JPH07120912A - 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 reaction products and a specified compd. into a photosensitive layer. CONSTITUTION:The photosensitive layer contains each one compd. of two reaction products and at least one compd. expressed by formulae III, IV and V. The one reaction product is obtd. by the reaction of a compd. having at least one structure expressed by formula I and a quinonediazide compd. The other reaction product is obtd. by the reaction of a compd. having at least one structure expressed by formula II with a quinonediazide compd. In formulae I-V, 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 R6 is at least one kind selected from among hydroxyl group, an alkali metal oxide, a halogen atom, amino group, mercapto group, alkoxy group, amide group, acyloxy group, alkanoyl group, formyl group, aryloxy group, etc.

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 waterless planographic printing plate precursors have a drawback that they have low sensitivity to light and cannot obtain sufficient image reproducibility.

In order to solve this problem, a method of adding a photosensitizer or the like can be considered, but it is faithful to a negative film or a positive film, but it is still insufficient for reproducing an image.

[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) a reaction product of a compound having at least one structure represented by the following general formula (I) with a quinonediazide compound,
(B) contains at least one of each of a reaction product of a compound having at least one structure represented by the following general formula (II) and a quinonediazide compound, and includes the following general formula (III) and the following general formula A waterless lithographic printing plate precursor comprising (IV) and at least one compound represented by the following general formula (V).

[0010]

[Chemical 6]

[Chemical 7]

[Chemical 8]

[Chemical 9]

[Chemical 10] (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. R6 is a substituent, which may be the same or different.R6 is a hydroxyl group, an alkali metal oxide group, a halogen atom, an amino group, a mercapto group, a substituted or unsubstituted alkyl group having 1 to 100 carbon atoms, an alkoxy group, Amido group, acyloxy group, alkanoyl group, formyl group, carboxyl group, carbon number 2 to 1
At least one selected from the group consisting of a substituted or unsubstituted alkenyl group of 00, an alkenyloxy group, a substituted or unsubstituted aryl group having 4 to 100 carbon atoms, and an aryloxy group. ) That is, both a reaction product of a compound having at least one structure represented by general formula (I) and a quinonediazide compound and a reaction product of a compound having at least one structure represented by general formula (II) and a quinonediazide compound By containing at least one of each of them, the photosensitive layer can be softened, and as a result, printing durability can be improved. Further, by containing at least one of the compounds represented by the general formulas (III) to (V), the sensitivity to light becomes good, and a waterless planographic printing plate having excellent image reproducibility can be obtained.

The support used in the present invention may be any of those used in ordinary waterless planographic printing plates or those proposed, for example, metal plates of aluminum, copper, zinc, steel or the like. , Polyethylene terephthalate, polystyrene, polypropylene and other plastic films or sheets, chloroprene rubber, N
Examples thereof include, but are not limited to, a support having rubber elasticity such as BR, or coated paper. Appropriate processing may be applied to the surface of these supports to improve the adhesion to the upper layer.

It is also possible to further coat a primer layer on these supports for the purpose of preventing halation or for other purposes and use them as a support. 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-peeling photosensitive layer comprises a reaction product of a compound having at least one structure represented by general formula (I) and a quinonediazide compound, a compound having at least one structure represented by general formula (II), and quinonediazide. It contains at least one of each of the reaction product with the compound, and has the following general formula (II
I), at least one of compounds represented by the following general formula (IV) and general formula (V).

[0015]

[Chemical 11]

[Chemical 12]

[Chemical 13]

[Chemical 14]

[Chemical 15] (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. R6 is a substituent, which may be the same or different.R6 is a hydroxyl group, an alkali metal oxide group, a halogen atom, an amino group, a mercapto group, a substituted or unsubstituted alkyl group having 1 to 100 carbon atoms, an alkoxy group, Amido group, acyloxy group, alkanoyl group, formyl group, carboxyl group, carbon number 2 to 1
At least one selected from the group consisting of a substituted or unsubstituted alkenyl group of 00, an alkenyloxy group, a substituted or unsubstituted aryl group having 4 to 100 carbon atoms, and an aryloxy group. In such a photosensitive layer, the exposed photosensitive layer and the silicone rubber layer thereon are removed by development when no crosslinking or modification is carried out. When crosslinking or modification is performed, the exposed photosensitive layer is not removed by development, and only the silicone rubber layer on the exposed photosensitive layer is removed.

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 methanol, ethanol, propanol, butanol, hexanol, heptanol, octanol, decanol, cyclohexanol, allyl alcohol, crotyl alcohol, 3-butene-. 1-ol, 3-butene-2-ol, 1-hexene-
13-ol, 2-hexene-1-ol, 3-hexene-
1-ol, 4-hexene-1-ol, 5-hexene-1
-Ol, 1-octene 3-ol, benzyl alcohol,
Naphthalenemethanol, naphthaleneethanol, 3-hydroxytetrahydrofuran, ethanolamine, 2-
Monovalent saturated or unsaturated alcohols such as mercaptoethanol, 1-mercapto-2-propanol, 3-mercapto-2-butanol, hydroxyethyl acrylate and hydroxyethyl methacrylate, 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-
Divalent saturated or unsaturated alcohols such as diol, 5-hexene-1,2-diol, 7-octene-1,2-diol, 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. The desired reaction product can be obtained by reacting one of these compounds or another compound having at least one structure represented by the general formula (I) alone or with two or more kinds of quinonediazide compounds.

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 phenol, naphthol, anthranol,
2,6-dihydroxyanthraquinone, anthralobin, phenol novolac resin, polyhydroxystyrene, etc.

The desired reaction product can be obtained by reacting one of these compounds or another compound having at least one structure represented by the general formula (II) alone or with two or more kinds of quinonediazide compounds. .

Examples of the quinonediazide compound include benzoquinone-1,2-diazidesulfonic acid and its derivatives,
Examples thereof include, but are not limited to, naphthoquinone-1,2-diazide sulfonic acid and its derivative, or diazodiphenylamine and its derivative. Of these, naphthoquinone-1,2-diazide sulfonic acid and its derivatives are particularly effective. As a quinonediazide compound, for example, when a sulfonic acid-based compound is used,
The target reaction product becomes an esterified product.

The reaction ratio between the compound having at least one structure represented by the general formula (I) and the quinonediazide compound and the reaction ratio between the compound having at least one structure represented by the general formula (II) and the quinonediazide compound are Although not particularly limited, preferably 0.01 to 1,000,000 parts by weight of the quinonediazide compound with respect to 100 parts by weight of the compound having at least one structure represented by the general formula (I) or the structure represented by the general formula (II), More preferably, the structure represented by the general formula (I) or the general formula (I
Compound 10 having at least one structure represented by I)
The quinonediazide compound is added in an amount of 0.1-10 parts by weight based on 0 part by weight.
It is preferably obtained by reacting 10,000 parts by weight.

Specific examples of the compound represented by the general formula (III) include benzoquinone-1,2-diazide sulfonic acid, sodium benzoquinone-1,2-diazide sulfonate, and benzoquinone-1,2-diazide sulfone. Acid potassium, benzoquinone-1,2-diazidesulfonic acid chloride, benzoquinone-1,2-diazidesulfonic acid bromide, benzoquinone-1,2-diazidesulfonic acid methyl ester, benzoquinone-1,2-diazidesulfonic acid Examples include, but are not limited to, ethyl esters. Among these, sodium benzoquinone-1,2-diazide sulfonate and benzoquinone-1,2-
Diazidosulfonic acid chloride is preferred.

Specific examples of the compound represented by the general formula (IV) include o-naphthoquinone-1,2-diazide-5-.
Sulfonic acid, o-naphthoquinone-1,2-diazide-5
-Sodium sulfonate, o-naphthoquinone-1,2-
Potassium diazide-5-sulfonate, o-naphthoquinone-1,2-diazide-5-sulfonic acid chloride, o-naphthoquinone-1,2-diazide-5-sulfonic acid bromide, o-naphthoquinone-1,2-diazide- Examples include, but are not limited to, 5-sulfonic acid methyl ester, o-naphthoquinone-1,2-diazide-5-sulfonic acid ethyl ester, and the like. Among these, sodium o-naphthoquinone-1,2-diazide-5-sulfonate and o-naphthoquinone-1,2-diazide-5-sulfonic acid chloride are preferable.

Specific examples of the compound represented by the general formula (V) include o-naphthoquinone-1,2-diazide-4-sulfonic acid and o-naphthoquinone-1,2-diazide-4-.
Sodium sulfonate, o-naphthoquinone-1,2-diazide-4-sulfonate potassium, o-naphthoquinone-
1,2-diazide-4-sulfonic acid chloride, o-naphthoquinone-1,2-diazide-4-sulfonic acid bromide, o-naphthoquinone-1,2-diazide-4-sulfonic acid methyl ester, o-naphthoquinone-1 , 2-diazide-4-sulfonic acid ethyl ester and the like, but not limited thereto. Among these, sodium o-naphthoquinone-1,2-diazide-4-sulfonate and o-naphthoquinone-1,2-diazide-4-sulfonic acid chloride are preferable.

When a crosslinking agent is used in the photosensitive layer, the crosslinking agent may be a polyfunctional isocyanate such as paraphenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, Hexamethylene diisocyanate, isophorone diisocyanate, polymethylene polyphenyl isocyanate or adducts thereof, or polyfunctional epoxy compounds such as polyethylene glycol diglycidyl ethers, polypropylene glycol diglycidyl ethers, bisphenol A diglycidyl ether , Trimethylolpropane triglycidyl ether and the like, but are not limited thereto.
These thermosettings are preferably carried out at a temperature that does not lose the photosensitivity of the photosensitive substance, usually at 130 ° C. or lower, and therefore, a catalyst or the like is usually used in combination.

Further, a monofunctional compound is reacted with a reaction product of a compound having at least one structure represented by the general formula (I) or a structure represented by the general formula (II) with a quinonediazide compound to modify it to obtain a developing solution. As a method for making the compound insoluble or insoluble, similarly, for example, esterification, amidation, or urethanization of the active group of the photosensitive compound can be mentioned. The compound that reacts with the active group of the photosensitive compound may be a low molecular weight compound or a relatively high molecular weight compound, or a monomer may be graft-polymerized to the photosensitive compound.

If necessary, it is possible to add an organic polymer compound which can be mixed with these compounds. 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 100 parts of the reaction product of the compound having at least one structure represented by the general formula (I) and the quinonediazide compound is used. 0.001 part by weight of a reaction product of a compound having at least one structure represented by the following general formula (II) and a quinonediazide compound:
1 to 100,000 parts by weight, 1 to 10000 parts by weight of the compound represented by the general formula (III) to general formula (V), or 0 to 1 part of the compound which reacts with the bridging group of the crosslinking agent or the photosensitive compound.
10,000,000 parts by weight, 0 to 10,000,000 parts by weight of an organic polymer compound, 0 to 10,000 parts by weight of a photoinitiator or a photosensitizer, and 0 to 10,000 parts of additives and known catalysts if necessary. In addition to parts by weight, the film thickness is 0.1 to 100 μm, preferably 0.5 to
It is preferable that the thickness is 10 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.

Molecular weight 1 represented by the following general formula (VI)
Those obtained by crosslinking 100 to 100,000, preferably 1,000 to 500,000 organic polysiloxanes.

[0042]

[Chemical 16] (In the formula, n is an integer of 2 or more, and R7 and R8 have 1 to 5 carbon atoms.
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 product obtained by cross-linking by an addition reaction between an organic polysiloxane having a group represented by the following general formula (VII) and a polysiloxane compound having a group represented by the following general formula (VIII).

[0045]

[Chemical 17]

[Chemical 18] (In the formula, R 9 and R 10 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, and 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 (VII) may be at either the terminal or the middle of the molecular chain. In addition, the general formula (VI
The group II) 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 (VII) and the group of the general formula (VIII) 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. An organic polysiloxane having a group represented by the general formula (VII) and a general formula (V
The molecular weight of the polysiloxane compound having a group represented by III) is preferably 100 to 1,000,000, and more preferably 1000 to 500,000. 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 (VI) is added directly 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 an organic polysiloxane having a group represented by the general formula (VI) is used.
Polysiloxane compound having group I) 0.1
100 to 100,000 parts by weight, and 0 to 100 parts of a known catalyst as necessary
It may be obtained by providing a composition having a composition added by weight of 0.1 to 100 μm, preferably 0.5 to 30 μm.

In the waterless planographic printing plate of the present invention, the 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. Therefore, it is possible to provide an adhesive layer between the layers or to add an adhesiveness improving component to each layer, if necessary. 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 providing such an adhesive layer,
The thickness of the adhesive layer is not particularly limited, but is 0.0
It is good to obtain it by providing 5 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.

Synthesis Example 1 20 g of 2-hydroxyethyl methacrylate, which is a compound having one structure represented by the general formula (I), and 10 g of o-naphthoquinone-1,2-diazide-5-sulfonic acid chloride were added to 100 g of dioxane. Dissolved. Next, 10 g of sodium carbonate was dissolved in 90 g of water, and a 10 wt% solution of this sodium carbonate was added to the above dioxane solution to prepare 1
It was added dropwise over 0 minutes. (At this time, the dioxane solution was stirred and the liquid temperature was kept at 40 ° C.) After the dropping was completed,
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. Remove the supernatant in the beaker,
It was dried under reduced pressure to obtain the target compound.

Synthesis Example 2 30 g of the compound obtained in Synthesis Example 1 was added to 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 liquid in the beaker was removed and dried under reduced pressure to obtain the target compound.

Synthesis Example 3 15 g of the compound obtained in Synthesis Example 1 and 15 g of 2-hydroxyethyl methacrylate were dissolved in 200 g of dioxane, 0.1 g of azobisisobutyronitrile was added, and the mixture was heated to 65 ° C. under a nitrogen atmosphere at 4 ° C. The copolymerization reaction was carried out for a time. After the reaction, the reaction solution was poured into a beaker containing 1000 g of methanol to precipitate and precipitate a product. The supernatant liquid in the beaker was removed and dried under reduced pressure to obtain the target compound.

Synthesis Example 4 20 g of glycerin, which is a compound having a structure represented by the general formula (I), and o-naphthoquinone-1,2-diazide-
5-sulfonic acid chloride 10g and dioxane 100g
Dissolved in. Next, 10 g of sodium carbonate and 90 g of water
10% by weight of this 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.

Synthesis Example 5 25 g of trimethanol propane, a compound having a structure represented by the general formula (I), and o-naphthoquinone-1,2.
10 g of diazide-4-sulfonic acid chloride were dissolved in 100 g of dioxane. Next, sodium carbonate 10
g 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 agitated at 40 ° C.
The liquid temperature was kept at. ) 4 hours at 40 ° C. after completion of dropping,
The reaction was carried out with stirring. After the reaction, the reaction solution was poured into a beaker containing 1000 g of water to precipitate and precipitate a product. Remove the supernatant in the beaker and dry under reduced pressure.
The target compound was obtained.

Synthesis Example 6 1, which is a compound having a structure represented by the general formula (I),
30 g of 6-hexanediol and o-naphthoquinone-1,
2-Diazide-4-sulfonic acid chloride (10 g) was dissolved in dioxane (100 g). Next, sodium carbonate 1
0 g 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 ℃. ) After completion of the dropwise addition, the mixture was reacted 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.

Synthesis Example 7 20 g of phenol, which is a compound having one structure represented by the general formula (II), and 10 g of o-naphthoquinone-1,2-diazide-5-sulfonic acid chloride were mixed with dioxane 1
It was dissolved in 00 g. 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.

Synthesis Example 8 25 g of 4-hydroxystyrene, which is a compound having one structure represented by the general formula (II), and o-naphthoquinone-
10 g of 1,2-diazide-4-sulfonic acid chloride was dissolved in 100 g of dioxane. Next, 10 g of sodium carbonate is dissolved in 90 g of water, and 1 g of this sodium carbonate is dissolved.
The 0 wt% solution was added dropwise to the above dioxane solution over 10 minutes. (At this time, the dioxane solution is stirred,
The liquid temperature was kept at 40 ° C. 4) At 40 ° C after the completion of dropping
The reaction was carried out for a period of time with stirring. After the reaction, 1000g of water
Pour the reaction solution into a beaker containing, precipitate the product,
Allowed to settle. The supernatant liquid in the beaker was removed and dried under reduced pressure to obtain the target compound.

Synthesis Example 9 30 g of the compound obtained in Synthesis Example 8 was added to 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 liquid in the beaker was removed and dried under reduced pressure to obtain the target compound.

Synthesis Example 10 15 g of the compound obtained in Synthesis Example 9 and 15 g of 4-hydroxystyrene were dissolved in 200 g of dioxane, 0.1 g of azobisisobutyronitrile was added, and the mixture was heated at 65 ° C. for 4 hours under a nitrogen atmosphere. A copolymerization reaction was performed. After the reaction, the reaction solution was poured into a beaker containing 1000 g of methanol to precipitate and precipitate a product. The supernatant liquid in the beaker was removed and dried under reduced pressure to obtain the target compound.

Synthesis Example 11 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 10 g of o-naphthoquinone-1,2-diazide-5-sulfonic acid chloride were mixed with 100 g of dioxane. Dissolved in.
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.

Synthesis Example 12 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 10 g of o-naphthoquinone-1,2-diazide-5-sulfonic acid chloride were mixed with 100 g of dioxane. Dissolved in.
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.

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 7 (c) 10 parts by weight of o-naphthoquinone-1,2-diazide-5-sulfonic acid chloride (D) 40 parts by weight of 4,4'-diphenylmethane diisocyanate (e) Polyurethane resin "Samprene" LQ-T1331 (manufactured by Sanyo Kasei Co., Ltd.) 10 parts by weight (f) Dibutyltin dilaurate 0.2 parts by weight (g) 4 , 4'-Dimethylaminobenzophenone 9 parts by weight (h) Formic acid 0.8 parts by weight (i) Tetrahydrofuran 740 parts by weight The following silicone rubber composition is coated on this photosensitive layer and heated at 90 ° C for 2 minutes. Film thickness after processing and drying 3μm
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. It was laminated with a roller to obtain a waterless planographic printing plate precursor.

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.

The printing plate precursor obtained as described above has 1
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, 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 the plate surface was 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 is 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 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 of o-naphthoquinone-1,2-diazide-5-sulfonic acid and phenol formaldehyde novolac resin (“Sumilite resin” PR 50622 manufactured by Sumitomo Durez) (degree of esterification by elemental analysis 25 %) 100 parts by weight (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 Parts (e) 4,4′-dimethylaminobenzophenone 9 parts by weight (f) Formic acid 0.8 parts by weight (g) Tetrahydrofuran 740 parts by weight When this printing plate was observed, one of the silicone rubber layers in the image-exposed part was observed. The part was not removed and the surface of the photosensitive layer was not exposed. On the other hand, a part of the silicone rubber layer in the non-image area where only the entire surface was exposed was peeled off, and an image faithfully reproducing the negative film could not be obtained.

Using this printing plate, a commercial off-wheel printer (“LITHOPIA”, Mitsubishi Heavy Industries, Ltd.) was used as in Example 1.
Manufactured by Dainippon Ink and Chemicals Co., Ltd., using "Dryo Color" ink, indigo, red, and 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 8 (c) 10 parts by weight of o-naphthoquinone-1,2-diazide-4-sulfonic acid chloride (D) 40 parts by weight of 2,4-toluene diisocyanate (e) Polyurethane resin "PANTEX" T-5201 (manufactured by Dainippon Ink and Chemicals, Inc.) 10 parts by weight (f) 0.2 parts by weight of dibutyltin diacetate ( g) 4,4′-Diethylaminobenzophenone 9 parts by weight (h) Acetic acid 0.8 parts by weight (i) Tetrahydrofuran 740 parts by weight The following silicone rubber composition is coated on this photosensitive layer, and the temperature is 90 ° C. for 2 minutes. Heat treatment at 3μm after drying
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. A waterless planographic printing plate precursor was obtained by laminating with a calendar roller.

A metal halide lamp (“Idle Fin” 2000 manufactured by Iwasaki Electric Co., Ltd.) was used for this printing plate precursor, and an illuminance of 11 mW / cm ² was measured with a UV meter (“Light Measure Type UV-402A” manufactured by Oak Manufacturing Co., Ltd.).
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 is 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 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 8 was changed to the compound synthesized in Synthesis Example 9. The same printing durability test as in 2 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 4. 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 8 was changed to the compound synthesized in Synthesis Example 10 in Example 2. The same printing durability test as in 2 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.

Example 7 Except that in Example 1, the compound synthesized in Synthesis Example 1 was changed to the compound synthesized in Synthesis Example 5, and the compound synthesized in Synthesis Example 7 was changed to the compound synthesized in Synthesis Example 11. A printing plate was prepared, exposed and developed in the same manner as in Example 1, and the same printing durability test as in Example 1 was performed. As a result, 20000
Good printed matter was printed even after printing 0 copy, and the printing plate was inspected after the printing was completed, but the printing plate was slightly damaged, and it was in a state where it was possible to continue printing.

Example 8 Except that in Example 1, the compound synthesized in Synthesis Example 1 was changed to the compound synthesized in Synthesis Example 6, and the compound synthesized in Synthesis Example 7 was changed to the compound synthesized in Synthesis Example 12. A printing plate was prepared, exposed and developed in the same manner as in Example 1, and the same printing durability test as in Example 1 was performed. As a result, 20000
Good printed matter was printed even after printing 0 copy, and the printing plate was inspected after the printing was completed, but the printing plate was slightly damaged, and it was in a state where it was possible to continue printing.

[0096]

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.

Claims (2)

[Claims] 1. A waterless lithographic 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) a structure represented by the following general formula (I). And a quinonediazide compound, and (B) a compound having at least one structure represented by the following general formula (II) and a quinonediazide compound. And a waterless planographic printing plate precursor containing at least one of the compounds represented by the following general formula (III), the following general formula (IV) and the following general formula (V). [Chemical 1] [Chemical 2] [Chemical 3] [Chemical 4] [Chemical 5] (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. R6 is a substituent, which may be the same or different.R6 is a hydroxyl group, an alkali metal oxide group, a halogen atom, an amino group, a mercapto group, a substituted or unsubstituted alkyl group having 1 to 100 carbon atoms, an alkoxy group, Amido group, acyloxy group, alkanoyl group, formyl group, carboxyl group, carbon number 2 to 1
At least one selected from the group consisting of a substituted or unsubstituted alkenyl group of 00, an alkenyloxy group, a substituted or unsubstituted aryl group having 4 to 100 carbon atoms, and an aryloxy group. ) 2. A waterless planographic printing plate obtained by selectively exposing and developing the waterless planographic printing plate precursor according to claim 1.