JP3059001B2 - Photosensitive lithographic printing plate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive photosensitive lithographic printing plate, and more particularly to a positive photosensitive lithographic printing plate containing a naphthoquinonediazide compound.

[0002]

2. Description of the Related Art Aluminum plates are widely and generally used as supports for lithographic printing plates. The aluminum plate is subjected to a surface treatment to improve hydrophilicity, water retention, adhesion to an image area, and strength of a non-image area. Examples of the surface treatment method include ball graining, wire graining, and brush graining methods that mechanically roughen the surface, electrolytic roughening using a direct current or an alternating current in a hydrochloric acid bath, a nitric acid bath, and the like, and a combination of these methods. Surface treatment has been performed. After this surface treatment, an anodic oxidation treatment is performed in a sulfuric acid or phosphoric acid bath. Further, a sealing treatment with silicate or hot water or a dipping treatment with polyvinyl sulfonic acid or the like may be performed.
A photosensitive material containing o-naphthoquinonediazide as a photosensitive material and a novolak resin, a vinyl resin, a urethane resin or the like as a binder is applied onto the aluminum support thus obtained. It is well known that a photosensitive lithographic printing plate is thereby produced. By using an o-naphthoquinonediazide compound of a polyhydroxy compound as such an o-naphthoquinonediazide compound, precipitation of crystals in the photosensitive layer can be prevented, storage stability can be improved, and adhesion to an aluminum support can be improved. It is already known to improve the properties, processing chemical resistance, developability and the like. For example,
As described in JP-A-28403, the use of an o-naphthoquinonediazidosulfonic acid ester of a polycondensation resin of pyrogallol and acetone, disclosed in JP-A-55-76.
No. 346, pyrogallol,
A method for controlling developability by using o-naphthoquinonediazidesulfonic acid ester of a polycondensation resin of a mixture of resorcinol and acetone, as described in JP-A-50-1044 and JP-A-50-1045. The use of a polycondensation resin of polyhydric phenol, benzaldehyde, and acetaldehyde to improve the developability and the treatment chemical resistance is disclosed.

[0003] However, the polycondensation resin of ketones or aldehydes of these polyhydroxyphenols has an o-
As a result of repeated studies using naphthoquinonediazidesulfonic acid ester, the following problems became clear. Generally, as a method of making a positive type lithographic printing plate,
A single positive film is prepared by pasting various patterns and text originals on the base, then this film is applied to the photosensitive layer of a photosensitive lithographic printing plate material, and is exposed to ultraviolet light, and further exposed. Is developed with a developer to form a printing plate. At this time, if higher printing resistance is desired, the photosensitive layer in the image area is thermally cured by a burning process. However, conventional polyhydroxyphenol ketone or aldehyde polycondensation resins o
When the positive film is applied to a photosensitive layer composed of naphthoquinonediazidesulfonic acid ester and exposed, the photosensitive layers at the edges of the various film bases stuck to the used positive original are not as strong as the image areas, And exposed on the plate in a semi-exposed state,
This semi-exposed photosensitive layer is strongly adhered on the plate surface,
It remains without being easily removed by the developer. When printing is performed using this plate, stains occur on the printed matter. The sticking marks generated in this manner cannot be completely erased by a so-called non-polluting erasing liquid (excluding hydrofluoric acid which is a powerful chemical), which is generally used for positive type lithographic printing. As a result, in actual printing, problems such as occurrence of scuffing of printed matter are caused. The pasting mark above
Burning, which is commonly performed to improve the printing durability, occurs more remarkably, and cannot be used in actual printing. However, when an o-naphthoquinonediazidosulfonic acid ester of a conventional polyhydroxyphenol ketone or aldehyde polycondensation resin is used in the photosensitive layer, other known o-naphthoquinonediazidesulfonic acid esters (for example, 2,
3,4,4'-tetrahydroxybenzophenone, m
-O-naphthoquinonediazide sulfonic acid ester of phenols such as cresol), even when the concentration of the developer is high, the problem that the photosensitive layer in the image area elutes hardly occurs, that is, an excellent point that the development latitude is wide. was there.

[0004]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a positive type ink which can erase the sticking mark even with an erasing liquid containing no hydrofluoric acid and which does not get ink on the part even after burning. An object of the present invention is to provide a photosensitive lithographic printing plate. It is another object of the present invention to provide a positive photosensitive lithographic printing plate having a wide developing latitude.

[0005]

SUMMARY OF THE INVENTION The object of the present invention is to provide an anodized aluminum plate having a grained surface,
In a photosensitive lithographic printing plate coated with a positive photosensitive composition containing at least one photosensitive substance and an alkali-soluble resin, the photosensitive substance is represented by the following general formula (I) or (II). Lithographic printing plates characterized in that they are 1,2 (and / or 2,1) -naphthoquinonediazide-5- (and / or -4-) sulfonic acid esters of polyhydroxy compounds to be prepared. .

[0006]

Embedded image

R ₁ is a hydrogen atom, a hydroxyl group, a halogen atom,
Represents an alkyl group, an alkoxy group, an alkenyl group, an aryl group, an aralkyl group, an alkoxycarbonyl group, an arylcarbonyl group, an acyloxy group, an acyl group, an aryloxy group or an aralkoxy group. R ₂ is a hydrogen atom,
Represents a halogen atom, a hydroxyl group, an alkyl group, or a carboxyl group. However, when R ₁ is a hydroxyl group, R ₂ is not a hydrogen atom. R _{3 to} R ₇ represent a hydroxyl group, a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or an alkenyl group. However, at least one of R _{3 to} R ₇ is a hydroxyl group.

Hereinafter, the present invention will be described in detail. In R ₁ and R ₂ of the above general formula (I), a halogen atom is a chlorine atom, a bromine atom or an iodine atom, and an alkyl group is a methyl group, an ethyl group, a propyl group, an n-butyl group, an isobutyl group, An alkyl group having 1 to 4 carbon atoms such as a sec-butyl group or a t-butyl group is a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, a hydroxypropoxy group, an isopropoxy group, an n-butoxy group. Group, isobutoxy group, sec
1 carbon atom such as -butoxy group or t-butoxy group
~ 4 alkoxy groups are preferred. As the alkenyl group, an alkenyl group having 2 to 4 carbon atoms such as a vinyl group, a propenyl group, an allyl group, or a butenyl group is preferable. Aryl groups include phenyl, xylyl, toluyl, and cumenyl groups; aralkyl groups include benzyl and phenethyl groups ; alkoxycarbonyl groups include methoxycarbonyl and ethoxycarbonyl groups; and arylcarbonyl groups include benzoyloxy groups. However, as the acyloxy group, a butyryloxy group, an acetoxy group,
The acyl group formyl group, an acetyl group, a butyryl group, a benzoyl group, cinnamoyl group, valeryl group, a phenoxy group as an aryloxy group, a benzyl group is preferably a aralkoxy group. General formula (I)
The compound represented by the following formula is described in, for example, JP-A-63-10745.
Nos. 63-41433, 64-25746, 64-26533, 64-63547 and 64-
No. 63548, No. 64-79136, JP-A-1-16
No. 0930, No. 1-160931, No. 1-16093
It can be obtained by the method described in No. 2. For example, the compound represented by the general formula (I) can be obtained by reacting a cyclohexanone represented by the general formula (III) with a phenol represented by the general formula (IV) in the presence of an acidic catalyst.

Embedded image (Wherein, R ₁ and R ₂ are as defined above.)

Catalysts which can be used for the reaction of the compound of the formula (III) with the compound of the formula (IV) include hydrogen chloride gas, hydrochloric acid, sulfuric acid, phosphoric acid, toluenesulfonic acid, BF ₃ , ZnCl ₂ , AlCl ₃ , S
Examples include nCl ₄ and a cation exchange resin having a transferable acidic group. The amount of these catalysts used ranges from 0.1 to 30 parts by weight per 100 parts by weight of the compound of the formula (III). The reaction rate can be increased by adding a cocatalyst. Active cocatalysts include methyl mercaptan,
Examples thereof include alkyl mercaptans such as ethyl mercaptan, n-propyl mercaptan, isopropyl mercaptan, n-butyl mercaptan, isobutyl mercaptan, and t-butyl mercaptan, and polymer alkyl mercaptans. Further, other sulfur compounds such as hydrogen sulfide, thiophenol, thioalcohol, thiosulfuric acid, polymer thioacetone, and dialkyl sulfide, and selenium compounds similar thereto can also be used.

In the above reaction, the amount of the phenol of the formula (IV) is preferably 2 to 10 parts by weight per 1 part by weight of the cyclohexanone of the formula (III). Reaction temperature is 30-10
It is in the range of 0 ° C, preferably in the range of 40 to 70 ° C. If the reaction temperature is too high, by-products increase and the yield decreases, which is not preferable. Specific examples of the compound represented by the general formula (I) thus obtained include 4,4'-bis (4
-Hydroxyphenyl) -cyclohexanecarboxylic acid,
4,4'-bis (3-tert-butyl-4-hydroxyphenyl) -cyclohexanecarboxylic acid, 2,2-bis (4-hydroxyphenyl) -cyclohexanecarboxylic acid, 2,2-bis (4-hydroxyphenyl) -3-methylcyclohexanecarboxylic acid, 2,2-bis (4-hydroxyphenyl) -4-methylcyclohexanecarboxylic acid, 2,2-bis (4-hydroxyphenyl) -5
Methylcyclohexanecarboxylic acid, 2,2-bis (4-
(Hydroxyphenyl) -6-methylcyclohexanecarboxylic acid, 2,2-bis (4-hydroxyphenyl) -3
-Ethylcyclohexanecarboxylic acid, 2,2-bis (4
-Hydroxyphenyl) -4-ethylcyclohexanecarboxylic acid, 2,2-bis (4-hydroxyphenyl)-
5-ethylcyclohexanecarboxylic acid, 2,2-bis (4-hydroxyphenyl) -6-ethylcyclohexanecarboxylic acid, 2,2-bis (4-hydroxyphenyl) -3,4-dimethylcyclohexanecarboxylic acid,
2,2-bis (4-hydroxyphenyl) -3,5-dimethylcyclohexanecarboxylic acid, 2,2-bis (4-
(Hydroxyphenyl) -3,6-dimethylcyclohexanecarboxylic acid, 2,2-bis (4-hydroxyphenyl) -4,5-dimethylcyclohexanecarboxylic acid,
2,2-bis (4-hydroxyphenyl) -4,6-dimethylcyclohexanecarboxylic acid, 2,2-bis (4-
(Hydroxyphenyl) -5,6-dimethylcyclohexanecarboxylic acid, 2,2-bis (4-hydroxy-2-methylphenyl) -cyclohexanecarboxylic acid, 2,2-
Bis (4-hydroxy-3-methylphenyl) -cyclohexanecarboxylic acid, 2,2-bis (4-hydroxy-
3,5-dimethylphenyl) -cyclohexanecarboxylic acid, 2,2-bis (4-hydroxy-3-methylphenyl) -4-methylcyclohexanecarboxylic acid, 2,2-
Bis (4-hydroxy-3,5-dimethylphenyl)-
5-methylcyclohexanecarboxylic acid, 1,1-bis (4-hydroxyphenyl) cyclohexane, 4-methyl-1,1-bis (4-hydroxyphenyl) cyclohexane, 3,3-bis (4-hydroxyphenyl) cyclohexanol And the like, but not limited thereto.

On the other hand, R _{3 of the} general formula (II) In to R _7, examples of the halogen atom, chlorine atom or iodine atom, the alkyl group methyl group, ethyl group, propyl group, n- butyl group, isobutyl group, sec - such as butyl or t- butyl group When the alkyl group having 1 to 4 carbon atoms is an alkoxy group, a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, a hydroxypropoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group or a t- An alkoxy group having 1 to 4 carbon atoms such as a butoxy group is preferred. As the alkenyl group, an alkenyl group having 2 to 4 carbon atoms such as a vinyl group, a propenyl group, an allyl group, or a butenyl group is preferable. The compound represented by the general formula (II) can be obtained, for example, by the method described in EP 208376, that is, by reacting cyanuric chloride with an aminophenol derivative. Specific examples of the compound thus obtained include 2,4,6-tris (3'-hydroxyphenyl) -amino-s-triazine and 2,4,6-tris (4'-hydroxyphenyl) -amino -S-triazine, 2,4,6-tris (3'-methyl-4'-hydroxyphenyl) -amino-s-triazine, 2,4,6
-Tris (3 ', 5'-dimethyl-4'-hydroxyphenyl) -amino-s-triazine, 2,4,6-tris (3'-chloro-4'-hydroxyphenyl) -amino-s-triazine, 2,4,6-tris (3 ', 5'
-Dichloro-4'-hydroxyphenyl) -amino-s
-Triazine, 2,4,6-tris (3 ', 5'-dibromo-4'-hydroxyphenyl) -amino-s-triazine, 2,4,6-tris (3'-bromo-4'-hydroxy- 5'-methylphenyl) -amino-s-triazine and the like, but are not limited thereto.

The photosensitive material of the present invention may be prepared, for example, by adding a part or all of the hydroxyl groups of the polyhydroxy compound to 1,2-
It is obtained by performing a normal esterification reaction with naphthoquinonediazide-5-sulfonyl chloride in the presence of a basic catalyst. That is, a predetermined amount of a polyhydroxy compound, 1,2-naphthoquinonediazide-5-sulfonyl chloride, dioxane, acetone, methyl ethyl ketone, N-
A solvent such as methylpyrrolidone is charged into the flask, and a basic catalyst such as sodium hydroxide, sodium hydrogen carbonate, triethylamine or the like is added dropwise to condense. The obtained product is washed with water, purified and dried. In the above-mentioned esterification reaction, a mixture having various esterification numbers and esterification positions is obtained. Therefore, the esterification rate referred to in the present invention is defined as an average value of this mixture.
The esterification rate thus defined is determined by comparing the raw material polyhydroxy compound with 1,2-naphthoquinonediazide-5.
-Controllable by the mixing ratio with sulfonyl chloride. That is, since the added 1,2-naphthoquinonediazide-5-sulfonyl chloride causes substantially all esterification reactions, to obtain a mixture having a desired esterification rate,
The molar ratio of the raw materials may be adjusted. Similarly, the photosensitive substance of the present invention can be obtained by reacting with 2,1-naphthoquinone-5-sulfonyl chloride, 1,2-naphthoquinonediazide-4-sulfonyl chloride or the like. The reaction temperature by the above method is usually -20 to 60C, preferably 0 to 40C. When the photosensitive substance of the present invention synthesized by the above method is used as a resin composition, it is used alone or in combination of two or more kinds and blended into an alkali-soluble resin or the like. The amount is 5 to 100 parts by weight, preferably 10 to 50 parts by weight of the compound per 100 parts by weight of the alkali-soluble resin. If the use ratio is less than 5 parts by weight, the residual film ratio is remarkably reduced, and if it exceeds 100 parts by weight, sensitivity and solubility in a solvent are reduced.

In the present invention, a known photosensitive material may be used in combination with the photosensitive material, if necessary. For example, as described in JP-B-43-28403,
Esters of 2-diazonaphthoquinone sulfonic acid chloride and pyrogallol-acetone resin, U.S. Pat. No. 3,046,1
JP-A-2-96163 and JP-A-2,163,210, esters of 1,2-diazonaphthoquinone-5-sulfonic acid chloride and phenol-formaldehyde resin described in JP-A Nos. -9616
No. 5, JP-A-2-96661, esters of 1,2-diazoquinone-4-sulfonic acid chloride and phenol-formaldehyde resin, JP-A-47-5303, JP-A-48-63802, Id 48-6
3803, 48-96575, 49-3870
No. 1, No. 48-13354, Japanese Patent Publication No. 37-18015
No. 41-11222, No. 45-9610, No. 4
No. 9-17481, U.S. Pat. No. 2,797,213,
No. 3,454,400, No. 3,544,323, No. 3,
No. 573,917, No. 3,674,495, No. 3,785,
No. 825, British Patent Nos. 1,227,602 and 1,251,
No. 345, No. 1,267,005, No. 1,329,888
No. 1,330,932, German Patent No. 854,890
Nos. And the like described in each specification can be used in combination. In this case, it can be used in an amount of 1 to 100 parts by weight, preferably 5 to 30 parts by weight, based on 100 parts by weight of the photosensitive substance of the present invention.

As the alkali-soluble resin used in the present invention, various resins having this property can be used. Preferred resins include the following novolak resins. For example, phenol formaldehyde resin, m-cresol formaldehyde resin, p-cresol formaldehyde resin, o-cresol formaldehyde resin, m- / p-mixed cresol formaldehyde resin, phenol / cresol (m-, p-, o
-Or m- / p- or m- / o-mixture) cresol formaldehyde resin such as mixed formaldehyde resin. In addition, resol type phenol resins are also preferably used, and phenol / cresol (m-, p-, o- or m- / p-, m- /
Mixed formaldehyde resins are preferred, and phenol resins described in JP-A-61-217034 are particularly preferred. A phenol-modified xylene resin, polyhydroxystyrene, polyhalogenated hydroxystyrene, JP-A-51-3471.
Various alkali-soluble resins such as an acrylic resin containing a phenolic hydroxyl group as disclosed in Japanese Patent Publication No. 1 (1993), an acrylic resin having a sulfonamide group described in JP-A-2-866, and a urethane resin. High molecular compounds can also be used. These alkali-soluble polymer compounds have a weight average molecular weight of 500 to 20,000 and a number average molecular weight.
Those with 200 to 60,000 are preferred. Such alkali-soluble polymer compounds may be used alone or in combination of two or more, and are used in an amount of 80% by weight or less of the total composition. Further, as described in U.S. Pat. No. 4,123,279, phenol having a C3-8 alkyl group as a substituent, such as t-butylphenol formaldehyde resin and octylphenol formaldehyde resin, and formaldehyde are used. It is preferred to use a condensate of the above in combination in order to improve the oil sensitivity of the image.

In the photosensitive composition of the present invention, it is preferable to add a cyclic acid anhydride, a phenol or an organic acid in order to increase the sensitivity. Cyclic acid anhydride include U.S. Pat phthalic anhydride as described in 4,115,128 Pat, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3,6-oxy - [delta ⁴ - tetrahydrophthalic anhydride Examples include phthalic acid, tetrachlorophthalic anhydride, maleic anhydride, chloromaleic anhydride, α-phenylmaleic anhydride, succinic anhydride, and pyromellitic anhydride. As phenols, bisphenol A, p-
Nitrophenol, p-ethoxyphenol, 2,3
4-trihydroxybenzophenone, 4-hydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 4,4,4 "-trihydroxy-triphenylmethane, 4,4 ', 3", 4 "-tetrahydroxy-
3,5,3 ', 5'-tetramethyltriphenylmethane and the like. As organic acids, JP-A-60-8
No. 8942, 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. -Toluenesulfonic acid, dodecylbenzenesulfonic acid, p-toluenesulfinic acid, ethyl sulfate, phenylphosphonic acid, phenylphosphinic acid, phenyl phosphate, diphenyl phosphate, benzoic acid, isophthalic acid, adipic acid, p-
Toluic acid, 3,4-dimethoxybenzoic acid, phthalic acid,
Terephthalic acid, 1,4-cyclohexene-2,2-dicarboxylic acid, erucic acid, lauric acid, n-undecanoic acid,
Ascorbic acid and the like. The proportion of the cyclic acid anhydrides, phenols and organic acids in the photosensitive composition is preferably in the range of 0.05 to 15% by weight,
Particularly, 0.1 to 5% by weight is preferable.

In the photosensitive composition of the present invention,
To expand the development latitude, Japanese Patent Application Laid-Open No. 62-251
Non-ionic surfactants described in JP-A-7-740 and JP-A-4-68355;
An amphoteric surfactant as described in JP-A-21044 and JP-A-4-13149 can be added. Specific examples of the nonionic surfactant include sorbitan tristearate, sorbitan monopalmitate, sorbitan triolate, monoglyceride stearate,
Examples thereof include polyoxyethylene sorbitan monooleate and polyoxyethylene nonylphenyl ether. Specific examples of the amphoteric surfactant include alkyl di (aminoethyl) glycine, alkyl polyaminoethyl glycine hydrochloride, and Ammogen K (trade name, Industrial 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 nonionic surfactant and the amphoteric surfactant 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, a printing-out agent for obtaining a visible image immediately after exposure, a dye as an image coloring agent and other fillers can be added. As a printing-out agent for obtaining a visible image immediately after exposure, a combination of a photosensitive compound that releases an acid upon exposure and an organic dye capable of forming a salt can be mentioned.

Various compounds have been proposed as photosensitive compounds which release an acid upon exposure, and specifically, o-naphthoquinonediazide-4 is disclosed in JP-A-50-36209.
-Halogenides of sulfonic acid, trihalomethyl-2-pyrone and trihalomethyltriazine in JP-A-53-36223, various o-naphthoquinonediazide compounds in JP-A-55-62444, and JP-A-55-77742. Has proposed a 2-trihalomethyl-5-aryl-1,3,4-oxadiazole compound and the like. Organic dyes that change color by interacting with these photolytic substances include diphenylmethane, triarylmethane, thiazine, oxazine, phenazine, xanthene, anthraquinone, iminonaphthoquinone, and azomethine. Dyes, such as brilliant green, eosin, ethyl violet, erythrosin B, methyl green, crystal violet, basic fuchsin, phenolphthalein, 1,3-diphenyltriazine, alizarin red S, thymol Phthalein, methyl violet 2B,
Quinaldine red, rose bengal, methanil yellow, thymol sulfophthalein, xylenol blue,
Methyl orange, orange IV, diphenylthiocarbazone, 2,7-dichlorofluorescein, paramethyl red, congo red, benzopurpurine 4B, α-naphthyl red, nile blue A, phenacetaline, methyl bio red, malachite green, parafuchsin, Oil Blue # 603 (manufactured by Orient Chemical Industry Co., Ltd.),
Oil Pink # 312 (Orient Chemical Industry Co., Ltd.)
Oil Red 5B (Orient Chemical Industry Co., Ltd.)
Oil Scar Red # 308 (made by Orient Chemical Industry Co., Ltd.), Oil Red OG (made by Orient Chemical Industry Co., Ltd.), Oil Red RR (made by Orient Chemical Industry Co., Ltd.), Oil Green # 502 (Orient Chemical Industry Co., Ltd.), Spiron Red BEH Special (Hodogaya Chemical Co., Ltd.), Victoria Pure Blue B
OH (manufactured by Hodogaya Chemical Co., Ltd.), Patent Pure Blue (manufactured by Sumitomo Mikuni Chemical Industry Co., Ltd.), Sudan Blue II
(Manufactured by BASF), m-cresol purple, cresol red, rhodamine B, rhodamine 6G, first acid violet R, sulforhodamine B, auramine, 4-p-diethylaminophenylimino naphthoquinone, 2-carboxyanilino-4-p -Diethylaminophenyliminonaphthoquinone, 2-carbostarylamino-4-p-dihydroxyethyl-amino-phenyliminonaphthoquinone, p-methoxybenzoyl-p '
-Diethylamino-o'-methylphenyliminoacetanilide, cyano-p-diethylaminophenyliminoacetanilide, 1-phenyl-3-methyl-4-p-
Diethylaminophenylimino-5-pyrazolin, 1-
β-naphthyl-4-p-diethylaminophenylimino-5-pyrazolone and the like can be mentioned.

Particularly useful dyes are described in JP-A-62-2.
A dye in which a counter anion of a basic dye such as Victoria Pure Blue or ethyl violet disclosed in JP-A-93247 is changed to an organic sulfonic acid. The photosensitive lithographic printing plate of the present invention is obtained by dissolving each of the above components in a solvent that dissolves the components, coating the solution on a support, and drying. The solvents used here include ethylene dichloride, cyclohexanone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate,
-Methoxy-2-propanol, 1-methoxy-2-propyl acetate, toluene, ethyl acetate, methyl lactate, ethyl lactate, dimethyl sulfoxide, dimethylacetamide, dimethylformamide, water, N-methylpyrrolidone, tetrahydrofurfuryl alcohol, acetone, Diacetone alcohol, methanol, ethanol,
There are 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 2 to 5
0% by weight. The coating amount varies depending on the application, but, for example, in the case of a photosensitive lithographic printing plate, the solid content is generally preferably 0.5 to 3.0 g / m ² . As the amount of coating decreases, the photosensitivity increases, but the physical properties of the photosensitive film deteriorate. In the photosensitive layer according to the invention, a surfactant for improving coating properties, for example, a fluorine-based surfactant described in JP-A-62-170950 can be added. The preferred amount of addition is 0.0% of the entire photosensitive composition.
The content is preferably 1 to 1% by weight, more preferably 0.05 to 0.5% by weight. The surface of the photosensitive layer provided as described above reduces the time of evacuation during close contact exposure using a vacuum furnace,
In addition, in order to prevent burning blur, it is preferable to form a mat. Specifically, a method of providing a mat layer as described in JP-A-50-125805, JP-B-57-6582 and JP-B-61-28986 is disclosed.
And a method of thermally fusing a solid powder as described in JP-A-62337.

The developer for the photosensitive composition of the present invention comprises:
Alkaline aqueous solutions substantially free of organic solvents are preferred, specifically sodium silicate, potassium silicate,
Sodium hydroxide, potassium hydroxide, lithium hydroxide,
Aqueous solutions such as sodium tertiary phosphate, dibasic sodium phosphate, tertiary ammonium phosphate, dibasic ammonium phosphate, sodium metasilicate, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, aqueous ammonia, etc. They are suitable and are added in such a way that their concentration is between 0.1 and 10% by weight, preferably between 0.5 and 5% by weight. Among these, potassium silicate, lithium silicate,
A developer containing an alkali silicate such as sodium silicate is preferable because it does not easily cause staining during printing. The composition of the alkali silicate is (SiO ₂ ) / (M) = 0.5 to _{2.5 in a} molar ratio.
5 (where (SiO ₂ ) and (M) indicate the molar concentration of SiO _{2 and} the molar concentration of the total alkali metal, respectively), and a developer containing 0.8 to 8% by weight of SiO ₂ is preferable. Used. In addition, water-soluble sulfites such as sodium sulfite, potassium sulfite, and magnesium sulfite, resorcin, methylresorcin, hydroquinone, and thiosalicylic acid can be added to the developer.
The preferred content of these compounds in the developer is 0.
002 to 4% by weight, preferably 0.01 to 1% by weight.

Further, in the developer, JP-A-50-5132
No. 4, JP-A-59-84241, an anionic surfactant, and an amphoteric surfactant,
JP-A-59-75255, JP-A-60-111246
Or at least one of the nonionic surfactants described in JP-A Nos. 60-213943 and 60-213943.
As described in JP-A-946-946 and JP-A-56-142528, the incorporation of a polymer electrolyte enhances wettability to the photosensitive composition and enhances development stability (development latitude). And it is preferably used. The addition amount of such a surfactant is preferably 0.001 to 2% by weight, and particularly preferably 0.003 to 0.5% by weight. 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 less generation of insolubles occurs in the developer, more preferably 90 mol% or more, and most preferably 10 mol% or more.
It is the case of 0 mol%. Further, the developing solution used in the present invention may contain some organic solvents such as alcohols and
Chelating agents described in JP-A-90952, metal salts as described in JP-B-1-30139,
An antifoaming agent such as an organic silane compound can be added. The light source used for exposure is a carbon arc lamp,
There are mercury lamps, xenon lamps, tungsten lamps, metal halide lamps and the like.

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,
After dehydration treatment after washing with water, desensitization treatment as it is, or treatment with an aqueous solution containing an acid, desensitization treatment may be performed. Furthermore, in the development process of this type of photosensitive lithographic printing plate, the alkaline aqueous solution is consumed depending on the processing amount to reduce the alkali concentration, or the alkali concentration is reduced by air due to long-time operation of the automatic developing machine, so that the processing capacity is reduced. At that time, Japanese Patent Application Laid-Open No. 54-62004
The processing capacity may be restored by using a replenisher as described in the above item. In this case, it is preferable to replenish by the method described in U.S. Pat. No. 4,882,246. The plate making process described above is described in JP-A-2-7054 and 2-3.
It is preferable to use an automatic developing machine as described in JP-A No. 2357. 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 to be erased, Japanese Patent Publication No. Hei 2-13293 is used.
It is preferable to use an erasing liquid as described in Japanese Patent Application Laid-Open No. H10-260,000. Further, as the desensitized gum which is optionally applied in the final step of the plate making process, JP-B-62-16834,
Nos. 62-25118, 63-52600, JP-A-62-7595, JP-A-62-11693, and 62-8
What is described in each gazette of 3194 is preferable.
Further, the photosensitive lithographic printing plate of the present invention is subjected to image exposure, developed,
Washing or rinsing, performing the desired erasing work, and burning after washing with water, before burning, the
1-2518, 55-28062 and JP-A-62-2
It is preferable to treat with a surface-regulating liquid as described in JP-A-31859 and JP-A-61-159655.

[0022]

The positive photosensitive lithographic printing plate of the present invention can completely erase the sticking marks even with an erasing liquid containing no hydrofluoric acid, and even if a burning treatment is performed, ink is left on the area. Absent. Further, even if the temperature of the developing solution becomes high, since the developing latitude is high, troubles such as elution of the image area hardly occur.

Hereinafter, the present invention will be described in more detail with reference to Examples, but it should not be construed that the invention is limited thereto. Here,% in the examples indicates% by weight. Examples 1 to 6 and Comparative Examples a to c 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. After etching by dipping in 10% sodium hydroxide at 70 ° C. for 60 seconds, the substrate was washed with running water, neutralized with 20% nitric acid, and washed with water. This is performed using a sinusoidal alternating current under a voltage of 12.7V.
The electrolytic surface treatment was performed in an aqueous solution of nitric acid at a rate of 160 coulombs / dm ^{2 at} the anode. When the surface roughness was measured, it was 0.6 μ (Ra display). Subsequently, it is immersed in a 30% aqueous sulfuric acid solution and desmutted at 55 ° C. for 2 minutes, and then anodized in a 20% aqueous sulfuric acid solution at a current density of 2 A / dm ^{2 to} a thickness of 2.7 g / m ² . The substrate was adjusted. The undercoat liquid (A) having the following composition was applied to the surface of the substrate thus treated, and dried at 80 ° C. for 30 seconds. The coating amount after drying was 30 mg / m ² . <Undercoat liquid A>-0.1 g of aminoethylphosphonic acid-0.15 g of phenylphosphonic acid-0.1 g of β-alanine-40 g of methanol-60 g of pure water Next, the following photosensitive solution was placed on this substrate. It was applied and dried at 100 ° C. for 1 minute to obtain a positive photosensitive printing plate. The coating amount after drying was 1.7 g / m ² .

<Photosensitive solution>-0.43 g of the photosensitive substance described in Table 1-Cresol-formaldehyde novolak resin (meta / 1.1 g, para ratio; 6 to 4, average molecular weight 1100, unreacted cresol 0.1%). M-cresol-formaldehyde resin (weight-average molecule 0.3 g, weight 1700, number-average molecular weight 600, containing 1% of unreacted cresol) N- (p-aminosulfonylphenyl) acrylamide / 0.1% 2 g n-butyl acrylate / diethylene glycol monomethyl ether methacrylate (40:40:20) copolymer • pn octylphenol-formaldehyde resin 0.02 g • naphthoquinone-1,2-diazide-4-sulfonic acid 0.01 g Chloride ・ Benzoic acid 0.02g ・ Tetrahydrophthalic anhydride 0.05g ・ 4- (p-N, N-di (ethoxy) 0.02g phenyl) -2,6-bis (trichloromethyl) -s-triazine. 4- (pN- (p-hydroxybenzoyl) amino 0.02g phenyl) -2,6-bis ( Trichloromethyl) -s-triazine 2-trichloromethyl-5- (4-hydroxystyryl)-0.01 g 1,3,4-oxadiazole 1-naph 0.01 g of counter ion of Victoria Pure Blue BOH Sulfonic acid dye-Ethyl violet counter ion 6-hydroxynaphthalene 0.01 g Sulfonic acid dye-Megafac F-176 (Dai Nippon Ink Chemical Co., Ltd., 0.06 g fluorine-based surfactant)・ Methyl ethyl ketone 25 g

The photosensitive lithographic printing plate thus produced is passed through a manuscript in which three positive films are pasted on a transparent base with a cellophage tape, using a halide lamp as a light source, in a vacuum frame. Exposure was carried out for 60 seconds, and then processing was carried out through an automatic developing machine equipped with a developer (manufactured by Fuji Photo Film Co., Ltd.), DP-4 (1: 8) and a rinsing solution FR-3 (1: 7). On the resulting plate, traces of film edges and tapes were found. Fuji Photo Film Co., Ltd.
The erasing solution PR-1 was applied to a brush, erased, washed with water, wiped with a burning surface smoothing solution BC-3 manufactured by Fuji Photo Film Co., Ltd., and treated with a burning device BP-1300 at 260 ° C. for 7 minutes. Next, Gum G manufactured by Fuji Photo Film Co., Ltd.
The plate surface was treated with a liquid obtained by diluting U-7 twice with water, left for one day, and then printed with a Heidel KOR-D machine. It was visually determined whether the erased film edge mark or the tape mark was stained on the printed matter. The temperature of the developing solution was 25 ° C. under the above-mentioned developing conditions. When the temperature rose to 40 ° C., it was visually determined whether or not the photosensitive layer in the image area was eluted. Table 2 shows the results. From these results, it was clarified that the positive photosensitive lithographic printing plate of the present invention exhibited better erasability and a larger development latitude than the comparative example.

[0026]

[Table 1]

[0027]

[Table 2] 40 ℃ by the mark of the tape, film essence, etc. Example 1 No dirt Film loss Slight Example 2 No dirt Film loss Slight Example 3 No dirt Film loss Slight Example 4 No dirt Film reduction Slight Example 5 No stain Film loss Slight Example 6 No dirt Film loss Slightly Comparative example a Stain large half film loss Comparative example b Stain large film loss large Comparative example c Soil large Half film loss ━━━━━━━━━━━━━━━ ━━━━━━━━━━━━━━━━━━━━

Continuation of the front page (56) References JP-A-61-107352 (JP, A) JP-A-3-240062 (JP, A) JP-A-4-86665 (JP, A) JP-A-60-121445 (JP) JP-A-5-224408 (JP, A) JP-A-5-303198 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03F ^7/ 00-7/42

Claims (1)

(57) [Claims] 1. A photosensitive lithographic printing method in which a positive photosensitive composition containing at least one kind of photosensitive substance and an alkali-soluble resin is applied on an aluminum plate whose grained surface is anodized. In the plate, the photosensitive material is 1,2 (and / or 2,1) -naphthoquinonediazide-5- (and / or -4-) of a polyhydroxy compound represented by the following general formula (I) or (II). A photosensitive lithographic printing plate comprising a sulfonic acid ester. Embedded image R ₁ is a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group,
Alkoxy group, alkenyl group, aryl group, aralkyl group, alkoxycarbonyl group, arylcarbonyl group,
Represents an acyloxy group, an acyl group, an aryloxy group or an aralkoxy group. R ₂ is a hydrogen atom, a halogen atom,
Represents a hydroxyl group, an alkyl group, or a carboxyl group.
However, when R ₁ is a hydroxyl group, R ₂ is not a hydrogen atom. R _{3 to} R ₇ represent a hydroxyl group, a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or an alkenyl group. However, at least one of R _{3 to} R ₇ is a hydroxyl group.