JPH0926664A - Photosensitive paleographic printing plate requiring no dampening water - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a paleographic printing plate excellent in sensitivity, tone reproducibility, printing and scuffing resistances and developable with an aq. developer by incorporating an urethane binder having carboxyl groups derived from a diol compd. into a photopolymerizable photosensitive layer. SOLUTION: A photopolymerizable photosensitive layer and a silicone rubber layer are successively laminated on a substrate. The photosensitive layer contains an urethane binder as a reactional product of diisocyanate compds. with diol compds. and at least one of the diol compds. has a carboxyl group. Since the urethane binder having carboxyl groups derived from one of the diol compds. is contained in the photosensitive layer, the photosensitive layer forming a non-image area after imagewise exposure has improved scuffing and printing resistances and sensitivity by the adhesion of the urethane binder to the silicone rubber. Owing to the hydrophilic property of the urethane binder, a satisfactory image can be formed even with an aq. developer.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention provides a photopolymerizable photosensitive layer and a silicone rubber layer on a substrate in this order, and is excellent in sensitivity, tone reproducibility, printing durability, and scratch resistance, and water or water as a main component. Aqueous solution of organic solvent (hereinafter referred to as aqueous developer)
And a photosensitive lithographic printing plate that does not require fountain solution (hereinafter referred to as waterless lithographic printing plate).

[0002]

2. Description of the Related Art Various waterless lithographic printing plates have been proposed for lithographic printing without using fountain solution. Among them, the one in which the photosensitive layer and the ink repellent layer are applied in this order on the substrate has extremely excellent performance. Ink repellent layers using silicone rubber are disclosed, for example, in JP-B-54-26923 and JP-B-55-22.
No. 781, JP-B-56-23150 and JP-A-2-
It is described in Japanese Patent No. 236550.

In the case of positive type waterless planographic printing plates, photopolymerizable photosensitive compositions which are cured by exposure have been used as the photosensitive layer. In the image area, the developing solution is allowed to penetrate through the silicone rubber layer, and a part or all of the uncured photosensitive layer composition is dissolved by the developing solution, and then the silicone rubber layer thereon is removed by physical force. It is formed. In the non-image area, the photosensitive layer is cured by exposure, and photoadhesion is made at the interface with the upper silicone rubber layer to firmly bond the two layers, suppressing penetration by the developer and accompanying elution of the photosensitive layer composition. To form a non-image portion including a silicone rubber layer.

As a method of developing a waterless planographic printing plate on which an image is formed in this manner, Japanese Patent Publication No. 56-23150 is available.
JP-A-57-13448 and JP-A-59-1460.
54 and JP-A-63-52145 are disclosed. However, these developing methods are expensive because the main component of the processing liquid is an organic solvent, and require special consideration in handling due to the risk of ignition. In order to solve this problem, JP-A-1-159644 discloses a developing solution containing water as a main component. In order to use such an aqueous developer, it is necessary to add a compound having hydrophilicity as a photopolymerizable monomer in the photosensitive layer,
Monomers having polyethylene oxide chains or polypropylene oxide chains are described in JP-A-4-174437, JP-A-4-338954, JP-A-5-94007, JP-A-5-224415, JP-A-6-118629 and the like. However, good images can be obtained by using these monomers. However, in the waterless planographic printing plate developed with a water-based developer, a waterless planographic printing plate satisfying all of sensitivity, tone reproducibility, printing durability, and scratch resistance has not been obtained so far.

[0005]

Therefore, the object of the present invention is to provide excellent sensitivity, tone reproducibility, printing durability, and scratch resistance,
It is intended to provide a waterless planographic printing plate which can be developed with an aqueous developer.

[0006]

The present inventors have laminated a photopolymerizable photosensitive layer and a silicone rubber layer in this order on a substrate, and the photopolymerizable photosensitive layer reacts with a diisocyanate compound and a diol compound. A waterless lithographic printing plate containing a urethane binder as a product, wherein at least one of the diol compounds has a carboxyl group, and while immersing the waterless lithographic printing plate in an aqueous developer, The object of the present invention has been achieved by a waterless planographic printing plate making method characterized by removing a silicone rubber layer to form an image.

[0007]

According to the present invention, the photopolymerizable photosensitive layer contains a urethane binder having a carboxyl group derived from a diol compound, so that the photosensitive layer forming a non-image area after image exposure has a urethane group having a carboxyl group. By improving the scratch resistance, printing durability and sensitivity by the adhesiveness between the binder and the silicone rubber layer, and by making the urethane binder having a carboxyl group hydrophilic, it is possible to form good images even with an aqueous developer. The inventors have reached the object of the present invention. The present invention will be described in detail below.

[Substrate] The waterless lithographic printing plate of the present invention must have flexibility so that it can be set in an ordinary printing machine, and at the same time withstand the load applied during printing. Therefore, as a typical substrate, coated paper, a metal plate such as aluminum, a plastic film such as polyethylene terephthalate, rubber or a combination thereof (for example, a composite plate in which the upper and lower sides of paper are sandwiched by aluminum) is used. And more preferably aluminum and aluminum-containing (eg, silicon, copper, manganese, magnesium, chromium, zinc, lead, bismuth,
Alloy with aluminum such as nickel and other metals) alloy. In order to remove the rolling oil on the surface of such an aluminum plate, degreasing treatment such as showering or dipping of an aqueous acid solution is performed. The acid used at this time may be any acid known as a metal cleaning acid, but is preferably sulfuric acid or phosphoric acid. After the acid treatment, it is preferable to wash with water for an appropriate time. After degreasing, a coating such as a photosensitive layer may be provided directly, but surface treatment such as graining, anodic oxidation, treatment with an aqueous solution of silicate such as sodium silicate or potassium silicate (also referred to as "silicate treatment") You may go. Of these, silicate treatment is preferable. Further, the support may be surface-treated with a silane coupling agent for the purpose of improving the adhesion to the coating film.

[Primer Layer] In the present invention, a primer layer may be provided between the support and the photosensitive layer. As the primer layer used in the present invention, various types can be used for the purpose of improving the adhesion between the substrate and the photopolymerizable photosensitive layer, preventing halation, dyeing an image and improving printing characteristics. For example, various photosensitive polymers as disclosed in JP-A-60-22903, which are exposed and cured before laminating a photosensitive layer, JP-A-62-507.
The epoxy resin disclosed in JP-A-60 is heat-cured, the gelatin disclosed in JP-A-63-133151 is hardened, and further JP-A-3-2.
The one using the urethane resin and the silane coupling agent disclosed in Japanese Patent Laid-Open No. 00965 and JP-A-3-27324.
Examples thereof include those using the urethane resin disclosed in JP-A-8. In addition, those obtained by hardening gelatin or casein are also effective. Further, for the purpose of softening the primer layer, a polyurethane, a polyamide, a styrene / butadiene rubber, a carboxy-modified styrene / butadiene rubber, an acrylonitrile / butadiene rubber, an acrylonitrile / butadiene rubber, a carboxy-modified acrylonitrile having a glass transition temperature of not more than room temperature are contained in the primer layer. / Polymer such as butadiene rubber, polyisoprene, acrylate rubber, polyethylene, chlorinated polyethylene and chlorinated polypropylene may be added. The addition ratio is arbitrary,
The primer layer may be formed only by the additive as long as the film layer can be formed. In addition, for these primer layers, a dye, a pH indicator, a printing-out agent, a photopolymerization initiator, an adhesion aid (for example, a polymerizable monomer, a diazo resin, a silane coupling agent, a titanate coupling, etc.) can be used in accordance with the above purpose. agent or aluminum coupling agent), pigment (for example, can also contain TiO ₂₎ and additives of the silica powder and the like. After the application, it can be cured by exposure. Generally, the coating amount of the primer layer is suitably in the range of 0.1 to 20 g / m ^{2 on} a dry weight basis, and preferably 1 to 10 g / m ² .

[Photosensitive layer] The photopolymerizable photosensitive layer used in the present invention comprises a polyurethane resin having a carboxyl group derived from at least a diol compound, a photopolymerizable monomer, and
Contains a photopolymerization initiator. Further, if necessary, a polymer compound other than the polyurethane resin having a carboxyl group derived from a diol compound may be contained.

Component: Polyurethane Resin Having Carboxyl Group Derived from Diol Compound The polyurethane resin preferably used in the present invention is a polyurethane resin which is a reaction product of a diol compound having at least one carboxyl group and a diisocyanate compound. And is a polyurethane resin having a carboxyl group derived from a diol compound. Preferably, a diisocyanate compound represented by the following general formula (I) and a carboxyl group represented by the structure of any one of the following general formulas (II), (III), (IV), (V) or (VI) A polyurethane resin having a structure represented by a reaction product with a diol compound containing at least one of the diol compounds having

[0012]

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In the formula (I), R ₁ represents a divalent aliphatic or aromatic hydrocarbon. Further, R ₁ may have a substituent (for example, alkyl, alkoxy, aryl, aryloxy, aralkyl, aralkoxy, halogeno),
It may have another functional group that does not react with an isocyanate group, for example, a carbonyl, ester, urethane, amide, or ether group. In formulas (II) to (VI), R ₂ and R ₈
Represents a hydrogen atom, an alkyl, an alkoxy or an aryloxy group, preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 15 carbon atoms. Furthermore, the alkyl, alkoxy, and aryloxy groups of R ₂ and R ₈ are a substituent (for example, cyano, nitro, a halogen atom (—F, —Cl, —Br, —I), —CONH ₂ , —C).
OOR ₉ , -OR ₉ , -NHCONHR ₉ , -NHCOO
_{R 9, -NHCOR 9, -OCONHR 9} , -CONHR 9
(Here, R ₉ represents an alkyl group having 1 to 10 carbon atoms or an aralkyl group having 7 to 15 carbon atoms) and the like. ) May be included. In formulas (II) to (VI),
R ₃ , R ₄ , R ₅ , R ₆ and R ₇ may be the same or different and each represents a single bond, a substituent (for example, an alkyl, alkoxy, aryl, aryloxy, aralkyl, aralkoxy or halogeno group). Preferred) are present and represent divalent aliphatic or aromatic hydrocarbons. It is preferably an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 15 carbon atoms, and more preferably an alkylene group having 1 to 8 carbon atoms. If necessary, R ₃ , R ₄ , R ₅ , R ₆ ,
R ₇ may have another functional group which does not react with an isocyanate group, for example, a carbonyl group, an ester group, a urethane group, an amide group or an ether group. R ₂ , R ₃ , R ₄ , R ₅ , R
_6, may form a ring Two or three of R _7. A
r represents a trivalent aromatic hydrocarbon which may have a substituent, and preferably represents an aromatic group having 6 to 15 carbon atoms.

Specific examples of the diisocyanate compound represented by the general formula (I) include those shown below.
That is, 2,4-tolylene diisocyanate, dimer of 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, p-xylylene diisocyanate, m
-Xylylene diisocyanate, 4,4'-diphenylmethane diisonoanoate, 1,5-naphthylene diisocyanate, 3,3'-dimethylbiphenyl-4,4'-
Aromatic diisocyanate compounds such as diisocyanate; aliphatic diisocyanate compounds such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, dimer acid diisocyanate; isophorone diisocyanate, 4,
Aliphatic diisocyanate compounds such as 4'-methylenebis (cyclohexylisocyanate), methylcyclohexane-2,4 (or 2,6) diisocyanate, 1,3- (isocyanatomethyl) cyclohexane and the like;
Examples thereof include a diisocyanate compound which is a reaction product of a diol and a diisocyanate such as an adduct of 1 mol of 1,3-butylene glycol and 2 mol of tolylene diisocyanate.

Specific examples of the diol compound having a carboxyl group represented by formula (II), (III), (IV), (V) or (VI) include those shown below. That is, 3,5-dihydroxybenzoic acid, 2,2-bis (hydroxymethyl) propionic acid, 2,2-bis (2-hydroxyethyl) propionic acid, 2,2-bis (3-hydroxypropyl) propionic acid, Bis (hydroxymethyl) acetic acid, bis (4-hydroxyphenyl) acetic acid,
4,4-bis (4-hydroxyphenyl) pentanoic acid,
Tartaric acid, N, N-dihydroxyethylglycine, N, N
Examples include -bis (2-hydroxyethyl) -3-carboxy-propionamide and 2,2-bis (hydroxymethyl) malonic acid. The polyurethane resin of the present invention is a diisocyanate compound represented by the general formula (I), a diol compound represented by the general formula (II), (III), (IV), (V) or (VI), or 2 It may be formed of one or more species.

Further, a diol compound which does not have a carboxyl group and may have other substituent which does not react with isocyanate may be used in combination. Specific examples of such diol compounds include the following. That is, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, neopentyl glycol, 1,3-butylene glycol, 1,6-hexanediol, 2-butene- 1,4
-Diol, 2,2,4-trimethyl-1,3-pentanediol, 1,4-bis-β-hydroxyethoxycyclohexane, cyclohexanedimethanol, tricyclodecanedimethanol, hydrogenated bisphenol A, hydrogenated bisphenol F, Bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct, bisphenol F ethylene oxide adduct,
Bisphenol F propylene oxide adduct, hydrogenated bisphenol A ethylene oxide adduct, hydrogenated bisphenol A propylene oxide adduct, hydroquinone dihydroxyethyl ether, p-xylylene glycol, dihydroxyethyl sulfone, bis (2-hydroxyethyl) -2,4-tolylene dicarbamate,
Examples thereof include bis (2-hydroxyethyl) -m-xylylene dicarbamate and bis (2-hydroxyethyl) isophthalate.

The polyurethane resin of the present invention comprises the above diisocyanate compound and the compounds represented by the general formulas (II), (III) and (I
A diol compound containing at least one of V), (V) or (VI) is added to an aprotic solvent in which a known catalyst having an activity corresponding to each reactivity is added and heated. For the diisocyanate compound used,
The total molar ratio of the diol compounds containing the compound of the general formula (II), (III), (IV), (V) or (VI) is preferably 0.8: 1 to 1.2: 1. When the isocyanate group remains at the terminal, it is finally treated in a form in which the isocyanate group does not remain by treating with alcohols or amines. The weight average molecular weight of the polyurethane resin having a carboxyl group used in the present invention is preferably in the range of 1,000 to 1,000,000, more preferably in the range of 5,000 to 500,000. These polyurethane resins having a carboxyl group may be used alone or in combination of two or more, and the content in the total photopolymerizable photosensitive layer composition is 1 to 85% by weight, preferably Is 10 to 75% by weight, and more preferably 25 to
70% by weight.

Specific examples of the binder having a carboxyl group as a component used in the present invention will be given below, but the binder is not limited thereto.

[0019]

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[0020]

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[0021]

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[0022]

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[0023]

[Chemical 6]

Chemical formulas (O), (P), (Q),
In the binder represented by (R), (W) and (X), PEG represents polyethylene glycol and PPG
Represents polypropylene glycol. The number following them represents the average molecular weight. Further, in the above binder, PEG or PPG is selected from those having different average molecular weights to form a binder with other monomers. Component: Photopolymerizable Monomer The photopolymerizable monomer may be used alone or in combination of two or more, and the content in the total photopolymerizable photosensitive layer composition is 1 to
80% by weight, preferably 5 to 70% by weight,
More preferably, it is 15 to 65% by weight. Examples of the monomers and oligomers that can be used in the present invention include (A) alcohols (eg, glycerin, hexanediol, trimethylolpropane,
Pentaerythritol, sorbitol, triethylene glycol, (poly) ethylene glycol, (poly) propylene glycol, etc., and further glycerin, hexanediol, trimethylolpropane, pentaerythritol,
Acrylic acid or methacrylic acid ester of ethylene oxide such as sorbitol, propylene oxide, or a mixed adduct thereof, (B) amines (for example, ethylamine, ethylenediamine, hexamethylenediamine, diethylenetriamine, xylylenediamine, ethanolamine, aniline) Etc.) and glycidyl acrylate,
Reaction products with glycidyl methacrylate or allyl glucidyl, (C) carboxylic acids (eg acrylic acid,
Reaction products of methacrylic acid, succinic acid, maleic acid, phthalic acid, etc.) with glycidyl acrylate, glycidyl methacrylate or allyl glucidyl, (D) amide derivatives (eg, methylenebisacrylamide, xylylenediacrylamide, etc.), etc. Can be mentioned.

More specifically, Japanese Patent Publication No. 48-41708
No., JP-B-50-6034, JP-A-51-37193.
Urethane acrylates described in JP-A-48-64183 and JP-B-49-4319.
No. 1, polyester acrylates and epoxy resins described in JP-B-52-30490 and (meth)
Polyfunctional acrylates and methacrylates such as epoxy acrylates reacted with acrylic acid, US Pat.
The N-methylolacrylamide derivative described in Japanese Patent No. 40649 can be exemplified. Furthermore, Japan Adhesives Association Vol. 20, No. 7, pages 300-308 (198)
Those described as photocurable monomers and oligomers in (4 years) and the like can also be used. However, the unsaturated group may be present in a mixture of acryl, methacryl, allyl, vinyl groups and the like, without being limited thereto. These may be used alone or in combination.

Component: Photopolymerization Initiator The photopolymerization initiator used in the present invention may be a compound capable of generating a radical by light, regardless of whether it is a sensitized system or a non-sensitized system. The following can be given as typical examples, but the present invention is not limited to these. (A) Benzophenone derivative, for example, benzophenone, dimethylaminobenzophenone, diethylaminobenzophenone, xanthone, anthrone, thioxanthone, acridone, 2-chloroacridone, 2-chloro-
N-n-butylacridone, 2,4-diethylthioxanthone, fluorenone, etc., (b) benzoin derivative, for example, benzoin, benzoin methyl ether, benzoin ethyl ether, etc., (c) quinones, for example, p-
Benzoquinone, β-naphthoquinone, β-methylanthraquinone, etc., (d) sulfur compounds such as dibenzyl disulfide, di-n-butyl disulfide, etc.
(E) Azo or diazo compound, for example, 2-azobisisobutyronitrile, 1-azo-bis-1-cyclohexanecarbonitrile, p-diazobenzylethylaniline, Congo red, etc., (f) Halogen compound, for example, Carbon tetrabromide, silver bromide, α-chloromethylnaphthalene, trihalomethyl-s-triazine compounds, trihalomethyloxadiazole compounds, etc. (g) Peroxides, for example, benzoyl peroxide, etc. You can These may be used alone or in combination. The addition amount of these photopolymerization initiators is 0.1 to 25% by weight, preferably 3%, based on the total photopolymerizable photosensitive layer composition.
-20% by weight.

Component: Polymer compound other than carboxyl group-containing urethane binder As the polymer compound other than the carboxyl group-containing urethane binder used in the present invention, the following polymers and copolymers can be used. (1) Vinyl polymers such as polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl methyl ether, polyvinyl chloride, polyethylene and the like, and copolymers thereof. (2) (Meth) acrylic acid ester polymers and alkyl (meth) acrylamide polymers such as ethyl poly (meth) acrylate, butyl poly (meth) acrylate, poly t-butyl acrylamide, poly diacetone acrylamide, etc., and copolymers thereof. , And copolymers with (meth) acrylic acid. (3) Unvulcanized rubber, for example natural rubber, polybutadiene,
Polyisobutylene, polyneoprene, etc., and copolymers thereof. (4) Polyether such as polyethylene oxide, polypropylene oxide, etc. (5) Polyamide, copolymer of the following monomers,
For example, caprolactam, laurolactam, hexamethylenediamine, 4,4'-bis-aminocyclohexylmethane, 2,4,4-trimethylhexamethylenediamine, isophoronediamine, diglycols, isophthalic acid, adipic acid, sebacic acid and the like. (6) Polyester, for example, a condensate of terephthalic acid, adipic acid and the like with ethylene glycol, 1,4-butanediol and the like. (7) Polyurethane, such as hexamethylene diisocyanate, toluene diisocyanate, naphthalene-1,
Diisocyanate compounds such as 5-diisocyanate and isophorone diisocyanate, ethylene glycol,
Polyurethane which is a reaction product with a diol compound having no carboxyl group such as 1,4-butanediol, polyester diol, and polyether. Further, a poly (urethane-urea) resin to which a diamine such as isophoronediamine or hexamethylenediamine is added as a chain extender may be used. Further, as the polymer compound other than the urethane binder having a carboxyl group, a polymer compound having a photopolymerizable or photocrosslinkable olefinic unsaturated double bond group in the side chain can be used. It is not limited. These may be used alone or in combination.

The polymer compounds of and can be contained together in an amount of 10 to 90% by weight, preferably 25 to 75% by weight, based on the total photopolymerizable photosensitive layer composition.

Other Components In addition to the above components, it is preferable to add a thermal polymerization inhibitor, for example, hydroquinone, p-methoxyphenol,
Di-t-butyl-p-cresol, pyrogallol, t-
Butyl catechol, 4,4'-thiobis (3-methyl-
6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2-mercaptobenzimidazole, etc. are useful, and in some cases, a dye for the purpose of coloring the photopolymerizable photosensitive layer. Alternatively, a pH indicator or a leuco dye may be added as a pigment and a printing agent. Depending on the purpose, a small amount of polydimethylsiloxane, methylstyrene-modified polydimethylsiloxane, olefin-modified polydimethylsiloxane, polyether-modified polydimethylsiloxane, silane coupling agent, silicone diacrylate, silicone dimethacrylate, etc. may be further contained in the photopolymerizable photosensitive layer. You may add the silicone compound of. A silicone-based surfactant or a fluorine-based surfactant may be added to improve coating properties. Further, a diazo resin may be added in order to improve the adhesion between the photopolymerizable photosensitive layer and the primer layer. In addition, a plasticizer (for example, polyethylene glycol, polypropylene glycol, tricresyl phosphate, etc.) and a stabilizer (for example, phosphoric acid) for imparting flexibility to the coating film may be added.
The addition amount of these additives is usually 10% by weight or less based on the total photopolymerizable photosensitive layer composition. In some cases, a hydrophobic silica powder treated with a (meth) acryloyl group- or allyl group-containing silane coupling agent may be added in an amount of 10% by weight or less based on the total photopolymerizable photosensitive layer composition.

The above-mentioned photopolymerizable photosensitive layer composition used in the present invention is, for example, water, 2-methoxyethanol, 2-methoxyethyl acetate, propylene glycol methyl ethyl acetate, methyl lactate, ethyl lactate, propylene glycol monomethyl ether, A suitable solvent such as ethanol, methyl ethyl ketone, N, N-dimethylacetamide, methyl pyruvate, ethyl pyruvate, and methyl 3-methoxypropionate alone or dissolved in a mixed solvent thereof is applied onto the substrate. Its coating weight is suitably in the range of 0.1 to 20 g / m ² in weight after drying, is preferably in the range of 0.5 to 10 g / m ²

[Ink Repellent Layer] As the ink repellent layer used in the present invention, a silicone rubber layer which is a film formed by curing the following composition A or B can be used. [Composition A (condensation type)] (a) Diorganopolysiloxane (number average molecular weight of 3,000 to 200,000) 100 parts by weight (b) Condensation type crosslinking agent 3 to 70 parts by weight (c) Catalyst 0. 01 to 40 parts by weight The diorganopolysiloxane of the component (a) is a polymer having a repeating unit represented by the following formula (a), R ₁₀ and R ₁₁ are alkyl groups having 1 to 10 carbon atoms,
It is a vinyl group or an aryl group, and may have other substituents. Generally, it is preferable that 60% or more of R ₁₀ and R ₁₁ are methyl groups, halogenated vinyl groups, halogenated phenyl groups, or the like.

[0032]

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It is preferable to use a diorganopolysiloxane having hydroxyl groups at both ends. The component (a) has a number average molecular weight of 3,000 to 200,
000, and more preferably 5,000 to 100,
000. The component (b) may be of any condensation type, but is preferably one represented by the following general formula (b).

[0034]

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In the general formula (b), R ₁₂ has a carbon number of 1 to
10 represents an alkyl group, a vinyl group or an aryl group,
Z is a hydrogen atom, a halogen atom (Cl, Br, I, etc.),
—OH, —OCOR ₁₃ , —OR ₁₃ (wherein R ₁₃ is the above R
Synonymous with ₁₂ ), or a group represented by the following formula (wherein R ₁₄ , R
₁₅ , R ₁₆ and R ₁₇ represent an alkyl group having 1 to 10 carbon atoms)
, A represents 0, 1 or 2, b represents 2, 3 or 4, and a + b is 4.

[0036]

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Component (c) is tin, zinc, lead, calcium,
Examples thereof include metal carboxylates such as manganese, for example, known catalysts such as dibutyl laurate, lead octylate, lead naphthenate, and chloroplatinic acid.

[Composition B (addition type)] (d) Diorganopolysiloxane having an addition-reactive functional group (number average molecular weight of 3,000 to 200,000) 100 parts by weight (e) Organohydrogenpolysiloxane 0.1-10 parts by weight (f) Addition catalyst 0.00001-1 part by weight The diorganopolysiloxane having an addition-reactive functional group of the component (d) is an alkenyl directly bonded to a silicon atom in one molecule. Organopolysiloxane having at least two (more preferably vinyl) (number average molecular weight of 3,000 to 200,000), and Japanese Patent Application No. 4-2384.
What was described in the 97th specification can be used.
The alkenyl may be at both ends of the molecule or in the middle,
The organic group other than alkenyl is substituted or unsubstituted alkyl or aryl having 1 to 10 carbon atoms. Also,
The component (d) may optionally have a small amount of hydroxyl groups.
The component (d) has a number average molecular weight of 3,000 to 200,0.
00, and more preferably 5,000 to 100,0
00. As the component (e), polydimethylsiloxane having hydrogen groups at both ends, α, ω-dimethylpolysiloxane, (methylsiloxane) (dimethylsiloxane) copolymer having methyl groups at both ends, cyclic polymethylsiloxane, trimethylsilyl group at both ends And poly (dimethylsiloxane) (methylsiloxane) copolymers having trimethylsilyl groups at both ends, which are disclosed in JP-A-4-68353. The component (f) is arbitrarily selected from known compounds, and is particularly preferably a platinum compound, such as platinum alone, platinum chloride, chloroplatinic acid, and olefin-coordinated platinum.

For the purpose of controlling the curing speed of these compositions, vinyl group-containing organopolysiloxanes such as tetracyclo (methylvinyl) siloxane, carbon-carbon triple bond-containing alcohols, acetone, methylethylketone, methanol, ethanol, propylene. It is also possible to add a crosslinking inhibitor such as glycol monomethyl ether. In addition, if necessary, the silicone rubber layer
Fine powders of inorganic substances such as silica, calcium carbonate and titanium oxide, silane coupling agents, adhesion aids such as titanate coupling agents and aluminum coupling agents and photopolymerization initiators, disclosed in JP-A-1-17947. An aromatic-substituted polydimethylsiloxane as described above,
Silicone oil may be added.

In the present invention, it is preferable to use the addition type silicone rubber in view of the curability of the silicone rubber.
The ink repellent layer according to the present invention has a problem that when the thickness is small, the ink repellent property is lowered and scratches easily occur, and when the thickness is large, the developability is deteriorated. It is preferably 5 to 5 g / m ² , more preferably 1
３3 g / m ² . In the waterless planographic printing plate described here, various ink repellent layers may be further coated on the ink repellent layer. Further, in order to increase the adhesive force between the photopolymerizable photosensitive layer and the ink repellent layer, or to prevent poisoning of the catalyst in the ink repellent layer composition, the photopolymerizable photosensitive layer and the ink repellent layer are An intermediate layer may be provided between them.

[Cover Film] Further, a transparent film on the ink repellent layer for protecting the surface of the ink repellent layer,
For example, polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyethylene terephthalate, cellophane, or the like may be laminated, or a polymer coating may be applied. These films may be used after being stretched. Further, this film may be matted to improve the vacuum adhesion in the baking frame at the time of image exposure, and a coating is applied to the contact surface of the film with the ink repellent layer to improve the peeling property of the film. May be.

[Development Treatment] The waterless planographic printing plate according to the present invention is a developer capable of dissolving or swelling a part or all of the photosensitive layer in the image area (unexposed area) after being exposed through a transparent original image, or It is developed with a developer capable of swelling the ink repellent layer. In this case, the photosensitive layer and the ink repellent layer in the image area may be removed or only the ink repellent layer in the image area may be removed, which can be controlled by the strength of the developing solution. As the developing solution used in the present invention, those known as a developing solution for a waterless planographic printing plate can be used, but an aqueous developing solution is particularly preferable. Known water-based developers include, in addition to water (tap water, pure water, distilled water, etc.), for example, the following polar organic solvents may be added to water, or water may be added to the water using a surfactant or the like. Examples include solubilized ones, and further alkaline agents (for example, sodium carbonate,
Diethanolamine, sodium hydroxide, etc.) may be added, but in view of safety and flammability, development with water alone is particularly desirable. -Alcohols (methanol, ethanol, propanol, isopropanol, benzyl alcohol, ethylene glycol monomethyl ether, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol Monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, etc.) Ketones (acetone, methyl ethyl ketone, etc.), esters (ethyl acetate, methyl lactate, butyl lactate,
Propylene glycol monomethyl ether acetate,
Diethylene glycol acetate, diethyl phthalate, etc.) Others (triethyl phosphate, tricresyl phosphate, etc.) In addition, dyes such as crystal violet, Victoria pure blue, and Astrazone red are added to the developer,
The image area can be dyed simultaneously with the development.

The development is carried out by a known method such as rubbing the plate surface while immersing the plate in the above developing solution with a developing vat, or pouring the developing solution onto the plate surface and then rubbing it in water with a developing brush. It can be carried out. The temperature of the developer can be developed at any temperature, but is preferably 10 ° C to 60 ° C. As a result, the ink repellent layer in the image area is removed, and that area becomes the ink receiving area. The printing plate thus obtained can be detected by dyeing the exposed image portion with a dye solution in order to confirm the image forming property. When the developer does not contain a dye for dyeing the exposed image portion, it is treated with the dye after development. By impregnating the dyeing solution with a soft pad and lightly rubbing the image portion, only the exposed image portion of the photosensitive layer is dyed, whereby it can be confirmed that the development is sufficiently performed up to the highlight portion. As the dyeing solution, one or more selected from water-soluble disperse dyes, acid dyes and basic dyes may be used alone or as a mixture of two or more of water, alcohols, ketones and ethers. What is dissolved or dispersed is used.
In order to improve the dyeability, carboxylic acids, amines,
It is also effective to add a surfactant, a dyeing aid, an antifoaming agent and the like. It is preferable that the printing plate dyed with the dyeing solution is then washed with water and then dried. This allows the dye adhering to the non-image area and the back surface of the plate to be removed and the stickiness of the plate surface to be suppressed. It is possible to improve the sex. When the plates thus processed are stacked and stored, it is preferable to insert and insert a slip sheet to protect the plates. The above-described development and dyeing, or subsequent washing and drying, are preferably performed by an automatic processor. A preferable example of such an automatic processor is described in JP-A-2-22661.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

[Synthesis Example] Synthesis Example 1 of Polyurethane Resin In a 500 ml three-necked round bottom flask equipped with a condenser and a stirrer, 8.71 g (0.065 mol) of 2,2-bis (hydroxymethyl) propionic acid and tetraethylene glycol 6.80 g (0.035 mol) was added, and N, N-
It was dissolved in 60 g of dimethylacetamide. 4,
4'-diphenylmethane diisocyanate 20.63 g
(0.082 mol) and hexamethylene diisocyanate (3.64 g, 0.021 mol) were added, and the mixture was heated with stirring at 100 ° C. for 6 hours. Then, it was diluted with 60 g of N, N-dimethylformamide and 120 g of methanol.
The reaction solution was poured into 2 liters of water while stirring to precipitate a white polymer. This polymer was separated by filtration, washed with water, and dried under vacuum to obtain 36 g of a polymer. Gel permeation chromatography (GPC)
The weight average molecular weight (polystyrene standard) was 46,000. Further, the carboxyl group content (acid value) was measured by titration to be 1.60 me.
It was q / g. (Polyurethane resin (a) of the present invention).

Polyurethane Resin Synthesis Example 2 2,2-bis (hydroxymethyl) propionic acid 8.7
3 g (0.065 mol), triethylene glycol 5.
27 g (0.035 mol) and 4,4'-diphenylmethane diisocyanate 20.6 g (0.082 mol), hexamethylene diisocyanate 3.67 g
(0.021 mol) was used and reacted and post-treated in the same manner as in Synthesis Example 1 to obtain 35 g of a white polymer. GP
When the molecular weight was measured by C, the weight average (polystyrene standard) was 39000. Moreover, the carboxyl group content (acid value) was measured by titration to be 1.71 me.
It was q / g. (Polyurethane resin (b) of the present invention).

Polyurethane Resin Synthesis Examples 3 to 11 In the same manner, polyurethane resins (c) to (k) of the present invention were synthesized using the diisocyanate compounds and diol compounds shown in Table 1. Furthermore, when the molecular weight was measured by GPC, it was found that the weight average (polystyrene standard) was 10,000 to 65,000.

Synthesis of Polyurethane Resin of Comparative Example In the same manner as in Synthesis Examples 1 to 11, polyurethane resins (1) to (n) of Comparative Example were synthesized using the diisocyanate compound and the diol compound shown in Table 2.

[0048]

[Table 1]

[0049]

[Table 2]

[0050]

[Table 3]

[0051]

【Example】

Examples 1 to 12 and Comparative Examples 1 to 3 [Primer layer] 0.3 mm thick JI degreased by a conventional method
An aluminum plate of SA 1050 material was dipped in a 1% aqueous solution of KBM603 (manufactured by Shin-Etsu Chemical Co., Ltd.), which is an aminosilane coupling agent, and then dried at room temperature. The following primer layer was applied on the aluminum plate so that the dry weight was 4 g / m ^2, and the coating was dried by heating at 140 ° C. for 2 minutes.・ Samprene IB1700D (manufactured by Sanyo Kasei Co., Ltd.) 10 parts by weight ・ Hexafluorophosphate salt of a condensation polymer of p-diazodiphenylamine and paraformaldehyde 0.1 parts by weight ・ TiO ₂ 0.1 parts by weight ・ MCF323 (large) Made by Nippon Ink Chemical Co., Ltd. 0.03 parts by weight ・ Propylene glycol methyl ether acetate 50 parts by weight ・ Methyl lactate 20 parts by weight ・ Pure water 1 part by weight After that, Nuark FT261V UDNS ULTRA-PLUS FLIPTOP
A PLATE MAKER vacuum exposure machine was used for 20 count exposures.

[Photosensitive layer] A photopolymerizable photosensitive solution having the following composition was dried on a aluminum plate coated with the above primer layer to a dry weight of 4
It was applied so as to be g / m ² and dried at 100 ° C. for 1 minute. -Polyurethane resin described in Table 1 (or Table 2) 1.5 parts by weight-Dimethacrylate ester of polyethylene glycol 1000 1.0 part by weight-Glycidyl methacrylate 4 mol and m-xylylene diamine 1 mol Addition reaction product of 0.5 part by weight-Ethyl Michler's ketone 0.35 part by weight-2-Chlorothioxanthone 0.10 part by weight-Victoria Pure Blue BOH naphthalene sulfonate 0.01 part by weight-MCF323 (Dainippon Ink and Chemicals) Chemical Industry Co., Ltd.) 0.03 parts by weight Methyl ethyl ketone 10 parts by weight Propylene glycol methyl ether 25 parts by weight

[Ink Repellent Layer] The following silicone rubber composition liquid was applied on the above photopolymerizable photosensitive layer so that the dry weight was 2 g / m ^2, and dried at 140 ° C. for 2 minutes.・ Α, ω-divinylpolydimethylsiloxane (polymerization degree: about 700) 9 parts by weight ・ (CH ₃ ) ₃ -Si-O- (SiH (CH ₃ ) -O) ₈ -Si (CH ₃ ) ₃ 0.5 part by weight Parts-polydimethylsiloxane (polymerization degree of about 8,000) 0.5 parts by weight-olefin-chloroplatinic acid 0.2 parts by weight-tetracyclo (methylvinyl) siloxane 0.3 parts by weight-ISOPAR G (Esso Chemical Co., Ltd.) Made) 140 parts by weight

On the surface of the silicone rubber layer obtained as described above, a 12 μm-thick single-sided matted biaxially oriented polypropylene film was laminated so that the non-matted surface was in contact with the silicone rubber layer. A waterless planographic printing plate was obtained. One of these printing plates was prepared, and a positive film having a halftone dot image of 200 lines / inch and a gray scale (G / S) having an optical density difference of 0.15 were overlaid, and FT261V UDNS ULTRA- manufactured by Nuark Co., Ltd. PLUS FLIPTOP P
It was exposed for 50 counts using a LATE MAKER vacuum exposure machine.
Then, the laminate film was peeled off, and the following development processing was immediately performed.

[Development Treatment] While immersing the printing plate in water at 35 ° C., it was rubbed with a developing pad to remove the silicone rubber layer in the unexposed area. Subsequently, it was dyed with a dyeing solution having the following composition, and the sensitivity (G / S clear sensitivity) and halftone dot reproducibility (reproducible halftone dot area, unit:%) were evaluated. (Staining solution) -Crystal violet 0.1 part by weight-Diethylene glycol monoethyl ether 15 parts by weight-Pure water 85 parts by weight Next, before printing, a scratch test of the non-image area was performed using a sapphire needle with a diameter of 0.5 mm ( HEIDON-14 scratch tester, load 100 g to 500 g) was performed, and using these plates, TOYO KING ULTRA TU manufactured by Toyo Ink Co., Ltd. was used in a Heidelberg GTO printing machine without a dampening water supply device.
After printing 100,000 sheets with K Aqualess G black ink, scratches on the non-image area begin to appear on the printed matter (scratch resistance), and the silicone rubber layer on the non-image area is destroyed until the printed matter becomes dirty. The number of printed sheets (printing durability) was evaluated. From Table 3, the waterless planographic printing plate of the present invention showed good sensitivity, developability, halftone dot reproducibility, printing durability and scratch resistance.

[0056]

[Table 4]

[0057]

According to the waterless lithographic printing plate of the present invention, a waterless lithographic printing plate having excellent printing durability and scratch resistance, and having good sensitivity and tone reproducibility when developed with an aqueous developer is obtained. can get.

Claims (1)

[Claims] 1. A photopolymerizable photosensitive layer and a silicone rubber layer are laminated in this order on a substrate, and the photopolymerizable photosensitive layer contains a polyurethane resin which is a reaction product of a diisocyanate compound and a diol compound, A photosensitive lithographic printing plate not requiring a fountain solution, wherein at least one of the diol compounds has a carboxyl group.