JPH04221956A - Photosensitive planographic printing plate - Google Patents

Abstract

PURPOSE:To obtain the planographic plate extremely less in malodor and toxicity during/after manufacture and improved in coatability and aptitudes to ball pens and 'scotch tape (R)'. CONSTITUTION:The substrate is coated with the photosensitive solution containing at least (a)an o-quinonediazido compound, (b) a fluorinated surfactant in an amount of 0.05-0.4wt.% of the solid freed of solvents, (c) an oxygen- containing nonionic surfactant in an amount of 0.5-5wt.% of the solvent-free solid, and (d) solvents composed of 50-90wt.% propyleneglycol 1-4C alkyl ether and 10-50wt.% diethyleneglycol 1-2C alkyl ether in the amount of 90-100wt.% in total of the solvent-free solid.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive lithographic printing plate, and more particularly to a photosensitive lithographic printing plate manufactured using a novel coating solvent with low odor and toxicity.

0002

2. Description of the Related Art Positive-working photosensitive lithographic printing plates generally have an ink-receptive photosensitive layer formed on a hydrophilic support, which becomes solubilized by exposure to light. When this photosensitive layer is subjected to imagewise exposure and development, the non-image areas are removed while leaving the image areas, thereby forming an image. In printing, the difference in properties of image areas being lipophilic and non-image areas being hydrophilic is utilized.

The photosensitive layer of such a positive photosensitive lithographic printing plate usually contains an orthoquinonediazide compound as a photosensitive substance and an alkali-soluble resin as a component for increasing film strength and alkali solubility. There is.

[0004] The above-mentioned photosensitive layer is usually formed by coating a support with a coating solution in which a composition containing an orthoquinone diazide compound or an alkali-soluble resin is dissolved in a coating solvent such as ethylene glycol monomethyl ether or ethylene glycol monoethyl ether. obtained by In such coating, a surfactant is usually added to the coating solution in order to prevent uneven coating and improve coating properties. For example, JP-A-62-36657 describes that coating unevenness can be improved by using a fluorosurfactant together with a specific organic solvent.

[0005]

[Problems to be Solved by the Invention] However, while the use of the above-mentioned fluorine-based surfactants is effective in improving coating properties, it also has the effect of improving the so-called "ballpoint pen suitability" and "cellotape suitability" as described below. It has become clear that it is inferior.

That is, when performing so-called multi-sided printing in which a plurality of film originals are printed one after another on a photosensitive planographic printing plate in different positions, in order to align the film originals,
The position of the document is sometimes marked on the photosensitive layer, but if the solvent of the ink of the oil-based ballpoint pen, which is usually used as a writing instrument, is an organic solvent, especially a high boiling point solvent such as a glycol-based solvent, the ink may cause the photosensitive layer to be marked. The photosensitive layer of the lithographic printing plate is eroded and dissolved. In particular, when the marked area is an image area, if the development process is performed as it is, the photosensitive layer in the marked area of the image area may be removed, causing a failure in which the mark trace is reproduced on the printed matter during printing. This property of oil-based ballpoint pens that is resistant to corrosion by ink is called "ballpoint pen suitability."

Furthermore, when exposing a photosensitive planographic printing plate, cellophane tape is often stuck directly onto the printing plate for the purpose of fixing the film original or overlapping the film original for exposure. In such cases, the glue from the cellophane tape that was peeled off during plate making remains on the printing plate, causing poor development and causing problems as plate surface stains during printing. This resistance to plate surface staining is referred to as "cellotape suitability."

[0008] Furthermore, both the above-mentioned coating solvent and the specific solvent used in the above-mentioned JP-A-Sho have strong odor and toxicity, which poses a major problem in terms of the working environment during and after production.

[0009] Accordingly, an object of the present invention is to provide a photosensitive lithographic printing plate which has extremely low odor and toxicity during or after manufacture, has improved coating properties, and has improved suitability for ballpoint pens and sellotape. There is a particular thing.

0010

[Means for Solving the Problems] In view of the above-mentioned problems, the present inventors have conducted intensive research and found that the above-mentioned object of the present invention is to provide at least (a) an orthoquinonediazide compound, (
b) 0.05 to 0.4% by weight of fluorosurfactant based on the solid content excluding solvent, (c) 0 based on the solid content excluding solvent
．． 5 to 5% by weight of an oxygen-containing nonionic surfactant, and (
d) 50 to 90% by weight of propylene glycol alkyl ether whose alkyl component has a carbon number of 1 to 4 and 10 to 50% by weight of a diethylene glycol alkyl ether whose alkyl component has 1 or 2 carbon atoms. It has been found that this can be achieved by providing a photosensitive lithographic printing plate coated with a photosensitive coating liquid containing a solvent containing 90 to 100% by weight of both.

The present invention will be explained in more detail below.

In the present invention, propylene glycol alkyl ether is used when the alkyl component thereof has 1 to 1 carbon atoms.
Preferably, propylene glycol monoalkyl ethers in which the number of carbon atoms in the alkyl component ranges from 1 to 4 are used, particularly propylene glycol monomethyl ether. , propylene glycol monoethyl ether,
Propylene glycol isopropyl ether, propylene glycol n-propyl ether, propylene glycol isobutyl ether, propylene glycol n-butyl ether and the like are preferably used.

The propylene glycol alkyl ether is contained in the coating solvent used in an amount of 50 to 90% by weight, preferably 60 to 90% by weight.

The diethylene glycol alkyl ether used in the present invention is one in which the alkyl component has 1 or 2 carbon atoms, but it is preferable that the alkyl component has 1 or 2 carbon atoms.
or 2, diethylene glycol monoalkyl ether or diethylene glycol dialkyl ether, particularly preferably diethylene glycol monomethyl ether, diethylene glycol monoethyl ether,
Diethylene glycol dimethyl ether or diethylene glycol diethyl ether is used.

The diethylene glycol alkyl ether is contained in the coating solvent used in an amount of 10 to 50% by weight, preferably 10 to 30% by weight.

In the present invention, the above-mentioned propylene glycol alkyl ether and diethylene glycol alkyl ether are contained in a coating solvent in a total amount of 90 to 100% by weight.

In the present invention, other coating solvents may be used in combination with the above-mentioned alkyl ethers as long as they do not impair the effects of the present invention. Examples of solvents that can be used in combination include alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, n-propyl alcohol, n-butanol, isobutanol, t-butanol, 1-pentanol, 2-pentanol, and 1-hexanol; Acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl isopropyl ketone, methyl-n
- Ketones such as butyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-butyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate,
Ethylene glycols such as ethylene glycol isopropyl ether acetate; Acetate esters such as ethyl acetate, n-propyl acetate, isopropyl acetate, butyl acetate; Other water, methyl lactate, ethyl lactate, diethyl ether, dioxane, dimethylformamide, dimethyl sulfoxide , γ-butyrolactone, 3-methoxy-1-
Examples include butanol, 3-methyl-3-methoxy-1-butanol, tetrahydrofuran, methylene chloride, and the like.

Examples of the fluorine-based surfactant used in the photosensitive lithographic printing plate of the present invention include (meth)acrylate polymers having a fluorinated alkyl group in the side chain, preferably a standard polystyrene equivalent number. Average molecular weight is 30,000 or less, more preferably 2,000 to 1
A value in the range 0,000 is used. In the present invention, acrylic and methacrylic compounds are collectively referred to as "(meth)acrylic..." hereinafter.

The acrylate structural unit or methacrylate structural unit of the moiety having a fluorinated alkyl group in the side chain in the (meth)acrylate polymer may be represented by, for example, the following general formula (I) or general formula (II). can.

[0020]

[Formula 1] (wherein, R is a hydrogen atom or a methyl group, and n is 0-
a represents an integer of 20, a represents an integer of 0 to 2, and b represents 0 or 1. )

[0021]

[Formula 2] (wherein, R is a hydrogen atom or a methyl group, and n is 1-
m is an integer of 0 to 20, and a is an integer of 0 to 20.
Indicates an integer of 2. ) Specifically, the following compounds 1 to 17 can be used as such compounds.

[0022]

[Chemical formula 3]

[0023]

[C4]

[0024]

[C5]

[0025]

embedded image Compounds represented by 18 to 32 below can also be used.

[0026]

[C7]

[0027]

[Image Omitted] Furthermore, in the present invention, commercially available products can be used as the fluorosurfactant, such as Surflon "S-38".
, "S-382", "SC-101", "SC-102"
”, “SC-103”, “SC-104” (all manufactured by Asahi Glass Co., Ltd.), Florado “FC-430”, “FC
-431'', ``FC-173'' (all manufactured by Fluorochemical-Sumitomo 3M), EFTOP ``EF352'',
"EF301", "EF303" (both manufactured by Shin-Akita Kasei Co., Ltd.), Schwego Fluor "8035", "80"
36” (all manufactured by Schwegmann), “BM1000”
", "BM1100" (both manufactured by BM Himy), etc. can be used.

In the present invention, the above-mentioned fluorine-containing surfactant is used in an amount of 0.0% based on the solid content excluding the solvent in the photosensitive coating solution.
It is preferably contained in an amount of 5 to 0.4% by weight, and similarly contained in a photosensitive planographic printing plate in an amount of 0.05 to 0.4% by weight.

The photosensitive lithographic printing plate of the present invention contains an oxygen-containing nonionic surfactant in addition to the above-mentioned fluorine surfactant. As such an oxygen-containing nonionic surfactant, polyalkylene glycol or polyoxyethylene sorbitol fatty acid ester compounds or ether compounds of the fatty acids are preferably used.

As the polyalkylene glycol, compounds having at least one of the following structural units (A) and (B) are preferably used.

[0031]

embedded image (In the formula, n represents an integer of 2 to 5,000.) As a compound having at least one of the above structural units (A) and (B), particularly the structural units (A) and (B) In each case, a compound in which n is an integer within the range of 2 to 5000 and a boiling point of 240°C or higher is preferable, and more preferably a compound in which n is an integer within the range of 2 to 500 and a boiling point of 280°C or higher. Among certain compounds, the most preferred are compounds in which n is within the range of 3 to 100.

Examples of such compounds include: - polyethylene glycol - polyoxyethylene alkyl ether - polyoxyethylene alkylphenyl ether - polyoxyethylene polystyrylphenyl ether - polyoxyethylene-
Polyoxypropylene glycol (including block polymers and random polymers) - Polyoxyethylene-polyoxypropylene alkyl ether (terminals form an alkyl ether) (
However, examples include random polymers) - Ethylene oxide derivatives of alkylphenol formalin condensates, polyoxyethylene polyhydric alcohol fatty acid partial esters, polyoxyethylene fatty acid esters, polyoxyethylene alkylamines, etc.

Specifically, for example, the following are preferable. Namely, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene higher alcohol ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate, polyoxyethylene tetraoleate Sorbit, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol monooleate, polyethylene glycol distearate, polyoxyethylene nonylphenyl ether formaldehyde condensate, oxyethylene oxypropylene block copolymer, polyethylene glycol, tetraethylene glycol, etc. It is.

As the polyoxyalkylene sorbitol fatty acid ester compound or the ether compound of the fatty acid,
Examples include a polyoxyethylene sorbitol fatty acid ester compound or an ether compound of the fatty acid, a polyoxypropylene sorbitol fatty acid ester compound or an ether compound of the fatty acid, a polyoxyethylene/polyoxypropylene sorbitol fatty acid ester compound or an ether compound of the fatty acid.

Specific examples include polyoxyethylene sorbit hexastearate, polyoxyethylene sorbit tetrastearate, polyoxyethylene sorbit tetraoleate, polyoxyethylene sorbit hexaoleate, polyoxyethylene sorbit monooleate, and polyoxyethylene sorbitol. Ethylene sorbit monolaurate, polyoxyethylene sorbit tetralaurate,
Polyoxyethylene sorbit hexalaurate, polyoxypropylene sorbit hexastearate, polyoxypropylene sorbit tetraoleate, polyoxypropylene sorbit hexaoleate, polyoxypropylene sorbit monolaurate, polyoxyethylene polyoxypropylene sorbit hexastearate rate, polyoxyethylene/polyoxypropylene sorbitate tetrastearate, polyoxyethylene/polyoxypropylene sorbitol monooleate, polyoxyethylene/polyoxypropylene sorbittetraoleate, polyoxyethylene sorbitol hexastearyl ether, polyoxyethylene sorbitol Examples include tetrastearyl ether, polyoxyethylene sorbittetraoleyl ether, polyoxyethylene sorbit monolauryl ether, polyoxyethylene sorbit monooleyl ether, and the like.

In the present invention, the oxygen-containing nonionic surfactant as described above is contained in the photosensitive coating solution in an amount of 0.5 to 5% by weight based on the solid content excluding the solvent, and is contained in the photosensitive planographic printing plate. Similarly, it is preferably contained in an amount of 0.5 to 5% by weight.

Examples of the orthoquinonediazide compound used in the present invention include ester compounds of orthonaphthoquinonediazide sulfonic acid and polycondensation resins of phenols and aldehydes or ketones.

Examples of the above-mentioned phenols include monohydric phenols such as phenol, o-cresol, m-cresol, p-cresol, 3,5-xylenol, carvacrol, and thymol, and dihydric phenols such as catechol, resorcinol, and hydroquinone. Examples include trihydric phenols such as hydric phenols, pyrogallol, and phloroglucin.

Examples of the aldehyde include formaldehyde, benzaldehyde, acetaldehyde, crotonaldehyde, and furfural. Preferred among these aldehydes are formaldehyde and benzaldehyde.

Further, examples of the above-mentioned ketones include acetone and methyl ethyl ketone. Specific examples of the polycondensation resin include phenol formaldehyde resin, m-cresol formaldehyde resin, m-, p-
Mixed cresol/formaldehyde resin, resorcinol/
Examples include benzaldehyde resin and pyrogallol acetone resin.

The condensation rate of o-naphthoquinonediazide sulfonic acid with respect to the OH group of the phenol in the orthonaphthoquinonediazide compound (reaction rate with respect to one OH group) is preferably 15 to 80%, more preferably 20 to 45%.
%.

The polymer compound containing orthoquinone diazide used in the present invention preferably has a weight average molecular weight of 1,000 or more, more preferably 1,500 or more, in view of coating properties. It is.

Further, examples of the orthoquinonediazide compounds used in the present invention include those described in JP-A-58-43451. Also, 2,3,4-trihydroxybenzophenone, 2,3,4,4-tetrahydroxybenzophenone, 2,3,4,2',4'-pentahydroxybenzophenone, 2,3,4,3',4
Condensation compounds of ',5'-hexahydroxybenzophenone and the like with orthoquinonediazide groups can also be used.

Among the above orthoquinone diazide compounds,
Most preferred is an orthoquinonediazide ester compound obtained by reacting 1,2-benzoquinonediazide sulfonyl chloride or 1,2-naphthoquinonediazide sulfonyl chloride with a pyrogallol acetone condensation resin or 2,3,4-trihydroxybenzophenone.

As the orthoquinonediazide compound used in the present invention, each of the above compounds may be used alone, or two or more compounds may be used in combination.

The preferred amount of the orthoquinone diazide compound used is 10 to 40% by weight of the nonvolatile components of the photosensitive planographic printing plate.

Particularly preferable orthoquinonediazide groups are 4- or 5-of 1,2-quinonediazide.
It is a sulfonic acid group or a 4- or 5-carboxyl group of 1,2-quinonediazide.

The above-mentioned orthoquinonediazide compound is preferably used in combination with an alkali-soluble resin. Examples of the alkali-soluble resin include novolac resin, vinyl polymer having a phenolic hydroxyl group, and JP-A-55-57.
Examples include condensation resins of polyhydric phenols and aldehydes or ketones described in Japanese Patent No. 841. Examples of novolac resins include phenol formaldehyde resin, cresol formaldehyde resin, and JP-A-55
Phenol-cresol-formaldehyde copolycondensation resin as described in Japanese Patent Laid-Open No. 57841, p-
Examples include copolycondensation resins of substituted phenol and phenol or cresol and formaldehyde.

The vinyl polymer having a phenolic hydroxyl group is a polymer having a unit having a phenolic hydroxyl group in its molecular structure, and has the following general formula (I
Polymers containing at least one structural unit of II) to (VII) are preferred.

[0050]

embedded image [In the formula, R1 and R2 each represent a hydrogen atom, an alkyl group, or a carboxyl group, and preferably a hydrogen atom. R3 represents a hydrogen atom, a halogen atom, or an alkyl group, preferably a hydrogen atom or an alkyl group such as a methyl group or an ethyl group. R4 represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, preferably a hydrogen atom. A represents an alkylene group optionally having a substituent that connects a nitrogen atom or an oxygen atom and an aromatic carbon atom, m represents an integer of 0 to 10, and B has a substituent. represents a phenylene group that may have a substituent or a naphthylene group that may have a substituent. ] The polymer used in the photosensitive lithographic printing plate of the present invention preferably has a copolymer type structure, and can be used in combination with the structural units represented by the above general formulas (III) to (VII), respectively. Examples of monomer units include ethylenically unsaturated olefins such as ethylene, propylene, isobutylene, butadiene, and isoprene, such as styrene, α-methylstyrene,
Styrenes such as p-methylstyrene and p-chlorostyrene, acrylic acids such as acrylic acid and methacrylic acid, unsaturated aliphatic dicarboxylic acids such as itaconic acid, maleic acid, and maleic anhydride, such as methyl acrylate, acrylic Ethyl acrylate, n-butyl acrylate, isobutyl acrylate, dodecyl acrylate, acrylic acid-2
- Esters of α-methylene aliphatic monocarboxylic acids such as chloroethyl, phenyl acrylate, methyl α-chloroacrylate, methyl methacrylate, ethyl methacrylate, ethyl ethacrylate, nitrites such as acrylonitrile, methacrylonitrile, e.g. Amides such as acrylamide, such as acrylanilide, p-chloroacrylanilide, m-nitroacrylanilide, m-
Anilides such as methoxyacrylanilide, vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate, vinyl butyrate, vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, β-chloroethyl vinyl ether, vinyl chloride , vinylidene chloride, vinylidene cyanide, such as 1-methyl-1-methoxyethylene, 1,1-dimethoxyethylene, 1,2-dimethoxyethylene, 1,1-dimethoxycarbonylethylene, 1-
Ethylene derivatives such as methyl-1-nitroethylene, such as N-vinylpyrrole, N-vinylcarbazole, N
- There are N-vinyl monomers such as vinyl indole, N-vinylpyrrolidene, and N-vinylpyrrolidone. These vinyl monomers exist in polymer compounds with a structure in which unsaturated double bonds are cleaved.

Among the above-mentioned monomers, esters of aliphatic monocarboxylic acids and nitriles are preferred because they exhibit excellent performance for the purpose of the present invention.

These alkali-soluble resins have 1,50
Those having a molecular weight of 0 or more are preferable, and those having a molecular weight of 2,500 or more are more preferable.

These alkali-soluble resins are added to the photosensitive composition of the present invention in an amount of 50 to 50% of the nonvolatile components of the photosensitive composition.
It is preferable to include 90% by weight.

In the present invention, a trihaloalkyl compound or a diazonium salt compound is used as a compound that generates an acid or a free radical upon irradiation with actinic rays in combination with the above-mentioned compound of the present invention, within a range that does not impair the effects of the present invention. be able to.

Further, the photosensitive lithographic printing plate of the present invention can contain a dye, and such a dye includes a pigment as well as a dye, and an inorganic pigment can also be used.
In particular, it is preferable to use an organic dye whose color tone can be changed by the above-mentioned acid.

Examples of the organic dyes used include diphenylmethane, triphenylmethane, thiazine,
Examples include oxazine-based, xanthene-based, anthraquinone-based, iminonaphthoquinone-based, and azomethine-based.

Examples of these organic dyes include Eisen Brilliant Basic Cyanine 6GH [manufactured by Hodogaya Chemical Co., Ltd.], Astra New Fuchsin, Alizarin Red S, Eosin, Ethyl Violet, Erythrosin B, Auramine, Oil Green #502 [Orient Chemical Co., Ltd.] Made by Kogyo Co., Ltd.], Oil Scarlet #308 [
Orient Chemical Industry Co., Ltd.], Oil Pink #312
[Manufactured by Orient Chemical Industry Co., Ltd.], Oil Blue #60
3 [Orient Chemical Industry Co., Ltd.], Oil Red 5B
[Manufactured by Orient Chemical Industry Co., Ltd.], Oil Red OG [
Orient Chemical Industry Co., Ltd.], Oil Red RR [Orient Chemical Industry Co., Ltd.], Orange IV, 2-carboxyanilino-4-p-diethylaminophenylimino naphthoquinone, 2-carbostearylamino-4-p
-dihydroxyethylaminophenylimino naphthoquinone, xylenol blue, quinaldine red, crystal violet, crystal violet F10B, m
-Cresol purple, cresol red, Congo red, cyano-p-diethylaminophenyliminoacetanilide, 4-p-diethylaminophenylimino naphthoquinone, 2,7-dichlorofluorescein, diphenylthiocarbazone, 1,3-diphenyltriazine,
Spin Red BEH Special [manufactured by Hodogaya Chemical Industry Co., Ltd.], sulforhodamine B, thymol sulfophthalein, thymol phthalein, thymol blue, Nile blue 2B, Nile blue A, 1-β-naphthyl-4-p-
Diethylaminophenylimino-5-pyrazolone, α-
Naphthyl red, paraphthacine, paramethyl red, Victoria Pure Blue BOH, Fast Acid Violet R, phenacetaline, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone, phenolphthalein, phenol red, fuchsin, Brilliant green, bromocresol purple, bromophenol blue, basic fuchsin,
Benzopurpurin 4B, magenta, malachite green, methanyl yellow, methyl orange, methyl green, methyl violet 2B, methyl violet, p-
Methoxybenzoyl-p'-diethylamino-o'-methylphenyliminoacetanilide, Rose Bengal,
Rhodamine 6G and Rhodamine B can be specifically mentioned.

Among these compounds, triphenylmethyl-based compounds are preferred from the viewpoint of degree of discoloration and storage stability.

Dyes particularly preferably used in the present invention include malachite green (CI42000),
Methyl violet (CI42535), methyl green (CI42585), crystal violet (CI
42555), brilliant green (CI42040)
), ethyl violet (CI42600), phenolphthalein, phenol red, bromophenol blue, thymol blue, bromocresol purple, Victoria Pure Blue BOH (CI42595), Eisen Brilliant Basic Cyanine 6GH [manufactured by Hodogaya Chemical Co., Ltd.] (CI42025) ), astraneufuchsin (CI42520), magenta (CI425
10), Crystal Violet F10B (manufactured by BASF) (CI42557), Fuchsin (CI42500)
can be mentioned.

The proportion of these dyes in the photosensitive layer of the photosensitive lithographic printing plate is preferably 0.1 to 10% by weight, and 0.1 to 10% by weight.
Particularly preferred is 3 to 5% by weight.

The photosensitive lithographic printing plate of the present invention may contain other additives, if necessary, in addition to the above-mentioned materials. For example, phthalate esters as plasticizers,
Various low-molecular compounds such as triphenyl phosphates and maleic esters, and coating property improvers include surfactants such as fluorine-based surfactants and nonionic surfactants typified by ethyl cellulose polyalkylene ether.

A sensitizer for improving sensitivity can also be added to the photosensitive composition of the present invention. Examples of the sensitizer include gallic acid derivatives described in JP-A-57-118237, phthalic anhydride, tetrahydrophthalic anhydride, hexahydro-phthalic anhydride, and the like described in JP-A-52-80022. Five-membered cyclic acid anhydrides such as phthalic anhydride, maleic anhydride, succinic anhydride, pyrometic acid, itaconic acid, etc., and glutaric anhydride and its derivatives as described in JP-A-58-11932. Examples include 6-membered cyclic acid anhydrides such as. Among these, cyclic acid anhydrides are preferred, and 6-membered cyclic acid anhydrides are particularly preferred.

In the present invention, the coating method for applying the photosensitive coating liquid to the support includes conventionally known methods, such as spin coating, wire bar coating, dip coating, air knife coating, roll coating, blade coating, and curtain coating. etc. are possible.

Supports on which the photosensitive layer is provided include metal plates such as aluminum, zinc, copper, and steel; metal plates plated or vapor-deposited with chromium, zinc, copper, nickel, aluminum, and iron; paper; Plastic film; paper coated with resin; paper covered with metal foil such as aluminum;
Examples include plastic films treated to make them hydrophilic. Among these, aluminum plates are preferred.

When an aluminum plate is used as a support, it is preferably subjected to surface treatments such as graining, anodizing, and, if necessary, sealing.

Examples of the graining treatment include a mechanical method and an electrolytic etching method. Examples of the mechanical method include a ball polishing method, a brush polishing method, a polishing method using liquid honing, and a buffing method. The various methods described above can be used alone or in combination depending on the composition of the aluminum material. A preferred method is electrolytic etching.

[0067] Electrolytic etching can be performed using phosphoric acid, sulfuric acid, hydrochloric acid,
It is carried out in a bath containing one or more inorganic acids such as nitric acid. After the graining process, desmutting is performed using an alkali or acid aqueous solution as necessary to neutralize the material, followed by washing with water.

[0068] In the anodizing treatment, one or two types of sulfuric acid, chromic acid, oxalic acid, phosphoric acid, malonic acid, etc. are used as the electrolyte.
Electrolysis is carried out using a solution containing at least one species, with an aluminum plate used as an anode. The amount of anodic oxide film formed is 1 to 5
0mg/dm2 is suitable, preferably 10-40m
g/dm2. The amount of anodized film can be determined by, for example, applying an aluminum plate to a phosphoric acid chromic acid solution (85% phosphoric acid solution: 35%
milliliter, chromium oxide (VI): prepared by dissolving 20 g in 1 liter of water) to dissolve the oxide film,
It is determined by measuring changes in weight before and after dissolving the film on the plate.

Specific examples of the sealing treatment include hot water treatment, steam treatment, sodium silicate treatment, and dichromate aqueous solution treatment. In addition, the aluminum plate support may be subjected to subbing treatment using an aqueous solution of a water-soluble polymer compound or a metal salt such as fluorinated zirconate.

In addition, when contact printing a film original onto a photosensitive lithographic printing plate, the printing frame is generally vacuumed.
This method of improving vacuum adhesion can also be applied to the photosensitive lithographic printing plate of the present invention. Methods for improving vacuum adhesion include a method of mechanically making unevenness on the surface of the photosensitive layer, a method of scattering solid powder on the surface of the photosensitive layer, and a method of spreading solid powder on the surface of the photosensitive layer.
A method of providing a matte layer on the surface of a photosensitive layer as described in Japanese Patent Application Laid-open No. 25805, and a method of heat-sealing a solid powder on the surface of a photosensitive layer as described in Japanese Patent Application Laid-open No. 12974/1984, etc. Can be mentioned.

The photosensitive lithographic printing plate of the present invention can be used in the same manner as those conventionally used. For example, by exposing a transparent positive film to a light source such as an ultra-high pressure mercury lamp, metal halide lamp, xenon lamp, or tungsten lamp, and then developing it with an alkaline developer, only the unexposed areas remain on the surface of the support, leaving a positive image. A positive relief image is created.

Examples of the alkaline developer used include alkali metal developers such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium metasilicate, potassium metasilicate, dibasic sodium phosphate, and tribasic sodium phosphate. Examples include aqueous solutions of salts. The concentration of the alkali metal salt is preferably 0.1 to 10% by weight. or,
An anionic surfactant, an amphoteric surfactant, and an organic solvent such as alcohol can be added to the developer, if necessary.

[0073]

[Examples] The present invention will be explained below with reference to Examples, but the present invention is not limited thereto.

Example 1 (Preparation of photosensitive lithographic printing plate sample) An aluminum plate with a thickness of 0.24 mm was degreased in a 5% by weight aqueous sodium hydroxide solution at 60°C for 1 minute, and then 1 liter of
Electrolytic etching treatment was performed in a 0.5 mol aqueous hydrochloric acid solution at a temperature of 25° C., a current density of 60 A/dm 2 , and a treatment time of 30 seconds. Next, after desmutting in a 5% by weight aqueous sodium hydroxide solution at 60°C for 10 seconds, desmutting was performed in a 20% by weight sulfuric acid solution at a temperature of 20°C and a current density of 3A/
Anodization treatment was performed under the conditions of dm2 and treatment time of 1 minute. Furthermore, perform hot water sealing treatment with hot water at 30°C for 20 seconds,
An aluminum plate was prepared to be used as a support for lithographic printing plate material.

A photosensitive composition coating solution having the following composition was applied to the aluminum plate prepared as described above using a roll coater, and dried at 90° C. for 4 minutes to obtain positive photosensitive lithographic printing plate sample No. I got 1. The amount of photosensitive composition applied was 24 m.
g/dm2.

(Photosensitive coating liquid composition) Binder resin (BD-1)

7.0g Orthoquinonediazide compound (QD-1
)
1.6g 2-trichloromethyl-5-(β-benzofurylvinyl)-1,3,4-oxadiazole

0.02g Victoria Pure Blue BO
H (manufactured by Hodogaya Chemical)
0.06g Polyoxyethylene sorbitan monolaurate 0.0
9g (Nikko Chemical “GO-430”) Fluorine surfactant “FC-430” (3M)
0.02g Propylene glycol monomethyl ether
70g ethyl acetate

30g In the above coating liquid composition, Table 1
Sample No. 2 to 13 were obtained.

[0077] The obtained sample No. First, the applicability of each of Nos. 1 to 13 was observed and evaluated. Next, a register mark was drawn on each of these samples using a register mark drawing machine, and after 2 minutes, the sample was placed in a developer solution containing 4 times diluted Konica SDR-1 at 27°C.
The suitability of the ballpoint pen was evaluated based on how the photosensitive layer was eroded by the ballpoint pen ink.

Cellotape suitability was determined by pasting cellophane tape on an unexposed sample and leaving it for 24 hours, then immersing it in a developer under the same conditions as for ballpoint pen aptitude evaluation, and checking the extent to which the photosensitive layer was affixed with cellophane tape. I evaluated it. These results are shown in Table 2.

[0079]

[Table 1]

[0080]

[Table 2] As is clear from Table 2, all of the photosensitive lithographic printing plate samples 1 to 9 obtained from the photosensitive coating liquid having the structure of the present invention had all of the coating properties, ballpoint pen suitability, and sellotape suitability. It also has excellent characteristics. *1 Quinonediazide compound

[0081]

[Chemical formula 11]

[0082]

[Chemical formula 12] *2 Binder resin BD-1 Copolymer resin of phenol, m-cresol, p-cresol (molar ratio 48:32:20) and formaldehyde

[0083]

[Chemical formula 13] *3 Oxygen-containing nonionic surfactant A: Product name "GO-430" (manufactured by Nikko Chemical) (polyoxyethylene sorbitan monolaurate) B: Product name "TWO-120" (manufactured by Kao) ( Polyoxyethylene sorbitan monooleate) C; Product name: PEG#200
0” (Daiichi Kagaku) (polyethylene glycol) *4 Solvent PGM: Propylene glycol monomethyl ether DG
DM: diethylene glycol dimethyl ether *5
Ballpoint pen suitability assessment A: Non-print areas are not affected at all B: Non-print areas are slightly attacked: C: Non-print areas are attacked, and sand grains are exposed using a magnifying glass D: Complete sand grain exposure is visually observed *6 Cellotape suitability evaluation A: No effect at all B: Slight residual photosensitive layer is observed, but no inkling C: Remaining of the photosensitive layer is observed, with slight inkling D
Clear fleshing is observed.

[0084]

Effects of the Invention As explained in detail above, the present invention has extremely low odor and toxicity during or after production, improved coating properties, and improved photosensitivity suitable for ballpoint pens and cellophane tape. A lithographic printing plate can be provided.

Claims (1)

[Claims] 1. On a support, at least (a) an orthoquinonediazide compound, (b) a fluorosurfactant in an amount of 0.05 to 0.4% by weight based on the solid content excluding the solvent, and (c)
0.5 to 5% by weight of an oxygen-containing nonionic surfactant based on the solid content excluding the solvent, and (d) a propylene glycol alkyl ether in which the alkyl component has a carbon atom number in the range of 50 to 4. 90% by weight and 10% to 50% by weight of diethylene glycol alkyl ether whose alkyl component has 1 or 2 carbon atoms.
A photosensitive lithographic printing plate coated with a photosensitive coating liquid containing a solvent containing % by weight.