JPH0498261A - Dyeing liquid for waterless planographic printing plate - Google Patents

Abstract

PURPOSE:To obtain a dye concn. sufficient for visible images by constituting the dyeing liquid for waterless planographic printing plates of the liquid which contains surfactants and does not substantially contain org. solvents. CONSTITUTION:This dyeing liquid contains water, dyes, and the nonionic surfactant, further contains at least one kind among the anionic surfactant, cationic surfactant and amphoteric surfactant and does not substantially contain the org. solvents. The amt. of the noionic surfactant to be added is 0.1 to 10wt.%, more preferably 0.2 to 5wt.% of the weight of the dyeing liquid and the HLB value is specified to a 13.0 to 19.0 range. The staining of the silicone layer of non-image parts, the rear surface of a base and the rubber roller, etc., of a developing machine is suppressed in this way. The effect of the nonionic surfactant is high when used in combination with the anionic surfactant.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to a staining solution for waterless lithographic printing plates, and more specifically, it is capable of obtaining sufficient staining properties to obtain a visible image and is free from aggregation. The present invention relates to a staining solution for waterless planographic printing plates that does not cause precipitation and is preferable in terms of environmental hygiene and working environment.

[Background of the invention] Conventionally, waterless planographic printing plates (hereinafter referred to as "plate materials" as necessary)
A known example is one in which a photosensitive layer and an ink repellent layer are sequentially coated on a support. By exposing and developing this plate material, a lithographic printing plate (hereinafter referred to as "printing plate" as necessary) that can be printed without using dampening water can be obtained.

This type of plate material is produced by dissolving the unexposed areas (image areas) of the photosensitive layer using an aqueous developer, as described in Japanese Patent Publication No. 55-22781, and thereby removing the upper silicone rubber layer. The one to be removed and the Special Publication No. 54-26923
As described in the issue, the exposed area (non-image area) is firmly adhered to the photosensitive layer by photoadhesion, and the unexposed area (image area) is
In some cases, the silicone rubber layer is removed using an organic solvent that swells only the silicone rubber layer.

Originally, these lithographic printing plates had a problem in that the discrimination between exposed areas and unexposed areas was insufficient, and so-called optometry was poor.

In order to solve this problem, lithographic printing plates have conventionally been dyed.

For example, Special Publication No. 61-53716, No. 63-22304
JP-A-63-280251 and other publications disclose dyeing liquids containing an organic solvent, water, a dye, and a nonionic surfactant.

However, this staining solution has problems such as insufficient concentration during staining or generation of tar in the staining solution.

Furthermore, during dyeing, it is effective to increase the dye concentration and the content of the poorly water-soluble organic solvent in order to increase the dyeing concentration.

However, when the dye concentration and the content of poorly water-soluble solvents are increased, tar-like aggregates are generated in the dye solution, which adhere to the front and back surfaces of the plate being processed and the phase of the automatic processor, causing stains. .

Furthermore, since conventional dyeing solutions contain organic solvents,
It has an odor and is undesirable from an environmental hygiene or work environment standpoint.

Therefore, the present inventors continued intensive research in order to improve the above-mentioned problems, and as a result, it was surprisingly possible to solve the above-mentioned problems by selecting a surfactant without adding an organic solvent. We have discovered that this can be done, and have completed the present invention.

[Purpose of the Invention] Therefore, the purpose of the present invention is to obtain a staining density sufficient to obtain a visible image, without causing aggregation or precipitation, and in addition, from the viewpoint of environmental hygiene or work environment (safety). The object of the present invention is to provide a preferable dyeing solution for waterless lithographic printing plates (improvement of color, reduction of odor, etc.).

[Structure of the Invention] The object of the present invention is to provide a dyeing solution for dyeing the image area of a waterless lithographic printing plate, which contains water, a dye, a nonionic surfactant, and further contains an anionic surfactant and a cationic surfactant. Alternatively, this can be achieved by a waterless lithographic printing plate staining solution containing at least one kind of amphoteric surfactant and containing substantially no organic solvent.

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

In the present invention, the dyeing solution of the waterless planographic printing plate contains a surfactant and does not substantially contain an organic solvent,
As a result, a staining solution with sufficient staining density for visible images, free from aggregation and precipitation, and favorable from the viewpoint of environmental hygiene or working environment can be obtained.

In the present invention, "containing substantially no organic solvent" means that the content of organic solvent is 2% by weight or less, preferably 1% by weight or less.

The dyeing solution of the present invention dyes either the photosensitive layer or the brimer layer, but it is clear that both the photosensitive layer and the brimer layer may be dyed.

As the nonionic surfactant used in the present invention, commonly used known nonionic surfactants can be used.

Preferably, it consists of at least one represented by the following general formula [I] or general formula [+1].

-Format [IcoR-0-+CH2CHO)II-+CI+2F:H20
) EHH3 Format [+1] [In the formula, R, R,, R2, and R3 are each a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, and a (1 is 1 to 1
Represents an integer of 0. ). Also, n and m are 0
An integer between ~300 and not O at the same time. ] In the present invention, a good staining liquid as described above can be obtained by incorporating a nonionic surfactant represented by the above general formula [I] or general formula [II] into the staining liquid of a waterless planographic printing plate. It will be done.

In the nonionic surfactant represented by the above formula [I] or general formula [II], the alkyl groups represented by R, R,, R2, and R3 include, for example, C113, C113,
)13CI(2,C113(CI+2)2,C)13
([82) s, C11, (CI+2),, CH3 (C112) 7, CIl* (CH2) a,
CI+3 (CJ) 0, Kano. (CH2)+1, Cll
3 (CH2) +3, C1b (CH2) +5, C
113(Cll.) 17, CH3(CH2)l 9, C
)+3(CH2)2+, G113(CH2)2s and the like are preferably linear or branched alkyl groups having 1 to 25 carbon atoms.

Examples of the aryl group include monocyclic or bicyclic aryl groups such as phenyl, and those having a substituent with a straight-chain or branched alkyl group.

Further, as an alkenyl group or an alkynyl group, for example, CH2-C11(C1+2) 7-1CH311:1h
GH-Cll (Cll2) 7-5CHa (Cll
2) 56H-Cll-2co3(Cll2) 7CI
I-CH-1C1h [C1h)sclI (Off)
C1hC1hCH-C1l (CH2)? -1[;
I3 (Cll2) 1 octl-CH(CJ) 4
-Cl5 (f:lh) 5CH-C)I (C)12
) e-1CI+3 (Cll2) 4ctl-C)I
Cl12CII=Cll (C1+2)? −.

GH301hCH-Cl[LCl-1-CIICthC
II-CH(C)12) 7-1CH3(CI42)
3(f;H-OH) 3(CH2)7-1CH3(CH
2) a (f; It-CI) a (C112),
+CO(C1-h) 2-1CH3(CH2) tc=
c (al12) 7-1CI+ (CH2) t+c
ll-C)I ([;112)? -1st grade carbon number 9~
There are 24 examples.

Examples of the aralkyl group include those having a structure in which an allyl group is added to an alkyl group, such as the following.

Further, in the above-mentioned form [1] or general formula [It], the values of n and m are preferably 1 to 1'00, particularly preferably 1 to 50. Furthermore, n:m is preferably 1:10 to 10:1.

General formula [I] or general formula [+1] 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 polyoxypropylene cetyl ether, polyoxyethylene polyoxypropylene behenyl ether, polyoxyethylene phenyl ether, polyoxy Ethylene ocdyl phenyl ether, oxyethylene oxybrobylene block polymer distyrenated phenol polyethylene oxyto adduct, tribenzylphenol polyethylene oxide adduct, octylphenol polyoxyethylene polyoxybrobylene adduct, etc.

Specific product examples of these nonionic surfactants include:
Examples include Nilacol manufactured by Nikko Chemicals (Saimi) and Emulgen 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 dyeing solution.

The above-mentioned nonionic surfactants can be used alone or in combination with other surfactants, such as anionic surfactants, cationic surfactants, or amphoteric surfactants. It can also be used as

Particularly preferably, nonionic surfactants are more effective in the present invention when used in combination with anionic surfactants.

The above-mentioned nonionic surfactants have an LB value in the range of 13.0 to 19.0, and are therefore useful for silicone layers in non-image areas, the back side of supports, and even rubber rollers of automatic processors. dirt is suppressed.

Examples of the anionic surfactant used in the present invention include higher alcohols, (Ca-C22) sulfate 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-81 (trade name: Shell Chemical Co., Ltd., sodium alkyl sulfate, etc.)], fatty acid alcohol phosphate ester salts (e.g., sodium salt of cetyl alcohol phosphate, etc.), alkylaryl sulfonate salts ( For example, 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, sulfonic acids of basic fatty acid esters, etc. There are 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 ether sulfates. salts (e.g. polyoxyethylene nonylphenyl ether sulfate, polyoxyethylene naphthyl ether sulfate, etc.), alkyl phosphates, polyoxyethylene alkyl ether phosphates, leaf thalene sulfonate formaldehyde condensates, polycarboxylic acid types Examples include polymeric surfactants.

The cationic surfactants include various compounds,
Examples of organic amine compounds include polyoxyethylene alkylamine, N-alkylpropylene diamine, and N-alkylpropylene diamine.
-Alkyl polyethylene polyamine, N-alkyl polyethylene polyamine dimethyl sulfate, alkyl biguanide, long chain amine oxide, alkylimidacyline, 1-
Hydroxylated 2-alkylimidacillin, 1-acedylaminoedylated 2-alkylimidacillin, 2-
Examples include alkyl-4-methyl-4-hydroxymethyloxazoline. Examples of quaternary ammonium salt compounds include long chain primary amine salts, alkyltrimedelammonium salts, dialkyldimethylammonium salts, alkylmethylammonium salts, alkyldimethylbenzylammonium salts, alkylpyridinium salts, and alkylquinolinium salts. salt, alkylisoquinolinium salt, alkylpyridinium sulfate, stearamidemethylpyridinium salt, acylaminoethyldiethylamine salt, acylaminoethylmethyldiethylammonium salt, alkylamidopropyldimethylbenzyl ammonium salt, fatty acid polyethyleneboryamide acylaminoethyl birylate Zinium salt, acylcholaminopormylmethylpyridinium salt, stearoxymethylpyridinium salt, fatty acid trimethanolamine, fatty acid triethanolamine formate, trioxyedylene fatty acid triethanolamine, fatty acid dibdelaminoethanol, cedyloxy Examples include methylpyridinium salt, p-octylphenoxyethoxyethyldimethylbenzylaminium salt, and the like. Among these compounds, cationic surfactants such as water-soluble quaternary ammonium salts are particularly effective, and include alkyltrimethylammonium salts, alkyldimethylbenzylammonium salts, ethylene oxide-added ammonium salts, and the like.

Furthermore, polymers having cationic components as repeating units are also generally cationic surfactants and are effective.

These cationic surfactants can also be used alone, but
Two or more types may be used in combination.

Among the above-mentioned amphoteric surfactants, there are those which have an amino group and an acid group in the molecule, and there are also betaine type, sulfobetaine type, sulfamino type and the like. Preferred amphoteric surfactants include N,N-dimethyl-N-alkyl-N-carboxymethylammonium betaine, N,N-dialkylaminoalkylene carboxylate, NNNN-trialkyl-N-sulfoalkylene ammonium betaine, N,N-dialkyl-
N,N-bispolyoxyethylene ammonium sulfate betaine, 2-alkyl-1-carboxymethyl-
Examples include 1-hydroxyethylimidazolinium betaine.

Further, in order to improve the dissolution of the dye, other surfactants or organic solvents within a permissible range may be added as necessary.

Dyes used in the present invention include diphenylmethane, triphenylmethane, acridine, thiazine,
There are azine-based, oxazine-based, phenazine-based, xanthine-based, anthraquinone-based, iminonaphthoquinone-based, and azomethine-based dyes, and specifically, there are the following.

Brilliant Green, Eosin, Ethyl Violet, Erythrosin B, Methyl Green, Lyristal Violet, Pesic Tsuksin, Phenolphthalein,
1.3-diphenyltriazine, alizarinlet S,
Thymolphthalein, Methyl Violet 2B, Quinaldine Red, Rose Bengal, Methanil Yellow, Thymolsulfophthalein, Xylenol Blue, Methyl Orange, Orange IV, Diphenylthiocarbazone, 2
．． 7-cyclofluorescein, paramethylet, Congo red, benzobrulin 4B, α-naphthyl red, nine blue 2B, Nile blue A1 phenacetaline, methyl violet malachite green, paratuxin, oil blue #603 (manufactured by Orient Chemical Industry Co., Ltd.) ), Oil Pink #312 (manufactured by Orient Chemical Industry Co., Ltd.), Oil Red 5B (manufactured by Orient Chemical Industry Co., Ltd.)
, Oil Blue Let #30B (manufactured by Orient Chemical Industry Co., Ltd.), Oil Red OG (manufactured by Orient Chemical Industry Co., Ltd.),
Oillet RR (manufactured by Orient Chemical Industry Co., Ltd.), Oil Green #502 (manufactured by Orient Chemical Industry Co., Ltd.), Spiron Red BEH Special (manufactured by Odogaya Chemical Industry Co., Ltd.),
Victoria Pure Blue BOH (manufactured by Odugaya Chemical Industries), Patent Pure Blue (manufactured by Sumitomo Mikuni Chemical Industries, Ltd.), Sudan Blue II (manufactured by BASF), m-cresol purple, cresol red, Rhodamine B, Rhodamine 6G, Fast Acid Violet R1 sulforhodamine B, auramine, 4-p-diethylaminophenylimino naphthoquinone, 2-carboxyanilino-4-p diethylaminophenylimino naphthoquinone,
2-carbostearylamino-4-p-dihydroxyethyl-amino-phenylimino naphthoquinone, p-methoxybenzoyl-p-diethylamino-0'methylphenyliminoacetanilide, cyano-p-diedylaminophenyliminoacetanilide, 1- Phenyl
3-Methyl-4-p-diethylaminophenylimino-
5-pyrazolone, 1-β-naphdyl-4-p-diethylaminophenylimino-5-pyrazolone, a dye having a counter anion of a basic dye or a sulfonic acid group, and the like.

Among these, triphenylmethane type, xanthine type,
Oxazine-based, thiazine-based, monoazo-based, and quinoneimide-based dyes are preferred, and triphenylmethane-based dyes are particularly preferred.

The amount of the dye used in the present invention is 0.1% to 5% by weight, preferably 0.2% to 3% by weight, based on the dye solution.

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

The dyeing liquid of the present invention is preferably used for dyeing waterless planographic plates, that is, plate materials in which a support is sequentially provided with a brimer layer, a photosensitive layer, and an ink repellent layer, such as a fluororesin or silicone rubber.

Acids such as inorganic acids and organic acids can be added to the staining solution of the present invention.

Preferably used inorganic acids include hydrochloric acid, phosphoric acid, polyphosphoric acid, sulfuric acid, nitric acid, sulfurous acid, nitrous acid, and boric acid.

Organic acids include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, oxalic acid, cyclohexanecarboxylic acid, cyclohexanedicarboxylic acid, tartaric acid, succinic acid, citric acid, malic acid, lactic acid, gluconic acid, tannic acid, and ascorbic acid. , levulinic acid, phthalic acid, benzoic acid, salicylic acid, gallic acid, naphthoic acid, hydroxynaphthoic acid, and the like.

Among these, particularly preferred are aliphatic carboxylic acids such as acetic acid, and oxyacids such as gluconic acid and citric acid. Furthermore, effects can be obtained even when these acids contain salts with alkali metals such as sodium and potassium.

The amount of acid added to the dyeing solution of the present invention is 0.01% by weight.
~10% by weight, preferably ~0.1% by weight
It is in the range of 5% by weight.

Furthermore, in the present invention, a chelating agent may be blended, and the chelating agent is preferably a compound that forms a chelate compound by coordinate bonding with a metal ion, such as polysulfonic acids, particularly aminopolycarboxylic acids.

This aminopolycarboxylic acid is formed by the formation 〉N (CH2+ 00011 (in the formula,
n represents 1 or 2, and R represents a hydrogen atom or an alkali metal. ) is a compound having a group represented by
If the +co2+CDOR group is represented by X, it can be classified as follows.

(1) RNX2 type compound (2) NX3 type compound (3) R-NX-C112-CH2-NX-R type compound (4) R-NX-CH2-CI-12-NH2 type compound (5) X2N-R '-NXi type and compounds 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.) Representative examples 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, carboxyethyl iminodiaic acid Il
l, N, N'-ethylenediaminediacetic acid, N-(2
-hydroxycyclohexyl)ethylenediaminetriacetic acid, N'-hydroxyethyl-ethylenediamine-N,
N,N'-triacetic acid, ethylenediaminetetraacetic acid,
Ethylenediamine-N.

N'-diacetic acid-N,N'-dipropionic acid, 1゜2-propylenediaminetetraacetic acid, trimethylenediaminetetraacetic acid, hexaethylenediaminetetraacetic acid, 1.2
-Cyclopentanediaminetetraacetic acid, trans-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-NNN-N'''-tetraacetic acid, trimethylenetetraminehexaacetic acid, and their sodium or potassium salts. .

Among these, ethylenediaminetetraacetic acid or its alkali metal salt is advantageous in terms of effectiveness and ease of availability.

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

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
This is a diazo resin shown by 1.

General formula [I] [wherein RI, R2 and R'' 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 PF6 or BF4, and Y represents -NH--3- 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, 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. Such lipophilic polymer compounds include monomers having aliphatic hydroxyl groups in their side chains, such as 2-hydroxyethyl acrylate-1 or 2-hydroxyethyl methacrylate, and other copolymerizable monomers. Examples include copolymers of 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,
Monomers having an aromatic hydroxyl group such as those 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, such as those described in U.S. Pat. No. 4,123.276. Polymers containing hydroxyethyl acrylate units or hydroxyethyl methacrylate units as the main repeating unit, natural resins such as shellac and rosin,
Polyvinyl alcohol, U.S. Patent No. 3,751,257
polyamide resins described in US Pat. No. 3,660,097, linear polyurethane resins described in US Pat. No. 3,660,097, phthalated resins of polyvinyl alcohol, epoxy resins condensed from bisphenol A and epichlorohydrin, Examples of alkali-soluble resins include novolac resins, vinyl polymers having phenolic hydroxyl groups, and condensation resins of polyhydric phenols and aldehydes or ketones described in JP-A-5557841. 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 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) -CI-CI-G- in the main chain or side chain of the polymer
Photosensitive compositions containing polymer compounds having groups such as polyesters, polyamides, and polycarbonates containing 10 H-CII-Ko as photosensitive groups in the main chain or side chain of the polymer. (e.g., U.S. Patent No. 3)
(2-Probeliden) such as cinnamylidene malonic acid;
Those based on photosensitive polyesters derived from malonic acid compounds and difunctional glycols (e.g., U.S. Pat. No. 2,956,878 and U.S. Pat. No. 3,173.7)
87); 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, 3
Photosensitive polymers such as those described in No. 72, No. 2,732,301, and the like.

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, trimedylolpropane 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-tolylene diurethane, di(2'-methacryloxyethyl)2,4-tolylene diurethane, Examples include reaction products of diol mono(meth)acrylates and diisocyanates, such as -acryloxyethyl) trimethylene diurethane.

As the photopolymerization initiator of the component (b), for example, J,
Kosar Station “Light Sensitive Systems”
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 (c). 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 their type, or generally depends on the photosensitive composition contained in the photosensitive coating solution. 0.01 to 20% by weight, preferably 0.05 to 20% by weight based on the product
10% by weight is suitable.

The ink repellent layer used in the present invention is not particularly limited as long as it has ink repellency, such as a silicone rubber layer or a fluororesin layer used in this technical field.

In particular, it is preferable to use a condensation crosslinked silicone rubber layer.

The silicone rubber used in the present invention is a linear organic polyester having a repeating unit represented by the following general formula [■], a molecular weight of several thousand to several hundred thousand, 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 [Ico+5i-0+-Fl where n is an integer of 2 or more, R is an alkyl group having 1 to 1 carbon atoms, a halogenated alkyl group, an alkoxyl group, a vinyl group, an aryl group, a silanol group (Of (group ), and
Preferably, 60% or more of R is a methyl group. The silanol group (OH 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 Rn5ix4-n (wherein, n is an integer of 1 to 3, and R is a monovalent 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 -011, -CR2, -0 to c, -o-N-c,
W substituents such as -CR1-Br and -In2 are not represented. Here, R2 and R3 represent the same thing as R above, and R2 and R3 may be the same or different. Moreover, Ac 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 paste polymer and a silicone crosslinking agent such as those listed above.

Specific examples of the silane coupling agent used in the present invention include HN[(CHz)+Si(OMe)+]2, vinyltriethoxysilane, Cj! (CH2) sSi (OM
e) 3,I,H3Si (08C)3,H5(Cl(
2) 3st (OMe) 3, 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 can be produced by reacting the above-mentioned base polymer with a silicone oil having repeating units represented by the following general formula [II], or by reacting a silicone oil in which about 3% of R is a vinyl group. It can also be obtained by addition reaction of silicone with a base polymer or reaction of the silicone oils with each other.

General formula [II] HR (wherein, 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 an integer of 0 or 1 or more. ) In order to obtain silicone rubber by such a crosslinking reaction, 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 (11) octoate, cobalt naphthenate, or chloroauric acid may be used.

Additionally, fillers can be mixed in to improve the strength of the silicone rubber and to obtain a silicone rubber that can withstand 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 5y10ff 23,5RX-257,5H2 manufactured by Toray Silicone.
There are silicone rubber dispersions for vapor coating such as No. 37.

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) 1hNl:H2Ct12NI((1:lh)
asi (OCH3) 5(b) tlJGE2clI
2NH(1;■2) 3si (OCH3) 2 (C
H3) (C) H2N (C1h) 3si (OEt
) 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, plastic films, glass plates, resin-coated paper, paper covered with metal foils such as aluminum, and the like.

Among these, aluminum plates are preferred.

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

Examples of the primer 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.

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 titanates 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.

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

Margin Examples 1 to 6 Below, a brimer layer with the following composition was applied on a smooth aluminum plate degreased in the usual manner so that the film thickness after curing was 15 μm. After drying, a high-pressure mercury lamp (output aow /c
m) was used to expose and cure. Note that parts represent parts by weight. Same below.

[Brimer layer composition] Copolymer of 2-hydroxyethyl methacrylate and methyl methacrylate in a molar ratio of 40/60 100 parts Trimethylolpropane triethoxy triacrylate 80 parts 2.4
-Diethylthioxanthone 4 parts p-dimethylaminobenzoic acid ethyl ester 4 parts Yellow pigment (KET-YELLOW402. Manufactured by Dainippon Ink Chemical Co., Ltd.) 8 parts White pigment (zinc oxide,
FINEX-25 (manufactured by Sakai Chemical Co., Ltd.) 25 parts Propylene glycol monomethyl ether 600 parts Next, a photosensitive composition having the following composition was applied on the brimer layer,
It was dried at 100° 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 of concentrated sulfuric acid under water cooling.

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

This reaction mixture was added dropwise to 500 mf of ethanol under ice cooling, and the resulting precipitate was filtered. After washing with ethanol, this precipitate was washed with 100mj! Dissolve in pure water and add 6. to this solution.
A cold concentrated aqueous solution of 8 g of zinc chloride was added.

The resulting precipitate was filtered, washed with ethanol, and dissolved in 150 mft of 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 lithographic printing plate requiring no dampening water was obtained.

[Silicone rubber layer composition] Dimethyl polysiloxane 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, 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 exposed plate material described above was processed using the automatic processing apparatus shown in FIG.

In Figure 1, A is the development process, B is the first water washing process, and C is the first water washing process.
indicates the dyeing process, and p indicates the second water washing process.

First, the exposed lithographic printing plate 1 is introduced into the developing process by the roller 3, and after being sprinkled with a developer, it is rubbed by the brush rolls 21, 22, 23. 64 is a tray.

Next, after being washed with water in washing section B, the material moves to dyeing step C, where it is dyed. After the staining liquid is filtered by the filter 63, it is circulated by the pump 7 and is injected from the nozzle 53.

After dyeing, it is washed with water in a second washing step.

The developer used here is 5DR-1, a positive PS plate developer manufactured by Konica Corporation, diluted 6 times with water and heated to 27°C.
A temperature-controlled solution was used.

Further, as a dyeing solution, a solution prepared according to the following composition was used and circulated for 101 minutes.

[Composition of staining solution] Crystal violet 0.2 parts Benzyl alcohol 30 parts Nonionic surfactant (polyoxyethylene lauryl ether IILB・17.0) 1
．． 0 parts anionic surfactant (sodium dodecylbenzenesulfonate) 0.2 parts water
100 parts The temperature of this staining solution was 25°C, and the staining time was 18 seconds.

In the present invention, the waterless lithographic printing plate was processed with a pre-print size of 500 lA using this development processing apparatus. At this time, the 5D
The developing tank was replenished by adding 10 cc of R-1 developer per plate.

In each plate, both the silicone rubber layer and the photosensitive layer in the image area were removed by development, and only the exposed brimer layer was evenly dyed blue, resulting in a printing plate with good visible image quality.

Further, in the dyeing solution having this composition, aggregates such as tar were not generated, and stains did not adhere to the rollers in the automatic processor or both the front and back surfaces of the plate.

Furthermore, after exposing the positive type waterless lithographic plate TAP manufactured by Toshisha Co., Ltd., the surface of the plate was rubbed with a pad using developer HP-7N manufactured by Toshisha Co., Ltd., and the silicone layer in the image area was removed and development was completed. These printing plates were dyed with a dye solution having the composition shown in Table 1.
It was inserted midway through the staining section of the processing apparatus shown in the figure, and continuous treatment was performed for a staining time of 18 seconds. The results are shown in Table-1.

Here, ΔD indicates the difference in reflection density between the image area and the non-image area.

As is clear from Margin Table 1 below, Examples 1 to 6 all had high dyeing densities and produced excellent printing plates free from agglomeration and precipitation. Moreover, since it does not contain organic solvents, an excellent staining solution can be obtained that is good for environmental hygiene and working environment.

[Effects of the Invention] The present invention provides a dyeing solution for a waterless lithographic printing plate that uses a nonionic surfactant and at least one other surfactant in combination to achieve a staining concentration sufficient to obtain a visible image. This prevents the adhesion of dirt due to agglomeration and precipitation. Furthermore, since it does not contain an organic solvent, it has the excellent effect of providing an excellent dyeing solution that is good for environmental hygiene and working environment.

[Brief explanation of the drawing]

FIG. 1 is a sectional view showing an automatic processing apparatus having a developing section and a staining section used in the present invention. Explanation of symbols 1: Passage of lithographic printing plate or lithographic printing plate 21.22.2
3.24...Brush roll 3 ・ ・ 4 ・ ・ 51 ・ 52. 53 ・61. 64 ・ 7 ・ ・ A ・ C Roller 31...Skewer roll tray 41...Guide plate/Developer shower 54.55...Wash water shower/Dyeing solution shower 62.63...Filter/Mesh filter pump/Development process B...First washing process/dying process D...Second washing process

Claims (1)

[Claims] A staining liquid for staining an image area of a waterless lithographic printing plate,
A water-free product characterized by containing water, a dye, a nonionic surfactant, further containing at least one kind of anionic surfactant, cationic surfactant, or amphoteric surfactant, and containing substantially no organic solvent. Dyeing liquid for lithographic printing plates.