JPH024252A - Waterless photosensitive planographic plate - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a negative waterless photosensitive lithographic printing plate capable of producing a waterless lithographic printing plate capable of printing without dampening water.

[Conventional technology]

Waterless lithographic printing involves making the image areas ink-receptive and the non-image areas ink-repellent.Using the difference in ink adhesion, ink is deposited only on the image areas, and then the paper In the lithographic printing method in which ink is transferred and printed onto a printing material such as, the non-image area is made of a layer of a material having ink repellency such as silicone rubber, and printing is possible without using dampening water. This is a unique printing method.

Many printing plates have been proposed for use in waterless lithographic printing, including those having a silicone rubber layer as an ink repellent layer, and those having a substrate, a photosensitive layer, and a silicone rubber layer in this order (silicone rubber upper layer type). ), a type in which a substrate, a silicone rubber layer, and a photosensitive layer are provided in this order (silicone rubber lower layer type), and a type in which a substrate and a photosensitive silicone rubber layer are further provided0 [Problems to be Solved by the Invention] ] Generally, in order to obtain a waterless photosensitive lithographic printing plate, it is necessary to provide a silicone rubber layer with high ink repellency, but due to its nature, it does not have good adhesion to other substances. Not shown.

Therefore, even if the waterless planographic printing plate obtained from this photosensitive planographic printing plate has good ink repellency, the adhesion between the photosensitive layer and the silicone rubber layer is insufficient, or even if the adhesion is good, the ink Repulsion may be insufficient. Tokukai Shōl
I? -8-O, JP-A No. 19-77702, JP-A No. 19-77702, JP-A No. 19-77702, JP-A No. 19-77702, JP-A-8-0 - In GBLθ3, etc., it has been proposed to improve the adhesion between the photosensitive layer and the silicone rubber layer by incorporating a silicone primer or a silane coupling agent into the photosensitive layer or the silicone rubber layer. In either case, the ink repellency is insufficient. especially,
In the case of the silicone rubber underlayer type, even if the adhesion between the photosensitive layer and the silicone rubber layer is improved, the photosensitive layer is not sufficiently removed by development, and the ink repellency of the silicone rubber layer surface decreases, causing the background to deteriorate during printing. It causes dirt. In order to remove the contamination layer that causes such dirt, Tokkosho &
-1. In Publication No. 3, it is proposed to use a developer mainly composed of seven or more aliphatic hydrocarbons having a carbon number of s to 20. The developing solution used as a component tends to cause environmental pollution problems,
Furthermore, there are various problems, such as the material of the developing processing device being limited.

[Failure to solve the problem]

The present inventor has developed a silicone rubber-based negative waterless photosensitive material that has good adhesion between the photosensitive layer and the silicone rubber layer, good ink repellency, and excellent ink receptivity. As a result of intensive research aimed at obtaining a lithographic printing plate, it was discovered that the above object could be achieved by applying a polymer compound with a specific structure to the photosensitive layer, and the present invention was achieved.

That is, the gist of the present invention is a negative waterless photosensitive lithographic printing plate in which a substrate, a silicone rubber layer, and a photosensitive layer are provided in this order, in which the photosensitive layer is made of a photosensitive diazo resin and a compound represented by the following formula CI). The present invention relates to a negative waterless photosensitive lithographic printing plate characterized by containing a polymer compound having /-30 molty of structural units.

÷CH2-C→ [1) (wherein, R is a hydrogen atom or a methyl group, X is an alkylene group, n represents 0 or the number of l, Y is an alkyl group or an alkoxy group, m is 0 indicating the number of θ to S) The present invention will be described in detail below.

The photosensitive diazo resin used in the photosensitive layer of the present invention is a diazo resin typified by a condensate of an aromatic diazonium salt and a compound containing an active carbonyl group, such as formaldehyde. It is a diazo resin that is insoluble in water.

The above-mentioned diazo resins are disclosed in Japanese Patent Publication No. 39-17602, Japanese Patent Application Publication No. Sho A-/210.3/, Japanese Patent Publication No. Sho &/-
1I22! A condensate of p-diazodiphenylamine or a p-diazodiphenylamine derivative such as 3-methoxydadiazodiphenylamine, dermethoxida'-diazodiphenylamine, formaldehyde or acetaldehyde, and hexafluoro- 7. Diazo resin inorganic salt soluble in organic solvents and nearly insoluble in water, which is the reaction product with phosphate salt, tetrafluoroborate salt, still US patent, 7. ．． 70
0,309, the above condensate and sulfonic acids such as para-toluenesulfonic acid or its salts; phosphinic acids such as benzenephosphinic acid or its salts; Examples include diazo resin organic acid salts that are soluble in organic solvents and almost insoluble in water, which are reaction products with hydroxyl group-containing compounds such as roxy q-methoxybenzophenone-5-sulfonic acid or its salts.

Furthermore, the photosensitive diazo resin used in the present invention is a condensation product of an aromatic diazonium compound as described in Japanese Patent Publication No. 1997-11-1, that is, a unit containing at least - formula: % formula %). These units are connected by a divalent intermediate member derived from a condensable carbonyl compound, and the condensation product is A(-D
)n/unit on average B about 0. θ/~50 units [provided that A in the above formula contains at least two members selected from the group consisting of an aromatic ring and an aromatic heterocycle, and at least one position is active in an acid medium. is a residue of a compound that can be condensed with a carbonyl compound, D is a diazonium base bonded to the aromatic carbon atom, and n is 7
is an integer of ~IO, and B is selected from the group consisting of aromatic amines, phenols, thiophenols, phenol ethers, aromatic thioethers, aromatic heterocycles, aromatic hydrocarbons, and organic acid amides; A diazo resin which is the residue of a compound that does not have a diazonium group,
Among them, those isolated as salts that are soluble in organic solvents and almost insoluble in water, such as hexafluorophosphates, tetrafluoroborates, and aliphatic or aromatic sulfonates, can be mentioned.

Specifically, for example, diazodiphenylamine/p-hydroxybenzoic acid/paraformaldehyde polycondensate, diazodiphenylamine/bis(hydroxymethyl)urea polycondensate, 3-methoxydiazodiphenylamine/u,u'-bis(methoxy methyl)diphenyl ether polycondensate, 3-methoxydadiazodiphenylamine, dermethylda'-methoxymethyldiphenyl ether, <c,u'-bis(methoxymethyl)diphenyl ether polycondensate, etc., hexafluorophosphate, cohyde Examples include roxy q-methoxybenzophenone-5-sulfonate and mesitylene sulfonate.

The molecular weight of the photosensitive diazo resin used in the present invention can be measured, for example, by gel permeation chromatography (hereinafter abbreviated as GPC) after separating it as a condensate with β-naphthol under alkaline conditions. . In the present invention, those having a weight average molecular weight of SOO to /θ,000 in terms of standard polystyrene can be suitably used, and those of /,000 to 7,000 are particularly preferred.

The photosensitive diazo resin used in the present invention is preferably contained in the photosensitive layer of the present invention in an amount of 7 to 70% by weight.
It is more preferable to contain tO by weight%.

The polymer compound having a structural unit represented by the above formula [I] to be contained in the photosensitive layer of the waterless photosensitive lithographic printing plate of the present invention is derived from a monomer represented by the following formula (II). It contains units of /~ SO mol, more preferably 5 to 2θ mol.

CH2=C (II) (wherein, R is a hydrogen atom or a methyl group, X is an alkylene group such as a methylene group or an ethylene group, n is O or the number of /, and Y is the number of carbon atoms / (It is an alkyl group such as an alkyl group with ~ carbon number / ~ da alkoxy group, where m represents a number from 0 to 3.) Specification of the monomer represented by the above-mentioned formula (If) Examples include, for example, N-phenylmethacrylamide, N-
Phenyl acrylamide, N-(3-methylphenyl)
Methacrylamide, N-(3-methylphenyl)acrylamide, N-(3-methoxyphenyl→methacrylamide, N-(3-methoxyphenyl)acrylamide,
N-(Q-ethylphenyl)methacrylamide, N-(
lI-ethylphenyl)acrylamide, N-(u-ethoxyphenyl)methacrylamide, N-(lI-ethoxyphenyl)acrylamide, N-(lI-butylphenyl)methacrylamide, N-(lI-butylphenyl)acrylamide, N1 -benzylmethacrylamide, N-benzylacrylamide, N-(lI-methylbenzyl)methacrylamide, N-
(lI-methylbenzyl)acrylamide, N-(<<
-methoxybenzyl) methacrylamide, N-(+-methoxybenzyl) acrylamide, N-(,?-ethylbenzyl) methacrylamide, N-(J-ethylbenzyl) acrylamide, N-(3-ethoxybenzyl) methacrylamide, Examples include N-(,?-ethoxybenzyl)acrylamide, N-(4'-butylbenzyl)methacrylamide, and N-(9-butylbenzyl)acrylamide. Preferred among these are N-phenylmethacrylamide, N-(3-methoxyphenyl)methacrylamide, and N-(lI-methoxyphenyl).
It is methacrylamide.

The polymer compound of the present invention can be obtained by copolymerizing the monomer represented by formula CII) with an addition polymerizable unsaturated compound as shown below.

Such addition-polymerizable unsaturated compounds include compounds having / each addition-polymerizable unsaturated bond, - formula (II)
Examples include compounds that do not have the structure represented by. Specifically, for example, (A) methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, amyl acrylate, λ-ethylhexyl acrylate, octyl acrylate, t-octyl acrylate, Co-chloroethyl acrylate, co-acrylate, 2-dimethyl-3-hydroxyglopyl, 2-hydroxyethyl acrylate, S-hydroxypentyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, glycidyl acrylate, acrylic acid Acrylic acid esters such as benzyl, dermethoxybenzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, and phenyl acrylate.

(B) Methyl methacrylate, ethyl methacrylate,
Propyl methacrylate, butyl methacrylate, isobutyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, octyl methacrylate, co-hydroxyethyl methacrylate, S-hydroxypentyl methacrylate, 2-chloroethyl methacrylate, co-methacrylate , -1-dimethyl-3-hydroxypropyl, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, glycidyl methacrylate, benzyl methacrylate, dermethoxybenzyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, phenyl methacrylate, etc. Methacrylic acid esters.

(C) N-methylacrylamide, N-ethylacrylamide, N-propylacrylamide, N-isopropylacrylamide, N-butylacrylamide, N-
-Cyclohexylacrylamide, N-(,2-hydroxyethyl)acrylamide, N-(u-hydroxyphenyl)acrylamide, N,N-dimethylacrylamide, N-methyl-N-phenylacrylamide, N-
Acrylamides such as (,2-hydroxyethyl)-N-methylacrylamide.

(D) N-methylmethacrylamide, N-ethylmethacrylamide, N-propylmethacrylamide, N-
Isopropyl methacrylamide, N-butyl methacrylamide, N-cyclohexyl methacrylamide, N-(
lI-hydroxyphenyl)methacrylamide, N,N
-Methacrylamides such as dimethylmethacrylamide, N-methyl-N-ethylmethacrylamide, N-methyl-N-phenylmethacrylamide, and N-(2-hydroxyethyl)-N-ethylmethacrylamide.

(E) Allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate,
Allyl compounds such as allyloxyethanol.

(F) Methoxyethyl vinyl ether, ethoxyethyl vinyl ether, /-methyl-, codimethylpropylene vinyl ether, co-hydroxyethyl vinyl ether, hexyl vinyl ether, -monoethylhexyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, benzyl vinyl ether, phenyl vinyl ether -1, I) Vinyl ethers.

(G) Vinyl esters such as vinyl benzoate and vinyl salicylate.

(H) Styrene, goomethylstyrene, 3. S-dimethylstyrene, 4'-7" tylstyrene, terchloromethylstyrene, goo-ethoxymethylstyrene, goo-methoxystyrene, q-methoxy-3-methylstyrene,
Styrenes such as goochlorostyrene and 3-furomostyrene.

(1) Crotonate esters such as butyl crotonate and hexyl crotonate.

ω) Itaconate diesters such as dimethyl itaconate and diethyl itaconate.

(K) N-vinyl compounds such as N-vinylpyrrole and N-vinylpyrrolidone.

(L) Others such as acrylic acid, methacrylic acid, acrylonitrile, methacrylonitrile, etc.

Furthermore, any addition polymerizable unsaturated compound that can be copolymerized with the monomer represented by formula (n) above may be used.

A polymer compound obtained by copolymerizing seven or more types of such addition-polymerizable unsaturated compounds and a monomer represented by the general formula [old] is used in the present invention, but as a polymer, Block bodies, random bodies, graft bodies, etc. can all be used. - Components to be copolymerized with the monomer represented by the formula [old] include alkyl acrylates such as methyl acrylate and ethyl acrylate, methacrylic esters such as methyl methacrylate, ethyl methacrylate, and co-hydroxyethyl methacrylate. Class, N-(4
Methacrylamides such as 1-hydroxyphenyl)methacrylamide and N-methylmethacrylamide, methacrylic acid, acrylic acid, acrylonitrile, and methacrylonitrile exhibit excellent overall performance and are preferred. As the polymer compound used in the present invention, the above-mentioned formula [■]
A monomer represented by /~Sθ molti, alkyl acrylates and/or methacrylic esters and/or methacrylamides 10 to 70 molti, acrylonitrile or methacrylonitrile o-1Io molti, acrylic acid or methacrylic acid θ A polymer compound obtained by copolymerizing ~10 molti is most preferred.

The molecular weight of the polymer compound used in the present invention is suitably approximately 10,000 to 1,000,000 in terms of weight average molecular weight, approximately 30,000 to 30,000 as measured by gel permeation chromatography.
A range of 10,000 is preferred.

In the waterless photosensitive lithographic printing plate of the present invention, the proportion of the polymer compound having the structural unit represented by formula CI) in the photosensitive layer is preferably 30 to 99% by weight,
30-? j% by weight is more preferred.

In order to improve storage stability, the photosensitive layer of the present invention contains phosphoric acid, phosphonic acid, phosphinic acid,
Inorganic acids such as sulfuric acid and hydrobromic acid; tartaric acid, citric acid, oxalic acid, organic sulfonic acids (e.g. toluenesulfonic acid,
Organic acids such as naphthalenesulfonic acid, goumethoxy-2-hydroxybenzophenone-3-sulfonic acid, etc.); and polyorganic acids such as polyacrylic acid, polyvinylphospho/acid, polyvinylsulfonic acid, etc. can also be contained.

The above-mentioned stabilizer is usually 0. / -J It is preferable to contain 0% by weight, and more preferably to contain 0.3 to 20% by weight.

Among the above stabilizers, polyacrylic acid is most preferred in the present invention. In the photosensitive layer of the present invention, polyacrylic acid contains O,
It is preferable to contain S to 20% by weight, and more preferably to contain 7 to 70% by weight.

The weight average molecular weight of polyacrylic acid is 300 to 100,
The range of 000 is preferable, /, 000 to g o, o o
o is more preferable.

The photosensitive layer of the present invention may further contain dyes, pigments,
A coating property improver, a plasticizer, etc. can be added.

Examples of dyes include Victoria Pure Blue BOH.
(manufactured by Hodogaya Chemical Co., Ltd.), Oil Blue≠603 (manufactured by Orient Chemical Co., Ltd.), Patent Pure Blue (manufactured by Sumitomo Mikuni Chemical Co., Ltd.), Crystal Violet, Brilliant Green, Ethyl Violet, Methyl Green, Erythrosin B1 Basic Tsuksin, Malachite Green , oil red, m-cresol purple, rhodamine B1 auramine, coup-diethylaminophenylimino naphthoquinone, cyano-p-diethylaminophenyl acetanilide, triphenylmethane type, diphenylmethane type, oxazine type, xanthine type, iminonaphthoquinone. Examples include azomethine-based, azomethine-based, and anthraquinone-based dyes.

The dye is generally contained in the photosensitive layer in an amount of about O.S to about IO, preferably about 0.5% by weight.

Examples of coating properties improvers include alkyl ethers (e.g., ethylcellulose, methylcellulose), fluorine-based surfactants [e.g., Florado FC-da 3o (Sumitomo 3),
(manufactured by M Company)] and nonionic surfactants [for example, Pluronic L-4'1 (manufactured by Kadenka Co., Ltd.)]. Plasticizers for imparting flexibility and abrasion resistance to the coating film include , such as butylphthalyl, polyethylene glycol, tributyl citrate, diethyl phthalate, diptyl phthalate,
Examples include dihexyl phthalate, dioctyl phthalate, tricresyl phosphate, tributyl phosphate, trioctyl phosphate, and tetrahydrofurfuryl oleate. 5s-B2 is a half-esterified product of a styrene-maleic anhydride copolymer with alcohol described in the publication.

Although these additives vary depending on the purpose for which they are used, it is usually preferable to include them in the photosensitive layer in an amount of 0.1 to 30% by weight.

In order to form the photosensitive layer used in the present invention, the components to be included in the photosensitive layer, namely, photosensitive diazo resin,
- A polymer compound having a structural unit represented by formula (1), optionally a stabilizer such as polyacrylic acid, and further optionally various additives such as a dye, a pigment, a coating improver, a plasticizer, etc. , various solvents such as comethoxyethanol, λ-ethoxyethanol, methyl cellosolve acetate, ethyl cellosolve acetate, l-methoxy-coprobanol, dioxane, tetrahydrofuran, acetone, methyl ethyl ketone, cyclohexanone, acetylacetone, dimethylformamide, dimethyl sulfoxide, trichloroethane, etc. alone or two
It is dissolved or dispersed in a mixture of two or more species, applied according to a conventional method, and dried usually at 170-/kO<0>C for 7 to 100 minutes. The preferred thickness of the photosensitive layer of the present invention is 0.
1 to 100 μm, more preferably O, S to go
μm1 is more preferably 7 to 30 μm.

The silicone rubber used in the silicone rubber layer of the present invention may be any silicone rubber suitable for the purpose, but for example, silicone rubber obtained by crosslinking an organopolysiloxane having the following repeating units as a main component may be used. preferable.

(Here, n is an integer of 2 or more. R1 and R2 are hydrogen atoms, unsubstituted or substituted (e.g., halogen atoms, cyan groups, amine groups) alkyl groups having 7 to 10 carbon atoms, alkenyl groups, or phenyl groups. The molecular weight is arbitrary, but the viscosity at 2S°C is /~
10,0θO Stokes is preferred.0 In order to crosslink these organopolysiloxanes to form a silicone rubber, a hydroxyl group, a hydrolyzable group (for example, an acyloxy group, an alkoxy group,
Crosslinking is carried out by a condensation reaction using an organopolysiloxane bonded with ketoximate groups, amino groups, amide groups, etc.

In the present invention, organopolysiloxanes having hydroxyl groups bonded to both ends, such as α,ω-dihydroxydimethylpolysiloxane, are particularly preferably used.

These have two hydrolyzable groups directly bonded to the silicon atom.
It is preferable to add a silicon compound having at least 1 silicon compound, a so-called crosslinking agent.

Specific examples of the crosslinking agent include r-(2-aminoethyl)aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, methyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, Examples include methyltriacetoxysilane, vinyltris(methylethylketoxime)silane, and methyltris(methylethylketoxime)silane.

Furthermore, organopolysiloxanes in which hydrogen atoms are directly bonded to silicon atoms, such as α,ω-dihydroxypolyhydrodienemethylsiloxane, α,ω-bis(trimethylsilyl)polyhydrosynmethylsiloxane,
3. ! ;,the law of nature,? - Pentamethylcyclopentasiloxane or the like may be added.

In order to obtain a silicone rubber layer, the silicone rubber layer, which is usually in an uncured state, is cured. As a catalyst for its curing,
It is preferable to add a known metal catalyst such as an organic tin compound or an organic titanium compound.

Specific examples include diptyltin diacetate, tributyltin acetate, diptyltin dilaurate, tetramethyl orthotitanate, and tetraethyl orthotitanate. These catalysts have a ratio of θ, 0/−! to the total weight of silicone rubber. ;wt%, preferably 0.
It is used in a range of 0 to 0% by weight.

It is also useful to add inorganic fillers such as silica and calcium carbonate for reinforcement purposes.

In order to form the silicone rubber layer of the present invention, each of the above components must be mixed with cyclohexane, methylcyclohexane,
It is dissolved in a mixed solvent of aliphatic hydrocarbons such as n-hexane, n-hebutane, and -monomethylhexane, or a small amount of aromatic hydrocarbons such as benzene, toluene, and xylene. The resulting silicone rubber solution is applied according to a conventional method and dried for a short time, usually at 20 DEG C. to IOOO DEG C. As soon as the solvent evaporates, a somewhat cured, still sticky silicone rubber layer is formed. When this is further heat-treated at a temperature of 30° C. to 0° C. for several minutes or more, a fully cured non-adhesive silicone rubber layer is formed.

The thickness of the silicone rubber layer of the waterless photosensitive lithographic printing plate of the present invention is preferably 0.7 to 200 μm, especially /~io
It is preferably 2 to 503 m.

The substrate used in the waterless photosensitive lithographic printing plate of the present invention is not particularly limited as long as it has the flexibility to be attached to a lithographic printing machine and can withstand the load applied during printing.

For example, paper such as coated paper; metal plates such as aluminum, iron, and zinc; organic polymer films such as polyolefin (e.g., polyethylene, polypropylene, etc.), polyester (e.g., polyethylene terephthalate, etc.), polyamide; Composite: Further examples include a composite of a material other than the above-mentioned metal plate and a metal foil such as aluminum foil. It is also possible to further coat these surfaces for the purpose of preventing halation, or to use paper, organic polymer film, or the like impregnated with or dispersed in an ultraviolet absorber as a substrate.

The method for producing the waterless photosensitive lithographic printing plate of the present invention usually involves the following steps:
It is manufactured according to the following method.

(1) A method in which a photosensitive layer and a silicone rubber layer are coated in this order on a polymer film, and the substrate and silicone rubber layer are pressed together so that they are in close contact with each other.

(2) A method of press-bonding a silicone rubber layer provided on a substrate and a photosensitive layer provided on a polymer film so that the silicone rubber layer and the photosensitive layer are in close contact with each other.

The above polymer film has a thickness of 0.1 to 5005 mm.
m polyethylene film, polypropylene film,
Examples include acrylonitrile-butadiene-styrene copolymer film, polystyrene film, acrylonitrile-styrene copolymer film, polymethyl methacrylate film, nylon 6 film, polyvinyl chloride film, polyvinylidene chloride film, polyethylene terephthalate film, etc. It may also be a film whose wettability has been improved by subjecting it to discharge treatment, surface roughening treatment, etc.

Furthermore, a silane coupling agent, a silicone primer, etc. may be added to the photosensitive layer or the silicone rubber layer for the purpose of improving the adhesion between the photosensitive layer and the silicone rubber layer, within a range that does not impair the effects of the present invention. good. Similarly, in order to improve the adhesion between the silicone rubber layer and the substrate, a silane coupling agent, silicone primer, etc. may be applied to the substrate, or a silane coupling agent, silicone primer, etc. may be applied to the silicone rubber layer. may be added.

A waterless lithographic printing plate can be obtained from the waterless photosensitive lithographic printing plate of the present invention as follows.

That is, from above the polymer film of the waterless photosensitive lithographic printing plate of the present invention, or after peeling off the polymer film, the photosensitive layer is exposed to carbon arc, high pressure mercury lamp, xenon lamp,
Metal halide lamps, fluorescent lamps, tungsten lamps, argon ion lasers, helium cadmium lasers, krypton lasers, etc. / ultraviolet rays of gOnm or more,
After imagewise exposure, preferably using a general-purpose light source including visible light, using an alkaline aqueous developer containing a small amount of an organic solvent, if the polymer film is soluble in this developer, then Alternatively, the polymer film is developed after being peeled off. During this development process, the photosensitive layer in the unexposed areas is dissolved or peeled off, and the surface of the ink-repellent silicone layer is exposed, forming a non-image area.On the other hand, the photosensitive layer in the exposed areas is hardened and developed. A waterless lithographic printing plate can be obtained by forming ink-receptive image areas without being removed by processing.

The developer used in the development of the waterless lithographic printing plate of the present invention preferably contains a specific organic solvent, an alkaline agent, and water. Here, the specific organic solvent is one that can dissolve or swell the exposed area (non-image area) of the photosensitive layer when contained in the developer, and has a solubility in water of 10% by weight at room temperature (20°C). Refers to the following organic solvents. Such organic solvents only need to have the above-mentioned properties, and examples thereof include ethyl acetate, propyl acetate, butyl acetate, amyl acetate, benzyl acetate, and ethylene glycol motubutyl acetate. , butyl lactate, butyl levulinate, and other carboxylic acid esters; ethyl butyl ketone, methyl isobutyl ketone, cyclohexanone, and other ketones; ethylene glycol motubutyl ether, ethylene glycol benzyl ether, ethylene glycol monophenyl ether, benzyl alcohol, methyl phenyl carboxylic acid Examples include alcohols such as alcohol, n-amyl alcohol, and methyl amyl alcohol; alkyl-substituted aromatic hydrocarbons such as xylene; and halogenated hydrocarbons such as methylene dichloride, ethylene dichloride, and monochlorobenzene.

Two or more kinds of these organic solvents may be used. Among these organic solvents, ethylene glycol monophenyl ether and benzyl alcohol are particularly effective.

The content of these organic solvents in the developer is usually O,
OS~-0% by weight, preferably 0.7 to 5% by weight.

On the other hand, the alkaline agents contained in the developer include (A) sodium silicate, potassium silicate, potassium hydroxide, sodium hydroxide, lithium hydroxide, secondary or tertiary phosphoric acid, or Ammonium salts, sodium metasilicate, sodium carbonate, potassium carbonate,
Inorganic alkaline agents such as ammonia (B) Mono, di or trimethylamine, mono, di or triethylamine, mono or diisopropylamine,
Examples include organic compounds such as n-butylamine, mono-, di-, or tri-ethanolamine, mono-, di-, or tri-isopropanolamine, ethyleneimine, and ethylenediamine.

The content of these alkaline agents in the developer is usually O,
OS--% by weight, preferably 7 to 6% by weight.

Certain solubilizers may also be included to aid in the dissolution of the organic solvents mentioned above in water. As such a solubilizing agent, it is preferable to use low-molecular alcohols and ketones. Furthermore, anionic surfactants, amphoteric surfactants, etc. can also be used. Examples of the alcohols and ketones include methanol, ethanol, propatool,
It is preferable to use butanol, acetone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methoxybutanol, ethoxybutanol, goomethoxymethylbutanol, N-methylpyrrolidone, and the like. Preferred examples of the surfactant include sodium inpropylnaphthalene sulfonate, sodium n-butylnaphthalene sulfonate, sodium N-methyl-N-pentadecylaminoacetate, and sodium lauryl sulfate. There is no particular restriction on the amount of solubilizers such as alcohols and ketones used, but it is generally preferred that the amount is about 30% by weight or less based on the entire developer.

[Examples] The present invention will be explained in more detail below using synthesis examples and examples, but the present invention is not limited to these examples.

Note that all parts used in the examples indicate parts by weight.

Synthesis Example 1 N-phenylmethacrylamide Q, O9, acrylonitrile, 3. ．． 19. Methyl acrylate 3. Co11 acrylic acid ether//,,! ;11, methacrylic acid/, /11
α,α′-azobisinbutyronitrile 0. A polymerization reaction was carried out using a mixture of 1/1 and methanol at reflux temperature under a nitrogen atmosphere.

After 5 hours, 1 Io of comethoxyethanol was added, and the temperature of the oil bath was raised to 130° C., and in about an hour and a half, methanol and unreacted monomers were removed by distillation, and at the same time unreacted initiator was decomposed.

After cooling, λ-methoxyethanol was further added to obtain a 33% by weight λ-methoxyethanol solution of the polymer compound. The yield is approx. It was 5chi.

Gel permeation chromatography under the following conditions (
When measured by GPC (hereinafter abbreviated as GPC), the superimposed average (GPC conditions) was calculated using standard polystyrene. Column: TSK-GEL GMHXL manufactured by Tosoh Corporation
, 2 solvents: Nato2hydrofuran Flow rate = 7.047 minutes Detection: UV 2'lnm Synthesis example N-7 enyl methacrylamide ti,oy, acrylonitrile, 2.71? , methyl acrylate 3.211゜methyl methacrylate 11 ethyl acrylate/0. 11 Methacrylic acid i, ry, α, α'-Azobisisobutyronitrile 0.11/Ii and methanol -〇-
After 0 # hours of polymerization reaction of the mixture at reflux temperature under nitrogen atmosphere, comethoxyethanol 4IO- was added, the temperature of the oil bath was raised to 130°C, and in about 2 hours methanol and unreacted 7 The unreacted initiator was decomposed at the same time as removing the zimmer by distillation.

After cooling, comethoxyethanol was further added to obtain a 35% by weight 2-methoxyethanol solution of the polymer compound. The yield was approximately 90 g.

The weight average molecular weight is 10,000.

Synthesis Example 3 N-(3-methoxyphenyl)methacrylamidoda, 11 acrylonitrile halog, methacrylic acid cohydroxy ether J, Jll, ethyl methacrylate S1
Acrylic acid fk/0. ! II.

A mixture of 3 g of methacrylic acid, α, α'-azobisisobutyronitrile θ, <c/, 9, and 30 methanol was subjected to a polymerization reaction at reflux temperature under a nitrogen atmosphere for 3 hours.

The subsequent treatment was carried out in the same manner as in Synthesis Example/1 to obtain a 35% by weight methoxyethanol solution of the polymer compound. The yield is approx. It was 3 chi.

The weight average molecular weight was //10,000.

Synthesis example N-(1-ethylphenyl) methacrylamide q, 7y
, N-(q-hydroxyphenyl)methacrylamide 2
, 211, acrylonitrile, 711 ethyl acrylate/110. A mixture of ty, acrylic acid/, 3.9, benzoyl peroxide, sg, and -monomethoxyethanol was heated under a nitrogen atmosphere at an oil bath temperature of 100%.
℃, and the polymerization reaction was carried out for 9 hours. After cooling, add comethoxyethanol to prepare the polymer compound 3! fwt%--methoxyethanol solution was obtained. Yield is about 90
%Met.

The weight average molecular weight was 14,000. Example 1 The inner surface of a polypropylene film 5o-20/-no made by Honshu Paper Co., Ltd. with a thickness of approximately SO μm (wet tension: 3 gdyne/c)
m), apply the following photosensitive liquid-7 to (-coat term/0 (
R, D, 5 specialiaties Inc.) and dried at 60° C. for S minutes to form a 2 μm thick photosensitive layer.

Photosensitive liquid-7 (a) Synthesis example/polymer compound (N-7 enylmethacrylamide/acrylonitrile/methyl acrylate/ethyl acrylate/methacrylic acid = 10/CoII//!;/Ill,/!; mol 33% by weight of
Comethoxyethanol solution...2'IO part (b
) Hexafluorophosphate of a polycondensate of p-diazodiphenylamine and formaldehyde (as a polycondensation reaction product with β-naphthol, weight average molecular weight s, g o o )...
lS part (C) Florado FC-1I manufactured by Sumitomo 3M■
30 -0.07 parts (d) Victoria Pure Blue BOH manufactured by Udougaya Chemical ■ 7 parts (e)
2-ethoxyethanol...750 parts (
f) -2-methoxyethanol...2g
Part o Next, on this photosensitive layer, the following silicone rubber solution -
/ using a spin coater at room temperature, io.

rpm, air-dried at room temperature for 3 minutes, and then dried at 60° C. for 72 minutes. It was still a sticky, uncured silicone rubber layer.

Silicone rubber solution - (a) Polydimethylsiloxane with hydroxyl groups at both ends (viscosity 73,000 Stokes, manufactured by Toray Silicone B)
Y/A-gO/)...100 parts (#3) Methyltris(methylethylketoxime)silane
... 70 parts (C) Diptyltin diacetate ... 0.2 parts (d) Methylcyclohexane ..., 700 parts On the other hand, thickness 0.217
Using a rotary coating machine, coat the aluminum plate at room temperature,
A primer layer was provided on the aluminum plate by applying SH-coco bob primer from Toray Silicone ■ at 0.000 rpm and air drying for S minutes at room temperature. On top of this, a polypropylene film with the photosensitive layer and silicone rubber layer laminated in this order was heated at 30°C using a laminator so that the primer layer and silicone rubber layer were in contact with each other. It was crimped in minutes. After heat-treating this at 60° C. for 3 minutes, the polypropylene film was peeled off. Furthermore, lI! at 60℃! r
The silicone rubber layer was sufficiently cured by heat treatment for a minute to obtain a waterless photosensitive lithographic printing plate.

The thickness of the completely cured silicone rubber layer is 70 μm.
It was m.

This plate was subjected to image exposure for 50 seconds from a distance of 70α using a 7 KW high-pressure mercury lamp UMH-3000 manufactured by Ushio Inc., through a negative original film according to a conventional method.

This was developed by immersing it in the following developer solution-7 at 10°C for 1 minute and rubbing it lightly. The photosensitive layer in the unexposed areas is removed, and the ink-repellent silicone rubber layer is exposed, forming a non-image area, while the photosensitive layer in the exposed areas is not removed.
A waterless lithographic printing plate with an ink-receptive image area was obtained.

Developer solution-7 *l Product name, manufactured by Kao ■, sodium salt of β-naphthalene sulfonic acid formalin condensation Using this plate, supply dampening water to a printing machine Sun Offset 220E manufactured by San Printing Machinery ■. When printing was carried out using Toyo King Ultra TKU Aquares G black ink manufactured by Toyo Ink Seisakusho, 70,000 beautiful prints with no background smudges were obtained from the beginning of printing. Furthermore, the ink receptivity in the image area was very good.

Comparative Example 1 The following photosensitive liquid-4 was used instead of photosensitive liquid-7 in Example/
A waterless photosensitive lithographic printing plate was prepared in the same manner as in Example 1 except that the following was changed.

Photosensitive liquid-1 (a) Benzyl methacrylate/acrylonitrile/
30% by weight comethoxy ethanol solution of methyl acrylate/ethyl acrylate/methacrylic acid (lO/21I//!1II6/!r mol%) copolymer (weight average molecular weight g, tr 10,000) ...;igo part (b) Hexafluorophosphate of a polycondensate of p-diazodiphenylamine and paraformaldehyde (used in Examples/) ... 1S part (
C) Florado FC-da 3θ manufactured by Sumitomo 3M■
o, oi part (d) Victoria Pure Blue BOH manufactured by Odougaya Chemical ■ 1 part (e)
J-nitoxyethanol ・・・iso part (
f) Comethoxyethanol...210
This was subjected to image exposure in the same manner as in Example/, and the developer solution-l
A waterless lithographic printing plate was obtained.

When this plate was printed under the same conditions as in Example 1, scumming occurred from the beginning of printing, and the scumming did not recover even after printing was continued. In addition, the solid area was damaged after printing i and ooθ sheets.

The following photosensitive liquid-3 was used instead of photosensitive liquid-1 in Comparative Example/Example.
A waterless photosensitive lithographic printing plate was prepared in the same manner as in Example 1 except that the following was changed.

Photosensitive liquid-3 (a) Benzyl acrylate/acrylonitrile/methyl acrylate/ethyl acrylate/methacrylic acid (to/2da//r/'Its/!rmolti) copolymer (weight average molecular weight to, ooo) 250 parts (b) Hexafluorophosphate of a polycondensate of p-diazodiphenylamine and paraformaldehyde (used in Examples) 1S parts (
C) Resident 3M made Florado FC-da 30...
0.07 parts (d) Victoria Pure Blue BOH manufactured by Odugaya Kagaku ■ 7 parts (e)
2-ethoxyethanol ・・・iso part (
f) 2-methoxyethanol...XSO
This was imagewise exposed in the same manner as in Example/, and the developer solution -/
A development process was performed using.

When the thus obtained waterless lithographic printing plate was printed under the same conditions as in Example, scumming occurred from the beginning of printing.

Furthermore, the ink receptivity was also very poor.

Examples Co-da The following photosensitive solution was applied to the polypropylene film used in Example 1 using Percoatterm 10 and dried at 60° C. for 6 minutes to provide a photosensitive layer with a thickness of about λ μm.

Photosensitive solution (a) 3 parts weight of the polymer compound in Table 1 [:% Comethoxyethanol solution...230 parts (b) p
-Hexafluorophosphate of polycondensate of diazodiphenylaminmint paraformaldehyde (used in Examples/)... 20 parts (C
) Julimar AC-#7L (Product name, Nippon Tsumugi Pharmaceutical ■
6 parts (d)
Resident 3M■ Florado FC-da 30...0.
Part 07 (e) Victoria Pure Blue BOH manufactured by Odugaya Kagaku ■ /, Part 2 (f
) -1-methoxyethanol..., 30
0 parts (g) 2-ethoxyethanol...
ioo section/Composition of polymer compound HPMA represents N-(tx-hydroxyphenyl) methacrylamide, and AA represents acrylic acid.

Next, on each photosensitive layer, silicone rubber solution-7 of Example 7 was applied in the same manner as in Example 1, and the subsequent treatment was also performed in the same manner as in Example 1. I got it.

After image exposure in the same manner as in Example 1, development treatment was performed by immersing the plates in the following developer solution-1 at 1.25°C for 20 seconds and rubbing lightly to obtain three types of waterless lithographic printing plates. Ta.

Developer - In Table 1, AN is acrylonitrile, MA is methyl acrylate, MMA is methyl methacrylate, EA is ethyl acrylate, MAA is methacrylic acid, HEMA is cohydroxyethyl methacrylate, EMA is ethyl methacrylate, *22 Part name: Made by Monomoto Yushi ■, Sodium dibutylnaphthalene sulfonate When these plates were used to print in the same manner as in Example/, the results were as follows.
More than 20,000 beautiful prints with no background smudges were obtained from the beginning of printing. However, the ink receptivity was still good.

〔Effect of the invention〕

According to the present invention, the adhesion between the photosensitive layer and the silicone rubber layer is good, the silicone rubber layer has good ink repellency,
The present invention is industrially extremely useful because it can provide a negative waterless photosensitive lithographic printing plate with excellent ink receptivity to the photosensitive layer.

Applicant: Mitsubishi Kasei Corporation Representative patent attorney Others/names

Claims (1)

[Claims] (1) In a negative waterless photosensitive lithographic printing plate in which a substrate, a silicone rubber layer and a photosensitive layer are provided in this order, the photosensitive layer contains a photosensitive diazo resin and a structural unit represented by the following general formula [I]. A negative waterless photosensitive lithographic printing plate, characterized in that it contains 1 to 50 mol% of a polymer compound. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [I] (In the formula, R is a hydrogen atom or a methyl group, X is an alkylene group, n is a number of 0 or 1, and Y is an alkyl group or an alkoxy group, and m represents a number from 0 to 5.)