JPH09288349A - Raw plate for waterless lithographic printing plate and its manufacture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the raw plate for the waterless lithographic printing plate superior in productivity by incorporating a quinonediazido compound and an diazonium compound in a photosensitive layer and hardening this layer through the photoreaction of the diazonium compound. SOLUTION: The raw plate of this printing plate is formed by laminating at least the photosensitive layer and a silicone rubber layer in this order on a support and this photosensitive layer has an cross-linking structure due to this diazonium compound and it is preferred to contain a binder polymer, and an effective quinonediazido compound is embodied by 1,2-naphthoquinone-2- diazido-4-sulfonic acid or its derivative, and it is preferred to contains it in an amount of 10-80weight% and, especially, 20-65weight% in the photosensitive layer, and as the diazonium compound, the condensation product of the diazo monomer, such as 4-diazodiphenylamine, with a condensing agent, and the like are used.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a waterless lithographic printing plate precursor and a waterless lithographic printing plate obtained by selectively exposing and developing the waterless lithographic printing plate precursor, and more specifically to improvement of a manufacturing process. The present invention relates to a waterless planographic printing plate precursor excellent in productivity and a waterless planographic printing plate obtained by selectively exposing and developing the waterless planographic printing plate precursor.

[0002]

2. Description of the Related Art Conventionally, a printing plate for performing lithographic printing using a silicone rubber or a fluororesin as an ink repellent layer without using a fountain solution, particularly a photosensitive lithographic printing plate obtained by selectively exposing and developing. Various editions have been proposed.

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 layer as an ink repellent layer is disclosed in, for example, JP-B-54-2.
6923, JP-B-56-23150 and the like, a waterless planographic printing plate in which a photopolymerizable adhesive layer and a silicone rubber layer are laminated on a substrate, JP-B-3-56622, JP-A-61-62622.
No. 153655 proposes a waterless planographic printing plate in which a photodimerization type photosensitive layer and a silicone rubber layer are laminated on a substrate.

A negative photosensitive lithographic printing plate having a silicone rubber layer as an ink repellent layer is disclosed in Japanese Examined Patent Publication No. 61-6.
No. 16, JP-B-61-54218 and the like propose a waterless planographic printing plate in which a photosensitive layer containing a quinonediazide compound is provided on a support and a silicone rubber layer is provided on the support with a photosensitive layer.

Further, there have been made many inventions relating to so-called burning treatment for improving UV ink resistance and solvent resistance of the plate after the printing plate is produced, that is, after development.

JP-B-61-617, JP-A-57-192
956, JP-A-57-192957, JP-A-57-20
5740, JP-A-60-133452, JP-A-60-1
69852 and the like.

For example, Japanese Patent Application Laid-Open No. Sho 60-133452 discloses a system containing a quinonediazide compound and a photocurable compound or composition. The effect is improved in improving the solvent resistance.

However, none of them exerts an effect on the solvent resistance of the plate during development. Therefore, in order to improve the solvent resistance during development, the components in the photosensitive layer are crosslinked or modified in some form. I needed to do it.

In Japanese Examined Patent Publication No. 61-54222, a partially esterified product of 1,2-naphthoquinone-2-diazide-5-sulfonic acid chloride and phenol formaldehyde novolac resin is crosslinked on a support with a polyfunctional isocyanate. A negative waterless lithographic printing plate having a light-peelable photosensitive layer and a silicone rubber layer as an ink repellent layer formed thereon is disclosed.

By adopting this method, not only the solvent resistance during development but also the U after development, that is, the U
The V ink resistance and the solvent resistance were also improved at the same time, and a plate that did not require a burning treatment was obtained except in special cases.

From such a viewpoint, a method of rendering a partially esterified product of 1,2-naphthoquinone-2-diazide-5-sulfonic acid of a phenol novolak resin insoluble or hardly soluble in a developing solution has heretofore been known as a method for preparing a polyfunctional isocyanate. The main method is that a compound, a polyfunctional epoxy compound, or a monofunctional compound is reacted during coating and drying of the photosensitive layer to crosslink or modify the photosensitive layer.

However, the reaction with the isocyanate compound or the epoxy compound causes the pot life of the liquid,
There is a problem with gelation and mixing of two liquids to avoid it, and since it is essentially due to thermal reaction, plate performance varies due to uneven heat conduction from the hot air to the substrate. It was also the cause. Furthermore, it was also disadvantageous in terms of energy from the viewpoint of thermal reaction.

[0014]

The present invention was devised in order to improve the various drawbacks of the prior art. The photosensitive layer contains a quinonediazide compound and a diazonium compound, and a photoreaction of the diazonium compound forms a photosensitive layer. The purpose of the present invention is to provide a waterless planographic printing plate precursor having excellent productivity by performing a curing reaction.

[0015]

SUMMARY OF THE INVENTION The object of the present invention is as follows.
Achieved by the following waterless lithography. That is,
(1) In a waterless planographic printing plate precursor in which at least a photosensitive layer and a silicone rubber layer are laminated in this order on a support, the photosensitive layer contains a quinonediazide compound and a diazonium compound, and the photosensitive layer is crosslinked with a diazonium compound. A waterless lithographic printing plate precursor having a structure, (2) a waterless lithographic printing plate precursor as described in (1), wherein the photosensitive layer contains a binder polymer, (3)
The quinonediazide compound is 1,2-naphthoquinone-2-
A waterless planographic printing plate precursor as described in any one of (1) and (2), which is a diazidosulfonic acid derivative.
(4) The waterless planographic printing plate precursor as described in any one of (1) to (3), wherein the photosensitive layer is a photo-releasing photosensitive layer, (5) at least a quinonediazide compound and a diazonium compound on a support. In a method for producing a waterless planographic printing plate precursor in which a photosensitive layer containing at least a silicone rubber layer is laminated at least in this order, a waterless planographic printing plate characterized by carrying out full exposure from after coating the photosensitive layer to before developing treatment This is achieved by a method of manufacturing a printing plate precursor.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The constitution of the present invention will be described below.
This will be described more specifically.

A feature of the present invention is that in a waterless planographic printing plate precursor in which at least a photosensitive layer and a silicone rubber layer are laminated in this order on a support, the photosensitive layer contains a quinonediazide compound and a diazonium compound. Especially.

The quinonediazide compound referred to in the present invention is
A compound obtained by diazotizing an aromatic compound having a hydroxyl group at the ortho or para position with respect to an amino group, a diazonium salt of a benzene or naphthalene derivative having a hydroxyl group at the ortho or para position with respect to the diazo group in an alkaline aqueous solution. It refers to a compound or the like obtained by heating, and generally, unlike the diazonium compound described below, the diazo group does not ionize and does not form a salt.

Specific examples include benzoquinone diazide sulfonic acid and its derivatives, naphthoquinone diazide sulfonic acid and its derivatives, which are usually used in positive PS plates, Wipon plates, photoresists and the like.
Specifically, 1,2-benzoquinone-2-diazido 4
-Sulfonic acid chloride, 1,2-benzoquinone-2-diazido-4-sulfonic acid sodium salt, 1,2-benzoquinone-2-diazido-4-sulfonic acid, 1,2-naphthoquinone-2-diazido-4-sulfonic acid chloride,
1,2-naphthoquinone-2-diazido-4-sulfonic acid sodium salt, 1,2-naphthoquinone-2-diazido-4-sulfonic acid, 1,2-naphthoquinone-2-diazido-5-sulfonic acid chloride, 1,2-naphthoquinone-
2-diazido 5-sulfonic acid sodium salt, 1,2-
Naphthoquinone-2-diazido-5-sulfonic acid, 1,2
-Naphthoquinone-2-diazido 6-sulfonic acid chloride, 1,2-naphthoquinone-2-diazido 6-sulfonic acid sodium salt, 1,2-naphthoquinone-2-diazido 6-sulfonic acid and the like, but not limited to these is not.

Among these, 1,2-naphthoquinone-2
-Diazido-4-sulfonic acid and its derivatives, and 1,2-naphthoquinone-2-diazido-5-sulfonic acid and its derivatives are effective.

Examples of the derivative of 1,2-naphthoquinone-2-diazide sulfonic acid include known esterification products and amidation products of a hydroxyl group-containing compound and an amino group-containing compound, which are referred to as adhesiveness to a silicone rubber layer. From the viewpoint, a 1,2-naphthoquinone-2-diazide sulfonic acid derivative containing a hydroxyl group, an amino group and the like in the molecule is preferable.

Specific examples of such compounds include 1,
Examples thereof include polyhydroxyphenyl of 2-naphthoquinone-2-diazide sulfonic acid, pyrogallol acetone resin, parahydroxystyrene copolymer, and ester of phenol formaldehyde novolac resin.

Further, as a method of introducing a functional group such as a hydroxyl group or an amino group, a reactive functional group of naphthoquinone diazide sulfonic acid esterified product or amidated product,
There is also a method of reacting a compound having a hydroxyl group, an amino group or the like.

The proportion of these quinonediazide compounds in the photosensitive layer is preferably 10% by weight or more and 80% by weight or less, more preferably 20% by weight or more and 65% by weight or less. When the amount of the quinonediazide compound is less than 10% by weight, the change in solvent resistance due to the quinonediazide compound during image exposure is small and the image reproducibility is poor, while when it is more than 80% by weight, the crosslinking component and other Since this means the reduction of the components, there may be a problem in the solvent resistance of the photosensitive layer to the developing solution.

Examples of the diazonium compound used in the present invention include Japanese Patent Publication No. 47-1167 and Japanese Patent Publication No.
As described in JP-A-7-43890 is used. Specific examples include the following.

A condensation product of a diazo monomer and a condensing agent. Examples of the diazo monomer include 4-diazodiphenylamine, 1-diazo-4-N, N-dimethylaminobenzene, 1-diazo-4-N, N-diethylaminobenzene, 1-diazo-4-N-ethyl-N-. Hydroxyethylaminobenzene, 1-diazo-4-N-methyl-N-
Hydroxyethylaminobenzene, 1-diazo-2,5
-Diethoxy-4-benzoylaminobenzene, 1-diazo-4-N-benzylaminobenzene, 1-diazo-
4-N, N-dimethylaminobenzene, 1-diazo-4
-Morpholinobenzene, 1-diazo-2,5-dimethoxy-4-p-tolylmercaptobenzene, 1-diazo-
2-ethoxy-4-N, N-dimethylaminobenzene,
p-diazodimethylaniline, 1-diazo-2,5-dibutoxy-4-morpholinobenzene, 1-diazo-2,5
-Diethoxy-4-morpholinobenzene, 1-diazo-
2,5-Dimethoxy-4-morpholinobenzene, 1-diazo-2,5-diethoxy-4-p-tolylmercaptobenzene, 1-diazo-4-N-ethyl-N-hydroxyethylaminobenzene, 1-diazo- 3-ethoxy-
4-N-methyl-N-benzylaminobenzene, 1-diazo-3-chloro-4-N, N-diethylaminobenzene, 1-diazo-3-methyl-4-pyrrolidinobenzene, 1-diazo-2-chloro -4-N, N-dimethylamino-5-methoxybenzene, 1-diazo-3-methoxy-4-pyrrolidinobenzene, 3-methoxy-4-diazodiphenylamine, 3-ethoxy-4-diazodiphenylamine, 3- ( Examples include n-propoxy) -4-diazodiphenylamine and 3- (isopropoxy) -4-diazodiphenylamine. Examples of the condensing agent include formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, and benzaldehyde. Further, as the anion, a water-soluble diazo resin can be obtained by using chlorine ion, tetrachlorohydrochlorite, or the like, and boron tetrafluoride, hexafluorophosphoric acid, triisopropylnaphthalenesulfonic acid, 4,4 '-Biphenyldisulfonic acid, 2,5-dimethylbenzenesulfonic acid, 2-
By using nitrobenzenesulfonic acid, 2-methoxy-4-hydroxy-5-benzoylbenzenesulfonic acid or the like, an organic solvent-soluble diazo resin can be obtained.

Further, equimolar reaction products of a diazonium compound and hydroxybenzophenones can also be used. However, the pH is 7.5 or less so that the two do not react with each other to form an azo compound. The same diazonium compound as the above-mentioned diazo resin is used. Hydroxybenzophenones include 2,
2 ′, 4,4′-tetrahydroxybenzophenone,
2,2'-dihydroxy-4,4'-dimethoxybenzophenone, alkaline salt of 2,2'-dihydroxy-4,4'-dimethoxy-5-sulfobenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid Are used. In particular, those containing a sulfonic acid group are excellent in stability.

The proportion of these diazonium compounds in the photosensitive layer is preferably 10 to 300 parts by weight, more preferably 20 to 100 parts by weight, based on 100 parts by weight of the quinonediazide compound. If the cross-linking agent is too small, curing of the photosensitive layer may be insufficient, and if too large, the cross-linking agent amount becomes excessive with respect to the cross-linking point.
As a result, the amount of adhesion between the silicone rubber layer and the photosensitive layer and the storage stability are adversely affected.

In the present invention, a binder polymer is added in order to enhance the curing efficiency of the photosensitive layer with the diazonium compound, to enhance the function of maintaining the shape of the photosensitive layer, and to improve the coating property of the photosensitive solution. May be. As the binder polymer, various vinyl polymers, unvulcanized rubber, polyoxides (polyethers), polyesters, polyurethanes, polyamides and the like, which are soluble in water or an organic solvent and have film-forming ability, are various. These may be used alone or in combination.

From the viewpoint of curing with a diazonium compound and adhesion between the silicone rubber layer and the photosensitive layer, those having a functional group such as a hydroxyl group, a mercapto group, an amino group or an unsaturated group in the molecule are preferable.

1. Vinyl Polymer Polymers and copolymers obtained from the following monomers and their derivatives, including polyvinyl alcohol and vinyl alcohol copolymers.

For example, ethylene, propylene, 1-butene, styrene, butadiene, isoprene, vinyl chloride,
Vinylidene chloride, vinyl acetate, (meth) acrylic acid and its ester derivatives, maleic acid, itaconic acid, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, acrylamide, N-methylol acrylamide, glycidyl methacrylate, acrylonitrile , Styrene, vinyltoluene, isobutene, 3-methyl-1-butene, butyl vinyl ether, N-vinylcarbazole, methyl vinyl ketone, nitroethylene, methyl α-cyanoacrylate, vinylidene cyanide, trimethylolethane tri (meth) acrylate, pentaerythritol tri ( (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, Xanthyl di (meth) acrylate, trimethylol propane tri (acryloyloxypropyl) ether, glycerin, trimethylol ethane, trimethylol propane and other polyfunctional alcohols were added with ethylene oxide and propylene oxide and then (meth) acrylated. And their derivatives.

Of these, vinyl polymers having functional groups such as hydroxyl groups and unsaturated groups are preferable, and specific examples thereof include the following.

Glycidyl (meth) acrylate is added to a homo- or copolymerization product of a monomer having a functional group such as hydroxyalkyl (meth) acrylate and a hydroxyl group, a mercapto group and an amino group, and a copolymer of (meth) acrylic acid and crotonic acid. Such as those reacted with epoxy group-containing acrylate compounds, homopolymers or copolymers of maleic anhydride, those obtained by half-esterifying addition of hydroxyl group-containing acrylate compounds such as pentaerythritol triacrylate and polyethylene glycol mono (meth) acrylate, Monomers or copolymerization products of monomers having functional groups such as hydroxyalkyl (meth) acrylates such as hydroxy groups, mercapto groups, amino groups, etc., can be added to polyisocyanates such as 4-tolylene diisocyanate and hydroxyalkyl (meth) acrylates. Those bets reaction products such as an isocyanate group-containing acrylate compound is reacted with a cinnamoyl group or a maleimide group (meth) acrylic acid copolymer esters such.

2. Unvulcanized rubber A homopolymer or copolymer selected from natural rubber (NR), butadiene and isoprene, such as polybutadiene (BR) and styrene-butadiene copolymer (SB
R), carboxy-modified styrene-butadiene copolymer,
Polyisoprene (NR), polychloroprene (CR),
Acrylic ester-butadiene copolymer, methacrylic acid ester-butadiene copolymer, isobutylene-isoprene copolymer (IIR), acrylonitrile-butadiene copolymer (NBR), carboxy-modified acrylonitrile-butadiene copolymer, acrylonitrile-chloroprene Copolymer, acrylonitrile-isoprene copolymer, vinylpyridine-styrene-butadiene copolymer,
A styrene-isoprene copolymer etc. are mentioned as what contains an unsaturated bond.

Those containing a hydroxyl group can be obtained by epoxidizing the double bond portion of the above-mentioned polymer having an unsaturated bond with a peroxide or the like and then reacting it with a carboxylic acid. In this case, when acrylic acid or methacrylic acid is used as the carboxylic acid, a polymer having both a hydroxyl group and an unsaturated bond is obtained. Also, a hydroxyl group-containing polymer can be obtained by reacting with an amine compound having active hydrogen instead of carboxylic acid. In this case, when a methacryl group-containing amine is used, a polymer having both a hydroxyl group and an unsaturated bond is obtained. Further, a copolymer of the above-mentioned butadiene or isoprene and a hydroxyl group-containing acrylic acid ester or a hydroxyl group-containing methacrylic acid ester may be used. further,
A hydroxyl group-containing polymer can also be obtained by reacting a copolymer of butadiene or isoprene with a glycidyl group-containing acrylic acid ester or a glycidyl group-containing methacrylic acid ester with a carboxylic acid. As a matter of course, in this case, when acrylic acid or methacrylic acid is used, a polymer having both a hydroxyl group and an unsaturated bond can be obtained. Similarly, a hydroxyl group-containing polymer can be obtained by reacting with an amine compound having active hydrogen.

3. Polyoxides (Polyethers) Examples of polymers having an unsaturated bond include poly (butadiene oxide), poly (1-butene oxide), and poly (isobutene oxide).

Those having a hydroxyl group can be obtained by epoxidizing the double bond portion of the above-mentioned polymer having an unsaturated bond with a peroxide and then reacting it with a carboxylic acid. In this case, when acrylic acid or methacrylic acid is used as the carboxylic acid, a polymer having both a hydroxyl group and an unsaturated bond is obtained. Also, a hydroxyl group-containing polymer can be obtained by reacting with an amine compound having active hydrogen instead of carboxylic acid. In this case, when a methacryl group-containing amine is used, a polymer having both a hydroxyl group and an unsaturated bond is obtained.

4. Polyesters Polyesters obtained by polycondensation of polyhydric alcohols and polycarboxylic acids as shown below, polyesters obtained by polymerization of polyhydric alcohols and polycarboxylic acid anhydrides, and polyhydric alcohols and polycarboxylic acids Examples thereof include polyesters obtained from a mixture of polyvalent carboxylic acid anhydrides and lactones. When a polymer having an unsaturated bond is obtained, either a polyhydric alcohol or a polyvalent carboxylic acid or a polyvalent carboxylic acid anhydride is used. At least one of them has an unsaturated bond. Also in the polyester obtained by ring-opening polymerization of lactone, it is important that the lactone has an unsaturated bond. In addition, when a polymer having a hydroxyl group is obtained, for example, the reaction may be performed so that at least one hydroxyl group of a polyhydric alcohol having 3 or more functional groups remains. Further, a hydroxyl group-containing polymer can be obtained also by reacting so that at least one carboxylic acid group of a trifunctional or higher polyvalent carboxylic acid remains, and then reacting with a glycidyl group-containing compound. In this case, a glycidyl group When glycidyl acrylate or glycidyl methacrylate is used as the containing compound, a polymer having both a hydroxyl group and an unsaturated bond can be obtained.

As the polyhydric alcohol, alcohols having no unsaturated bond are ethylene glycol, propylene glycol, 1,3-propanediol, 1,4.
-Butanediol, 1,3-butylene glycol, 1,
5-pentanediol, 6-hexanediol, diethylene glycol, dipropylene glycol, neopentyl glycol, triethylene glycol, p-xylylene glycol, hydrogenated bisphenol A, bisphenol dihydroxypropyl ether, glycerin, trimethylolethane, trimethylolpropane , Trishydroxymethylaminomethane, pentaerythritol,
Examples include dipentaerythritol and sorbitol. . As the alcohol having an unsaturated bond, 1,6
-Hexenediol, 7-octene-1,2-diol, 1 mol of glycerin reacted with 1 mol of acrylic acid, 1 mol of glycerin reacted with 1 mol of methacrylic acid, 1 mol of trimethylolethane with acrylic acid 1
Moles reacted, 1 mole trimethylolethane reacted with 1 mole methacrylic acid, 1 mole trimethylolpropane reacted with 1 mole acrylic acid,
One in which 1 mol of methacrylic acid is reacted with 1 mol of trimethylolpropane, one mol of pentaerythritol is reacted with 1 mol or 2 mol of acrylic acid, and one mol of pentaerythritol is 1 mol or 2 mol of methacrylic acid.
Examples thereof include those obtained by reacting 1 mol of dipentaerythritol with 1 to 4 mol of acrylic acid and 1 mol of dipentaerythritol reacted with 1 to 4 mol of methacrylic acid.

As the polyvalent carboxylic acid and polycarboxylic acid anhydride, as the carboxylic acid and carboxylic acid anhydride having no unsaturated bond, there are phthalic acid, isophthalic acid, terephthalic acid, adipic acid, azelaic acid, sebacine. acid,
Examples thereof include phthalic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, trimellitic acid and trimellitic anhydride. Examples of the carboxylic acid and carboxylic acid anhydride having an unsaturated bond include maleic acid, maleic anhydride, fumaric acid, itaconic acid, tetrahydrophthalic acid tetrahydrophthalic anhydride, methylcyclohexene tricarboxylic acid, and methylhexene tricarboxylic acid anhydride. To be

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

5. Polyurethanes Polyurethanes obtained from the following polyisocyanates and polyhydric alcohols.

In this case, at least one of the polyhydric alcohol and the polyisocyanate must have an unsaturated bond in order to obtain a polymer having an unsaturated bond.

Examples of the polyhydric alcohol include the polyhydric alcohols described in the section of polyester and the following polyhydric alcohols, and both terminals obtained by polycondensation of these polyhydric alcohols and the polyhydric carboxylic acid described in the section of polyester. A condensed polyester polyol in which is a hydroxyl group, a polymerized polyester polyol obtained from the above lactones, a polycarbonate diol, a polyether polyol obtained by ring-opening polymerization of propylene oxide or tetrahydrofuran or modification of an epoxy resin, or an acrylic group having a hydroxyl group ( Alternatively, an acrylic polyol, polybutadiene polyol, or the like, which is a copolymer of a methacrylic monomer and an acrylic (or methacrylic) acid ester, can be used. Also in this case, as in the case of the above-mentioned polyester, a hydroxyl group-containing polymer can be obtained by reacting so that at least one hydroxyl group of a polyfunctional alcohol having 3 or more functional groups remains.

Polypropylene glycol, polyethylene glycol, polytetramethylene glycol, ethylene oxide-propylene oxide copolymer, tetrahydrofuran-ethylene oxide copolymer, tetrahydrofuran-propylene oxide copolymer, various phosphorus-containing polyols, halogen-containing polyols and the like.

The isocyanates having no unsaturated bond include paraphenylene diisocyanate, 2,4- or 2,6-toluylene diisocyanate (TDI), 4,4-diphenylmethane diisocyanate (MDI), Trizine Isocyanate (TODI), Xylylene Diisocyanate (XDI)
Hydrogenated xylylene diisocyanate, cyclohexane diisocyanate, meta-xylylene diisocyanate (M
XDI), lysine diisocyanate (LDI) (also known as 2,6-diisocyanate methylcaproate), 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- (isocyanate methyl) cyclohexane), isophorone diisocyanate (IPI), diphenyl ether diisocyanate, trimethylhexamethylene diisocyanate (TMDI), tetramethyl xylylene diisocyanate, polymethylene phenyl isocyanate, dimer acid diisocyanate (DDI), triphenyl Methane triisocyanate, tris (isocyanate phenyl) thiophosphate, tetramethyl xylylene diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyl octane, 1,3,6 -Hexamethylene triisocyanate, bicycloheptane triisocyanate, etc. and polyisocyanate Polyhydric alcohol adduct of bets such,
Alternatively, polymers of polyisocyanates may be mentioned.
As the isocyanate having an unsaturated bond, a trifunctional or higher functional isocyanate among the above-mentioned isocyanates is used, and a hydroxyl group-containing acrylate or methacrylate (for example, hydroxyethyl acrylate or hydroxyethyl methacrylate) is added to the isocyanate group portion. The thing which was made to react is mentioned.

6 Polyamides As the polyamide having an unsaturated bond or a hydroxyl group, for example, one obtained by reacting a terminal carboxylic acid with a hydroxyl group-containing acrylate or methacrylate, one reacted with a glycidyl acrylate or glycidyl methacrylate, and the one shown in the above-mentioned polyester section Examples thereof include those obtained by reacting polyhydric alcohol. In such a case, as the main chain skeleton of polyamide, a commonly known polyamide skeleton can be mentioned. Specific examples of the main chain skeleton include ring-opened ε-caprolactam, ω-caprolactam, and the like, a reaction product of hexamethylenediamine and adipic acid, a reaction product of hexamethylenediamine and sebacic acid, and the like.

The amount of the binder polymer is preferably 5% by weight or more in terms of the coating ratio of the photosensitive solution and the physical properties of the photosensitive layer. However, 80
When the content is more than wt%, it means that the amount of the quinonediazide compound is reduced, resulting in problems in image reproducibility, developability, SK adhesive strength and the like.

In addition to the above components, it is optional to add additives such as a photosensitizer, an acid, a base, a dye, a pigment, a photocoloring agent, a surfactant and a catalyst, if necessary. In particular, in order to improve the plate inspection property of the exposed and developed printing plate, a printing plate precursor excellent in visible image reproducibility can be obtained by using an appropriate dye, pigment, photocoloring agent or the like alone or in combination of two or more kinds. Can be.

The photo-peeling type photosensitive layer used in the present invention is a layer in which the silicone rubber layer thereon is removed by the exposure and development processes without substantially removing the exposed layer photosensitive layer. There, a photosensitive layer composition containing a known quinonediazide compound as described above and a known diazonium compound as described above is coated on a substrate or a substrate coated with a primer layer, and then the entire surface is exposed before development processing. It is obtained by

From after the application of the photosensitive layer to before the image exposure, specifically, (1) immediately after the application of the photosensitive layer, that is, before the application of the silicone rubber layer, (2) immediately after application of the photosensitive layer and the silicone rubber layer, (3) After application of the photosensitive layer and the silicone rubber layer, after a while, (4) after application of the photosensitive layer and the silicone rubber layer, immediately before image exposure, (5) immediately after image exposure, and (6) development processing. Just before, and so on. Considering stable production of the waterless planographic printing plate precursor and production efficiency, among these timings, in particular, immediately after the application of the photosensitive layer of (1), before the application of the silicone rubber layer, and (2) the photosensitive layer and the silicone. Immediately after the application of the rubber layer, and (3) after the application of the photosensitive layer and the silicone rubber layer, and after a while, it is preferable.

As the light source used for the whole surface exposure, a light source usually used for making a printing plate, that is, a light source used for image exposure can be used. Specifically, it is a mercury lamp, a carbon arc lamp, a xenon lamp, a metal halide lamp, a tungsten lamp, a fluorescent lamp or the like.

In the whole surface exposure, it is necessary that the photoreactive functional group of the quinonediazide compound, that is, the quinonediazide group, is not reacted (deactivated) by the treatment. Therefore, by specifically reacting the diazonium compound while suppressing the reaction of the quinonediazide compound using light sources of different wavelengths, when using a light source of the same wavelength range, perform a total exposure of less than the image exposure, It is preferable to carry out the photoreaction of the diazonium compound while leaving the photoreactivity of the quinonediazide compound.

By the above-mentioned whole surface exposure treatment, the C—N bond of the diazo group of the diazonium compound is dissociated, and the radical intermediate or carbonium ion generated thereby reacts with the quinonediazide compound or the binder polymer in the photosensitive layer. As a result, a crosslinked structure is formed in the photosensitive layer. As a result, the photosensitive layer becomes insoluble or hardly soluble in the developing solution to form a photo-peeling photosensitive layer.

The thickness of the photosensitive layer is 0.1 to 100 μm.
m, preferably about 0.5-10 μm. If it is too thin, pinholes are likely to occur in the photosensitive layer, while if it is too thick, it is economically disadvantageous, so the above range is preferred.

The support used in the present invention may be any of those used in ordinary waterless planographic printing plates or those proposed. That is, it is sufficient that it can be set in an ordinary planographic printing machine and can withstand the load applied during printing.

For example, metal plates such as aluminum, copper, zinc, steel, and zinc, copper, nickel, aluminum,
And metal plates plated or vapor-deposited with iron, plastic films or sheets such as polyethylene terephthalate, polyethylene naphthalate, polyethylene, polystyrene, polypropylene, etc., rubber elasticity such as chloroprene rubber, NBR. Examples thereof include a support having the same, a support having such rubber elasticity, paper, resin-coated paper, paper covered with a metal foil such as aluminum, and the like. It is also possible to coat other substances on these supports for the purpose of preventing halation and for using them as a support.

Of these, a metal plate is preferable,
A metal plate made of aluminum is particularly preferable. Such a metal plate may be used as it is, or may be made into a plane by degreasing treatment with an alkaline aqueous solution or the like before use. Alternatively, the grain shape may be formed by a mechanical method, an electrolytic etching method, or the like. At this time, it is optional to perform the degreasing treatment before forming the grain shape.

Alternatively, the support may be provided with a primer layer in order to obtain sufficient adhesion between the photosensitive layer and the support.

As the primer layer, various types have been proposed in the past, and any primer layer can be used. That is, a primer layer containing gelatin, casein or natural protein, a primer layer using a flexible polyurethane, and a primer layer containing an epoxy resin as a component are known.

Among the thermosetting primer layers, a primer layer containing an epoxy resin as a component and a primer layer containing polyurethane and obtained by thermal crosslinking with a block type isocyanate and / or an epoxy resin are preferably used. .

Further, as the photo-curing type primer layer, a photo-dimerization type one, a photo-crosslinking type one containing a diazo resin, and a photo-polymerization type one containing an ethylenically unsaturated compound are also used in the present invention.

In both the thermosetting type and the photocuring type, a silane coupling agent can be used as the anchor agent constituting the primer layer, and organic titanate is also effective. A white pigment or a yellow pigment such as titanium oxide, calcium carbonate or zinc oxide may be added for the purpose of preventing halation from the substrate and improving the plate inspection property. Further, it is optional to add a surfactant or the like for the purpose of improving the coatability.

The thickness of the primer layer is 0.1 to 100 μm,
Preferably 0.3 to 50 μm, more preferably 0.5 to
30 μm is selected. If it is too thin, the effect of blocking morphological defects and adverse chemical effects on the substrate surface is poor, while if it is too thick, it is economically disadvantageous, so the above range is preferred.

In the waterless planographic printing plate of the present invention, the adhesion between the photosensitive layer and the ink repellent layer is very important for basic plate performance such as image reproducibility and printing durability. It is possible to provide an adhesive layer between layers and add an adhesion improving component to each layer. For adhesion between the photosensitive layer and the ink-repellent layer, it is effective to provide a known silicone primer or silane coupling agent between the layers or add a silicone primer or silane coupling agent to the ink-repellent layer or photosensitive layer. .

As the ink repellent layer used in the present invention, any known ink repellent layer that can be used in a waterless planographic printing plate can be used. Among these, those using silicone rubber are preferably used.

When a silicone rubber is used as the ink repellent layer, the silicone rubber layer is usually composed mainly of a linear organic polysiloxane having a repeating unit represented by the following general formula and having a molecular weight of several thousand to several hundred thousand. Is.

[0069]

Embedded image (In the formula, n is an integer of 2 or more, and R1 and R2 have 1 to 5 carbon atoms.
0-substituted or unsubstituted alkyl group, 2 to 50 carbon atoms
A substituted or unsubstituted alkenyl group having 4 to 50 carbon atoms
Of at least one substituted or unsubstituted aryl group, which may be the same or different. It is preferable that 40% or less of all R1 and R2 are vinyl, phenyl, vinyl halide, and phenyl halide, and 60% or more of all R1 and R2 are methyl groups. Such a linear organic polysiloxane can be made into a further crosslinked silicone rubber by adding an organic peroxide and subjecting it to heat treatment.

The linear organic polysiloxane is usually crosslinked by adding a crosslinking agent represented by the following general formula (II).

R3nSiX4-n (II) (In the formula, m is an integer of 0 to 2, R3 is an alkyl group,
An alkenyl group, an aryl group, or a group in which these are combined is shown, and these have a functional group such as a halogen atom, an amine group, a hydroxy group, an alkoxy group, an aryloxy group, a (meth) acryloxy group, and a thiol group as a substituent. You may have. X represents a hydrogen atom, a hydroxyl group, an alkoxy group, an acyloxy group, a ketoxime group, an amide group, an aminooxy group, an amino group, an alkenyloxy group, or other functional group. As the cross-linking agent, a polyfunctional silane compound used in the above-mentioned so-called room temperature (low temperature) curable silicone rubber can be mentioned. Examples thereof include, but are not limited to, acetoxysilane, ketoximesilane, alkoxysilane, aminosilane, and amidosilane having a trimethoxysilyl group, amino group, glycidyl group, methacryl group, allyl group, vinyl group, and the like.

These are usually combined with a linear organic polysiloxane having a hydroxyl group at the terminal to obtain a silicone rubber of deacetic acid type, deoxime type, dealcohol type, deamine type, deamidation type or the like. Become.

Silicone rubbers that undergo such condensation-type crosslinking include metal carboxylates such as tin, zinc, lead, calcium and manganese, such as dibutyltin laurate, tin (II) octoate and naphthenate. Alternatively, a catalyst such as chloroplatinic acid or a known catalyst other than this may be added.

It is also possible to cure the linear organic polysiloxane with a radical initiator to give a silicone rubber. At this time, it is optional to add an appropriate amount of a known radical initiator.

Further, an addition type silicone rubber layer which is crosslinked by an addition reaction between a SiH group and a —CH═CH— group is also useful. The addition type silicone rubber layer used here is composed of polyvalent hydrogenorganopolysiloxane and 2 per molecule.
Obtained by reaction with a polysiloxane compound having one or more -CH = CH- bonds, and preferably the following components: (1) Alkenyl group (preferably vinyl group) directly bonded to silicon atom in one molecule. (2) Organopolysiloxane having at least two (2) A composition comprising an organopolysiloxane having at least two SiH bonds in one molecule (3) an addition catalyst, which is crosslinked and cured. Ingredient (1)
The alkenyl group may be at either the terminal or the middle of the molecular chain. Examples of the group other than the alkenyl group include, but are not limited to, a substituted or unsubstituted alkyl group and aryl group. Component (1) may contain a trace amount of hydroxyl groups. The component (2) reacts with the component (1) to form a silicone rubber layer, and also plays a role of imparting adhesiveness to the photosensitive layer. The hydroxyl group of the component (2) may be at the terminal of the molecular chain or at the middle thereof. The organic group other than hydrogen is selected from the same groups as the component (1). From the viewpoint of improving the ink resilience, it is preferable that the organic groups of the components (1) and (2) are methyl groups in a total number of 60% or more. The molecular structures of the components (1) and (2) may be linear, cyclic or branched, and it is preferable that at least one of them has a molecular weight of more than 1,000 from the viewpoint of rubber physical properties,
Furthermore, it is preferable that the molecular weight of the component (1) exceeds 1,000.

Examples of the component (1) include α, ω-divinylpolydimethylsiloxane and a (methylsiloxane) (dimethylsiloxane) copolymer having methyl groups at both ends, and the component (2) includes hydroxyl groups at both ends. Examples thereof include polydimethylsiloxane, α, ω-dimethylpolymethylhydrogensiloxane, (methylpolymethylhydrogensiloxane) (dimethylsiloxane) copolymer having methyl groups at both ends, and cyclic polymethylhydrogensiloxane. However, the present invention is not limited to this and may be another one.

The addition catalyst of the component (3) is arbitrarily selected from known ones, but a platinum compound is particularly desirable,
Platinum alone, platinum chloride, olefin-coordinated platinum and the like are exemplified. In order to control the curing rate of these compositions, a vinyl group-containing organopolysiloxane such as tetracyclo (methylvinyl) siloxane, a carbon-carbon triple bond alcohol, acetone, methyl ethyl ketone, methanol,
It is also possible to add an appropriate amount of a crosslinking inhibitor such as ethanol or propylene glycol monomethyl ether.

In addition to these compositions, a known adhesion-imparting agent such as alkenyltrialkoxysilane is added, a hydroxyl group-containing organopolysiloxane which is a composition of a condensation type silicone rubber layer, and a terminal is a trimethylsilyl group. Silicone oil made of dimethylpolysiloxane, dimethylpolysiloxane having a trimethylsilyl group at the end, and hydrolyzable functional group-containing silane (or siloxane) may be added. Further, a known filler such as silica may be added to improve the rubber strength.

The thickness of the silicone rubber layer is about 0.5 to 10
0 μm, preferably about 0.5-10 μm,
If it is too thin, problems may occur in terms of printing durability and ink resilience, while if it is too thick, it not only is economically disadvantageous, but it also makes it difficult to remove the silicone rubber layer during development, resulting in image reproduction. Cause a decrease in sex.

In the waterless planographic printing plate precursor constructed as described above, the printing plate can be subjected to image exposure, development treatment and the like by a conventionally proposed method to be used for printing. .

[0081]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

Synthesis Example 1 (Synthesis of diazo resin-1) 14.5 g of p-diazophenylamine sulfate was dissolved in 40.9 g of concentrated sulfuric acid under ice cooling, and 1.0 g of paraformaldehyde was reacted with this solution. The temperature was slowly dropped so that the temperature did not exceed 10 ° C. Thereafter, stirring was continued for 2 hours under ice cooling. The reaction mixture was added dropwise to 500 ml of ethanol under ice cooling, and the resulting precipitate was filtered. 100 ml of precipitate washed with ethanol
Was dissolved in pure water, and a cold concentrated aqueous solution containing 6.8 g of zinc chloride was added to this solution. The generated precipitate was filtered, washed with ethanol, and dissolved in 150 ml of pure water. To this solution was added a cold concentrated aqueous solution in which 8 g of ammonium hexafluorophosphate was dissolved. The resulting precipitate was collected by filtration, washed with water, and dried at 30 ° C. for 24 hours to obtain a diazo resin.

Example 1 An aluminum plate having a thickness of 0.3 mm (manufactured by Sumitomo Metal Co., Ltd.) was coated with the following primer composition using a bar coater, and 18
Heat treatment was performed at 0 ° C. for 1 minute to provide a 3 μm primer layer.

(A) 100 parts by weight of “KP Color 8704 clear” (epoxy / urea resin manufactured by Kansai Paint Co., Ltd.) (b) 450 parts by weight of ethyl cellosolve (c) 450 parts by weight of ethyl cellosolve acetate (d) phosphoric acid 0.1 parts by weight Subsequently, the following photosensitive layer composition was coated on this primer layer using a bar coater and dried in hot air at 120 ° C. for 1 minute to form a photosensitive layer having a thickness of 1.5 μm. Provided.

(A) 1,2-naphthoquinone-2-diazide-5-sulfonic acid chloride partially esterified product of phenol formaldehyde novolak resin (Sumitomo Durez: "Sumilite Resin" PR50622) (degree of esterification by elemental analysis) 36%) 70 parts by weight (b) Diazo resin-1 30 parts by weight (c) Polyurethane resin "Samprene IB-104" (manufactured by Sanyo Kasei Co., Ltd.) 40 parts by weight (e) Dibutyltin diacetate 0.2 (F) Methyl cellosolve 800 parts by weight Next, a silicone rubber composition having the following composition was spin-coated on this photosensitive layer, and then 115 ° C., dew point 30 ° C., and 3.
It was heat-cured for 5 minutes to form a silicone rubber layer having a thickness of 2 μm.

(A) Polydimethylsiloxane (molecular weight of about 25,000, terminal hydroxyl group) 100 parts by weight (b) Ethyltriacetoxysilane 12 parts by weight (c) “Isopa-E” (manufactured by Exxon Chemical Co., Ltd.) 1400 parts by weight Part A polypropylene film “Trephan” having a thickness of 10 μm (manufactured by Toray Industries, Inc.) was added to the laminate obtained as described above.
Was laminated using a calendar roller to obtain a waterless planographic printing plate precursor.

A metal halide lamp (Idlefin 2000 manufactured by Iwasaki Electric Co., Ltd.) was used for the printing original plate.
The entire surface was exposed with a UV meter (Light Measure Type UV-402A, manufactured by Oak Manufacturing Co., Ltd.) at an illuminance of 11 mW / cm ² for 6 seconds.

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

Then, the exposed plate "Trephan" was peeled off, and "isopar-H" / diethylene glycol dimethyl ether / ethyl cellosolve / N-methyldiethanolamine = 87 /
A treatment liquid consisting of 7/3/3 (weight ratio) was applied to the plate surface using a brush. After processing for 1 minute, the processing solution adhering to the plate surface was removed with a rubber squeegee, and then the developing solution (water / butyl carbitol / 2-ethylbutyric acid / crystal violet = 70/30/2/0. When 2 (weight ratio) was poured and the plate surface was lightly rubbed with a developing pad, the silicone rubber layer in the image-exposed portion was removed and the surface of the photosensitive layer was exposed. The silicone rubber layer remained firmly, and a negative image faithfully reproducing the film was obtained.

Comparative Example 1 A plate was prepared in the same manner as in Example 1 except that the entire surface was exposed, and under the same conditions, and imagewise exposure and development were performed in the same manner. The photosensitive layer and the silicone rubber layer peeled off regardless of the exposed area.

Example 2 A photosensitive layer having the following composition was coated on the primer layer used in Example 1 and dried in hot air at 120 ° C. for 1 minute to form a photosensitive layer having a thickness of 1.5 μm.

(A) 1,2-naphthoquinone-2-diazide-5-sulfonic acid chloride partially esterified product of phenol formaldehyde novolac resin (Sumitomo Dures: "Sumilite Resin" PR50622) (esterification degree by elemental analysis) 36%) 40 parts by weight (b) Diazo resin-1 40 parts by weight (c) Polyurethane resin "Samprene IB-104" (manufactured by Sanyo Kasei Co., Ltd.) 40 parts by weight (e) Dibutyltin diacetate 0.2 (F) Methyl cellosolve 800 parts by weight Next, a silicone rubber layer similar to that in Example 1 was provided on this photosensitive layer, and "trephan" was laminated in the same manner as in Example 1 to perform waterless planographic printing. I got the original edition.

Using the same metal halide lamp as in Example 1, the printing original plate was subjected to full exposure for 3 seconds at an illuminance of 11 mW / cm ² .

1 is added to the printing original plate obtained as described above.
When a film having a halftone dot image of 50 lines / inch was vacuum-contacted and similarly imagewise exposed and developed, the silicone rubber layer in the exposed portion remained firmly, while only the entire surface was exposed. The silicone rubber layer was peeled off from the exposed portion, and a positive image faithfully reproducing the film was obtained.

Example 3 An aluminum plate (made by Sumitomo Metal Industries, Ltd.) having a thickness of 0.3 mm was coated with the following primer composition using a bar coater,
Heat treatment was performed at 0 ° C. for 2 minutes to provide a 5 μm primer layer.

(A) Polyurethane resin “Miractran P22S” (manufactured by Nippon Miractolan Co., Ltd.) 100 parts by weight (b) Block isocyanate “Takenate B830” (manufactured by Takeda Pharmaceutical Co., Ltd.) 20 parts by weight ( c) Epoxy phenol urea resin "SJ9372" (manufactured by Kansai Paint Co., Ltd.) 8 parts by weight (d) Titanium oxide 10 parts by weight (e) Dibutyltin diacetate 0.5 parts by weight (f) Mono ( 2-methacryloyloxyethyl) acid phosphate 1 part by weight (g) dimethylformamide 725 parts by weight Subsequently, the following photosensitive layer composition was coated thereon with a bar coater and heated in hot air at 120 ° C. for 1 minute. Dry to thickness 1.
A 5 μm photosensitive layer was provided.

(A) 1,2-naphthoquinone-2-diazide-5-sulfonic acid chloride and 4,4′-diaminobenzophenone partially amidated product (amidation degree 52% by elemental analysis) 60 parts by weight (b) diazo Resin "FDR-PF6" (Nippon Siegel Hegner Co., Ltd.) 30 parts by weight (c) 2-allyloxyethyl methacrylate / methacrylic acid / triethylene glycol monomethacrylate: 80/5/15 sodium salt 30 parts by weight (d) Methyl cellosolve 500 parts by weight Next, a silicone rubber solution having the following composition was applied on the photosensitive layer using a slit die coater, and then 1
It was heated and cured at 20 ° C. for 4 minutes to provide a 1.8 μm silicone rubber layer.

(A) Polydimethylsiloxane having vinyl groups at both ends (degree of polymerization: up to 700) 100 parts by weight (b) (CH3) 3Si-O- (Si (CH3) 2-O) 30- (SiH (CH3) -O ) 10-Si (CH3) 3 10 parts by weight (c) Chloroplatinic acid / methyl vinyl cyclics complex 0.1 parts by weight (d) Acetylacetone alcohol 0.1 parts by weight (e) Polydimethylsiloxane (degree of polymerization up to 8000) 10 parts by weight (f) "Isopa-E" (manufactured by Exxon Chemical Co., Ltd.) 1000 parts by weight On the laminated plate obtained as described above, a polyester film "Lumirror" having a thickness of 8 μm (manufactured by Toray Industries, Inc.) Was laminated using a calendar roller to obtain a waterless planographic printing plate precursor.

After subjecting the printing plate precursor to the same overall exposure process as in Example 1, image exposure was performed using a film having a halftone dot image of 150 lines / inch.

Next, the exposed plate was dipped in water at 40 ° C. for 3 minutes and then rubbed vigorously in water using a “Sofpad”. As a result, the silicone rubber layer peeled off from the exposed area,
A printing plate in which the silicone rubber layer remained in the unexposed area could be obtained.

Example 4 A 0.24 mm-thick chemical conversion-treated aluminum plate (manufactured by Sumitomo Metal Co., Ltd.) was coated with the following primer composition by using a whirler.
A primer layer was provided by coating at 0 ° C. and further drying at 80 ° C. for 4 minutes.

(A) Diazo resin-18 parts by weight (b) 90 parts by weight of a copolymer resin (Mw = 4.0 × 10 ⁴ ) having a molar ratio of 2-hydroxyethyl methacrylate and methyl methacrylate of 40/60 (c) ) Γ-methacryloxypropyltrimethoxysilane (manufactured by Toshiba Silicone) 5 parts by weight (d) zinc oxide (Sakai Kagaku (manufactured) fine zinc flower) 55 parts by weight (e) "KET-YELLOW 402" (Dainippon Ink Chemicals ( Yellow pigment) 12 parts by weight (f) "Nonipol" (Sanyo Chemical Co., Ltd. nonionic surfactant) 5 parts by weight (g) Methyl lactate 700 parts by weight (h) Cyclohexanone 100 parts by weight Metal halide after coating and drying 400 mJ / cm with lamp
² exposure and drying at 115 ° C. for 5 minutes provided a primer layer having a dry film thickness of 4.5 μm.

Subsequently, the following photosensitive layer composition was applied thereon.
It was applied using a coater and dried in hot air at 120 ° C. for 1 minute to form a photosensitive layer having a thickness of 1.5 μm.

(A) Partial esterification product of 1,2-naphthoquinone-2-diazide-5-sulfonic acid chloride and phenol formaldehyde novolac resin (Sumitomo Durez: “Sumilite Resin” PR50622) (degree of esterification by elemental analysis) 36%) 100 parts by weight (b) Diazo resin "FDR-PF6" (Nippon Siegel Hegner Co., Ltd.) 30 parts by weight (c) N- (4-hydroxyphenyl) methacrylamide / hi 70 parts by weight droxyethyl methacrylate / Acrylic acid: 45/45/10 (molar ratio) copolymer (d) Methyl cellosolve 500 parts by weight Next, a metal halide lamp (Idlefin 2000, manufactured by Iwasaki Electric Co., Ltd.) was used for this photosensitive layer, and a UV meter ( Oak Manufacturing, light measure type UV-40
2A) was subjected to a full exposure for 6 seconds with an illuminance of 11 mW / cm ² .

Next, a silicone rubber composition having the following composition was spin-coated under a stream of dry nitrogen, and then heat-cured for 3.5 minutes under the conditions of 115 ° C. and a dew point of 30 ° C. to 2.3.
A μm silicone rubber layer was provided.

(A) Polydimethylsiloxane (molecular weight about 35,000, terminal hydroxyl group) 100 parts by weight (b) Vinyltri (methylethylketoxime) silane 10 parts by weight (c) Dibutyltin diacetate 0.1 parts by weight (d) "Isopa-G" (manufactured by Exxon Chemical Co., Ltd.) 1200 parts by weight On the laminated plate obtained as described above, a polyester film "Lumirror" (manufactured by Toray Co., Ltd.) having a thickness of 8 μm is calendered. Laminating was carried out using-to obtain a waterless planographic printing plate precursor.

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

Next, the above-mentioned exposed plate "Lumira" was peeled off, and TWL116 was prepared under the conditions of room temperature of 25 ° C. and humidity of 80%.
Development was carried out using No. 0 (developing device for waterless planographic printing plate manufactured by Toray Industries, Inc.). Here, as the pretreatment liquid, a liquid having the following composition was used.

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

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

Example 5 A photosensitive layer having the following composition was coated on the primer layer used in Example 1 and dried in hot air at 90 ° C. for 6 minutes to form a photosensitive layer having a dry film thickness of 1.5 μm. .

(A) 1,2-Naphthoquinone-2-diazide-5-sulfonic acid 4 parts by weight sodium salt (b) Water-soluble diazo resin “HM-1” 2 parts by weight (manufactured by Nippon Sigel Hegner Co., Ltd.) (C) Acrylic emulsion "ALMATEX SP560" 6 parts by weight (manufactured by Mitsui Toatsu Chemicals, Inc.) (d) Polyvinyl alcohol "Gothenol KL-05" 4 parts by weight (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) (e) Purified water 285 parts by weight Next, a silicone rubber composition having the following composition was spin-coated under a stream of dry nitrogen and then cured at 100 ° C. for 2 minutes to provide a silicone rubber layer having a dry film thickness of 1.5 μm.

(A) Polydimethylsiloxane 100 parts by weight (molecular weight 35,000, hydroxyl groups at both ends) (b) Methyltri (acetoxy) silane 20 parts by weight (c) Dibutyltin diacetate 0.05 parts by weight (d) Acetone 100 Parts by weight (e) "Isopar E" 1100 parts by weight (manufactured by Exxon Chemical Co., Ltd.) A metal halide lamp (Idlefin 2000, manufactured by Iwasaki Electric Co., Ltd.) is used for the laminated body, and a UV meter (oak) is used. Manufactured by light measure type UV-40
2A), the whole surface was exposed for 2 seconds at an illuminance of 11 mW / cm ² , and then a polyester film “Lumirror” (manufactured by Toray Industries, Inc.) having a thickness of 8 μm was laminated with a calendar roller to obtain a waterless planographic printing plate precursor. Got

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

Then, the exposed plate was rubbed with a developing pad (manufactured by 3M Co., Ltd.) impregnated with tap water. As a result, the silicone rubber layer was peeled off at the exposed part and the silicone rubber layer was peeled off at the unexposed part. The remaining printing plate could be obtained.

[0116]

INDUSTRIAL APPLICABILITY The present invention provides a waterless planographic printing plate in which at least a photosensitive layer and a silicone rubber layer are laminated in this order on a support, and the photosensitive layer contains at least a quinonediazide compound and a diazonium compound. Conventionally, compounds that are difficult to control the reaction can be used to insolubilize or make the photosensitive layer insoluble, and compounds that are relatively easy to control the reaction can be replaced with photoreaction instead of the conventional thermal reaction. Therefore, the productivity of the waterless planographic printing plate precursor can be improved.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location G03F 7/038 G03F 7/038 7/38 501 7/38 501

Claims (6)

[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 support, wherein the photosensitive layer contains a quinonediazide compound and a diazonium compound, and the photosensitive layer is a diazonium compound. A waterless planographic printing plate precursor characterized by having a cross-linked structure according to. 2. The waterless planographic printing plate precursor as claimed in claim 1, wherein the photosensitive layer contains a binder polymer. 3. The waterless lithographic printing plate precursor as claimed in claim 1, wherein the quinonediazide compound is a 1,2-naphthoquinone-2-diazidesulfonic acid derivative. 4. The waterless lithographic printing plate precursor as claimed in claim 1, wherein the photosensitive layer is a photo-peeling photosensitive layer. 5. A waterless lithographic printing plate obtained by selectively exposing and developing the waterless lithographic printing plate precursor according to claim 1. 6. A method for producing a waterless lithographic printing plate precursor comprising a support, and at least a photosensitive layer containing at least a quinonediazide compound and a diazonium compound and a silicone rubber layer, which are laminated in this order. A method for producing a waterless planographic printing plate precursor, which comprises exposing the entire surface to the previous step.