JPH083626B2 - Method for producing photosensitive lithographic printing plate material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (a) Field of Industrial Application The present invention relates to a method for producing a photosensitive lithographic printing plate material that prevents desensitization of a photosensitive resin due to oxygen in the air.

(B) Problems to be Solved by the Related Art and Invention The photosensitive lithographic printing plate material comprises a support coated with a photosensitive resin. There are two main types of photosensitive resin, photo-curing type and photo-degrading type, both of which are less susceptible to photo-curing or photo-degrading under the influence of oxygen in the air (that is, desensitization). There was that. When the photosensitive lithographic printing plate material is stored, it is possible to prevent the influence of oxygen in the air by storing it in a closed container. The influence cannot be prevented.

Therefore, a protective layer that can be removed by development on the photosensitive resin layer (for example, a polyvinyl alcohol film is typical)
Is provided. The photosensitive lithographic printing plate material provided with the protective layer is suitable because it is not required to be housed in a closed container because the photosensitive resin is not easily affected by oxygen in the air, and desensitization is not likely to occur during exposure. However, when providing the protective layer, the protective layer must be applied after the photosensitive resin layer has been applied, which has a drawback that a two-step application process is required. Further, the polyvinyl alcohol film, which is a representative of the protective layer, is liable to deteriorate due to the influence of moisture in the air, and if it is not stored in a closed container, partial peeling of the protective layer occurs during long-term storage. There was a drawback.

Therefore, the present invention is intended to provide a method for producing a photosensitive lithographic printing plate material in which a protective layer can be provided in a single-step coating process and the protective layer is not easily affected by moisture in the air. .

(C) Means for Solving the Problems That is, the present invention is directed to an organic solvent solution in which a photosensitive resin is dissolved in an organic solvent having a boiling point of 100 ° C. or higher, polyvinyl alcohol and a chelate compound coordinated with the polyvinyl alcohol. The present invention relates to a method for producing a photosensitive lithographic printing plate material, which comprises applying an O / W type emulsion comprising an aqueous solution in which a metal compound that produces the above is dissolved on a support and then drying.

First, in the present invention, an O / W emulsion comprising an organic solvent solution in which a photosensitive resin is dissolved, and an aqueous solution in which a polyvinyl alcohol and a metal compound which forms a chelate compound by being coordinated with the polyvinyl alcohol are dissolved. Adjust.

As the photosensitive resin, a photocurable photosensitive resin or a photodegradable photosensitive resin can be used. Examples of the photocurable photosensitive resin include acrylic acid, methacrylic acid, methyl acrylate, methotre methacrylate, butyl acrylate, cyclohexyl acrylate, benzyl acrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, polyethylene glycol diacrylate, butylene glycol diacrylate, 1,4-
Monofunctional or polyfunctional acrylic resins such as butanediol diacrylate, allyl polyfunctional resins such as diallyl phthalate, diallyl isophthalate, diallyl maleate, diallyl chlorendate and diallyl adipate, hexamethylene bisacrylamide Unsaturated acid amide resin such as, polyester resin having unsaturated group in the side chain,
A photocrosslinkable polymer compound such as polyvinyl cinnamate, a photocurable diazo resin, and a photocurable azide resin are used. As the photodegradable photosensitive resin, polymethyl vinyl ketone, polyvinyl phenyl ketone, polysulfone, photodegradable diazo compound and the like are used.

When using the photocurable photosensitive resin, it is preferable to use a photopolymerization initiator in combination. Examples of the photopolymerization initiator include benzoin, ptyroin, trioin, acetoin, α-methylbenzoin, α-phenylbenzoin, α-allylbenzoin, α-benzylbenzoin, benzoin methyl ether, benzoin ethyl ether, piparoin ethyl ether, anisoin. Ether, anthraquinone, 2-
Methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-
Bromanthraquinone, 2-nitroanthraquinone, anthraquinone-1-aldehyde, anthraquinone-2-thiol, 4-cyclohexylanthraquinone, 1,4-dimethylanthraquinone, 1-methoxyanthraquinone, anthraquinone-1-carbonyl chloride, tetraethylthiuranium disulfide, diphenyl Disulfide, benzyl, diacetyl, uranyl propionate, azobisbutyronitrile, methyldiethanolamine, dimethylethanolamine, ethyldiethanolamine, diethylethanolamine, triethanolamine, dimethylaminoethylbenzoate, ethyl-3-dimethylaminobenzoate, 4- Dimethylaminobenzophenone, 4-diethylaminobenzophenone, 4,4'-bis (diethylamino) benzophenone, 4,4 ′ -Bis (dimethylamino)
Examples thereof include benzophenone, N, N-diethylaniline, phenylmethylethanolamine, phenylethylethanolamine, phenyldiethanolamine, N, N, N ', N'-tetramethyl-1,3-butanediamine and the like.

When a photocrosslinkable polymer is used in the photocurable photosensitive resin, a crosslinking agent is generally used together. As the cross-linking agent, acrylic acid, α-chloroacrylic acid, methacrylic acid, acrylamide, methacrylamide, N, N-dimethylacrylamide, N-isopropylacrylamide, N
-Hexylacrylamide, N-cyclohexylacrylamide, N-methylolacrylamide, N-ethylolacrylamide, N-amylolacrylamide, N-allylacrylamide, N, N'-methylenebisacrylamide,
N, N'-trimethylenebisacrylamide, N, N'-hexamethylenebisacrylamide, N, N'-decamethylenebisacrylamide, N-methoxymethylacrylamide, N
-Methoxyethylacrylamide, N-ethoxymethylacrylamide, N-methylmethacrylamide, N-allylmethacrylamide, N-methylolmethacrylamide, N, N '
-Methylenebismethacrylamide, N-methoxymethylmethacrylamide, N-ethoxyethylmethacrylamide, N
-Methoxyethyl methacrylamide, methyl acrylate, ethyl acrylate, butyl acrylate, isobutyl acrylate, n-propyl acrylate, isopropyl acrylate, 2-ethylhexyl acrylate, n-
Octyl acrylate, n-decyl acrylate, n-tetradecyl acrylate, allyl acrylate, furfuryl acrylate, glycidyl acrylate, methyl-2
-Chloro acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, furfuryl methacrylate, diethylene glycol diacrylate, tetraethylene glycol diacrylate, ethylene glycol monomethacrylate, diethylene glycol monoacrylate,
Hexamethylene glycol dimethacrylate, tetradecyl ethylene glycol dimethacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxyhexyl methacrylate, glycidyl methacrylate, tetramethylol methane tetraacrylate, tetramethylol methane tetramethacrylate, tetramethylol methanetri Acrylate, tetramethylolmethane trimethacrylate, styrene,
Divinylbenzene, α-methylstyrene, vinyltoluene, α-chlorostyrene, vinylchlorobenzene, vinylphenol, aminostyrene, vinylbenzoic acid, ethoxystyrene, allylbenzene, diallylbenzene, allyltoluene, monoallylphthalate, diallylphthalate, allyl Alcohol, allyl acetate, vinyl acetate, vinyl propionate, maleic acid, fumaric acid, itaconic acid, dimethyl maleate, diethyl maleate, dimethyl fumarate, diethyl fumarate, dimethyl itaconate, diethyl itaconate, cinnamic acid, ethyl Vanyl ether, propyl vinyl ether, methyl vinyl ketone, acrolein, vinylidene chloride,
Examples thereof include vinyl pyridine, vinyl pyrrolidone, diethyl vinyl amine and vinyl carbazole.

As the organic solvent having a boiling point of 100 ° C. or higher for dissolving the photosensitive resin, butanol, cellosolve, toluene, xylene and the like are used. Using an organic solvent having a boiling point of 100 ° C. or higher means that water in an aqueous solution portion in which polyvinyl alcohol or the like is dissolved is evaporated first, and that polyvinyl alcohol or the like is unevenly distributed on the photosensitive resin layer due to a migration effect. Because it will be.

Polyvinyl alcohol and a metal compound that forms a chelate compound by being coordinated with the polyvinyl alcohol are dissolved in the aqueous solution. As the metal compound, zirconium nitrate is generally used, but other zirconium salts and the like can be used. When water is evaporated and a polyvinyl alcohol film is formed, the hydroxyl groups of polyvinyl alcohol are coordinated with the metal compound and chelated. Therefore,
The hydroxyl groups of polyvinyl alcohol are less likely to be affected by moisture (for example, water adsorption due to hydrogen bonds), and the polyvinyl alcohol film is less likely to be deteriorated by moisture in the air.

The concentration of the photosensitive resin in the organic solvent solution and the concentration of polyvinyl alcohol in the aqueous solution are appropriately determined, but are usually about 10 to 50% by weight. An O / W emulsion can be obtained by mixing the organic solvent solution and the aqueous solution in a volume ratio of about 10 to 20:40 to 80 and stirring. At this time, it is preferable to prepare the emulsion by using a surfactant, particularly a nonionic surfactant such as sorbitan fatty acid ester (Span) or a product obtained by adding ethylene oxide to this (Tween).

Next, the emulsion prepared as described above is applied to a support using a bar coater or the like. As the support, any support may be used as long as it is inexpensive and satisfies the required performance as a lithographic printing plate, and is made of a simple metal such as aluminum, iron, copper, zinc or lead, or an alloy thereof. Foil or board, polyester, polypropylene, polyimide, polyacrylonitrile, polycarbonate, polyamide, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyethylene and other plastic film or sheet-like molded products, synthetic paper, art paper, coated paper, cardboard Various materials such as thin paper can be used. Aluminum, zinc, iron and the like are suitable as the metal base material. As the plastics base material, polyethylene, polyimide, and polycarbonate, which have relatively high dimensional stability, are suitable. As the paper base material, synthetic paper, coated paper, art paper and cardboard are suitable.

Then, the coated emulsion is dried at a drying temperature of 100 ° C. or higher to obtain a photosensitive lithographic printing plate material.

(D) Action and effect of the invention The organic solvent solution in which the photosensitive resin is dissolved in the organic solvent having a boiling point of 100 ° C or higher, and the polyvinyl alcohol and the metal compound which forms a chelate compound by being coordinated with the polyvinyl alcohol are dissolved. When an O / W type emulsion consisting of an aqueous solution is applied to the support and dried at 100 ° C or higher,
Water in the aqueous solution portion first evaporates, and the aqueous solution portion aggregates on the organic solvent liquid due to the migration effect.
As a result, the organic solvent solution portion aggregates on the support, and the aqueous solution portion aggregates on the organic solvent solution portion. Then, as the drying progresses, the support-photosensitive resin-polyvinyl alcohol film are arranged in this order. That is, in the photosensitive lithographic printing plate material produced by the method of the present invention, the photosensitive resin is protected by the polyvinyl alcohol film, and is less affected by oxygen in the air. Therefore, the photosensitive resin is not desensitized during exposure, and the exposure time can be shortened. In other words, the present invention has an effect that a protective layer similar to the conventional one can be provided in a single-step coating process, and the manufacturing process is rationalized.

In addition, since the metal compound for coordinating polyvinyl alcohol to form a chelate compound is mixed in the aqueous solution portion of the O / W type emulsion used in the present invention, the hydroxyl group of polyvinyl alcohol is blocked with the metal compound and is in the air. It is difficult to absorb water. Therefore, the polyvinyl alcohol film, which is the protective layer, is unlikely to deteriorate due to moisture in the air,
There is also an effect that a photosensitive lithographic printing plate material whose quality does not change over a long period of time can be obtained without storing in a closed container.

Claims (1)

[Claims] 1. An organic solvent solution in which a photosensitive resin is dissolved in an organic solvent having a boiling point of 100 ° C. or higher, and an aqueous solution in which polyvinyl alcohol and a metal compound which forms a chelate compound by coordination with the polyvinyl alcohol are dissolved. Consists of
A method for producing a photosensitive lithographic printing plate material, which comprises applying an O / W type emulsion to a support and then drying.