JPS6261136B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing a photosensitive lithographic printing plate,
In particular, the present invention relates to a method for producing a photosensitive lithographic printing plate in which an ink-receptive layer is coated with an aqueous medium. Early photosensitive lithographic printing plates, which used dichromate as a photosensitive material and combined water-soluble colloidal substances such as egg white, albumin, and polyvinyl alcohol, inevitably used water as the coating solvent, but The image is hydrophilic and will not accept oil-based ink as it is. For this reason, after exposure and before development, a greasy ink is applied to the entire surface and the unexposed areas are removed.
Foundation (The Graphic Arts)
Technical Foundation). The Lithographers Manual, published by , Inc.
After removing the unexposed area, a hydrophobic resin is applied from an organic solvent, and after drying, it is formed by image exposure. Plano-intaglio plate for stripping off resist (The Lithographers Manual)
Manual) Chapter 10, page 28, No. 7 Deep Etch Plates (see Deep Etch Plates)
etc., post-processing is required to make the image area lipophilic, and efforts have been made to do so. Subsequent technological advances made possible the use of hydrophobic photoreceptors. This technology made it possible to directly obtain hydrophobic images by simply exposing and developing, and at the same time, the stability was improved. In particular, its stability under high humidity conditions was dramatically improved, which led to it becoming a mass product, and it quickly became popular as a presensitized lithographic printing plate (hereinafter referred to as PS plate). A typical PS plate of this type has a photosensitive layer made of a mixture of a photosensitive diazo compound and a resin provided on a support, and the latter resin is
To ensure that the image area (area that repels water and accepts printing ink) of a lithographic printing plate obtained by image exposure and development of a PS plate has higher oil sensitivity (ability to accept printing ink). In addition, the lithographic printing plate is used to produce more printed matter. Since the photosensitive layer is coated from a suitable solvent, the resin must also be soluble in an organic solvent, and the organic solvent must also be capable of dissolving the photosensitive diazo compound. Moreover, this resin must not inhibit the stability of the photosensitive diazo compound when mixed with the photosensitive diazo compound. However, in reality, it is difficult to find a resin that satisfies all of these requirements. The reality is that resins are used that have somewhat poor properties. On the other hand, Japanese Patent Publication No. 37-11558 discloses a PS plate in which a photosensitive diazo compound layer and a hydrophobic, solvent-softening, developer-permeable, and actinic ray-transparent resin layer are sequentially provided on a support. has been done. but,
Even in PS plates with this structure, there are restrictions on the resin that can be used in the resin layer, and the developer must be able to pass through the resin layer, so the developer that can be used must also have a special composition. I get used to it. Furthermore, in any of the above embodiments, an organic solvent must be used as a coating solvent;
Issues such as the toxicity and explosiveness of organic solvents had to be taken into consideration, and a large amount of investment was required in manufacturing equipment. On the other hand, JP-A-52-2520 discloses a PS plate in which a photosensitive layer is provided by coating a polymer emulsion with a water-soluble diazo compound on a support. PS plates can be manufactured without using organic solvents. However, this PS plate is easily affected by moisture, and therefore its storage stability (PS plate after storage is different from PS plate immediately after manufacture).
The quality of maintaining the performance of the plate) was poor. Therefore, an object of the present invention is to provide a photosensitive lithographic printing plate with excellent storage stability. Another object of the present invention is to provide a photosensitive lithographic printing plate from which a lithographic printing plate having image areas with high oil sensitivity can be obtained. Another object of the present invention is to provide a photosensitive lithographic printing plate which can be developed with a normal developer rather than a developer with a special composition, and which can yield a lithographic printing plate having a highly oil-sensitive image area. That's true. Another object of the present invention is to provide a method for producing a photosensitive lithographic printing plate, in which a coating layer of the photosensitive lithographic printing plate giving a highly oil-sensitive image area can be coated from an aqueous medium. The above objects are: (a) a support having a hydrophilic surface;
(2) a layer of a photosensitive diazo compound coated on the hydrophilic surface; and (3) an ink receptive layer in contact with the layer of the photosensitive diazo compound, and the ink receptive layer is an aqueous emulsion of a lipophilic resin. This was achieved with a photosensitive lithographic printing plate coated from The support used in the present invention is a dimensionally stable plate. Such dimensionally stable plate-like materials include those conventionally used as supports for printing plates, and they can be suitably used in the present invention. Such supports include paper, plastics (e.g. polyethylene, polypropylene,
paper laminated with polystyrene (e.g., polystyrene), sheets of metal such as aluminum (including aluminum alloys), zinc, copper, etc., e.g., cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, Included are plastic films such as cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc., and paper or plastic films laminated or vapor-deposited with metals such as those mentioned above. Among these supports, aluminum plates are particularly preferred because they are extremely dimensionally stable and inexpensive. Furthermore, a composite sheet in which an aluminum sheet is bonded to a polyethylene terephthalate film as described in Japanese Patent Publication No. 18327/1984 is also preferred. The surface of the support must be hydrophilic. In the present invention, a hydrophilic surface refers to a surface that becomes wet with dampening water and repels ink when the printing plate is mounted on a lithographic printing machine and printed under standard conditions. There are various ways to provide such a hydrophilic surface. For example, in the case of supports with plastic surfaces, so-called surface treatment methods such as chemical treatment, electric discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment (for example, US Pat. No. 2764520, No. 3497407
No. 3145242, No. 3376208, No. 3072483, No. 3475193,
3360448, British Patent No. 788365, etc.) and a method in which a subbing layer is applied to the plastic after the surface treatment. A variety of coating methods have been developed, including the multilayer method in which a hydrophobic resin layer that adheres well to plastic and has good solubility is applied as one layer, and a hydrophilic resin layer is applied as a second layer using the same polymer. There is a single layer method in which a resin layer containing hydrophobic groups and hydrophilic groups is applied. In addition, in the case of a support having a metal surface, especially aluminum, surface treatments such as graining treatment, immersion treatment in an aqueous solution of sodium silicate, potassium fluorozirconate, phosphate, etc., or anodization treatment are performed. Preferably. In addition, as described in U.S. Patent No. 2,714,066, an aluminum plate which has been grained and then immersed in a sodium silicate aqueous solution, and an aluminum plate as described in Japanese Patent Publication No. 47-5125, can be used as an anode. Those obtained by oxidation treatment and then immersion treatment in an aqueous solution of an alkali metal silicate are also suitably used. The above anodic oxidation treatment can be performed using, for example, phosphoric acid, chromic acid, sulfuric acid,
It is carried out by passing an electric current through an aluminum plate as an anode in an electrolytic solution consisting of an aqueous solution or a non-aqueous solution of an inorganic acid such as boric acid, an organic acid such as oxalic acid or sulfamic acid, or a salt thereof, or a combination of two or more thereof. Ru. Also effective is silicate electrodeposition as described in US Pat. No. 3,658,662. Furthermore, Japanese Patent Publication No. 1974-27481, Japanese Patent Application Publication No. 1972-
Also useful is a surface treatment that combines a support coated with electrolytic grains with the above-mentioned anodic oxidation treatment and sodium silicate treatment as disclosed in JP-A-58602 and JP-A-52-30503. These hydrophilic treatments are performed not only to make the surface of the support hydrophilic, but also to prevent harmful reactions with the photosensitive composition provided thereon, and to improve adhesion with the photosensitive layer. It is performed for purposes such as improving sexual performance. The photosensitive diazo compounds used in the present invention include diazonium salts disclosed in U.S. Pat. A condensation product (so-called photosensitive diazo resin) of diphenylamine-P-diazonium salt, which is a reaction product with formaldehyde, is preferably used. Other useful condensed diazo compounds are Japanese Patent Publication Nos. 49-48001, 49-45322, 49
- Disclosed in various publications such as No. 45323. These types of photosensitive diazo compounds are usually obtained in the form of water-soluble inorganic salts and can therefore be coated from aqueous solution. In addition, these aqueous diazo compounds were
A substantially water-insoluble reaction product obtained by reacting with an aromatic or aliphatic compound having one or more phenolic hydroxyl groups, sulfonic acid groups, or both by the method disclosed in Publication No. 47-1167. It is also possible to use photosensitive diazo resins. Examples of reactants having phenolic hydroxyl groups include diphenolic acids such as hydroxybenzophenone, 4,4-bis(4'-hydroxyphenyl)pentanoic acid, resorcinol, or diresorcinol, which may further include It may have a substituent. Hydroxybenzophenone has 2,
4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone or 2,2',4,4'-tetrahydroxybenzophenone is included. Preferred sulfonic acids include:
Examples include aromatic sulfonic acids such as sulfonic acids such as benzene, toluene, xylene, naphthalene, phenol, naphthol and benzophenone, or soluble salts thereof, such as ammonium and alkali metal salts. Sulfonic acid group-containing compounds may generally be substituted with lower alkyl, nitro groups, halo groups, and/or another sulfonic acid group. Preferred examples of such compounds include benzenesulfonic acid, toluenesulfonic acid, naphthalenesulfonic acid, 2,5-dimethylbenzenesulfonic acid, sodium benzenesulfonate, naphthalene-2-sulfonic acid, 1-naphthol-2 (or 4)-Sulfonic acid, 2,4-
Dinitro-1-naphthol-7-sulfonic acid, 2
-Hydroxy-4-methoxybenzophenone-5
-sulfonic acid, m-(P'-anilinophenylazo)benzenesulfonic acid sodium, alizarin sulfonic acid, 0-toluidine-m-sulfonic acid and ethanesulfonic acid. Sulfonic esters of alcohols and their salts are also useful. Such compounds are usually readily available as anionic surfactants. Examples include ammonium or alkali metal salts such as lauryl sulfate, alkylaryl sulfate, P-nonylphenyl sulfate, 2-phenylethyl sulfate, isooctylphenoxydiethoxyethyl sulfate. These substantially water-insoluble photosensitive diazo compounds can be precipitated by mixing a water-soluble photosensitive diazo compound and an aqueous solution of the aromatic or aliphatic compound, preferably in approximately equal amounts. isolated. The obtained substantially water-insoluble photosensitive diazo compound can be applied by dissolving it in a solvent such as methyl cellosolve, dimethyl formamide, methanol-ethylene dichloride, or a mixture thereof. As with the water-soluble photosensitive diazo compound, the coating method is not particularly limited, and methods such as roller coating, gravure coating, and dip coating can be used. Coating amounts can range from about 1 to about 500 mg/ ^m2 , with a preferred range of 10 to 100 mg/ ^m2 . The ink-receptive layer provided on and in contact with this layer of photosensitive diazo compound is provided by coating from an aqueous emulsion of a lipophilic resin. This emulsion has a film-forming ability, and the resulting film is tough and wear-resistant, forms a hydrophobic surface that easily accepts printing ink, is transparent to actinic rays, and is highly active of the photosensitive diazo resin. In the region of photolysis by light, the adhesion of the film formed from the emulsion to the support is stronger in the developer than in the unexposed region, and when the image-exposed plate is rubbed in the developer. It is desirable to use an emulsion that has the property that exposed areas remain intact and unexposed areas are removed cleanly. As the emulsion, a lipophilic resin latex can be used. The latex useful in the present invention is a homopolymer of monomers selected from the following Group A, a copolymer of two or more monomers selected from the following Group A, or at least one type of each of the monomers selected from Group A and Group B. These are polymer latexes obtained by copolymerization of monomers, or polymer latexes obtained by combining them with at least one monomer of group C. Group A: Monomers represented by the following general formula [In the formula, X: hydrogen atom, methyl group or -COOR ¹ group Y: hydrogen atom, methyl group or -
(CH ₂ ) _o COOR ² halogen, nitrile, Z: aryl group, -COOR ³ , -OR ³ ,

[Formula] - CONR ³ , halogen, nitrile R ¹ , R ² , R ³ : These may be the same or different, aliphatic group or aromatic group n: Integer from 0 to 3] Group B: Free An ethylene monomer having at least one carboxylic acid group, sulfonic acid group, phosphoric acid group, or a salt thereof. A hydroxyalkyl ester or amide of the carboxylic acid. Group C: Sivinyl monomers. Among the groups represented by R ¹ to ^{R 3} in the general formula of Group A, aliphatic groups include direct or branched alkyl groups (including cyclic ones) and substituted alkyl groups. The number of carbon atoms in the alkyl group is preferably 1 to 12. Substituents for the substituted alkyl group include aryl group, aryloxy group, halogen atom, cyano group,
Acyl group, alkylcarbonyloxy group, arylcarbonyloxy group, amino group (including substituted amino groups, substituents include alkyl group, aryl group, etc. The number of substituents is 1 to 2), hydroxy group, alkoxy group , heterocyclic residues (hetero atoms include, for example, oxygen atoms, nitrogen atoms, sulfur atoms, etc. The number of members in the ring is preferably 5 to 6, and the ring may be unsaturated or saturated. The heterocyclic ring may further include an aromatic ring. may be condensed.). Of the groups represented by R ¹ to ^{R 3} , the aryl group naturally includes substituted phenyl and naphthyl groups, and the substituents include alkyl Examples include groups. Group A monomers include, for example, acrylic esters, methacrylic esters, crotonic esters, vinyl esters, maleic diesters,
Examples include monofunctional monomers such as fumaric acid diester, itaconic acid diester, and styrenes. Furthermore, specific monomers include, for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, amyl acrylate, hexyl acrylate, and 2-ethylhexyl acrylate. , octyl acrylate,
tert-octyl acrylate, 2-phenoxyethyl acrylate, 2-chloroethyl acrylate, 2-bromoethyl acrylate, 4-chlorobutyl acrylate, cyanoethyl acrylate, 2-acetoxyethyl acrylate, dimethylaminoethyl acrylate, benzyl acrylate, methoxybenzyl Acrylate, 2-chlorocyclohexyl acrylate, cyclohexyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, phenyl acrylate, 5-hydroxypentyl acrylate,
2,2-dimethyl-3-hydroxypropyl acrylate, 2-methoxyethyl acrylate, 3
-Methoxybutyl acrylate, 2-ethoxyethyl acrylate, 2-iso-propoxyethyl acrylate, 2-butoxyethyl acrylate, 2-(2-methoxyethoxy)ethyl acrylate, 2-(2-butoxyethoxy)ethyl acrylate, ω-methoxy Polyethylene glycol acrylate (number of moles added = 9), 1-bromo-2-methoxyethyl acrylate, 1,1-
Dichloro-2-ethoxyethyl acrylate, methyl methacrylate, ethyl methacrylate, n
-Propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, N-ethyl-N-
Phenylaminoethyl methacrylate, 2-(3
-Phenylpropyloxy)ethyl methacrylate, dimethylaminophenoxyethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4
-Hydroxybutyl methacrylate, triethylene glycol monomethacrylate, dipropylene glycol monomethacrylate, 2-methoxyethyl methacrylate, 3-methoxybutyl methacrylate, 2-acetoxyethyl methacrylate, acetoacetoxyethyl methacrylate, 2
-Ethoxyethyl methacrylate, 2-iso-propoxyethyl methacrylate, 2-butoxyethyl methacrylate, 2-(2-methoxyethoxy)ethyl methacrylate, 2-(2-ethoxyethoxy)ethyl methacrylate, 2-(2-butoxyethoxy)ethyl Methacrylate, ω-methoxypolyethylene glycol methacrylate (additional mole number n = 6), vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl dimethyl propionate, vinyl ethyl butyrate, vinyl valerate ), vinylcaproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxy acetate, vinyl butoxy acetate, vinyl phenyl acetate, vinyl acetoacetate, vinyl lactate, vinyl-β-phenyl butyrate,
Vinyl cyclohexyl carboxylate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate, styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene,
Diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, decylstyrene, benzylstyrene,
Chloromethylstyrene, trifluoromethylstyrene, ethoxymethylstyrene, acetoxymethylstyrene, methoxystyrene, 4-methoxy-
3-methylstyrene, dimethoxystyrene, chlorstyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorstyrene, bromstyrene, dibromstyrene, iodostyrene, fluorostyrene, trifluorstyrene, 2-bromo-4- Trifluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene, vinylbenzoic acid methyl ester, butyl crotonate, hexyl crotonate, glycerin monocrotonate, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, diethyl maleate , dimethyl maleate, dibutyl maleate, diethyl fumarate, dihexyl fumarate,
Dibutyl methyl acrylamide fumarate, ethyl acrylamide, propylacrylamide, isopropylacrylamide, butylacrylamide, tert-butylacrylamide, heptyl acrylamide, tert-octylacrylamide, cyclohexylacrylamide, benzylacrylamide, hydroxymethyl acrylamide, methoxyethylacrylamide, dimethylaminoethylacrylamide, Hydroxyethyl acrylamide, phenylacrylamide, hydroxyphenylacrylamide, tolylacrylamide, naphthylacrylamide, dimethylacrylamide, diethylacrylamide, dibutylacrylamide, diisobutylacrylamide, N-
(1,1-dimethyl-3-oxobutyl)acrylamide, methylbenzylacrylamide, benzyloxyethylacrylamide, β-cyanoethylacrylamide, acryloylmorpholine,
N-methyl-N-acryloylpiperazine, N-
Acryloylpiperidine, N-(1,1-dimethyl-3-hydroxybutyl)acrylamide, N
-β-morpholinoethyl acrylamide, N-acryloylhexamethyleneimine, N-hydroxyethyl-N-methylacrylamide, N-2-
Acetamide ethyl-N-acetylacrylamide, methylmethacrylamide, tert-butylmethacrylamide, tert-octylmethacrylamide, benzylmethacrylamide, cyclohexylmethacrylamide, phenylmethacrylamide,
Dimethylmethacrylamide, diethylmethacrylamide, dipropylmethacrylamide, hydroxyethyl-N-methylmethacrylamide, N-methyl-N-phenylmethacrylamide, N-ethyl-N-phenylmethacrylamide, methacrylhydrazine, etc.; Allyl compounds :For example, allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate,
Allyl benzoate, allyl acetoacetate, allyl lactate, allyloxyethanol, allyl butyl ether, allyl phenyl ether, etc. Vinyl ethers: For example, methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether , ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1
-Methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, etc.; Vinyl ketones: for example, methyl vinyl ketone, phenyl vinyl ketone, methoxyethyl vinyl ketone, etc.; Olefins: For example, dicyclopentadiene, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene,
5-methyl-1-nonene, 5,5-dimethyl-1
-Octene, 4-methyl-1-hexene, 4,4
-dimethyl-1-pentene, 5-methyl-1-hexene, 4-methyl-1-heptene, 5-methyl-1-heptene, 4,4-dimethyl-1-hexene, 5,5,6-trimethyl-1 -Heptene, 1
- unsubstituted hydrocarbons such as dodecene and 1-octadecene; diene compounds such as butadiene, isoprene, and chloroprene; (for example, 5 to 6, and an aromatic ring may be further bonded to this ring): For example, N
-Vinyloxazolidone, vinylpyridine, vinylpicoline, N-vinylimidazole, N-vinyl-2-methylimidazole, N-vinyltriazole, N-vinyl-3,5-dimethyltriazole, N-vinylpyrrolidone, N-vinyl- 3,5
-Dimethylpyrazole, N-vinylcarbazole, vinylthiophene, N-vinylsuccinimide, N-vinylglutarimide, N-vinyladipimide, N-vinylpyrrolidone, N-vinylpiperidone, N-vinyl-ε-caprolactam, N-
Vinyl-2-pyridone, etc.; Unsaturated nitriles: e.g. acrylonitrile,
Vinyl halide compounds such as methachronitrile; vinyl chloride, vinylidene chloride, vinyl bromide,
vinyl iodide, etc. Specific examples of Group B monomers include the following monofunctional monomers. Acrylic acid, methacrylic acid, itaconic acid, maleic acid, monoalkyl itaconate (e.g. monomethyl itaconate, monoethyl itaconate, monobutyl itaconate, etc.), monoalkyl maleate (e.g. monomethyl maleate, monoethyl maleate, monobutyl maleate, etc.) monooctyl maleate, etc.), citraconic acid, styrene sulfonic acid, vinylbenzyl sulfonic acid, vinyl sulfonic acid, acryloyloxyalkyl sulfonic acid,
(e.g., acryloyloxymethylsulfonic acid, acryloyloxyethylsulfonic acid, acryloyloxypropylsulfonic acid, acryloyloxybutylsulfonic acid, etc.), methacryloyloxyalkylsulfonic acid (e.g., methacryloyloxymethylsulfonic acid, methacryloyloxyethylsulfonic acid, methacryloyloxy propyl sulfonic acid, methacryloyloxybutyl sulfonic acid, etc.), acrylamide alkyl sulfonic acid (e.g. 2-acrylamido-2-methylethanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-acrylamide-
2-methylbutanesulfonic acid, etc.), methacrylamide alkylsulfonic acid (e.g. 2-methacrylamido-2-methylethanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylbutanesulfone) acids, etc.), acryloyloxyalkyl phosphates (e.g., acryloyloxyethyl phosphate, 3-acryloyloxypropyl phosphate, etc.), methacryloyloxyalkyl phosphates (e.g., methacryloyloxyethyl phosphate, 3-methacryloyloxypropyl phosphate, etc.) Such. Further, the alkyl group in the acid monomer has, for example, about 1 to 8 carbon atoms. These acids contain alkali metal ions (preferably Na ⁺ ,
K ⁺ ) or an ammonium ion salt. Specific examples of monomers of group C include unsaturated esters of polyols, in particular such esters of α-methylenecarboxylic acid, such as ethylene di(meth)
Acrylate, diethylene glycol di(meth)
Acrylate, glycerol di(meth)acrylate, glycerol tri(meth)acrylate,
1,3-propylene di(meth)acrylate,
1,4-cyclohexanediol (meth)acrylate, 1,4-benzenediol di(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,3-propylene glycol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate (meth)acrylate, trimethylolpropane tri(meth)acrylate. Unsaturated amides, especially amides of α-methylenecarboxylic acid and especially α,ω-diamines and ω with intermediate oxygen
-Diamines, such as methylenebis(meth)
Acrylamide, ethylene bis(meth)acrylamide, 1,6-hexamethylene bis(meth)acrylamide and diethylenetriamine tris(meth)acrylamide, divinyl succinate, divinyl adipate, divinyl phthalate,
Divinyl terephthalate, divinylbenzene
1,3-disulfonate and divinylbutane-
Vinyl esters such as 1,4-disulfonate, unsaturated aldehydes such as sorbaldehyde or 2,4-hexadienal. (meth)acrylates, neutral α-methylene carboxylic acid polyesters such as (meth)acrylamide, polyamides and/or first and second
Amino alcohols, amino polyols or ester amides of polyamino alcohols or polyols and similar derivatives of said alcohols, such as β
-Methacrylamide ethyl (meth)acrylamide, N-(β-hydroxyethyl)-β-(methacrylamide)ethyl acrylate, N,N-
Bis(β-methacryloxyethyl)acrylamide, other urethane compounds derived from divinylbenzene, xylylene diisocyanate, and hydroxyethyl (meth)acrylate, such as those having the chemical structure below. Urethane compounds made from isocyanates and hydroxyalkyl compounds such as are useful. In addition, in the above, "(meth)acrylate" means both "acrylate" and "methacrylate", and "(meth)acrylamide" also means the same thing. Latex polymers that can be used here are manufactured by, for example, Preparative Methods of Polymer Chemistry Interscience Publishers.
Polymer Chemistry, Interscience Publishers)
It can be synthesized according to the emulsion polymerization method described on pages 216 and 238 of the publication. One example is the following. 1 in a three-necked flask
Take 420ml of distilled water and add potassium metabisulfite.
Add 0.225g, stir to dissolve, and then purge with nitrogen to add 33.37g of acrylonitrile, 145.3g of vinylidene chloride, 14.1g of acrylic acid, and Triton 770.
(Surfactant) Add 14.1g of potassium persulfate
0.45 g was added, and the mixture was stirred at a rotation speed of 150 rpm at a temperature of 30° C. to react. Resins for which emulsion polymerization methods cannot be used in the preparation of latex, such as formal resins or acetal resins such as butyral resins, cellulose acetate, cellulose propionate, cellulose butyrate,
Cellulose esters such as cellulose crotonate, the ester compounds and phthalic acid, succinic acid,
coester compounds with dicarboxylic acids such as sebacic acid and maleic acid, cellulose ether compounds such as methylcellulose, ethylcellulose, propiocellulose, butylcellulose, allylcellulose, benzylcellulose, cyclohexylcellulose, and cyanoethylcellulose, polyester, polyamide, polyurethane, etc. High molecular compounds produced by condensation polymerization are also useful as lipophilic resins that can be used in the present invention. Emuldimon can be prepared from this compound by the method disclosed in JP-A-52-3653. Group A, Group B in the above copolymer latex,
The ratio of group C can be appropriately selected in consideration of the developability, ink receptivity, printing durability, and other performances of the ink receptive layer coated from the latex. The monomer components of group A mainly control ink receptivity and printing durability. Therefore, the amount of the Group A monomer component is preferably 20 to 100% by weight, particularly preferably 60 to 100% by weight, based on the solid content of the latex polymer. The amount of the Group B monomer component is preferably 0 to 25% by weight, particularly preferably 0 to 10% by weight, based on the solid content of the latex polymer. The C group monomer component is preferably 0 to 80% by weight, particularly preferably 0 to 40% by weight. Furthermore, commercially available emulsion paints, latex, etc. can also be used. For example, Nippon Paint Co., Ltd.
vinyl acetate resin emulsion; vinylex
5000, acrylic resin emulsion; vinylex
5000 Super, water-based paint Asahipen from Asahipen Co., Ltd., acrylic emulsion from Dainippon Toyo Co., Ltd.; Acrose #100, vinyl acetate emulsion from Kansai Paint Co., Ltd.; Vinypaint, vinyl acetate emulsion from Hoechst Kasei Co., Ltd. Rousillon, acrylic resin emulsion; Movinyl, etc. can be used. However, when using commercially available latex, it is necessary to take into account that the performance is affected by the type of emulsion stabilizer used. Polymers forming the ink-receptive layer, including latexes prepared by methods that do not rely on emulsion polymerization, have hydroxyl, amino, amide, imino, imide, nitrilo, carboxyl, sulfonyl, sulfonoxy, Isocyanate, urethane, azoimide,
Those containing at least one group selected from azo, hydrazino, carbamide, carbamyl, epoxy, mercapto, thio, and sulfonamido groups are preferred. There are no particular restrictions on the particle size of the lipophilic resin in the emulsion, but particles with a distribution within the range of approximately 0.03 to 10μ can generally be used, but preferably 0.05 to 10μ.
It is about 5μ. The polymer forming the emulsion particles can range from high molecular weight to oligomeric polymers, from about 2,000 to about 200,000 in molecular weight, or may be a mixture of these polymers. or,
The polymer forming the particles may itself be crosslinked, or may have the property of being cured by actinic rays or heat. The coating amount of the emulsion is preferably in the range of 0.1 to 5 g/m ² , more preferably 0.3 to 3 g/m ² . As the coating method, well-known methods such as dip coating, roller coating, spin coating, and gravure coating can be used.
The concentration of the coating solution is determined from the coating method, coating conditions, and coating amount, and is left to the discretion of those skilled in the art. Various other additives can also be added to the ink-receptive imaging layer of the present invention. For example, dyes such as acridine dyes, cyanine dyes, merocyanine dyes, styryl dyes, triphenylmethane dyes, and organic pigments can be added as coloring substances for visualizing images. Similarly, a photochromic substance or a photochromic substance can be added for the purpose of obtaining a visible image by exposure. For example, combinations of aromatic azides, carbonyl azides, sulfonyl azides, polyhalomethyl compounds, etc. and leuco dyes, etc., can be used.The amount added varies depending on the degree of the desired visible image, but in general, the ink receptivity is An addition ratio of about 1 to 5 by weight in the layer is sufficient. Furthermore, stabilizers, surfactants, plasticizers, etc. can also be added as appropriate. The additive component may be contained within the particles of the emulsion or may be contained outside the particles. The photosensitive lithographic printing plate of the present invention is subjected to imagewise exposure through actinic rays, and then dipped in water, an aqueous surfactant solution, an aqueous organic solvent solution, or a mixture thereof, etc. When the plate surface is rubbed with a material, the ink-receiving layer in the unexposed area is removed, and at the same time, the photosensitive diazo compound is also removed and the hydrophilic layer is exposed. On the other hand, the exposed area remains intact. Its surface is hydrophobic, so it can be installed directly into an offset printing machine to immediately produce high-quality printed matter. Surfactants useful as the above developer include fatty acid salts, higher alcohol sulfate ester salts, fatty alcohol phosphate ester salts, sulfonate salts of dibasic fatty acid esters, fatty acid amides, sulfonate salts, and alkylaryl sulfonate salts. , anionic surfactants such as formaldehyde condensed naphthalene sulfonates, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenol ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, polyoxypropylene polyoxyethylene These include nonionic surfactants such as ethers. Typical organic solvents are ethanol, lower alcohols such as n-propanol and isopropanol, benzyl alcohol, esters such as butyl acetate, ethers such as methyl cellosolve, ketones such as cyclohexane and acetone, and Dow Chemical. Dowanol P-Mix. (polypropylene glycol ether) commercially available from Co., Ltd. Other developers that can be used are those described in Japanese Patent Application Laid-open No. 1983-
44202, U.S. Patent No. 3669660, U.S. Patent No. 302994
No. 303072 and No. 303071. The photosensitive lithographic printing plate of the present invention has excellent storage stability even though the ink-receptive layer can be coated from an aqueous coating solution.
Moreover, since the lipophilic resin constituting the ink-receptive layer can be selected from a wide range of types, a photosensitive lithographic printing plate that provides a lithographic printing plate having an image area with high oil sensitivity can be obtained with excellent results. Hereinafter, the present invention will be explained in more detail based on examples. Example 1 Photosensitive diazo of paraformaldehyde condensation product of P-diazodiphenylamine and 2-oxy-4-methoxy-benzophenone-5-sulfonic acid synthesized by the method described in Japanese Patent Publication No. 42-5364 A 1 weight percent solution was prepared by dissolving the reaction products in methyl cellosolve. On the other hand, a 3S aluminum plate was degreased by immersing it in a 10% by weight aqueous solution of tribasic sodium phosphate kept at 80°C for 3 minutes, and then washed with water. Next, it was desmatted using a 70% by weight nitric acid solution, washed with water, and then immersed for 1 minute in a 2% by weight solution of JIS No. 3 sodium silicate at 70°C. After washing with water and drying, the above prepared solution was applied. After drying, latex made by diluting Movinyl 50M (vinyl acetate polymer latex) sold by Hoechst Kasei Co., Ltd. 15 times with pure water was applied using a whiler coating machine, and dried at 100°C for 1 minute. . The printing plate material thus produced could be plate-made by a conventional method. For example, by immersing a printing plate exposed through a negative film in water using a 30 Amp. carbon arc lamp from a distance of 70 cm for 1 minute, and then rubbing the plate surface lightly with absorbent cotton, only the unexposed areas can be peeled off and removed, making it hydrophilic. The support surface was exposed. On the other hand, there was no dropout in the exposed area. The plates were printed either as they were or after applying a gum solution and then mounted on an offset printing machine. Good quality prints with no defects were obtained. Example 2 A 2S aluminum plate with a thickness of 0.2 mm was degreased by immersing it in a 10% by weight aqueous solution of trisodium phosphate kept at 80°C for 30 seconds, and after washing with water, the pumice was made into a slurry and poured onto the aluminum plate. I sanded it by rubbing it with a nylon brush. After washing with water, it was washed by immersion in a sodium aluminate solution, and then washed with a 3 weight percent aqueous solution of sodium hydrogen sulfate. This aluminum plate was anodized in 20 weight percent sulfuric acid at a current density of 2 A/dm ² for 2 minutes, and in the next step was treated with a 2.5 weight percent sodium silicate aqueous solution at 70° C. for 1 minute to produce an anodized aluminum plate. This aluminum plate was coated with Fairmont Chemical, a paraformaldehyde condensation product of P-diazodiphenylamine.
A 2 weight percent aqueous solution of Diazo No. 4L, commercially available from Co., Ltd., Newark, New Jersey, was applied. The aluminum plate was immersed in a bath of coating solution, then nipped with two rubber rollers to squeeze out excess solution, and then dried. Next, dilute Asahipen, a blue water-based paint manufactured by Asahipen Co., Ltd., with approximately 15 times pure water.
This reverse roller coater was used to coat the surface of the diazo photosensitive layer. The photosensitive printing plate material thus prepared was subjected to image pattern exposure for 30 seconds using a Berky Ascor exposure device manufactured by Berky Photo Inc.. For development, a 15 to 20 weight percent aqueous solution of n-propyl alcohol was spread on the printing plate and rubbed with absorbent cotton. Only the unexposed areas were peeled off, leaving the exposed areas as a blue image. Example 3 300ml of 1,2-dichloroethane in a 500ml beaker
g, and polyvinyl formal (polymerization degree of approx.
800, vinyl acetate residue 10.5±1.5, polyvinyl residue 5.5±0.5, #100 manufactured by Denki Kagaku Kogyo Co., Ltd.) were added and dissolved with stirring. Separately, prepare a three-neck flask (No. 2) equipped with a stirrer and a dropping funnel, take 700 ml of pure water, and add 10 g of polyvinyl alcohol (GL-05 manufactured by Nippon Gosei Co., Ltd., degree of saponification 86.5 ~
89 mol%, average degree of polymerization 500) and 2 g sodium lauryl alcohol sulfate (active purity 75).
~80%) was added and dissolved under stirring. Next, the rotation speed was increased to 1000 RPM, and the polyvinyl formal solution prepared earlier was dropped from the dropping funnel at a rate of about 50 ml/min. After the dropwise addition was completed, stirring was continued at room temperature for about 10 minutes, and then the flask was heated to about 80°C and stirred at this temperature for about 2 hours to remove 1,2-dichloroethane. The obtained emulsion was diluted with 2000 ml of pure water and applied to a plate coated with diazo resin prepared in the same manner as in Example 1 using a rotary coating machine. After drying at 100°C for 1 minute, live light was irradiated through a transparent negative film. Subsequently, a developer consisting of 25% n-propyl alcohol, 1% lauryl alcohol sulfate, and 0.5% potassium sulfate was spread on the printing plate and rubbed with a flocked cloth. Only the unexposed areas were removed, resulting in a lithographic printing plate with an ink-receptive image.

Claims (1)

[Claims] 1 (a) a support having a hydrophilic surface, (b) a layer of a photosensitive diazo compound provided on the hydrophilic surface, and (c)
A photosensitive lithographic printing plate comprising an ink receptive layer in contact with the photosensitive diazo compound layer, the ink receptive layer being coated from an aqueous emulsion of a lipophilic resin.