JP3136227B2 - Photosensitive composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive composition suitable for producing a lithographic printing plate, an IC circuit or a photomask. More specifically, the present invention relates to a photosensitive composition containing a positive-working photosensitive substance and a polymer compound soluble in an alkaline aqueous solution or an alkaline solvent mainly composed of water (hereinafter, referred to as “soluble in alkaline water”). It is.

2. Description of the Related Art A photosensitive composition comprising an o-naphthoquinonediazide compound and a novolak-type phenol resin has been industrially used as a very excellent photosensitive composition for producing a lithographic printing plate or as a photoresist. However, due to the properties of the novolak type phenol resin used as the main component, the adhesion to the substrate is poor, the film is brittle, the abrasion resistance is poor, and the printing durability when used for a lithographic printing plate is not sufficient. There were points to be considered, and there were limitations in application.

In order to solve such a problem, various polymers have been studied as binders. For example, the use of polyhydroxystyrene or a hydroxystyrene copolymer described in JP-B-52-41050 improves the film properties, but has a problem that the abrasion resistance is poor. Japanese Patent Application Laid-Open No. Sho 63-226641 discloses that an alkali water-soluble polymer having an active imino group is used as a binder in order to improve film properties, adhesion to a substrate, and abrasion resistance. However, in order to maintain a wide range of appropriate development conditions,
Since it had to be used in combination with a novolak type resin conventionally used, sufficient printing durability was not necessarily obtained. In addition, a conventional photosensitive composition using a phenol resin had to be developed with an alkaline aqueous solution having a high pH of usually 13 or more. Was not preferable from the viewpoint of processing suitability. pH lower than pH13
In order to enable development with an alkaline aqueous solution having
It is desirable that the pKa of the alkali-soluble binder used is lower than the pKa of the conventional phenol resin. Japanese Patent Publication No. 1-53451 proposes using a polymer compound obtained by polymerizing a polymerization unit of an acrylic acid derivative as a binder. Also, JP-A-3-68
No. 946 proposes to use a polymer compound obtained by polymerizing polymerized units of an N-phenylacrylamide derivative having a carboxylic acid group in a waterless photosensitive lithographic printing plate as a binder. With any of the binders, development was possible with an alkaline aqueous solution having a pH of 12.5 or less. However, the development resulted in complete dissolution of the positive image, giving a very soft image, and slight fluctuations in the development conditions. There was a problem that the formability fluctuated greatly.

[0002]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a good positive image which can be developed even with an aqueous alkaline solution having a relatively low pH and which has little change in image forming property due to a change in developing conditions. It is to provide a photosensitive composition. Another object of the present invention is to provide a photosensitive composition that provides a lithographic printing plate with high printing durability. A further object of the present invention is to provide a photosensitive composition having good adhesion to a substrate and providing a flexible film. Still another object of the present invention is to provide an image forming method using a photosensitive material having a photosensitive layer containing the above photosensitive composition.

[0003]

As a result of various studies, the present inventors have found that a binder obtained by polymerizing a carboxylic acid derivative having a specific structure achieves the object of the present invention. That is, the present invention provides a photosensitive composition comprising a polymer compound obtained by polymerizing at least one polymer unit represented by the following general formula, and a positive-acting photosensitive substance. To provide.

[0004]

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In the formula, A represents a hydrogen atom, a halogen atom, or an alkyl group, and X represents an oxygen atom, NH, or N-
R ₅ (where R ₅ represents an alkyl group),
R ₁ , R ₂ , R ₃ , and R ₄ each independently represent a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, —OR ₆ , —OCO—R ₇ , NHCO-R ₈ ,
-NHCONHR ₉ , -OCONH-R ₁₀ , -COOR ₁₁ , -CONHR ₁₂ , -CO
R ₁₃ , -CONR ₁₄ R ₁₅ , -CN, or -CHO represents a group, or R ₁ , R ₂ , R ₃ , and R ₄ represent a group in which two of them combine to form a ring Often, R _{6 to} R ₁₅ represent an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group. However, at least one of R ₁ , R ₂ , R ₃ and R ₄ represents a group other than a hydrogen atom. Further, the present invention is characterized in that after a photosensitive material having a photosensitive layer containing the above photosensitive composition is image-exposed, the photosensitive material is developed with an aqueous alkaline solution having a pH of 12.5 or less to remove the exposed portion of the photosensitive layer. To provide an image forming method. It is just surprising that the above-mentioned polymer compound gives a photosensitive composition which can be developed with an alkaline aqueous solution having a pH of 12.5 or less, has excellent abrasion resistance, and has a wide range of appropriate developing conditions (wide development tolerance). It should have been. In the above formula, A represents a hydrogen atom, a halogen atom, or an alkyl group. The halogen atom is preferably chlorine or bromine. As the alkyl group,
Those having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms can be used. In the above formula, R ₁ , R ₂ , R ₃ , and R
₄ is each independently a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group,
-OR ₆ , -OCO-R ₇ , -NHCO-R ₈ , -NHCONHR ₉ , -OCONH-R ₁₀ ,
-COOR ₁₁ , -CONHR ₁₂ , -COR ₁₃ , -CONR ₁₄ R ₁₅ , -CN or -CHO represents a group. As the alkyl group, one having 1 to 2 carbon atoms
0 groups are used, and more preferably 1 to 8 alkyl groups are used. As the aromatic group, one having 6 to 20 carbon atoms such as phenyl and naphthyl is used, and more preferably one having 6 to 10 carbon atoms is used. Examples of the substituent of the substituted alkyl group and the substituted aromatic group include an aromatic group,
Examples thereof include an alkoxy group having 1 to 10 carbon atoms, a halogen atom, an alkoxycarbonyl group, an acyloxy group, a formyl group, and an ether group. Further, as the substituent of the substituted aromatic group, in addition to those described above, one having 1 carbon atom may be used.
There may be mentioned up to 10 alkyl groups.

[0006] _{Two of} R ₁ , R ₂ , R ₃ and R ₄ may combine to form a ring. As the ring formed by combining two of R _{1 to} R ₄ , a 5- to 7-membered ring is preferable, and cyclopentane, cyclohexane, benzene,
Examples thereof include an aliphatic ring having 4 to 14 carbon atoms such as naphthalene, an aryl ring, and a hetero ring containing 1 to 4 hetero atoms such as pyridyl, furyl, pyrrole, and indole. R ₅ is an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms. R _{6 to} R ₁₅ represent an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group. As the alkyl group, one having 1 to 20 carbon atoms is used, and more preferably, an alkyl group having 1 to 8 carbon atoms is used. Examples of the aryl group include phenyl, naphthyl and the like having 6 to 2 carbon atoms.
0 pieces are used, and more preferably 6 to 10 pieces are used. Examples of the substituent of the substituted alkyl group and the substituted aryl group include an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogen atom, an alkoxycarbonyl group having 2 to 10 carbon atoms, and 1 carbon atom. -10
Acyloxy group, formyl group and the like. Examples of the substituent of the substituted aromatic group include, in addition to those described above, an alkyl group having 1 to 10 carbon atoms. In the above formula, A is preferably a hydrogen atom or a methyl group, and X is preferably NH. The R ₁ to R _4, halogen atom, an alkyl group having 8 carbon atoms from 1: halogen atom, aryl group, or a total carbon number of 1-15 which is substituted with an alkoxy alkyl group; -OR ₆ group -OCOR ₇ group; -OCONHR ₉ group (where R ₆ , R ₇ and R ₉ are each independently an alkyl group having 1 to 8 carbon atoms; an aryl group; a halogen atom, an aryl group or an alkoxy group. A substituted alkyl group having 1 to 15 carbon atoms in total; or a 6 to 1 carbon atom substituted with a halogen atom, an alkyl group or an alkoxy group.
5 substituted aryl groups are preferred) and R
It is also preferred that two of _{1 to} R ₄ are combined to form a ring. Specific examples of preferred rings include naphthalene, tetralin, indene, indanone, and condensed with an aryl group to which a carboxyl group is bonded.
Tetralone, benzofuran or indole. Next, specific examples of the polymerized unit represented by the above general formula [I] are shown below. However, the present invention is not limited to this specific example.

[0007]

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[0008]

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[0009]

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[0010]

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[0011]

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The polymerized unit represented by the general formula [I] can be easily synthesized by reacting a compound represented by the following general formula [II] or [III] with a compound represented by the general formula [IV]. be able to.

[0013]

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In the general formulas [II] to [IV], A,
X and R _{1 to} R ₄ have the same meanings as those in formula [I]. The polymer compound in the present invention is a polymer obtained by polymerizing a single polymer unit represented by the general formula [I], or a polymer represented by the general formula [I] and the polymer unit A represented by the general formula [I]. However, a copolymer obtained by polymerizing B having a different polymerization unit from A may be used. Also, a multi-component copolymer obtained by copolymerizing one or more known vinyl monomers may be used. However, in the present invention, the polymerization unit represented by the general formula [I] is 10 mol% to 100 mol% based on the number of moles of all the polymerization units in the polymer compound.
More preferably, it is contained in an amount of 20 mol% to 100 mol%. Examples of the vinyl monomer that can be used in combination with the polymerization unit represented by the general formula (I) include:
(i) for example, ethylenically unsaturated olefins such as ethylene, propylene, isobutylene, butadiene, and isobrene; (ii) styrenes such as styrene, α-methylstyrene, p-methylstyrene, and p-chlorostyrene;
ii) acrylic acids such as acrylic acid and methacrylic acid; (iv) unsaturated aliphatic dicarboxylic acids such as itaconic acid, maleic acid and maleic anhydride; and (v) diethyl maleate, dibutyl maleate and dimaleic acid. -2
-Ethylhexyl, butyl fumarate, di-2-fumarate
Diesters of unsaturated dicarboxylic acids such as ethylhexyl, (vi) methyl acrylate, ethyl acrylate,
Α-methylene aliphatic monocarboxylates such as n-butyl acrylate, isobutyl acrylate, dodecyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, methyl α-chloroacrylate, methyl methacrylate, ethyl ethacrylate (Vii) acrylonitrile, nitriles such as methacrylonitrile, (viii) amides such as acrylamide, (ix) acrylanilide, p-chloroacrylanilide, m-nitroacrylanilide, m-methoxyacrylanilide, etc. Anilides, (x) vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, β-chloroethyl vinyl ether, (xi) vinyl chloride, vinylidene chloride, vinylidene cyanide, (xii) 1-methyl-1 Methoxy ethylene,
Ethylene derivatives such as 1,1-dimethoxyethylene, 1,2-dimethoxyethylene, 1,1-dimethoxycarbonylethylene, 1-methyl-1-nitroethylene, (xii
i) For example, N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole, N-vinyl pyrrolidene, N
Vinyl monomers such as N-vinyl compounds such as -vinylpyrrolidone; and (xiv) monomers having an alcoholic hydroxyl group such as hydroxyethyl acrylate and hydroxyethyl methacrylate.

Other monomers that can be used in combination with the polymerized unit represented by the general formula [I] include monomers having an active imino group as described in JP-A-63-226641. Body, JP-A-4-204448
No. 4,910,119, a monomer having a sulfonamide group as described in
No. 68946, JP-B-52-34933, and monomers having a hydroxyl group such as N- (hydroxyphenyl) methacrylamide and N (hydroxyphenyl) acrylamide or JP-B-52-41.
And carboxyl group-containing monomers as described in JP-A-052. A polymer compound obtained by polymerizing the polymerization unit represented by the general formula [I] can be generally produced by a radical chain polymerization method ("Textbook of Polymer Science" 3rd ed, (1984) F.
See W. Billmeyer, A Wiley-Interscience Publication). The molecular weight of the polymer compound obtained by polymerizing the polymerized unit represented by the general formula [I] may be in a wide range, but when measured by gel permeation chromatography or light scattering method using polystyrene as a standard, The average molecular weight Mw is preferably in the range of 500 to 2,000,000, and more preferably in the range of 2,000 to 1,000,000. The polymer compound obtained by polymerizing the polymerization unit represented by the general formula [I] is preferably 20 to 95% by weight, more preferably 50 to 90% by weight, based on the total weight of the composition. Included in the photosensitive composition.

As the positive-working photosensitive substance used in the present invention, an o-naphthoquinonediazide compound is preferable. For example, 1,2-diazonaphthoquinonesulfonic acid described in JP-B-43-28403 can be used. Esters of chloride and pyrogallol-acetone resin or esters of 1,2-diazonaphthoquinonesulfonic acid chloride and 2,3,4-trihydroxybenzophenone are preferred. Other suitable o-naphthoquinonediazide compounds include 1,2-diazonaphthoquinone sulfonic acid chloride and phenol described in U.S. Pat.Nos. 3,046,120 and 3,188,210.
There are esters with formaldehyde resins. As other useful o-naphthoquinonediazide compounds, those reported and known in many patents can be used. For example, JP-A-47-5303 and JP-A-48-5303
No. 63802, No. 48-63803, No. 48-9
Nos. 6575, 49-38701, 48-13
No. 354, Japanese Patent Publication No. 41-11222, No. 45-96
10, No. 49-17481, U.S. Pat.
No. 7,213, No. 3,454,400, No. 3,544,323, No.
No. 3,573,917, No. 3,674,495, No. 3,785,825,
UK Patent Nos. 1,227,602, 1,251,345, 1,26
No. 7,005, No. 1,329,888, No. 1,330,932, German Patent No. 854,890 and the like can be mentioned. In addition, as a photosensitive substance acting in a positive type other than the o-naphthoquinonediazide compound, a polymer compound having an orthonitrocarbinol ester group described in the specification of JP-B-56-2696 is also used in the present invention. can do.

A compound that generates an acid by photolysis,
A mixture with a compound having a C—O—C group or a C—O—Si group dissociated by an acid can also be used in the present invention as a photosensitive substance. For example, a combination of a compound capable of generating an acid by photolysis with an acetal or an O, N-acetal compound (JP-A-48-90303), or a combination of an orthoester or amide acetal compound (JP-A-51-1983)
120714), a combination with a polymer having an acetal or ketal group in the main chain (JP-A-53-133429).
No.), a combination with an enol ether compound (Japanese Unexamined Patent Publication No.
-12995), a combination with an N-acyliminocarbonate compound (JP-A-55-126236), a combination with a polymer having an orthoester group in the main chain (JP-A-56-1).
No. 7345), a combination with a silyl ester compound (JP-A-60-10247), a combination with a silyl ether compound (JP-A-60-37549, JP-A-60-121).
No. 446). These positive-acting photosensitive materials are preferably from 5 to 80% by weight, more preferably from 10 to 50% by weight, based on the total weight of the composition.
In the photosensitive composition.

Various additives can be added to the photosensitive composition of the present invention. For example, printing durability, print-out,
Known alkali-soluble polymers such as phenol formaldehyde resin, cresol formaldehyde resin, phenol-modified xylene resin, polyhydroxystyrene, and polyhalogenated hydroxystyrene for the purpose of improving various properties such as burning property, chemical resistance, and developability Compounds can be included. Such an alkali-soluble polymer compound is used in an amount of 0 to 200% by weight, more preferably 0 to 100% by weight, based on the polymer having the structural unit represented by the above general formula [I], based on the total weight of the composition. %. In the photosensitive composition of the present invention,
A cyclic acid anhydride for increasing sensitivity, a printing-out agent for obtaining a visible image immediately after exposure, a dye or other filler as an image colorant, and the like can be added. The cyclic acid anhydride U.S. Pat phthalic anhydride as described in 4,115,128 Pat, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3,6-oxy - [delta ⁴
-Tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, maleic anhydride, chloromaleic anhydride, α-phenylmaleic anhydride, succinic anhydride, pyromellitic acid and the like. By containing these cyclic anhydrides in an amount of 1 to 15% by weight based on the total weight of the composition, the sensitivity can be increased up to about three times. As a printing-out agent for obtaining a visible image immediately after exposure, a combination of a photosensitive substance which releases an acid upon exposure and an organic dye which can form a salt can be mentioned as a representative. More specifically,
And combinations of o-naphthoquinonediazide-4-sulfonic acid halogenide and salt-forming organic dyes described in JP-A-36209 and JP-A-53-8128.
Combinations of trihalomethyl compounds and salt-forming organic dyes described in JP-A-3-36223, JP-A-54-74728, JP-A-63-58440, and EP-A-0,505,903A. be able to. As the image coloring agent, other dyes can be used in addition to the above-mentioned salt-forming organic dye. Suitable dyes, including also salt-forming organic dyes, include various oil-soluble dyes and base dyes. Specifically, Oil Yellow # 101, Oil Yellow # 130, Oil Pink # 312, Oil Green BG, Oil Blue BO
S, Oil Blue # 603, Oil Black BY, Oil Black BS, Oil Black T-505 (all manufactured by Orient Chemical Industries, Ltd.), Crystal Violet (CI42555), Methyl Violet (CI42)
535), ethyl violet (CI42600), rhodamine B (CI45170B), malachite green (CI42000), methylene blue (CI5201)
5) and the like. Among them, Japanese Patent Application Laid-Open
The dyes described in JP 93247 A are particularly preferred.

Alkyl ethers (for example, ethylcellulose and methylcellulose) for improving coating properties, and fluorinated surfactants (for example, JP-A-62-17)
No. 0950), a nonionic surfactant (especially a fluorine surfactant), and a plasticizer (for example, butylphthalyl, polyethylene glycol) for imparting flexibility and abrasion resistance to the coating film ,
Tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, tricresyl phosphate, tributyl phosphate, trioctyl phosphate, tetrahydrofurfuryl oleate, oligomers and polymers of acrylic acid or methacrylic acid, among which And tricresyl phosphate are particularly preferred), and a sensitizer for improving the liposensitivity of the image area (for example, JP-A-55-527).
Half-esterified product of styrene-maleic anhydride copolymer with alcohol, octylphenol formaldehyde novolak resin, 50% fatty acid esterified product of p-hydroxystyrene, etc. described in JP-A No. 2000-163, etc.) are preferably used. The amount of these additives varies depending on the purpose of use, but is generally 0.0 to the total solids in the composition.
1 to 30% by weight.

A photosensitive layer can be formed by dissolving the photosensitive composition of the present invention in a solvent capable of dissolving the above-mentioned components, coating the solution on a support, and drying the coating. Examples of the solvent used here include ethylene dichloride, cyclohexanone, methyl ethyl ketone, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether,
-Methoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, toluene, ethyl acetate and the like, and these solvents can be used alone or as a mixture. The concentration (solid content) of the above components in the solution is preferably 2 to 50% by weight. Although the amount of application varies depending on the application, for example, in the case of a photosensitive lithographic printing plate, it is generally preferable that the solid content be 0.5 to 3.0 g / m ² . Although the photosensitivity increases as the coating amount decreases,
The physical properties of the coating film of the photosensitive layer decrease.

Although the photosensitive composition of the present invention can be used as a photoresist for IC production, it is particularly suitable as a photosensitive layer of a photosensitive lithographic printing plate. Hereinafter, aspects of the photosensitive lithographic printing plate will be described in detail. The support is desirably a dimensionally stable plate. As such a dimensionally stable plate, those conventionally used as a support for printed matter can be suitably used. Examples of such a support include paper; paper laminated with plastics (eg, polyethylene, polypropylene, polystyrene, etc.); metal plates such as aluminum (including aluminum alloys), zinc, and copper; cellulose diacetate, triacetic acid Plastic film such as cellulose, cellulose propionate, cellulose acetate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc .; paper or plastic film on which the above metal is laminated or deposited And so on. Among these supports, the aluminum plate is preferable because it is extremely stable in dimension, is inexpensive, and has particularly good adhesion to the photosensitive layer of the present invention. 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 metal, particularly an aluminum support, it is preferable that a surface treatment such as a graining treatment and an anodic oxidation treatment is performed. In order to further enhance the hydrophilicity of the surface, immersion treatment in an aqueous solution of sodium silicate, potassium fluorozirconate, phosphate or the like may be performed.
As described in U.S. Pat. No. 2,714,066, an aluminum plate grained and then immersed in an aqueous solution of sodium silicate, and an anodized aluminum plate as described in JP-B-47-5125. After that, it is preferable to perform immersion treatment in an aqueous solution of an alkali metal silicate. Further, silicate electrodeposition as described in U.S. Pat. No. 3,658,662,
-27481, JP-A-52-58602,
It is also useful to combine an electric field grain as disclosed in JP-A-52-30503 with the above-described anodic oxidation treatment and sodium silicate treatment. Also, JP-A-56-
As disclosed in Japanese Patent No. 28893, a brush grain, an electric field grain, an anodizing treatment, and a sodium silicate treatment sequentially performed are also suitable.

Before the photosensitive layer is coated on the aluminum plate, an organic undercoat layer is provided if necessary. Examples of the organic compound used in the organic undercoat layer include carboxymethyl cellulose, dextrin, gum arabic,
-Phosphonic acids having an amino group such as -aminoethylphosphonic acid, phenylphosphonic acid which may have a substituent,
Organic phosphonic acids such as naphthylphosphonic acid, alkylphosphonic acid, glycerophosphonic acid, methylenediphosphonic acid and ethylenediphosphonic acid; Organic phosphoric acid esters, optionally substituted phenylphosphinic acid, naphthylphosphinic acid, organic phosphinic acids such as alkylphosphinic acid and glycerophosphinic acid, amino acids such as glycine and β-alanine, and hydrochloric acid of triethanolamine Hydrochlorides of amines having a hydroxyl group such as salts can be used alone or in combination of two or more. This organic undercoat layer can be provided by the following method. That is, a method in which a solution obtained by dissolving the above organic compound in water or an organic solvent such as methanol, ethanol, or methyl ethyl ketone or a mixed solvent thereof is applied to an aluminum plate and dried to form a water or methanol, ethanol, methyl ethyl ketone. An aluminum plate is immersed in a solution in which the above organic compound is dissolved in an organic solvent such as an organic solvent or a mixed solvent thereof to adsorb the organic compound, and then washed with water and dried, and dried to form an organic undercoat layer. It is a method of providing. In the former method, a solution of the above organic compound having a concentration of 0.005 to 10% by weight can be applied to an aluminum plate by various methods. For example, any method such as bar coater coating, spin coating, spray coating, and curtain coating may be used. In the latter method, the aluminum plate is placed in a solution of the organic compound at a concentration of 0.01 to 20% by weight, preferably 0.05 to 5% by weight, at 20 to 90 ° C, preferably 25 to 50 ° C. At an immersion temperature of 0.1 seconds to 20 minutes, preferably 2 seconds to 1 minute to form an organic undercoat layer. The above solution is prepared with basic substances such as ammonia, triethylamine and potassium hydroxide, and acidic substances such as hydrochloric acid and phosphoric acid.
The pH can be adjusted and used in the range of pH 1 to 12. Further, a yellow dye may be added for improving the tone reproducibility of the photosensitive lithographic printing plate.

The coating amount of the organic undercoat layer after drying is from 2 to 20.
0 mg / m ² is suitable, preferably 5 to 100 mg / m ^2
2 If the coating amount is less than 2 mg / m ² , sufficient printing durability cannot be obtained. The same is true even if it is larger than 200 mg / m ² . The photosensitive planographic printing plate having the photosensitive layer formed as described above, after image exposure, pH
It can be developed with an alkaline aqueous solution of 12.5 or less.
The surface of the photosensitive layer of the photosensitive lithographic printing plate is preferably matted in order to reduce the time for evacuation and prevent blurring during contact exposure using a vacuum printing frame. In particular,
JP-A-50-125805, JP-B-57-6582
And a method of thermally fusing a solid powder as described in JP-B-62-62337.

The light source used for image exposure of the photosensitive lithographic printing plate of the present invention includes a carbon arc lamp, a mercury lamp, a xenon lamp, a tungsten lamp, a metal halide lamp and the like. As the developer for the photosensitive lithographic printing plate of the present invention, an aqueous alkaline solution having a pH of 12.5 or less can be used, and more preferably, an aqueous alkaline solution having a pH of 8 to 11 is used. In order to obtain such a pH value, basic compounds used include sodium tribasic phosphate, potassium tribasic phosphate, ammonium tribasic phosphate, dibasic sodium phosphate, dibasic potassium phosphate, and dibasic potassium phosphate. Phosphates such as ammonium phosphate, carbonates such as ammonium bicarbonate, sodium carbonate, potassium carbonate, ammonium carbonate, sodium bicarbonate and potassium bicarbonate; borates such as sodium borate, potassium borate, and ammonium borate And alkali metal hydroxides such as potassium hydroxide, sodium hydroxide, lithium hydroxide and ammonium hydroxide. Particularly preferred are combinations of carbonate and bicarbonate. These may be used alone or as a mixture. As another basic compound, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanol Water-soluble organic amine compounds such as amine, ethyleneimine, ethylenediamine, pyridine and the like can be mentioned. Among them, monoethanolamine, diethanolamine, triethanolamine and the like are particularly preferable, and may be used in combination with an inorganic alkali metal salt or the like.

The concentration of these basic compounds in an aqueous solution is, as described above, pH 12.5 or less, more preferably pH 8 or less.
Although it is used in the range of 11 to 11, it can be generally selected from the range of 0.05 to 10% by weight. If necessary, an anionic surfactant may be added to the developer. Examples of the anionic surfactant include higher alcohol sulfates having 8 to 22 carbon atoms such as sodium salt of lauryl alcohol sulfate, sodium salt of octyl alcohol sulfate, ammonium salt of lauryl alcohol sulfate, and secondary sodium alkyl sulfate. Salts, for example, aliphatic alcohol phosphate salts such as cetyl alcohol phosphate sodium salt, and alkyl such as dodecylbenzenesulfonic acid sodium salt, isopropylnaphthalenesulfonic acid sodium salt, metanitrobenzenesulfonic acid sodium salt, and the like. arylsulfonic acid salts, e.g., _{C 17 H 33 CON (CH 3} ) CH 2 CH 2 sO 3 sulfonates of alkylamides such as Na, such as sodium dioctylsulfosuccinate, Na Sulfonic acid salts of dibasic fatty acid esters such as Riumusuruho succinic acid dihexyl ester include. It is appropriate that the anionic surfactant is contained in the range of 0.1 to 5% by weight based on the total weight of the developing solution at the time of use. When the amount is less than 0.1% by weight, the effect of the use is reduced. When the amount is more than 5% by weight, the dissolution (color loss) of the dye in the image area becomes excessive, There are adverse effects such as deterioration of chemical strength. Further, an organic solvent that can be mixed with water, such as benzyl alcohol, may be added to the developer. As the organic solvent, those having a solubility in water of about 10% by weight or less are suitable, and are preferably selected from those having a solubility of 5% by weight or less. For example, 1-phenylethanol, 2-phenylethanol, 3-phenylpropanol-1,4-phenylbutanol-1,4-phenylbutanol-2,2-phenylbutanol-1,2-hexyethanol, 2-benzyloxyethanol , O-
Examples include methoxybenzyl alcohol, m-methoxybenzyl alcohol, p-methoxybenzyl alcohol, benzyl alcohol, cyclohexanol, 2-methylcyclohexanol, 4-methylcyclohexanol, 3-methylcyclohexanol, and the like. The content of the organic solvent is 1 to 5 with respect to the total weight of the developing solution at the time of use.
% By weight is preferred. The amount used is closely related to the amount used of the anionic surfactant, and it is preferable to increase the amount of the anionic surfactant as the amount of the organic solvent increases. This is when the amount of anionic surfactant is small,
If a large amount of the organic solvent is used, the organic solvent does not dissolve, so that good development property cannot be expected.

Further, if necessary, additives such as an antifoaming agent and a water softener can be contained in the developer. Examples of the water softener include Na ₂ P ₂ O ₇ and Na ₅ P ₃
Polyphosphates such as O ₃ , Na ₃ P ₃ O ₉ , Na ₂ O ₄ P (NaO ₃ P) PO ₃ Na ₂ , and calgon (sodium polymetaphosphate), for example, ethylenediaminetetraacetic acid, its potassium salt, its sodium salt; Diethylenetriaminepentaacetic acid, its potassium salt and its sodium salt; triethylenetetramine hexaacetic acid, its potassium salt and its sodium salt; hydroxyethylethylenediaminetriacetic acid, its potassium salt and its sodium salt; nitrilotriacetic acid, its potassium salt and its sodium salt; 1,2-diaminocyclohexanetetraacetic acid, its potassium salt, its sodium salt; 1,3-
In addition to aminopolycarboxylic acids such as diamino-2-propanoltetraacetic acid, its potassium salt and its sodium salt, 2-phosphonobutanetricarboxylic acid-1,
2,4, potassium salt thereof, sodium salt thereof; 2-phosphonobutanetricarboxylic acid-2,3,4, potassium salt thereof, sodium salt thereof; 1-phosphonoethanetricarboxylic acid-1,2,2, potassium salt thereof Salts, sodium salts thereof; 1-hydroxyethane-1,1-diphosphonic acid, potassium salts, sodium salts thereof; and organic phosphonic acids such as aminotri (methylenephosphonic acid), potassium salts, sodium salts thereof. Can be. The optimum amount of such a water softener varies depending on the hardness of the hard water used and the amount used, but is generally 0.01 to 5% by weight, more preferably 0.01 to 5% by weight in the developer at the time of use. 0.0
It is contained in the range of 1 to 0.5% by weight.

The photosensitive lithographic printing plate of the present invention is disclosed in
JP-A-8002, JP-A-55-115045 and JP-A-59-15045.
It goes without saying that the plate-making process may be performed by the method described in each of the publications of No. 58431. That is, after the development processing,
A desensitization treatment after washing with water, a desensitization treatment as it is, a treatment with an aqueous solution containing an acid, or a treatment with an aqueous solution containing an acid may be followed by a desensitization treatment. Further, in the development process of this type of photosensitive lithographic printing plate, the developing solution becomes fatigued depending on the processing amount. Therefore, a replenisher or a fresh developing solution may be added to restore the developing ability. In this case, it is preferable to replenish by the method described in U.S. Pat. No. 4,882,246. Further, the above plate making process is preferably performed by an automatic developing machine as described in JP-A-2-7054 and JP-A-2-32357. Further, when 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 and JP-B-62-25118.
No. 63-52600, JP-A-62-7595,
Those described in JP-A-62-11693 and JP-A-62-83194 are 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 burning after washing with water, before burning, the Japanese Patent Publication No. 61-251 is required.
No. 8, No. 55-28062, JP-A-62-31859.
And JP-A-61-159655. Hereinafter, the present invention will be described in more detail with reference to Synthesis Examples and Examples, but the present invention is not limited thereto. Unless otherwise specified, all percentages indicate% by weight.

EXAMPLES Synthesis Example 1 Synthesis of N- (2-carboxy-4-chlorophenyl) methacrylamide (Compound of Specific Example 1) 145.8 g of 2-amino-5-chloro-benzoic acid in a 1-liter three-necked flask (0.85 mol), 220 ml of N, N-dimethylformamide, 223.6 g of triethylamine
(2.21 mol). Next, the temperature was set to 2 under ice water cooling.
While maintaining the temperature at 0 ° C. or lower, methacrylic anhydride 1
A mixed solution of 70.4 g (1.11 mol) and 110 ml of N, N-dimethylformamide was added dropwise. After completion of the dropwise addition, the mixture was stirred for 4 hours except for the ice water bath. After completion of the reaction, the reaction solution was
The mixture was poured into a beaker containing 1 g of -butyl pyrocatechol, ethyl acetate, diluted sulfuric acid, and ice, transferred to a separating funnel, and the organic layer was washed twice with a saturated saline solution.

After drying the organic layer over magnesium sulfate,
Suction filtration was performed. The solvent was distilled off under reduced pressure while adding toluene to the filtrate to precipitate crystals. The crystals were collected by filtration and dried to give pale yellow crystals having a melting point of 209 to 210 ° C.
g was obtained. (Yield 70%) The crystal structure was identified from the following NMR spectrum and elemental analysis values. ¹ H-NMR (δ: DMSO-d ₆ ) 2.01 (S, 3H), 5.61 (S, 1H), 5.90 (S, 1H), 7.67 (dd,
J = 9.1, 2.7Hz, 1H), 7.94 (d, J = 2.7Hz, 1H), 8.64 (d,
J = 9.1 Hz, 1H), 11.65 (S, 1H) Elemental analysis: C: 55.21%, H: 4.27%, N: 5.6
9% [Synthesis Example 2] Synthesis of N- (2-carboxy-4-chlorophenyl) acrylamide (compound of Specific Example 2) In a 500 ml three-necked flask, 49.8 g (0.29 mol) of 2-amino-5-chlorobenzoic acid was added. ), N, N-dimethylformamide 100 ml, triethylamine 105.6 g (1.0
4 mol). Next, 47.2 g (0.5%) of acrylic acid chloride was stirred under cooling with ice water while maintaining the temperature at 20 ° C. or lower.
2 mol) and 50 ml of N, N-dimethylformamide were added dropwise. After the addition, the ice water bath was removed and the mixture was stirred for 4 hours. After the completion of the reaction, the same treatment as in Synthesis Example 1 was carried out to obtain 30.8 g of pale yellow crystals having a melting point of 184 to 186 ° C. (Yield 47%)

The structure of the crystal was identified by the following NMR spectrum and elemental analysis. ^{1 H-NMR (δ: DMSO} -d 6) 5.85 (d, J = 10.0Hz, 1H), 6.26 (d, J = 17.0Hz, 1H), 6.
41 (dd, J = 17.0, 10.0Hz, 1H), 7.67 (d, J = 9.0Hz, 1H),
7.92 (S, 1H), 8.52 (d, J = 9.0 Hz, 1H), 11.24 (S, 1H) Elemental analysis value C: 53.40%, H: 3.41%, N: 6.0
7% [Synthesis Example 3] Synthesis of N- (2-carboxy-4-bromophenyl) methacrylamide (compound of Specific Example 5) 43.2 g (0.2 mol) of 2-amino-5-bromobenzoic acid, triethylamine Using 52.6 g (0.52 mol), 40.1 g (0.26 mol) of methacrylic anhydride and 100 ml of N, N-dimethylformamide, the reaction was carried out in the same manner as in Synthesis Example 1, and the melting point was 204. 28.8 g of pale yellow crystals having a temperature of 5 to 205.5 ° C. were obtained. (Yield 51%)

The structure of the crystal was identified by the following NMR spectrum and elemental analysis. ¹ H-NMR (δ: DMSO-d ₆ ) 2.01 (S, 3H), 5.62 (S, 1H), 5.90 (S, 1H), 7.79 (dd,
J = 9.1, 2.0Hz, 1H), 8.08 (d, J = 2.0Hz, 1H), 8.59 (d,
J = 9.1 Hz, 1H), 11.66 (S, 1H) Elemental analysis: C: 46.39%, H: 3.51%, N: 4.8
5% [Synthesis Example 4] Synthesis of (2-carboxy-4,6-dichlorophenyl) methacrylate (compound of specific example 10) 51.8 g (0.25 mol) of 3,5-dichlorosalisaric acid in a 200 ml three-necked flask , Methacrylic anhydride 57.8
g (0.37 mol) and 1 ml of concentrated sulfuric acid were added, and the mixture was heated and stirred at 60 to 70 ° C for 4 hours. After completion of the reaction, the reaction solution was
-Butyl pyrocatechol 0.5g, ethyl acetate and water were poured into a beaker and transferred to a separatory funnel. After concentrating the organic layer, it was purified by silica gel chromatography. The obtained crystals were recrystallized from ethyl acetate / toluene / hexane to give 35.8 g of white crystals having a melting point of 139 to 141 ° C. (Yield 52%)

The structure of the crystal was identified by the following NMR spectrum and elemental analysis. ^{1 H-NMR 2.01 (S,} 3H), 5.96 (S, 1H), 6.30 (S, 1H), 7.89 (S,
1H), 8.07 (S, 1H) Elemental analysis value C: 48.20%, H: 2.88% [Synthesis Examples 5 to 9] From the raw materials shown in the following Table 1, Synthesis Example 1
Compounds shown in Table 1 were synthesized in the same manner as in Example 1 or 2.

[0032]

Table 1 Synthesis Example Raw Material Synthesis Method Product 5 2-Amino-4-chloro-benzoic acid According to Synthesis Example 1 Compound of Specific Example 3 Methacrylic anhydride 6 2-Amino-5-methyl-benzoic acid Synthesis According to Example 1 Compound of specific example 6 Methacrylic anhydride 7 2-amino-3,5-dimethyl-benzoic acid Compound of specific example 8 Methacrylic anhydride according to Synthesis example 8 3-Hydroxy-2-naphthoic acid Synthesis According to Example 2, compound acrylic acid chloride 9 of Example 12 3-Amino-2-naphthoic acid According to Synthesis Example 1, compound methacrylic acid chloride of Example 13

Synthesis Example 10 N- (2-carboxyl-
240 g of 4-chlorophenyl) methacrylamide (compound of Synthesis Example 1), N, N-dimethylformamide 480
g was placed in a two-liter three-necked flask and kept at 65 ° C. while stirring under a nitrogen stream. 2,2'-azobis (2,4
Dimethylvaleronitrile) (249 mg) and stirring was continued. Two hours later, 622 mg of 2,2'-azobis (2,4-dimethylvaleronitrile) was further added. After 2 hours, 622 mg of 2,2'-azobis (2,4-dimethylvaleronitrile was further added. After stirring for 2 hours, the mixture was cooled to room temperature, 200 ml of acetone was added, and 8.2 liter of the reaction solution was added. The precipitated solid was collected by filtration and dried, and the solid was a polymer compound having a weight average molecular weight of 240,000 according to a light scattering method.Yield: 286 g [Synthesis Examples 11 to 22] Various polymer compounds as shown in Table 2 were synthesized in the same manner.

[0034]

[Table 2]

[0035]

[Table 3]

[0036]

[Table 4]

[0037]

[Table 5]

Examples 1 to 4 and Comparative Examples 1 to 3 A 0.30 mm thick aluminum plate was
The surface was sand-grained using a 0-mesh pumistone aqueous suspension, and then thoroughly washed with water. The aluminum plate was immersed in a 10% aqueous sodium hydroxide solution at 70 ° C. for 60 seconds for etching, washed with running water, washed with 20% HNO ₃ , and washed with water. This was subjected to electrolytic surface roughening treatment in a 1% nitric acid aqueous solution at an anode-time electricity quantity of 160 clones / dm ³ using a sine wave alternating current under the condition of V _A = 12.7 V. When the surface roughness was measured, it was 0.6 μ (Ra indication). Subsequently, the aluminum plate was reduced to 30%
After immersion in an aqueous solution of H ₂ SO _{4 and} desmutting at 55 ° C. for 2 minutes, anodic oxidation in an aqueous solution of 20% H ₂ SO ₄ at a current density of 2 A / dm ^{3 to} an oxide film weight of 2.7 g / m ^2. did. After that, the aluminum plate was treated with 70% sodium silicate 2.
It was immersed in a 5% aqueous solution for 1 minute, washed with water, and dried. An undercoat solution (A) having the following composition was applied to the surface of the aluminum plate treated in this manner, and dried at 80 ° C. for 30 seconds.
(I) was prepared. The coating amount after drying was 30 mg / m ² . Undercoat liquid (A) Phenylphosphonic acid 0.10 g Methanol 40 g Pure water 60 g

Next, the following photosensitive solution (A) was applied on the substrate (I) by rod coating in an amount of 25 ml / m ² and dried at 100 ° C. for 1 minute to obtain a positive photosensitive lithographic printing plate. Obtained. The coated amount after drying was about 2.0 g / m ² . Photosensitive solution (A) Esterification reaction product of 1,2-naphthoquinonediazido-5-sulfonyl chloride and 0.5 g 2,3,4-trihydroxybenzophenone Polymer compound produced in Synthesis Example 2.0 g 2- (p -Butoxyphenyl) -4,6-0.02 g bis (trichloromethyl) -S-triazine naphthoquinone-1,2-diazide-4-sulfonic acid chloride 0.03 g crystal violet 0.01 g oil blue # 603 (Orient Chemical Industries Co., Ltd.) 0.015 g Ethylene dichloride 18 g 2-Methoxyethyl acetate 12 g

Each of these photosensitive lithographic printing plates was 2 kw
Was exposed through a positive transparent original from a distance of 1 m for 40 seconds with a metal halide lamp. The exposed photosensitive lithographic printing plate was developed under the following conditions. That is, first, a developing solution (pH 1) was prepared by diluting the following undeveloped developing solution-1 with water four-fold in an automatic developing machine Stublon 900NP manufactured by Fuji Photo Film Co., Ltd.
0) and Finisher FP-2 manufactured by Fuji Film Co., Ltd., respectively, and were subjected to a development process under the conditions of a developer temperature of 30 ° C. and a development time of 30 seconds. Developing stock solution-1 Sodium carbonate / monohydrate 6 g Sodium bicarbonate 3 g Ethylenediaminetetraacetic acid 2 g Sodium dodecylbenzenesulfonate 1 g Water 100 g

It was evaluated whether an image could be obtained after the development processing. If the photosensitive film could not be developed and was left as it was, the image forming property was evaluated as x (defective development), and if the photosensitive film was completely dissolved and not left, the image was evaluated as x (overdeveloped). Was evaluated as 形成 in image forming properties. The resulting image was processed according to a conventional method to obtain a lithographic printing plate. The lithographic printing plate thus obtained was printed on an offset printing machine and a printing durability test was performed. If the printing durability is poor, the image portion wears out with a small number of sheets, and the ink does not adhere to the printed portion, so that a normal printed matter cannot be obtained. In order to examine the range of the range of suitable development conditions (development tolerance), the exposed photosensitive planographic printing plate was immersed in the above developer for 5 minutes and developed, and immersed for 30 seconds in development. The change in tone reproducibility was examined. A symbol indicating little change was indicated by a mark, a symbol indicating a significant change was indicated by a mark, and an intermediate mark was indicated by a mark. Table 3 shows the results. As a comparative example,
The following C1 and C2 were used in place of the polymer compound produced in the synthesis example.
Alternatively, a photosensitive planographic printing plate was produced using a polymer compound of C5, and image forming properties were evaluated in the same manner as in the examples. Table 3 shows the results.

[0042]

[Table 6] Table III Example Polymer compounds Image forming Developing Time tolerance Number of printings １1 Polymer produced in Synthesis Example 10 Compound ○ ○ 140,000 2 Polymer compound produced in Synthesis Example 11 ○ ○ 100,000 3 Polymer compound produced in Synthesis Example 12 ○ ○ 90,000 Polymer compound produced in Synthesis Example 13 ○ △ 80,000 Comparative Example 1 C1 × (over-development) 2 C2 × (over-development) 3 C5 × (defect in development) ────────────────────────────── ─────

Comparative Polymer

Embedded image

Examples 5 to 6 and Comparative Example 4 A JIS A 1050 aluminum plate having a thickness of 0.24 mm was supplied to a surface of aluminum with a suspension of pumistone having an average particle size of about 21 μm and water. Brush graining with a first rotating nylon brush with a hair diameter of 0.95 mm and a flocking density of 70 hairs / cm ^{2 and} a second rotating nylon brush with a hair length of 80 mm, a hair diameter of 0.295 mm and a flocking density of 670 hairs / cm ² The rotation of each of the treated brush rolls was 250 rpm. Following brush graining, wash the aluminum plate thoroughly with water and then add 60% aqueous solution of 10% sodium hydroxide.
Etching was performed by immersion at 25 ° C. for 25 seconds, followed by washing with running water, neutralizing and washing with 20% nitric acid, and washing with water. These are referred to as V _A
= 12.7V, using a sinusoidal alternating current,
The electrolytic surface-roughening treatment was performed in 1% nitric acid in a solution at an anode charge of 160 coulomb / dm ² . The surface roughness was measured and found to be 0.79 μm ( _Ra display). Subsequently, the aluminum plate was placed in a 1% aqueous sodium hydroxide solution for 4 hours.
After immersion at 0 ° C. for 30 seconds, immersion in a 30% sulfuric acid aqueous solution and desmutting at 60 ° C. for 40 seconds, an oxide film of 1.6 g / m ^{2 in} a 20% sulfuric acid aqueous solution at a current density of 2 A / dm ² . Anodized with direct current to weight. Thereafter, the aluminum plate was immersed in a 2.5% aqueous solution of sodium silicate at 40 ° C. for 1 minute and dried. The undercoat liquid (A) was applied to the surface of the aluminum plate thus treated under the same conditions as in Examples 1 to 4, and dried to prepare a substrate (II).

Next, the photosensitive liquid (A) was applied on the substrate (II) in the same manner as in Examples 1 to 4, and dried to obtain a positive photosensitive lithographic printing plate. Each of these photosensitive lithographic printing plates was exposed for 40 seconds through a positive transparent original from a distance of 1 m with a 2 kW metal halide lamp. The exposed photosensitive lithographic printing plate was developed under the following conditions. That is, Fuji Photo Film Co., Ltd.'s automatic machine Stublon 900
A developing solution (pH 10.5) obtained by diluting the following undeveloped solution-2 in water with NP and Finisher FP manufactured by Fuji Film Co., Ltd.
-2, a developer temperature of 30 ° C. and a development time of 30
The development was performed under the condition of seconds. Developing stock solution-2 Sodium carbonate / monohydrate 9g Sodium bicarbonate 1.5g Diethylenetriaminepentaacetic acid 2g Sodium metanitrobenzenesulfonate 1g Water 100g The same method as in Examples 1-4 was used to evaluate whether an image could be obtained after development. did.

The resulting image was processed according to a conventional method to obtain a lithographic printing plate. The lithographic printing plate thus obtained was printed on an offset printing machine, and a printing durability test was performed. Further, the range of the suitable developing conditions (developability) was evaluated in the same manner as in Examples 1 to 4, and the results are shown in Table 4. As a comparative example, a photosensitive planographic printing plate was produced using a polymer compound of C3 in place of the polymer compound produced in the synthesis example, and image forming properties were evaluated in the same manner as in Examples 1 to 4. . Table 4 shows the results.

[0047]

[Table 7] Table 4 Example: Polymer compound Image-forming Development Time tolerance Number of printings ─────────────────────────────────── 5 Polymer produced in Synthesis Example 14 Compound ○ △ 90,000 High molecular compound produced in Synthesis Example 15 ○ △ 80,000 Comparative Example 4 C3 × (overdevelopment) ────────────────────── ─────────────

[0048]

Embedded image

Examples 7-8 and Comparative Example 6 A substrate (II) was prepared by treating an aluminum plate under the same conditions as in Examples 5-6. Next, the following photosensitive solution (B) was applied onto this substrate (II) using a wheeler,
After drying for a minute, a positive photosensitive lithographic printing plate was obtained. The coated amount after drying was about 1.9 g / m ² . Photosensitive solution (B) Esterified product of 1,2-diazonaphthoquinone-5-sulfonyl chloride and 0.45 g pyrogallol-acetone resin (described in Example 1 of US Pat. No. 3,635,709) Synthesis Example 1.2 g naphthoquinonediazide-1,2-diazide-4-0.01 g Sulfonyl chloride tetrahydrophthalic anhydride 0.02 g Benzoic acid 0.02 g Pyrogallol 0.05 g 4- [p-N, N -Bis (ethoxycarbonylmethyl) 0.005 g aminophenyl] -2,6-bis (trichloromethyl) -S-triazine (hereinafter abbreviated as triazine A) N- (1,2-naphthoquinone-2-diazide-4-0) .01g Sulfonyloxy) -cyclohexane-1,2-dicarboxylic imide Victoria Pure-Blue BOH [Hodogaya Chemical (Manufactured by Dainippon Ink and Chemicals, Inc.) 0.045 g of a dye in which the counter anion has been changed to 1-naphthalenesulfonic acid Megafac F-177 (manufactured by Dainippon Ink and Chemicals, Inc. 0.015 g of a fluorine-based surfactant) 10g

Next, each of these photosensitive lithographic printing plates was exposed to light through a transparent positive film in a vacuum baking frame from a distance of 1 m with a 3 kw metal halide lamp for 1 minute, and then SiO ₂ / Na at 30 ° C. for 30 seconds. ₂ O (molar ratio
2.0) 3.5% aqueous solution of sodium silicate (pH = 12.4)
Developed. It was evaluated in the same manner as in Examples 1 to 4 whether or not an image could be obtained after the development processing. The resulting image was processed according to a conventional method to obtain a lithographic printing plate.
The lithographic printing plate thus obtained was printed on an offset printing machine, and a printing durability test was performed. In addition, the range of suitable development conditions (developability) was evaluated in the same manner as in Examples 1 to 4, and the results are shown in Table 5. As a comparative example, a photosensitive planographic printing plate was produced using a polymer compound of C4 instead of the polymer compound produced in the synthesis example. Image forming properties were evaluated in the same manner as in Examples 1 to 4. Table 5 shows the results.

[0051]

[Table 8] Example 5 Polymer Compound Image Forming Development Time tolerance Number of printings 高分子 7 Polymer produced in Synthesis Example 16 Compound ○ △ 80,000 8 High molecular compound produced in Synthesis Example 17 ○ △ 90,000 Comparative Example 6 C4 × (overdevelopment) ────────────────────── ─────────────

[0052]

Embedded image

Examples 9 to 10 and Comparative Example 7 An aluminum plate was treated under the same conditions as in Examples 1 to 4 to produce a substrate (I). Next, the photosensitive liquid (B) was applied on the substrate (I) in the same manner as in Examples 7 and 8, and dried to obtain a positive photosensitive lithographic printing plate. The coating amount after drying was 2.0 g / m ² . Each of these photosensitive lithographic printing plates was exposed for 40 seconds through a positive transparent original from a distance of 1 m with a 2 kW metal halide lamp.

The exposed photosensitive lithographic printing plate was developed under the following conditions. That is, first, a developing solution (pH 10) obtained by diluting the following undiluted developing solution-3 twice with water and a finisher FP-2 manufactured by Fuji Film Co., Ltd. were charged into an automatic developing machine Stublon 900NP manufactured by Fuji Photo Film Co., Ltd.
The developing process was performed under the conditions of a developing solution temperature of 30 ° C. and a developing time of 30 seconds. Stock solution for development-3 10 g of benzyl alcohol 10 g of triethanolamine 10 g of sodium isopropylnaphthalenesulfonate 10 g of water 500 g The same method as in Examples 1 to 4 was used to evaluate whether images could be obtained after development processing. Further, in order to examine the range of the range of suitable development conditions (development tolerance), the exposed photosensitive planographic printing plate was developed with a developer obtained by diluting the above-mentioned stock solution-3 to 1.5 times with water. The change in tone reproducibility when developed with a developing solution diluted twice was examined. ○: little change, ×: large change, △ in middle
Displayed with. Table 6 shows the results.

As a comparative example, a photosensitive planographic printing plate was produced using a polymer compound of C5 instead of the polymer compound produced in the synthesis example. Image forming properties were evaluated in the same manner as in Examples 1 to 4. Table 6 shows the results.

[Table 9] Table 6 Example Polymer compounds Image forming ability Development density tolerance ９ 9 Polymer compound produced in Synthesis Example 18 ○ △ 10 Prepared in Synthesis Example 20 Polymer compound ○ ○ Comparative Example 7 C5 × (defective development) ──────────────────────────────── Table 3 ~ As is apparent from No. 6, a photosensitive planographic printing plate having good image forming properties and a wide range of suitable developing conditions (development allowance) was obtained by the photosensitive composition of the present invention. A planographic printing plate manufactured from a printing plate has high printing durability.

────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Keisa Akiyama 4000 Kawajiri, Yoshida-cho, Haibara-gun, Shizuoka Prefecture Fuji Photo Film Co., Ltd. (56) References JP-A-3-68946 (JP, A) (58) Survey Field (Int.Cl. ⁷ , DB name) G03F 7/033 G03F 7/039 G03F 7/00 503

Claims (2)

(57) [Claims] 1. A photosensitive composition comprising: a polymer compound obtained by polymerizing at least one polymerized unit represented by the following general formula [I]; and a positive-working photosensitive material. object. Embedded image In the formula, A represents a hydrogen atom, a halogen atom, or an alkyl group; X represents an oxygen atom, NH, or N—R ₅ (where R ₅ represents an alkyl group); R ₁ , R ₂ , R ₃ , and R ₄ are each independently a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, -OR ₆ , -OCO-R ₇ , -NHCO-R ₈ ,
-NHCONHR ₉ , -OCONH-R ₁₀ , -COOR ₁₁ , -CONHR ₁₂ , -CO
R ₁₃ , -CONR ₁₄ R ₁₅ , -CN, or -CHO represents a group, or R ₁ , R ₂ , R ₃ , and R ₄ represent a group in which two of them combine to form a ring Often, R _{6 to} R ₁₅ represent an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group. However, at least one of R ₁ , R ₂ , R ₃ and R ₄ represents a group other than a hydrogen atom. 2. After imagewise exposing a photosensitive material having a photosensitive layer containing the photosensitive composition according to claim 1 on a substrate, pH is adjusted.
An image forming method comprising developing with an aqueous alkali solution of 12.5 or less to remove the exposed portion of the photosensitive layer.