JPH039356A - Photosensitive planographic printing plate requiring no dampening water - Google Patents

Abstract

PURPOSE:To obtain a planographic printing plate having satisfactory dot reproducibility as well as to obtain a printing plate material having superior shelf life, developable with an aq. developer and extending development latitude by using a binder resin and diazo resin in 50:50-10:90 ratio. CONSTITUTION:A photosensitive layer contg. a binder resin and diazo resin in 50:50-10:90 weight ratio is formed. The diazo monomer of the diazo resin may be 4-diazodiphinylamine or 1-diazo-4-N,N-dimethlaminobenzene. The diazo resin is preferably used as a mixture with a film forming resin, especially a high molecular compd. having hydroxyl groups such as poly-2-hydroxyethyl acrylate. A pringing plate material having superior shelf life, developable with an aq. developer and extending development latitude is obtd. and a pringing plate having satisfactory dot reprducibility is also obtd.

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, a lithographic printing plate material that does not require dampening water and has excellent preservability can be obtained. The present invention also relates to a photosensitive lithographic printing plate that can be developed with an aqueous developer, has a wide development latitude, and does not require dampening water, and can provide a printing plate with good halftone dot reproducibility.

[Background of the Invention] Conventionally, photosensitive lithographic printing plates (hereinafter referred to as "plate materials" as necessary) that do not require dampening water 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 by swelling agents.

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 it may peel off during development and a stable image may not be formed. , a silane coupling agent is added to a photosensitive layer or a silicone rubber layer to strengthen the adhesive force between the photosensitive layer and the silicone rubber layer.

However, although the adhesion can be improved to some extent by adding a silane coupling agent, it is not enough to obtain a printing plate with good halftone reproducibility, and the development latitude is not wide enough. .

In addition, in the latter case where only the silicone rubber layer in the unexposed 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. Since the process can only be developed using 100% polyurethane, it poses a problem in terms of working environment and pollution.

Therefore, the present inventors continued intensive research in order to improve the above-mentioned problems, and as a result, by setting the ratio of the binder resin and diazo resin in the photosensitive layer to a specific weight ratio, the photosensitive layer in the exposed area They discovered that it is possible to strengthen the adhesive force with the silicone rubber layer, and as a result, it is possible to obtain a printing plate with good halftone reproducibility using an aqueous developer containing mainly water, and have completed the present invention. Ta.

[Object of the Invention] Therefore, the object of the present invention is to obtain a photosensitive lithographic printing plate which has excellent storage stability and does not require dampening water, and which can be developed with an aqueous developer, and furthermore, the development radiation range 1-1 can be expanded. An object of the present invention is to provide a photosensitive lithographic printing plate that does not require dampening water and can provide a printing plate with good halftone dot reproducibility.

[Structure of the Invention] The object of the present invention is to provide 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 binder resin or a diazo resin. , and the weight ratio of these binder resins to the diazo resin is 5
This was achieved using a photosensitive lithographic printing plate that does not require dampening water and is characterized by a ratio of 0+50 to 1o:90.

The present invention will be explained in more detail below.

The diazo resin used in the present invention includes various types, but is preferably a diazo resin typified by a condensate of p-diazodiphenylamine and formaldehyde,
Water-insoluble and solvent-soluble, preferably water-insoluble and ordinary organic solvent-soluble as described in Japanese Patent Publication No. 47-1167 and Japanese Patent Publication No. 57-4:3890, etc. . Particularly preferably, the following general formula [
It is a diazo resin represented by I].

General Formula [I] [In the formula, RI R2 and R3 represent a hydrogen atom, an alkyl group, or an alkoxy group, and R4 represents a hydrogen atom, an alkyl group, or a phenyl group.

X represents PF8 or BF4, and Y represents -NH-5- or -0-. ] Examples of the diazo monomer added to the diazo resin used in the present invention include 4-diazo-diphenylamine,
1-diazo-4-N,N-dimethylaminobenzene, l
-Diazo-4-N,N-diethylaminobenzene, 1-
Diazo-4-N-ethyl-N-hydroxyethylaminobenzene, 1-diazo-4-N-methyl-N-hydroxyethylaminobenzene, 1-diazo-2,5-diethoxy-4-benzoylaminobenzene, 1- Diazo
4-N-benzylaminobenzene, 1-diazo-4-
N,N-dimethylaminobenzene, 1-diazo-4--
E-ruphorinobenzene, l-diazo-2,5-dimethoxy-4-p-tolylmercaptobenzene, l-diazo-
2-ethoxy-4-N,N-dimethylaminobenzene,
p-Diazodimedylaniline, 1-diazo-2,5-
Dibutoxy-4-morpholinobenzene, 1-diazo-2
,5-thie1-xy4-dimethoxy-4-morpholinobenzene,1-diazo-2
,5-jethoxy-4-p-tolylmercap]benzene, 1-diazo-4-N-ethyl-N-hydroxyedylaminobenzene, 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-me]xy-4-pyrrolidinobenzene, 3-methoxy-4-diazodiphenylamine, 3- Examples include hydroxy-4-diazodiphenylamine, 3-(n-propoxy)-4-diazodiphenylamine, and 3-(isopropoxy)-4-diazodiphenylamine.

Examples of the aldehyde used as a condensing agent with the diazo monomer include formaldehyde, acetaldehyde, 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,
2-21herobenzenesulfonic acid, 2-methoxy-4-
By using 1-nitroxy-5-benzoyl-pensene sulfonic acid or the like, 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 polymer compound having 1 to 1 hydroxyl groups. Particularly preferably, the polymer compound is a copolymer having an aliphatic hydroxyl group on the side button, such as 2-hydroxyethyl acrylate or a copolymer of 2-hydroxyethyl acrylate and another copolymerizable copolymer. Can be mentioned.

In addition to these, polyvinyl butyral resins, polyurethane resins, polyamide resins, epoxy resins, novolak resins, natural resins, etc. may be added as necessary.

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, 0-1m+, or P-hydroxyphenyl methacrylate with other monomers, hydroxyethyl acrylate as described in U.S. Pat. No. 4,123.27B. Examples include polymers containing hydroxyethyl methacrylate units or hydroxyethyl methacrylate units as main repeating units.

In addition to these, natural resins such as polyvinyl butyral resin, polyurethane resin, polyamide resin, epoxy resin, novolac resin, shellac, rosin, etc.
Polyvinyl alcohol, U.S. Patent No. 3,751.257
Polyamide resins described in US Pat. No. 3,660,097, linear polyurethane resins, phthalated polyvinyl alcohol resins, epoxy resins condensed from bisphenol A and epichlorohydrin, Contains celluloses such as cellulose acetate and cellulose acetate phthalate.

Examples of the alkali-soluble resin include novolac resin, vinyl polymer having a phenolic hydroxyl group, and JP-A-55-5
Examples include condensation resins of polyhydric phenols and aldehydes or ketones described in Japanese Patent No. 7841. Examples of novolac resins include phenol/formaldehyde resin, cresol/formaldehyde resin, and JP-A-5
Phenol-cresol-formaldehyde copolycondensation resin as described in Japanese Patent Application Laid-Open No. 55-127553,
Examples include copolycondensation resins of substituted phenol and phenol or cresol and formaldehyde.

The diazo resin used in the present invention is used in a mixture with a binder resin, and the ratio of the binder resin Li5 to the binder resin 7 is 50:50 by weight.
``10:90 is preferable R7.Binder-resin is 10 Minuma Nodoki, which does not have the benefit of adding a binder resin, has no taste, has poor storage stability, and is insufficiently developed with an aqueous developer. When the diazo resin exceeds 50, the halftone dot reproducibility deteriorates.Furthermore, when the diazo resin is less than 50, the halftone reproducibility deteriorates, and when it exceeds 90, the storage stability deteriorates.

A total of 6 sensations with the binder Jugetsuji and the diaso Japanese moonji ~
The proportion of the solid content of the steam layer is preferably 80% to 1C)01%, and more preferably 90% to 1%.
-99.5% by weight to weight.

To these photosensitive compositions, other dyes, dyes such as pigments, fat-sensitizing agents, plasticizers, surfactants, etc. can be added. It is used in an amount of 0.1% to 2.0% by weight, preferably 0.5% to .10% by weight, in the solid content of the photosensitive layer.

As the ink repellent layer used in the present invention, a silicone rubber layer is mainly used, but a Lun-Fluorine 21 oil layer can also be used. A preferred silicone rubber has a repeating unit represented by the following general formula [1] with a molecular weight of several years and a hydroxyl group in the main chain or at the end of the main chain. Preferably, the main component is a linear organic polycycloxane.

General formula [1] %Formula% Here, n is an integer of 2 or more, and R is a carbon number of 1. = 10 alkyl group, halogenated alkyl group, alkoxyl group, vinyl group, aryl group, silanol group (011 group), and it is preferable that R [i0% or more is methylcy(t) 6 Note that the above silanol The group (O11 group) may be located either in the main chain or at the end of the main chain, but is preferably located at the end.

The silane coupling agent (or silico crosslinking agent) used in the present invention is Rn5iX,n (wherein, n is an integer of 1 to 3, and R is argyl, aryl, alkenyl, or a combination thereof. In addition, these groups may have a functional group such as halogen, amine, hydroxy, alkoxy, aryloxy, or diol.

2 X is -01-1, -OR', -0A c, -o-N-c
represents a substituent such as -cp, -Br, -In2, etc. Here, R2 and R3 represent the same thing as R above, and even if R2 and R3 are the same, they are different.
) may also be used, and Ac represents an acetyl group. )
This is a silane compound represented by

The silicone rubber useful in the present invention is obtained by the condensation reaction of the silicone base polymer 61 with a silicone crosslinking agent such as those listed below.

(1) R-5t+OR')s (2) R-5i+0Ac)s (3) R-5i(ON-CR'z)s where R is a substituent of the polymer represented by general formula [I] It has the same meaning as R, 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), ]R2, vinylto-rithoxydisilane, Cj? (C)12)3Sj (
OMe) 3, CH, 5i (08C) 3, R5 (CL)
Examples include ssI (OMe) 3 and vinyltohelis (medyl edyl ketoxime) silane cap.

The silicone rubber mentioned above is also available as a commercial product, such as YE-3085 manufactured by Toshiba Silicone Corporation. Mai
= Other suitable silicone rubber CJ, as mentioned above.
-Su polymer, like this! General formula [1! 1) Reaction with a silicone male having an enzymatic structure, or (d-addition reaction, or It cannot be obtained even by the reaction between silicone 1-yl, 3, and the general formula [II Co 1] (II is an integer of 2 or more, n is O or an integer of 1 or more.) In order to obtain silicone rubber by such a crosslinking reaction, the crosslinking reaction is carried out using a catalyst. are tin, zinc, cobalt,
Organic carboxylic acid salts of metals such as lead, calcium, manganese, etc., such as dibutyltin laurate, tin (II) octoate L., cohal 15 phthenate, etc., or chloroauric acid, etc. are used.

In order to improve the strength of the silicone rubber and to make the silicone rubber resistant to the frictional forces generated during printing operations, a filler may be mixed therein. Silicone rubber mixed with filler in advance is silicone rubber.
Rubber rubber) 1 or silicone rubber dispersion 2' If it is not desirable to obtain a silicone rubber film by a coach band as in the present invention, a noise version of RTV or LTV silicone rubber is preferably used. I need., i-,)-una example and 1 no cho are tone 1 no silicon company f: A, syl Off 23.5RX-on 57
．． There are silicone rubber dispersions for vapor coating such as 5ti237.

In the present invention, it is preferable to use a synthetically crosslinked 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 the following:
H3) 3(b) H2NCE2CH2NH(C1b)
*Si (OCII3) 2 (Cth) (c) IIJ
(CH2)ssi(OEt):i The silicone rubber layer used in the present invention may contain a small amount of an additional photosensitizer.

The silicone rubber layer used in the present invention is
After dissolving the cone rubber in a suitable solvent, it is applied to the photosensitive layer and dried.

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

Preferred among these is monoluminium plate.

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. , beer chloride/beer acetate copolymer, acrylic resin, beer chloride resin, polyamide resin, polyvinyl butyral resin, Evo Ashioj fat, acrylate copolymer, vinyl acetate copolymer, phenoxy resin, Boliu 1
Examples include notanioΔ1 fat, polycarbonate resin, polyacryloni-I-lylbutadiene, polyvinyl acetate, and the like.

Further, as the asocuring agent constituting the brimer layer, for example, silane coupling *lJ, 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 50-400 μm, preferably 100 μm.
□300 μm, photosensitive layer is 0.05-1101I
, preferably 01 to 1.0 μm, and the silicone rubber layer has a thickness of 0
5 to 100 μm, preferably 1 = 4 μm4. In the present invention, the silicone rubber layer may have a layer i (having a layer j) on the upper surface as necessary.

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

A composition solution to form a photosensitive layer is applied to a support 1 using a conventional coater such as a reverse roll coater, an air knife coater, a Meyer bar coater, or a rotary coating device 4 such as a Whaler and is dried.

If necessary, after setting and numbering 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 on 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 a laminator.

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

It is vacuum-adhered to the old surface of the original positive-type plate, which is a positive film, 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 a developer, it is used as a developer for plate materials that do not require water.
Although any known developer can be used, preferably an aqueous developer is used.

The aqueous developer is a developer whose main component is water, such as those described in JP-A No. 61-275759, etc., which contain water in an amount of 30% by weight or more, preferably 5031% by weight or more.
Examples include a developer containing 98% by weight, an organic solvent, and a surfactant, and more preferably an alkali agent.

Regarding organic solvents contained in developing solutions whose main component is wood,
For example, aliphatic hydrocarbons (hexane, heptane, "Isopar E, H, G" (trade name of aliphatic hydrocarbons manufactured by Esso Chemical Co., Ltd.), gasoline, kerosene, etc.), aromatic hydrocarbons (toluene, Add the following polar solvents to halogenated hydrocarbons (such as trichlene) or halogenated hydrocarbons (such as trichlene).
It is preferable that

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) Toll, butyl carpitol, dioxane, diethylene glycol dibutyl ether, diethylene glycol dibutyl ether, diethylene glycol dibutyl ether, ethylene glycol dibutyl ether, propylene glycol, dibrobylene 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-dioxolan-2-one, etc.), esters (ethyl acetate, acetic acid, etc.) propyl, hexyl acetate, methyl butyrate, propyl butyrate, diethyl succinate, dibutyl oxalate, diethyl maleate, benzyl benzoate, methyl cellosolve acetate, cellosolve acetate, carpitol acetate, etc.).

Examples of the surfactant that can be added to the developer of the present invention include anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric ionic surfactants, and specifically 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) Alkylarylsulfonic acid salts (e.g., sodium dodecylbenzenesulfonic acid salt, isopropylnaphthalenesulfonic acid sodium salt, dinaphthalenesulfonic acid sodium salt, metanitrobenzenesulfonic acid sodium salt, etc.) ) (4) Alkylamide sulfonates (5) Sulfonates of dibasic aliphatic esters (e.g. sodium sulfosuccinate dioctyl ester, sodium F-
(6) A formaldehyde condensate of an alkylnaphthalene sulfonate (for example, a formaldehyde condensate of sulfur/lium dibutylnaphthalene sulfonate, 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 amount f of the surfactant used in the present invention ranges from 0.01% to 60% by weight, preferably from 0.1 to 1% by weight.
0% by weight is suitable.

Further, the surfactant used in the present invention is preferably used together with an alkaline agent, and the alkaline agent includes (1) sodium silicate, potassium silicate, potassium hydroxide, sodium hydroxide, lidium 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 )-liisobrobanolamine, ethyleneimine, and ethylenediimine.

The amount of alkaline agent used is 0.05% by weight to 20@i%,
Preferably, 0.2% by weight to -10% by weight is appropriate.

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.

[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 mm was immersed in a 3% aqueous sodium hydroxide solution to degrease it, washed with water, and then diluted with 1% hydrochloric acid concentration.
In an aqueous solution with a concentration of boric acid of 1%, electrolytic etching was performed at a temperature of 25°C for 5 minutes at a rate of 3A/dm', and after washing with water, etching was performed in an aqueous solution of 40% sulfuric acid at a temperature of 1.5°C at a temperature of 30°C.
Anodize for 2 minutes at A/dm', wash with water,
% sodium metasilicate aqueous solution for 37 seconds at a temperature of 85°C.

It was immersed in water (poa, 5) at a temperature of 90° C. for 25 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 0.5/1 fit.

[Photosensitive composition] (1) Diazo resin - 165 parts (2) Copolymer of 2-hydroxyethyl methacrylate, acrylonitrile, methyl methacrylate, ethyl acrylate, and acrylic acid in a molar ratio of 55/10/1015/20 Combined 35 parts (3) Victoria Pure Blue BOH (dye manufactured by Hodogaya Chemical Co., Ltd.) 1 part (4) Methyl cellosolve 900 parts Synthesis of diazo resin-1 Diazo resin-1 was synthesized as follows. did.

5 g (50 mmol) of p-cyacine phenylamine sulfate IL was dissolved in 40.9 g of concentrated sulfuric acid under ice cooling. To this reaction solution, 1.35 (45 milliliters) of paraformaldehyde was slowly added so that the reaction temperature did not exceed 10°C.

The reaction mixture was poured into 500 ml of alcohol under ice-cooling, and the resulting precipitate was filtered. After washing under ethanol, this precipitate was dissolved in pure jooml, and a concentrated aqueous solution containing 6.8 g of zinc chloride was added to this solution.
Ta. The resulting precipitate was filtered, washed with ethanol, and the resulting precipitate was dissolved in 150111 pure water. A concentrated aqueous solution containing 88 ammonium hexafluorophosphate was added to this solution. After filtering out the precipitate from the fresh raw meat and washing it with water, *
2 to obtain diazo resin-1.

Next, apply the following silicone rubber composition on the above photosensitive layer so that it becomes 1.53 parts by drying. This is the lithographic printing plate material.

"Silicone rubber layer composition: dimethylpolysiloxine having hydroxyl groups at both ends (molecular weight: 152,000) 100 parts triacetoxymethylsilane 10 parts dibutyltin
/ -1 to 08 parts Isopar G (manufactured by Tsuzo Kagaku Co., Ltd.) 900 parts Next, the surface of the plate material was soaked with the developer, and the unexposed areas of the photosensitive layer and the silicon were separated using three passes. U-], the rubber layer was not removed, and the halftone dots were good: r'f+, a printing plate with excellent reproduction was obtained.

[Developer composition] Ethylene glycol monophenyl ether 5 parts Bio: 1. No A = 44B (anionic surfactant manufactured by Takemoto Yushi Co., Ltd.) 5 parts jetanolamine 1 part wood
89 parts [Comparative example] Except for changing the photosensitive composition of Example 1 as follows,
A lithographic printing plate requiring no dampening water was obtained in the same manner as in Example 1.

[Photosensitive composition] (1) Diazo resin - 130 parts (2) 2-hydroxyethyl methacrylate 1, acrylonitrile, methyl methacrylate, ethyl acrylate, acrylic acid in a molar ratio of 55/10/10/
5/20 copolymer 70 parts (3) Victoria Pure Blue BOH (dye manufactured by Odogaya Kagaku Co., Ltd.) 1 part (4) Methyl cellosolve 900 parts Next, this lithographic printing plate that did not require dampening water was used in Example 1. It was developed with the developer used in . The first printing plate obtained had poor reproducibility in shadow areas.

Example 2 A photosensitive composition having the following composition was coated on aluminum root a and dried at 100° C. for 2 minutes to form a photosensitive layer with a thickness of 05 μm.

[Photosensitive composition (1) Diazo resin - 260 parts (2) High molecular compound - 140 parts (3) Victoria Pure Blue BOH (dye manufactured by Odugaya Kagaku Co., Ltd.) 1 part (4) Methyl cellosolve 900 parts The photosensitive layer soil thus obtained was coated with the same silicone rubber composition as in Example 1 to a dry weight of 15 g/m'.
A lithographic printing plate preparation which was dried at 20° C. for 2 minutes and wetted for 17 minutes without the need for water was obtained.

” = After vacuum-adhering the positive film to the top surface of the printing plate material, it was exposed with a light source and a metal halide driver.
2. Ta. Next, it was developed using the following developer. During development, by rubbing the surface of the plate material with a developer-soaked pad °C, the appearance of unexposed areas can be removed.
-The rubber layer is removed! 1. A printing plate with good halftone dots was obtained.

1] Development swamp; Composition] Benzyl alcohol 8 parts BeL/Tux NBL (Anionic surfactant manufactured by Hana, EF-7' I・Las 7) 5 parts Jetanolamine 2 parts Water
85 parts Dicho~fOj1 Fat-2 Synthesis Table p-hydroxybenzoic acid 3.5 g (o, n25 mol) and 4-diazo-4'-methoxydiphenylamine sulfate 22.0 g (0, 0.075 mmol) was added to 90 g (7) of parasulfuric acid (0.075 mmol) under water cooling.
mol) was added slowly, making sure the reaction temperature was 10°C.

Thereafter, stirring was continued for 2 hours under ice-cooling, and the reaction mixture was poured into ice-cold T. 1 P ethanol, and the fresh precipitate was filtered. After washing with water, dissolve this precipitate in 200 ml of pure water, and add 10.58 g of a concentrated aqueous solution of zinc chloride to this solution.

The mixture was washed with ethanol (11) and dissolved in 300 ml of water. Dissolve the ammonium fluorophosphate in 1'1.7): 1. ．． ．． ．． IL: Added Reimu Atsui Soruji. The resulting precipitate was collected by filtration, washed with water, and then dried at 30° C. for one day and night to obtain diazo resin 2.

Synthesis example 2 of copolymer, -hydroxydiylmethacryle-1-71,5fi
, 17.3 g of acrylic acid 1 lyl of acrylonitrile 5.3 g
, -Idelacryle-)-5.0g, Methiga methacrylate 10g and azobisisobutylo:':l-lyl 1
．． 85 g'1, dissolved in T-tanol 400 mp, purged with nitrogen, heated at 70°C to 80°C for 8 hours. After completion of the reaction, the reaction solution was poured into a wooden plate with stirring, and the resulting white d' The precipitate was filtered and dried to obtain 96 g of lipophilic polymer 11 compound 1.

Effects of the invention] The present invention provides the following advantages:
It is possible to obtain a printing plate with an IH of 50: 50 - 10890f, :), which can be developed with an aqueous developer, and can be developed with a water-based developer. υ1
Statue Lachichu 1. A lithographic printing plate with good spread and halftone dot reproducibility and no need for dampening water can be obtained.

1 frequent visitor

Claims (1)

[Claims] In a photosensitive lithographic printing plate that does not require dampening water and has a photosensitive layer and an ink repellent layer in this order on a support, the photosensitive layer contains a binder resin and a diazo resin, and the weight of these binder resin and diazo resin is Ratio is 50:50 to 10:90
A photosensitive lithographic printing plate that does not require dampening water.