JPH039355A - Photosensitive planographic printing plate requiring no dampening water - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a photosensitive lithographic printing plate that does not require dampening water, and more specifically, it can be developed with an aqueous developer, has a wider development latitude, and has improved halftone reproducibility. The present invention relates to a photosensitive lithographic printing plate that does not require dampening water and provides a good printing plate.

[Background of the Invention] Conventionally, photosensitive lithographic printing plates that do not require dampening water (hereinafter referred to as "R plate material" as necessary) have been known to have a photosensitive layer and an ink repellent layer coated on a support in this order. It is being 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.

As described in Japanese Patent Publication No. 55-22781, for example, such plate materials are made by dissolving the unexposed areas (image areas) of the photosensitive layer using a developer, and thereby dissolving the upper silicone rubber layer. As described in Japanese Patent Publication No. 54-26923, the exposed area (non-image area) is firmly adhered to the photosensitive layer by photoadhesion, and only the silicone rubber layer in the unexposed area (image area) is removed. Some are removed using swelling organic solvents.

Of these, the former, which dissolves the photosensitive layer, dissolves the photosensitive layer in the unexposed area (image area) and forcibly removes the silicone rubber layer above it to form an image. If the adhesive strength between the photosensitive layer in the area (non-image area) and the silicone rubber layer thereon is not sufficient, part of the photosensitive layer will peel off during development, and a stable image will not be formed. Therefore, in this technique, a silane coupling agent is usually added to the photosensitive layer or the silicone rubber layer to strengthen the adhesive strength between the photosensitive layer and the silicone rubber layer.

However, although the adhesion is improved to some extent by adding a silane coupling agent, it is not sufficient to obtain a printing plate with good halftone dot reproducibility, and there are problems in that the development latitude is not good enough.

In addition, in the latter case where only the silicone rubber layer in the non-hazy area (image area) is removed, a developer mainly containing an organic solvent that swells the silicone rubber layer, such as a hydrocarbon solvent such as kerosene or Isopar G, is used. Can I only develop it?
There are many problems with the working environment and pollution.

Therefore, in order to improve the above-mentioned problems, we continued to conduct intensive research on undiscovered town names. As a result, the present inventors have discovered that it is possible to obtain a printing plate or the like which has a wide development latitude and good halftone reproducibility when using a water-based developer or an aqueous developer, and has completed the present invention.

[Objectives of the Invention] 1. However, the object of the present invention is to develop a printing plate that can be developed using a water-based convenient method, has a wide development radius, and has good halftone reproducibility. [Structure of the Invention] The object of the present invention is to provide a photosensitive lithographic printing plate which does not require dampening water and which has silicon, a light layer, and an ink repellent layer on a support in this order. The present invention was achieved by a 4,z L, adhesive-free photosensitive lithographic printing plate characterized in that the photosensitive layer contains a cellulose derivative.

The present invention will be explained in more detail below.

The present invention (J) is that by adding a cellulose derivative to the photosensitive layer of a photosensitive lithographic printing plate that does not require water, the adhesive force between the photosensitive area of the exposed area and the silicone rubber layer is strengthened. The cellulose derivative is contained in the photosensitive layer in an amount of 1% to 90% by weight, preferably 3% to 70% by weight, more preferably 5mf% to 40% by weight in the solid content of the composition. Examples of the rust conductor include cellulose acetate, cellulose acetate phthalate, hydroxypropylmethylcellulose phthalate-1-, carboxymethylcellulose, carboxymethylethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, hydroxypropylcellulose phthalate, Hydroxypropyl methylcellulose acetate succinate, methylcellulose,
Examples include ethyl cellulose, ethyl hydroxyethyl cellulose, carboxymethyl ethyl cellulose, etc., but hydroxy brohycellulose, hydroxypropyl methyl cellulose, and hydroxypropyl methyl cellulose phthalate are preferred.

Preferably, an organic solvent-soluble cell X'l-rus conductor is used.

As the photosensitive composition used in the present invention, any known photosensitive composition can be used, but preferably
A diazo resin and a photopolymerizable compound are used, and a diazo resin is particularly preferred.

The photosensitive composition will be specifically explained below.

(1) Photosensitive composition containing diazo resin The diazo resin used in the present invention is preferably a diazo resin typified by a condensate of p-diazodiphenylamine and formaldehyde, although it should not be used in various ways. ,
Those that are water-insoluble and soluble in organic solvents are used, preferably those that are water-insoluble and soluble in ordinary organic solvents as described in Japanese Patent Publications No. 47-1167 and Japanese Patent Publication No. 57-43890. Particularly preferably one of the following: 44'2
It is a diazo resin represented by formula [I].

- Monna EXE [In the formula, RI R2 and R3 represent a hydrogen atom, )'alkyl group or alkyl group, and R'? : Indicates an L* atom, an alkyl group, or a phenyl group.

X represents PF6 or BF4, and Y represents -NH--8- or -0-. ] Examples of the diazo monomer in the diazo resin used in the present invention include 4-diazo-diphenylamine, 1
-Diazo-4-N,N-dimethylaminobenzene, 1-
Diazo-4-N, N-diethylaminobenzene, 1-diazo-4-N-ethyl-N-hydroxyethylaminobenzene, 1-diazo-4-N-methyl-N-hydroxyethylaminobenzene, 1-diazo-2 , 5-jethoxy-4-benzoylaminobenzene, 1-diazo-4-
N-benzylaminobenzene, 1-diazo-4-N,N
-dimethylaminobenzene, l-diazo-4-morpholinobenzene, l-diazo-2,5-dimethoxy-4-p
-Tolylmercaptobenzene, 1-diazo-2-ethoxy-4-N,N-dimethylaminobenzene, p-diazodimethylaniline, 1-diazo-2,5-dibutoxy-4-morpholinobenzene, 1-diazo- 2,5-jethoxy-4-morpholinobenzene, l-diazo-2,5
-dimethoxy-4-morpholinobenzene, 1-diazo-
2,5-jethoxy-4-p-tolylmercaptobenzene, l-diazo-4-N-ethyl-N-hydroxyethylaminobenzene, 1-diazo-3-ethoxy-4-N
-Methyl-N-benzylaminobenzene, l-diazo-
3-chloro-4-N,N-diethylaminobenzene, 1
-Diazo-3-methyl-4-pyrrolidinobenzene, l-
Diazo-2-chloro-4-N,N-dimethylamino-5
-methoxybenzene, 1-diazo-3-methoxy-4-
Examples include pyrrolidinobenzene, 3-methoxy-4-diazodiphenylamine, 3-ethoxy-4-diazodiphenylamine, 3-(n-propoxy)-4-diazodiphenylamine, 3-(isopropoxy)-4-diazodiphenylamine, etc. .

Examples of the aldehyde used as a condensing agent with the diazo monomer include formaldehyde, adetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, and benzaldehyde.

Furthermore, water-soluble diazo resins can be obtained by using chloride ions, tetrachlorozinc acid, etc. as anions, and boron tetrafluoride, hexafluorophosphoric acid, triisopropylnaphthalenesulfonic acid, 4.4° -biphenyldisulfonic acid, 2,5-dimethylbenzenesulfonic acid,
By using 2-nitrobenzenesulfonic acid, 2-methoxy-4-hydroxy-5-benzoyl-benzenesulfonic acid, etc., an organic solvent-soluble diazo resin can be obtained. Particularly preferably, a diazo resin made of hexafluorophosphoric acid is used.

The diazo resin is preferably used in combination with a film-forming resin, particularly a lipophilic polymer compound having a hydroxyl group. Examples of such lipophilic polymer compounds include copolymers of monomers having aliphatic hydroxyl groups in side chains, such as 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate, and other copolymerizable polymers. It will be done. In addition to these, polyvinyl butyral resin, polyurethane resin, polyamide resin, epoxy resin,
Novolak resin, natural resin, etc. may be added.

In addition, various polymer compounds can be used as the binder used in combination with the diazonium salt, but preferably,
A monomer having an aromatic hydroxyl group as described in Japanese Patent No. 4-98613, such as N-(4-hydroxyphenyl)acrylamide, N-(4-hydroxyphenyl)methacrylamide, o+, m+, or p - copolymers of hydroxystyrene, o+, m+, or p-hydroxyphenyl methacrylate and the like with other monomers, hydroxyethyl acrylate units as described in U.S. Pat. No. 4,123,276; Polymers containing hydroxyethyl methacrylate units as the main repeating unit Natural resins such as shellac and rosin, polyvinyl alcohol, polyamide resins described in U.S. Pat. No. 3,751,257, and U.S. Pat.
．． 660,097, linear polyurethane resins, polyvinyl alcohol phthalate resins, epoxy resins condensed from bisphenol A and epichlorohydrin, alkali-soluble resins such as novolac resins, and vinyl-based resins having phenolic hydroxyl groups. Examples include polymers, condensation resins of polyhydric phenols and aldehydes or ketones described in JP-A-55-57841, and the like. Examples of the novolac resin include phenol-formaldehyde resin, cresol-formaldehyde resin, phenol-cresol-formaldehyde copolycondensation resin as described in JP-A-55-57841, and phenol-cresol-formaldehyde copolycondensation resin as described in JP-A-55-127553. Examples include copolycondensation resins of P-substituted phenol and phenol or cresol and formaldehyde as described above.

In addition to the materials listed in "2," these photosensitive compositions may also contain pigments such as dyes and pigments, sensitizers, plasticizers, surfactants, organic acids, acid anhydrides, and other additives that can be added to It is possible to add a compound etc. that can generate acid.

These binders are present in an amount of 10 to 95% in the solid content of the photosensitive composition.
It is contained in an amount of 5% by weight, preferably 40 to 80% by weight. The diazo resin is contained in an amount of 5 to somm%, preferably 15 to 60% by weight.

Other dyes, pigments such as pigments, fat-sensitizing agents, plasticizers, surfactants, etc. can be added to these photosensitive compositions.

1 (2) A photosensitive composition containing a polymer compound having -CH-C- groups in the main chain or side chain of the polymer. Those whose main component is a photosensitive polymer such as polyesters, polyamides, and polycarbonates containing -C-CH-C- as a photosensitive group (e.g., U.S. Pat. No. 3,030,208, U.S. Pat. 3.707.373 and 3,453.237-?: Compounds as described in cinnamylidene malonic acid '24 (2'
- photosensitive polyesters derived from malonic acid compounds and difunctional glycols (e.g., as described in U.S. Pat. No. 2,956,878 and U.S. Pat. No. 3,173,787). cinnamate esters of hydroxyl-containing polymers such as polyvinyl alcohol, starch, cellulose and the like (e.g., U.S. Pat. No. 2,690,966; No. 2,752,372, No. 2.732.301
Examples include photosensitive polymers such as those described in No.

The photosensitive composition of Gonera may contain other sensitizers, stabilizers, plasticizers, pigments, dyes, and the like.

(3) Photopolymerizable composition comprising an addition polymerizable unsaturated compound This composition preferably comprises (a) a vinyl monomer having at least two terminal vinyl groups, (b) a photopolymerization initiator, and ( C) Consists of a polymer compound as a binder.

This component (a) vinyl monomer and 1.
-5093, 35-14719, 44-287
It is described in each publication No. 27.

Acrylic or methacrylic esters of polyols, i.e. diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acryl/ = )-,
Pentaerythritol tri(meth)acrylic No. 1.
Trimethylolpropane tri(meth)acrylate, etc.
or bis(meth)acrylamides such as medilene bis(meth)acrylamide, ethylene bis(meth)acrylamide, or unsaturated monomers containing a 1/tan group, such as di(2'-methacryloxyethyl).
Examples include reaction products of diol mono(meth)acrylate and diisocyanate such as -2,4=tolylene diurethane and di(2-acryloquinethyl)trimethylene diurethane.

The photopolymerization initiator of the component (b) is, for example, J,
"Light Sensitive Systems" by Kosar
Examples include carbonyl compounds, organic sulfur compounds, perfusate compounds, redox compounds, azo and diazo compounds, halogen compounds, and photoreducible dyes as described in Chapter 5. More specifically, it is disclosed in British Patent No. 1,459,563.

Furthermore, various known polymers can be used as the binder for component (C). Details of specific binders can be found in U.S. Patent No. 4. o72.527.

These photopolymerizable compositions contain thermal polymerization inhibitors, plasticizers,
It can contain dyes, pigments, etc.

A liposensitizing agent and a surfactant added to the photosensitive composition,
The amount of additives such as sensitizers, stabilizers, thermal polymerization inhibitors, plasticizers, and pigments such as dyes and pigments varies depending on the type, but in general, they are included in the photosensitive composition contained in the photosensitive coating liquid. 0.01 to 20% by weight, preferably 0.05 to 20% by weight based on the product
10% by weight is suitable.

As the ink repellent layer used in the present invention, a silicone rubber layer is mainly used, but a fluorine-containing resin layer can also be used. Preferred silicone rubbers include linear organic polycycloxanes having repeating units represented by the following general formula [I] and having a molecular weight of several thousand to several hundred thousand and having a hydroxyl group in the main chain or at the end of the main chain. It is preferable to use it as a component.

General formula [I] +5i-OTh where n is an integer of 2 or more, R is an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group, an alkoxyl group, a vinyl group, an aryl group, a silanol group (OH group), Yes, R
Preferably, 60% or more of the silanol group (OH group) is present in the main chain or at the end of the main chain, but is preferably at the end.

The silane coupling agent (or silicone crosslinking agent) used in the present invention is Rn5iX4-0 (wherein, n is an integer of 1 to 3, and R is alkyl, aryl, alkenyl, or a combination thereof. represents a group, and these groups may have a functional group such as halogen, amine, hydroxy, alkoxy, aryloxy, thiol, etc.

X is 10H, -OR", -0^c, -0-N・C:
Represents a substituent such as -Cj, -Br, -■R', etc., where R2 and Ha represent the same as R above, R2 and Rs may be the same or different, and ^ctt represents an acetyl group. ) is a silane compound represented by

The silicone rubber useful in the present invention is obtained by a condensation reaction between such a silicone base polymer and a silicone crosslinking agent as listed below.

(1) R-5i+OR')s (2) R-Si+0Ac)s (3) R-5t (ON-CR',).

Here, R has the same meaning as R, which is a substituent of the polymer represented by -Momonena [1], R' is an alkyl group such as a methyl group or an ethyl group, and Ac is an acetyl group.

Specific examples of the silane coupling agent used in the present invention include HN [(CH2) 3Si (OMe) s]z,
Vinyltriethoxysilane, Cj (CH2) sSi
(OMe) s, CH35t (0^C)S, R5(
CHI)ssi(OMe)s, vinyltris(methylethylketoxime)silane, and the like.

The silicone rubber described above is also available as a commercial product, such as YE-3085 manufactured by Toshiba Silicone Co., Ltd. Other useful silicone rubbers include base polymers such as those described above and the general formula [I! ], or reaction with silicone oil having a repeating unit represented by R
It can also be obtained by an addition reaction with a base polymer of silicone, about 3% of which is vinyl groups, or by reaction between the silicone oils.

(In the formula, R has the same meaning as R, which is a substituent of the polymer represented by general formula [I], m is an integer of 2 or more, and n is O or an integer of 1 or more.) Such a crosslinking reaction To obtain silicone rubber, the crosslinking reaction is carried out using a catalyst. Examples of the catalyst include organic carboxylates of metals such as tin, zinc, cobalt, lead, calcium, and manganese, such as dibutyltin laurate, tin(II) octoate-1-, cobalt naphthenate, or chloroauric acid. etc. are used.

Further, in order to improve the strength of the silicone rubber and obtain a silicone rubber that can withstand the g-rubbing that occurs during printing operations, a filler may be mixed. Silicone rubber mixed with filler in advance is commercially available as silicone rubber stock or silicone rubber dispersion, and when it is preferable to obtain a silicone rubber film by coating as in the present invention, R, T
V or LTV silicone rubber disvergine is preferably used. An example of this is Syl (Iff 23.5RX-257) manufactured by Toray Silicone.
, 5) There are silicone rubber dispersions for vapor coating such as 1237.

In the present invention, it is preferable to use condensation and crosslinking type silicone rubber.

The silicone rubber layer preferably contains a silane coupling agent having an amino group in order to further improve adhesiveness.

Examples of preferred silane coupling agents include Example E.

There are some examples such as:

(a) HJClhCllJH (CI+2) 3si
(DCI+3> 3(h) tlJ(:E2C1hNH
(CH2) ssi (0 to H3) 2 (C1,)(
C) HJ (CI(2) sSi copt) sThe silicone rubber layer used in the present invention can further contain a small amount of a photosensitizer.

The silicone rubber layer used in the present invention is prepared by dissolving silicone rubber in a suitable solvent, applying it onto the photosensitive layer, and drying it.

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 aluminum, zinc, etc. Gold-jΣ plates such as copper and steel, metal plates plated or vapor-deposited with chromium, zinc, copper, nickel, aluminum, iron, etc., paper, plastic films, glass plates, resin coated paper, metal foils such as aluminum For example, paper covered with

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,
Vinyl chloride resin, polyamide resin, polyvinyl butyral resin, epoxy resin, acrylate copolymer, vinyl acetate copolymer, phenoxy resin, Boliu I/tan resin, polycarbonate resin, polyacrylonitrile butadiene, polyvinyl acetate, etc. It will be done.

In addition, as the anchor agent constituting the above-mentioned brimer layer,
For example, silane coupling agents, organic titanates, etc. are also effective.

The thickness of each layer constituting the printing plate of the present invention is as follows: The support is 50 to 400 μm, preferably 100 μm.
~300 μm, photosensitive layer 0.05-10 μml
, 67 or preferably 0.1 = 1.0 .mu.m.The silicone rubber layer has a thickness of 0.5.about.100 .mu.m, preferably 1-4 .mu.m.

In the present invention, a protective layer may be provided on the upper surface of the silicone rubber 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 constituting the 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 coating device such as a POULER, and then dried.

If necessary, after providing a brimer layer between the support and the photosensitive layer in the same manner as for the photosensitive layer, a silicone rubber solution is applied to the photosensitive layer in the same manner.
Heat treatment at a temperature of ~120°C for several minutes to fully cure and form a silicone rubber layer. If necessary, a protective film can be provided on the silicone rubber layer using an uminator.

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.

It is vacuum-adhered to the surface of the original, a positive film, and exposed to light. 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 can be used for plate materials that do not require dampening water, but preferably an aqueous developer is used.

The aqueous developer is a developer containing water as a main component, such as those described in Japanese Patent Laid-Open No. 61-275759, etc., which contain water in an amount of 30% by weight or more, preferably 50% by weight to 9% by weight.
Examples include a developer containing 8% by weight, an organic solvent, and a surfactant, and more preferably an alkali agent.

Organic solvents contained in water-based developers include:
For example, aliphatic hydrocarbons (hexane, heptane, Isopar E, H, G'' (manufactured by Esso Chemical Co., Ltd., product name of aliphatic hydrocarbons), gasoline, kerosene, etc.), aromatic hydrocarbons (toluene, xylene, etc.) etc.), or halogenated hydrocarbons (triclene, etc.) to which the following polar solvents are added are suitable.

Alcohols (methanol, ethanol, 1-butoxy-2-propatol, 3-methyl-3-methoxybutanol, benzyl alcohol, etc.), ethers (methyl cellosolve, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, methyl carpitol, ethyl carpitol) Thor, butyl carpitol, dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, ethylene glycol dibutyl ether, propylene glycol, dipropylene glycol butyl ether, tripropylene glycol methyl ether, polypropylene glycol methyl ether, etc.), ketones (acetone, Methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, 4-methyl-1,3-dioxolane-
2-one, etc.), esters (ethyl acetate, propyl acetate, hexyl acetate, methyl butyrate, propyl butyrate, diethyl succinate, dibutyl oxalate, diethyl maleate, benzyl benzoate, methyl cellosolve acetate, cellosolve acetate, carpitol acetate, etc.) ) etc.

As the surfactant added to the developer of the present invention, anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric ionic surfactants are used, and specific examples include the following.

Examples of anionic surfactants include (1) higher alcohol sulfate esters (e.g. sodium salt of lauryl alcohol sulfate, ammonium salt of octyl alcohol sulfate, ammonium salt of lauryl alcohol sulfate, sulfur sodium alkyl sulfate, etc.) (2) Fat Group alcohol phosphate ester salts (e.g.
(3) Alkylaryl sulfonic acid salts (e.g., dodecylbenzenesulfonic acid sodium salt, isopropylnaphthalenesulfonic acid sodium salt, dinaphthalenesulfonic acid sodium salt, metanitrobenzenesulfonic acid sodium salt, etc.) (4) Alkylamide sulfonates (C+t)IssCON-CH2CH2SO3Na, etc.)
C) 13 (5) Sulfonic acid salts of dibasic aliphatic esters (e.g., sodium sulfosuccinate dioctyl ester, sodium sulfosuccinate dihexyl ester, etc.) (6) Formaldehyde condensates of alkylnaphthalene sulfonates (e.g., dibutylnaphthalene sulfonic acid) formaldehyde condensates of sodium, etc.).

Examples of nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene alkylphenol ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, glycerin fatty acid ester, oxyethylene oxybrobylene block polymer, etc. Can be mentioned.

Examples of the cationic surfactant include alkylamine salts, quaternary ammonium salts, polyoxyethylene alkylamines, and the like.

Examples of amphoteric surfactants include alkyl betaines, and among these, anionic surfactants are suitable.

These surfactants can be used alone or in combination of two or more.

The appropriate amount of the surfactant used in the present invention is 0.01% to 60% by weight, preferably 0% to 10% by weight.

Further, the surfactant used in the present invention is preferably used together with an alkaline agent, and the alkaline agents include (1) sodium silicate, potassium silicate, potassium hydroxide, sodium hydroxide, lithium hydroxide, or inorganic alkaline agents such as trisodium or ammonium phosphate, sodium metasilicate, sodium carbonate, ammonia, (2) mono, di or trimethylamine, mono, di or triethylamine, mono or diisopropylamine, n-butylamine, mono, Examples include organic amine compounds such as di- or triethanolamine, mono-, di- or triisopropanolamine, ethyleneimine, and ethylenediimine.

The amount of alkaline agent used is 0.05% to 20% by weight.
, preferably 0.2% to 10% by weight.

It is also possible to dye the image area simultaneously with development by adding a dye such as crystal violet or astrazonelet to the developer.

Development can be carried out, for example, by rubbing with a developing pad containing a developer as described above, or by pouring a developer onto the printing plate and then rubbing with a developing brush.

By the above development, a printing plate is obtained in which the photosensitive layer and silicone rubber in the unexposed areas are removed, or a printing plate in which the silicone rubber layer is removed and the photosensitive layer is exposed, and the silicone rubber layer remains in the exposed areas.

Example 1 [Manufacture of aluminum plate a] An aluminum plate with a thickness of 0.2 ml + a was immersed in a 3% aqueous sodium hydroxide solution to degrease it, washed with water, and then immersed in an aqueous solution with a hydrochloric acid concentration of 1% and a boric acid concentration of 1%. , temperature 25
Electrolytic etching was performed at 3A/da2 for 5 minutes at 30°C, and after washing with water, etching was performed at 30°C in a 40% sulfuric acid aqueous solution.
Anodic oxidation was performed for 2 minutes under the condition of 5A/ds+'', washed with water, and injected into a 1% sodium metasilicate aqueous solution at a temperature of 85℃ for 3 minutes.
Immerse for 7 seconds, then soak in water (pH 8.5) at a temperature of 90°C for 2 seconds.
It was immersed for 5 seconds, washed with water, and dried to obtain 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 2 μl.

[Photosensitive composition] (1) A resin in which glycidyl methacrylate is added to the carboxyl group of a copolymer resin of styrene, acrylonitrile, butyl acrylate, and acrylic acid in a molar ratio of 49/10/4/37 (Japanese Patent Publication No. 49/1989) 30 parts (2-1) of glycidyl methacrylate and metaxylene diamine (synthesized by the method described in Japanese Patent No. 17874)
1 adduct 30 parts (2-2)-limerolpropane triacrylate

20 parts (3) HP-5
55 (Hydroxypropyl methylcellulose phthalate, manufactured by Shin-Etsu Chemical Co., Ltd.) 20 parts (4) 2,4-diethylthioxanthone 10.5 parts (5) p-dimethylaminobenzoic acid isoamyl ester 3 parts (6) Victoria Pure Blue BOH (removed) Tsuchigaya Chemical Co., Ltd. Dye) 0.2 parts (4) Methyl cellosolve 500 parts Next, the following silicone rubber composition was added on the above photosensitive layer at a dry weight of 1.5 g/
m' and dried at 90° C. for 10 minutes to obtain a lithographic printing plate material that does not require dampening water.

[Silicone rubber layer composition] Dimethylpolysiloxane having hydroxyl groups at both ends (molecular weight 52.OO'O) 100 parts Triacetoxymethylsilane 10 parts Dibutyltin laurate 0.8 parts Isopar G (manufactured by Esso Chemical) 900 parts Above version After a positive film was vacuum-adhered to the upper surface of the material, it was exposed to light using a metal halide lamp as a light source and developed using the following developer. By rubbing the surface of the plate material with a pad impregnated with a developer, the silicone rubber layer in the unexposed areas was removed, and a printing plate with good halftone dot reproducibility was obtained.

[Developer composition] 5 parts ethylene glycol monophenyl ether Bionin A-44B (anionic surfactant manufactured by Monomoto Yushi Co., Ltd.) 5 parts jetanolamine
1 part water
89 parts [Comparative Example-1] HP-55 of the photosensitive composition of Example 1 was added to the carboxyl group of a copolymer resin with a molar ratio of styrene, acrylonitrile, butyl acrylate, and acrylic acid of 49.10.4.37. A lithographic printing plate material that does not require dampening water was obtained in the same manner as in Example 1, except that 30 parts of the resin to which glycidyl methacrylate was added was used to create a photosensitive composition containing 50 parts of the same resin. .

Next, this lithographic printing plate that did not require dampening water was developed with the same developer used in Example 1, but no development was achieved.

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

[Photosensitive composition] (1) Diazo resin - 140 parts (2) High molecular compound - 140 parts (3) HP-55520 parts (4) Victoria Pure Blue BOH 2 parts (5) Methyl cellosolve 900 parts Obtained in this manner The following silicone rubber composition was applied to the photosensitive layer at a dry weight of 2.0 g/! 1' and dried at 120° C. for 2 minutes to obtain a lithographic printing plate material that does not require dampening water.

[Silicone rubber layer composition] Dimethylpolysiloxane having hydroxyl groups at both ends (molecular weight 52,000) 100 parts triacetoxymethylsilane 10 parts dibutyltin laurate 0.8 parts Isopar G (manufactured by Esso Chemical) 900 parts After a positive film was vacuum-adhered to the upper surface of the material, it was exposed to light using a metal halide lamp as a light source and developed using the following developer. During development, by rubbing the surface of the plate material with a pad impregnated with a developer, the unexposed portions of the photosensitive layer and silicone rubber layer were removed, and a printing plate with good halftone dot reproducibility was obtained.

[Developer composition] Benzyl alcohol 8 parts Perex NBL (Anionic surfactant manufactured by Kao Atlas Co., Ltd.)
5 part jetanolamine
2 parts water
85 parts [Comparative Example-2] A lithographic plate without dampening water was produced in the same manner as in Example-2, except that HP-55 in Example 2 was replaced with polymer compound-1, and the polymer compound was changed to 60 parts. A printing plate material was obtained.

Then, when development was performed using the above developer, the reproducibility of the shadow area was poor.

Synthesis of diazo resin-1 Note that diazo resin-1 was synthesized as follows.

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, 1.5 g (50 mmol) of rose formaldehyde was slowly added dropwise. At this time, the reaction temperature is 1
Add it so that the temperature does not exceed 0℃.
Stirring was continued under water cooling for an hour.

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 pure 100a+1, and 6.
A cold concentrated aqueous solution of 8 g of zinc chloride was added. After filtering the resulting precipitate, it was washed with ethanol and
Dissolved in 0ml 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 then dried at 30°C for one day and night to obtain a diazo resin drop.

Synthesis of polymer compound 1 N-(4-hydroxyphenyl) methacrylamide 35
．． 4g, 2-hydroxyethyl metatarylate 39
．． Og, methacrylic acid 8.5'' 3.7 crylonitrile 5
．． 3 g, 200 g of methyl methacrylate and 1.64 g of azobisisobutyronitol were added to 1.3 g of acetate. The mixture was dissolved in 400ml of a 1:1 (volume ratio) mixed solvent of methanol and methanol, and after purging with nitrogen, it was heated at 60°C for 8 hours.

After completion of the reaction, the reaction solution was poured into 5 parts of water with stirring, and the resulting white precipitate was filtered and dried to obtain 110 parts of lipophilic polymer compound 1.
I got g.

Example 3 A lithographic printing plate royalty that did not require dampening water was prepared in the same manner as in Example 2, except that the following photosensitive composition was used instead of the photosensitive composition of Example 2.

[Photosensitive composition (1) Diazo resin - 140 parts (2) High molecular compound - 130 parts (3) HPCL-P (manufactured by Shin-Etsu Chemical Co., Ltd., hydroxypropyl cellulose)
30 parts (4) Victoria Pure Blue BOH 2 parts (5) Methyl cellosolve
900 copies or less A printing plate with good halftone dot reproducibility was obtained in the same manner as in Example 2.

Example 4 A lithographic printing plate royalty that did not require dampening water was prepared in the same manner as in Example 2, except that the following photosensitive composition was used instead of the photosensitive composition of Example 2.

[Photosensitive composition] (1) Diazo resin - 140 parts (2) High molecular compound - 150 parts (3) N-10-G (manufactured by Shin-Etsu Chemical Co., Ltd., Godil Cellulose) 10 parts (4) Victoria Pure Blue BOI (2 parts (5) Methyl cellosolve 900 parts or less A printing plate with good halftone dot reproducibility was obtained in the same manner as in Example 2.

[Effects of the Invention] By adding a cellulose derivative to the photosensitive layer, the present invention makes it glossy when developed with an aqueous developer, and also strengthens the adhesion between the photosensitive layer and the silicone rubber layer in the exposed area, thereby reducing the development lag. A lithographic printing plate with good spreading and halftone dot reproducibility and no need for dampening water can be obtained.

Claims (1)

[Claims] A photosensitive lithographic printing plate that does not require dampening water and has a photosensitive layer and an ink repellent layer on a support in that order, wherein the photosensitive layer contains a cellulose derivative. Print version.