JP2000250216A - Photosensitive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition capable of giving a planographic printing plate being developed by an aqueous alkaline developing solution, excellent in wear resistance and having high printing durability by incorporating a vinyl polymerized polymer compound, which has urethane bonds on its side chains, is water-insoluble and soluble in alkaline solutions, and a naphthoquinonediazide compound. SOLUTION: The composition contains a vinyl-polymerized polymer compound having urethane bonds on its side chains, water-insoluble and soluble in an alkaline solution and a naphthoquinonediazide. The vinyl-polymerized polymer compound contains the structure units expressed by the formulas I and II, wherein X1 and X2 are each -O- or -NR7-; R2 and R4 are each -H or -CH3; R2, R3, R5 and R6 are each 1-12C alkylene group, cycloalkylene group, arylene group or the like, each may have substituents; Z1 and Z2 are each -OH or -COOH or the like; R7 is hydrogen atom or 1-12C alkyl group which may have substituents.

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, the present invention relates to a photosensitive composition which comprises a photosensitive compound acting in a positive type and a polymer compound excellent in abrasion resistance and chemical resistance, has a wide range of development conditions, and does not cause staining during printing. is there.

[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, the novolak type phenol resin used as the main component has poor adhesion to the substrate due to its properties, the film is brittle, the coatability is poor, the abrasion resistance is poor, and the printing durability when used in lithographic printing plates Are not sufficient, and furthermore, the chemical resistance is poor, and especially when UV ink is used, the printing durability is extremely insufficient. As a method for improving these various performances, a burning process (exposure, development, and heat treatment) is generally used. However, when the burning treatment is performed, there is a problem that the low-molecular compound sublimates from the photosensitive layer in the image area and adheres to the non-image area and the like, and there is a problem that stain is easily generated during printing. In order to solve such a problem, various polymer compounds have been studied as binders. For example, the polyhydroxystyrene or hydroxystyrene copolymer described in JP-B-52-41050 certainly has improved film properties,
It had the drawback of poor abrasion resistance and chemical resistance. JP-A-51-34711 proposes to use a polymer having a structural unit of an acrylic acid derivative in a molecular structure as a binder. There are problems that the range is narrow and the abrasion resistance is not sufficient. In addition, Japanese Unexamined Patent Publication
When a polyurethane resin having a sulfonyluureide group described in JP-A-3-261350 is used for a photosensitive lithographic printing plate, the developing property is also reduced, and becomes a developing residue in a developing solution, and adheres to a non-image portion or the like. It has the disadvantage that stains are likely to occur during printing. Furthermore, this polyurethane resin is liable to gel during synthesis, and has been difficult to use as a photosensitive composition.

[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. Another object of the present invention is to provide a photosensitive composition which is excellent in chemical resistance and provides a lithographic printing plate having a high printing durability even when printing using a UV ink without performing a burning treatment. . It is a further object of the present invention to provide a photosensitive composition that provides a lithographic printing plate that has a wide range of development conditions and does not cause staining during printing. Furthermore, the object of the present invention is good adhesion to the substrate,
An object of the present invention is to provide a photosensitive composition which gives a flexible film and has excellent organic solvent solubility.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and have found that a vinyl polymer-based polymer compound having a urethane bond in a side chain and being water-insoluble and soluble in an alkaline aqueous solution is obtained. It has been found that these objects can be achieved by a positive-acting photosensitive composition characterized by containing an o-naphthoquinonediazide compound, and the present invention has been achieved.

[0005]

Embodiments of the present invention will be described below in detail. The vinyl polymer compound having a urethane bond in a side chain and being water-insoluble and soluble in an alkaline aqueous solution, which is used in the present invention, refers to one or more urethane bonds and one or more alkalis in one molecule. It is a polymer compound obtained by polymerizing a low molecular compound having a soluble group and one or more polymerizable unsaturated bonds in a suitable solvent using a known polymerization initiator.

As the vinyl polymer-based polymer compound having a urethane bond in the side chain and being water-insoluble and soluble in an alkaline aqueous solution, for example, polyacrylates, polystyrenes, and polyvinyl ethers are preferred. Can be used for In addition, this polymer compound includes, as groups that act as alkaline soluble groups, for example, a phenolic hydroxyl group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, a sulfonamide group, an N-sulfonylamide group, an N-
It is preferable that the resin skeleton has a sulfonylureido group, an N-aminosulfonylamide group, an N-sulfonylsulfonamide group, and an active methylene group. Of these, a phenolic hydroxyl group, a carboxyl group, and a sulfonamide group are more preferable. preferable.

[0007] In the present invention, among the low molecular weight compounds having one or more urethane bonds, one or more alkali-soluble groups and one or more polymerizable unsaturated bonds in one molecule, preferably used as low molecular weight compounds. Has the general formula (I) or (I
Compounds represented by I) are mentioned.

[0008]

Embedded image

Wherein X ¹ and X ² are each —O— or
-NR ⁷ -is shown. R ¹ and R ⁴ are each —H or —CH ₃
Is shown. R ² and R ⁵ each represent an optionally substituted alkylene group having 1 to 12 carbon atoms, a cycloalkylene group, an arylene group or an aralkylene group. R ³ and R ⁶ each represent an optionally substituted alkylene group having 1 to 12 carbon atoms, a cycloalkylene group, an arylene group, or an aralkylene group. Z ¹ and Z ² are -OH and -COO, respectively.
^{_{H, -SO 2 NHR 8, -NHSO}} 2 R 9, -CONHSO 2 R
_{^{10, -SO 2 NHCOR 11, -NHCONHSO}} 2 R 12, -
SO ₂ NHCONHR ¹³ , -CONHSO ₂ NHR ¹⁴ , -N
_{^{HSO 2 NHCOR 15, -SO 2 NHSO}} 2 R 1 6 , or -
COCH ₂ COR ¹⁷ is shown. R ⁷ represents a hydrogen atom or an optionally substituted alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group.
R ⁸ , R ¹³ and R ^{14 each} represent a hydrogen atom or an optionally substituted alkyl, cycloalkyl, aryl or aralkyl group having 1 to 12 carbon atoms. R ⁹ , R ¹⁰ ,
R ¹¹ , R ¹² , R ¹⁵ and R ¹⁶ each represent an optionally substituted alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group. )

Among the low molecular weight compounds represented by the general formula (I) or (II), those particularly preferably used in the present invention are those wherein R ² and R ⁵ are each an alkylene group having 2 to 6 carbon atoms, An alkylene group, or a phenylene group or a naphthylene group which may have a substituent, R ³ and R ⁶ are a phenylene group and an aralkylene, respectively, R ⁷ is a hydrogen atom, and a hydrogen atom or a carbon atom An alkyl group of 6,
The compound is a phenyl group which may have a substituent.
Examples of such low-molecular compounds include the following compounds.

[0011]

Embedded image

[0012]

Embedded image

[0013]

Embedded image

[0014]

Embedded image

[0015]

Embedded image

[0016]

Embedded image

[0017]

Embedded image

[0018]

Embedded image

[0019]

Embedded image

[0020]

Embedded image

The high molecular compound used in the present invention may be a homopolymer or a copolymer of two or more low molecular compounds represented by the general formulas (I) and (II). It is a copolymer with at least one compound containing one or more polymerizable unsaturated bonds and not containing a urethane bond. Compounds containing such a polymerizable unsaturated bond and containing no urethane bond include, for example, acrylic acid, methacrylic acid, acrylic esters, acrylamides, methacrylic esters, methacrylamides, allyl compounds, 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 acrylate (the alkyl group preferably has 1 to 10 carbon atoms) (for example, methyl acrylate, ethyl acrylate, propyl acrylate,
Butyl acrylate, amyl acrylate, ethylhexyl acrylate, octyl acrylate, tert-octyl acrylate, chloroethyl acrylate, 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane monoacrylate, pentaerythritol Monoacrylates, glycidyl acrylates, benzyl acrylates, methoxybenzyl acrylates, furfuryl acrylates, tetrahydrofurfuryl acrylates, and the like, and aryl acrylates (such as phenyl acrylate): methacrylates, such as alkyl methacrylates (carbon atoms of the alkyl group The number is preferably 1 to 10) (for example, 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 (for example, phenyl methacrylate) , Cresyl methacrylate, naphthyl methacrylate, etc.): acrylamides, for example, acrylamide, N-alkylacrylamide (the alkyl group having 1 to 10 carbon atoms, for example, methyl, ethyl, propyl, butyl, t -Butyl group, heptyl group, octyl group, cyclohexyl group, hydroxyethyl group, benzyl group, etc.), N-arylacryl Amides (for example, the aryl group includes a phenyl group, a tolyl group, a nitrophenyl group, a naphthyl group, and a hydroxyphenyl group), N, N-dialkylacrylamide (the alkyl group has 1 to 10 carbon atoms). , For example, a methyl group, an ethyl group, a butyl group, an isobutyl group, an ethylhexyl group, a cyclohexyl group, etc.), N, N-arylacrylamide (as the aryl group, for example, a phenyl group), N -Methyl-N-phenylacrylamide, N-hydroxyethyl-N-methylacrylamide, N-2-acetamidoethyl-N-acetylacrylamide and the like: methacrylamides such as methacrylamide, N-alkylmethacrylamide (as the alkyl group Having 1 to 10 carbon atoms, eg For example, a methyl group, an ethyl group, a t-butyl group, an ethylhexyl group, a hydroxyethyl group, a cyclohexyl group, etc.), an 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 and the like), N, N-diaryl methacrylamide (the aryl group includes a phenyl group and the like), N-hydroxy Ethyl-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 and the like, 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, and vinyl trimethyl Acetate, vinyl diethyl acetate, vinyl barate, vinyl capro Over DOO, vinyl chloroacetate, vinyl di- chloroacetate, 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 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, benzyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxy methyl styrene,
Acetoxymethylstyrene, etc.), alkoxystyrene (eg, methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene, etc.), halogen styrene (eg, chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromo) Styrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2
-Bromo-4-trifluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene and the like): crotonic esters such as alkyl crotonates (such as butyl crotonate, hexyl crotonate, glycerin monocrotonate and the like): 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. .

Of these compounds having a polymerizable unsaturated bond, methacrylic esters, acrylic esters, methacrylamic acid, acrylamides, acrylonitrile, methacrylonitrile, methacrylic acid, acryl Is an acid. One or more of these compounds having a polymerizable unsaturated bond and a compound represented by the general formula (I):
Alternatively, as the one or more copolymers of the low molecular compound represented by (II), any of block, random, and graft forms can be used. In these copolymers, the content of the urethane bond-containing structural unit is preferably 5 mol% or more, and more preferably 10 to 90 mol%, based on all the structural units constituting the copolymer. preferable.

Examples of the solvent used for synthesizing such a polymer compound include ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether,
Methoxyethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N,
N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, toluene, ethyl acetate,
Examples include methyl lactate and ethyl lactate. These solvents may be 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 in weight average and 1,000 in number average.
That is all. More preferably, the weight average is 5,000-30.
In the range of 2,000 to 250,000. The polydispersity (weight average molecular weight / number average molecular weight) is preferably 1 or more, and more preferably 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 weight or less. The polymer compound of the present invention may be used alone or as a mixture of two or more. The content of these high molecular compounds contained in the photosensitive composition is about 5 to 95% by weight, preferably about 10 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 1,2-diazonaphthoquinone sulfonic acid chloride and phenol-formaldehyde resin described in U.S. Pat. Nos. 3,046,120 and 3,188,210. And esters.
Other useful o-naphthoquinonediazide compounds have been reported in many patents and are known. For example, JP-A-47-5303 and JP-A-48-63802
No. 48-63803, 48-96575
No., 1988-38701, 48-13354
No., Japanese Patent Publication No. 37-18015, and No. 41-11222
Nos. 45-9610, 49-17481, U.S. Pat. Nos. 2,797,213 and 3,454,400.
No. 3,544,323, No. 3,573,917, No. 3,674,495, No. 3,785,825, British Patent No. 1,227,602, No. 1,251,345, 1,2
No. 67,005, No. 1,329,888, No. 1,330,9
No. 32, German Patent No. 854,890, and the like.

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,
No. 58-150948, No. 58-203434, No. 59-165053, No. 60-112445, No. 6
0-134235, 60-16043, 61
-118744, 62-10645, 62-1
Nos. 0646, 62-153950, 62-178
No. 562, Japanese Patent Application No. 72-233292, U.S. Pat.
No. 102,809, No. 3,126,281 No. 3,130,0
No. 47, No. 3,148,983, No. 3,184,310
No. 3,188,210 and No. 4,639,406.

When synthesizing these o-naphthoquinonediazide compounds, it is preferable to react 0.2 to 1.2 equivalents of 1,2-diazonaphthoquinonesulfonic acid chloride with respect to the hydroxyl group of the polyhydroxy compound.
Preferably, the reaction is performed in an amount of 0.3 to 1.0 equivalent. The obtained o-naphthoquinonediazide compound is a mixture of various compounds having different positions and introduced amounts of 1,2-diazonaphthoquinonesulfonic acid ester groups, but all of the hydroxyl groups are converted to 1,2-diazonaphthoquinonesulfonic acid ester. The proportion of the compound in the mixture (content of the completely esterified compound) is preferably at least 5 mol%, more preferably 20 to 99 mol%. The amount of the o-naphthoquinonediazide compound in the photosensitive composition of the present invention is 5 to 50% by weight, more preferably 15 to 40% by weight.

In the composition of the present invention, in addition to the polymer compound having a urethane bond, a phenol formaldehyde resin, m-cresol formaldehyde resin, p-cresol formaldehyde resin, m- / p-mixed cresol formaldehyde resin, phenol / Cresol (m-, p-, or m- / p-mixture) Mixed alkali-soluble cresol formaldehyde resin such as formaldehyde resin, phenol-modified xylene resin, polyhydroxystyrene, polyhalogenated hydroxystyrene, etc. Can be contained. These alkali-soluble polymer compounds preferably have a weight average molecular weight of 500 to 20,000 and a number average molecular weight of 200 to 60,000. Such an alkali-soluble polymer compound is used in an amount of 70% by weight or less of the total composition.

Further, as described in US Pat. No. 4,123,279, an alkyl group having 3 to 8 carbon atoms as a substituent such as a t-butylphenol formaldehyde resin or an octylphenol formaldehyde resin is used. It is preferable to use a condensate of phenol and formaldehyde in combination 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. As cyclic acid anhydrides, US Pat.
Phthalic anhydride as described in 15,128 Pat, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3,6-oxy - [delta ⁴ - tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, maleic anhydride Chloromaleic anhydride, α-phenylmaleic anhydride, succinic anhydride, pyromellitic anhydride and the like. Examples of phenols include 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.

As the organic acids, JP-A-60-8894
No. 2, JP-A-2-96755 and the like. 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 Sulfuric acid, phenylphosphonic acid,
Phenylphosphinic acid, phenyl phosphate, diphenyl phosphate, benzoic acid, isophthalic acid, adibic acid, p-toluic acid, 3,4-dimethoxybenzoic acid, phthalic acid, terephthalic acid, 1,4-cyclohexene-2,2- Examples thereof include dicarboxylic acid, erucic acid, lauric acid, n-undecanoic acid, and ascorbic acid. The above cyclic acid anhydrides,
The proportion of the phenols and organic acids in the photosensitive composition is preferably 0.05% to 15% by weight, more preferably
0.1 to 5% by weight.

Further, in the photosensitive composition of the present invention, in order to widen the latitude of development, Japanese Patent Application Laid-Open No.
Non-ionic surfactants as described in JP-A-251740 and Japanese Patent Application No. 2-181248, JP-A-59-121044, Japanese Patent Application No. 2-1159992.
Amphoteric surfactants as described in the specification can be added. Specific examples of the nonionic surfactant include sorbitan tristearate, sorbitan monobalmitate, sorbitan triolate, monoglyceride stearate, polyoxyethylene sorbitan monooleate, polyoxyethylene nonyl phenyl ether, and the like. Specific examples of the surfactant 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. The proportion of the above nonionic surfactant and amphoteric surfactant in the photosensitive composition is preferably 0.05 to 15% by weight, more preferably 0.1 to 5% by weight.

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. Examples of the dye that can be used in the present invention include a cation having a basic dye skeleton described in JP-A-5-313359 and a sulfonic acid group as the only exchange group, and having 1 to 3 hydroxyl groups. A basic dye comprising a salt with an organic anion having 10 or more carbon atoms can be used. The amount of addition is 0.2 to 5% by weight of the total photosensitive composition. Further, compounds described in the above-mentioned JP-A-5-313359, which generate a photo-decomposition product which interacts with the dye to change the color tone, for example, JP-A-50-36209 (U.S. Pat. No. 3,969,118) O-naphthoquinonediazide-4-sulfonic acid halogenide described in JP-A-53-3622.
No. 3 (U.S. Pat. No. 4,160,671), trihalomethyl-2-pyrone and trihalomethyltriazine, and various o-types described in JP-A-55-62444 (U.S. Pat. No. 2,038,801). Naphthoquinonediazide compound, JP-A-5
For example, a 2-trihalomethyl-5-aryl 1,3,4-oxadiazole compound described in 5-77742 (U.S. Pat. No. 4,279,982) can be added. These compounds can be used alone or as a mixture.

As a colorant for an image, the above-mentioned Japanese Patent Application Laid-Open No. Hei 5-3
Other dyes can be used in addition to the dyes described in JP-A-13359. Suitable dyes including salt-forming organic dyes include oil-soluble dyes and basic dyes.
Specifically, Oil Green BG, Oil Blue BO
S, Oil Blue # 603 (original manufactured by Orient Chemical Co., Ltd.), Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.), Rhodamine B (C145170)
B), malachite green (C142000), methylene blue (C152015) and the like.

When a lithographic printing plate is produced using the photosensitive composition of the present invention, the support may be a hydrophilic aluminum plate, for example, a silicate-treated aluminum plate, an anodized aluminum plate, or a grained aluminum plate. And aluminum plate which has been electrodeposited with silicate, and other types of zinc plate, stainless steel plate, chromed steel plate, plastic film or paper which has been hydrophilized.

In the present invention, a photosensitive lithographic printing plate can be obtained by dissolving the components of each photosensitive composition described above in a solvent capable of dissolving and applying the resulting solution to 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-propanol Propyl acetate, toluene, ethyl acetate, methyl lactate, ethyl lactate, dimethyl sulfoxide,
Dimethylacetamide, dimethylformamide, water, N
-Methylpyrrolidone, tetrahydrofurfuryl alcohol, acetone, diacetone alcohol, methanol, ethanol, isopropanol, diethylene glycol dimethyl ether and the like, and these solvents are used alone or in combination. The concentration (solid content) in the above components is suitably 2 to 50% by weight. Although the amount of application varies depending on the application, for example, a photosensitive lithographic printing plate generally preferably has a solid content of 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.

In the photosensitive layer comprising the photosensitive composition of the present invention, a surfactant for improving coating properties, for example, a fluorine-based interface as described in JP-A-62-170950. An activator can be added. A preferable addition amount is 0.01 to 1% by weight, more preferably 0.05 to 0.5% by weight of the whole photosensitive composition. The surface of the photosensitive layer provided as described above is preferably matted in order to reduce the time for evacuation during contact exposure using a vacuum printing frame and to prevent printing blur. Specifically, Japanese Patent Application Laid-Open Nos. 50-125805, 57-6582, and 6
Examples thereof include a method of providing a mat layer as described in each of JP-A-28986 and a method of thermally fusing a solid powder as described in JP-B-62-62337.

The developer for the photosensitive lithographic printing plate obtained by using the photosensitive composition of the present invention is preferably an alkaline aqueous solution containing substantially no organic solvent, and specific examples thereof include sodium silicate and potassium silicate. , Sodium hydroxide, potassium hydroxide, lithium hydroxide, tribasic sodium phosphate, dibasic sodium phosphate, tribasic ammonium phosphate,
Aqueous solutions such as ammonium diphosphate, 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 weight, preferably 0.5
-5% by weight. Among these, a developer containing an alkali silicate such as potassium silicate, lithium silicate, and sodium silicate is preferable because stain during printing is less likely to occur, and the alkali silicate has a molar ratio of [SiO ₂ ] / [M] = 0.5 to 2.5 (where [Si
O ₂ ] and [M] indicate the molar concentration of SiO _{2 and} the molar concentration of the total alkali metal, respectively. ) And SiO ₂
A developer containing 0.8 to 8% by weight is preferably used.
In the developer, for example, sodium sulfite, potassium sulfite, water-soluble sulfites such as magnesium sulfite, resorcin, methylresorcin, hydroquinone,
Thiosalicylic acid and the like can be added. The preferred content of these compounds in the developer is 0.002 to 0.002.
It is 4% by weight, preferably 0.01 to 1% by weight.

Further, in the developer, JP-A-50-5132
4, JP-A-59-84241 and JP-A-59-84241, and JP-A-59-75255, JP-A-60-111246 and JP-A-60-213943. JP-A-55-95946, by incorporating at least one nonionic surfactant as described in Japanese Patent Publications
As described in JP-A-56-142528, a polymer electrolyte is contained to enhance wettability to a photosensitive composition and development stability (development latitude). Are preferably used. The amount of the surfactant added is 0.001-2% by weight.
Is particularly preferable, and 0.003 to 0.5% by weight is particularly preferable. Further, as the alkali metal of the alkali silicate, it is preferable that potassium is contained in an amount of 20 mol% or more in all the alkali metals because generation of insolubles in the developer is small. More preferably 9
0 mol% or more, most preferably 100 mol% of potassium
Is the case.

Further, the developing solution used in the present invention may contain a small amount of an organic solvent such as an alcohol or the like and JP-A-58-190952.
Chelating agent described in Japanese Patent Publication No. 1-301
An antifoaming agent such as a metal salt or an organic silane compound described in JP-A-39 can be added. Light sources used for exposure include a carbon arc lamp, a mercury lamp, a xenon lamp, a tungsten lamp, and a metal halide lamp.

The photosensitive lithographic printing plate described above is disclosed in
-8002, 55-115045 and 59-58
Needless to say, the plate-making process may be performed by the method described in each publication of No. 431. 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, it is preferable to replenish by the method described in U.S. Pat. No. 4,882,246. Further, the above-described plate making process is preferably performed by an automatic developing machine as described in JP-A-2-7054 and JP-A-2-32357.

In the case where the photosensitive lithographic printing plate of the present invention is subjected to image exposure, development, washing or rinsing, and then unnecessary image portions are erased, it is described in JP-B-2-13293. It is preferable to use such an erasing liquid. Examples of the desensitized gum which is applied as required in the final step of the plate making process include JP-B-62-16834, JP-B-62-25118, JP-B-63-52600 and JP-A-6-52600.
Nos. 2-7595, 62-11693 and 62-83
What is described in each gazette of No. 194 is preferable. Furthermore, when the photosensitive lithographic printing plate of the present invention is subjected to image exposure, development, washing or rinsing, erasing if desired, and washing after washing with water, before burning, Japanese Patent Publication No. 61-2518 is used. And JP-A-55-28062, JP-A-62-31859, and JP-A-61-159655.

[0043]

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] 1 L equipped with a stirrer and a cooling pipe
4-hydroxybenzyl alcohol 6 in a three-necked flask
2.1 g (0.5 mole), 77.6 g (0.5 mole) of methacryloyloxyethyl isocyanate, 0.04 g (0.3 mmol) of p-methoxyphenol, 0.2 g (0.2 g) of di-n-butyltin dilaurate 3 ml) and 700 ml of acetone were added and dissolved by stirring, and the mixture was stirred for 8 hours while heating to 50 ° C. using an oil bath. After completion of the reaction, the reaction mixture was poured into 3 L of water with stirring, stirred for 30 minutes, and then filtered to obtain Compound M4 (yield: 55.9 g). 9.5 g (0.034 mole) of compound M4 thus obtained
And 5.9 g (0.112 mole) of acrylonitrile, 5.4 g (0.054 mole) of methyl methacrylate, and 40 ml of N, N-dimethylacetamide were placed in a 200 ml three-necked flask equipped with a stirrer and stirred while heating to 65 ° C. in a hot water bath. did. 0.33 g of α, α'-azobisisobutyronitrile was added to the mixture, and the mixture was stirred for 5 hours under a nitrogen stream while maintaining the temperature at 65 ° C. After completion of the reaction, this reaction mixture was poured into 2 L of water with stirring, stirred for 30 minutes, and then filtered and dried to obtain 16 g of a white solid. The weight average molecular weight of this polymer compound (polystyrene standard) was measured by gel permeation chromatography and found to be 62,000. (Polymer compound (a) of the present invention)

[Synthesis Example 2] 1 L equipped with a stirrer and a cooling pipe
In a three-necked flask, 86.6 g (0.5 mole) of 4-hydroxybenzenesulfonamide, 77.6 g (0.5 mole) of methacryloyloxyethyl isocyanate, 0.04 g (0.3 mmol) of p-methoxyphenol, and di-lauric acid di-n
0.2 g (0.3 mmole) of butyltin, 700 ml of acetone
After stirring and dissolving, the mixture was stirred for 8 hours while heating to 50 ° C. using an oil bath. After completion of the reaction, the reaction mixture was poured into 3 L of water with stirring, stirred for 30 minutes, and filtered to obtain Compound M3 (yield: 90.3).
g). 10.8 g of the compound M3 thus obtained (0.0
33 mole) and 1.6 g (0.030 mol) of acrylonitrile
e), 3.7 g (0.037 mole) of methyl methacrylate,
30 ml of N, N-dimethylacetamide was placed in a 200 ml three-necked flask equipped with a stirrer and stirred while heating to 65 ° C. in 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 1 hour under a nitrogen stream while maintaining the temperature at 65 ° C. The reaction mixture was further added with compound M3
A mixture of 10.8 g, 1.6 g of acrylonitrile, 3.7 g of methyl methacrylate, 30 ml of N, N-dimethylacetamide and V-650.25 g was added dropwise by a dropping funnel over 2 hours. After completion of the dropwise addition, 40 ml of methanol was added thereto, and the mixture was cooled, poured into 2 L of water with stirring, stirred for 30 minutes, and filtered and dried to obtain 26 g of a white solid. The weight average molecular weight (polystyrene standard) of the polymer compound measured by gel permeation chromatography was 48,000. (Polymer compound (b) of the present invention)

[Synthesis Examples 3 to 6] Polymer compounds (c) to (f) shown in Table 1 were synthesized in the same manner as in Synthesis Example 1 or 2. The weight average molecular weights (polystyrene standard) of these compounds (c) to (f) were 36,000, 80,
2,000, 26,000, 13,000, and 28,000.

[0047]

[Table 1]

Hereinafter, the present invention will be described more specifically with reference to examples. In the examples, "%" indicates "% by weight" unless otherwise specified.

[Examples 1 to 6 and Comparative Examples 1 and 2] Thickness
The surface of a 0.30 mm aluminum plate was grained using a nylon brush and a 400 mesh aqueous suspension of pumicestone, and then thoroughly washed with water. After etching by dipping in a 10% sodium hydroxide solution at 70 ° C. for 60 seconds, the substrate was washed with running water, neutralized with 20% HNO ₃ , and washed with water. This was subjected to electrolytic surface roughening treatment in a 1% aqueous nitric acid solution at an anode electricity of 160 coulomb / dm ² using a sine wave alternating current under the condition of VA = 12.7V. When the surface roughness was measured, it was 0.6 μ (Ra indication). Then immersed in a 30% aqueous H ₂ SO ₄ solution at 55 ° C.
After desmutting for 20 minutes, the substrate was anodized in a 20% H ₂ SO ₄ aqueous solution at a current density of 2 A / dm ^{2 to} a thickness of 2.7 g / m ² to prepare a substrate. An undercoat liquid (A) having the following composition was applied to the surface of the substrate thus treated,
Dry at 30 ° C. for 30 seconds. The coating amount after drying was 30 mg / m ² .

Undercoating liquid (A) 0.10 g of aminoethylphosphonic acid 0.15 g of phenylphosphonic acid 0.05 g of triethanolamine 0.10 g of β-alanine 40 g of methanol 60 g of pure water In this manner, the substrate (I) was prepared.

Next, the next photosensitive liquid (B) is placed on the substrate (I).
Was coated at 25 ml / m ² by rod coating, and dried at 100 ° C. for 1 minute to form a positive photosensitive lithographic printing plate [B] -1.
[B] -7 was obtained. The coated amount after drying was about 1.7 g / m ² . The compounds of the present invention or comparative polymers used in the photosensitive solutions [B] -1 to [B] -7 were those shown in Table 1.

[Photosensitive Solution (B)] Esterified product of 1,2-diazonaphthoquinone-5-sulfonyl chloride and pyrogallol-acetone resin (described in Example 1 of US Pat. No. 3,635,709). 0.45 g cresol-formaldehyde novolak resin (meta / para ratio: 6 to 4, weight average molecular weight 3,000, number average molecular weight 1,100, containing 0.7% of unreacted cresol) 2 g m-cresol-formaldehyde novolak resin (weight average molecular weight 1,700, number average molecular weight 600, containing 1% of unreacted cresol) 0.3 g condensation product of pyrogallol and acetone (weight average molecular weight 2,200, (Number average molecular weight 700) 0.1 g Polymer compound of the present invention (or comparative polymer compound) 1.1 g p-n-octylphenol-formaldehyde Fat (described in U.S. Pat. No. 4,123,279) 0.02 g Naphthoquinonediazide-1,2-diazide-4-sulfonic acid chloride 0.011 g Tetrahydrophthalic anhydride 0.02 g Benzoic acid 0 0.02 g 4- [p-N- (p-hydroxybenzoyl) aminophenyl] -2,6-bis (trichloromethyl) -s-triazine 0.02 g N- (1,2-naphthoquinone-2-diazide-4 -Sulfonyloxy) -cyclohexane-1,2-dicarboxylic acid imid 0.01 g Dye in which the counter anion of Victoria Pure-Blue BOH [produced by Hodogaya Chemical Co., Ltd.] is changed to 1-naphthalenesulfonic acid 0.05 g Curcumin 0.005 g 1- [α-methyl-α- (4-hydroxy-3,5-dihydroxymethylphenyl) ethyl] -4- [α, α-bis (4- (Droxy-3,5-dihydroxymethylphenyl) ethyl] benzene 0.04 g (Compound (X) of JP-A-6-28067) Megafac F-176 (manufactured by Dainippon Ink and Chemicals, Inc.) Agent) 0.01 g methyl ethyl ketone 20 g

Next, as Comparative Example 2, the following photosensitive solution [C] was applied in the same manner as the photosensitive solution [B], and a photosensitive lithographic printing plate [C] was prepared.
Was prepared. The coating weight after drying was 1.7 g / m ² . [Photosensitive solution (C)] 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) 0.45 g Cresol-formaldehyde novolak resin (meta / para ratio: 6 to 4, weight average molecular weight 3,000, number average molecular weight 1,100, containing 0.7% of unreacted cresol) 1.3 g m- Cresol-formaldehyde novolak resin (weight average molecular weight 1,700, number average molecular weight 600, containing 1% of unreacted cresol) 0.3 g Condensation product of pyrogallol and acetone (weight average molecular weight 2,200, number average molecular weight 700) 0.1 g p-normal octylphenol-formaldehyde resin (as described in U.S. Pat. No. 4,123,279) 0.02 Naphthoquinonediazide-1,2-diazide-4-sulfonic acid chloride 0.01 g Tetrahydrophthalic anhydride 0.02 g Benzoic acid 0.02 g 4- [p-N- (p-hydroxybenzoyl) aminophenyl] -2,6- Bis (trichloromethyl) -s-triazine 0.02 g N- (1,2-naphthoquinone-2-diazido-4-sulfonyloxy) -cyclohexane-1,2-dicarboxylic acid imid 0.011 g Victoria Pure-Blue BOH A dye in which the counter anion of [Hodogaya Chemical Co., Ltd.] is changed to 1-naphthalenesulfonic acid 0.05 g Curcumin 0.005 g 1- [α-methyl-α- (4-hydroxy-3,5-dihydroxymethyl) Phenyl) ethyl] -4- [α, α-bis (4-hydroxy-3,5-dihydroxymethylphenyl) ethyl] benzene 0.04 g (Compound (X) described in JP-A-6-282067) Megafac F-176 (a fluorinated surfactant manufactured by Dainippon Ink and Chemicals, Inc.) 0.01 g methyl ethyl ketone 20 g

A positive transparent original image of a line image and a halftone dot image was brought into close contact with the photosensitive layers of the photosensitive lithographic printing plates [B] -1 to 7 and [C], and exposed with a 30-amp carbon arc lamp from a distance of 70 cm. Done. The exposed photosensitive lithographic printing plates [B] -1 to [B] and [C] were immersed and developed in an 8-fold diluted aqueous solution of DP-4 (trade name, manufactured by Fuji Photo Film Co., Ltd.) at 25 ° C. for 60 seconds. The resulting lithographic printing plate [B]-
Using Nos. 1 to 7 and [C], printing was performed on high quality paper using a commercially available ordinary ink and UV ink on a KOR type printer manufactured by Heidelberg. The final number of printed sheets of the lithographic printing plates [B] -1 to 7 and [C] and the stains on the printed matter were examined. As can be seen from Table 2, the lithographic printing plates [B] -1 to 6 (Examples 1 to 6) using the polymer compound of the present invention were obtained using [B] -7 (Comparative Example 1) and [C] ( Compared with Comparative Example 2), the number of prints was large in both cases of using the normal ink and the UV ink, and the printing durability was very excellent and the stain performance was also excellent.

[0055]

[Table 2] * Visual evaluation ○: good, ×: severe dirt

[0056]

EFFECT OF THE INVENTION The photosensitive composition of the present invention is excellent in coatability when coated on a support, and after coating, drying and image exposure.
Excellent developability when using the exposed part with an aqueous alkaline developer. The obtained relief image has good abrasion resistance and good adhesion to a support, and when used as a printing plate, a large number of good printed matter can be obtained. Further, even when printing using UV ink is performed, a large number of good printed matters can be obtained.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2H025 AA00 AA04 AA06 AA12 AA13 AA14 AB03 AB16 AC01 AD03 BE01 CB14 CB41 CB42 CB43 CB45 FA17 2H096 AA06 AA25 BA10 EA02 GA08

Claims (2)

[Claims] 1. A positive-acting photosensitizer comprising a vinyl polymer compound having a urethane bond in a side chain, insoluble in water and soluble in an alkaline aqueous solution, and an o-naphthoquinonediazide compound. Composition. 2. A vinyl polymer compound having a urethane bond in a side chain and being water-insoluble and soluble in an alkaline aqueous solution, comprising a structural unit represented by the following general formula (I) or (II). The positive-working photosensitive composition according to claim 1. Embedded image (In the formula, X ¹ and X ² each represent —O— or —NR ⁷ —. R ¹ and R ⁴ each represent —H or —CH ₃ .
R ² and R ⁵ each have 1 to 1 carbon atoms which may have a substituent.
2 represents an alkylene group, a cycloalkylene group, an arylene group or an aralkylene group. R ³ and R ⁶ each represent an optionally substituted alkylene group having 1 to 12 carbon atoms, a cycloalkylene group, an arylene group or an aralkylene group. Z ¹ and Z ² are each —OH, —COOH, and —SO ₂ N
_{^{HR 8, -NHSO 2 R 9,}} -CONHSO 2 R 10, -SO 2 N
HCOR ¹¹ , -NHCONHSO ₂ R ¹² , -SO ₂ NHCO
NHR ¹³ , -CONHSO ₂ NHR ¹⁴ , -NHSO ₂ NHC
OR ¹⁵ , —SO ₂ NHSO ₂ R ¹⁶ , or —COCH ₂ CO
Shows the R ^17. R ⁷ represents a hydrogen atom or an optionally substituted alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group. R ⁸ , R ¹³ , R ¹⁴
Is a hydrogen atom or a carbon atom having 1 to 12 carbon atoms which may have a substituent.
Represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹⁵ , R
¹⁶ represents an alkyl group having 1 to 12 carbon atoms which may have a substituent, a cycloalkyl group, an aryl group or an aralkyl group. )