JPH0980745A - Damping-waterless photosensitive planographic printing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a damping-waterless photosensitive planographic printing plate for heat mode writing-type direct plate making with which direct recording of digital data of a computer, etc., by using a solid-state laser and semiconductor laser (heat mode) having a light emission region from near IR to IR is possible and which is usable for both of a positive type and negative type. SOLUTION: The photosensitive layer of the damping-waterless photosensitive planographic printing plate constituted by laminating a photosensitive layer and silicone rubber layer in this order on a base contains at least (a) a compd. contg. at least two pieces of ether groups expressed by formula (R<1> )(R<2> )C=(R<3> )- O-, (b) a linear polymer compd., (C) an IR absorbent and (d) an acid precursor. In the formula, R<1> , R<2> , R<3> respectively independently denote hydrogen, alkyl group or aryl group. The two among these groups may be bound to form a satd. or olefinic unsatd. ring.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive lithographic printing plate which does not require fountain solution and can be printed without using fountain solution, and more particularly, a fountain solution for direct plate making which can be directly drawn from digital signals of a computer or the like. No need for photosensitive lithographic printing plate.

[0002]

2. Description of the Related Art In recent years, the development of lasers has been remarkable, and in particular, solid-state lasers and semiconductor lasers having a near-infrared to infrared emission region have been easily available with high output and small size. These lasers are very useful as an exposure light source when directly making a plate from digital data of a computer or the like. As a photosensitive lithographic printing plate which does not require fountain solution and can be directly drawn from digital data of a conventional computer, JP-B-57-3516 and JP-A-53-5.
Japanese Patent No. 5211 discloses a printing plate in which an electrophotographic image is used to form a toner image on an ink repellent layer made of a silicone resin to form an image portion. JP-A-54-449
No. 05 discloses a printing plate in which silver salt emulsion layers are laminated and which can be exposed with light having a wide range of wavelengths with high sensitivity. U.S. Pat. No. 4,958,562 discloses a printing plate of a type in which a silicone rubber layer is laminated on a substrate and an image portion is formed by discharge breakdown.

However, a printing plate using an electrophotographic system is complicated in charging, exposure and development, and a printing plate using a toner image as an image portion has an adhesive property between an ink repellent layer and an image portion and at the time of printing. There is a problem that it is difficult to achieve both soiling. A printing plate using a silver salt sensitive material has the drawbacks of complicated processing and high cost. Further, the printing plate of the type in which the silicone rubber layer is destroyed by electric discharge or laser light has a problem that the silicone residue remaining on the plate surface must be removed. Thus, the conventional lithographic printing plate capable of directly drawing from digital data of a computer or the like has not been sufficiently satisfactory. Further, the negative type is advantageous because the positive type material requires a considerable writing time when the digital data of the computer is directly made by laser light. As a negative type dampening water unnecessary photosensitive lithographic printing plate,
JP-B-61-54222 and JP-B-61-616 disclose that a dampening water-free photosensitive lithographic printing plate having a silicone rubber layer on a photodegradable photosensitive layer made of O-naphthoquinonediazide backed by a support. Is proposed. Further, JP-A-59-17552 and JP-B-3-56223 propose that a similar printing plate can be used as both a positive type and a negative type by adjusting the processing method. The quinonediazide compounds used in these printing plates have been widely used in the fields of photosensitive lithographic printing plates and photoresists, but they do not exhibit sufficient sensitivity, and since the photosensitive wavelength is further fixed, they are directly exposed to laser light. It was not suitable for drawing.

Recently, a negative type fountain solution-free photosensitive lithographic printing plate which replaces them is used as a compound that generates an acid in the photosensitive layer by light (photoacid generator) and a compound that undergoes hydrolysis or the like by an acid to change its solubility. A composition containing a binder resin and the like as required has been reported. For example, JP-A-63
-88556 describes a photosensitive layer containing a photo-acid generator, a compound having an acid-decomposable C-O-C bond and a water-insoluble binder on a support, and an intermediate layer made of amorphous silicic acid. After exposing the photosensitive lithographic printing plate having no silicone fountain solution through the exposure, the photosensitive layer solubilized with a developing solution is dissolved and removed, and at the same time, the silicone rubber layer on it is also removed to remove the aluminum substrate. A method of using an exposed image portion has been proposed. However, in this case as well, the sensitivity is low, and most of the practically effective photoacid generators used in this technology absorb only below 450 nm. Not suitable for writing.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to enable direct recording of digital data from a computer or the like using a solid-state laser or semiconductor laser (thermal mode) having an emission region from near infrared to infrared. Furthermore, it is to provide a photosensitive planographic printing plate which does not require a fountain solution for heat mode writing type direct plate making and can be used for both positive type and negative type.

[0006]

SUMMARY OF THE INVENTION The present invention provides a method for manufacturing a semiconductor device comprising the steps of:
A photosensitive layer and a silicone rubber layer are laminated in this order, and the photosensitive layer comprises (a) a compound having at least two enol ether groups represented by the following general formula (I), and (b) a linear polymer compound. And (c) an infrared absorber, and (d) an acid precursor, which is a photosensitive lithographic printing plate not requiring a fountain solution. (R ¹ ) (R ² ) C═C (R ³ ) —O— (I) (In the formula, R ¹ , R ² and R ³ each independently represent hydrogen, an alkyl group or an aryl group. 2 of
May combine to form a saturated or olefinically unsaturated ring. )

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The photosensitive lithographic printing plate not requiring fountain solution of the present invention is a positive or negative type photosensitive lithographic printing plate requiring no fountain solution depending on the conditions for forming a photosensitive film. When a photosensitive layer is coated and dried at a relatively low temperature on a support and a silicone rubber layer is laminated, the infrared precursor in the photosensitive layer decomposes by the thermal energy obtained by the absorption of infrared rays to generate an acid. As a result, the cationic polymerization of the enol ether group-containing compound proceeds, and at the same time, the adhesion with the silicone rubber layer is improved, resulting in a positive type fountain solution-free lithographic printing plate. On the other hand, when the photosensitive layer is dried at a relatively high temperature, the enol ether group-containing compound and the binder containing an acid group are thermally crosslinked and become insoluble in a solvent, an alkaline aqueous solution or the like. When this composition absorbs infrared light, its thermally cross-linked portion is hydrolyzed by the acid generated from the acid precursor, the adhesion with the silicone rubber layer is reduced, and a negative type fountain solution-free photosensitive lithographic printing plate is used. Becomes Hereinafter, the present invention will be described in detail.

The photosensitive layer used in the present invention has the above-mentioned (a),
A photosensitive composition containing the components (b), (c) and (d). First, the compound having an enol ether group as the component (a) of the present invention will be described. General formula (I)
In the enol ether group of, when R ¹ , R ² and R ³ represent an alkyl group, it preferably has 1 to 2 carbon atoms.
0 represents a saturated or unsaturated linear, branched or alicyclic alkyl group (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclohexyl group, etc.), a halogen atom, a cyano group, an ester group, an alkoxy group, It may be substituted with an aryloxy group or an aryl group. Also, R
^{When 1} , R ² and R ³ represent an aryl group, they generally represent an aryl group having 6 to 20 carbon atoms (for example, a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, etc.), an alkyl group, an alkoxy group, an aryl group. It may be substituted with an oxy group, an acyl group, an acyloxy group, an alkylmercapto group, an amino group, an aminoacyl group, a carboalkoxy group, a nitro group, a sulfonyl group, a cyano group or a halogen atom. Further, as an example of the case where any ^{two of} R ¹ , R ² and R ³ are combined to form a saturated or olefinically unsaturated ring, a ring having usually 3 to 8 members, preferably 5 or 6 members is used. Rings, for example cycloalkyl or cycloalkenyl groups.

In the present invention, preferred among the enol ether groups of the general formula (I) are R ¹ , R ² and R.
One of the ^three is an enol ether group in which one is a methyl group or an ethyl group and the rest are hydrogen atoms, and more preferred is a vinyl ether group in which R ¹ , R ² and R ³ are all hydrogen. Although various compounds containing two or more enol ether groups can be used in the present invention,
These are preferably compounds having a boiling point of 60 ° C. or higher under atmospheric pressure. Preferred examples of the component (a) include enol ether compounds represented by the following general formula (II) or (III). A - [- (O-R 4) n-O-CH = CH 2] m (II) A - [- B-R 4 -O-CH = CH 2] m (III) wherein, A is an m-valent Represents an alkylene group, an arylene group or a heterocyclic group, B represents —CO—O—, —NHCOO— or —NHCONH—, and R ⁴ has 1 to 10 carbon atoms.
Is a linear or branched alkylene group. n is 0 or 1
The integer of 10 and m show the integer of 2-6. The compound represented by the general formula (II) is, for example, Stephen. C. Lapin, Polymer.
s Paint Color Journal, 179 (4237), 321 (1989), that is, reaction of polyhydric alcohol or polyphenol with acetylene, or polyhydric alcohol or polyphenol with halogenated alkyl vinyl ether. It can be synthesized according to the reaction.

Specific examples of the enol ether compound represented by the general formula (II) include ethylene glycol divinyl ether, triethylene glycol divinyl ether,
1,3-butanediol divinyl ether, tetramethylene glycol divinyl ether, neopentyl glycol divinyl ether, trimethylolpropane trivinyl ether, trimethylolethane trivinyl ether, hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, tetraethylene glycol Divinyl ether, pentaerythritol divinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, sorbitol tetravinyl ether, sorbitol pentavinyl ether, ethylene glycol diethylene vinyl ether, triethylene glycol diethylene vinyl ether, ethylene glycol dipropylene vinyl ether, triethylene glycol Call diethylene vinyl ether, trimethylolpropane triethylene vinyl ether, trimethylolpropane diethylene vinyl ether, pentaerythritol diethylene vinyl ether,
Pentaerythritol triethylene vinyl ether, pentaerythritol tetraethylene vinyl ether,
1,2-di (vinyl ether methoxy) benzene, 1,
Examples thereof include 2-di (vinyl ether ethoxy) benzene, and compounds represented by the following II-1 to II-41, but are not limited thereto.

[0011]

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[0012]

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[0013]

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[0014]

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[0015]

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[0016]

[Chemical 6]

[0017]

[Chemical 7]

[0018]

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[0019]

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On the other hand, the compound represented by the general formula (III) (when B = -CO-O-) can be produced by reacting a polyvalent carboxylic acid with a halogenated alkyl vinyl ether. Specific examples include terephthalic acid diethylene vinyl ether, phthalic acid diethylene vinyl ether, isophthalic acid diethylene vinyl ether, phthalic acid dipropylene vinyl ether, terephthalic acid dipropylene vinyl ether, isophthalic acid dipropylene vinyl ether,
Examples thereof include, but are not limited to, maleic acid diethylene vinyl ether, fumaric acid diethylene vinyl ether, and itaconic acid diethylene vinyl ether.

Further, as the vinyl ether group-containing compound preferably used in the present invention, the following general formula (IV):
Examples thereof include vinyl ether group-containing compounds synthesized by reacting a vinyl ether compound having active hydrogen represented by (V) and (VI) with a compound having an isocyanate group. CH ₂ ═CH—O—R ⁵ —OH (IV) CH ₂ ═CH—O—R ⁵ —COOH (V) CH ₂ ═CH—O—R ⁵ —NH ₂ (VI) where R ⁵ is carbon. A linear or branched alkylene group having 1 to 10 atoms is shown. Examples of the compound containing an isocyanate group include cross-linking agent handbook (published by Taiseisha, 19
Compounds published in 1981) can be used.

Specifically, triphenylmethane triisocyanate, diphenylmethane diisocyanate, tolylene diisocyanate, dimer of 2,4-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-tolylene diisocyanate, polymethylene polyisocyanate. Polyisocyanate type such as phenyl isocyanate, hexamethylene diisocyanate, adduct of tolylene diisocyanate and trimethylolpropane, adduct of hexamethylene diisocyanate and water, polyisocyanate adduct of xylene diisocyanate and trimethylolpropane, etc. Can be mentioned. By reacting the isocyanate group-containing compound with the active hydrogen-containing vinyl ether group-containing compound, various compounds having a vinyl ether group at the terminal can be produced. Examples of such compounds are listed below, but the scope of the present invention is not limited thereto.

[0023]

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[0024]

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[0025]

[Chemical 12]

The compounds containing at least two enol ether groups described above can be used alone, but may be used as a mixture of several kinds. The addition amount of the compound containing an enol ether group in the photosensitive composition is in the range of 1 to 80% by weight, preferably 5 to 50% by weight based on the total solid content of the photosensitive composition. Within this range, in the case of the positive type, the cationic polymerization of the exposed area efficiently occurs and the adhesion of the silicone rubber layer is improved. In the case of the negative type, the thermal cross-linking at the time of film formation is sufficient and the unexposed portion can be made into a film excellent in strength.

The linear polymer (b) used in the present invention is
The compound (a) having at least two polymerizable enol ether groups can be arbitrarily selected and used from those having compatibility with the compound (a). When a positive-type fountain solution-free photosensitive lithographic printing plate is prepared, the linear polymer can be arbitrarily selected from those having film-forming ability as exemplified below. (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. . (3) Unvulcanized rubber, for example natural rubber, polybutadiene,
Polyisobutylene, polyneoprene, etc., and copolymers thereof. (4) Polyethers such as polyethylene oxide and polypropylene oxide. (5) Polyamide, a 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,
Polyurethane of 5-diisocyanate, isophorone diisocyanate, etc. and ethylene glycol, 1,4-butanediol, polyester. Further, isophoronediamine, hexamethylenediamine, or the like may be used as the chain extender.

Further, as the polymer compound capable of forming a film, a polymer compound having a photopolymerizable or photocrosslinkable olefinic unsaturated double bond group in its side chain can be used. It is not limited.
The linear organic high molecular weight polymer used for preparing these positive type fountain solution-free photosensitive lithographic printing plates can be used alone, but may be used as a mixture of several kinds, Any amount can be incorporated into the composition. However, when it exceeds 90% by weight based on the total solid content of the photosensitive composition, preferable results are not obtained in terms of the strength of the image formed. It is preferably 30 to 85% by weight. The weight ratio of the photopolymerizable vinyl ether compound to the linear organic polymer is preferably 10:90 to 70:30. A more preferable range is 30:70 to 50:50.

On the other hand, in the case of producing a negative-working photosensitive lithographic printing plate not requiring fountain solution, the linear polymer has an acid group capable of thermally reacting with an enol ether group-containing compound to form a three-dimensional crosslinked resin. However, it can be arbitrarily selected and used as long as its crosslinked portion is efficiently decomposed by an acid. The linear polymer can be generally synthesized by a known method for obtaining a linear polymer. For example, a vinyl monomer having an acid group, preferably a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a sulfonamide group, or the like and those It can be obtained by copolymerizing another vinyl monomer copolymerizable with
Examples of the vinyl monomer containing an acid group include acrylic acid, methacrylic acid, maleic acid, itaconic acid, crotonic acid, isocrotonic acid, p-vinylbenzoic acid, p-vinylbenzenesulfonic acid, p-vinylcinnamic acid, maleic acid. Monomethyl ether, maleic acid monoethyl ether,
Examples thereof include 2- (acrylamido) -2-methylpropanesulfonic acid, but are not limited thereto.

Other monomers copolymerizable with the above monomers include, for example, acrylonitrile, acrylamide,
Methacrylamide, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate,
Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, benzyl acrylate, benzyl methacrylate, vinyl benzoate, vinyl chloride, vinylidene chloride, styrene,
Vinyl acetate, N- (4-sulfamoylphenyl) methacrylamide, N-phenylphosphonylmethacrylamide, butadiene, chloroprene, isoprene, 2-hydroxyethylstyrene, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, p- 2-
Hydroxyethylstyrene, p-hydroxystyrene,
Examples thereof include 3-mercaptoethyl acrylate and 2-mercaptoethyl methacrylate, but are not limited thereto.

Although the vinyl monomer containing an acid group and the other copolymerizable monomer can be copolymerized in any combination and in any number of monomers, the vinyl monomer containing an acid group and another copolymerizable monomer can be copolymerized. The proportion of the polymerizable monomer is appropriately in the range of 2:98 to 80:20 by weight%, the preferable range is 5:95 to 50:50, and the more preferable range is 5:95 to 30:70. is there. The linear polymer (b) having an acid group can be obtained by a reaction between a dihydroxy compound having an acid group and a diisocyanate compound, a cocondensation of a dihydroxy compound having an acid group and a dicarboxylic acid compound, and the like.

For example, 3,5-dihydroxybenzoic acid,
2,2-bis (hydroxymethyl) propionic acid, 2,
2-bis (2-hydroxyethyl) propionic acid, 2,
Dihydroxy having an acid group such as 2-bis (3-hydroxypropyl) propionic acid, bis (hydroxymethyl) acetic acid, bis (4-hydroxyphenyl) acetic acid, 4,4-bis (4-hydroxyphenyl) pentanoic acid, tartaric acid Compound and 2,4-tolylene diisocyanate, 2,4
Dimer of tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4'-
A linear polyurethane resin containing a carboxyl group is obtained by reacting a diisocyanate compound such as methylenebis (cyclohexylisocyanate) in an equivalent amount. Further, a diol compound which does not have a carboxyl group and may have another substituent which does not react with isocyanate may be used in combination. For example, ethylene glycol,
Examples thereof include, but are not limited to, diethylene glycol, triethylene glycol, neopentyl glycol, 1,3-butylene glycol, bisphenol A, hydrogenated bisphenol A, hydrogenated bisphenol F, and an ethylene oxide adduct of bisphenol A. Not a thing.

The linear polymer (b) is a diol having the above-mentioned acid group, and, if necessary, the above-mentioned other diol and a difunctional carboxylic acid such as phthalic acid, isophthalic acid, terephthalic acid, fumaric acid or itaconic acid. , Adipic acid, and the like can be obtained. The ratio of the diol containing an acid group to the other monomer unit is 2:% by weight.
A range of 98 to 80:20 is suitable, a preferable range is 5:95 to 50:50, and a more preferable range is
It is 5:95 to 30:70. As the linear polymer (b) having an acid group used in the present invention, a resin containing a phenolic hydroxyl group can be mentioned. Specifically, phenol formaldehyde resin, m-cresol formaldehyde resin, p-cresol formaldehyde resin, o-cresol formaldehyde resin, m- /
P-mixed cresol formaldehyde resin, novolac resin such as phenol / cresol formaldehyde resin, resol type phenol resin, phenol-modified xylene resin, polyhydroxystyrene, polyhalogenated hydroxystyrene, acrylic resin having phenolic hydroxyl group, etc. However, the present invention is not limited to these.

The molecular weight of these linear polymers is 1,000 to 1,
It is, 000,000, preferably 1,500 to 200,000. Among these, linear polymers preferably used include copolymers containing a monomer containing an acid group and a monomer containing a hydroxyl group or a mercapto group in a fixed ratio. The content of the monomer containing an acid group in the copolymer is 2 to 80% by weight, preferably 5 to 50% by weight, more preferably 5 to 30% by weight, and the content of the monomer containing a hydroxyl group or a mercapto group is 2-80% by weight, preferably 5-50% by weight, more preferably 5-3
0% by weight of linear polymer is particularly preferably used. The linear polymers used for preparing the negative-type photosensitive lithographic printing plates requiring no fountain solution may be used alone, or may be used as a mixture of several kinds. The amount of linear polymer added to the photosensitive composition is 1 to 90% by weight, preferably 20 to 90% by weight, and more preferably 3% by weight based on the total solid content of the photosensitive composition.
It is in the range of 0 to 85% by weight, and the image forming property is good in this range.

In the present invention, various known pigments or dyes are used as the infrared absorber (c).
Carbon black is preferably used as a pigment that absorbs infrared light. Examples of the dye that absorbs infrared light include cyanine dyes, merocyanine dyes, phthalocyanine dyes, squarylium dyes, metal dithiolenes, naphthoquinone dyes, and pyrylium dyes. For example, JP-A-58-12524.
No. 6, No. 59-84356, No. 59-202829.
Nos. 60-78787 and the like, cyanine dyes described in JP-A Nos. 58-173696 and 58-1816.
90, 58-194595 and the like, methine dyes described in JP-A Nos. 58-112793 and 58-22.
No. 4793, No. 59-48187, No. 59-7399.
6, naphthoquinone dyes described in JP-A Nos. 60-52940 and 60-63744, and JP-A-58-11.
The squarylium dyes described in 2792 and the like, the cyanine dyes described in British Patent 434,875, and the like are preferably used. Further, near-infrared absorbers described in US Pat. No. 5,156,938, substituted arylbenzo (thio) pyrylium salts described in US Pat. No. 3,881,924, and trimer described in JP-A-57-142645. Chinthiopyrylium salt, JP-A-58-181051, 58-220
No. 143, No. 59-41363, No. 59-84248.
No. 59-84249, No. 59-146063,
Pyrylium compounds described in JP-A-59-146061, cyanine dyes described in JP-A-59-216146, pentamethinethiopyrylium salts described in U.S. Pat. No. 4,283,475, and JP-B-5-13514, JP-A-5-13514. -19702
The pyrylium compound disclosed in the publication is particularly preferably used. Another particularly preferable example is the near infrared absorbing dyes described as formulas (I) and (II) in US Pat. No. 4,756,993. These pigments or dyes are contained in an amount of 0.01 to 50% by weight, preferably 0.1 to 50% by weight, based on the total solid content of the photosensitive layer composition.
It can be added in a proportion of 20% by weight.

Examples of the acid precursor (d) used in the present invention include photoinitiators for photocationic polymerization, photoinitiators for photoradical polymerization, photobleaching agents for dyes, photochromic agents, micro resists, and the like. The known acid-generating compounds used in (1) and mixtures thereof can be appropriately selected and used. For example SI Schlesinger, Photogr. Sci.
Eng., 18, 387 (1974), TS Bal et al, Polymer, 2
1,423 (1980) diazonium salts, U.S. Pat.
69,055, 4,069,056, ammonium salts described in JP-A-4-365049, DC Necker et al, Macromolecul
es, 17, 2468 (1984), CS Wen et al, Teh, Proc.
Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988), U.S. Pat.Nos. 4,069,055 and 4,069,056, phosphonium salts, JV Crivello et al, Macromolecules, 10
(6), 1307 (1977), Chem. & Eng. News, Nov. 28, p31.
(1988), European Patent 104,143, U.S. Patent 339,049.
No. 410,201, JP-A No. 2-150848, and JP-A No. 2-2965.
No. 14, iodonium salt, JV Crivello et al,
Polymer J. 17, 73 (1985), JV Crivello et al. J.
Org. Chem., 43, 3055 (1978), WR Watt et al, J. P.
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JV Crivello et al, Polymer Bull., 14, 279 (1985)
, JV Crivello et al, Macromolecules, 14 (5), 11
41 (1981), JV Crivello et al, J. Polymer Sci.,
Polymer Chem. Ed., 17, 2877 (1979), European Patent 37
0,693, 233,567, 297,443, 297,442
U.S. Pat.Nos. 4,933,377, 4,760,013 and 4,73
4,444, 2,833,827, German Patent 2,904,626,
Sulfonium salts described in 3,604,580 and 3,604,581,

JV Crivello et al, Macromolecules,
10 (6), 1307 (1977), JV Crivelloet al, J. Polyme.
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5, JP-B-46-4605, JP-A-48-36281, JP-A-55-
32070, JP-A-60-239736, JP-A-61-169835,
JP-A-61-169837, JP-A-62-58241, JP-A-62-212
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, A photoacid generator having an o-nitrobenzyl type protecting group, M. Tunooka et al, Polymer Preprints Japan, 3
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8,564, 4,371,605, 4,431,774, JP-A-64
-18143, JP-A-2-245756, JP-A-4-365048 and other iminosulfonates and the like, compounds which photolyze to generate sulfonic acid, JP-A-61-166544 The disulfone compound can be mentioned.

A group in which an acid-generating group or a compound is introduced into the main chain or side chain of a polymer, for example, ME Woodhouse et al, J. Am. Chem. So.
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4, JP-A-62-69263, JP-A-63-1460387, JP-A-63
The compounds described in JP-A-163452, JP-A-62-153853 and JP-A-63-146029 can be used. Furthermore, VNR
Pillai, Synthesis, (1), 1 (1980), A. Abad et al, T
etrahedron Lett., (47) 4555 (1971), DHR Barto
n et al, J. Chem. Soc., (C), 329 (1970), U.S. Pat.
The compounds capable of generating an acid by light described in 3,779,778 and EP 126,712 can also be used.

Among the above-mentioned acid precursors, those which are particularly effectively used will be described below. (1) An oxazole derivative represented by the following general formula (VII) substituted with a trihalomethyl group or an S-triazine derivative represented by the following general formula (VIII).

[0040]

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In the formula, R ⁶ is a substituted or unsubstituted aryl group or alkenyl group, and R ⁷ is a substituted or unsubstituted aryl group, alkenyl group, alkyl group or --CY.
Represents ₃ . Y represents a chlorine atom or a bromine atom. The oxazole derivative (VII) and the S-triazine derivative (VII
Specific examples of I) include the following VII-1 to VII-8 and V
Examples thereof include compounds III-1 to VIII-10, but are not limited thereto.

[0042]

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[0043]

[Chemical 15]

[0044]

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[0045]

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[0046]

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(2) An iodonium salt represented by the following general formula (IX) or a sulfonium salt represented by the following general formula (X).

[0048]

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In the formula, Ar ¹ and Ar ² each independently represent a substituted or unsubstituted aryl group. Preferred substituents include an alkyl group, a haloalkyl group, a cycloalkyl group,
Examples thereof include an aryl group, an alkoxy group, a nitro group, a carboxyl group, an alkoxycarbonyl group, a hydroxy group, a mercapto group and a halogen atom. R ⁸ , R ⁹ and R
Each ¹⁰ independently represents a substituted or unsubstituted alkyl group or aryl group. It is preferably an aryl group having 6 to 14 carbon atoms, an alkyl group having 1 to 8 carbon atoms, or a substituted derivative thereof. Preferred substituents are an alkoxy group having 1 to 8 carbon atoms, and an aryl group having 1 carbon atom.
Is an alkyl group, a nitro group, a carboxyl group, a hydroxy group or a halogen atom having 8 to 8 carbon atoms, and an alkoxy group having 1 to 8 carbon atoms, a carboxyl group or an alkoxycarbonyl group with respect to the alkyl group. Z ⁻ represents a counter anion, for example, BF ₄ ⁻ , AsF ₆ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , SiF ₆ ⁻ ,
_{^{ClO 4 -, CF 3 SO -}} , BPh 4 -, (Ph = phenyl), naphthalene-1-sulfonic acid anion, condensed polynuclear aromatic sulfonic acid anion such as anthraquinone sulfonic acid anion,
Examples thereof include, but are not limited to, sulfonic acid group-containing dyes. Also, R ⁸ , R ⁹ and R
Two of the ^ten and Ar ¹ and Ar ² may each be bonded via a single bond or a substituent.

The onium salts represented by the general formulas (IX) and (X) are known, and for example, JW Knapczyk et al,
J. Am. Chem. Soc., 91, 145 (1969), AL Maycok e
t al, J. Org. Chem., 35, 2532 (1970), E. Goethas e
t al, Bull. Soc. Chem. Belg., 73, 546, (1964), H.
M. Leicester, J. Am. Chem. Soc., 51, 3587 (1929)
, JB Crivello et al, J. Polym. Chem. Ed., 18,
2677 (1980), U.S. Pat.Nos. 2,807,648 and 4,247,473.
And the method described in JP-A-53-101331. Specific examples of the onium compounds of the general formulas (IX) and (X) include compounds IX-1 to IX-2 shown below.
0 and X-1 to X-34, but the present invention is not limited thereto.

[0051]

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[0052]

[Chemical 21]

[0053]

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[0054]

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[0055]

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[0056]

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[0057]

[Chemical formula 26]

[0058]

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[0059]

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[0060]

[Chemical 29]

[0061]

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[0062]

[Chemical 31]

[0063]

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[0064]

[Chemical 33]

[0065]

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(3) A disulfone derivative represented by the following general formula (XI) or an iminosulfonate derivative represented by the following general formula (XII).

[0067]

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In the formula, Ar^ThreeAnd Ar^FourAre each independently substituted
Or an unsubstituted aryl group. R ¹¹Is replaced or not
It represents a substituted alkyl group or aryl group. A¹Is also a replacement
Or an unsubstituted alkylene group, alkenylene group or ari
Represents a len group. Compounds represented by the general formulas (XI) and (XII)
Specific examples of the compound include compounds XI-1 to XI- shown below.
12 and XII-1 to XII-12.
However, the present invention is not limited to this.

[0069]

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[0070]

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[0071]

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[0072]

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[0073]

[Chemical 40]

[0074]

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[0075]

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[0076]

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The addition amount of these acid precursors is in the range of 0.001 to 40% by weight, preferably 0.1 to 20% by weight, based on the total solid content of the photosensitive composition. If the amount of the acid precursor added is too small, the sensitivity is lowered, and if it is too large, the sensitivity does not rise above a certain level, which is disadvantageous in cost.

As a printing-out agent for obtaining a visible image immediately after exposure, there may be mentioned a combination of a compound which releases an acid by the heat of exposure and an organic dye capable of forming a salt. Specifically, a combination of an o-naphthoquinonediazide-4-sulfonic acid halogenide and a salt-forming organic dye described in JP-A-50-36209 and JP-A-53-8128, and JP-A-53-36223. , JP-A-54-74
A combination of a trihalomethyl compound and a salt-forming organic dye described in Japanese Patent No. 728 can be mentioned. As the image colorant, dyes other than the above-mentioned salt-forming organic dyes can be used. Suitable dyes including salt-forming organic dyes are oil-soluble dyes or basic dyes. Specifically, for example, Oil Yellow # 101, Oil Yellow # 130, Oil Pink # 312, Oil Green BG, Oil Blue BOS, Oil Black BY, Oil Black BS,
Oil Black T-505 (all manufactured by Oriental Chemical Co., Ltd.), Crystal Violet (CI4255)
5), methyl violet (CI42535), rhodamine B (CI45170B), malachite green (C
I42000), methylene blue (CI52015) and the like. These dyes are 0.01 to 10% by weight, preferably 0.01 to 10% by weight, based on the total solid content of the photosensitive composition.
It can be added to the photosensitive composition in a proportion of 0.1 to 3% by weight. If a visible image having a sufficient density can be obtained by the infrared absorbent of the present invention, it is not necessary to add such a dye.

In the photosensitive composition of the present invention, if necessary, alkyl ethers (for example, ethyl cellulose, methyl cellulose), silicone-based surfactants, fluorine-based surfactants and fluorine-based surface alignments for improving coating properties are added. Agents, plasticizers for imparting film flexibility and abrasion resistance (eg tricresyl phosphate, dimethyl phthalate,
Trioctyl phosphate, tributyl phosphate, tributyl citrate, polyethylene glycol, polypropylene glycol, etc.) and additional sensitizers can be added. Further, a silane coupling agent, a titanium coupling agent, or the like may be added to enhance the adhesiveness with the silicone rubber layer. The addition amount varies depending on the purpose of use, but generally 0.3 to 30% by weight based on the total solid content of the photosensitive composition.
It is.

The photosensitive composition of the present invention is applied by dissolving it in a solvent that dissolves each of the above components. As the solvent used here, ethylene dichloride, cyclohexanone, methyl ethyl ketone, methanol, ethanol, propanol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, 1-methoxy- 2-propyl acetate, dimethoxyethane,
There are methyl lactate, ethyl lactate, N, N-dimethylacetamide, N, N-dimethylformamide, tetramethylurea, N-methylpyrrolidone, dimethylsulfoxide, sulfolane, γ-butyrolactone, toluene, ethyl acetate, dioxane, and the like. Solvents may be used alone or as a mixture. The concentration of the above components (total solids including additives) in the solvent is preferably 2 to 50% by weight. Further, the coating amount is generally preferably 0.2 as solid content.
~ 5.0 g / m ² , but more preferably 0.3 to 3.0 g / m ^2.
m ² .

The above-mentioned coating solution is coated on the support using a known coating technique. Examples of the coating technique include a spin coating method, a wire bar coating method, a dip coating method, an air knife coating method, a roll coating method, a blade coating method, a curtain coating method and a spray coating method.
The layer of the photosensitive composition applied as described above is dried for 30 seconds to 10 minutes using a hot air dryer, an infrared dryer or the like. When a positive type fountain solution-free photosensitive lithographic printing plate is prepared, it is preferably dried at 50 to 100 ° C. On the other hand, in the case of producing a negative type photosensitive lithographic printing plate that does not require fountain solution, it is preferable to dry at 100 to 150 ° C. in order to crosslink the component (a) and the component (b). You may use the method etc. which heats the photosensitive composition after drying anew.

The support used in the present invention must be flexible enough to be set in an ordinary printing machine and capable of withstanding the load applied during printing. Therefore, as a typical support, coated paper, a metal plate such as aluminum, a plastic film such as polyethylene terephthalate, rubber, or a composite thereof can be mentioned, and more preferably aluminum and an aluminum-containing alloy. (For example, an alloy of a metal such as silicon, copper, manganese, magnesium, chromium, zinc, lead, bismuth, and nickel with aluminum) is an alloy.

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 improving the adhesion between the substrate and the photosensitive layer, preventing halation, dyeing an image and improving printing characteristics. For example, JP-A-60-
Various photosensitive polymers as disclosed in JP-A No. 22903, which are exposed and cured before laminating a photosensitive layer, and an epoxy resin disclosed in JP-A-62-50760, which is thermally cured. , Japanese Patent Laid-Open No. 63-13
The gelatin disclosed in Japanese Patent No. 3151, which has a hardened film, the one using a urethane resin and the silane coupling agent disclosed in Japanese Patent Laid-Open No. 3-200965, and the one disclosed in Japanese Patent Laid-Open No. 3-273248. It is possible to cite, for example, those using a urethane resin that is used.
In addition to these, those obtained by hardening gelatin or casein are also effective. Further, for the purpose of softening the primer layer, polyurethane, polyamide, styrene / butadiene rubber having a glass transition temperature of room temperature or lower in the primer layer,
Polymers such as carboxy-modified styrene / butadiene rubber, acrylonitrile / butadiene rubber, carboxylic acid-modified acrylonitrile / butadiene rubber, polyisoprene, acrylate rubber, polyethylene, chlorinated polyethylene, and chlorinated polypropylene may be added. The addition ratio is arbitrary, and the primer layer may be formed only with the additive as long as the film layer can be formed. Further, in 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 agent or aluminum) is used according to the above purpose. (Coupling agent), pigments, and additives such as silica powder and titanium oxide powder can also be included. Further, after coating, it can be cured by exposure. Generally, the coating amount of the primer layer is appropriately in the range of 0.1 to 20 g / m ² , preferably 1 to 10 g / m ² , and more preferably 1 to 5 g / m ^2.
2

The crosslinked silicone rubber layer used in the present invention is a film formed by curing the following composition A or B. Composition A Diorganopolysiloxane (Number average molecular weight is 3,000 to 40,000) 100 parts by weight Condensation type cross-linking agent 3 to 70 parts by weight Catalyst 0.01 to 40 parts by weight The diorganopolysiloxane as the component is represented by the following general formula. R having a repeating unit such as
¹² and R ¹³ are alkyl groups having 1 to 10 carbon atoms, vinyl groups, aryl groups, and may have other appropriate substituents. Generally, 60 for R ¹² and R ¹³
Those in which% or more is a methyl group, a vinyl halide group, a halogenated phenyl group or the like are preferable. —SiR ¹² R ¹³ —O— It is preferable to use such a diorganopolysiloxane having a hydroxyl group at both ends. The above-mentioned component has a number average molecular weight of 3,000 to 40,000, more preferably 5,000 to 36,000.

Any component may be used as long as it is a condensation type, but those represented by the following general formula are preferable. R ¹⁴ m · Si · Xn (m + n = 4, n is 2 or more) Here, R ¹⁴ has the same meaning as R ¹² described above, and X
Is halogen such as Cl, Br, I; H or OH; O
^{COR 15, OR 15, -O-} N = CR 16 R 17, -NR 16 R
An organic substituent such as ¹⁷ is shown. Where R ¹⁵ is 1 carbon atom
An alkyl group having 10 to 10 and an aryl group having 6 to 20 carbon atoms, and R ¹⁶ and R ¹⁷ each represent an alkyl group having 1 to 10 carbon atoms. The components include metal carboxylates of tin, zinc, lead, calcium, manganese, etc., such as dibutyl laurate, lead octylate, lead naphthenate, etc., or known catalysts such as chloroplatinic acid.

Composition B Diorganopolysiloxane having an addition-reactive functional group (number average molecular weight is 3,000 to 100,000) 100 parts by weight Organohydrogenpolysiloxane 0.1 to 10 parts by weight Addition catalyst 0.00001 to 1 part by weight The above-mentioned diorganopolysiloxane having an addition-reactive functional group is an organopolysiloxane having at least two alkenyl groups (more preferably vinyl groups) directly bonded to a silicon atom in one molecule, and the alkenyl group has a molecular chain. The organic group other than the alkenyl group, which may be at the terminal or in the middle, has 1 or less carbon atoms, which may be substituted or unsubstituted.
10 are alkyl groups and aryl groups. It is also optional that the component has a small amount of hydroxyl groups. The number average molecular weight of the component is 3,000 to 40,000, more preferably 5,
It is 000 to 36,000.

The components include polydimethylsiloxane having hydroxyl groups at both ends, α, ω-dimethylpolysiloxane, (methylsiloxane) (dimethylsiloxane) copolymer having methyl groups at both ends, cyclic polymethylsiloxane, and trimethylsilyl groups at both ends. Examples thereof include polymethylsiloxane and a (dimethylsiloxane) (methylsiloxane) copolymer having trimethylsilyl groups at both ends. The component is arbitrarily selected from known ones, but a platinum-based compound is particularly preferable, and platinum simple substance, platinum chloride, chloroplatinic acid, olefin-coordinated platinum, etc. are exemplified. For the purpose of controlling the curing speed of these compositions, vinyl group-containing organopolysiloxane such as tetracyclo (methylvinyl) siloxane, carbon-carbon triple bond-containing alcohol, acetone, methyl ethyl ketone, methanol, ethanol, propylene glycol monomethyl ether. It is also possible to add a crosslinking inhibitor such as.

If necessary, the silicone rubber layer may be powdered with an inorganic substance such as silica, calcium carbonate or titanium oxide.
Adhesion aids such as the above-mentioned silane coupling agent, titanate coupling agent and aluminum-based coupling agent, and a photopolymerization initiator may be added. The silicone rubber layer in the present invention serves as a printing ink repellent layer, and when the thickness is small, there are problems such as a decrease in ink repelling property and easy scratches. When the thickness is large, developability is deteriorated. from the point, the thickness is preferably 0.5 to 5 g / m ^2, preferably from 1 to 3 g / m ^2.

In the photosensitive lithographic printing plate requiring no fountain solution described above, various silicone rubber layers may be further coated on the silicone rubber layer. Further, in order to protect the surface of the silicone rubber layer, a transparent film such as polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyethylene terephthalate, or cellophane is laminated on the silicone rubber layer or coated with a polymer. May be. These films may be used after being stretched. A mat may be applied to these films.

The fountain solution-free photosensitive lithographic printing plate of the present invention is usually subjected to image exposure and development steps. As a light source for actinic rays used in the printing plate of the present invention, a light source having an emission wavelength in the near infrared to infrared region is preferable, and for example, a solid laser and a semiconductor laser are particularly preferable. However, depending on the type of acid precursor used, image formation is possible with electron beams, X-rays, ion beams, far-ultraviolet rays, etc. in addition to ultraviolet rays from mercury lamps, metal halide lamps, xenon lamps, chemical lamps and carbon arc lamps. is there. The g-line, i-line, and Deep-UV light used as a light source for photoresist can also be used, and scanning exposure with a high-density energy beam (laser beam or electron beam) can also be used in the present invention. Examples of such a laser beam include a helium / neon laser, an argon laser, a krypton ion laser, a helium / cadmium laser, and a KrF excimer laser.

The photosensitive lithographic printing plate not requiring fountain solution according to the present invention may be exposed and then heated to accelerate the reaction by the acid generated from the acid precursor. This heating process is 80 ~
It is preferable that the heating is performed in the temperature range of 150 ° C. for 5 seconds to 20 minutes. A photosensitive lithographic printing plate that does not require dampening water that has undergone exposure and optionally a heating step is a developer capable of dissolving or swelling a part or all of the photosensitive layer in the image area, or a developer capable of swelling a silicone rubber layer. To be developed.
In this case, the photosensitive layer in the image area and the silicone rubber layer on it may be removed, or only the silicone rubber layer in the image area may be removed, which can be controlled by the strength of the developing solution.

As the developer for the photosensitive lithographic printing plate not requiring fountain solution of the present invention, a known developer can be used. For example, aliphatic hydrocarbons (hexane, heptane, “Isopar E,
H, G "(trade name of aliphatic hydrocarbons manufactured by Esso Kagaku) or gasoline, kerosene, etc., aromatic hydrocarbons (toluene, xylene, etc.), or halogenated hydrocarbons (tricrene, etc.) Alcohols (methanol, ethanol, propanol, benzyl alcohol, ethylene glycol monophenyl ether, 2-methoxyethanol, 2-ethoxyethanol, carbitol monomethyl ether, carbitol mono) are suitable. Ethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, polyethylene glycol monomethyl ether, propylene glycol Ren glycol, polypropylene glycol, triethylene glycol, tetraethylene glycol) ・ Ketones (acetone, methyl ethyl ketone) ・ Esters (ethyl acetate, methyl lactate, ethyl lactate,
Butyl lactate, propylene glycol monomethyl ether acetate, carbitol acetate, dimethyl phthalate, diethyl phthalate) ・ Others (triethyl phosphate, tricresyl phosphate)

Further, water is added to the above organic solvent type developer, or the above solvent is solubilized in water by using a surface active agent, and further an alkaline agent such as sodium silicate,
Potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium phosphate tribasic, sodium phosphate dibasic, ammonium phosphate tribasic, ammonium phosphate dibasic, sodium metasilicate, sodium bicarbonate, aqueous ammonia, etc. And an organic alkali agent such as tetraalkylammonium hydride, monoethanolamine, diethanolamine, triethanolamine, etc. can be added. In some cases, tap water or alkaline water can be simply used as a developing solution, and a surfactant or the above-mentioned organic solvent can be added if necessary. It is also possible to add a dye such as crystal violet or astrazone red to a developing solution to perform development and dye the image area at the same time.
The development can be carried out by a known method such as rubbing the plate surface with a developing pad containing a developer as described above, or pouring the developer onto the plate surface and then rubbing it with a developing brush in water. The temperature of the developer is arbitrary, but is preferably 10 ° C to 50 ° C.
° C.

In the printing plate thus obtained, the exposed image portion can be dyed with a dyeing solution so as to be detected so as to confirm the image forming property. When the developer does not contain a dye for dyeing the exposed image area, it is dyed with a dyeing solution after development. By impregnating the dyeing solution into a soft pad and rubbing the image area lightly, only the image area is dyed, whereby it can be confirmed that the development is sufficiently performed up to the highlight area. As the dyeing solution, one or more selected from water-soluble disperse dyes, acid dyes and basic dyes are dissolved in water, alcohols, ketones, ethers, etc. alone or in a mixture of two or more kinds. Alternatively, a dispersed product is used. It is also effective to add a carboxylic acid, an amine, a surfactant, a dyeing aid, an antifoaming agent or the like in order to improve the dyeability.

The printing plate dyed with the dyeing solution is preferably washed with water and then dried, whereby the stickiness of the printing plate can be suppressed and the handling property of the printing plate can be improved. When the printing plates thus treated are stacked and stored, it is preferable to insert and sandwich a slip sheet to protect the plate surface. It is preferable that the above-mentioned development processing, dyeing processing, and subsequent water washing and drying processing are carried out by an automatic processor. A preferable example of such an automatic processor is described in JP-A-2-220061.

[0096]

The photosensitive lithographic printing plate not requiring fountain solution of the present invention is a lithographic printing plate requiring no fountain solution for heat mode type direct plate making which can be used for both positive type and negative type. It is possible to make a plate directly from a digital signal from a computer or the like by using a solid-state laser / semiconductor laser having an infrared emission region.

[0097]

[Preparation of photosensitive lithographic printing plate that does not require positive dampening water]

(Creation of substrate) 8 of 2S aluminum plate with a thickness of 0.24 mm
After immersing in a 10% aqueous solution of sodium triphosphate kept at 0 ° C for 3 minutes to degrease it and graining with a nylon brush,
It was etched with sodium aluminate for about 10 minutes, and desmutted with a 3% aqueous solution of sodium hydrogen sulfate. This aluminum plate is subjected to a current density of 2 A in 20% sulfuric acid.
Anodization was performed for 2 minutes at / dm ² .

(Preparation of Carbon Black Dispersion) A composition having the following weight ratio was dispersed with glass beads for 10 minutes to obtain a carbon black dispersion. Carbon black 1 part by weight Benzyl methacrylate / methacrylic acid copolymer 1.6 parts by weight (molar ratio 72/28, weight average molecular weight 70,000) Cyclohexanone 1.6 parts by weight Methoxypropyl acetate 3.8 parts by weight

(Photosensitive Layer) A photosensitive solution having the following composition was applied on the above aluminum plate and dried at 80 ° C. for 2 minutes. The weight after drying was 2 g / m ² . 10 parts by weight of the above carbon black dispersion 3 parts by weight of enol ether compound of Table-1 0.3 parts by weight of acid precursor of table-1 10 parts by weight of methyl methacrylate / methacrylic acid copolymer (molar ratio 70/30, Weight average molecular weight 30,000) MCF323 0.1 part by weight (Dainippon Ink and Chemicals, Inc., surfactant) Methyl ethyl ketone 50 parts by weight

(Silicone Rubber Layer) The following silicone rubber composition liquid was applied onto the photosensitive layer so that the dry weight was 2 g / m ^2, and dried at 100 ° 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 about 8,000) 0.5 parts by weight olefin - chloroplatinic acid 0.2 parts by weight inhibitor _{(CH 2 = CHSi (CH 3} ) 2 OSi (CH 3) 3) 0.3 By weight: Isopar E (manufactured by Esso Chemical Co., Ltd.) 140 parts by weight On the surface of the silicone rubber layer obtained as described above,
A biaxially stretched polypropylene film having a thickness of 9 μm was laminated to obtain a photosensitive lithographic printing plate not requiring dampening water.

The printing plate thus obtained was exposed to a YAG laser adjusted to a plate surface output of 2 W, the laminated film was peeled off, the printing plate was immersed in a solution of tripropylene glycol at 40 ° C. for 1 minute and developed in water. When rubbed with a pad, a positive type fountain solution-free lithographic printing plate in which the silicone rubber layer remained in the exposed portion and the photosensitive layer was exposed in the unexposed portion was obtained in any of the printing plates of Examples.

[0102]

[Table 1] Table-1 Enol ether compound Acid precursor Example 1 II-11 IX-2 Example 2 VI-3 IX-2 Example 3 II-11 VII-2 Example 4 II-11 VIII-2 Implementation Example 5 II-11 XI-8

Comparative Example 1 In the photosensitive liquid composition of Example 1, an oil-soluble dye (Victoria Pure Blue BOH) was used in place of the carbon black dispersion.
A fountain solution-free photosensitive lithographic printing plate was prepared in the same manner as in Example 1 except that 25 parts by weight was used. When this photosensitive lithographic printing plate requiring no fountain solution was exposed and developed in the same manner as in Example 1, the silicone rubber layer was peeled off over the entire surface, and no image was obtained.

Example 6 A photosensitive lithographic printing plate was prepared in the same manner as in Example 1, except that the dye (0.02 parts by weight) shown below was used instead of 10 parts by weight of the carbon black dispersion used in Example 1. Dye: 2,6-di-t-butyl-4- [5- (2,6-di-t-butyl-4H-
Thiopyran-4-ylidene) -penta-1,3-dienyl] thiopyrylium tetrafluoroborate (US Pat. No. 4,2,4)
Compounds described in No. 83,475) The obtained photosensitive lithographic printing plate was used as a semiconductor laser (wavelength 825 n
m, spot diameter: 1 / e ² = 11.9 μm), linear velocity 8 m / se
c, the plate surface was exposed at 110 mW. When the same developing treatment as in Example 1 was carried out, a positive type fountain solution-free lithographic printing plate was obtained.

Example 7 Instead of the silicone rubber layer used in Example 1, a silicone rubber liquid having the following composition was applied on the photosensitive layer of Example 1 so that the dry weight was 2 g / m ^2, and the temperature was 100 ° C. It was dried for 2 minutes, and a cover film was provided to prepare a photosensitive lithographic printing plate not requiring dampening water. Dimethylpolysiloxane having hydroxyl groups at both ends (polymerization degree 700) 9 parts by weight Methyltriacetoxysilane 0.3 parts by weight Trimethoxysilylpropyl-3,5-diallyl isocyanurate 0.3 parts by weight Dibutyltin dioctanoate 0.03 parts by weight Isopar E (manufactured by Esso Chemical Co., Ltd.) 160 parts by weight When this printing plate was exposed and developed in the same manner as in Example 1, a positive type fountain solution-free lithographic printing plate was obtained. Was given.

Example 8 [ Preparation of a negative-type dampening water-free photosensitive lithographic printing plate] Example 1
The photosensitive solution of Example 1 was applied to the aluminum substrate prepared in 1. and dried at 120 ° C. for 10 minutes to form a photosensitive layer. On the photosensitive layer, a silicone rubber layer was formed and a film was laminated in the same manner as in Example 1 to prepare a photosensitive lithographic printing plate not requiring dampening water. The printing plate obtained is printed with a plate output of 2 W.
After exposing with a YAG laser adjusted to, the laminated film was peeled off, and 40 parts of tripropylene glycol was removed.
When the printing plate was immersed in a liquid at ℃ for 1 minute and rubbed with a development pad in water, the silicone rubber layer remained in the unexposed area and the photosensitive layer was exposed in the exposed area. Was obtained.

Comparative Example 2 Oil-soluble dye (Victoria Pure Blue BOH) 1.2 in place of the carbon black dispersion in the photosensitive liquid composition of Example 8 was used.
A planographic printing plate unnecessary for fountain solution was prepared in the same manner as in Example 8 except that 5 parts by weight was used. When this printing plate was exposed and developed in the same manner as in Example 8, the silicone rubber layer was not peeled off over the entire surface and an image could not be obtained.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical indication location G03F 7/033 G03F 7/033

Claims (1)

[Claims] 1. A compound in which a photosensitive layer and a silicone rubber layer are laminated in this order on a support, and the photosensitive layer has at least (a) at least two enol ether groups represented by the general formula (I), A photosensitive lithographic printing plate not requiring a fountain solution, which comprises (b) a linear polymer compound (c) an infrared absorber (d) an acid precursor. (R ¹ ) (R ² ) C═C (R ³ ) —O— (I) (In the formula, R ¹ , R ² , and R ³ each independently represent hydrogen, an alkyl group, or an aryl group. Two of them may combine to form a saturated or olefinically unsaturated ring.)