JPH0498262A - Processing method for waterless planographic printing plate - Google Patents

Abstract

PURPOSE:To eliminate the need for a dyeing liquid and to provide processing in good working environment by previously incorporating leuco dyes into ink deposited layers and processing the layer with a processing liquid contg. an acid or phenolic compd.. after or simultaneously with development to develop the colors of only the image parts. CONSTITUTION:The exposed printing plate is processed by the processing liquid contg. the acid or the phenolic compd., by which the images developed in colors only in the image parts are obtd. in the stage for incorporating the leuco dyes into the ink deposited layers and exposing the ink deposited layers of the image parts or the post stage thereof. The leuco dyes are the material, such as bisphenol A, which has the property to develop dark colors when brought into contact with an electron acceptive material. The content in the ink deposited layers is specified to 0.1 to 50wt.%, more preferably 1.0 to 50wt.%. The content of the acid or phenolic compd. in the processing liquid is specified to 0.1 to 50wt.%, more preferably 2.0 to 30wt.% and the pH is specified to 0.5 to 5.0, more preferably 1.0 to 3.5. The images having an excellent plate inspecting property are obtd. without using the dyeing liquid in this way and the staining of the hand, clothing and automatic developing machine, etc., is obviated. The working environment is thus improved.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to a method for processing a waterless lithographic printing plate, and more specifically to an IA method for a waterless lithographic printing plate that does not require a dyeing process using a staining solution. Regarding processing method.

[Background of the invention] Conventionally, waterless lithographic printing plates (hereinafter referred to as "plate materials" as necessary) have been used.
A known example is one in which a photosensitive layer and an ink repellent layer are sequentially coated on a support. A printing plate can be obtained by exposing and developing this plate material.

For such plate materials, it is necessary to examine the condition of the plate (developability, scratches, stains on the plate, etc.) during or after development, and therefore it must have excellent plate inspection properties.

In order to improve this optometry, conventionally,
As described in Japanese Patent Publication No. 3716 and Japanese Patent Publication No. 63-22304, after development, the image area is dyed with an aqueous dye solution or developed with a dye developer to obtain a visible image. There is.

However, if the plate material is subjected to IA treatment with a staining solution containing dye in order to visualize the image area after development, hands and clothes may get stained when replenishing the dyeing solution or replacing the dyeing solution, etc. The dyeing process increases the number of processing steps, which increases the size of the automatic developing machine, which is not desirable in terms of equipment.

Therefore, the present inventors considered the above-mentioned plate inspection properties and conducted various studies on methods that do not use a staining solution, and as a result, the inventors included a leuco dye in the inked layer in advance and developed it either after or after development. At the same time, it was discovered that by treating with a processing liquid containing an acid or a phenolic compound to develop color only in the image area, an image in which only the image area was colored could be obtained, and the present invention was thus completed.

[Object of the Invention] Therefore, the object of the present invention is to provide waterless lithographic printing which eliminates the need for a dyeing solution, eliminates the trouble of staining hands and clothes with the dyeing solution, and does not cause the trouble of staining an automatic processor, and provides a good working environment. The purpose is to provide a method for processing editions.

[Structure of the Invention] The object of the present invention is to imagewise expose a waterless lithographic printing plate whose inked layer contains a leuco dye and whose top layer is a silicone rubber layer, and then expose the inked layer in the image area. This is achieved by a method for treating a waterless lithographic printing plate, which is characterized in that the exposed printing plate is treated with a treatment liquid containing an acid or a phenolic compound in the step of exposing the exposed printing plate or in the step after the step.

Below, the configuration of the present invention will be explained in more detail.

The present invention provides an ink-applied layer of a waterless lithographic printing plate containing a leuco dye, and a processing liquid containing an acid or a phenolic compound in the step of exposing the ink-applied layer in the image area or in the process subsequent to this step. By processing the exposed printing plate, an image in which only the image area is colored can be obtained, so an image with excellent optometry can be obtained without using a staining solution,
Furthermore, there is no dirt on hands, clothes, automatic developing machines, etc., resulting in an excellent working environment.

The waterless lithographic printing plate used in the present invention consists of a support coated with a primer layer, a photosensitive layer, and a silicone rubber layer in this order, and the inking layer includes the photosensitive layer and the primer layer. I am using it.

The ink layer of the waterless lithographic printing plate used in the present invention contains a leuco dye, which is itself an almost colorless substance, but has electron-accepting properties such as bisphenol A. A substance that has the property of developing a deep color when it comes into contact with other substances, and the following are used.

1) Triphenylmethane-based leuco compound 3.3-bis(p-dimethylaminophenyl)phthalide 3.3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide (CVL) 3.3-bis (p-dimethylaminophenyl)-6-dimethylaminophenyl 4-hydroxy-4'-dimethylaminotriphenyl methane lactone 44'-bisdihydroxy-3,3'-bisdiaminotriphenyl methane lactone 2) Fluoran-based leuco 3-dimethylamino-6-methoxyfluoran 36-bis-β-methoxyethoxyfluoran 3-diethylamino-6-methyl-7-chlorofluoran 3.7-pis-diethylaninofluoran 3-diethylamino-7-methoxy Fluoran 3) Leuco derivative of spiropyran series 3-phenyl-8'-methoxyhenzoindolinos biropyran 8'-methoxybenzoindolinos biropyran 4 7.
8'-1 Limethoxybenzoindolinos birobilane 4) Auramine-based leuco form 44'-bisdimedylamino-34-chlorphenylleucoauramine 4.4'-bisdimethylaminoviverazine hydrol 5) Phenodeazine-based leuco form Various types of leuco derivatives such as p-methoxybenzoyl leucomedylene blue and above are used, and depending on the type, various colors such as blue, black, red, green, and orange can be obtained.

The content of this leuco dye in the inked layer is 0.
1% to 50% by weight, preferably 10% to 50% by weight
It is 30% by weight.

The waterless lithographic printing plate used in the present invention is colored by being treated with a processing solution containing an acid or phenolic compound at the same time or after development. Examples include clay acids such as acid clay, kaolin, and zeolite; organic acids such as oxalic acid, maleic acid, citric acid, stearic acid, benzoic acid, and gallic acid; and phenolic acids such as the following. There are compounds.

Catechol, resorcinol, hydroquinone, α-naphthol, β-naphthol, 3.5-xylenol, dimol,
Pyrogallol, phloroglucin, phloroglucincarboxylic acid, 4-tert-butylphenol, 4-phenylphenol, 4-hydroxyciphenoxyto, 4-hydroxyacetophenone, methyl-4-hydroxybenzoate, 4-tart-ofdercatechol, 4. 4
'Secondary butylidene diphenol, 22' dihydroxydiphenol, 4.47-itupropylidene diphenol (bisphenol A), 2.2'-methylenebis (4-medy-6-tertbutylphenol),
4.4'-cyclohexylidenephenol, 4.4'-
Isopropylidene bis(2-chlorophenol), phenol formaldehyde, novolac type phenol resin, halogenated novolac type phenol resin, etc. can also be used.

The amount of acid or phenolic compound added to the processing solution is
The amount is 0.1% to 50% by weight, preferably 2.0% to 30% by weight.

Moreover, pl+ of this treatment liquid is 0.5 to 5.0, preferably 1.0 to 3.5.

It is preferable to add a buffer or a salt to the treatment solution used in the present invention, such as sodium chloride, potassium chloride, potassium hydrogen phthalate, hydrochloric acid, sodium hydroxide, glycine, citric acid, sodium citrate, citric acid Potassium, potassium hydrogen citrate, succinic acid, sodium tetraborate, tartaric acid, sodium tartrate, lactic acid, sodium lactate, acetic acid, sodium acetate, disodium hydrogen phosphate, trisodium phosphate, diethylbarbic acid, boric acid, Sodium 41iIII acid and tris(hydroxymethyl)aminomethane are used alone or in combination.

Further, it is preferable to add an organic solvent, a surfactant, a salt, etc. to the treatment liquid used in the present invention.

As preferred organic solvents, known organic solvents can be used; for example, most of those described in "Solvent Pocket Book" (Ohm Co., Ltd.) can be used.

Examples of organic solvents having a solubility in water at 20°C of less than 10% by weight, so-called poorly water-soluble organic solvents, include citrate ketone, acetophenone, isophorone, diethyl succinate, methyl benzoate, diethyl oxalate, dimethyl phthalate, and isobutyl acetate. , benzyl benzoate, ethylene glycol sonophenyl ether, ethylene glycol dibutyl ether, ethylene glycol benzyl ether, diethylene glycol di-n-butyl ether, diethyl glycol diacetate, n-amyl alcohol, benzyl alcohol, cyclohexanone, cyclohexanol, N- Examples include benzylethanolamine, anisyl alcohol, dimethylpencylcarpitol, 2-N-ethylanilinoethanol, propylene glycol monophenyl ether, and N-phenylethanolamine.

Among these, ethylene glycol monophenyl ether, ethylene glycol benzyl ether, benzyl alcohol, cyclohexanone, cyclohexanol, N
-Benzylethanolamine, anisyl alcohol, dimethylpencylcarpitol, 2-N-ethylanilinoethanol, propylene glycol monophenyl ether, and N-phenylethanolamine are particularly effective.

The amount of organic solvent used in the present invention is 5 to 1% by weight.
0% by weight, preferably 2% to 6% by weight is preferred.

Particularly preferred organic solvents used in the present invention are those having a solubility in water of 10% or more at 20°C, and examples of alcohols include methanol, ethanol, n-propanol, isopropanol, n-
Examples include butanol, 5ee-butanol, t-butanol, furfuryl alcohol, and tetrahydrofurfuryl alcohol.

Examples of the ether or acetal include 1,2-propylene oxide, 1,4-dioxane, tetrahydrofuran, methitool, and the like.

Examples of the ketone include acetone, methylacetone, methylethylketone, acetone oil, acetonylacetone, diacetone alcohol, and the like.

Examples of esters include methyl formate, methyl acetate, methyl lactate, and ethyl lactate.

Polyhydric alcohols and their derivatives include ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol isobrobyl ether, and ethylene glycol dibutyl ether. Butyl ether, ethylene glycol dibutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol isoamyl ether, ethylene glycol monophenyl ether,
Methoxymethoxyethanol, ethylene glycol monoacetate, ethylene glycol diacetate, ethylene chlorohydrin, diethylene glycol, diethylene glycol methyl ether, diethylene glycol diethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl Ether, diethylene glycol acetate, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tetraethylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, 1-butoxyethoxypropanol, propylene chlorohydrin, dipropylene Glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, trimethylene glycol, butanediol, 1,5-bentanediol,
Examples include hexylene glycol, glycerin, glyceryl monoacetate, glyceryl diacetate, glycerin ether, glycerin-α-monochlorohydrin, glycerin-α, γ-dichlorohydrin, trimethylolpropane, 1,2.6-hexanetriol, and the like.

Examples of nitrogen compounds include monomethylamine, dimethylamine, trimethylamine, monomethylamine, diethylamine, triethylamine, isopropylamine, n-butylamine, isobutylamine, 5ec-butylamine, n-amylamine, 5ec-amylamine, 5ec-
Hexylamine, cyclohexylamine, monoethanolamine, jetanolamine, triethanolamine, ethyl monoethanolamine, n-butyl monoethanolamine, diethylethanolamine, diethylethanolamine, ethyl diethanolamine, n-butyl jetanolamine, triisopropylene Paturamine, isopropaturamine (mixture), formamide, acetamide, acetonitrile, biridine, α-picoline, β-picoline, γ-picoline, 2,4-lutidine, 2
, 6-lutidine, quinoline, morpholine and the like.

Among these organic solvents, alcohols, polyhydric alcohols and their derivatives are preferably used.

The content of these organic solvents is 0.1% to 40% by weight, preferably 0.5% to 1% by weight based on the processing liquid.
It is 5% by weight.

Both of the organic solvents used in the present invention can be used alone or in a mixture of two or more. It is also possible to use a mixture of both organic solvents.

As the nonionic surfactant added to the treatment liquid used in the present invention, commonly used known nonionic surfactants can be used.

It preferably consists of at least one represented by the following general formula [r] or general formula [n].

Formation [I General formula [II] Further, n and m are integers from 0 to 300, and are not 0 at the same time. ] In the nonionic surfactant represented by -formation [i] or general formula [II], the alkyl groups represented by R, R,, R2, and R3 include, for example, CH3, CH
sC112, CH3(CH2) 2, CH3(CI42
) 3, Cll3 (Cth) 4, CH8 (co2),, CHs (f; H2) a, CH
3 (CH2) 9, CH3 (CI+□), 1, +1; H
3 (H2) l 3, CH3 (CH12) +5, C
H3 (C1h) + 7, C1h (CH2) + 9
, CHa (C)12) 2 +, CH3(CH2)
A straight chain or branched alkyl group having 1 to 25 carbon atoms such as 23 is preferred.

Examples of the aryl group include a phenyl group, [wherein R
, R, , R2, R, are each a hydrogen atom, an alkyl group,
It represents any one of an aryl group, an aralkyl group, and (Il represents an integer from 1 to 10), and includes a straight or branched alkyl group having a substituent.

Further, as the alkenyl group or alkynyl group, for example, Cth-CH(Cth) 7-1C)I3C1hCII
-CH(C1h)? -5C1h (CL) 5f:f
lll:H-1C)+3 (Cll2) 7CII-C
H-1C1l, (C)12) 5CI+ (011)
C112C112CI-ell (c++2), -
1CH3(CH2)+oCH-CH(CI(2)4-1
CH3(Cll2) 5cl-1-Cll (CHz)
9-.

CH3(fl, H2) 4C11-C1lf:11□C
l1-CH(Cll2) 7-1CH3CH2GH-C
llCH2CH-CHCH2CH-CH(II:th)
7-1C1h (CH2) 3 (CI-C1l) 3
(C1h) 7-1C)+3 (C1-12) a
(C)l-C)I) 3(Cfh) 4GO(Cll2
) 2-1CI(3(f;lh) 7(=C(CH2
)? -1CH3(CI(219cH-[;H(Cll
□) Examples include those having 9 to 24 carbon atoms such as 7-1.

In addition, as aralkyl groups, monocyclic or bicyclic aryl groups such as
Examples include those having a structure in which an allyl group is added to an alkyl group, such as 3 L 113.

In addition, in the above-formation [I] or general formula [11],
The values of n and m are preferably 1 to 100, particularly preferably 1
~50. Further, n;m is preferably 1:10 to 10:1.

General formula [I] or general formula [11] used in the present invention
Preferred specific examples of the nonionic surfactant represented by are shown below, but are not limited thereto.

For example, polyethylene glycol, polyoxyethylene lauryl ether, polyoxyethylene nonyl ether,
Polyoxyethylene nonyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene behenyl ether, polyoxyethylene polyoxybrobylene sedyl ether, polyoxyethylene polyoxypropylene behenyl ether, polyoxyethylene phenyl ether, Polyoxyethylene octylphenyl ether, oxyethylene oxybrobylene block polymer distylenated phenol polyethylene oxide adduct, tripentylphenol polyoxyethylene oxide adduct, octylphenol polyoxyethylene polyoxybrobylene adduct, etc. .

Specific product examples of these nonionic surfactants include:
Examples include Nilacol manufactured by Nikko Chemicals Co., Ltd. and Emulken manufactured by Kako Co., Ltd.

The amount of these nonionic surfactants added is 0.1% to 10% by weight, preferably 0.2% to 5% by weight, based on the treatment liquid.

One or more of the above nonionic surfactants can be used in combination.

The above-mentioned nonionic surfactants have an HLB value of 1.
It is in the range of 3.0 to 1 g, 0.

Examples of the anionic surfactant used in the present invention include higher alcohols, (Ca-C2z)vt acid ester salts [e.g., sodium salt of lauryl alcohol sulfate, sodium salt of octyl alcohol sulfate, ammonium salt of lauryl alcohol sulfate] , "T-Ball B-8M (trade name, manufactured by Shell Chemical, secondary sodium alkyl sulfate, etc.)", fatty acid alcohol phosphate ester salts (e.g., sodium salt of cedyl alcohol phosphate ester, etc.), alkylaryl sulfonates (e.g., sodium salt of dodecylbenzenesulfonic acid, sodium salt of isopropylnaphthalenesulfonic acid, sodium salt of sinapthalenedisulfonic acid, sodium salt of metanitrobenzenesulfonic acid, etc.), sulfonic acid salts of alkylamides, and basic fatty acid esters. There are sulfonic acid salts (eg, sodium sulfosuccinate dioctyl ester, sodium sulfosuccinate dihexyl ester, etc.).

In addition, the anionic surfactants preferably used in the present invention include α-olefin sulfonates, dialkyl sulfosuccinates, α-sulfonated fatty acid salts, polyoxyethylene alkyl ether sulfates, and polyoxyethylene alkylaryl ethers. Sulfates (e.g. polyoxyethylene nonylphenyl ether sulfate, polyoxyethylene naphthyl ether sulfate, etc.), alkyl phosphates, polyoxyethylene alkyl ether phosphates, naphthalene sulfonate formaldehyde complexes, polycarboxylic acid types Examples include polymeric surfactants.

It is preferable to add a commonly used chelating agent to the treatment liquid used in the present invention.

The chelating agent used in the present invention is preferably a compound that forms a chelate compound by coordinating with a metal ion, such as polysulfonic acids, polyphosphates, oxyacids, and aminopolycarboxylic acids.

These aminopolycarboxylic acids are compounds having a group represented by the general formula >N+cu2+coon (in the formula, n represents 1 or 2, and R represents a hydrogen atom or an alkali metal) in the molecule, and (C
If the 12+GOOR group is represented by X, it can be classified as follows.

(1) RNX2 type compound (2) NX3 type compound (3) R-NX-CH2-CH2-NX-R type compound (4) R-NX-C)I2-C112-NH2 type compound (5) X2N-R '-NX2 type and a compound containing 4 or more represents an organic group such as a cyclic or cyclic alkylene group or a phenylene group, or a substituted product thereof.

) Examples of typical compounds of aminopolycarboxylic acids include:
Iminodiacetic acid, iminodipropionic acid, N-(3,3-
dimethylbutyl)iminodiacetic acid, mercaptoethyliminodiacetic acid, methoxyethyliminodiacetic acid, methylthioethyliminodiacetic acid, N-(carbamoyl)iminodiacetic acid, aminoethyliminodiacetic acid, 2-ethoxycarbonylaminoethyliminodiacetic acid, sulfoethyl iminodiacetic acid, nitrilotriacetic acid, carboxyethyliminodiacetic acid,
N,N'-ethylenediaminediacetic acid, N(2-hydroxycyclohexyl)ethylenediaminetriacetic acid, N'
-Hydroxyethyl-ethylenediamine-N, N, N'
-triacetic acid, ethylenediaminetetraacetic acid, ethylenediamine-NH4-diacetic acid-N,N'-dipropionic acid,
12-Propylenediaminetetraacetic acid, trimedylenediaminetetraacetic acid, hexaethylenediaminetetraacetic acid, 1,2-cyclopentanediaminetetraacetic acid, tra
ns-cyclohexane-1,2-diaminetetraacetic acid,
2.2'-diaminoethyl ether-N, N, N'
, N'-tetraacetic acid, diethylenetriaminepentaacetic acid, glycoldiaminetetraacetic acid, thioglycoldiaminetetraacetic acid, 2.2'-diaminoethylthioether-N,N,N', N'-tetraacetic acid, N',N
”-dimethyltrimethylenetetramine-N,N,N-N
″-tetraacetic acid, trimedylenetetraminehexaacetic acid,
and their sodium or potassium salts.

Examples of organic phosphonic acids or bospontricarboxylic acids include 2-phosphonobutanetricarboxylic acid-1,2,
4, its potassium salt, its sodium salt, 2-phosphonobutanetricarboxylic acid-2,3,4, its potassium salt,
its sodium salt, 1-phosphonoethanetricarboxylic acid-12,2, its potassium salt, its sodium salt, 1-
Hydroxyethane-1,1-diphosphonic acid, its potassium salt, its sodium salt, aminotri(methylenephosphonic acid), its potassium salt, its sodium salt, etc. can be mentioned. Organic amine salts are also effective in place of the potassium or sodium salts of the above chelating agents.

As polyphosphates, Na2P207, Na5P30
3. Na5P30. , Na204P (Na03P)
PO5Na2, carvone (sodium polymetaphosphate)
etc.

Examples of the oxyacid include aliphatic oxyacids such as citric acid, tartaric acid, and gluconic acid, and aromatic oxyacids such as salicylic acid and hydroxynaphthoic acid.

Among these, particularly preferred are polyphosphates and aliphatic oxyacids.

The staining solution used in the present invention contains at least one of the above chelating agents in a range of 0.01% to 2% by weight, preferably in a range of 0.05% to 0.5% by weight. be.

Examples of the brimer layer used in the present invention include polyester resin, vinyl chloride-vinyl acetate copolymer, acrylic resin, vinyl chloride resin, polyamide resin, polyvinyl butyral resin, epoxy resin, acrylate copolymer, and vinyl acetate copolymer. Examples include polymers, phenoxy resins, polyurethane resins, polycarbonate resins, polyacrylonitrile butadiene, polyvinyl acetate, and the like.

Preferred examples include acrylic resin, polyester resin, and urethane resin. These resins are preferably used in the form of being cured by heat or light. Particularly preferred is a brimer layer cured by thermal polymerization or photopolymerization.

For example, when an acrylic resin containing a hydroxyl group and/or a carboxyl group is cured by heat, a melamine resin, diisocyanates, etc. can be used as a crosslinking agent. Further, when photocuring, diazo resin or the like can be used.

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 ditanates and the like are also effective.

The thickness of the brimer layer is usually 0.1 to 20 μm, preferably 0.3 to 10 μm.

Margin below As the photosensitive composition used in the photosensitive layer of the waterless lithographic printing plate used in the present invention, any known photosensitive composition can be used, but preferably a diazo resin and a photopolymerizable compound are used. Particularly preferred are diazo resins.

The photosensitive composition will be specifically explained below.

(1) Photosensitive composition containing diazo resin 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,
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, the following general formula [1
] It is a diazo resin shown by.

- Formation [1] [In the formula, Rl, 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 PF or BF4, and Y represents -N)l-5- or -0-. Examples of the diazo monomer in the diazo resin used in the present invention include 4-diazo-diphenylamine, 3
-Methoxy-4-diazodiphenylamine, 3-ethoxy-4-diazodiphenylamine, 3(n-propoxy)-4-diazodiphenylamine, 3-(isopropoxy)-4-diazodiphenylamine, and the like.

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, triisopropylnaphthalene sulfonic acid, 4,4 -Biphenyldisulfonic acid, 2,5-dimethylbenzenesulfonic acid, 2
By using -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. Such a lipophilic polymer compound includes a monomer having an aliphatic hydroxyl group in a side chain, such as a copolymer of 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate with other copolymerizable monomers. can be mentioned. 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 Copolymers of p-hydroxystyrene, o-, m-, or p-hydroxyphenyl methacrylate, etc., with other monomers, hydroxyethyl as described in U.S. Pat. No. 4,123,276. Polymers containing acrylate units or 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, 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. Polymers, condensation resins of polyhydric phenols and aldehydes or ketones described in JP-A-5557841, and the like can be mentioned. Examples of novolac resins include phenol and
Formaldehyde tree B, talesol/formaldehyde resin, phenol/cresol/formaldehyde copolycondensation resin as described in JP-A-55-57841, as described in JP-A-55-127553 Examples include copolycondensation resins of p-substituted phenol and phenol, or copolycondensation resins of cresol and formaldehyde.

In addition to the above-mentioned materials, these photosensitive compositions may also contain colorants such as dyes and pigments, sensitizing agents, plasticizers, surfactants, organic acids, acid anhydrides, and acids that can be removed by exposure to light. Compounds that may be generated can be added.

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 40 to 80% by weight. The diazo resin is contained in an amount of 5 to 80% by weight, 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.

(2) -CH-CII-C- in the main chain or side chain of the polymer
Photosensitive composition containing a polymer compound having a group Examples of such a polymer compound include polyesters, polyamides, etc. containing -CH-CII-C- as a photosensitive group in the main chain or side chain of the polymer; Those whose main component is a photosensitive polymer such as polycarbonates (for example, U.S. Pat. No. 3,030,208, U.S. Pat. No. 3,707,373)
No. 3,453,237); photosensitive polyesters derived from (2-properidene) malonic acid compounds such as cinnamylidene malonic acid and difunctional glycols; The main component is (
For example, U.S. Patent Nos. 2,956,878 and 3,1
73.787)
; cinnamate esters of hydroxyl-containing polymers such as polyvinyl alcohol, starch, cellulose, and the like (e.g., U.S. Pat. No. 2,690.966, U.S. Pat. No. 2.7;
52,372, 2.732,301, etc.).

These photosensitive compositions 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 ethylenically unsaturated double bonds; (b) photopolymerizable It consists of an initiator and (c) a polymer compound as a binder resin.

The vinyl monomer of this component (a) is
No. 5093, No. 35-14719, No. 44-2872
It is described in each publication No. 7.

Acrylic or methacrylic esters of polyols, such as diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, or methylene bis(meth)acrylate Acrylamide, bis(meth)acrylamides such as ethylene bis(meth)acrylamide, or unsaturated monomers containing urethane groups, such as di(2'-methacryloxyethyl)2.4-1-
Diol mono(meth) such as lylene diurethane, di(2-acryloxyethyl) trimethylene diurethane, etc.
Examples include reaction products of acrylate and diisocyanate.

As the photopolymerization initiator of the component (b), 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 resin (binder) of component (e). Furthermore, the polymer compounds mentioned above as binders for the diazo resin can also be preferably used. For details on specific binder resins, see
Described in U.S. Pat. No. 4,072.527.

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 generally the photosensitive coating amount is %, preferably 0. 05~
10% by weight is suitable.

The silicone rubber used in the present invention is a linear organic polymer having a repeating unit represented by the following general formula [■] and having a molecular weight of several thousand to hundreds of thousands and a hydroxyl group in the main chain or at the end of the main chain. Those containing siloxane as a main component are preferred.

General formula [11% formula% 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, 1 silanol group (0)), and
Preferably, 60% or more of R is a methyl group. The silanol group (011 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 silicone crosslinking agent) used in the present invention is R,1SiX4-n (wherein, n is an integer of 1 to 3, and R is alkyl, aryl, alkenyl, or a combination thereof. It represents a monovalent group, and these groups may have a functional group such as halogen, amine, hydroxy, alkoxy, aryloxy, thiol, etc.

X is 101l, -〇R2, -〇AC1-0-N-C
, -cp, -Br, -■, and other substituents. Here, R2 and R3 represent the same as R above, and R2 and R3
may be the same or different. 8c again
represents an acetyl group. ) is a silane compound represented by

That is, 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 such as those listed above.

Specific examples of the silane coupling agent used in the present invention include 11N[(C1+2)3si(OMe)3co2, vinyltris-i xysilane, CJ) (CI+2)3sI
(OMe) 3,Cl13Si(08C)3,IIs
(elf) 5Si(OIJe) 3, vinyl tris(methyl edyl ketoxime) 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. In addition, other useful silicone rubbers can be produced by reacting the above-mentioned base polymer with a silicone oil having repeating units represented by the following general formula [11], or by reacting R
It can also be obtained by addition reaction with a base polymer of silicone, of which about 3% 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], ■ 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. This catalyst includes tin, zinc, cobalt, lead,
Organic carboxylates of metals such as calcium, manganese, etc.
For example, dibutyltin laurate, tin (I+) octoate, cobalt naphthenate, or chloroauric acid can be used.

Fillers can also be mixed in to improve the strength of the silicone rubber and to make it resistant to the frictional forces generated during printing operations. 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, RTV
Alternatively, dispersion of LTV silicone rubber is preferably used. An example of this is Syl Off 23.5RX-257,5H manufactured by Toray Silicone.
There are silicone rubber dispersions for vapor coating such as 237.

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 preferable silane coupling agents include the following.

(a) 1IiNclhcHJII (CI+2) 3
51 (OCH3) 5(b) HJCE2C1lJl
l (C112) 3sI (OCH3) 2 (C1
l,ri (C) H2N (f;L) 3si (OEt
) 3 The silicone rubber layer used in the present invention may further contain a small amount of 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 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 metal plates such as aluminum, zinc, copper, and steel, and metal plates such as chromium, zinc, Examples include metal plates plated or vapor-deposited with copper, nickel, aluminum, iron, etc., paper, plus deck film, glass plates, resin coated paper, paper covered with metal foil such as aluminum, and the like.

Nine of these are made of aluminum plates.

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

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

[Example] The present invention will be explained below using Examples.
It is not limited to these examples.

Example-1 A photosensitive composition having the following composition was deposited on an aluminum substrate to a thickness of 10
It was provided as a μ photocurable photosensitive layer.

[Photosensitive composition] Lipoxy 5P-1509 (manufactured by Showa Kobunshi Co., Ltd., bisphenol A-based epoxy acrylate) 100 parts Trimethylolpropane triethoxy triacrylate 80 parts 2.4-diethylthioxanthone 4 parts p-dimethylaminobenzoic acid edyl ester 4 Part: Crystal Violet Lactone 30 parts Yellow pigment (KET-YELLOW402, manufactured by Inu Nippon Ink Chemical Co., Ltd.) 8 parts Tropeolin
5 parts Then, the following silicone rubber composition was coated on the photosensitive layer at a dry weight of 2.0 g/m 2 and dried at 90° C. for 10 minutes to obtain a waterless lithographic printing plate.

[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 Next, a positive film was vacuum-adhered onto the silicone rubber layer, and then exposed to light using a metal halide lamp as a light source.

When the exposed plate material thus obtained was developed by rubbing the plate surface with a vat using Toshisha's waterless lithographic developer HP-7N, the silicone rubber layer in the image area was removed. .

After washing this plate material with water, it was immersed in the following treatment solution for 30 seconds. The liquid temperature was 25°C.

[Processing liquid] Water
100 parts Propylene glycol monophenyl ether 2 parts Oxalic acid 10 parts Polyoxyethylene lauryl ether (nonionic surfactant) 0
．． 5 parts Sodium dodecylbenzenesulfonate (anionic surfactant) 1 part Tetrasodium ethylenediaminetetraacetate 0.05 parts The color of the image area obtained by the above treatment is blue, and a good visible image is obtained. Obtained.

Example 2 A brimer layer with the following composition was coated on a smooth aluminum plate degreased in a conventional manner so that the film thickness after curing was 15 μm, and after drying,
m) was used to expose and cure. Note that parts represent parts by weight. The same applies below.

[Primer layer composition copolymer of co-2-hydroxyedyl methacrylate and methyl methacrylate in a molar ratio of 40/60 100 parts trimedylolpropane triethoxy triacrylate 80 parts 2.4
-Diethylthioxanthone 4 parts p-dimedylaminobenzoic acid ethyl ester 4 parts Crystal violet lactone 50 parts Yellow pigment (M
ET-YELLOW402, manufactured by Dainichi Ink Chemical Co., Ltd.)
8 Yellow-white pigment (zinc oxide, FTN
EX-25, manufactured by Sakai Chemical Co.)
25 parts brobylene glycol monomethyl ether 600 parts Next, a photosensitive composition having the following composition was coated on the above-mentioned brimer layer, and 1
It was dried at 00° C. for 2 minutes to form a photosensitive layer with a thickness of 0.5 μm.

(Photosensitive composition) Diazo resin - 140 parts 2-hydroxyethyl methacrylate, N-(4-hydroxyphenyl) methacrylamide, acrylic acid in a molar ratio of 50/47/3 copolymer 50 parts (manufactured by Tsuchigaya Kagaku Co., Ltd., dye) 1 part methyl cellosolve 900 parts Synthesis of diazo resin-1 Diazo resin-1 was synthesized as follows.

p-diazodiphenylamine sulfate 14.5g (50
mmol) was dissolved in 40.9 g (7) of concentrated sulfuric acid under water cooling. Add 1. +sg (4s mmol) of rose formaldehyde was added slowly so that the reaction temperature did not exceed 10°C.

This reaction mixture was added dropwise to 500 mA+ ethanol under water cooling, and the resulting precipitate was filtered. After washing with ethanol,
100nbl of this precipitate! of pure water, and to this solution was added a cold concentrated aqueous solution containing 6.8 g of zinc chloride.

The resulting precipitate was filtered, washed with ethanol, and dissolved in 150 mjZ 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 to obtain diazo resin-1.

Next, the following silicone rubber composition was coated on the photosensitive layer at a dry weight of 2.0 g/m2 and heated at 90°C for 1
After drying for 0 minutes, a waterless lithographic printing plate was obtained.

[Silicone rubber layer composition] Dimethylpolysiloxane having hydroxyl groups at both ends (molecular weight 52,000), 100 parts triacetoxymethylsilane 10 parts diptyltin laurate 0.8 parts Isopar G (manufactured by Esso Chemical) 900 parts Next, After a positive film was vacuum-adhered onto the silicone rubber layer, it was exposed to light using a metal halide lamp as a light source.

Next, development and post-processing were performed using a processing apparatus having a developer solution 5 and a post-processing solution 6 shown in FIG.

The outer diameter of the brush rolls 12 and 13 in the developing section is 80 mm each.
mm, 100mm, and the diameter of the brush bristles is 9.
4H, 0.15Il1m, hair length is 1
It was set to 5 mm. Also, nylon 6/12 was used for the brush bristles. The rotational speed of the brush rolls 12 and 13 was adjusted so that both of them were 120 m/min. This sharpening development time was 60 seconds, and the post-processing time was 20 seconds.

The developer 5 is a positive PS plate developer SDR-1 manufactured by Konica Corporation.
was diluted 6 times with water and used at 27°C.

As the post-treatment liquid, a liquid having the following composition was used after adjusting the temperature to 30°C.

[Post-treatment liquid] Water
100 parts benzyl alcohol
4 parts polyoxyethylene lauryl ether (nonionic surfactant) 1.5 parts sodium dodecylbenzenesulfonate (anionic surfactant) 1 part citric acid
10 parts potassium citrate
10 parts ethylenediaminetetraacetic acid tetrasodium 0.05 parts After development, use post-processing solution! By processing A, a printing plate with good visible image quality in which the primer layer in the image area was colored blue was obtained.

When processing the 1000th edition of the previous edition, use 5c of developer per plate.
As a result of continuous 1A processing while replenishing 5 cc of post-treatment liquid per plate, good printing plates were obtained in all cases.

Example 3 A photosensitive composition having the following composition was applied onto the brimer layer of Example 2 and dried at 100° C. for 2 minutes to form a 0.5 μm thick photosensitive layer.

[Photosensitive composition] Copolymer of medyl methacrylate and N,N-dimedylaminoedyl methacrylate in a molar ratio of 50150
10 parts Pentaerythritol triacrylate 4 parts Nisrex W-201 (manufactured by Sekisui Plastics Co., Ltd., water-soluble polyvinyl acetal resin)
, 3 parts 2.4-diethylthioxanthone 0.4 part p-dimedylaminobenzoic acid ethyl ester 0.4 part CH2-CH3i (011:H2C1hO011:I
I+) 20, 3 parts water
200 parts methanol 100 parts crystal violet lactone 5 parts Next, 2.0 parts of the following silicone rubber composition was applied on the photosensitive layer by dry weight. [1g/m
2 and dried at 90° C. for 10 minutes to obtain a waterless lithographic printing plate.

[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 Next, the above After a positive film was vacuum-adhered onto the silicone rubber layer, it was exposed to light using a metal halide lamp as a light source.

The thus obtained exposed plate material was subjected to IA treatment in the same manner as in Example 2, except that the post-treatment solution of Example 2 was used as the developer and the treatment was performed with water after the development IA treatment.

The obtained plate material was a printing plate with good visible image quality in which the brimer layer in the image area was colored blue.

Example 4 Using the waterless lithographic printing plate prepared in Example 2 and the developer used in Example 2, gallic acid was added in place of citric acid to the post-processing section C of the automatic processor shown in FIG. The same treatment solution used in Example 2 was added, except that 10 parts was used, and the treatment was carried out after controlling the temperature to 30°C.

That is, the automatic developing machine has a developing process A, a first water washing process B,
, a post-treatment step C1 comprising a second water washing step,
In the developing step A, the planographic printing plate 1 that is fed by the roll 3 is sprayed with a developer by a developer shower 51 on a tray 41, and then rubbed with brush swirls 21 to 23 to be developed.

Subsequently, in a first water washing step B, the material is washed with water while being rubbed with a brush roll 24. After washing with water, the printing plate undergoes post-processing step C.
In the shower 53, a treatment liquid is applied to develop color. Finally, the plate was washed with water to obtain a good printing plate in which the image area was visualized.

[Effects of the Invention] The present invention includes a leuco dye in the inked layer of a waterless lithographic printing plate, and processes this plate material with a treatment solution containing an acid or a phenolic compound, thereby reducing the dyeing process using the dyeing solution. As a result, there is no need to worry about stains on children or clothes, and there is no need to worry about stains, resulting in an excellent working environment.

[Brief explanation of drawings]

FIG. 1 is a sectional view showing a processing apparatus having a developing section and a processing liquid section used in the present invention. FIG. 2 is a sectional view showing another automatic processing apparatus having a developing section and a processing liquid section used in the present invention. Explanation of symbols 1: Passage of lithographic printing plate or lithographic printing plate 12.13.2
1.22.23.24...Brush roll 3...Roller 31...Skewer roll 41...Tray 4.51...Developer shower 42...Guide plate 52.54.55...Wash water shower 8.53・Processing liquid shower 5 ・ ・ Phenomenon 4 So 6 ・ ・
%%Rin night tank 61.62.63... Filter 64... Washing tank 65... Reticulated filter 7... Pump 9... Temperature sensor, heater, temperature control unit, developing process, processing process, 1st washing Process/Second washing process

Claims (1)

[Claims] After imagewise exposing a waterless lithographic printing plate whose inked layer contains a leuco dye and whose top layer is a silicone rubber layer, an acid or A method for processing a waterless lithographic printing plate, comprising processing the exposed printing plate with a processing liquid containing a phenolic compound.