JPH036562A - Planographic printing material requiring no damping water - Google Patents

Abstract

PURPOSE:To obtain excellent plate wear and image reproducibility by incorporating a specific diazo resin into a photosensitive layer and forming an ink repulsion layer of a fluorine-contained polymer. CONSTITUTION:The diazo resin expressed by formula I is incorporated into the photosensitive layer and the ink repulsion layer is formed of the fluorine- contained polymer. In the formula I, R1 to R3 respectively denote a hydrogen atom, halogen atom, alkyl group, alkoxy group, carboxy group or carboxylate group; R denotes a hydrogen atom, alkyl group or phenyl group; X denotes PF6 or BF4; n denotes 2 to 200 integer. The damping waterless planographic printing plate with which the plate material having an excellent preservable property and which can be developed by an aq. developing soln., is widened in developing latitude and has good dot reproducibility is obtd. in this way.

Description

[Detailed Description of the Invention] [Field of Application in Industry A] The present invention relates to a lithographic printing plate material that does not require dampening water, and more specifically, a planographic printing plate material that has a wide development latitude, is hard to scratch the plate surface, and is also suitable for use in printing. The present invention relates to a lithographic printing plate material which has excellent printing durability and good image reproducibility and does not require dampening water.

[Prior Art] Conventionally, as a lithographic printing plate material that does not require dampening water (hereinafter referred to as 1-plate material as necessary), one in which a photosensitive layer and an ink repellent layer are sequentially coated on a support is known. ing. By exposing and developing this plate material, a lithographic printing plate that does not require dampening water (hereinafter referred to as "printing plate" as necessary) can be obtained.

A technique using a fluororesin as an ink repellent layer is known. For example, JP-A No. 58-215411 discloses a plate material in which a copolymer containing a specific fluorine-containing acrylic caramer and a monomer having a photosensitive group is used as an ink-repellent layer.

However, the printing plate obtained from this plate material does not have sufficient printing durability, and has the drawback of poor shadow area and small dot reproducibility.

Furthermore, although this plate material can be developed with a fluorine-based developer such as meta-xylene hexafluoride, it cannot be developed with a developer other than a fluorine-based developer, so it lacks ease of developer selection. Furthermore, due to the strong reaction activity of fluorine, it is not easy to handle, and there are problems in waste liquid treatment. Furthermore, since fluorine-based solvents are highly volatile, there is also the problem that they cannot be used as developing solutions in automatic processors.

In addition, when the content of photosensitive groups in the printing plate obtained from this plate material is increased in an attempt to improve printing durability and reproducibility, the ink repellency of the resulting printing plate decreases and There is also the problem that stains are more likely to occur.

On the other hand, plate materials in which a photosensitive layer and a fluororesin layer are sequentially coated on a support do not have sufficient adhesion between the photosensitive layer and the fluororesin layer, and the fluororesin layer in non-image areas peels off during development. It has the disadvantages of being easy to develop and having a narrow development latitude. Therefore, in order to improve the adhesion between such a photosensitive layer and a fluororesin layer, for example, WO 33-02175 discloses that an ink repellent layer is provided with a metal atom and a functional group bonded to the metal atom. A plate material using an ink repellent layer made of a perfluoroalkyl compound having the following is disclosed. This plate material improves adhesion due to the presence of metal atoms, and the thickness of the ink repellent layer can be made extremely thin, around 10 mm, so printing plates obtained from this plate material are characterized by high resolution. be.

However, this printing plate also has insufficient stiffness resistance, and there is a problem in that streak-like stains occur over the entire plate surface.

Therefore, the present inventors continued intensive research to improve the above-mentioned problems and drawbacks, and as a result, the photosensitive layer was formed using the general formula [! ] It was discovered that by using a diazo resin represented by the formula and a fluororesin for the ink repellent layer, the adhesion between the two was improved, thereby improving stiffness resistance and image reproducibility, and in completing the present invention. It's arrived.

[Objective of the Invention] Therefore, an object of the present invention is to enable the use of a developer using an organic solvent other than fluorine-based solvents, widen the development latitude during development processing, and further improve printing durability, and improve shadow area and An object of the present invention is to provide a lithographic printing plate material which does not require dampening water and provides a printing plate which has excellent dot reproducibility and does not cause scumming on the plate surface.

[Structure of the Invention] The object of the present invention is to provide a lithographic printing plate material that does not require dampening water and has a photosensitive layer and an ink repellent layer in this order on a support.
This was achieved by a lithographic printing plate material that does not require dampening water, wherein the photosensitive layer contains a diazo resin represented by the general formula [1], and the ink-repellent layer is a fluorine-containing polymer. .

General formula [11 [In the formula, RIRx and R5 each represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a carboxy group, or a carboxylic acid ester group, R represents a hydrogen atom, an alkyl group, or a phenyl group, and X represents a represents pFe or BF4, and n represents an integer from 2 to 200.] [Function] The plate material of the present invention changes the solubility or swelling degree of the photosensitive layer in the developer, or changes the fluororesin layer of the photosensitive layer. Since changes in the degree of adhesion are utilized, development can be performed with a solvent that dissolves or swells the photosensitive layer.

Furthermore, since the plate material of the present invention uses a diazo resin represented by the general formula CI as a compound in the photosensitive layer, the fluororesin layer and the photosensitive layer are strongly bonded, and the development latitude is widened. , the printing plate obtained from this plate material is
It has excellent printing durability and excellent reproducibility in shadow areas and dots, and does not cause background stains on the plate surface.

[Specific structure of the invention] The present invention will be explained in detail below.

In the general formula [11], the alkyl group represented by R1-R3 is preferably an alkyl group having 1 to 3 carbon atoms, and examples of such alkyl groups include methyl group, ethyl group, n-propyl group, etc. group, 1so-propyl group, and the like. This alkyl group also includes those having substituents.

In addition, the alkoxy group of R, -43 has a carbon atom number of 1
-3 alkoxy groups are preferred, and examples of such aflecoxy groups include methoxy, ethoxy, n-propoxy, and 1so-propoxy groups.

The alkyl group represented by R is preferably an alkyl group having 1 to 2 carbon atoms, such as a methyl group or an ethyl group.

Further, the phenyl group represented by R may have a substituent. Representative examples of the substituent include a hydroxyl group, a halogen atom, an alkoxy group, and the like.

Particularly preferred among the groups R1, R2 and R3 are a hydrogen atom and a methoxy group. Particularly preferred R is a hydrogen atom or a phenyl group.

n represents an integer of 2 to 200, preferably 2 to 50, particularly preferably 3 to 10. Also, X is PFs or BF
, preferably PF6.

Next, specific examples of the compounds represented by the general formula [I] will be described below, but the compounds of the present invention are not limited thereto.

Exemplary Compounds The above-mentioned photosensitive diazo resins can be prepared by known methods, for example, Photographic Science and Engineering (Photo-Sci-Eng.) Vol. 17, p. 33 (1973), U.S. Patent No. 2,083°631. No. 2,679,498, JP-A No. 60-6751, No. 6
No. 1-91654, No. 59-222834 and No. 59
-78340 According to the method described in each specification, diazonium salt and aldehyde in sulfuric acid, phosphoric acid or hydrochloric acid,
For example, it can be obtained by polycondensing formaldehyde, acetaldehyde, and benzaldehyde.

At that time, the molar ratio of diazonium salt and aldehyde is usually 1:0.8 to 1:2, preferably 1:0.7 to 1.
: 1.5 and reacted at a low temperature for a short time, for example at 10° C. or lower, for about 3 hours, a highly sensitive diazo resin can be obtained.

The lithographic printing plate which does not require dampening water of the present invention contains a photosensitive diazo resin represented by the general formula [11] in the photosensitive layer. Such a photosensitive diazo resin preferably contains 20 mol% or more, more preferably 20 to 70 mol%, of a resin in which n in the general formula [11] is 5 or more.

The photosensitive diazo resin is preferably contained in the photosensitive composition forming the photosensitive layer in an amount of 1 to 90% by weight, more preferably 5 to 5% by weight.
Contains 0% by weight.

The photosensitive layer provided in the planographic printing plate that does not require dampening water of the present invention preferably contains a polymer compound as a binder resin in addition to the photosensitive diazo resin.

Examples of such polymer compounds include polyamide, polyether, polyester, polycarbonate, polystyrene, polyurethane, polyvinyl chloride and its copolymers, polyvinyl butyral resin, polyvinyl formal resin, shellac, epoxy resin, phenol resin, acrylic resin, and the like.

Among the above polymer compounds, the following (1) to (
A copolymer of any of the monomers shown in 12), usually having a molecular weight of 20,000 to 200,000, is used.

(1) For example, N-(4
-hydroxyphenyl)acrylamide or N-(4-
hydroxyphenyl)methacrylamide, N-(4-hydroxyphenyl)maleimide, o-m-p-hydroxystyrene, o-m-p-hydroxyphenyl-acrylate or -methacrylate, (2) aliphatic hydroxyl group-containing 1 For example, 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate; (3) α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic anhydride; (4) methyl acrylate, ethyl acrylate, acrylic acid. Propyl, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, acrylic acid-
(Substituted) alkyl acrylates such as 2-chloroethyl, 2-hydroxyethyl acrylate, glycidyl acrylate, N-dimethylaminoethyl acrylate, (5) methyl methacrylate, ethyl methacrylate,
Propyl methacrylate, butyl methacrylate, amyl methacrylate, cyclohexyl methacrylate, 2
-Hydroxyethyl methacrylate; 4-hydroxybutyl methacrylate, glycidyl methacrylate, N
- (substituted) alkyl methacrylates such as dimethylaminoethyl methacrylate, (6) acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, N-ethyl acrylamide, N-hexyl methacrylamide, N-cyclohexyl acrylamide, N- - Acrylamides or methacrylamides such as hydroxyethyl acrylamide, N-phenylacrylamide, N-nitrophenyl acrylamide, N-ethyl-N-phenylacrylamide, etc. (7) Ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether , vinyl ethers such as butyl vinyl ether, octyl vinyl ether, and phenyl vinyl ether; (8) vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate, and vinyl benzoate; (g) styrene, α-methylstyrene, and methylstyrene. , styrenes such as chloromethylstyrene, (10) vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, phenyl vinyl ketone, (11) olefins such as ethylene, propylene, isobutylene, butadiene, isoprene, etc. (12) ) N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine, acrylonitrile, methacrylateril, etc.

It also includes, but is not limited to, copolymers obtained by copolymerizing the above-mentioned polymers and modified with glycidyl methacrylate, glycidyl acrylate, and the like.

More specifically, a copolymer containing a monomer having a hydroxyl group listed in (1) or (2) above is preferred, and a copolymer having an alcoholic hydroxyl group is even more preferred.

Further, polyvinyl butyral resin, polyurethane resin, polyamide resin, epoxy resin, novolac resin, natural resin, etc. may be added to the above copolymer as necessary.

The above-mentioned polymer compound is usually contained in an amount of 10 to 99%, preferably 50% in the solid content of the photosensitive composition forming the photosensitive layer.
Contains ~95% by weight.

The photosensitive layer of the lithographic printing plate that does not require dampening water of the present invention may further contain a color change agent that changes color tone by reacting with free radicals or acids. The color change agent is used for the purpose of obtaining image printout properties upon exposure.

As the color changing agent, any agent that changes color tone by reacting with free radicals or acids can be used. Here, "the tone changes" includes either a change from colorless to colored, a change from colored to colorless, or a different colored tone. Preferred color changing agents are those that react with acids to form salts and change color tone.

For example, Victoria Pure Blue BOH [manufactured by Hodogaya Chemical Co., Ltd.], Oil Blue #603 [manufactured by Orient Chemical Industry Co., Ltd.], Patent Pure Blue [manufactured by Jujuokoku Kagaku Co., Ltd.], Crystal Violet (II:, I.

Ba5ic V1o1et3), brilliant green (C,I.

Ba5ic Green 1), z Chill Violet ((:, I.

Ba5ic Violet4), methyl violet (C,I.

Ba5ic Violetl), Methyl Green (
C,1,Ba5icBlue20) Erythrosin B (C,1,Ac1d Red51), Pesic Tsuksin (C,1,Ba5ic Violetl4), Malachite Green (C,1,Ba5ic Green4)
), oil red (C,1,5olvent Red
24), m-cresol purple, rhodamine B (
C:,I.

Ba5ic Violetl O), auramine (C
, 1, BasicYellow2), 4-p-diethylaminophenylimino naphthoquinone, cyano-p
- Examples of color-changing agents that change triphenylmethane-based, diphenylmethane-based, oxazine-based, xanthine-based, iminonaphthoquinone-based, azomethine-based, or anthraquinone-based pigments, such as diethylaminophenylacetanilide, from colored to colorless or to a different colored tone. It is mentioned as. (However, C,1, represents a color index).

On the other hand, examples of color changing agents that change from colorless to colored include leuco dyes and, for example, triphenylamine, diphenylamine, O-chloroaniline, 1,2,3-triphenylguanidine, naphthylamine, diaminodiphenylmethane, p, p bis-dimethyl aminodiphenylamine,
1.2-dianilinoethylene, p, p, p-tris-dimethylaminotriphenylmethane, p, p
-bis-dimethylaminodiphenylmethylimine, p,
p,p-triamino-O-methyltriphenylmethane, p,p-bis-dimethylaminodiphenyl-4
Examples include primary or secondary arylamine dyes represented by -anilinonaphthylmethane, p,p,p-triaminotriphenylmethane.

Particularly preferably triphenylmethane and diphenylmethane dyes are effectively used, more preferably triphenylmethane dyes, especially Victoria Pure Blue BOH.

The above-mentioned color changing agent is usually included in the photosensitive composition from about 0.5 to about 10
The content is preferably 1i% by weight, more preferably about 1 to 5% by weight.

Various additives can be further added to the photosensitive composition forming the photosensitive layer.

Examples of such additives include - photosensitive diazo resins other than formula [I], 2-hydroxy-4-methoxybenzophenone as a counter anion of the diazo resin described in JP-A-61-100744; 5-sulfonic acid, p
- Organic salts of diazo resins such as toluenesulfonic acid, alkyl ethers (e.g. ethyl cellulose, methyl cellulose), fluorine surfactants, nonionic surfactants [e.g. Pluronic L-64] to improve coating properties. (manufactured by Asahi Denka Co., Ltd.) Plasticizers for imparting flexibility and abrasion resistance to coatings (e.g., butyl phthalyl, polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, phthalic acid) dioctyl, tricresyl phosphate, tributyl phosphate, trioctyl phosphate, tetrahydrofurfuryl oleate, oligolimers and polymers of acrylic acid or methacrylic acid), oil-sensitizing agents (for example, special (e.g. half ester of styrene-maleic anhydride copolymer with alcohol described in 1983-527), stabilizers [e.g. phosphoric acid, phosphorous acid, organic acids (citric acid, oxalic acid, benzenesulfonic acid) , naphthalenesulfonic acid, 4-methoxy-2-hydroxybenzophenone-5-sulfonic acid, tartaric acid, etc.)]
etc. The amount of these additives added varies depending on the purpose for which they are used, but is generally 0.01 to 30% by weight, respectively, based on the total solid content of the photosensitive composition.

In order to form a photosensitive layer by depositing such a photosensitive composition on a support, predetermined amounts of the photosensitive diazo resin and various additives as necessary are added to a suitable solvent (methyl cellosolve, ethyl cellosolve, etc.). , methyl cellosolve acetate, acetone, methyl ethyl ketone, methanol, dimethyl formamide, dimethyl sulfoxide, water or a mixture thereof, etc.) to prepare a coating solution of the photosensitive composition,
This may be applied onto a support and dried. The concentration of the photosensitive composition during coating is preferably in the range of 1 to 50% by weight.

The lithographic printing plate material of the present invention that does not require dampening water has a
A photosensitive layer is provided in this order, followed by a fluororesin layer. Specifically, this fluororesin layer acts as an ink repellent layer, and the fluororesin used for this layer is as follows. is used.

The fluororesin layer used in the present invention is made of a compound CF3-1-CF2- -CF-1CF3-0-1-C which has the following structural unit in its molecule.
F2-0-CF-0- (fluorine content is 30% by weight or more, preferably 50% by weight or more) and/or (1) has the following structural units in its molecule, CF,
-1-CF2- -(:F-1CF!-0-1-CF2
-0-CF-0- (Fluorine content is 30% by weight or more, preferably 50% by weight or more) and (2) A compound that has a functional group that can react with a crosslinking agent in its molecule, or the following mutually A compound having a functional group capable of crosslinking is used.

Bar 0)1. -COOH, -NH,, -CH-CH*
, -NCO, -NH-, etc.

Specifically, the following polymers are exemplified.

■ Copolymer resin of perfluoroalkyl methacrylate and an acrylic monomer having a hydroxyl group, such as 2-hydroxyethyl methacrylate ■ Copolymer resin of perfluoroalkyl methacrylate and glycidyl methacrylate Copolymer resin of acrylate and 2-methacryloyloxyethyl The fluororesin used in the invention is preferably a copolymer resin of a fluorine-containing acrylic monomer and a resin having a functional group capable of reacting with a crosslinking agent.

As the fluorine-containing acrylic monomer, monomers having the following general formula are preferred.

In the formula, Rf is a substituted fluorine alkyl group or a substituted fluorine polyether group, and R is a hydrogen atom or an alkyl group.

Preferred examples of the fluorine-containing acrylic monomer include the following.

Examples of monomers having functional groups that can react with crosslinking agents include glycidyl methacrylate, methacrylic acid,
Examples include 2-hydroxy methacrylate.

The fluorine-containing resin used in the present invention is a copolymer resin of the above-mentioned fluorine-containing acrylic monomer and a monomer having a functional group that can react with a crosslinking agent, and a third polymer is added to the resin to improve film-forming properties. Copolymerization is also preferred. Examples of the third additive include styrene, methyl methacrylate (MMA), butyl acrylate, acrylonitrile, and ethyl acrylate.

The fluororesin of the present invention is -0f(, -COOH, -NH2
, -Nl(-, etc.), the crosslinking agent can be used as a crosslinking agent. Compounds are preferably used, and specific examples include the following compounds.

(1) Hexamethylene diisocyanate (bisphenol A diglycidyl diniter) In addition, the fluororesin of the present invention is -CH-C)I, -
When the compound has a functional group capable of reacting with active hydrogen such as N GO, a compound having an active hydrogen functional group such as -0H1-GOOHl-NH2, -N)l-, or an acid anhydride (
For example, pentaerythritol, diethylenetriamine, hexahydrophthalic anhydride) can be used as a crosslinking agent.

When the fluororesin of the present invention has both an active hydrogen functional group and a functional group that can react with active hydrogen, or a fluororesin that has an active hydrogen functional group and a fluororesin that has a functional group that can react with active hydrogen are mixed. When used as a cross-linking agent, a cross-linking agent may not be used.

The most preferred combination of a fluororesin and a crosslinking agent in the present invention is a fluororesin having an alcoholic hydroxyl group and a crosslinking agent having an isocyanate group.

Further, in the present invention, it is preferable that a functional group capable of reacting with a crosslinking agent exists in the photosensitive layer.

The amount of the fluororesin used in the fluororesin layer of the present invention is 60 to 100% by weight, preferably 80 to 9% by weight.
Very effective at 8% by weight.

The support used in the plate material of the present invention is preferably one that is flexible enough to be set in a normal lithographic printing machine and that can withstand the load applied during printing, such as a metal plate made of aluminum, zinc, copper, steel, etc. and chromium, zinc, copper,
Examples include metal plates plated or vapor-deposited with nickel, aluminum, iron, etc., paper, plastic films, glass plates, resin-coated paper, paper covered with metal foil such as aluminum, and the like.

Among these, aluminum plates are preferred.

The treatment for the support itself to improve the adhesion is not particularly limited, and includes various surface roughening treatments.

In addition, before coating the photosensitive layer on the support, a brimer layer may be provided on the support in order to obtain sufficient adhesion between the photosensitive layer and the support. -Vinyl acetate copolymer, acrylic resin,
Examples include vinyl chloride resin, polyamide resin, polyvinyl butyral resin, epoxy resin, acrylate copolymer, vinyl acetate copolymer, phenoxy resin, polyurethane resin, polycarbonate resin, polyacrylonitrile butadiene, polyvinyl acetate, and the like.

In addition, as the anchor agent constituting the above-mentioned brimer layer,
For example, silane coupling agents, silicone primers, etc. can be used, and organic titanates and the like are also effective.

The thickness of each layer constituting the plate material of the present invention is as follows. That is, the support has a thickness of 50 to 400 μm, preferably 100 μm.
~300μ■, photosensitive layer 0.05~1Oμ11 preferably 0.5~5μl, fluororesin layer 0.01~1Oμ1
1 preferably 0. I N1 μl.

In the present invention, a protective layer may be provided on the upper surface of the ink repellent layer, if necessary.

The plate material of the present invention that does not require dampening water is manufactured, for example, as follows.

A composition solution to form a photosensitive layer is coated onto the support using a conventional coater such as a reverse roll coater, an air knife coater, a Meyer bar coater, or a rotary coater such as a Whaler, and then dried and heated if necessary. Kiea.

If necessary, a brimer layer may be provided between the support and the photosensitive layer in the same manner as in the case of the photosensitive layer.

Next, a fluororesin and a crosslinking agent are coated on the photosensitive layer in the same manner, and heat-treated for several minutes at a temperature of usually 100 to 120°C to sufficiently cure the coated resin to form a fluororesin layer. A protective film can be provided on the fluororesin layer thus formed using a laminator, if necessary.

When forming the ink repellent layer used in the present invention, the fluororesin and crosslinking agent are dissolved in a suitable solvent, and then the fluororesin is crosslinked by coating, drying, and heat treatment on the photosensitive layer.

In addition to the above-mentioned components, the ink repellent layer used in the present invention also contains catalysts for crosslinking reactions, such as tin compounds such as dibutyltin laurate, and quaternary or tertiary catalysts such as triethylbenzylammonium chloride and benzyldimethylamine. A small amount of an amine compound or the like can be contained.

Next, a method for manufacturing a printing plate that does not require dampening water using the plate material that does not require dampening water of the present invention will be explained.

A positive film, which is the manuscript, is vacuum-adhered to the surface of the positive plate material and exposed. As a light source for this exposure, a mercury lamp, a carbon arc lamp, a xenon lamp, a metal halide lamp, a fluorescent lamp, etc., which generate abundant ultraviolet light, are used.

Next, the positive film is peeled off and developed using a developer. As the developer, any known developer for plate materials that does not require dampening water can be used. product names) or gasoline, kerosene, etc.), aromatic hydrocarbons (toluene, xylene, etc.),
Alternatively, it is preferable to use a halogenated hydrocarbon (triclene, etc.) to which the following polar solvent is added.

Water, alcohols (methanol, ethanol, water, etc.),
Ethers (methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl calpitol, ethyl calpitol, butyl calpitol, dioxane, etc.), ketones (acetone, methyl ethyl ketone, etc.), esters (ethyl acetate, methyl cellosolve acetate, cellosolve acetate, carpi (tall acetate, etc.) It is also possible to dye the image area at the same time as development by adding a dye such as crystal violet or astrazonolet to the developer.

Development can be carried out by a known method, such as by rubbing with a developing hat containing a developer as described above, or by pouring the developer onto the printing plate and then rubbing with a developing brush.

By the above development, the fluororesin in the unexposed areas is removed to expose the photosensitive layer, the support, or the brimer layer, and a printing plate is obtained in which the fluororesin layer remains in the exposed areas.

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

Example 1 [Manufacture of aluminum plate a] An aluminum plate with a thickness of 0.2 nv was immersed in a 3% aqueous sodium hydroxide solution to degrease it, washed with water, and then diluted with hydrochloric acid at a concentration of 1%.
Electrolytic etching was performed for 5 minutes at a temperature of 25°C and 3A/dm in an aqueous solution with a boric acid concentration of 1%, and after washing with water, etching was performed in an aqueous solution of 40% sulfuric acid at a temperature of 30°C for 1.5 minutes.
Anodize for 2 minutes at A/dm2, wash with water,
% sodium metasilicate aqueous solution at a temperature of 85°C for 37 seconds, and further immersed in water (pH 8.5) at a temperature of 90°C for 25 seconds, washed with water, and dried to obtain an aluminum plate a.

A photosensitive composition having the composition shown below was applied to an aluminum plate a and dried at 100° C. for 2 minutes to form a photosensitive layer having a thickness of 0.5 μm.

[Photosensitive composition] (1) Diazo resin - 130 parts (2) Copolymerization of 2-hydroxyethyl methacrylate, acrylonitrile, methyl methacrylate, ethyl acrylate, and acrylic acid in a molar ratio of 65/10/1015/10 Resin 60 parts (3) Victoria Pure Blue BOH (manufactured by Hodokugaya Chemical Co., Ltd., dye) 1 part (4) Methyl cellosolve 900 parts Next, fluororesin composition-1 having the following composition was applied on the above photosensitive layer. Apply and heat to 90℃
The fluororesin was crosslinked by heating for 3 minutes to form a cured fluororesin layer with a thickness of 1.0 μm, thereby obtaining a lithographic printing plate material that did not require dampening water.

[Fluororesin composition-1] (1) IH, IH, 2) 1.28-hebutadecafluorodecyl acrylate ((:Hz=CHCOO(CH2
) 2 (CF2) 9F), 2-hydroxyethyl methacrylate, methyl methacrylate molar ratio is 50
．． 10.40 copolymer resin 50 parts (2) Coronate EH (manufactured by Nippon Polyurethane Co., Ltd., polyisocyanate)
5 parts (3) Dibutyltin dilaurate 0.05 parts (4) Freon-11
3,500 parts (5) 20 parts of methyl ethyl ketone After a positive film was vacuum-adhered to the upper surface of the plate material, it was exposed to light using a metal halide lamp as a light source. Next, after being immersed in the following developer, the surface of the plate material was developed by rubbing it with a development pad. Only the unexposed portions of the fluororesin layer were removed, and a printing plate with good halftone dot reproducibility was obtained.

[Developer composition] Isopar H5 parts 5s-taoo <manufactured by Mitsubishi Oil Co., Ltd.] 50 parts diethylene glycol dimethyl ether 30 parts Turfitz (manufactured by Clarei Soprene Chemical Co., Ltd.) 15 parts Then, it was added to a Komori Sprint printing machine with the dampening water supply device removed. The above printing plate was installed and 15,000 good prints were obtained.

Examples 2 to 5 Printing plates were prepared in the same manner as in Example 1, except that Diazo Resin-2 to Diazo Resin-5 were used in place of Diazo Resin-1 in the photosensitive composition of Example 1.

When printing was carried out in the same manner as in Example 1, 17,000 copies, 14,000 copies, 13,000 copies, and 10,000 copies of good printed matter were obtained, respectively.

Note that the diazo resin was synthesized as follows.

Synthesis of Diazo Resin-1 14.5 g (50 mmol) of p-diazodiphenylamine sulfate was dissolved in 40.9 g of concentrated sulfuric acid under water cooling.

To this reaction solution, 1.35 (45 mmol) of paraformaldehyde was slowly added so that the reaction temperature did not exceed 10°C.

This reaction mixture was added dropwise to 500 ml of ethanol under water cooling, and the resulting precipitate was filtered. After washing with ethanol, this precipitate was dissolved in 100 ml of pure water, and 6.8
A cold concentrated aqueous solution of 1 g of zinc chloride was added. After filtering the resulting precipitate, it was washed with ethanol, and then washed with 150
Dissolved in ml pure water. To this liquid was added a cold concentrated aqueous solution in which 8 g of ammonium hexafluorophosphate was dissolved. The resulting precipitate was collected by filtration, washed with water, and dried to form a diazo resin.
I got 1.

Synthesis of Diazo Resin-2 3.5 g (0,025 mol) of p-hydroxybenzoic acid and 22.0 g (0,075 mmol) of 4-diazo-4'-methoxydiphenylamine sulfate were mixed with 90 g of concentrated sulfuric acid under water cooling. dissolved in. 2.7 g of rose formaldehyde (0.09 mol) was slowly added to this reaction solution, and the addition was carried out so that the reaction temperature did not exceed 10°C.

Thereafter, stirring was continued for 2 hours under water cooling. This reaction mixture was added dropwise to 1 ρ of ethanol under water cooling, and the resulting precipitate was filtered. After washing with ethanol, this precipitate was dissolved in 200 ml of pure water, and a cold concentrated aqueous solution of 10.5 g of zinc chloride was added to this solution.

The resulting precipitate was filtered, washed with ethanol, and dissolved in 300 ml of pure water. To this liquid was added a cold concentrated aqueous solution in which 13.7 g of ammonium hexafluorophosphate was dissolved. The resulting precipitate was collected by filtration, washed with water, and then dried at 30° C. for 1 day to obtain diazo resin 2.

Synthesis of Diazo Resin-3 32.5 g of 4-diazo-3-methoxydiphenylamine sulfate (purity 99.8%) was gradually added to 70 liters of 85% phosphoric acid at 30° C. and stirred for 20 minutes.

Approx. 3.09g of rose formaldehyde (92% purity)
was added gradually over 0 minutes and the mixture was heated at 50°C for about 10 minutes.
Stir for hours. The reaction product was poured into isopropanol IJ2 with stirring, resulting in a precipitate.

The precipitate was collected by absorption filtration, and the dry solid was dissolved in 11 parts of water, cooled with ice, and treated with an aqueous solution containing 29 g of potassium hexafluorophosphate. The precipitate was collected by filtration and air-dried to give 33.5 g of diazo compound.
I got it. The obtained diazo compound is dissolved in 250@n methyl cellosolve and this solution is slowly added to the stirred sewage water 21, resulting in a yellow precipitate. Filter this and
After washing with water, it was dried to obtain 31.6 g of diazo resin-3.

Synthesis of diazo resin-4 4-diazo-4'-methoxydiphenylamine phosphate (
Purity 'J7, 0%) 33.3g at 10℃ 96%
70 mJ2 of sulfuric acid was slowly added and stirred for 20 minutes. 3.26 g of rose formaldehyde (purity 72%) was gradually added over about 30 minutes, and the mixture was heated at 10°C for 1 hour.
The reaction product stirred for 0 hours was poured into water ice 21 with stirring and treated with a cold concentrated aqueous solution in which 130 g of zinc chloride was dissolved. The precipitate was collected by suction filtration, the partially dried solid was dissolved in 11 g of water, filtered, cooled with ice and treated with an aqueous solution in which 23 g of potassium hexafluorophosphate had been dissolved. The precipitate was filtered, collected and air dried to yield Resin-4.

Synthesis of diazo resin-5 17.5 g of 2-methyl-5propyl-diphenylamine-4-diazonium sulfate was mixed with 60 g of 98% concentrated sulfuric acid.
was added gradually over 2 hours with stirring at 6°C or below.
The reaction mixture was further stirred at the same temperature for 3 hours. At an internal temperature of 2° C. to 10° C., 2.1 g of rose formaldehyde was added over 4 hours, followed by stirring for 6 hours. Add this mixed solution to 18 hI of diethylene glycol methyl ether.
L, 10.0 g of zinc chloride in a solution of 3 liters of water at 5℃~
The mixture was added dropwise with stirring at 12°C, and then stirred for 2 hours.

The precipitated solid matter was filtered by suction, and the solid matter was further filtered by 40 mj.
Washed with Z acetone. This solid was then dissolved in IJl water, filtered and treated with an aqueous solution containing 15 g of potassium hexafluorophosphate. The precipitate was filtered, collected, and air dried to yield diazo resin-5.

[Effect of the invention] The present invention has a ratio of binder resin and diazo resin of 50.
:50 to 1:90, it is possible to obtain a plate material with excellent storage stability, which can be developed with an aqueous developer, has a wide development latitude, has good halftone reproducibility, and does not require dampening water. A printing plate is obtained.

Claims (1)

[Scope of Claim] A lithographic printing plate material that does not require dampening water and has a photosensitive layer and an ink repellent layer in this order on a support, wherein the photosensitive layer has the general formula [
A lithographic printing plate material that does not require dampening water and is characterized in that the ink repellent layer is a fluorine-containing polymer, and the ink repellent layer is a fluorine-containing polymer. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. hydrogen atom,
Represents an alkyl group or a phenyl group, X is PF_5 or B
F_4 is represented, and n represents an integer from 2 to 200. ]