JPH07120911A - Waterless lithographic printing master plate - Google Patents

Abstract

PURPOSE:To obtain a master plate having excellent printing durability and high sensitivity by incorporating specified several compds. into a photosensitive layer. CONSTITUTION:The photosensitive layer contains at least each one compd. of two ester compds. One is obtd. by partially crosslinking a compd. having at least one structure expressed by formula I with a polyfunctional crosslinking agent and then estrifying the compd. with a quinonediazide compd. The other is obtd. by partially crosslinking a compd. having at least one structure expressed by formula II with a polyfunctional crosslinking agent and then partially estrifying the compd. with a quinonediazide compd. In formulae I and II, R1 is at least one element selected from sulfur atom, substd. or unsubstd. nitrogen atom, substd. or unsubstd. carbon atom, and substd. or unsubstd. silicon atom. R2-R5 are substituents and may be the same or different from each other.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a waterless planographic printing plate, and more specifically, a waterless planographic printing plate comprising a support and a photosensitive layer and an ink-repellent silicone rubber layer in this order. It is about.

[0002]

2. Description of the Related Art Conventionally, various printing plates have been proposed for using a silicone rubber layer as an ink repellent layer and performing lithographic printing without using fountain solution.

Among these, waterless planographic printing plate precursors in which a silicone rubber layer is provided on a photosensitive layer made of a quinonediazide compound and a resin such as phenol novolac resin on a support are JP-B-61-54222 and JP-B-42222. 61-5
8824, Japanese Patent Publication No. 63-23546, Japanese Patent Publication No. 2-617
30, Japanese Patent Publication No. 2-62857, Japanese Patent Publication No. 3-36208,
Japanese Patent Publication 3-56365, Japanese Patent Publication 3-56624, Japanese Patent Publication 3-65539, Japanese Patent Publication 4-1900, Japanese Patent Publication 4-29
42, JP-B-4-3864, JP-B-4-44262, JP-B-4-49702 and the like.

For the photosensitive layer of these waterless planographic printing plate precursors, those obtained by reacting a quinonediazide compound with a hydroxyl group of a resin such as a phenol novolac resin are used, but these resins have the drawback of being hard and brittle. In particular, when offset printing is carried out, the photosensitive layer is destroyed, and the silicone rubber layer is cracked, resulting in a drawback that high printing durability cannot be obtained.

In order to solve this problem, a method of using a compound having a hydroxyl group on an aliphatic hydrocarbon instead of a compound having a hydroxyl group directly on an aromatic ring such as phenol is conceivable, but has the disadvantage of poor sensitivity. Had. Further, when such a compound having a hydroxyl group in an aliphatic hydrocarbon is used, the shape retention of the film is low and minute cissing occurs when the film is formed into a thin film.

Further, these compounds have poor solvent resistance to an organic solvent, and when developing with an organic solvent, a part of the photosensitive layer is dissolved, or a part of the photosensitive layer is also dissolved by the solvent in the ink. However, it has a drawback that high printing durability cannot be obtained.

In order to solve this problem, there are known methods of crosslinking the photosensitive layer with a polyfunctional crosslinking agent or making it insoluble by using a monofunctional compound. However, a resin such as a phenol novolac resin is partially modified with a quinonediazide compound. It is difficult to react the esterified compound with a polyfunctional crosslinking agent or a monofunctional compound, resulting in insufficient reaction,
When printing for a long time, sufficient printing durability could not be obtained.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above problems and to provide a waterless lithographic printing plate precursor having excellent printing durability and high sensitivity. It is in.

[0009]

The object of the invention is to provide a waterless planographic printing plate precursor comprising a support and a photosensitive layer and a silicone rubber layer laminated in this order on the support.
(A) After partially crosslinking a compound having at least one structure represented by the following general formula (I) with a polyfunctional crosslinking agent,
A compound esterified with a quinonediazide compound,
(B) A compound having at least one structure represented by the following general formula (II) is partially crosslinked with a polyfunctional crosslinking agent and then at least one of each of the compounds partially esterified with a quinonediazide compound is contained. Achieved by a waterless lithographic printing plate precursor featuring.

[0010]

[Chemical 3]

[Chemical 4] (In the formula, R1 is at least one selected from the group consisting of a sulfur atom, a substituted or unsubstituted nitrogen atom, a substituted or unsubstituted carbon atom, and a substituted or unsubstituted silicon atom. R2, R3, R4, R5. Are substituents, which may be the same or different.) The support used in the present invention may be any of those used in ordinary waterless planographic printing plates or those proposed. Examples thereof include metal plates such as aluminum, copper, zinc and steel, plastic films or sheets such as polyethylene terephthalate, polystyrene and polypropylene, chloroprene rubber, supports having rubber elasticity such as NBR, and coated paper. Not limited to. Appropriate processing may be applied to the surface of these supports to improve the adhesion to the upper layer.

It is possible to further coat a primer layer on these supports for the purpose of preventing halation and for other purposes. As the constituent components of the primer layer, for example, epoxy resin, acrylic resin, urea resin, polyurethane resin, polyester resin, polystyrene resin, amide resin, menamine resin, benzoguanamine resin, phenol resin, milk casein, gelatin,
Examples include, but are not limited to, soy protein, albumin, and the like. These resins can be used alone or in combination of two or more. By adding a crosslinking agent such as a polyfunctional isocyanate compound or a silane coupling agent to these resins, it is possible to improve the adhesiveness to the support or the photosensitive layer. Further, it is optional to add additives such as dyes, pigments, and photo-color formers for the purpose of improving the plate inspection property and other purposes. Further, it is also optional to add a known catalyst.

The blending ratio of each component in the primer layer is not particularly limited, but preferably 100 parts by weight of one or more of the above resins, and optionally 0 to 100 parts by weight of a crosslinking agent, a dye or Add no additives such as pigments
˜100 parts by weight, a known catalyst in an amount of 0 to 10 parts by weight, and a film thickness of 0.1 to 100 μm, more preferably 0.5 to 50 μm.
What is obtained by providing m is preferable.

Examples of the photosensitive layer used in the present invention include a photo-peeling photosensitive layer. Such a photo-releasing photosensitive layer comprises a compound having at least one structure represented by the following general formula (I) partially crosslinked with a polyfunctional crosslinking agent and then esterified with a quinonediazide compound; ) Each of the compounds having at least one structure represented by the formula (1) is partially crosslinked with a polyfunctional crosslinking agent and then esterified with a quinonediazide compound.

[0014]

[Chemical 5]

[Chemical 6] (In the formula, R1 is at least one selected from the group consisting of a sulfur atom, a substituted or unsubstituted nitrogen atom, a substituted or unsubstituted carbon atom, and a substituted or unsubstituted silicon atom. R2, R3, R4, R5. Are substituents, which may be the same or different.) A compound in which a compound having at least one structure represented by the general formula (I) is partially crosslinked with a polyfunctional crosslinking agent and then esterified with a quinonediazide compound, By containing at least one of each of the compounds having at least one structure represented by the following general formula (II) partially crosslinked with a polyfunctional crosslinking agent and then esterified with a quinonediazide compound, solvent resistance is improved. Excellent,
A part of the photosensitive layer is not dissolved and the entire photosensitive layer becomes flexible, and as a result, a waterless planographic printing plate having high printing durability can be obtained.

Specific examples of the substituent of R1 in the general formula (I) include a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group,
Amino group, mercapto group, cyano group, sulfonyl group,
A nitroso group, a substituted or unsubstituted alkyl group having 1 to 100 carbon atoms, an alkoxy group, an amide group, an acyloxy group, an alkanoyl group, a formyl group, a carboxyl group, a substituted or unsubstituted alkenyl group having 2 to 100 carbon atoms,
At least one selected from the group consisting of an alkenyloxy group, a substituted or unsubstituted aryl group having 4 to 100 carbon atoms, and an aryloxy group can be mentioned, but the present invention is not limited thereto. In addition, R2, R3, R4, R5 in the general formula (II)
As specific examples of, a hydrogen atom, a halogen atom, a hydroxyl group,
Nitro group, amino group, mercapto group, cyano group, sulfonyl group, nitroso group, substituted or unsubstituted alkyl group having 1 to 100 carbon atoms, alkoxy group, amide group, acyloxy group, alkanoyl group, formyl group, carboxyl group, At least one selected from the group consisting of a substituted or unsubstituted alkenyl group having 2 to 100 carbon atoms, an alkenyloxy group, a substituted or unsubstituted aryl group having 4 to 100 carbon atoms, and an aryloxy group, which may be the same or different. However, the present invention is not limited to these, and other materials may be used.

Examples of the compound having at least one structure represented by the general formula (I) include, but are not limited to, the following compounds.

A substituted or unsubstituted aliphatic alcohol having 1 to 10 million carbon atoms, such as ethylene glycol, propylene glycol, 1,3-butanediol, 1,4
-Butanediol, 1,6-hexanediol, 1,8
-Octanediol, 1,10-decanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, 2-butene-1,4-diol, 5
-Hexene-1,2-diol, 7-octene-1,2
-Diols, divalent saturated or unsaturated alcohols such as 3-mercapto-1,2-propanediol, glycerin, trimethylolpropane, 1,2,4-butanetriol, pentaerythritol, polyvinyl alcohol, polyhydroxyethyl acrylate, Polyhydric saturated or unsaturated alcohols such as polyhydroxyethyl methacrylate.

These compounds or other compounds having at least one structure represented by the general formula (I) are reacted alone or with two or more kinds of polyfunctional crosslinking agents to obtain a desired reaction product. You can

As the polyfunctional cross-linking agent, polyfunctional isocyanate compounds such as paraphenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, Polymethylene polyphenyl isocyanate or an adduct thereof, for example, a reaction product of glycerin and paraphenylene diisocyanate, glycerin and 4,4
Reaction product of ′ -diphenylmethane diisocyanate, reaction product of glycerin and hexamethylene diisocyanate, reaction product of trimethylolpropane and paraphenylene diisocyanate, reaction product of trimethylolpropane and 4,4′-diphenylmethane diisocyanate, trimethylolpropane and hexamethylene diisocyanate And polyfunctional epoxy compounds such as polyethylene glycol diglycidyl ethers, polypropylene glycol diglycidyl ethers, bisphenol A diglycidyl ether, trimethylolpropane triglycidyl ether, and the like. Not limited to.

The reaction ratio between the compound having at least one structure represented by the general formula (I) and the polyfunctional crosslinking agent may be any ratio as long as a hydroxyl group which can react with the quinonediazide compound remains. Preferably, the polyfunctional crosslinking agent is added in an amount of 10 to 100 relative to 100 parts by weight of the compound having at least one structure represented by the general formula (I).
It is better to react by weight. At this time, it is optional to add a known catalyst to accelerate the reaction.

Next, the compound obtained by partially crosslinking the compound having at least one structure represented by the general formula (I) with a polyfunctional crosslinking agent is esterified with a quinonediazide compound. Specific examples thereof include, but are not limited to, benzoquinone-1,2-diazidesulfonic acid and its derivative, naphthoquinone-1,2-diazidesulfonic acid and its derivative, or diazodiphenylamine and its derivative. Among these, naphthoquinone-
1,2-diazidesulfonic acid and its derivatives, especially naphthoquinone-1,2-diazidesulfonic acid chloride, naphthoquinone-1,2-diazidesulfonic acid bromide, naphthoquinone-1,2-diazidesulfonic acid sodium salt are It is valid. The esterification reaction is carried out using these quinonediazide compounds so that the degree of esterification is preferably in the range of 5 to 95%. At the time of this esterification reaction, it is optional to add a basic compound such as triethylamine, pyridine, triethylbenzylammonium chloride, triethylbenzylammonium bromide, sodium hydrogencarbonate or sodium carbonate to accelerate the reaction. The degree of esterification by the quinonediazide compound thus obtained can be determined by an elemental analysis method using the Yanagimoto Seisakusho Elemental Analyzer CHN Coder MT-3 Model.

Examples of the compound having at least one structure represented by the general formula (II) include, but are not limited to, the following compounds.

Compounds in which a hydroxyl group is directly bonded to an aromatic ring, such as 2,6-dihydroxyanthraquinone, anthralobin, phenol novolac resin and polyhydroxystyrene.

These compounds or other compounds having at least one structure represented by the general formula (II) are reacted alone or with two or more kinds of polyfunctional crosslinking agents to obtain a desired reaction product. You can

As the polyfunctional crosslinking agent, polyfunctional isocyanate compounds such as paraphenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, poly Methylene polyphenyl isocyanate or an adduct thereof, such as a reaction product of glycerin and paraphenylene diisocyanate, glycerin and 4,4
Reaction product of ′ -diphenylmethane diisocyanate, reaction product of glycerin and hexamethylene diisocyanate, reaction product of trimethylolpropane and paraphenylene diisocyanate, reaction product of trimethylolpropane and 4,4′-diphenylmethane diisocyanate, trimethylolpropane and hexamethylene diisocyanate And the like, or polyfunctional epoxy compounds such as polyethylene glycol diglycidyl ethers, polypropylene glycol diglycidyl ethers, bisphenol A diglycidyl ether, and trimethylolpropane triglycidyl ether, but are not limited thereto.

The reaction ratio between the compound having at least one structure represented by the general formula (II) and the polyfunctional crosslinking agent may be any ratio as long as a hydroxyl group capable of reacting with the quinonediazide compound remains. Preferably, the polyfunctional crosslinking agent is added in an amount of 10 to 10 relative to 100 parts by weight of the compound having at least one structure represented by formula (I).
It is preferable to react 0 part by weight. At this time, it is optional to add a known catalyst to accelerate the reaction.

Next, the compound having at least one structure represented by the general formula (II) thus partially crosslinked with a polyfunctional crosslinking agent is esterified with a quinonediazide compound. Specific examples include benzoquinone-1,2-diazidesulfonic acid and its derivatives, naphthoquinone-1,2.
Examples include, but are not limited to, diazide sulfonic acid and its derivatives, or diazodiphenylamine and its derivatives. Among these, naphthoquinone-1,2-diazidesulfonic acid and its derivatives, especially naphthoquinone-1,2-diazidesulfonic acid chloride, naphthoquinone-1,2-diazidesulfonic acid bromide, naphthoquinone-1,2-dicarboxylic acid. Azidosulfonic acid sodium salt is effective. The esterification reaction is carried out using these quinonediazide compounds so that the degree of esterification is preferably in the range of 5 to 95%. At the time of this esterification reaction, it is optional to add a basic compound such as triethylamine, pyridine, triethylbenzylammonium chloride, triethylbenzylammonium bromide, sodium hydrogencarbonate or sodium carbonate in order to accelerate the reaction. The degree of esterification by the thus-obtained quinonediazide compound can be determined by an elemental analysis method using an elemental analyzer CHN Coder MT-3 type manufactured by Yanagimoto Seisakusho.

By further cross-linking the quinonediazide-containing compound thus obtained with a polyfunctional cross-linking agent, the solvent resistance can be made higher. Examples of such a cross-linking agent include the above polyfunctional isocyanate compounds such as paraphenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, poly Methylene polyphenyl isocyanate or an adduct thereof, for example, a reaction product of glycerin and paraphenylene diisocyanate, a reaction product of glycerin and 4,4′-diphenylmethane diisocyanate, a reaction product of glycerin and hexamethylene diisocyanate, a trimethylolpropane and paraphenylene diisocyanate Reaction product, reaction product of trimethylolpropane and 4,4'-diphenylmethane diisocyanate, trimethylolpropane and hexamethylene Examples thereof include, but are not limited to, a reaction product of diisocyanate or a polyfunctional epoxy compound such as polyethylene glycol diglycidyl ethers, polypropylene glycol diglycidyl ethers, bisphenol A diglycidyl ether, and trimethylolpropane triglycidyl ether. . These curing are within the range that does not lose the photosensitivity of the photosensitive material, usually 13
It is preferable to carry out at 0 ° C. or lower, and therefore, a catalyst or the like is usually used together.

If necessary, an organic polymer compound which can be mixed with these compounds can be added to the photosensitive layer. Examples of such organic polymer compounds include, but are not limited to, the following polymers and copolymers.

Polymers of acrylic acid esters, methacrylic acid esters, acrylonitrile, such as polyethyl acrylate, polybutyl acrylate, polymethyl methacrylate, and the like, and copolymers thereof.

Unblended rubbers such as polybutadiene, polyisobutylene, polychloroprene, styrene-butadiene rubber and the like.

Vinyl polymers such as polyvinyl acetate,
Polyvinyl alcohol, polybutyl butyral and the like, and copolymers thereof.

Polyethers such as polyethylene oxide.

Reaction products of polyesters such as phthalic acid, isophthalic acid, maleic acid and adipic acid with ethylene glycol, 1,4-butanediol, 1,6-hexanediol and neopentyl glycol.

Reaction formation of polyurethane, for example, tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, etc. with polyester polyol obtained from 1,4-butanediol, 1,6-hexanediol, polyether polyol, etc. object.

Epoxy Resin Polyamide These organic polymer compounds may be used alone or in combination of two or more to improve the shape retention of the film and the like. Of these organic polymer compounds, and are particularly preferable.

Further, a known photoinitiator or photosensitizer may be added for the purpose of improving the photoreactivity of the quinonediazide compound and other purposes. As the photoinitiator or photosensitizer to be added, benzoin methyl ether, benzoin isopropyl ether, α, α-dimethoxy-α-
Benzoin derivatives such as phenylacetophenone, benzophenone, fluorenone, xanthone, thioxanthone, N-methylacridone, N-butylacridone,
4,4'-bis (dimethylamino) benzophenone,
4,4'-bis (diethylamino) benzophenone, 2
-Chlorothioxanthone, 2-isopropylthioxanthone, 2,4-diethylthioxanthone and the like, but are not limited thereto. Among these, benzophenones are particularly effective.

In addition to the above components, if necessary, a dye,
Addition of additives such as pigments and photo-color formers and known catalysts to the photosensitive layer is optional.

The mixing ratio of each component in the light-peeling photosensitive layer is not particularly limited, but preferably, the compound having at least one structure represented by the general formula (I) is partially crosslinked with a polyfunctional crosslinking agent. Degree of post-esterification 5-9
100 parts by weight of a compound partially esterified with a quinonediazide compound in a range of 5%, and a compound having at least one structure represented by the following general formula (II) are partially crosslinked with a polyfunctional crosslinking agent and then the degree of esterification is 5 to 5. 0.001 to 100,000 parts by weight of a compound partially esterified with a quinonediazide compound in a range of 95%, and 0 to 1000 of a compound which reacts with a bridging group of a crosslinking agent or a photosensitive compound.
10,000 parts by weight, 0 to 10 million parts by weight of organic polymer compound,
The photoinitiator or photosensitizer is added in an amount of 0 to 10,000 parts by weight, and if necessary, an additive or a known catalyst is added in an amount of 0 to 10,000 parts by weight to give a film thickness of 0.1 to 100 μm, preferably 0.5. -10
It is preferable to obtain it by setting the thickness in μm. If it is too thin, cissing tends to occur in the photosensitive layer, and if it is too thick, it is economically disadvantageous, so the above range is preferred.

The silicone rubber layer used in the present invention is
The following silicone rubbers can be mentioned,
It is not limited to these.

A product obtained by crosslinking an organic polysiloxane represented by the following general formula (III) and having a molecular weight of 100 to 1,000,000, preferably 1,000 to 500,000.

[0042]

[Chemical 7] (In the formula, n is an integer of 2 or more, R6 and R7 are carbon numbers 1 to 5
0-substituted or unsubstituted alkyl group, 2 to 50 carbon atoms
A substituted or unsubstituted alkenyl group having 5 to 50 carbon atoms
Of at least one substituted or unsubstituted aryl group, which may be the same or different, and particularly preferably a methyl group of 60% or more. ) Such an organic polysiloxane can be made into a further crosslinked silicone rubber by adding an organic peroxide and subjecting it to heat treatment.

As a general method for crosslinking an organic polysiloxane, a method for crosslinking an organic polysiloxane with a silicon compound having a hydrolyzable functional group directly bonded to a silicon atom can be mentioned. In particular, an organic compound having a silanol structure at its terminal is used. Cured by the reaction of polysiloxane and a silicon compound having two or more functional groups such as an alkoxy group, an acyloxy group, a ketoxime group, an amide group, an aminooxy group, an amino group, an alkenyloxy group and hydrogen directly bonded to a silicon atom. Making rubber is a commonly used method. It is also possible to cure the organic polysiloxane into a rubber with a radical initiator. In these curing, addition of a known catalyst is optional.

A compound obtained by cross-linking by an addition reaction between an organic polysiloxane having a group represented by the following general formula (IV) and a polysiloxane compound having a group represented by the following general formula (V).

[0045]

[Chemical 8]

[Chemical 9] (In the formula, R8 and R9 are each a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms. At least one selected from the group may be the same or different.) Such a silicone rubber has a polyvalent hydrogen organopolysiloxane and two or more ethylenically unsaturated bonds in one molecule. Obtained by reaction with a polysiloxane compound. Here, the group of general formula (IV) may be at either the terminal or the middle of the molecular chain. In addition, the general formula (V)
The group may be at either the terminal or the middle of the molecular chain. Examples of the organic group other than the group of the general formula (IV) and the group of the general formula (V) include a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms, Examples thereof include a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, and a methyl group having 60% or more is particularly preferable. The molecular weights of the organic polysiloxane having a group represented by the general formula (IV) and the polysiloxane compound having a group represented by the general formula (V) are preferably 100 to 1,000,000, and preferably 1,000 to 500,000. The thing is more preferable. In this addition reaction, adding a known catalyst is optional.

The blending ratio of each component in the silicone rubber layer is not particularly limited, but in the case of the silicone rubber layer, 100 parts by weight of the organic polysiloxane represented by the general formula (III) is added to the silicone rubber layer directly bonded to the silicon atom. 0.1 to 100 parts by weight of a decomposable functional group-containing silicon compound, and optionally 0 to 50 parts by weight of a known catalyst, and a film thickness of 0.1 to 100 μm, preferably 0.5 to 30 μm. It is good to obtain by providing. In the case of the silicone rubber layer, 100 parts by weight of the organic polysiloxane having a group represented by the general formula (IV), the general formula (V)
Polysiloxane compound having a group represented by 0.1-1
It may be obtained by providing it with a film thickness of 0.1 to 100 μm, preferably 0.5 to 30 μm, with a composition in which 0 to 100 parts by weight, if necessary, a known catalyst of 0 to 100 parts by weight are added.

In the waterless planographic printing plate precursor of the present invention,
Adhesion between the support and the photosensitive layer and between the photosensitive layer and the silicone rubber layer is very important for basic plate performance such as image reproducibility and printing durability. It is possible to provide or add an adhesion improving component to each layer. In particular, for adhesion between the photosensitive layer and the silicone rubber layer, it is effective to provide a known silicone primer or a silane coupling agent between the layers or add a silicone primer or a silane coupling agent to the silicone rubber layer or the photosensitive layer. When such an adhesive layer is provided, the thickness of the adhesive layer is not particularly limited,
It is good to obtain it by providing it with 0.05 to 100 μm, preferably 0.5 to 30 μm.

For the purpose of protecting the silicone rubber layer forming the surface of the waterless lithographic printing plate precursor constructed as described above, a protective film having a plain or uneven surface treatment is laminated or formed on the surface of the silicone rubber layer. It is also possible to apply or transfer a plastic sheet material to form a protective layer. The thickness of such a protective film or protective layer is not particularly limited, but is 0.0
It is good to obtain it by providing the thickness of 5 to 1000 μm, preferably 0.5 to 100 μm.

The waterless planographic printing plate precursor used in the present invention is produced, for example, as follows, but is not limited thereto. First of all, on a support, a normal roll coater such as a reverse roll coater, an air knife coater, a Mayer bar coater,
Alternatively, using a spin coater such as a hoela, or other coating device, apply a composition solution to form a primer layer if necessary, dry it, heat cure if necessary, and then form a photosensitive layer on it. The composition solution is applied, dried, and thermally cured if necessary, and then, if necessary, the composition solution for forming the adhesive layer on the photosensitive layer is applied, dried, and optionally thermally cured, and then The composition solution for forming the silicone rubber layer is applied, dried, and thermally cured if necessary, and finally, if necessary, a protective film is applied using a laminator or the like.

The waterless lithographic printing plate precursor produced in this manner is used, for example, in the case of a light-transmitting protective film as it is or after peeling, and in the case of a film having poor light-transmitting property, it is vacuum-bonded to a negative. Exposed to actinic radiation through the film. The light source used in this exposure step is one that generates abundant ultraviolet rays, and a mercury lamp, a carbon arc lamp, a xenon lamp, a metal halide lamp, a tungsten lamp, a fluorescent lamp or the like can be used.
It is not limited to these.

Then, if there is a protective film, peel it off, and then rub the plate surface with a developing pad containing a developing solution to remove the silicone rubber layer in the exposed area and, in some cases, the photosensitive layer below it. It serves as a receiver and a waterless planographic printing plate is obtained.

The developing solution used in the present invention may be any of those proposed as a developing solution for waterless lithographic printing plates, for example, water, aliphatic hydrocarbons, aromatic carbonization. Examples thereof include, but are not limited to, hydrogens, alcohols, ethers, esters, and mixtures of two or more of these.

The developing method may be manual development or development by a known developing device, but it is preferable to use a developing device in which a pretreatment section, a development section, and a posttreatment section are provided in this order.

[0054]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto.

The degree of esterification was measured by an elemental analysis method using an elemental analyzer CHN Coder MT-3 type manufactured by Yanagimoto Seisakusho.

Synthesis Example 1 50 g of 2-hydroxyethyl methacrylate was dissolved in 200 g of dioxane, 0.1 g of azobisisobutyronitrile was added, and a copolymerization reaction was carried out at 65 ° C. for 4 hours under a nitrogen atmosphere. After the reaction, the reaction solution was poured into a beaker containing 1000 g of methanol to precipitate and precipitate a product. The supernatant in the beaker was removed and dried under reduced pressure to obtain a compound having one structure represented by the general formula (I).

20 g of this compound and 2 g of hexamethylene diisocyanate were dissolved in 100 g of dioxane and 3
The reaction was carried out at 0 ° C for 6 hours.

10 g of o-naphthoquinone-1,2-diazide-5-sulfonic acid chloride was dissolved in this solution.
Next, 10 g of sodium carbonate was dissolved in 90 g of water, and the 10 wt% sodium carbonate solution was added dropwise to the above dioxane solution over 10 minutes. (At this time, the dioxane solution was stirred and the liquid temperature was kept at 40 ° C.) After completion of the dropping, the reaction was carried out at 40 ° C. for 4 hours with stirring. After the reaction, the reaction solution was poured into a beaker containing 1000 g of water to precipitate and precipitate a product. The supernatant liquid in the beaker was removed and dried under reduced pressure to obtain the target compound. The degree of esterification was 30%.

Synthesis Example 2 20 g of glycerin which is a compound having a structure represented by the general formula (I) and 3 g of diphenylmethane diisocyanate
And were dissolved in 100 g of dioxane and reacted at 30 ° C. for 6 hours.

10 g of o-naphthoquinone-1,2-diazide-4-sulfonic acid chloride was dissolved in this solution.
Next, 10 g of sodium carbonate was dissolved in 90 g of water, and the 10 wt% sodium carbonate solution was added dropwise to the above dioxane solution over 10 minutes. (At this time, the dioxane solution was stirred and the liquid temperature was kept at 40 ° C.) After completion of the dropping, the reaction was carried out at 40 ° C. for 4 hours with stirring. After the reaction, the reaction solution was poured into a beaker containing 1000 g of water to precipitate and precipitate a product. The supernatant liquid in the beaker was removed and dried under reduced pressure to obtain the target compound. The degree of esterification was 35%.

Synthesis Example 3 25 g of trimethanol propane, which is a compound having a structure represented by the general formula (I), and 2 g of paraphenylene diisocyanate were dissolved in 100 g of dioxane, and 30
The reaction was carried out at 0 ° C for 6 hours.

10 g of o-naphthoquinone-1,2-diazide-5-sulfonic acid chloride was dissolved in this solution.
Next, 10 g of sodium carbonate was dissolved in 90 g of water, and the 10 wt% sodium carbonate solution was added dropwise to the above dioxane solution over 10 minutes. (At this time, the dioxane solution was stirred and the liquid temperature was kept at 40 ° C.) After completion of the dropping, the reaction was carried out at 40 ° C. for 4 hours with stirring. After the reaction, the reaction solution was poured into a beaker containing 1000 g of water to precipitate and precipitate a product. The supernatant liquid in the beaker was removed and dried under reduced pressure to obtain the target compound. The degree of esterification was 40%.

Synthesis Example 4 25 g of poly (4-hydroxystyrene), which is a compound having one structure represented by the general formula (II), and 2 g of hexamethylene diisocyanate were dissolved in 100 g of dioxane and reacted at 30 ° C. for 6 hours. It was

10 g of o-naphthoquinone-1,2-diazide-5-sulfonic acid chloride was dissolved in this solution.
Next, 10 g of sodium carbonate was dissolved in 90 g of water, and the 10 wt% sodium carbonate solution was added dropwise to the above dioxane solution over 10 minutes. (At this time, the dioxane solution was stirred and the liquid temperature was kept at 40 ° C.) After completion of the dropping, the reaction was carried out at 40 ° C. for 4 hours with stirring. After the reaction, the reaction solution was poured into a beaker containing 1000 g of water to precipitate and precipitate a product. The supernatant liquid in the beaker was removed and dried under reduced pressure to obtain the target compound. The degree of esterification was 25%.

Synthesis Example 5 20 g of a phenol novolac resin (average molecular weight 600), which is a compound having a structure represented by the general formula (II), and 3 g of diphenylmethane diisocyanate were dissolved in 100 g of dioxane and reacted at 30 ° C. for 6 hours.

10 g of o-naphthoquinone-1,2-diazide-4-sulfonic acid chloride was dissolved in this solution.
Next, 10 g of sodium carbonate was dissolved in 90 g of water, and the 10 wt% sodium carbonate solution was added dropwise to the above dioxane solution over 10 minutes. (At this time, the dioxane solution was stirred and the liquid temperature was kept at 40 ° C.) After completion of the dropping, the reaction was carried out at 40 ° C. for 4 hours with stirring. After the reaction, the reaction solution was poured into a beaker containing 1000 g of water to precipitate and precipitate a product. The supernatant liquid in the beaker was removed and dried under reduced pressure to obtain the target compound. The degree of esterification was 25%.

Synthesis Example 6 10 g of a phenol novolac resin (average molecular weight 600), which is a compound having a structure represented by the general formula (II), and 2 g of paraphenylene diisocyanate were dissolved in 100 g of dioxane, and the mixture was heated at 30 ° C. for 6 hours. It was made to react.

10 g of o-naphthoquinone-1,2-diazide-5-sulfonic acid bromide was dissolved in this solution.
Next, 10 g of sodium carbonate was dissolved in 90 g of water, and the 10 wt% sodium carbonate solution was added dropwise to the above dioxane solution over 10 minutes. (At this time, the dioxane solution was stirred and the liquid temperature was kept at 40 ° C.) After completion of the dropping, the reaction was carried out at 40 ° C. for 4 hours with stirring. After the reaction, the reaction solution was poured into a beaker containing 1000 g of water to precipitate and precipitate a product. The supernatant liquid in the beaker was removed and dried under reduced pressure to obtain the target compound. The degree of esterification was 20%.

Example 1 An aluminum plate having a thickness of 0.3 mm was coated with the following primer composition and heat-treated at 200 ° C. for 2 minutes to give a film thickness of 5 after drying.
A μm primer layer was formed.

(A) Polyurethane resin “Samprene” LQ-T1331 (manufactured by Sanyo Kasei Co., Ltd.) 100 parts by weight (b) Blocked isocyanate “Taketate” B830 (manufactured by Takeda Pharmaceutical Co., Ltd.) 20 parts by weight (c) Epoxy -Phenolic resin "Cancoat" 90T-25-3094 (manufactured by Kansai Paint Co., Ltd.) 10 parts by weight (d) dimethylformamide 570 parts by weight The following photosensitive solution was applied thereon, and heat-treated at 110 ° C for 1 minute. Then, a photosensitive layer having a thickness of 2 μm after drying was formed.

(A) 50 parts by weight of the compound synthesized in Synthesis Example 1 (b) 50 parts by weight of the compound synthesized in Synthesis Example 4 (c) 40 parts by weight of 4,4′-diphenylmethane diisocyanate (d) Polyurethane resin “Samprene” LQ-T1331 (manufactured by Sanyo Kasei Co., Ltd.) 10 parts by weight (e) Dibutyltin dilaurate 0.2 parts by weight (f) 4,4'-Dimethylaminobenzophenone 9 parts by weight (g) Formic acid 0.8 parts by weight (h) ) Tetrahydrofuran 740 parts by weight The following silicone rubber composition is coated on this photosensitive layer, and heat-treated at 90 ° C. for 2 minutes to give a film thickness of 3 μm after drying.
The silicone rubber layer was formed.

(A) Polydimethylsiloxane having silanol groups at both ends (average molecular weight 35,000) 100 parts by weight (b) Ethyltriacetoxysilane 9.9 parts by weight (c) Dibutyltin dilaurate 0.1 parts by weight (d) Aliphatic Hydrocarbon solvent “Isopar” E (manufactured by Exxon Chemical Co., Ltd.) 590 parts by weight A 10 μm thick polypropylene film “Trefan” (manufactured by Toray Co., Ltd.) is calendered on the surface of the silicone rubber layer thus provided. A waterless planographic printing plate was obtained by laminating with a roller.

A metal halide lamp (“Idle Fin” 2000 manufactured by Iwasaki Electric Co., Ltd.) was used for this printing plate precursor, and a UV meter (“Light Measure Type UV-402A” manufactured by Oak Manufacturing Co., Ltd.) was used with an illuminance of 11 mW / cm ^2.
The whole surface was exposed for a second.

1 is added to the printing plate precursor obtained as described above.
A negative film having a halftone dot image of 50 lines / inch was vacuum-contacted and exposed for 60 seconds from a distance of 1 m using the above metal halide lamp.

After exposure, the protective film "Trephan" was peeled off, and a pretreatment liquid having the following composition was applied to the plate surface under the conditions of room temperature of 32 ° C. and humidity of 80%, and treated for 1 minute.

(A) Aliphatic hydrocarbon solvent “Isopar” H (manufactured by Exxon Chemical Co., Ltd.) 87 parts by weight (b) Diethylene glycol dimethyl ether 7 parts by weight (c) Ethyl cellosolve 3 parts by weight (d) N-methyldiethanolamine 3 parts by weight A processing solution adhering to the plate surface was removed with a rubber squeegee, and then a developing solution having the following composition was poured on the plate surface and the developing pad.

(A) 70 parts by weight of water (b) 28 parts by weight of butyl carbitol (c) 1.8 parts by weight of 2-ethylbutyric acid (d) 0.2 parts by weight of crystal violet When the plate surface is lightly rubbed with a developing pad, The silicone rubber layer in the image-exposed portion was removed, and the photosensitive layer surface was exposed. On the other hand, the silicone rubber layer remained firmly in the non-image area where only the entire surface was exposed, and an image faithfully reproducing the negative film was obtained.

This printing plate was applied to a commercial off-wheel printing press (“LIT
HOPIA "Made by Mitsubishi Heavy Industries, Ltd.", Dainippon Ink and Chemicals Co., Ltd. "Dry color" ink, indigo, red,
Using yellow ink, 600r. p. m. Printing on high-quality paper at a speed of 100
Good printed matter was printed even after printing 00 copies, and the printing plate was inspected after the printing was completed, but the printing plate was found to be slightly damaged, and it was possible to continue printing.

Comparative Example 1 In the waterless planographic printing plate precursor of Example 1, a printing plate was prepared, exposed and developed in the same manner as in Example 1 except that the photosensitive layer was provided by the following composition liquid. .

(A) Partial ester (esterification degree 25%) of o-naphthoquinone-1,2-diazide-5-sulfonic acid and phenol formaldehyde novolac resin (“Sumilite resin” PR 50622 manufactured by Sumitomo Durez) 100% by weight Parts (b) 4,4'-diphenylmethane diisocyanate 40 parts by weight (c) Polyurethane resin "Samprene" LQ-T1331 (manufactured by Sanyo Kasei Co., Ltd.) 10 parts by weight (d) Dibutyltin dilaurate 0.2 parts by weight (e) 4,4′-Dimethylaminobenzophenone 9 parts by weight (f) Formic acid 0.8 parts by weight (g) Tetrahydrofuran 740 parts by weight Using this printing plate, a commercial off-wheel printer (“LITHOPIA” Mitsubishi Heavy Industries) was used in the same manner as in Example 1. "Dry color" manufactured by Dainippon Ink and Chemicals, Inc.
Ink, indigo, crimson, yellow ink, 600 r. p. m. As a result of printing durability test after printing on high-quality paper at the speed of, the printed matter was stained after printing 50,000 copies, and when the printing plate was inspected, the printing plate was severely damaged and it was not possible to continue printing. It was possible.

Example 2 An aluminum plate having a thickness of 0.3 mm was coated with the following primer composition and heat-treated at 200 ° C. for 2 minutes to give a film thickness of 5 after drying.
A μm primer layer was formed.

(A) Polyurethane resin “PANTEX” T-5201 (manufactured by Dainippon Ink and Chemicals, Inc.) 100 parts by weight (b) Blocked isocyanate “Coronate” 2503 (manufactured by Nippon Polyurethane Industry Co., Ltd.) 20 parts by weight (C) Epoxy / phenol / urea resin SJ9372 (manufactured by Kansai Paint Co., Ltd.) 10 parts by weight (d) dimethylformamide 570 parts by weight Onto this, the following photosensitive solution was applied and heated at 110 ° C. for 1 minute, A photosensitive layer having a thickness of 2 μm after drying was formed.

(A) 30 parts by weight of the compound synthesized in Synthesis Example 2 (b) 70 parts by weight of the compound synthesized in Synthesis Example 5 (c) 40 parts by weight of 2,4-toluene diisocyanate (d) Polyurethane resin “PANTEX” T-5201 (manufactured by Dainippon Ink and Chemicals, Inc.) 10 parts by weight (e) Dibutyltin diacetate 0.2 parts by weight (f) 4,4'-Diethylaminobenzophenone 9 parts by weight (g) Acetic acid 0.8 parts by weight (H) Tetrahydrofuran 740 parts by weight The following silicone rubber composition was applied onto this photosensitive layer, heat-treated at 90 ° C. for 2 minutes, and the film thickness after drying was 3 μm.
The silicone rubber layer was formed.

(A) Polydimethylsiloxane having silanol groups at both ends (average molecular weight 35000) 100 parts by weight (b) Vinyltrioxime silane 9.9 parts by weight (c) Dibutyltin dioctate 0.1 parts by weight (d) Fat 590 parts by weight of group-based hydrocarbon solvent “Isopar” G (manufactured by Exxon Chemical Co., Ltd.), and a 8 μm thick polyester film “Lumirror” (manufactured by Toray Industries, Inc.) on the surface of the silicone rubber layer thus provided. It was laminated with a calendar roller to obtain a waterless planographic printing plate.

A metal halide lamp (“Idle Fin” 2000 manufactured by Iwasaki Electric Co., Ltd.) was used for this printing plate precursor, and a UV meter (“Light Measure Type UV-402A” manufactured by Oak Manufacturing Co., Ltd.) was used at an illuminance of 11 mW / cm ² for 6 minutes.
The whole surface was exposed for a second.

1 is added to the printing plate precursor obtained as described above.
A negative film having a halftone dot image of 50 lines / inch was vacuum-contacted and exposed for 60 seconds from a distance of 1 m using the above metal halide lamp.

After exposure, the protective film "Lumirror" was peeled off, and TWL-116 was prepared under the conditions of room temperature of 32 ° C. and humidity of 80%.
Development was carried out using No. 0 (developing device for waterless planographic printing plate manufactured by Toray Industries, Inc.). Here, as the pretreatment liquid, a liquid having the following composition was used.

(A) 80 parts by weight of diethylene glycol (b) 14 parts by weight of diglycolamine (c) 6 parts by weight of water Further, water was used as the developing solution. A liquid having the following composition was used as the dyeing liquid.

(A) 18 parts by weight of ethyl carbitol (b) 79.9 parts by weight of water (c) 0.1 part by weight of crystal violet (d) 2 parts by weight of 2-ethylhexanoic acid The printing plate coming out of the developing device. Was observed, the silicone rubber layer in the image-exposed portion was removed, and the surface of the photosensitive layer was exposed. On the other hand, the silicone rubber layer remained firmly in the non-image area where only the entire surface was exposed, and an image faithfully reproducing the negative film was obtained.

This printing plate was commercial off-wheel printing press ("LIT
HOPIA "Made by Mitsubishi Heavy Industries, Ltd.", Dainippon Ink and Chemicals Co., Ltd. "Dry color" ink, indigo, red,
Using yellow ink, 600r. p. m. Printing on high-quality paper at a speed of 1900
Good printed matter was printed even after printing 00 copies, and the printing plate was inspected after the printing was completed, but the printing plate was found to be slightly damaged, and it was possible to continue printing.

Example 3 A printing plate was prepared, exposed and developed in the same manner as in Example 1 except that the compound synthesized in Synthesis Example 1 was changed to the compound synthesized in Synthesis Example 3. The same printing durability test as in No. 1 was performed. As a result, a good printed material was printed even after printing 19000 copies, and the printing plate was inspected after the printing was completed. However, the printing plate was slightly damaged, and it was in a state in which printing could be continued.

Example 4 A printing plate was prepared, exposed and developed in the same manner as in Example 1 except that the compound synthesized in Synthesis Example 5 was changed to the compound synthesized in Synthesis Example 6 in Example 2. The same printing durability test as in No. 1 was performed. As a result, a good printed material was printed even after printing 200,000 copies, and the printing plate was inspected after the printing was completed, but the printing plate was slightly damaged, and it was in a state in which printing could be continued.

Example 5 A printing plate was prepared, exposed and developed in the same manner as in Example 1, except that the compound synthesized in Synthesis Example 1 was changed to the compound synthesized in Synthesis Example 2. The same printing durability test as in No. 1 was performed. As a result, a good printed material was printed even after printing 200,000 copies, and the printing plate was inspected after the printing was completed, but the printing plate was slightly damaged, and it was in a state in which printing could be continued.

Example 6 A printing plate was prepared, exposed and developed in the same manner as in Example 1 except that the compound synthesized in Synthesis Example 5 was changed to the compound synthesized in Synthesis Example 4 in Example 2. The same printing durability test as in No. 1 was performed. As a result, a good printed material was printed even after printing 210000 copies, and the printing plate was inspected after the printing was completed. However, the printing plate was slightly damaged, and it was possible to continue printing.

[0095]

Since the present invention is constructed as described above, it is possible to obtain a waterless lithographic printing plate having high sensitivity and excellent printing durability even when offset printing is performed.
Therefore, the printing plate has a long life and is economically advantageous.

Claims (4)

[Claims] 1. A waterless planographic printing plate precursor comprising a support and a photosensitive layer and a silicone rubber layer laminated in this order on the support, wherein the photosensitive layer has at least a structure represented by the following general formula (I). A compound obtained by partially crosslinking a compound having one with a polyfunctional crosslinking agent and then esterifying the compound with a quinonediazide compound and (B) a compound having at least one structure represented by the following general formula (II) with the polyfunctional crosslinking agent. A waterless lithographic printing plate precursor comprising at least one of each of the compounds which have been cross-linked and then partially esterified with a quinonediazide compound. [Chemical 1] [Chemical 2] (In the formula, R1 is at least one selected from the group consisting of a sulfur atom, a substituted or unsubstituted nitrogen atom, a substituted or unsubstituted carbon atom, and a substituted or unsubstituted silicon atom. R2, R3, R4, R5. Are substituents, which may be the same or different.) 2. The waterless lithographic printing plate precursor according to claim 1, wherein the polyfunctional crosslinking agent used in the photosensitive layer is a polyfunctional isocyanate compound. 3. The waterless lithographic printing plate precursor as claimed in claim 1, wherein at least one of the compounds esterified with the quinonediazide compound used in the photosensitive layer has an esterification degree of 5 to 95%. . 4. A waterless lithographic printing plate obtained by selectively exposing and developing the waterless lithographic printing plate precursor according to claim 1.