JPH11352672A - Waterless planographic original printing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photosensitive layer remaining type negative waterless planographic original printing plate having excellent image reproducibility and preservable stability. SOLUTION: In the waterless planographic original printing plate formed by laminating at least a photosensitive layer and a silicone rubber layer on a supporting body in this order, the photosensitive layer is separated into 2 phases of a phase consisting essentially of a compound having hydroxide group and quinone diazide group and a phase consisting essentially of a polymer and a specific addition type silicone rubber layer is used as the silicone rubber layer. As a result, the waterless planographic original printing plate having excellent image reproducibility and preservable stability is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lithographic printing plate precursor without water, and more particularly, to a lithographic printing plate precursor having good image reproducibility and excellent storage stability.

[0002]

2. Description of the Related Art Conventionally, various printing plates have been proposed for performing lithographic printing using silicone rubber or fluororesin as an ink repellent layer without using dampening water.

As photosensitive lithographic printing plates using a fluororesin for the ink repellent layer, there are JP-A-2-254449 and JP-A-2-85855, and the like.
H, 1H, 2H, 2H-heptadecafluorodecyl acrylate and 1H, 1H, 2H, 2H-heptadecafluorodecyl methacrylate are used.

A positive type photosensitive lithographic printing plate having a silicone rubber as an ink repellent layer is disclosed in, for example, JP-B-54-26.
No. 923, Japanese Patent Publication No. 56-23150, etc., a waterless planographic printing plate in which a photopolymerizable adhesive layer and a silicone rubber layer are laminated on a substrate;
No. 5, JP-B-3-56622 and the like, and a waterless planographic printing plate in which a photodimerizing photosensitive layer and a silicone rubber layer are laminated on a substrate.

A negative type photosensitive lithographic printing plate using silicone rubber for the ink repellent layer is disclosed in Japanese Patent Publication No. 61-6 / 1986.
No. 16, JP-B-61-54218, etc. propose a waterless planographic printing plate having a photosensitive layer containing a quinonediazide compound on a support and a silicone rubber layer provided on the photosensitive layer via an adhesive layer.

Various inventions have also been made on methods for improving the UV ink resistance and solvent resistance of a printing plate after the printing plate is manufactured. For example, JP-B-61-617, JP-A-57-192965, and JP-A-57-192957.
JP-A-57-205740, JP-A-60-133
452 and JP-A-60-169852.

[0007] Of these, Japanese Patent Application Laid-Open No. Sho 60-169852
In Japanese Patent Laid-Open Publication No. H11-264, a waterless lithographic plate having a photosensitive layer using a compound obtained by adding a quinonediazide group to an acetone pyrogallol resin is proposed. However, in this method, the developability is unstable because the acetone pyrogallol resin is not crosslinked in the raw plate state, and it is necessary to perform image exposure and overall exposure after development in order to improve the solvent resistance of the photosensitive layer. Therefore, the workability was poor and the effect of improving the solvent resistance was low, so that it was not practically used. Furthermore, this method is a so-called solution-developing type waterless lithographic plate in which the photosensitive layer is dissolved by development, so that there is also a problem that the ink deposition property and the ink mileage are inferior.

In Japanese Patent Application Laid-Open Nos. 60-133453 and 60-35735, waterless lithographic plates using a compound obtained by adding a quinonediazide group to an acetone pyrogallol resin have been proposed. The waterless lithographic plate has poor ink deposition and ink mileage, and requires heat treatment to improve the solvent resistance of the unexposed areas after development, resulting in poor workability and low effect of improving solvent resistance. It was not a target.

As a method for solving these problems, for example, Japanese Patent Publication No. 61-54222 discloses a method in which 1,2 is coated on a support.
Negative having a photo-peelable photosensitive layer in which a partially esterified product of naphthoquinone-2-diazide-5-sulfonic acid chloride and phenol formaldehyde hydronovolak resin is cross-linked with a polyfunctional isocyanate, and the photosensitive layer in the image area remains during development. Lithographic printing plates without mold water have been proposed. By this method, not only the solvent resistance during development but also the UV
Ink resistance and solvent resistance were also improved.

However, these waterless lithographic plates have a problem that the photosensitive layer is stiff and easily detached when the number of printed sheets is large because the photosensitive layer is rigid, resulting in insufficient printing durability.

As a method for improving the printing durability, for example, JP-A-8-286364, JP-A-8-305008 and JP-A-8-30509 disclose a method of softening the photosensitive layer by adding polyurethane to the photosensitive layer. Has been proposed.

However, these waterless lithographic plates have a problem that image reproducibility and storage stability are inferior to those of plates containing no polyurethane.

On the other hand, as the silicone rubber layer used as the ink repellent layer of the waterless planographic printing plate precursor, a condensation type silicone rubber has conventionally been generally used. However, the condensation type reaction is susceptible to the influence of humidity. There is a problem that it is difficult to control the speed and the adhesiveness with the photosensitive layer.
During storage, the condensation reaction of the silicone rubber layer progresses and reacts with the compound having a hydroxyl group in the photosensitive layer, so that the adhesion between the silicone rubber layer and the photosensitive layer increases and the developability decreases, which is also a problem of so-called poor storage stability. Had.

As a method for solving these problems, various methods using an addition type silicone rubber have been proposed. Unlike the condensation type silicone, the addition type silicone completes the addition reaction at the time of plate production, so it is considered that the adhesiveness to the photosensitive layer during storage is unlikely to change. JP-A-4-68353
In JP-A No. 9-264, a positive waterless planographic printing plate precursor is proposed in which an addition type silicone rubber layer containing a hydrogen siloxane having a specific structure is coated on a photopolymerizable photosensitive layer. However, the adhesiveness with the photopolymerizable photosensitive layer is insufficient,
There is a problem that the curability of the silicone rubber layer is not sufficient and it takes time to cure. Therefore, JP-A-4-
JP-A-174443 and JP-A-5-94007 propose a method of improving the curability of a silicone rubber layer by using a photopolymerizable monomer having a specific structure as a photopolymerizable monomer in a photosensitive layer. Japanese Patent Application Laid-Open No. H4-174437 proposes a method using a photopolymerizable monomer having 6 to 60 ethylene oxide groups or propylene oxide groups in one molecule.

Further, Japanese Patent Application Laid-Open No. 6-202313 discloses an addition type containing a tertiary amine-based organosilicon compound having a hydrolyzable group as an adhesion promoter on a photopolymerizable, photocrosslinkable or photoremovable photosensitive layer. A method of applying a silicone rubber layer has been proposed. Although the adhesiveness with the photosensitive layer can be improved by this method, the adhesiveness changes depending on the humidity at the time of coating the silicone rubber layer, and it is difficult to obtain stable adhesiveness. There is a problem that ink resilience decreases.

Japanese Unexamined Patent Publication (Kokai) No. 6-202313 discloses a waterless planographic printing plate precursor containing an acetone pyrogallol resin having a quinonediazide group in a photosensitive layer and an addition type silicone rubber in a silicone rubber layer.
Since the photosensitive layer is not cross-linked, the curability of the silicone rubber layer is insufficient, and the solvent resistance of the non-image area is inadequate, and the ink adhesion and ink mileage are poor. Has not been put to practical use because it is insufficient.

[0017]

An object of the present invention is to provide a waterless planographic printing plate precursor having good image reproducibility and excellent storage stability.

[0018]

As a result of repeated studies, the present inventors have found that the above-mentioned problems can be solved by the following method.

That is, an object of the present invention is to provide (1) a compound having a hydroxyl group and a quinonediazide group in a waterless planographic printing plate precursor comprising at least a photosensitive layer and a silicone rubber layer laminated on a substrate in this order. Is separated into two phases, a phase mainly containing a polymer and a phase mainly containing a polymer. Further, the silicone rubber layer has a polysiloxane having a vinyl group having a molecular weight of 100,000 or less, and 3 to 20 parts per 1 of the vinyl group. A waterless lithographic printing plate precursor comprising hydrogen siloxane in a ratio having hydrogen groups directly bonded to silicon atoms, wherein said vinyl groups and hydrogen groups directly bonded to silicon atoms are cross-linked by an addition reaction. .

(2) The waterless planographic printing plate precursor as described in (1), wherein the compound having a hydroxyl group and a quinonediazide group is crosslinked with isocyanate.

(3) The waterless lithographic printing plate precursor as described in (1) or (2), wherein the polymer is polyurethane.

(4) The silicone rubber layer contains an organopolysiloxane having two or more vinyl groups in a molecule, a hydrogensiloxane having three or more SiH groups in a molecule, and a platinum compound. ) ~
(3) The waterless planographic printing plate precursor described in (3).

(5) The value of the number of SiH groups / molecular weight in the molecule of the hydrogen siloxane is 0.001 mol /
g. or more, the waterless lithographic printing plate precursor as described in any one of (1) to (4) above.

(6) The compound having a hydroxyl group and a quinonediazide group is a phenol novolak resin, which is 1,2-naphthoquinone-2-diazide-5-sulfonic acid chloride or 1,2-naphthoquinone-2-diazide-4-sulfone. The waterless lithographic printing plate precursor as described in any one of (1) to (5), which is esterified with an acid chloride and has a degree of esterification of 1 to 60%.

(7) The waterless planographic printing plate precursor as described in (1) to (6), wherein the content of the isocyanate in the photosensitive layer is 5 to 45% by weight based on the quinonediazide compound.

Is achieved by:

[0027]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.

First, the waterless planographic substrate used in the present invention will be described. The waterless lithographic printing plate of the present invention must be flexible enough to be set in a normal printing press and withstand the load applied during printing. Accordingly, typical substrates include coated paper, metal plates such as aluminum, plastic films such as polyethylene terephthalate, rubber, and composites thereof. The surface of these substrates can be further coated with a primer layer or the like for the purpose of preventing halation and for other purposes.

The primer layer is obtained, for example, by curing various photosensitive polymers proposed in Japanese Patent Application Laid-Open No. Sho 60-22903 before exposing the photosensitive layers to each other. A methacrylic phosphorus-containing monomer proposed in Japanese Patent Application Laid-Open No. H07-15095 cured by exposing it before laminating a photosensitive layer, and a methacrylic epoxy compound proposed in JP-A-2-7049 before laminating a photosensitive layer. Exposed and cured, JP-A-62-5
No. 0760, epoxy resin cured by heat, gelatin disclosed in JP-A-63-133151, hardened gelatin, JP-A-1-2
No. 82270 and Japanese Patent Application Laid-Open No. 2-21072 using a urethane resin. In addition, a casein cured case is also effective.

For the purpose of further softening the primer layer, the primer layer has a glass transition temperature of room temperature or lower, such as polyurethane, polyamide, styrene / butadiene rubber, carboxy-modified styrene / butadiene rubber, acrylonitrile / butadiene rubber, carboxy-modified acrylonitrile / Polymers such as butadiene rubber, polyisoprene rubber, acrylate rubber, polyethylene, chlorinated polyethylene and chlorinated polypropylene may be added.
The addition ratio is arbitrary, and the primer layer may be formed only with the additives as long as the film layer can be formed.

Further, these primer layers may be provided with a dye, a pH indicator, an exposure baking agent, a photochromic compound, a photopolymerization initiator, an adhesion auxiliary agent such as a polymerizable monomer, a diazo resin, Additives such as coupling agents, titanate coupling agents, aluminum coupling agents, zirconia coupling agents, and boron coupling agents), white pigments, and silica particles.

The thickness of the primer layer used in the present invention is preferably in the range of 0.1 to 20 g / m ^{2 on} a dry weight basis.
The range of from 10 to 10 g / m ² is more preferable.

Next, the photosensitive layer of the present invention will be described.

The photosensitive layer of the present invention needs to form a phase-separated structure composed of at least two phases having a hydroxyl group and having a quinonediazide compound as a main component and a phase having a polymer as a main component.

As the quinonediazide compound having a hydroxyl group, a compound obtained by adding a quinonediazide group to a phenol novolak resin or an acetone pyrogallol resin is preferable.

As a method of adding a quinonediazide group to a phenol novolak resin or an acetone pyrogallol resin, a method of esterification with benzoquinonediazidesulfonic acid, naphthoquinonediazidesulfonic acid or the like is preferable.

As such a quinonediazide compound, specifically, 1,2-benzoquinone-2-diazide-4-
Sulfonic acid chloride, 1,2-benzoquinone-2-diazide-4-sulfonic acid, 1,2-naphthoquinone-2-diazide-4-sulfonic acid chloride, 1,2-naphthoquinone-2-diazide-4-sulfonic acid, 1,2-naphthoquinone-2-diazide-5-sulfonic acid chloride, 1,2
-Naphthoquinone-2-diazide-5-sulfonic acid, 1,
Examples thereof include 2-naphthoquinone-2-diazide-6-sulfonic acid chloride and 1,2-naphthoquinone-2-diazide-6-sulfonic acid, but the present invention is not limited thereto. Among these compounds, 1,2-naphthoquinone-
2-diazide-4-sulfonic acid chloride and 1,2
-Naphthoquinone-2-diazide-5-sulfonic acid chloride is particularly effective.

The addition amount of the quinonediazide compound is as follows:
The esterification rate is preferably 5 to 67%, more preferably 15 to 60%, and still more preferably 30 to 50%.
Is preferred. The esterification ratio is a ratio of the number of hydroxyl groups esterified with the quinonediazide compound to the number of hydroxyl groups of the phenol novolak resin or the acetone pyrogallol resin expressed as a percentage. When the esterification ratio is less than 5%, the photosensitive components tend to decrease, and the image reproducibility tends to decrease.
%, The residual hydroxyl groups, which are the cross-linking points of the phenol novolak resin or acetone pyrogallol resin, decrease, so that the cross-linking density decreases, and as a result, the solvent resistance of the photosensitive layer decreases, which is not preferable.

The above-mentioned quinonediazide compound may have a silyl group for the purpose of lowering the compatibility with the polymer phase and facilitating the formation of a phase-separated structure. A method for adding a silyl group is obtained by reacting a silyl compound having a functional group capable of undergoing an addition reaction with a remaining hydroxyl group of a phenol novolak resin.

Examples of the group capable of reacting with a hydroxyl group include an isocyanate group, a carboxyl group and an epoxy group.

In the photosensitive layer of the present invention, the quinonediazide group compound preferably forms a crosslinked structure from the viewpoint of the solvent resistance of the image area on the printing plate. As a method of forming a crosslinked structure, a method of adding a polyfunctional isocyanate or a polyfunctional epoxy compound described below and performing thermal crosslinking is preferable.

Examples of polyfunctional isocyanates include paraphenylene diisocyanate, 2,4- or 2,6-toluylene diisocyanate (TDI), 4,4-diphenylmethane diisocyanate (MDI), tolidine diisocyanate (TODI), and xylylene diisocyanate. XDI), hydrogenated xylylene diisocyanate, cyclohexane diisocyanate, meta-xylylene diisocyanate (MXDI), hexamethylene diisocyanate (HDI or HMDI), lysine diisocyanate (LDI) (also known as 2,6-diisocyanatomethylcaproate), hydrogenated MDI (H12MDI) (also known as 4,4'-methylenebis (cyclohexyl isocyanate)), hydrogenated TDI (HTDI) (also known as methylcyclohexane 2,4 (2 , 6) diisocyanate), hydrogenated XDI (H6XDI) (also known as 1,3- (isocyanatomethyl) cyclohexane), isophorone diisocyanate (IPDI), diphenyl ether isocyanate,
Trimethylhexamethylene diisocyanate (IPD
I), diphenyl ether isocyanate, trimethylhexamethylene diisocyanate (TMDI), tetramethyl xylylene diisocyanate, polymethylene polyphenyl isocyanate, dimer acid diisocyanate (DDI), triphenylmethane triisocyanate,
Tris (isocyanatephenyl) thiophosphate, tetramethylxylylene diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4
-Isocyanate methyl octane, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate and the like, polyhydric alcohol adducts of polyisocyanates, and polymers of polyisocyanates.

Examples of the polyfunctional epoxy compound include compounds obtained by reacting a hydroxyl-containing compound with epihalohydrin.

Specific examples of the polyfunctional hydroxyl group-containing compound include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 1,3-
Butanediol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-
Nonanediol, 1,10-decanediol, 2-butene-1,4-diol, 5-hexene-1,2-diol, 7-octene-1,2-diol, 3-mercapto-1,2-propanediol , Hydroquinone, dihydroxyanthraquinone, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, bisphenol A, bisphenol S, phenol formaldehyde novolak resin, resole resin, resorcinbenzaldehyde resin, pyrogallol acetone resin, hydroxystyrene polymers and copolymers, glycerin , Diglycerin, trimethylolpropane, 1,2,4-butanetriol, pentaerythritol, dipentaerythritol, sorbitol, sorbitan, polyvinyla Call, cellulose and its derivatives, polymers and copolymers of hydroxyethyl (meth) acrylate, and the like.

Among these, it is preferable to thermally crosslink with a polyfunctional isocyanate compound.

The amount of the polyfunctional compound to be used is preferably 1 to 80 parts by weight, more preferably 2 to 50 parts by weight, based on 100 parts by weight of the quinonediazide compound.
More preferably, 2 to 20 parts by weight is preferable.

These thermal cross-linking reactions must be carried out at a temperature at which the photosensitivity of the quinonediazide group is not lost, usually at 150 ° C. or lower. For this purpose, it is preferable to use a catalyst in combination.

The polymer that forms a phase-separated structure with the quinonediazide compound in the photosensitive layer of the present invention will be described.

As the polymer, any polymer can be used as long as it is soluble in an organic solvent and has a film forming ability. The following are specific examples of the polymer, but the present invention is not particularly limited to these examples.

(1) Vinyl polymers Specifically, monopolymers having an unsaturated double bond such as ethylene, propylene, 1-butene, styrene, butadiene, isoprene, vinyl chloride, vinyl acetate, acrylic acid derivatives and methacrylic acid derivatives Polymers and copolymers obtained from the monomers and their derivatives.

(2) Unvulcanized rubber Specifically, natural rubber, (NR), a homopolymer or a copolymer selected from butadiene, isoprene, styrene, acrylonitrile, acrylic acid ester, methacrylic acid ester, or these. Epoxidation, chlorination, carboxylation and the like.

(3) Polyoxides (polyethers) Trioxane, ethylene oxide, propylene oxide, 2,3-epoxybutane, 3,4-epoxybutene, 2,3-epoxypentane, 1,2-epoxyhexane, epoxycyclohexane , Epoxycycloheptane, epoxycyclooctane, styrene oxide, 2-
Phenyl-1,2-epoxypropane, tetramethylethylene oxide, epichlorohydrin, epibromohydrin, allyl glycidyl ether, phenyl glycidyl ether, n-butyl glycidyl ether, 1,4-dichloro-2,3-epoxybutane, 2,3 -Polymers and copolymers by ring-opening polymerization of epoxypropionaldehyde, 2,3-epoxy-2-methylpropionaldehyde, 2,3-epoxydiethylacetal, and the like.

(4) Polyesters Polyesters obtained by polycondensation of polyhydric alcohols and polycarboxylic acids as shown below, polyesters obtained by polymerization of polyhydric alcohols and polycarboxylic anhydrides, and ring opening of lactones Examples include polyester obtained by polymerization and the like, and polyester obtained from a mixture of these polyhydric alcohols, polycarboxylic acids, polycarboxylic anhydrides, and lactones.

Specific examples of the polyhydric alcohol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butylene glycol, 1,5-pentanediol, and 1,6-pentanediol. Hexanediol, diethylene glycol, dipropylene glycol, neopentyl glycol, triethylene glycol, p-xylene glycol, hydrogenated bisphenol A, bisphenol hydroxypropyl ether,
Glycerin, trimethylolethane, trimethylolpropane, trishydroxymethylaminomethane, pentaerythritol, dipentaerythritol, sorbitol and the like can be mentioned.

Specific examples of polycarboxylic acids and polycarboxylic anhydrides include phthalic anhydride, isophthalic acid, terephthalic acid, succinic anhydride, adipic acid, azelaic acid,
Sebacic acid, Tetrahydrophthalic anhydride, Hexahydrophthalic anhydride, Tetrabromophthalic anhydride, Tetrachlorophthalic anhydride, Hetic anhydride, Hymic anhydride, Maleic anhydride, Fumaric acid, Itaconic acid, Trimellitic anhydride, Methylcyclohexentricarboxylic acid Anhydride, pyromellitic anhydride and the like can be mentioned.

Examples of the lactone include β-propiolactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone and the like.

Specific examples of the polyester having a glass transition temperature of 0 ° C. or lower include poly [1,4- (2-butene)
Sebacate], [1,4- (2-butyne) sebacate], poly (decamethylenadipate), poly (ethylene adipate), poly (oxydiethylene adipate),
Poly (oxydiethylene azelate), poly (oxydiethylene dodecanediate), poly (oxydiethylene glutarate), poly (oxydiethylene heptyl malonate), poly (oxydiethylene nonyl malonate), poly (oxydiethylene octadecandiate) Eight), poly (oxydietin oxalate), poly (oxydiethylene pentyl malonate), poly (oxydiethylene pimerate), poly (oxydiethylene propyl malonate), poly (oxydiethylene sebacate), poly (oxydiethylene sebacate) Oxydiethylene superate), poly (oxyethylene succinate), poly (pentamethylene adipate), poly (tetramethylene adipate), poly (tetramethylene sebacate), poly (trimethylene adipate) and the like. .

(5) Polyurethanes Polyurethanes obtained from the following polyisocyanates and polyhydric alcohols can also be used as the binder polymer. As the polyhydric alcohol, the polyhydric alcohols described in the section of the polyester and the following polyhydric alcohols, both ends obtained by polycondensation of these polyhydric alcohols and the polycarboxylic acid described in the section of the polyester are hydroxyl groups. Certain polyester polyols, polymerized polyester polyols obtained from the above lactones, polycarbonate diols, polyether polyols obtained by ring-opening polymerization of propylene oxide or tetrahydrofuran or modification of epoxy resins, or having a hydroxyl group (meth)
An acrylic polyol, which is a copolymer of an acrylic monomer and a (meth) acrylic acid ester, a polybutadiene polyol, and the like can be given.

Examples of isocyanates include paraphenylene diisocyanate, 2,4- or 2,6-toluylene diisocyanate (TDI), 4,4-diphenylmethane diisocyanate (MDI), tolidine diisocyanate (TODI), and xylylene diisocyanate (XD
I), hydrogenated xylylene diisocyanate, cyclohexane diisocyanate, meta-xylylene diisocyanate (MXDI), hexamethylene diisocyanate (H
DI or HMDI), lysine diisocyanate (L
DI) (alias 4,4′-methylenebis (cyclohexyl isocyanate)), hydrogenated TDI (HTDI) (alias methylcyclohexane 2,4 (2,6) diisocyanate), hydrogenated XDI (H6XDI) (alias 1,3- ( Isocyanatomethyl) cyclohexane), isophorone diisocyanate (IPDI), diphenyl ether isocyanate, trimethylhexamethylene diisocyanate (TMDI), tetramethyl xylylene diisocyanate, polymethylene polyphenyl isocyanate, dimer acid diisocyanate (DDI), triphenylmethane triisocyanate, tris (Isocyanate phenyl) thiophosphate, tetramethyl xylylene diisocyanate, lysine ester triisocyanate,
1,6,11-undecane triisocyanate, 1,8
-Diisocyanate-4-isocyanatomethyloctane, 1,3,6-hexamethylene triisocyanate,
Examples include bicycloheptane triisocyanate and the like, polyhydric alcohol adducts of polyisocyanates, and polymers of polyisocyanates.

Representative polyhydric alcohols other than those described in the section of polyester include polypropylene glycol, polyethylene glycol, polytetramethylene glycol, ethylene oxide-propylene oxide copolymer, and tetrahydrofuran-propylene oxide copolymer. , And as the polyester diol, polyethylene adipate, polypropylene adipate,
Polyhexamethylene neopentyl adipate, polyneopentyl adipate, polyhexamethylene neopentyl adipate,
Examples thereof include polyethylene hexamethylene adipate and the like, and poly-ε-caprolactone diol, polyhexamethylene carbonate diol, polytetramethylene adipate, sorbitol, methyl glucosit, sucrose and the like.

Various phosphorus-containing polyols and halogen-containing polyols can also be used as the polyol.

The above-mentioned isocyanates and polyols can be reacted with each other by a known method to obtain a desired polyurethane, and those obtained by elongating the molecular chain with a known diamine compound can also be used.

(6) Polyamides Copolymers of the following monomers may be mentioned. As monomers, ε-caprolactam, ω-laurolactam, ω-aminoundecanoic acid, hexamethylenediamine, 4,4-bis-aminocyclohexylmethane, 2,
4,4-trimethylhexamethylenediamine, isophoronediamine, glycols, isophthalic acid, adipic acid, sebacic acid, dodecanenilic acid and the like.

More specifically, polyamides are generally classified into water-soluble polyamides and alcohol-soluble polyamides. Examples of the water-soluble polyamide include, for example,
A polyamide containing a sulfonic acid group or a sulfonate group obtained by copolymerizing sodium 3,5-dicarboxybenzenesulfonate as disclosed in JP-A-8-72250, disclosed in JP-A-49-43465. Polyamides having an ether bond obtained by copolymerizing any one of dicarboxylic acids, diamines or cyclic amides having an ether bond in the molecule as described in JP-A-50-7605. Polyamides containing a basic nitrogen obtained by copolymerizing N, N'-di (γ-aminopropyl) piperazine and the like, and polyamides obtained by quaternizing these polyamides with acrylic acid or the like; Japanese Patent Application Laid-Open No. 55-74537 discloses a copolymer containing a polyether segment having a molecular weight of 150 to 1500. If polyamides, and alpha-(N,
Ring-opening polymerization of N′-dialkylamino) -ε-caprolactam or α- (N, N′-dialkylamino) -ε-
Examples include polyamides obtained by ring-opening copolymerization of caprolactam and ε-caprolactam.

Examples of the alcohol-soluble polyamide include linear polyamides synthesized by a known method from dibasic acid fatty acids and diamines, ω-amino acids, lactams or derivatives thereof. Polymers and the like can also be used. Typical examples include nylon 3, 4, 5, 6, 8, 1
1, 12, 13, 66, 610, 6/10, 13/1
3, polyamide from meta-xylylenediamine and adipic acid, polyamide from trimethylhexamethylenediamine or isophoronediamine and adipic acid, ε-caprolactam / adipic acid / hexamethylenediamine /
4,4′-diaminodicyclohexylmethane copolymerized polyamide, ε-caprolactam / adipic acid / hexamethylenediamine / 2,4,4′-trimethylhexamethylenediamine copolymerized polyamide, ε-caprolactam / adipic acid / hexamethylenediamine / isophorone Diamine copolymerized polyamides, polyamides containing these components, N-methylol and N-alkoxymethyl derivatives thereof can also be used.

The above polyamides can be used alone or in combination for the primer layer of the present invention.

Among these polymers, polyesters and polyurethanes are preferred for use in the photosensitive layer of the present invention.

More preferably, hexamethylene diisocyanate, toluene diisocyanate, naphthalene-1,
5-diisocyanate and 1,4-butanediol,
Polyurethanes with 1,6-hexanediol, polypropylene glycol and polyethylene glycol are preferred.

The amount of the binder polymer used is preferably from 5 to 50% by weight, more preferably from 5 to 50% by weight, based on the weight of the photosensitive layer components.
40% by weight. When the amount of the binder polymer is less than 5% by weight, it is difficult to exert the effect of softening the photosensitive layer for the purpose of containing the polymer. On the other hand, when the amount is more than 50% by weight, the quinonediazide group is reduced. Therefore, image reproducibility and developability deteriorate, which is not preferable.

Next, the phase separation structure of the photosensitive layer of the present invention will be described. In the photosensitive layer of the present invention, it is necessary that a phase mainly composed of a quinonediazide compound and a phase mainly composed of a polymer form a phase-separated structure. The form of the phase separation structure of the photosensitive layer can be classified into the following three types.

(1) A form in which one is a continuous phase and the other is a dispersed phase (2) A form in which each of two phases has a continuous phase and a dispersed phase (3) A form in which each of them is a continuous phase The phase separation structure can be confirmed by observing the image portion of the printing plate after development with an optical microscope or a transmission electron microscope after dyeing with a known dye if necessary. Examples of the phase separation structures (1) to (3) are shown in FIGS.

In the dispersion form (1), when the quinonediazide compound is in a dispersed phase, the sensitivity of the printing plate is extremely lowered, which is not preferable. When the polymer is in the dispersed phase, the photosensitive layer becomes hard and brittle. This is not preferable because the printing durability of the printing plate is reduced.

The preferred phase-separated structure of the photosensitive layer of the present invention is preferably such that (2) has a continuous phase and a dispersed phase, and (3) each has a continuous phase. More preferably, each of (3) is preferably in the form of a continuous phase. In this case, the size of each phase is preferably 0.01 to 5 μm in the width of the continuous phase. 0.01 μm
If it is less than 3, the effect of softening the photosensitive layer, which is the purpose of including the polymer in the photosensitive layer, is not obtained, and as a result, the printing durability decreases. If it is more than 5 μm, reproducibility of fine halftone dots Is undesirably reduced.

The phase separation structure in the form of (2) or (3) is, for example, the kind of solvent of the photosensitive layer solution, the solid concentration, the set time after the application of the photosensitive solution, the drying method, the compatibility of the quinonediazide compound and the polymer. It can be formed by controlling such factors.

Among these, the method of controlling the combination of solvents is most preferable. Examples of the combination of solvents for forming the phase-separated structure in the above-mentioned form (2) or (3) include: (a) one of a quinonediazide compound and a polymer having a higher affinity than the other, and a photosensitive layer; Use a solvent that has a higher boiling point than the other solvents used in the solution.

(B) A good solvent for both the quinonediazide compound and the polymer is used as a main component, and a small amount of a solvent that becomes a poor solvent for both or only one of them is mixed.

And the like.

In addition to the above-mentioned components, it is optional to add additives such as acids, dyes, pigments, photochromic agents, and catalysts to the photosensitive layer composition, if necessary.

Preferred compositions of the water-free lithographic photosensitive layer of the present invention include the following.

(1) 50 to 100 parts by weight of a quinonediazide compound having a hydroxyl group (2) 5 to 50 parts by weight of a polyfunctional compound (3) 5 to 50 parts by weight of a binder polymer having a shape-retaining property drying is preferably 0.5 to 3 g / m ² in weight, 1.0~5g / m ² from the viewpoint of workability during production
Is more preferred. If the thickness of the photosensitive layer is less than 0.5 g / m ^2, pinholes and the like are likely to occur, which is not preferable in view of coatability. On the other hand, if it exceeds 5 g / m ² , it is disadvantageous from an economic point of view and is not preferred.

Next, the addition type silicone rubber layer used in the present invention will be described. The addition type silicone rubber layer that can be used in the present invention has a thickness of 0.5 to 50 g / m ² , preferably 0.5 to 10 g / m ² , and has transparency through which ultraviolet rays can pass.

Such an addition type silicone rubber layer comprises an organopolysiloxane having at least two vinyl groups in a molecule and at least three SiHs in a molecule.
A solution obtained by diluting a hydrogen siloxane having a group and a platinum compound with an appropriate solvent is coated on the photosensitive layer,
It is formed by heating, drying and curing.

Examples of the organopolysiloxane having at least two vinyl groups in the molecule used in the silicone rubber layer of the present invention include those having a vinyl group at either the molecular chain terminal or in the middle, and an alkenyl group. Preferred as the organic group other than the above are a substituted or unsubstituted alkyl group and an aryl group. Further, it may contain a trace amount of hydroxyl group.

The following are specific examples of the organopolysiloxane having two or more vinyl groups in the molecule, but the present invention is not limited thereto.

Polydimethylsiloxane having vinyl groups at both ends, (methylvinylsiloxane) (dimethylsiloxane) copolymer having methyl groups at both ends, (methylvinylsiloxane) (dimethylsiloxane) copolymer having vinyl groups at both ends, A compound in which two or more molecules of a vinyl group polydimethylsiloxane are cross-linked by dimethylene, a (methyl 1-hexene siloxane) (dimethyl siloxane) copolymer having a methyl group at both terminals, and a (methyl 1-
Hexene siloxane) (dimethyl siloxane) copolymer and the like.

The organopolysiloxane having two or more vinyl groups in the molecule preferably has a molecular weight of 5,000 or more, more preferably 10,000 or more, in view of rubber properties after curing.

Further, these organopolysiloxanes having two or more vinyl groups in the molecule can be used singly or as a mixture of a plurality of kinds at an arbitrary ratio.

Hydrogensiloxane having at least three or more SiH groups in the molecule includes a molecular chain terminal,
A compound having a SiH group at any one of the intermediates,
Preferred as the organic group other than the iH group are a substituted or unsubstituted alkyl group and an aryl group.

Specific examples of the hydrogen siloxane having at least three or more SiH groups in the molecule include the following, but the present invention is not limited thereto.

Polydimethylsiloxane having SiH groups at both terminals, polymethylhydrogensiloxane having methyl groups at both terminals, (methylhydrogensiloxane) (dimethylsiloxane) copolymer having methyl groups at both terminals, SiH groups at both terminals
(Methyl hydrogen siloxane) (dimethyl siloxane) copolymer, cyclic polymethyl hydrogen siloxane and the like.

Among these, those which can be preferably used in the present invention include at least three or more SiHs in the molecule.
The value obtained by dividing the number of SiH groups in the hydrogen siloxane having a group by the molecular weight is preferably 0.001 mol / g or more, more preferably 0.002 mol / g or more. If the amount is less than 0.001 mol / g, the curing rate is undesirably reduced.

[0092] Hydrogensiloxanes having three or more SiH groups in the molecule can be used alone, or a plurality of types can be used as a mixture at an arbitrary ratio.

The organic groups of the organopolysiloxane having two or more vinyl groups in the molecule and the hydrogensiloxane having three or more SiH groups in the molecule generally account for at least 60% of the number of groups in terms of improving ink repellency. Is preferably a methyl group.

When the organopolysiloxane having two or more vinyl groups in the molecule and the hydrogensiloxane having three or more SiH groups in the molecule are mixed and used, the ratio of the vinyl in the silicone rubber composition is as follows. When the number of groups is 1, the mixing ratio is preferably such that the number of SiH groups is 1.5 to 15, and more preferably 1.5 to 12.

The number of SiH groups is 1.5 per 1 vinyl group.
If it is less than 1, the curability of the silicone rubber layer decreases, and
If it is larger than 5, the silicone rubber becomes brittle and the wear resistance is undesirably reduced.

The platinum compound preferably used in the silicone rubber layer of the present invention is arbitrarily selected from known compounds, and includes platinum alone, platinum chloride, chloroplatinic acid, and olefin-coordinated platinum. Among these, olefin-coordinated platinum is preferable.

In order to control the curing rate of the addition type silicone rubber composition, tetracyclo (methyl vinyl)
Vinyl group-containing organopolysiloxane such as siloxane, alcohol containing carbon-carbon triple bond, acetone,
It is preferable to add a reaction inhibitor such as methyl ethyl ketone, methanol, ethanol, and propylene glycol monomethyl ether.

The general forms of the addition type silicone rubber composition preferably used in the present invention include the following.

(1) 100 parts by weight of an organopolysiloxane having two or more vinyl groups in the molecule (2) 0.1 to 10,000 parts by weight of a hydrogen siloxane having three or more SiH groups in the molecule (3) Platinum compound 0.00001 to 10 parts by weight (4) Reaction inhibitor 0.1 to 10 parts by weight (5) Solvent 100 to 4000 parts by weight In addition to these compositions, a known adhesion promoter such as alkenyl trialkoxysilane is added. Or addition of a hydroxyl group-containing organopolysiloxane or a hydrolyzable functional group-containing silane (or siloxane), which is a composition of the condensation type silicone rubber layer, and silica for the purpose of improving rubber strength. It is also optional to add a known filler such as.

In the waterless lithographic printing plate described herein, it is optional to further coat various silicone rubber layers on the silicone rubber layer, and the adhesive force between the photosensitive resin layer and the silicone rubber layer can be reduced. It is optional to provide an adhesive layer between the photosensitive resin layer and the silicone rubber layer for the purpose of raising or for preventing poisoning of the catalyst in the silicone rubber composition.

The silicone rubber layer forming the surface layer of the waterless planographic printing plate precursor thus configured has problems that it is easily damaged during handling and that the negative film is hard to adhere to the vacuum in the exposure step. It is preferable to attach a transparent protective film on the silicone rubber layer. The protective film is useful in the exposure step, but needs to be removed by peeling or dissolving in the development step.

The protective film has a UV-transmitting property,
Those having a thickness of 0 μm or less, preferably 10 μm or less are preferred. Specific examples of the protective film include polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyethylene terephthalate, cellophane, and the like. These films may be provided with a mat in order to improve the vacuum adhesion in the printing frame during image exposure.

Further, instead of the protective film, a polymer which can be dissolved and removed may be coated to form a protective layer.

Next, the method for producing a waterless planographic printing plate precursor according to the present invention will be described. The primer layer composition is applied to the substrate using a normal coater such as a slit die coater, a reverse roll coater, an air knife coater, or a Meyer bar coater, or a rotary coater such as a wheyer, if necessary, and coated at 100 to 300 ° C. After curing at a temperature of several minutes, a coating solution for a photosensitive layer composition is applied,
After drying at a temperature of 0 ° C. for several minutes and heat curing as required, a silicone rubber layer composition is coated thereon,
Heat-treated at a temperature of 150 ° C. for several minutes to cure the rubber and form. Thereafter, a protective film is laminated as necessary.

Further, it is preferable that the entire surface of the lithographic printing plate of the present invention is exposed to weak light before the image exposure in order to enhance the adhesion between the photosensitive layer and the silicone rubber layer. As the light source used for the overall exposure, a light source usually used for image exposure of a printing plate can be used. Specifically, there are a mercury lamp, a carbon arc lamp, a xenon lamp, a metal halide lamp, a tungsten lamp, a fluorescent lamp and the like.

In the overall exposure, it is necessary that the photoreactive functional group of the quinonediazide compound, that is, the quinonediazide group is not completely reacted (deactivated) by the treatment.

The lithographic printing plate precursor of the present invention thus produced is exposed to actinic rays through a vacuum-contacted negative film. As a light source used in this exposure step, a high-pressure mercury lamp, a carbon arc lamp, a xenon lamp, a fluorescent lamp or the like can be usually used.

The exposed printing plate is peeled off the protective film, immersed in a developer, and developed using a developing pad or a developing brush. At this time, the silicone rubber layer at the exposed portion is peeled off and the photosensitive layer is exposed. As the developer used in the present invention, those known as developers for lithographic printing plates without water can be used. For example, aliphatic hydrocarbons (hexane, heptane, "Isoper E, H, G" (trade names of aliphatic hydrocarbons manufactured by Esso Chemical Co., Ltd.) or gasoline, kerosene, etc.), aromatic hydrocarbons (toluene,
Xylene), or a halogenated hydrocarbon (such as tricrene) to which the following polar solvent is added, or the polar solvent itself is preferable.

(1) alcohols methanol, ethanol, propanol, benzyl alcohol, ethylene glycol monophenyl ether,
-Methoxyethanol, 2-ethoxyethanol, carbitol monoethyl ether, carbitol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, polypropylene glycol monomethyl ether, polypropylene Glycol, triethylene glycol, tetraethylene glycol and the like.

(2) Ketones Examples include acetone and methyl ethyl ketone.

(3) Esters Ethyl acetate, methyl lactate, ethyl lactate, butyl lactate, propylene glycol monomethyl ether acetate, carbitol acetate, dibutyl phthalate, diethyl phthalate and the like can be mentioned.

(4) Others Triethyl phosphate, tricresyl phosphate and the like can be mentioned.

Further, water is added to the organic solvent-based developer and the organic solvent is solubilized in water using a surfactant or the like, or an alkali agent such as sodium carbonate or monoethanolamine is further added thereon. An inorganic alkaline agent such as diethanolamine, triethanolamine, sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, sodium borate, or mono, di, or triethanolamine, mono, di, or triethylamine; Mono, diisopropylamine, n-butylamine,
Organic amine compounds such as mono-, di-, or triisopropanolamine, ethyleneimine, and ethylenediimine can also be used.

Further, known basic dyes such as crystal violet, Victoria Pure Blue, and Astrazone Red, acid dyes, and oil-soluble dyes can be added to a developing solution, and the image area can be dyed simultaneously with the development.

However, the most preferable method for developing the waterless planographic printing plate precursor of the present invention is disclosed in Japanese Patent Publication No. 4-386.
No. 5 and Japanese Patent Publication No. 4-29053 are preferable to process the exposed plate with a pretreatment liquid containing a basic compound and then develop with water or a developer containing water as a main component.

When developing the waterless planographic printing plate used in the present invention, the plate surface is pretreated with the above-mentioned developer using an automatic developing machine commercially available from, for example, Toray Industries, Inc. After that, the developing can be suitably performed by rubbing the rotating brush plate surface while showering with tap water or the like. A specific example of the developing machine is TWL-1 manufactured by Toray Industries, Inc.
160, TWL-860, TWL-650, TWL-4
00, or JP-A-4-2265 or JP-A-5-265.
2272 and JP-A-5-6000. When an automatic developing machine is used, NP-1 (Toray Industries, Inc.)
Pretreatment liquid for lithographic negative mold without water production), NA as post-treatment liquid
It is preferable to use -1 (a post-treatment liquid for a waterless planographic negative mold manufactured by Toray Industries, Inc.). Also, instead of the above-mentioned developing machine,
Development can also be performed by spraying hot water or steam onto the plate surface.

[0117]

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

Synthesis Example 1 50 g of pyrogallol was dissolved in 350 g of acetone, and 5 g of phosphorus oxychloride was added with stirring. After being left overnight at room temperature, the mixture was dropped into water while stirring to obtain a tar-like resin. After dissolving this resin again in acetone, it was poured into a large amount of water to obtain a solid. The solid was dried under vacuum to obtain the desired acetone pyrogallol resin.

The molecular weight of the obtained acetone pyrogallol resin was measured by using GPC and found to be Mw = 1300.

Next, 50 g of the above-mentioned acetone pyrogallol resin was used.
(About 0.04 mol) and 83 g (about 0.31 mol) of 1,2-naphthoquinone-2-diazide-5-sulfonic acid chloride were dissolved in 500 g of 1,4-dioxane. Next, 80 g of a 10% by weight aqueous solution of sodium carbonate was added dropwise over 20 minutes, and the mixture was stirred and reacted for 4 hours while maintaining the solution temperature at 40 ° C. After completion of the reaction, the solution was put into 1000 g of water to precipitate and sediment the product. The supernatant was removed and the residue was dried under reduced pressure to obtain acetone pyrogallol resin-1 having a quinonediazide group.

Example 1 The following primer composition was applied to a 0.24 mm-thick aluminum plate (manufactured by Sumitomo Metal Co., Ltd.) degreased by an ordinary method, and heat-treated at 200 ° C. for 2 minutes to give 5 g / m 2. ² primer layers were applied.

<Solid Component: Coating Concentration 12%> (1) Polyurethane resin “SAMPLEN LQ-SZ18” (manufactured by Sanyo Chemical Industries, Ltd.) 75 parts by weight (2) Blocked isocyanate “Takenate B830” (Takeda Pharmaceutical Co., Ltd.) 15 parts by weight (3) Epoxy / urea resin 10 parts by weight <Solvent component> (4) Dimethylformamide Subsequently, a photosensitive layer composition having the following composition was added on top of this.
After drying at 20 ° C. for 30 seconds, a photosensitive layer of 1.2 g / m ² was provided.

(1) Partially esterified product of 1,2-naphthoquinone-2-diazide-5-sulfonic acid chloride and phenol formaldehyde novolak resin (“Sumilite Resin” PR50622 manufactured by Sumitomo Durez) (degree of esterification: 36%) 100 Parts by weight (2) 21,4 parts by weight of 4,4'-diphenylmethane diisocyanate (3) 10 parts by weight of polyurethane resin "SAMPLEN LQ-T1331" (manufactured by Sanyo Chemical Industries, Ltd.) 0.2 parts by weight of dibutyltin diacetate (5) P-toluenesulfonic acid 0.8 parts by weight (6) tetrahydrofuran 832 parts by weight (7) diethylene glycol monoethyl ether 236 parts by weight (8) N, N'-dimethylformamide 118 parts by weight A silicone rubber layer with the following composition And fabric was coated with a silicone rubber layer by thermal drying.

The following composition was applied by a bar coater as an addition reaction crosslinkable silicone rubber layer, and heat-cured at 130 ° C. for 1 minute to apply a 2 g / m ² silicone rubber layer.

<Solid component: 10%> (1) 100 parts by weight of α, ω-divinylpolydimethylsiloxane (polymerization degree: 770) (2) HMS-501 (manufactured by Chisso Corporation, both ends methyl (methyl hydrogen siloxane)) (Dimethylsiloxane) copolymer SiH groups / molecular weight = 0.69 mol / g) 4 parts by weight (3) Olefin-coordinated platinum 0.02 parts by weight (4) Reaction inhibitor 0.3 parts by weight <Solvent component> ( 5) "Isopar" E (manufactured by Esso Chemical Co., Ltd.) In the above silicone rubber layer composition, the number of SiH groups per one vinyl group was about 7.9.

The laminated plate obtained as described above was
A biaxially-stretched biaxially-stretched polypropylene film having a thickness of μm was laminated using a calender roller so that the non-matted surface was in contact with the silicone rubber layer, to obtain a negative type waterless planographic printing plate precursor.

Using a metal halide lamp (Idol Fin 2000, manufactured by Iwasaki Electric Co., Ltd.), the printing plate was subjected to a UV meter (a light measure type UV, manufactured by Oak Manufacturing Co., Ltd.).
At -402 A), the entire surface was exposed at an illuminance of 11 mW / cm ² for 6 seconds.

The printing plate obtained as described above has a thickness of 150
A positive film having 1-99% halftone dots in lines / inch and a gray scale (G / S) having an optical density difference of 0.15 steps were vacuum-adhered for 30 seconds using the above metal halide lamp. Thereafter, the laminate film was exposed from a distance of 1 m for 60 seconds to peel off the laminate film.

Thereafter, an automatic processor (TWL manufactured by Toray Industries, Inc .: TWL)
-1160) in a NP-1 pretreatment liquid at a liquid temperature of 45 ° C. (manufactured by Toray Industries, Inc .: a pretreatment liquid for an automatic developing machine) for 1 minute, and in pure water at a liquid temperature of 25 ° C. The silicone rubber layer in the exposed area was peeled off and removed with a developing brush, and the photosensitive layer in the image area was dyed with an NA-1 post-treatment liquid (manufactured by Toray Industries, Inc .: post-treatment liquid for an automatic developing machine) to form a printing plate.

The image portion where the photosensitive layer of the printing plate was exposed was observed for its phase-separated structure using an optical microscope, and classified into modes (1) to (3) of the phase-separated structure. FIGS. 1 to 3 show the classified forms of the phase separation structure.

Further, the width of a continuous phase or a dispersed phase forming a phase-separated structure was measured by a micrograph. Microscopic F
TIR (paragon10 manufactured by PerkinElmer Inc.)
00 AUTOIMAGE system), it was confirmed that the surface of the photosensitive layer was phase-separated into a phase mainly containing a compound having a quinonediazide group and a phase mainly containing a polymer.

Further, the gray scale sensitivity on the printing plate was visually evaluated. The gray scale sensitivity means the number of gray scale densities at which the silicone rubber layer was not removed after development, and the higher the result, the higher the sensitivity.

Further, the unexposed lithographic plate without water was stored in an atmosphere of 50 ° C. and 70% RH for 10 days, and after storage, the same image reproducibility was evaluated as described above. The difference between the gray scale sensitivities before and after storage was evaluated as an index of storage stability.

Example 2 A waterless planographic printing plate precursor was prepared in the same manner as in Example 1 except that the composition of the photosensitive layer used in Example 1 was changed to the following, and evaluation was performed in the same manner as in Example 1. Was.

(1) Partially esterified product of 1,2-naphthoquinone-2-diazide-5-sulfonic acid chloride and phenol formaldehyde novolak resin (“Sumilite Resin” PR50622 manufactured by Sumitomo Durez) (degree of esterification: 36%) 100 Parts by weight (2) 21,4 parts by weight of 4,4'-diphenylmethane diisocyanate (3) 10 parts by weight of polyurethane resin "SAMPLEN LQ-T1331" (manufactured by Sanyo Chemical Industries, Ltd.) 0.2 parts by weight of dibutyltin diacetate (5) P-toluenesulfonic acid 0.8 parts by weight (6) Tetrahydrofuran 832 parts by weight (7) Methyl isobutyl ketone 236 parts by weight (8) N, N'-dimethylformamide 118 parts by weight Example 3 Used in Example 1 Example 1 was repeated except that the composition of the photosensitive layer was changed to the following. Without water to prepare a lithographic printing plate precursor was evaluated in the same manner as in Example 1.

(1) Partially esterified product of 1,2-naphthoquinone-2-diazide-5-sulfonic acid chloride and phenol formaldehyde novolak resin (“Sumilite Resin” PR50622 manufactured by Sumitomo Durez) (degree of esterification: 36%) 100 Parts by weight (2) 21,4 parts by weight of 4,4'-diphenylmethane diisocyanate (3) 10 parts by weight of polyurethane resin "SAMPLEN LQ-T1331" (manufactured by Sanyo Chemical Industries, Ltd.) 0.2 parts by weight of dibutyltin diacetate (5) P-toluenesulfonic acid 0.8 parts by weight (6) isopropyl ether 594 parts by weight (7) tetrahydrofuran 475 parts by weight (8) 2-methylcyclohexanol 118 parts by weight Example 4 Photosensitive layer used in Example 1 Same as Example 1 except that the composition was changed to the following None preparing Lithographic printing plate precursor was evaluated in the same manner as in Example 1.

(1) Partially esterified product of 1,2-naphthoquinone-2-diazide-5-sulfonic acid chloride and phenol formaldehyde novolak resin (“Sumilite Resin” PR50622 manufactured by Sumitomo Durez) (degree of esterification: 36%) 70 Parts by weight (2) 21,4 parts by weight of 4,4'-diphenylmethane diisocyanate (3) 30 parts by weight of polyurethane resin "SAMPLEN LQ-T1331" (manufactured by Sanyo Chemical Industries, Ltd.) 0.2 parts by weight of dibutyltin diacetate (5) 0.8 parts by weight of P-toluenesulfonic acid (6) 832 parts by weight of tetrahydrofuran (7) 236 parts by weight of isopropyl ether (8) 118 parts by weight of N, N'-dimethylformamide Example 5 Used in Example 1. Water was prepared in the same manner as in Example 1 except that the composition of the photosensitive layer was changed to the following. To prepare a lithographic printing plate precursor was evaluated in the same manner as in Example 1.

(1) Acetone pyrogallol resin having quinonediazide group obtained in Synthesis Example 1-1 (degree of esterification: 33%) 50 parts by weight (2) 4,4′-diphenylmethane diisocyanate 21 parts by weight (3) Polyurethane resin "SAMPLEN LQ-909L" (manufactured by Sanyo Chemical Industries, Ltd.) 50 parts by weight (4) Dibutyltin diacetate 0.2 parts by weight (5) P-toluenesulfonic acid 0.8 parts by weight (6) isopropyl ether 594 parts by weight Part (7) 475 parts by weight of tetrahydrofuran (8) 118 parts by weight of 2-methylcyclohexanol Example 6 The same procedure as in Example 1 was carried out except that the silicone rubber layer composition used in Example 1 was changed to the following. A lithographic printing plate precursor was prepared and evaluated in the same manner as in Example 1.

Silicone Rubber Layer Composition <Solid Component 10%> (1) 100 parts by weight of α, ω-divinylpolydimethylsiloxane (degree of polymerization 770) (2) HMS-151 (manufactured by Chisso Corp. (Gen siloxane) (dimethyl siloxane) copolymer Number of SiH groups / molecular weight = 0.25 mol / g) 4 parts by weight (3) 0.02 parts by weight of olefin-coordinated platinum (4) 0.3 parts by weight of reaction inhibitor <solvent Ingredients> (5) "Isopar" E (manufactured by Esso Chemical Co., Ltd.) The number of SiH groups per one vinyl group in the above silicone rubber layer composition was about 2.9.

Example 7 A waterless planographic printing plate precursor was prepared in the same manner as in Example 1 except that the composition of the silicone rubber layer used in Example 1 was changed to the following, and evaluation was performed in the same manner as in Example 1. went.

Silicone rubber layer composition <solid component 10%> (1) 100 parts by weight of α, ω-divinylpolydimethylsiloxane (degree of polymerization 770) (2) SH-1107 (manufactured by Dow Corning Toray Silicone Toray Co., Ltd.) Terminal methyl polymethyl hydrogen siloxane Number of SiH groups / molecular weight = 1.67 mol / g) 3 parts by weight (3) Olefin-coordinated platinum 0.02 parts by weight (4) Reaction inhibitor 0.3 parts by weight <Solvent component> ( 5) "Isopar" E (manufactured by Esso Chemical Co., Ltd.) The number of SiH groups per 1 vinyl group in the above silicone rubber layer composition was about 13.8.

Example 8 A negative type waterless planographic printing plate precursor was prepared in the same manner as in Example 1 except that the composition of the silicone rubber layer used in Example 1 was changed as follows, and evaluated in the same manner as in Example 1. went.

<Solid component: 10%> (1) 100 parts by weight of α, ω-divinylpolydimethylsiloxane (polymerization degree: 770) (2) HMS-501 (manufactured by Chisso Corp., both ends methyl (methyl hydrogen siloxane)) (Dimethylsiloxane) copolymer Number of SiH groups / molecular weight = 0.69 mol / g) 1 part by weight (3) 0.02 parts by weight of olefin-coordinated platinum (4) 0.3 parts by weight of reaction inhibitor <Solvent component> ( 5) "Isopar" E (manufactured by Esso Chemical Co., Ltd.) The number of SiH groups per one vinyl group in the above silicone rubber layer composition was about 2.0.

Comparative Example 1 A waterless planographic printing plate precursor was prepared in the same manner as in Example 1 except that the composition of the photosensitive layer used in Example 1 was changed to the following, and evaluation was performed in the same manner as in Example 1. Was.

(1) Partially esterified product of 1,2-naphthoquinone-2-diazide-5-sulfonic acid chloride and phenol formaldehyde novolak resin (“Sumilite Resin” PR50622 manufactured by Sumitomo Durez) (degree of esterification: 36%) 100 Parts by weight (2) 21,4 parts by weight of 4,4'-diphenylmethane diisocyanate (3) 10 parts by weight of polyurethane resin "SAMPLEN LQ-T1331" (manufactured by Sanyo Chemical Industries, Ltd.) 0.2 parts by weight of dibutyltin diacetate (5) 0.8 parts by weight of P-toluenesulfonic acid (6) 1188 parts by weight of tetrahydrofuran Comparative Example 2 The same procedure as in Example 1 was carried out except that the composition of the photosensitive layer used in Example 1 was changed to the following. A lithographic printing plate precursor was prepared and evaluated in the same manner as in Example 1.

(1) Partially esterified product of 1,2-naphthoquinone-2-diazide-5-sulfonic acid chloride and phenol formaldehyde novolak resin (“Sumilite Resin” PR50622 manufactured by Sumitomo Durez) (degree of esterification: 36%) 100 Parts by weight (2) 21,4 parts by weight of 4,4'-diphenylmethane diisocyanate (3) 10 parts by weight of polyurethane resin "SAMPLEN LQ-T1331" (manufactured by Sanyo Chemical Industries, Ltd.) 0.2 parts by weight of dibutyltin diacetate (5) 0.8 parts by weight of P-toluenesulfonic acid (6) 1188 parts by weight of N, N'-dimethylformamide Comparative Example 3 Example 1 except that the photosensitive layer composition used in Example 1 was changed to the following. A lithographic printing plate precursor without water was prepared in the same manner as in Example 1 and evaluated in the same manner as in Example 1.

(1) Partially esterified product of 1,2-naphthoquinone-2-diazide-5-sulfonic acid chloride and phenol formaldehyde novolak resin (“Sumilite Resin” PR50622 manufactured by Sumitomo Durez) (esterification degree: 36%) 70 Parts by weight (2) 21,4 parts by weight of 4,4'-diphenylmethane diisocyanate (3) 30 parts by weight of polyurethane resin "SAMPLEN LQ-T1331" (manufactured by Sanyo Chemical Industries, Ltd.) 0.2 parts by weight of dibutyltin diacetate (5) 0.8 parts by weight of P-toluenesulfonic acid (6) 1188 parts by weight of N, N'-dimethylformamide Comparative Example 4 Example 1 except that the photosensitive layer composition used in Example 1 was changed to the following. A lithographic printing plate precursor without water was prepared in the same manner as in Example 1 and evaluated in the same manner as in Example 1.

(1) Acetone pyrogallol resin having quinonediazide group obtained in Synthesis Example 1-1 (degree of esterification 33%) 50 parts by weight (2) 4,4′-diphenylmethane diisocyanate 21 parts by weight (3) Polyurethane resin "SAMPLEN LQ-909L" (manufactured by Sanyo Chemical Industries, Ltd.) 50 parts by weight (4) Dibutyltin diacetate 0.2 parts by weight (5) P-toluenesulfonic acid 0.8 parts by weight (6) N, N ' 1188 parts by weight of dimethylformamide Tables 1 and 2 show the results of evaluating the morphology of the phase separation structure of the photosensitive layer, the width of the continuous or dispersed phase, the image reproducibility and the storage stability of Examples 1 to 8 and Comparative Examples 1 to 4. Table 2 shows the composition of the silicone rubber layer used.

[0149]

[Table 1]

[Table 2]

[Table 3] As shown in Tables 1 and 2, good image reproducibility and storage stability were obtained in all the examples having the photosensitive layer having the phase separation structure as defined in the claims. It can be seen that in the comparative examples without, the image reproducibility and the storage stability were inferior.

[0150]

According to the present invention, in a waterless planographic printing plate precursor comprising at least a photosensitive layer and a silicone rubber layer laminated in this order on a substrate, the photosensitive layer mainly comprises a compound having a hydroxyl group and a quinonediazide group. Separated into two phases, a main phase and a polymer-based phase. By using a specific addition type silicone rubber layer for the silicone rubber layer, there is no water with good image reproducibility and excellent storage stability. A lithographic printing plate precursor is obtained.

[Brief description of the drawings]

FIG. 1 is a morphological diagram of a phase separation structure corresponding to classification (1).

FIG. 2 is a view showing a form of a phase separation structure corresponding to classification (2).

FIG. 3 is a morphological diagram of a phase separation structure corresponding to classification (3).

Claims (7)

[Claims] 1. A waterless lithographic printing plate precursor comprising at least a photosensitive layer and a silicone rubber layer laminated in this order on a substrate, wherein the photosensitive layer is mainly composed of a compound having a hydroxyl group and a quinonediazide group. And a silicone rubber layer having a vinyl group-containing polysiloxane having a molecular weight of 100,000 or less and hydrogen directly bonded to 3 to 20 silicon atoms per 1 vinyl group. A waterless planographic printing plate precursor comprising a hydrogen siloxane so as to have a group, and wherein the vinyl group and a hydrogen group directly bonded to a silicon atom are crosslinked by an addition reaction. 2. The waterless lithographic printing plate precursor as claimed in claim 1, wherein the compound having a hydroxyl group and a quinonediazide group is crosslinked with isocyanate. 3. The waterless planographic printing plate precursor as claimed in claim 1, wherein the polymer is a polyurethane. 4. A silicone rubber layer comprising an organopolysiloxane having two or more vinyl groups in a molecule, a hydrogen siloxane having three or more SiH groups in a molecule, and a platinum compound. Items 1-3
A lithographic printing plate precursor without water as described in any of the above. 5. The lithographic printing plate precursor as claimed in claim 1, wherein the value of the number of SiH groups / molecular weight in the molecule of the hydrogen siloxane is 0.001 mol / g or more. . 6. A compound having a hydroxyl group and a quinonediazide group, wherein the phenol novolak resin is 1,2-naphthoquinone-2-diazide-5-sulfonic acid chloride or
2. The composition of claim 1, which is esterified with 1,2-naphthoquinone-2-diazide-4-sulfonic acid chloride and has a degree of esterification of 1 to 60%.
A lithographic printing plate precursor without water as described in any one of Items 1 to 5. 7. The lithographic printing plate precursor according to claim 1, wherein the content of the isocyanate in the photosensitive layer is 5 to 45% by weight based on the quinonediazide compound.