (polystyrene standard) measured by gel permeation chromatography was 3.5 × 10 ⁴ . Example 1 A substrate was manufactured by the method disclosed in Japanese Patent Application Laid-Open No. 56-28893. That is, an aluminum plate having a thickness of 0.24 mm was grained using a nylon brush and an aqueous suspension of pumicestone of 400 mesh, and then washed thoroughly with water. Then, the film was etched by dipping in 10% sodium hydroxide at 70 ° C. for 60 seconds, washed with running water and then washed with 20% HNO 3.
_After neutralization and washing with ₃ , washing with water was performed. When the anode voltage is 12.7
Under the condition that the ratio of the quantity of electricity at the cathode to the quantity of electricity at the anode at 0.8 is 0.8, using a sinusoidal alternating waveform current, the electrolytic rough surface in a 1% nitric acid aqueous solution at 160 coulombs / dm ^{2 in} the quantity of electricity at the anode Treatment. The surface roughness measured at this time was 0.6.
μ (Ra indication). Subsequently, it is immersed in 30% sulfuric acid, desmutted at 55 ° C. for 2 minutes, and then anodized in 20% sulfuric acid at a current density of 2 A / dm ² for a thickness of 2.7 g / m ² for 2 minutes. did. Thereafter, it was immersed in a 2.5% aqueous solution of sodium silicate at 70 ° C. for 1 minute, washed with water and dried. On the substrate thus prepared, the following photosensitive solution [V]-
1 to [V] -10 using a wheeler, 100 ° C
For 2 minutes. The dry weight was 2 g / m ² .

The copolymers of the present invention used in the photosensitive solutions [V] -1 to [V] -10 are shown in Table 3. Photosensitive solution [V]: 5.0 g of the copolymer of the present invention (Table 3)

[0083]

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0.1 g of 4-diazodiphenylamine and phenoxyacetic acid and 4-n-dodecylbenzenesulfonate of formaldehyde condensate Copper phthalocyanine pigment (CI Pigment Blue 15) 1.0 g Plasticizer 10% dispersion FC-430 ( 0.05 g 1-methoxy-2-propanol 100 g Next, as a comparative example, a copolymer for comparison was used in place of the copolymer of the present invention in the above photosensitive solution. Photosensitive solution [W] -1
[W] -2 was similarly applied and dried. Dry weight 2g /
It was m ^2. Table 3 also shows comparative copolymers used for the photosensitive solutions [W] -1 to [W] -2.

The respective photosensitive lithographic printing plates [V] -1 to [V]-obtained using the photosensitive solutions [V] -1 to [V] -10 and [W] -1 to [W] -2. 10 and [W] -1
Each of [W] -2 is PS manufactured by Fuji Photo Film Co., Ltd.
The image was exposed to light for 1 minute from a distance of 1 m, immersed in the following developer [S] for 50 seconds, and the surface was lightly rubbed with a brush to remove unexposed portions. The pH of the developer [S] is 12
It was below.

Developer [S]: NaHCO ₃ 10 g Na ₂ CO ₃ 20 g

[0087]

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920 g of water The obtained lithographic printing plate was attached to a GTO type printing machine manufactured by Heidelberg Co., Ltd., and printed on high quality paper using a commercially available oil-based ink. Lithographic printing plates [V] -1 to [V] -10 and [W]
When the final number of printed sheets of -1 to [W] -2 was examined, it was as shown in Table 3. As can be seen from Table 3, the lithographic printing plates [V] -1 to [V] -10 of the present invention are the same as [W]-
The number of printed sheets was larger than that of 1 to [W] -2, and the printing durability was excellent.

Table 3 枚 数 Copolymer used in photosensitive lithographic printing plate Number of printed sheets ──── ───────────────────────── [V] -1 GP-1 50,000 [V] -2 GP-2 52,000 [V] -3 GP-3 50,000 [V] -4 GP-4 55,000 [V] -5 GP-5 53,000 [V] -6 GP-6 46,000 [V] -7 GP-748 [V] -8 GP-8 45,000 [V] -9 GP-9 43,000 [V] -10 GP-10 45,000 (Comparative Example) [W] -1 LP-1 37,000 [W] -2 LP-2 32,000 { Example 2 } Obtained according to Example 1. Exposure The lithographic printing plate [V] -1,
[V] -9, [W] -1, and [W] -2 were each image-exposed with a PS light manufactured by Fuji Photo Film Co., Ltd. for 1 minute from a distance of 1 m, and the following developer [T] or [U ] For 50 seconds, and the surface was lightly rubbed with a brush to remove unexposed portions. The pH of each of the developing solutions [T] and [U] was 12 or less.

Developing solution [T]: NaHCO ₃ 15 g Na ₂ CO ₃ 25 g Water 960 g Developing solution [U]: Triethanolamine 20 g Monoethanolamine 2 g Water 978 g The obtained planographic printing plate was transferred to a Heidelberg GTO printer. Attached and printed on high quality paper using a commercially available oil-based ink. Lithographic printing plates [V] -1, [V] -9 and [W]-
The final number of printed sheets of 1, [W] -2 was examined. As can be seen from Table 4, the planographic printing plates [V] -1 and [V] -9 of the present invention correspond to [W] -1 and
The number of prints was larger than that of [W] -2, and the printing durability was excellent.

Table 4 枚 数 Copolymer using photosensitive lithographic printing plate Number of printed sheets ──── ───────────────────────── [V] -1 [T] 48,000 [V] -9 [T] 43,000 [W] -1 (comparative example) [T] 36,000 [W] -2 (comparative example) [T] 32,000 [V] -1 [U] 50,000 [V] -9 [U] 42,000 [ W] -1 (Comparative example) [U] 37,000 [W] -2 (Comparative example) [U] 33,000 ────────

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-3-129352 (JP, A) JP-A-3-64755 (JP, A) JP-A-2-189547 (JP, A) JP-A-2- 285353 (JP, A) JP-A-2-157762 (JP, A) JP-A-52-99102 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) G03F 7/038 G03F 7 / 00 G03F 7/027 G03F 7/028 H01L 21/027

Claims (1)

(57) [Claims] 1. Photosensitivity containing a photocrosslinkable polymer compound
In the composition, the photocrosslinkable polymer compound is represented by the following general formula:
The structural unit represented by (I) and the following general formula (IV)
Characterized in that it is a copolymer having the structural unit
Photosensitive composition. − [CH_Two−C (R¹) (− R^Two-A)]------- (I) where R¹Represents a hydrogen atom or a methyl group;^TwoIs a single bond or 2 selected from C, H, N, O, S
A represents a divalent linking group comprising at least three kinds of atoms, and A represents a functional group represented by the following general formula (II) or (III)
Show. Embedded image(Where R^Three, R^FourAre hydrogen and halogen, respectively
Or C₁₂The following alkyl groups are represented by R^ThreeAnd R^FourTogether
To form a 5- or 6-membered ring. R^Five, R⁶Are hydrogen, halogen, cyano
Group, nitro group or C₁₂The following alkyl groups are represented:⁷Is an optionally substituted C₁₂The following aromatic groups,
Shows a heteroaromatic group. )｝ − [CH_Two−C (R⁸) (− X −R⁹−Y)] − ------ (IV) where R⁸Represents a hydrogen atom or a methyl group; X represents a single bond, an ester bond or an amide bond;⁹Is a single bond or 2 selected from C, H, N, O, S
Y represents a divalent linking group composed of at least one kind of atom, and Y includes a structural unit represented by the following general formula (V);
A polymer component having an average molecular weight of 500 or more is shown. − [CH_Two−C (R^Ten) (−R¹¹-Z)]------- (V) (where R^TenRepresents a hydrogen atom or a methyl group;¹¹Is a single bond or 2 selected from C, H, N, O, S
Z represents a divalent linking group consisting of at least one kind of atom, and Z represents -COOH, -O-PO (OH) (OR¹²), -PO (OH) (OR¹³), -S
O_ThreeH, -CONHSO_TwoR¹⁴Indicates one of Note that R¹², R¹³Each has a hydrogen atom or a substituent
May be C₁~ C _FifteenA hydrocarbon group of R¹⁴Is an optionally substituted C₁~ C_FifteenHydrocarbons
Represents a group. )｝