JPH03273247A - Dampening-waterless photosensitive planographic printing plate - Google Patents

Abstract

PURPOSE:To prevent the staining of hands and clothing or the staining of an automatic developing machine by a dyeing liquid by incorporating a material which develops a color by reacting with the components in a processing liquid into a primer layer. CONSTITUTION:The material which develops the color by reacting with the component is the processing liquid is incorporated into the primer layer of the dampening-waterless planographic printing plate formed by successively laminating the primer layer, a photosensitive layer and an ink repulsive layer on a substrate. The color developing material to be incorporated into the primer layer is more preferably a photosensitive material and more preferably this photosensitive material causes a photochemical reaction by exposing, by which the material is decomposed or changed in properties and the capacity to develop the color by reacting with the components (couplers) in the photosensitive layer is lost without developing the color. The sharp images after the development are obtd. in this way and the staining of the hand, clothing and automatic developing machine by the dyeing liquid is prevented.

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 relates to printing that does not require dampening water and provides a clear image after development. The present invention relates to a photosensitive lithographic printing plate which does not require dampening water and does not require staining of hands or clothing with dyeing solution after development.

[Background of the Invention Ik] Conventionally, photosensitive lithographic printing plates that do not require dampening water (hereinafter referred to as 1-plate material if necessary) have been prepared by coating a photosensitive layer and an ink repellent layer in this order on a support. Are known. By exposing and developing this plate material, a lithographic printing plate that does not require dampening water (hereinafter referred to as "r printing plate" if necessary) can be obtained.

This type of plate material, as described in Japanese Patent Publication No. 55-22781, uses an aqueous developer to dissolve the unexposed area (image area) of the photosensitive layer, and as a result, the upper silicone rubber layer is dissolved. The one to be removed and the Special Publication No. 54-26923
(As described in No. 1, 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.

Among these, the one that elutes the former photosensitive layer is the one that elutes the exposed area (
Because the adhesive force between the photosensitive layer in the non-exposed area (non-image area) and the silicone rubber layer on it is sufficient, the photosensitive layer in the non-exposed area (image area) and the silicone rubber layer on it are forcibly removed (removed to remove the image). Even when formed, a printing plate with excellent scratch resistance and abrasion resistance can be produced without impairing developability.

However, with such types that elute the photosensitive layer, the photosensitive layer is removed during development, so if the photosensitive layer is colored, the resulting image after development will be a negative image. , when observing images, there is a problem that it is very difficult to see. Examples of solutions to this problem include JP-A-54-103103 and JP-A-63-13.
There are publications such as No. 3153, which specifically state that the exposed photosensitive layer and primer layer are dyed with a dye after development, but since these methods use a dyeing solution, the dye remaining after processing is This is undesirable because the liquid stains your hands and clothes, or it stains the automatic processor.

Therefore, the present inventors continued intensive research in order to improve the above-mentioned problems, and as a result, by incorporating a substance that develops color by reacting with the components in the processing liquid into the primer layer, printing plates with clear images can be produced. The present inventors have discovered that not only can dyeing liquid be obtained, but also that the dyeing solution does not stain hands or clothes or stain an automatic developing machine, leading to the completion of the present invention.

[Purpose of the Invention] Accordingly, the purpose of the present invention is to obtain a printing plate that does not require dampening water and provides a clear image after development, and to avoid staining hands or clothing with staining solution after development, etc. To provide a photosensitive planographic printing plate that does not require dampening water and does not stain a developing machine.

[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 is formed by sequentially laminating a primer layer, a photosensitive layer, and an ink repellent layer on a substrate, in which the primer layer is This was achieved using a photosensitive lithographic printing plate that does not require dampening water and is characterized by containing a substance that develops color by reacting with components.

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

The present invention is characterized in that the primer layer of a photosensitive lithographic printing plate that does not require dampening water contains a substance that develops color at the same time as development or during post-development processing. There are cases in which the developer or post-development processing solution contains a substance that reacts with the color-forming substance to form a pigment, that is, a coupler, and cases in which the primer layer contains a color-forming substance and a coupler. .

In the latter case, the color-forming substance and coupler react with each other under the catalytic action of the processing liquid to form a dye and develop color.

Preferably, the color-forming substance contained in the primer layer is a photosensitive substance, and more preferably, the photosensitive substance causes a photochemical reaction upon exposure to decompose or change in quality, resulting in a component (coupler) in the processing solution or photosensitive layer. In this case, the primer layer remaining in the non-image area has lost its ability to develop color, so the processing solution is passed through the silicone rubber layer above it. Even if it penetrates, no color develops. The revised printing plate has a thicker contrast between printed areas and non-printed areas, which is particularly advantageous.

The term "processing liquid" is used to mean either a developer or a liquid for treating a lithographic printing plate after development.

Specific examples of substances that develop color by reacting with couplers include diazo resins, such as hydrochlorides of diazo compounds, tetrafluoroborates, hexafluorophosphates, zinc chloride double salts, etc. Examples include the following:

1.

3.

Sushi 41'I9 9.

10゜11゜The treatment liquid and/or the primer layer contain a substance or coupler that reacts with the color-forming substance present in the primer to form a pigment and develop color, and the coupler includes acyl. Examples include acetanilides, 1.3-substituted pyrazolones, phenols, and naphthols. Specific compounds used include, for example, β-naphthol, 1-phenyl-3-methyl-5-pyrazolone, and 1,5-dihydroxynaphthalene, and in addition, the following compounds.

Blur is an example.

H 8.

9.

10゜n! 4 11゜n■ IH 12゜13゜11 In the present invention, a photosensitive lithographic printing plate that does not require dampening water is used, in which the primer layer contains a substance that develops color at the same time as development or during processing after development. When the printing plate is treated with a processing liquid after exposure, at the same time as development, or after development, a printing plate with excellent plate inspection properties can be obtained by processing with the processing liquid and developing color.

In addition to the above-mentioned couplers, this processing liquid contains an organic solvent for dissolving the couplers, water, a surfactant, an alkaline agent, and the like.

As the surfactant added to the treatment liquid used in the present invention, anionic surfactants, nonionic surfactants, cationic surfactants, and zwitterionic surfactants are used,
Specifically, the following can be mentioned.

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, secondary sodium alkyl sulfate, etc.) (2) Fatty alcohol phosphate ester salts (e.g.
(3) Alkylaryl sulfonate Xi (e.g., dodecylbenzenesulfonic acid sodium salt, isopropylnaphthalenesulfonic acid sodium salt, dinaphthalenesulfonic acid sodium salt, metanitrobenzenesulfonic acid sodium salt, etc.) ) (4) Alkylamide sulfonates (C+ y)IssCON-CHzC)lzsO3Na
etc.) C) Is (5) Sulfonic acid salts of dibasic aliphatic esters (e.g., sodium sulfosuccinate dioctyl ester, sodium sulfosuccinate dihexyl ester, etc.) (6) Formaldehyde condensates of alkylnaphthalene sulfonates (e.g., dibutylnaphthalene) (formaldehyde condensate of sodium 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 oxypropylene 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, but among these, anionic surfactants are commonly used.

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

The appropriate amount of the surfactant used in the present invention is 0.01% to 60% by weight, preferably 0.1% to 10% by weight.

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

The amount of alkali agent used is O,OS weight% to 20 weight%,
Preferably, 0.2% to 10% by weight is appropriate.

In the present invention, the processing solution containing a substance or coupler that reacts with the color-forming substance present in the primer layer may be the same as or different from the developer, but it is possible to develop the color at the same time as the development. It is preferable that the developing solution and the processing solution are the same.

Further, in the present invention, before coating the support with the photosensitive layer, a primer layer is provided on the support in order to obtain sufficient adhesion between the photosensitive layer and the support.

The primer layer includes, for example, polyester resin, vinyl chloride-vinyl acetate copolymer, acrylic resin, vinyl chloride 1M
Examples include resins, polyamide resins, polyvinyl butyral resins, epoxy resins, acrylate copolymers, vinyl acetate copolymers, phenoxy resins, polyurethane resins, polycarbonate S1 resins, polyacrylonitrile butadiene, and polyvinyl acetate.

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

The silicone rubber layer used in the present invention is a linear organic rubber layer having a repeating unit represented by the following general formula [I] 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 polycycloxane as a main component are preferred.

-Format [1] %Formula% Here, this is an integer of 2 or more, R is an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group, an alkoxyl group, a vinyl group, an aryl group, a silanol group (O)I 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 includes RyISIX4-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.

2 X is -OH, -0R2, -0AC1-o-N-c<-C
represents a substituent such as j, -Br, -■3, etc., where 82 and R3 represent the same as R above, R2 and R3 may be the same or different, and AC is This is a silane compound represented by ), which represents an acetyl group.

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

Specific examples of the silane coupling agent used in the present invention include HN[(CH2)ssi(OMa)slz, vinyltriethoxysilane, C1(CHz)ssi(OMa)
s, CHsSj(O^C)S,R5(CHd ssi
(OMe)s, vinyltris(methylethylketoxime)silane, and the like.

The silicone rubber described above is also available as a commercial product, such as YE-3085 manufactured by Toshiba Silicone Co., Ltd. Other useful silicone rubbers 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.

(In the formula, R has the same meaning as R, which is a substituent of the polymer represented by general formula [I], and n is an integer of 2 or more, and n is O or an integer of 1 or more.) Such a crosslinking reaction (Thus, in order 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(II) octoate, cobalt naphthenate, or chloroplatinic acid may be used.

It also improves the strength of the silicone rubber and prevents the 11! In order to obtain a silicone rubber that can withstand rubbing forces, fillers can also be mixed. Silicone rubber pre-mixed with fillers is commercially available as silicone rubber stock or silicone rubber dispersion, and when it is preferable to obtain a silicone rubber film by coating as in the present invention, R
TV or LTV silicone rubber dispersions are preferably used. Examples of this include Syl Off 23.5RX-257 manufactured by Toray Silicone.
There are silicone rubber dispersions for paper coating such as 5H237.

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) )lJcHzc)H2N)I (C)12)
ssf (DC)Is) 5(b)H2NCE2CH2
Nl((C)+2) ssl (OCI(s) x (
CHs)(c)HJ(CH2)ssi(OEt)sThe silicone rubber layer used in the present invention may further contain a small amount of a photosensitizer.

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

As the photosensitive composition used in the present invention, any known photosensitive composition can be used, but diazo resins and photopolymerizable compounds are preferably used, and diazo resins are particularly preferred.

The photosensitive composition will be specifically explained below.

(1) Photosensitive composition containing diazo tM resin The diazo resin used in the present invention includes various types, but preferably,
A diazo resin typified by a condensate of p-diazodiphenylacon and formaldehyde, which is insoluble in water and soluble in organic solvents.
Those which are water-insoluble and soluble in ordinary organic solvents are used, such as those described in Japanese Patent No. 57-43890 and the like. Particularly preferred is a diazo resin represented by the following general formula [1].

The following is a general formula [I] in which 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 an anion, Y represents -NH--5- or -〇-.As the diazo monomer in the diazo resin used in the present invention, the above-mentioned diazo compounds can be used, preferably, for example, , 4-diazodiphenylamine, 3
-methoxy-4-diazodiphenylamine and 3-ethoxy-4-diazodiphenylamine.

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

Furthermore, as the anion, use of chlorine ion, tetrachlorozinc acid, etc. (more water-soluble diazo resin can be obtained, and boron tetrafluoride, hexafluorophosphoric acid, triisopropylnaphthalene sulfonic acid, etc.) 4.4 '-Biphenyldisulfonic acid, 2,5-dimethylbenzenesulfonic acid, 2-nitrobenzenesulfonic acid, 2-methoxy-4-
By using hydroxy-5-benzoyl-benzenesulfonic acid or the like, an organic solvent-soluble diazo resin can be obtained. Particularly preferably, a diazo resin made of hexafluorophosphoric acid is used.

It is preferable to use the diazo resin in combination with a film-forming resin (binder), especially a lipophilic polymer compound having a hydroxyl group. Mention may be made of copolymers of monomers such as 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate with other copolymerizable monomers. In addition to these, polyvinyl butyral resin, polyurethane resin, polyamide resin, epoxy resin, novolac resin, other 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,
Carmers 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-1m-1 or p-hydroxyphenyl methacrylate, etc. with other monomers, hydroxyethyl acrylate as described in U.S. Pat. No. 4,123,276; Polymers containing hydroxyethyl methacrylate units or hydroxyethyl methacrylate units as main repeating units, natural resins such as shellac and rosin, boria yodo phase resins described in polyvinyl alcohol, U.S. Pat. No. 3,66
Linear polyurethane resins described in the specification of No. 0,097, phthalated resins of polyvinyl alcohol, epoxy resins condensed from bisphenol A and epichlorohydrin, alkali-soluble resins such as novolac resins, vinyl having phenolic hydroxyl groups, etc. Examples include condensation resins of polyhydric phenols and aldehydes or ketones described in JP-A-55-57841. Examples of the novolac resin include phenol/formaldehyde resin, cresol/formaldehyde resin, phenol/cresol/formaldehyde copolycondensation resin as described in JP-A-55-127553, and JP-A-55-1-27553. p-substituted phenols and phenols as described in
Examples include copolycondensation resins of cresol and formaldehyde.

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

1 (2) A photosensitive composition containing a polymer compound having one CH-C)I-ε- group in the main chain or side chain of the polymer. Those whose main component is a photosensitive polymer such as polyesters, polyamides, and polycarbonates containing one CH-CH-(nee) as a photosensitive group in the side chain (for example, U.S. Pat. No. YS 3,030,208, 3.

707,373 and N3,453,237); photosensitive polyesters derived from (2-probelidene) malonic acid compounds such as cinnamylidene malonic acid and difunctional glycols; (e.g. photopolymers such as those described in U.S. Pat. Nos. 2,956,878 and 3,173,787); polyvinyl alcohol, starch, cellulose and the like. cinnamate esters of hydroxyl-containing polymers such as
No. 2,752,372, No. 2.732,30
Photosensitive polymers such as those described in No. 1 etc.

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

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 acid 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)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( Examples include reaction products of diol mono(meth)acrylate and diisocyanate such as 2-acryloxethyl)trimethylene diurethane.

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 N5. More specifically, it is disclosed in British Patent No. 11,459,563.

Furthermore, various known polymers can be used as the binder for component (c). Details of specific binders are described in US Pat. No. 4,072,527.

a fat-sensitizing agent added to the photosensitive composition as necessary;
The amount of additives such as surfactants, sensitizers, stabilizers, thermal polymerization inhibitors, plasticizers, and pigments such as dyes and pigments varies depending on the type, but they are generally included in photosensitive coating solutions. A suitable amount is 0.01 to 20% by weight, preferably 0.05 to 10% by weight, based on the photosensitive composition.

The support used in the plate material of the present invention is preferably one that is flexible enough to be set in a normal lithographic printing machine and that can withstand the applied load, such as a metal plate such as aluminum, zinc, copper, or steel. , and 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 foil such as aluminum, and the like.

Among these, aluminum plates are preferred.

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

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

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

The thickness of each layer constituting the plate material of the present invention is as follows. That is, the support is 50 to 1000μ straw, preferably 10
0 to 300 μm, photosensitive layer O, OS to 10 μm, preferably 0.5 to 5.0 μm, silicone rubber layer 0.5 to 10 μm
It is 100 μm, preferably 1 to 4 μm.

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

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

A composition solution to form a photosensitive layer is applied onto a support using a conventional coater such as a reverse roll coater, an air knife coater, a Meyer bar coater, or a rotary wave cloth apparatus such as a Whaler, and then dried.

If necessary, a primer layer is provided between the support and the photosensitive layer in the same manner as for the photosensitive layer, and after curing by heating or exposure, the photosensitive layer is coated and dried, and then a silicone layer is applied on the photosensitive layer. A rubber solution is applied in a similar manner, usually 10
Heat treatment is performed at a temperature of 0 to 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 dampening water using the plate material that does not require dampening water of the present invention will be explained.

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

Next, the positive film is peeled off and developed using a developer. As the developer, any known developer can be used for plate materials that do not require dampening water, but preferably an aqueous developer is used.

The aqueous developer refers to 301% or more of water, preferably 5% or more of water.
Examples include a developer containing an organic solvent and a surfactant in an amount of 0% to 98% by weight, and more preferably an alkali agent.

More preferably, the photosensitive layer contains a substance that reacts with the color-forming substance or the above-mentioned coupler so that the color-forming substance present in the photosensitive layer can develop color at the same time as development.

Organic solvents contained in water-based developers include:
For example, aliphatic hydrocarbons (hexane, heptane, 'Isoper E, H, G' (trade name of aliphatic hydrocarbons manufactured by Esso Chemical Co., Ltd.), gasoline, kerosene, etc.), aromatic hydrocarbons (toluene, xylene, etc.), halogenated hydrocarbons (triclene, etc.), alcohols (methanol,
Ethanol, 1-butoxy-2-propatol, 3-methyl-3-methoxybutanol, benzyl alcohol, etc.), ethers (methyl cellosolve, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, methyl calpitol, ethyl calpitol, butyl calpitol) ,
dioxane, diethylene glycol dimethyl ether,
Diethylene glycol diethyl ether, diethylene glycol dibutyl ether, ethylene glycol dibutyl ether, propylene glycol, dipropylene glycol butyl ether, tripropylene glycol methyl ether, polypropylene glycol methyl ether, etc.), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, 4- methyl-1,3-dioxolan-2-one, etc.), esters (
ethyl acetate, propyl acetate, hexyl acetate, methyl butyrate, propyl butyrate, diethyl succinate, dibutyl oxalate, diethyl maleate, benzyl benzoate, methyl cellosolve acetate, cellosolve acetate, carpitol acetate, etc.).

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

Examples of anionic surfactants include (1) higher alcohol sulfate esters (e.g. sodium salt of lauryl alcohol sulfate, ammonium salt of octyl alcohol sulfate, ammonium salt of lauryl alcohol sulfate, sulfur sodium alkyl sulfate, etc.) (2) Fat Group alcohol phosphate ester salts (e.g.
(3) Alkylaryl sulfonic acid salts (e.g., dodecylbenzenesulfonic acid sodium salt, isopropylnaphthalenesulfonic acid sodium salt, dinaphthalenesulfonic acid sodium salt, metanitrobenzenesulfonic acid sodium salt, etc.) (4) Alkylamide sulfonates (C17)135CON-C)12CH2SOsNa, etc.) H3 (5) Sulfonates of dibasic aliphatic esters (e.g. sodium sulfosuccinate dioctyl ester, sodium sulfosuccinate dihexyl ester, etc.) (6) Examples include formaldehyde condensates of alkylnaphthalene sulfonates (for example, formaldehyde condensates of sodium 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 oxypropylene block polymer, etc. Can be mentioned.

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

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

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

The appropriate amount of the surfactant used in the present invention is 0.01% to 60% by weight, preferably 0.11% to 10% by weight.

Furthermore, the alkaline agents used in the present invention C include (1) sodium silicate, potassium silicate, potassium hydroxide, sodium hydroxide, lithium hydroxide, dibasic or tribasic sodium or ammonium phosphate, metasilicic acid; Inorganic alkaline agents such as sodium, sodium carbonate, ammonia, (2) mono, di or trimethylamine, mono, di or triethylamine, mono or diisopropylamine, n-butylamine, mono, di or triethanolamine, mono, di or triisopropylamine. Examples include organic amine compounds such as patoolamine, ethyleneimine, and ethylenediimine.

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

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, the printing plate from which part or all of the photosensitive layer and the silicone rubber in the unexposed area have been removed, or only the silicone rubber layer is removed, exposing the photosensitive layer or the colored primer layer, and the exposed area is covered with silicone. A printing plate is obtained in which the rubber layer and the photosensitive layer which does not substantially develop C color remain.

Example-1 Synthesis of diazo resin-1 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 5 QOtnl of ethanol under water cooling, and the resulting precipitate was filtered. After washing with ethanol,
Dissolve this precipitate in 100 mA' pure water, and add 6
．． A cold concentrated aqueous solution of 8 g of zinc chloride was added.

The resulting precipitate was filtered, washed with ethanol, and dissolved in 15 On+u 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.

Manufacture of aluminum plate a: An aluminum plate with a thickness of 0.2 (is) was immersed in a 3% aqueous sodium hydroxide solution to degrease it, washed with water, and then immersed in a 32% aqueous sulfuric acid solution at a temperature of 30°C under the conditions of 5 A/ds. anodized for 10 seconds, washed with water, immersed in a 2% sodium metasilicate aqueous solution at a temperature of 85°C for 37 seconds, further immersed in water (pH 8.5) at a temperature of 90°C for 25 seconds, washed with water,
It was dried to obtain aluminum plate a.

A primer layer composition having the composition shown below was applied to an aluminum plate a, and after drying at 85°C for 3 minutes, it was heated to 1000°C using a 3KW ultra-high pressure mercury lamp. The entire surface of IJ/C1 was exposed.

Further, it was dried at 100° C. for 4 minutes to form a primer layer with a thickness of 3.0 μI.

Primer layer composition (1) Diazo resin - 18 parts (2) Copolymer resin of 2-hydroxyethyl methacrylate and methyl methacrylate in a molar ratio of 34/84 - 192 parts (3) FINEX-25 (manufactured by Sakai Chemical Co., Ltd.) Zinc oxide pigment) 30 parts (4) Methyl cellosolve 870 parts Next, the support on which the primer layer was formed was immersed in the following diazo compound solution for 1 minute to incorporate the diazo compound into the primer layer, and was washed with water and dried.

[Diazo compound solution] 2.5-dibutoxy-4-morpholinobenzenediazonium fluoroborate 10 parts 2-methyl-4
-N,N-diethylaminobenzenediazonium fluoroborate 10 parts tartaric acid
10 parts methanol 3
00 parts acetone 600 parts methyl ethyl ketone ioo parts Next, a photosensitive composition having the following composition was applied on the primer layer, and 1
The photosensitive layer was dried at 00° C. for 2 minutes to form a photosensitive layer with a thickness of 0.3 μm.

[rSS photosensitive composition here 1) Diazo resin - 150 parts (2) 2-hydroxyethyl methacrylate, N(4-
Copolymer resin of hydroxyphenyl) methacrylamide and methacrylic acid with a molar ratio of 4515015 - 150 parts (3) Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd.)
Co., Ltd., Dye) 1 part (5) Methyl lactate 3900 parts Next, the following silicone rubber composition was applied to the photosensitive layer at a dry weight of 1.8 g/m.
It was applied and dried at 90°C for 10 minutes.

[Silicone rubber layer composition] (1) 100 parts of dimethylpolysiloxane having hydroxyl groups at both ends (molecular weight 82,000) (2) 5 parts of triacetoxymethylsilane (3) Tris(trimethoxysilylpropyl) cyanurate
2.5 parts (4) dibutyltin laurate
0.8 parts (5) Isopar E (Esso Chemical) 900
Next, a 5 μm thick polypropylene film was laminated on the silicone rubber layer to obtain a waterless planographic plate.

After vacuum-adhering a positive film to the top surface of the above plate material, it was exposed to light using a metal halide lamp as a light source.
Next, after immersing it in the developer-1 below for 1 minute, the surface of the plate material is rubbed with a pad impregnated with the developer.
A printing plate was obtained in which the silicone rubber layer in the unexposed areas was removed, the halftone dots were well reproduced, and the primer layer in the unexposed areas, which were the image areas, was colored blue.

[Developer-1] Benzyl alcohol 5 parts Perex NBL (manufactured by Kao Atlas Co., Ltd. Anionic surfactant 3
5% aqueous solution) 6 parts jetanolamine
2-part monoethanolamine
3-part 2-hydroxy-N-(2-methylphenyl)-3-naphthamide
3 parts propylene glycol 10 parts water

8 parts 7 parts Example 2 Photosensitive composition of Example-1, silicone rubber layer composition,
A lithographic printing plate material that did not require dampening water was obtained in the same manner as in Example 1, except that the developer was changed as follows.

[Photosensitive composition-2] (1) 2-hydroxyethyl methacrylate, N(4-
Molar ratio of hydroxyphenyl) methacrylamide, methacrylic acid, acrylonitrile, allyl methacrylate: 4
0/40/1515/10 copolymer resin - 265 parts (2) Pentaerythritol triacrylate 15 parts (3> Tetramethylolmethane tetraacrylate)


201! (4) Victoria Pure Blue B
OH (manufactured by Hodogaya Chemical Co., Ltd., dye)
Part 1 (5) Kayacure DETX (Nippon Kayaku Co., Ltd.)
5 parts (6) Kayacure FEP (manufactured by Nippon Kayaku Co., Ltd., photopolymerization initiator) 2 parts (7) Methyl lactate
1900 parts [Silicone rubber layer composition] Dimethylpolysiloxane having hydroxyl groups at both ends (molecular weight 82.0 (10)) 100 parts triacetoxyvinylsilane 5 parts 1-trimethoxysilylpropyl-3,5-diallyl cyanurate 2
．． 5 parts dibutyltin laurate 0.8 parts Isopar E (manufactured by Esso Chemical) 900 parts [Developer -2
Cobenzyl alcohol 2 parts Perex NBL (Kao Atlas Co., Ltd. Anionic surfactant 3
5% aqueous solution) 6 parts jetanolamine
2 parts N-(2-hydroxyethyl)-3,5-dihydroxybenzamide
3 parts propylene glycol 20
Department water
A printing plate was obtained in which the 6th and 7th halftone dots were well reproduced and the primer layer in the unexposed area, which was the image area, was red (colored).

Comparative Example 1 A lithographic printing plate material requiring no dampening water was obtained in the same manner as in Example 1, except that the immersion treatment with the diazo compound solution in Example 1 was not performed.

Same as Example-1 Il&: A printing plate with good halftone dots was obtained, but the image area did not develop color and the image after development was unclear.
It was necessary to stain the printed areas with a dye solution.

Example-3 Photosensitive composition of Example-1, silicone rubber layer composition,
A lithographic printing plate material that did not require dampening water was obtained in the same manner as in Example 1, except that the developer was changed as follows.

[Developer-3] Benzyl alcohol 2 parts Perex NBL (manufactured by Kao Atlas Co., Ltd. Anionic surfactant 3
5% aqueous solution) 6 parts jetanolamine
2 parts N-(2-hydroxyethyl)-3,5-dihydroxybenzamide
3 parts propylene glycol 2
0 parts water
A printing plate was obtained in which the 67-part halftone dot was well reproduced and the primer layer in the unexposed area, which was the image area, was colored red.

Example-4 A primer layer composition having the following composition was applied to the aluminum plate a produced in Example-1, and after drying at 85°C for 3 minutes, a 3KW ultra-high pressure mercury lamp was used to heat the primer layer at 100hJ/c+o.
"The entire surface was exposed to light. Further, it was dried at 100° C. for 4 minutes to form a primer layer with a thickness of 3.0 μm.

Primer layer composition (1) Diazo resin - 18 parts (2) Copolymer resin of 2-hydroxyethyl methacrylate and methyl methacrylate in a molar ratio of 34/64 - 192 parts (3) FINEX-25 (manufactured by Sakai Chemical Co., Ltd.) (zinc oxide pigment) 30 parts (4) 870 parts of methylcerone lubricant Next, the support on which the above primer layer was formed was added to a solution of the following diazo compound and coupler.
The diazo compound and coupler were incorporated into the primer layer, washed with water, and dried.

[Diazo compound solution] 2.5-dibutoxy-4-morpholinobenzenediazonium fluoroborate 10 parts 2-methyl-4
-N,N-diethylaminobenzenediazonium fluoroborate 10 parts tartaric acid
10 parts methanol
300 parts Acetone 600 parts Methyl ethyl ketone Ioo parts 2-Hydroxy-N-(2-methylphenyl)-3-naphthamide 18 parts Next, apply a photosensitive composition having the following composition on the primer layer! ! ! A photosensitive layer having a thickness of 0.3 μm was formed by drying at 100° C. for 2 minutes.

[Photosensitive composition] (1) Diazo resin - 150 parts (2) 2-hydroxyethyl methacrylate, N(4-
Copolymer resin of hydroxyphenyl) methacrylamide and methacrylic acid with a molar ratio of 4515015 - 150 parts (3) Victoria Vinia Blue BOH (Hodogaya Chemical Co., Ltd.)
Co., Ltd., Dye) 1 part (5) Methyl lactate 3900 parts Next, the following silicone rubber composition was spread on the photosensitive layer at a dry weight of 1.8 g/l, and dried at 90°C for 10 minutes. .

(Silicone rubber layer composition) (1) Dimethylpolysiloxane having hydroxyl groups at both ends (molecular weight 82,000) 100 parts (2) Triacetoxymethylsilane 5 parts (3) Tris(trimethoxysilylpropyl) cyanurate
2.5 parts (4) dibutyltin laurate
0.8 parts (5) Isopar E (Esso Chemical) 900
Next, a 5 μm thick polypropylene film was laminated on the silicone rubber layer to obtain a waterless planographic plate.

After the upper surface of the above plate material was brought into close contact with the 2-positive film in vacuum, it was exposed to light using a metal halide lamp as a light source.
Next, after immersing it in the developer-1 below for 1 minute, the surface of the plate material is rubbed with a pad impregnated with the developer.
A printing plate was obtained in which the silicone rubber layer in the unexposed areas was removed, the halftone dots were well reproduced, and the primer layer in the unexposed areas, which were the image areas, was colored blue.

[Developer-4] Benzyl alcohol 5 parts Perex NBL (manufactured by Kao Atlas Co., Ltd. Anionic surfactant 3
5% aqueous solution) 6 parts jetanolamine
2-part monoethanolamine
3-part propylene glycol
10 parts water
8 parts 7 parts Example-5 After exposing the dampening water-free lithographic printing plate material obtained in Example-4,
0 developed in the same manner as in Example-4 using the following developer-5.
Then, it was immersed in the following treatment liquid-1 for 1 minute. Example-4
Similarly, a printing plate was obtained in which the halftone dots were well reproduced and the unexposed areas, which were the image areas, were colored blue.

(Developer-5) Benzyl alcohol 5 parts Perex NBL 6 parts Propylene glycol 29 parts Water
60 parts (processing liquid-r
) Monoethanolamine 3 parts water
9
The image area on copy 7 does not develop color during development;
Color developed only after treatment with treatment solution-1.

Example 6 A lithographic printing plate material requiring no dampening water was obtained in the same manner as in Example 4, except that the photosensitive composition and silicone rubber layer composition of Example 4 were changed as follows.

[Photosensitive composition-2] (1) 2-hydroxyethyl methacrylate, N(4-
Molar ratio of hydroxyphenyl) methacrylamide, methacrylic acid, acrylonitrile, allyl methacrylate: 4
Copolymerization of 0/40/1515/1O 1 [-265 parts (2) 15 parts of pentaerythritol triacrylate (3) Tetramethylolmethane tetraacrylate


20 parts (4) Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd., dye) 1 part (
5) Kayacure DETX (manufactured by Nippon Ka1ii Co., Ltd.,
Photopolymerization initiator) 5 parts (6) Kayacure FEP (manufactured by Nippon Kayaku C Co., Ltd., photopolymerization accelerator)
Part 2 (7) Methyl lactate
1900 parts [Silicone rubber layer composition] Dimethylpolysiloxane having hydroxyl groups at both ends (molecular weight 82,000) 100 parts triacetoxyvinylsilane 5 parts 1-trimethoxysilylpropyl-3,5-diallyl cyanurate
2.5 parts dibutyltin laurate
O, a part Isopar E (manufactured by Esso Chemical)
A printing plate was obtained in which the 900-copy halftone dots were well reproduced and the primer layer in the unexposed areas, which were the image areas, was colored blue.

Comparative Example 1 A lithographic printing plate material requiring no dampening water was obtained in the same manner as in Example 1, except that the immersion treatment with the diazo compound solution in Example 1 was not performed.

A printing plate with good halftone dots was obtained as in Example-1, but
The image area did not develop color and the image after development was unclear, requiring staining of the image area with a dye solution.

Example 7 A lithographic printing plate material that did not require dampening water was obtained in the same manner as in Example 4, except that the diazo compound solution in Example 911-4 was changed as follows.

[Diazo compound solution] 2.5-dibutoxy-4-solfolinobenzenediazonium fluoroborate 10 parts 1 methyl-4-
N,N-diethylaminobenzenediazonium fluoroborate 10 parts tartaric acid
10 parts methanol 3
00 parts Acetone 600 parts Methyl ethyl ketone 100 parts N-(2-
Hydroxyethyl) -3,5-dihydroxybenzamide 18 A printing plate was obtained in which the halftone dots were well reproduced and the primer layer in the unexposed areas, which were the image areas, was colored red.

[Effects of the Invention] The present invention provides a clear image after development or processing by containing a substance that develops color in the primer layer at the same time as development or during relaxation after development; You won't get your hands or clothes dirty with the dye solution, or your automatic processor.

Claims (1)

[Claims] In a photosensitive lithographic printing plate that does not require dampening water and is formed by sequentially laminating a primer layer, a photosensitive layer, and an ink repellent layer on a substrate, the primer layer contains a substance that develops color at the same time as development or during post-development processing. A photosensitive lithographic printing plate that does not require dampening water.