JPH08328240A - Production of wetting-waterless photosensitive planographic printing plate - Google Patents

Abstract

PURPOSE: To obtain a new wetting-waterless photosensitive planographic printing plate for negative working which has high sensitivity and is usable for a wide range of wavelength light by applying a coating liquid contg. specific compds. on a photosensitive layer. CONSTITUTION: This method comprises producing the wetting-waterless photosensitive planographic printing plate obtd. by applying a coating liquid contg. following compds. on the photosensitive layer for 30 seconds to 10 minutes at 60 to 150 deg.C: The compd. contains at least >=2 enol either groups expressed by (R<1> ) (R<2> )C=C(R<3> )-O- or enol thiother groups expressed by (R<1> ) (R<2> )C=C(R<3> )-S-, a linear polymer compd. having an acid group and hydroxyl group or mercapto group and a compd. which is dispersed to generate an acid by irradiation with active rays or radiation. In the formulas, R<1> to R<3> respectively independently denote hydrogen, alkyl groups or aryl groups. The two among these may bond 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 dampening water-free photosensitive lithographic printing plate which can be printed without dampening water, and more particularly to a negative type dampening water-free photosensitive lithographic printing plate having excellent sensitivity. It is a thing.

[0002]

2. Description of the Related Art Various photosensitive working lithographic printing plates for negative working have been proposed in which a photosensitive resin layer and a silicone rubber layer are successively coated on a support.
Japanese Examined Patent Publication No. 46-16044 describes a photosensitive lithographic printing plate which does not require a fountain solution in which a silicone rubber layer is provided via an adhesive layer on a light-soluble diazo photosensitive layer lined with an aluminum substrate. Taking advantage of the fact that the diazonium salt in the exposed area becomes soluble in the developing solution due to photolysis, the photosensitive layer in the exposed area is dissolved and removed using the developing solution, and at the same time, the silicone rubber layer above it is also removed to remove the aluminum substrate. It has been proposed to form an exposed image portion, but it does not exhibit sufficient sensitivity, and the diazonium salt is thermally unstable, which causes a problem in storage stability of the plate material. See also Sho 61-5
No. 4222 and Japanese Examined Patent Publication No. 61-616 show that after exposing a photosensitive lithographic printing plate which does not need a fountain solution, a silicone rubber layer is provided on a photodegradable photosensitive layer made of O-naphthoquinonediazide backed by a support. It has been proposed that after development, the exposed portion of the silicone rubber layer and, in some cases, the photosensitive layer are removed together to expose the photosensitive layer or the support to form an image portion.
Quinonediazide compounds have been widely used in the fields of lithographic printing plates and photoresists as photosensitive substances that act positively, but they have not shown sufficient sensitivity. This is because it is difficult to sensitize the quinonediazide compound photochemically, and the quantum yield thereof does not essentially exceed 1. Also, since the photosensitive wavelength is fixed, the suitability for a light source is poor, and it is difficult to provide safety for white lamps.

Recently, a negative working fountain solution-free photosensitive lithographic printing plate which replaces them is used as a photosensitive lithographic printing plate, a compound which generates an acid by light in the photosensitive layer and a compound whose solubility is changed by hydrolysis by an acid, and a binder if necessary. A composition containing a resin or the like has been reported. For example, JP-A-63-8
No. 8556, a silicone rubber is provided on a support through a photosensitive layer containing a compound which generates a strong acid by light, a compound having a COC bond decomposable by an acid and a water-insoluble binder, and an intermediate layer composed of amorphous silicic acid. After exposing the photosensitive lithographic printing plate that does not require fountain solution to a layer, the photosensitive layer solubilized with a developing solution is dissolved and removed, and at the same time, the silicone rubber layer on the photosensitive layer is also removed to expose the aluminum substrate. Is proposed. However, also in this case, since the sensitivity is low and the difference in solubility between the unexposed area and the exposed area is small, a clear image can be obtained only under limited conditions. Further, the adhesiveness to the silicone rubber layer was not sufficient without the intermediate layer.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a novel negative working fountain solution-free photosensitive lithographic printing plate which has high sensitivity and can be used in a wide range of wavelength light. Especially.

[0005]

The object of the present invention can be achieved by the following constitutions. (1) A method for producing a photosensitive lithographic printing plate which does not require fountain solution, in which a photosensitive layer and a silicone rubber layer are applied in this order on a support, wherein the photosensitive layer is represented by (a) the general formula (I). A compound having at least two enol thioether groups represented by (II), a linear polymer compound having (b) an acid group and a hydroxyl group or a mercapto group, and (c) an actinic ray or radiation. A photosensitive lithographic printing plate not requiring a fountain solution, which is obtained by applying a coating solution containing a compound that decomposes to generate an acid upon irradiation with, and heating at 60 to 150 ° C. for 30 seconds to 10 minutes. Manufacturing method.

(R ¹ ) (R ² ) C = C (R ³ ) -O- (I) (R ¹ ) (R ² ) C = C (R ³ ) -S- (II) (wherein R ¹ , ¹ , R ² and R ³ each independently represent hydrogen, an alkyl group or an aryl group, and two of them may combine to form a saturated or olefinically unsaturated ring. With the constitution of the present invention, high sensitivity to ultraviolet rays, visible rays, electron beams or X-rays and a clear image can be formed under a wide range of developing conditions.

Further, in the present invention, it is preferable that the linear polymer as the component (b) has a hydroxyl group and / or a mercapto group from the viewpoint of stability of the crosslinked portion.

In the method for producing a photosensitive lithographic printing plate not requiring fountain solution of the present invention, a crosslink of an acetal structure or a thioacetal structure is formed by heating during coating drying or after coating drying to form a three-dimensional crosslinked resin. Is a feature. Therefore,
The cross-linked portion is efficiently hydrolyzed in the presence of an acid generated from a compound that generates an acid by light (hereinafter, sometimes referred to as a photo-acid generator) to improve the releasability of the silicone rubber layer in the exposed portion. Therefore, it has excellent sensitivity and developability.

On the other hand, when three-dimensionally cross-linked in advance before coating, this resin is difficult to dissolve in the coating solution and cannot be coated well on the support. That is, the present invention can have both the ease of production and the performance as the photosensitive lithographic printing plate described above.

The present invention will be described in detail below. The photosensitive layer used in the present invention is primarily characterized in that the enol ether group- or enol thioether group-containing compound of component (a) and the linear polymer of component (b) form a three-dimensional crosslinked structure thermally. There is a feature of. First, the compound having an enol ether group and an enol thioether group as the component (a) of the present invention will be described.

In the enol ether group of the general formula (I) and the enol thioether group of the general formula (I),
When R ¹ , R ² and R ³ are aryl groups, they are generally 6 to 2
Has 0 carbon atoms (eg, phenyl group, naphthyl group, anthryl group, phenanthryl group, etc.), alkyl group,
Alkoxy group, aryloxy group, acyl group, acyloxy group, alkylmercapto group, amino group, aminoacyl group, carboalkoxy group, nitro group, sulfonyl group,
It may be substituted with a cyano group or a halogen atom.

When R ¹ , R ² and R ³ represent an alkyl group, it is preferably a saturated or unsaturated linear, branched or alicyclic alkyl group having 1 to 20 carbon atoms (eg methyl group, ethyl group). , A propyl group, an isopropyl group, a cyclohexyl group, etc.), a halogen atom, a cyano group, an ester group,
It may be substituted with an alkoxy group, an aryloxy group or an aryl group. Further, when any ^{two of} R ¹ , R ² and R ³ are combined to form a cycloalkyl group or a cycloalkenyl group, it is usually 3 to 8, preferably 5
Or represents a 6-membered ring.

In the present invention, among the enol ether group of the general formula (I) and the enol thioether group of the general formula (II), preferred one is one of R ¹ , R ² and R ³ is a methyl group or an ethyl group. Among the groups, an enol ether group or an enol thioether group in which the rest are hydrogen atoms, and more preferred is a vinyl ether group or a vinyl thioether group in which R ¹ , R ² and R ³ are all hydrogen.

Various compounds containing two or more enol ether groups or enol thioether groups can be used in the present invention, but these are at 60 ° C. under atmospheric pressure.
A compound having a boiling point above is preferable. Preferred compounds of the component (a) include compounds represented by the following general formula (II
The enol ether compound or the enol thioether compound represented by I) or (IV) may be mentioned.

A-[-(O-R ⁴ ) n- X-CH = CH ₂ ] m (III) A-[-B-R ⁴ -X-CH = CH ₂ ] m (IV) where A Represents an m-valent alkylene group, an arylene group or a heterocyclic group, and B represents -CO-O-, -NHCOO-.
Or indicates -NHCONH-, R ⁴ is a carbon number 1 to 1
0 represents a straight-chain or branched alkylene group, and X represents an oxygen atom or a sulfur atom. n is 0 or an integer of 1 to 10, m is 2
Represents an integer of from 6 to 6.

The compound represented by the general formula (III) is, for example, Stephen. C. Lapin, Polymers Paint Color Journa.
l, 179 (4237), 321 (1988), that is, according to the reaction of polyhydric alcohol or polyhydric phenol with acetylene, or the reaction of polyhydric alcohol or polyhydric phenol with halogenated alkyl vinyl ether. Can be synthesized.

Specific examples of the enol ether compound represented by the general formula (III) include ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,3-butanediol divinyl ether, tetramethylene glycol divinyl ether and 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 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 general formulas (III-1) to (III-41), but are not limited thereto.

[0018]

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[0019]

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[0020]

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[0021]

[Chemical 4]

[0022]

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[0023]

[Chemical 6]

[0024]

[Chemical 7]

[0025]

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[0026]

[Chemical 9]

Specific examples of the enol thioether compound represented by the general formula (III) include ethylene glycol divinyl thioether, triethylene glycol divinyl thioether, 1,3-butanediol divinyl thioether, tetramethylene glycol divinyl thioether,
Neopentyl glycol divinyl thioether, trimethylolpropane trivinyl thioether, trimethylol ethane trivinyl thioether, hexanediol divinyl thioether, 1,4-cyclohexanediol divinyl thioether, tetraethylene glycol divinyl thioether, pentaerythritol tetravinyl thioether, sorbitol tetravinyl thioether ,
Sorbitol pentavinyl thioether, ethylene glycol diethylene vinyl thioether, triethylene glycol diethylene vinyl thioether, ethylene glycol dipropylene vinyl thioether, trimethylolpropane triethylene vinyl thioether, trimethylol propane diethylene vinyl thioether, pentaerythritol diethylene vinyl thioether, pentaerythritol triethylene Vinyl thioether, 1,2-
Examples thereof include, but are not limited to, di (vinylthioethermethoxy) benzene, 1,2-di (vinylthioetherethoxy) benzene, and the following compounds.

[0028]

[Chemical 10]

[0029]

[Chemical 11]

[0030]

[Chemical 12]

On the other hand, the compound represented by the general formula (IV) (when B = CO-O-) can be produced by reacting a polycarboxylic 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, maleic acid diethylene vinyl ether, fumaric acid diethylene vinyl ether, itaconic acid diethylene. Vinyl ether, terephthalic acid diethylene vinyl thioether, phthalic acid diethylene vinyl thioether, isophthalic acid diethylene vinyl thioether, phthalic acid dipropylene vinyl thioether, terephthalic acid dipropylene vinyl thioether, isophthalic acid dipropylene vinyl thioether, maleic acid diethylene vinyl thioether, fumarate diethylene Vinyl Thioe Ether, it can be mentioned itaconic acid diethylene vinyl thioether, but is not limited thereto.

Further, the vinyl ether group- or vinyl thioether group-containing compound preferably used in the present invention is a vinyl ether compound or vinyl thioether compound having active hydrogen represented by the following general formulas (V), (VI) and (VII). Examples thereof include a vinyl ether group- or vinyl thioether group-containing compound synthesized by the reaction of a compound having an isocyanate group.

CH ₂ ═CH—X—R ⁵ —OH (V) CH ₂ ═CH—X—R ⁵ —COOH (VI) CH ₂ ═CH—X—R ⁵ —NH ₂ (VII) where R ⁵ represents a linear or branched alkylene group having 1 to 10 carbon atoms. X represents an oxygen atom or a sulfur atom. As the compound having an isocyanate group, for example, the compounds described in Crosslinking Agent Handbook (Taisei-sha, 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 polyphenyl isocyanate, polyisocyanate type such as hexamethylene diisocyanate, adduct of tolylene diisocyanate and trimethylol propane, adduct of hexamethylene diisocyanate and water, xylene di Examples thereof include polyisocyanate adduct types such as adducts of isocyanate and trimethylolpropane.

By reacting the above-mentioned isocyanate group-containing compound with the active hydrogen-containing vinyl ether group- or vinyl thioether group-containing compound, various compounds having a vinyl ether group or vinyl thioether group at the terminal can be prepared. Examples of such compounds are listed below, but the scope of the present invention is not limited thereto.

[0036]

[Chemical 13]

[0037]

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[0038]

[Chemical 15]

[0039]

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The compounds containing at least two enol ether groups or enol thioether groups described above can be used alone, but may be used as a mixture of several kinds. In the presence of an acid, the enol ether group-containing compound or enol thioether group-containing compound of the present invention and a thermally crosslinkable linear polymer compound are dissolved in a coating solvent and applied with heat during or after drying. A resin having a hydrolyzable cross-linking structure is obtained, and the addition amount of the compound containing an enol ether group or an enol thioether group in this case is 1 to 80% by weight based on the total solid content of the photosensitive composition. , Preferably 3 to 50% by weight,
It is more preferably in the range of 5 to 30% by weight. If the amount of the enol ether group- or enol thioether group-containing compound added is small, the crosslinkability will be insufficient, so that the image ON / OF
If F is lowered, and if it is too large, the sensitivity is lowered.

Next, the linear polymer (b) containing an acid group which thermally reacts with an enol ether compound or an enol thioether compound to form a three-dimensional crosslinked resin will be described. The linear polymer (b) having an acid group and a hydroxyl group or a mercapto group used in the present invention has at least 2 enol ether groups or enol thioether groups.
Any compound can be arbitrarily selected and used as long as it is thermally crosslinked with the individual compound [component (a)] and the crosslinked portion is efficiently decomposed by an acid. In this case, the acid group can also serve as the crosslinkable group.

The above linear polymer can be generally synthesized by a known method for obtaining a linear polymer. For example, vinyl having an acid group, preferably a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a sulfonamide group, etc. It can be obtained by copolymerizing a monomer and another vinyl monomer copolymerizable therewith (preferably one containing a hydroxyl group or a mercapto group).

As the vinyl monomer containing an acid group,
For example, 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, 2 Examples thereof include, but are not limited to,-(acrylamide) -2-methylpropanesulfonic acid.

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 can be copolymerized with another monomer. The proportion of the polymerizable monomer is preferably in the range of 2:98 to 80:20 by weight, the preferred range is 5:95 to 70:30, and the more preferred range is 5:95 to 30:70. .

The linear polymer (b) having an acid group and a hydroxyl group or a mercapto group can be obtained by reacting a dihydroxy compound having an acid group with a diisocyanate compound, a dihydroxy compound having an acid group and a dicarboxylic acid compound. It can be obtained by co-condensation with For example, 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,
Dihydroxy compounds having an acid group such as bis (4-hydroxyphenyl) acetic acid, 4,4-bis (4-hydroxyphenyl) pentanoic acid, tartaric acid, 2,4-tolylene diisocyanate, and 2,4-tolylene diisocyanate Dimer of nato, 4,4'-diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), etc. By reacting the diisocyanate compound (1) in an equivalent amount, a linear polyurethane resin containing a carboxyl group can be obtained. 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, diethylene glycol, triethylene glycol, neopentyl glycol, 1,3
-Butylene glycol, bisphenol A, hydrogenated bisphenol A, hydrogenated bisphenol F, bisphenol A
Examples of the ethylene oxide adduct thereof include, but are not limited to, these.

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 weight ratio of the diol containing an acid group to the other monomer units is 2: 9.
A range of 8 to 80:20 is suitable, a preferred range is 5:95 to 70:30, and a more preferred range is 5:95.
95-30: 70.

As the linear polymer (b) having an acid group and a hydroxyl group or a mercapto 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, and resol type resin. Phenolic resins,
Examples thereof include phenol-modified xylene resin, polyhydroxystyrene, polyhalogenated hydroxystyrene, and acrylic resin having a phenolic hydroxyl group, but are not limited thereto.

The molecular weight of these linear polymers is 1,000 to
It is 1,000,000, preferably 1,500 to 200,000. If the molecular weight of the linear polymer is too low, the crosslinkability will decrease, and if it is too high, the sensitivity will decrease. 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 5 to 50% by weight, preferably 5 to 40% by weight, more preferably 10 to 30% by weight, and the content of the monomer containing a hydroxyl group or a mercapto group is 5 to 5. A linear polymer of 50% by weight, preferably 5-40% by weight, more preferably 10-30% by weight is particularly preferably used.

The linear polymer of the present invention can be used alone, but may be used as a mixture of several kinds. The amount of linear polymer added to the photosensitive composition is 1 to 95% by weight, preferably 20 to 90% by weight, based on the total solid content of the photosensitive composition.
More preferably, it is in the range of 30 to 80% by weight. If the amount of the linear polymer added is too small, the sensitivity will decrease, and if it is too large, the crosslinkability will be insufficient.

Examples of the compound used in the present invention which decomposes upon irradiation with actinic rays or radiation to generate an acid include a photoinitiator for photocationic polymerization, a photoinitiator for photoradical polymerization, and a photobleaching agent for dyes. , A photochromic agent, a known compound that generates an acid by light, which is used for a micro resist or the like, and a mixture thereof can be appropriately selected and used.

For example, SI Schlesinger, Photogr. Sc
i. Eng., 18, 387 (1974), TS Bal et al, Polymer,
21, 423 (1980), diazonium salt, U.S. Pat.
Ammonium salts described in the specifications of 4,069,055, 4,069,056, Re 27,992, and Japanese Patent Application No. 3-140140, DC
Necker et al, Macromolecules, 17, 2468 (1984), C.
S. Wen et al, Teh, Proc. Conf. Rad. Curing ASIA, p
478 Tokyo, Oct (1988), U.S. Pat.No. 4,069,055,
Phosphonium salt described in 4,069,056, JV Crivello
et al, Macromorecules, 10 (6), 1307 (1977), Chem.
& Eng. News, Nov. 28, p31 (1988), European Patent 104,143.
U.S. Pat.Nos. 339,049 and 410,201, JP-A-2-
150848, iodonium salt described in JP-A-2-296514,
JV Crivello et al, Polymer J. 17, 73 (1985), J.
V. Crivello et al. J. Org. Chem., 43, 30505 (197)
8), WR Watt et al, J. Polymer Sci., Polymer Che
m. Ed., 22, 1789 (1984), JV Crivello et al, Po
lymer Bull., 14, 279 (1985),

JV Crivello et al, Macromorecules,
14 (5), 1141 (1981), JV Crivelloet al, J. Polyme
r Sci., Polymer Chem. Ed., 17, 2877 (1979), European Patents 370,693, 3,902,114, 233,567, and
297,443, 297,442, U.S. Pat.No. 4,933,377,
161,811, 410,201, 339,049, 4,760,
013, 4,734,444, 2,833,827, German Patent No.
2,904,626, 3,604,580 and 3,604,581 sulfonium salts, JV Crivello et al, Macromorec
ules, 10 (6), 1307 (1977), JV Crivello et al, J.
Polymer Sci., Polymer Chem. Ed., 17, 1047 (1979)
Selenonium salt described in CS Wen et al, Teh, Pro
c. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988)
Onium salts such as the arsonium salts described in U.S. Pat.
905,815, JP-B-46-4605, JP-A-48-36281, JP-A-55-32070, JP-A-60-239736, JP-A-61-16983
5, JP 61-169837, JP 62-58241, JP
62-212401, JP-A-63-70243, JP-A-63-298339, K. Meier et al, J. Ra
d. Curing, 13 (4), 26 (1986), TP Gill et al, Ino
rg. Chem., 19, 3007 (1980), D. Astruc, Acc. Chem.
Res., 19 (12), 377 (1896), Organic metal / organic halides described in JP-A No. 2-161445, S. Hayase et al, J. P.
olymer Sci., 25, 753 (1987), E. Reichmanis et al,
J. Polymer Sci., Polymer Chem. Ed., 23, 1 (1985),
QQ Zhu et al, J. Photochem., 36, 85, 39, 317 (19
87), B. Amit et al, Tetrahedron Lett., (24) 2205
(1973),

DHR Barton et al, J. Chem Soc., 3
571 (1965), PM Collins et al, J. Chem. Soc., Pe.
rkin I, 1695 (1975), M. Rudinstein et al, Tetrahe
dron Lett., (17), 1445 (1975), JW Walker et a
l, J. Am. Chem. Soc., 110, 7170 (1988), SC Bus
man et al, J. Imaging Technol., 11 (4), 191 (198
5), HM Houlihan et al, Macoromolecules, 21, 200
1 (1988), PM Collinset al, J. Chem. Soc., Chem.
Commun., 532 (1972), S. Hayase et al, Macromolec
ules, 18, 1799 (1985), E. Reichmanis et al, J. Ele
ctrochem. Soc., Solid State Sci. Technol., 130
(6), FM Houlihan et al, Macromolecules, 21, 2001
(1988), European Patent Nos. 0290,750, 046,083 and 15
6,535, 271,851, 0,388,343, U.S. Patent No.
3,901,710, 4,181,531, JP-A-60-198538,
A photoacid generator having an o-nitrobenzyl type protecting group described in JP-A-53-133022, M. TUNOOKA et al, Polymer Pr.
eprints Japan, 38 (8), G. Berner et al, J. Rad. Cur
ing, 13 (4), WJ Mijs et al, Coating Technol., 55
(697), 45 (1983), Akzo, H. Adachi et al, Polymer P
reprints, Japan, 37 (3), EP 0199,672, 84
515, 199,672, 044,115, 0101,122,
U.S. Pat.Nos. 4,618,564, 4,371,605 and 4,431,77
4, JP-A-64-18143, JP-A-2-245756, Japanese Patent Application No. 3-
Compounds that photolyze to generate sulfonic acid, represented by iminosulfonates described in JP-A-140109, JP-A-61-61
-166544, disulfone compounds, G. Buhr et al, S
PIE (1086), 117, (1989), R. Hayase et al, J. Photopolyme
r Sci. Technol, 6 (4), 495 (1993), JP-A-53-8128, and Japanese Patent Application No. 2-212947 can be exemplified by O-naphthoquinonediazide compounds.

Further, 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.
c., 104, 5586 (1982), SP Pappas et al, J. Imagin
g Sci., 30 (5), 218 (1986), S. Kondo er al. Makromo
l. Chem., Rapid Commun., 9,625 (1988), Y. Yamada e
t al, Makromol. Chem., 152, 153, 163 (1972), JV
Crivello er al. J. Polymer Sci., Polymer Chem. E
d., 17, 3845 (1979), U.S. Pat.No. 3,849,137, German Patent No. 3,914,407, JP-A-63-26653, JP-A-55-16482.
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, Tetrahedron Lett., (47) 45.
55 (1971), DHR Barton et al, J. Chem. Soc.,
(C), 329 (1970), U.S. Patent No. 3,779,778, European Patent No.
The compounds capable of generating an acid by light described in 126,712 can also be used.

Among the compounds which decompose to generate an acid upon irradiation with actinic rays or radiation, those which are particularly effectively used are described below. (1) The following general formula (VIII) substituted with a trihalomethyl group
An oxazole derivative represented by or an S-triazine derivative represented by the following general formula (IX).

[0058]

[Chemical 17]

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 (VIII) and the S-triazine derivative (I
Specific examples of X) include the following VIII-1 to 8 and compound I
Examples thereof include, but are not limited to, X-1 to 10.

[0060]

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[0061]

[Chemical 19]

[0062]

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[0063]

[Chemical 21]

[0064]

[Chemical formula 22]

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

[0066]

[Chemical formula 23]

In the formula, Ar ¹ and Ar ² each independently represent a substituted or unsubstituted aryl group. Preferred substituents are 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. Preferred is 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, an alkyl group having 1 to 8 carbon atoms, a nitro group, a carboxyl group, a hydroxy group or a halogen atom for the aryl group, and a carbon atom for the alkyl group. 1-8 alkoxy groups, carboxyl groups and alkoxycarbonyl groups.

Z ⁻ represents a counter anion, for example, BF
_{^{4 -, AsF 6 -, PF}} 6 -, SbF 6 -, SiF 6 -, ClO 4 -, CF 3 S
_{^{O -, BPh 4 - (Ph}} = phenyl), naphthalene-1-sulfonic acid anion, condensed polynuclear aromatic sulfonic acid anion such as anthraquinone sulfonic acid anion, there may be mentioned the sulfonic acid group-containing dyes, limited to It is not something that will be done.

Two of R ⁸ , R ⁹ and R ¹⁰ and Ar ¹ and Ar ² may be bonded to each other via a single bond or a substituent. The onium salts represented by the general formulas (X) and (XI) are known, and for example, JW Knapczyk
et al, J. Am. Chem. Soc., 91, 145 (1969), AL
Maycok et al, J. Org. Chem., 35, 2532 (1970), E. G.
oethas etal, Bull. Soc. Chem. Belg., 73, 546, (196
4), HM 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 4,24.
It can be synthesized by the method described in JP-A-7,473 and JP-A-53-101,331.

Specific examples of the onium compounds represented by the general formulas (X) and (XI) include compounds X-1 to 22 and compounds X-1 to 22 shown below.
XI-1 to 34, but not limited thereto.

[0071]

[Chemical formula 24]

[0072]

[Chemical 25]

[0073]

[Chemical formula 26]

[0074]

[Chemical 27]

[0075]

[Chemical 28]

[0076]

[Chemical 29]

[0077]

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[0078]

[Chemical 31]

[0079]

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[0080]

[Chemical 33]

[0081]

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[0082]

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[0083]

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[0084]

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[0085]

[Chemical 38]

[0086]

[Chemical Formula 39]

(3) A disulfone derivative represented by the following general formula (XII) or an iminosulfonate derivative represented by the following general formula (XIII). _{^{Ar 3 -SO 2 -SO 2 -Ar 4}} (XII)

[0088]

[Chemical 40]

In the formula, Ar³And Ar^FourReplace each independently
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. Represented by the general formulas (XII) and (XIII)
Specific examples of the compound include compounds XII-1 to
12 and XIII-1 to 12 but are not limited to these.
It is not something that will be done.

[0090]

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[0091]

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[0092]

[Chemical 43]

[0093]

[Chemical 44]

[0094]

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[0095]

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[0096]

[Chemical 47]

[0097]

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(4) O-naphthoquinonediazide compound represented by the following general formula (XIV)

[0099]

[Chemical 49]

In the formula, A ² may be a divalent substituted or unsubstituted aliphatic residue or a divalent substituted or unsubstituted aromatic group. Specific examples of the compound represented by the general formula (XIV) include compounds XIV-1 to 24 shown below, but the compound is not limited to these.

[0101]

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[0102]

[Chemical 51]

[0103]

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[0104]

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[0105]

[Chemical 54]

[0106]

[Chemical 55]

[0107]

[Chemical 56]

The amount of the compound which decomposes upon irradiation with actinic rays or radiation to generate an acid is usually 0.001 to 40% by weight based on the total solid content of the photosensitive composition, and preferably Is in the range of 0.1 to 20% by weight, more preferably 0.2 to 10% by weight. If the amount of the compound that generates an acid is too small, the sensitivity will decrease, and if it is too large, the sensitivity will not rise above a certain level and the cost will increase.

In the photosensitive composition of the present invention, if necessary,
Various known compounds such as compounds (sensitizers), dyes, pigments, and plasticizers that increase the photoacid generation efficiency of the acid-generating compounds can be added.

As the sensitizer, electron donating compounds such as pyrene and perylene, merocyanine dyes, cyanine dyes and the like can be used, but the sensitizer is not limited to these. The ratio of these sensitizers to the component (b) is preferably 0.01 / 1 to 20/1 in molar ratio and 0.1 / in weight ratio.
It is in the range of 1 to 5/1.

A dye can be used as a colorant in the photosensitive composition of the present invention, and suitable dyes include oil-soluble dyes and 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 can be added to the photosensitive composition in a proportion of 0.01 to 10% by weight, preferably 0.1 to 3% by weight, based on the total solid content of the photosensitive composition. .

Further, a small amount of a silane coupling agent, a titanium coupling agent, or the like may be added to enhance the adhesiveness with the silicone rubber layer. A silicone-based surfactant, a fluorine-based surfactant or a fluorine-based surface aligning agent may be added to improve coatability.

The photosensitive composition of the present invention is dissolved in a solvent capable of dissolving the above components and used for coating. 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, methyl lactate, ethyl lactate, N, N-dimethylacetamide, N, N-dimethylformamide, tetramethylurea, N-methylpyrrolidone, dimethylsulfoxide, sulfolane, γ-butyrolactone, There are toluene, ethyl acetate, dioxane and the like, and these solvents are 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. Also, the coating amount is generally 0.2 to 5.0 g as solid content.
/ M ² , but more preferably 0.3 to 3.0 g / m ² .

The above 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 40
It is dried at ~ 150 ° C for 30 seconds to 10 minutes using a hot air dryer, an infrared dryer or the like. Crosslinking between the component (a) and the component (b) may be carried out by applying heat during coating and drying of the photosensitive composition or by applying heat after coating and drying. The heating is preferably 60 ° C to 150 ° C, more preferably 8 ° C.
0 ° C to 130 ° C, 5 seconds to 20 minutes, preferably 20
Perform for 5 seconds to 5 seconds.

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, a 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 aluminum-containing ( For example, an alloy of aluminum with a metal such as silicon, copper, manganese, magnesium, chromium, zinc, lead, bismuth, nickel.

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 is hardened, and the one using the 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 crosslinking agent 3 to 70 parts by weight Catalyst 0.01 to 40 parts by weight A polymer having a repeating unit represented by the formula:
¹² and R ¹³ are an alkyl group having 1 to 10 carbon atoms, a vinyl group or an aryl group, and may have other appropriate substituents. Generally 60% of R ¹² and R ¹³
The above is preferably a methyl group, a vinyl halide group, a halogenated phenyl group, or the like.

[0121]

[Chemical 57]

It is preferable to use a diorganopolysiloxane having a hydroxyl group at both ends. Further, the component has a number average molecular weight of 3,000 to 40,000,
It is more preferably 5,000 to 36,000. Further, the component may be any one if it is a condensation type, but the one represented by the following general formula is preferable.

R ¹² m · Si · Xn (m + n = 4, n is 2 or more) Here, R ¹² has the same meaning as R ¹² described above, and X is a substituent as shown below. -Halogen such as Cl, Br, I-H or OH, OCOR ¹⁴ , OR ¹⁴ , -ON = CR
¹⁵ R ^16, an organic substituent such as -NR ¹⁵ R ^16.

Here, R ¹⁴ is an alkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 20 carbon atoms, and R ¹⁵ and R ¹⁶ are alkyl groups having 1 to 10 carbon atoms. The ingredients are tin, zinc,
Examples thereof include metal carboxylates of 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 (number average molecular weight). Is 3,000 to 40,000), and the alkenyl group may be at the terminal or in the middle of the molecular chain, and the organic group other than the alkenyl group is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms or an aryl group. 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 5,000 to 36,0.
00.

As the component, polydimethylsiloxane having hydroxyl groups at both ends, α, ω-dimethylpolysiloxane, (methylsiloxane) (dimethylsiloxane) copolymer having methyl groups at both ends, cyclic polymethylsiloxane, and trimethylsilyl group having both terminals at both ends. Examples thereof include polymethylsiloxane and a (dimethylsiloxane) (methylsiloxane) copolymer having trimethylsilyl groups at both ends.

The components are arbitrarily selected from known ones, but platinum compounds are particularly preferable, and simple platinum, platinum chloride, chloroplatinic acid, olefin coordinated platinum and the like 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 contains powder of an inorganic material such as silica, calcium carbonate, titanium oxide, or the like.
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, and when the thickness is large, the developability deteriorates. from, 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 not requiring 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 stretched before use. Furthermore, this film may be matted to improve the vacuum adhesion in the baking frame during image exposure.

The fountain solution-free photosensitive lithographic printing plate of the present invention is usually subjected to image exposure and development steps. Examples of the light source of the actinic ray used for image exposure include a mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, a carbon arc lamp, and the like. Radiation is electron beam, X
Rays, ion beams, deep ultraviolet rays, etc. 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. Such laser beams include helium / neon laser, argon laser, krypton ion laser, helium / cadmium laser, Kr.
F excimer laser etc. are mentioned.

The photosensitive lithographic printing plate requiring no fountain solution according to the present invention is exposed with a transparent original image, and then, a developing solution capable of dissolving or swelling part or all of the photosensitive layer in the image area (exposed area), or It is developed with a developer capable of swelling the silicone rubber layer. 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 used for developing the photosensitive composition of the present invention, those known as a developer for a negative type fountain solution-free photosensitive lithographic printing plate can be used. For example, aliphatic hydrocarbons {hexane, heptane, "Isopar E, H,
G "[trade name of aliphatic hydrocarbons manufactured by Esso Chemical Co., Ltd.]
Alternatively, gasoline, kerosene, etc., aromatic hydrocarbons (toluene, xylene, etc.), or halogenated hydrocarbons (tricrene, etc.) to which the following polar solvent is added, or the polar solvent itself is preferable. -Alcohols (methanol, ethanol, propanol, benzyl alcohol, ethylene glycol monophenyl ether, 2-methoxyethanol, 2-ethoxyethanol, carbitol monomethyl ether, carbitol monoethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether) Ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, polyethylene glycol monomethyl ether, propylene 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, tricresidyl phosphate) Also, water is added to the organic solvent-based developer or the solvent is used as an interface. Those solubilized in water using an activator, and further alkali agents such as sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium triphosphate, and dibasic sodium phosphate. Inorganic alkaline agents such as ammonium triphosphate, ammonium diphosphate, sodium metasilicate, sodium bicarbonate, aqueous ammonia, tetraalkylammonium hydride, monoethanolamine, diethanolamine, triethanolamine. It may be added an organic alkali agent such as emissions.

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.

Development can be carried out by a known method such as rubbing the plate surface with a developing pad containing the above-mentioned developing solution or pouring the developing solution onto the plate surface and then rubbing it with a developing brush in water. The temperature of the developer can be developed at any temperature, but is preferably 10 ° C to 50 ° C.

In the printing plate thus obtained, the exposed image portion can be dyed with a dyeing solution so as to be detected in order 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 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 developing treatment, dyeing treatment, and subsequent washing and drying treatment are carried out by an automatic processor. A preferred automatic processor of this kind is disclosed in JP-A-2-
220061.

[0139]

EXAMPLES The present invention will now be described in more detail by way of examples, which should not be construed as limiting the invention thereto. Examples 1 to 24, Comparative Examples 1 to 3 A 2S aluminum plate having a thickness of 0.24 mm was immersed in a 10% aqueous solution of sodium triphosphate kept at 80 ° C for 3 minutes for degreasing, and after graining with a nylon brush. , Sodium aluminate for about 10 minutes, and desmutted with a 3% aqueous solution of sodium hydrogen sulfate. This aluminum plate is 2% at a current density of 2 A / dm ² in 20% sulfuric acid.
Anodization was performed for a minute.

Using the compounds shown in Table 1, 27 kinds of photosensitive liquids [A] -1 to [A] -2 were prepared according to the following prescription.
4, [A ']-1 to [A']-3 were prepared. This sensitizing solution is applied on an anodized aluminum plate and heated to 100 ° C.
And dried for 10 minutes. The coating amount at this time was adjusted so that the dry weight was 1.7 g / m ² .

Photosensitive Solution Formulation [A] Linear polymer in Table 1 2.0 g Enol ether compound or enol thioether compound in Table 1 0.4 g Photo acid generator in Table 1 0.1 g Dioxane 50.0 g

In order to confirm the cross-linking of the photosensitive layer due to heat during drying, the photosensitive material coated with the above photosensitive solution on an anodized aluminum plate and dried was immersed in the solvent shown in Table 2 for 5 minutes,
After washing with water, the dissolved state of the coating film was observed. The results are shown in Table 2. A is insoluble, B is partially dissolved (film reduction), and C is dissolved. As a result of Table 2, Examples 1 to 18 containing the linear polymer of the present invention and a compound containing an enol ether group or an enol thioether group are unnecessary for tripropylene glycol, methyl ethyl ketone, dioxane, and toluene and are sufficiently cross-linked. You can see that On the other hand, Comparative Example 3 containing no linear polymer of the present invention,
Comparative Example 2 containing no enol ether group- or enol thioether group-containing compound is not sufficiently crosslinked.

Next, the composition liquid for the silicone rubber layer described below was applied to the photosensitive layer of the photosensitive material dried and applied to the anodized aluminum plate so that the dry weight was 2.0 g / m ^2. The composition was applied and dried at 140 ° C. for 2 minutes to obtain a silicone rubber cured layer. α, ω-Divinylpolydimethylsiloxane (Polymerization degree about 700) 9.0 g (CH ₃ ) ₃ -Si-O- (Si (CH ₃ ) _2- O) _30- (SiH (CH ₃ ) -O) _10- Si (CH _{3) 3} 1.2 g polydimethylsiloxane (polymerization degree about 8,000) 0.5 g olefin - chloroplatinic acid 0.2g inhibitor 0.3g Isopar G [manufactured by Esso chemical Co.] chloride 140.0g above A 12 μm-thick, single-sided, matt biaxially oriented polypropylene film was laminated on the surface of the silicone rubber layer obtained as described above so that the non-matted surface was in contact with the silicone rubber layer. Obtained.

A gray scale having a density difference of 0.15 was brought into close contact with this printing plate and exposed for 20 seconds from a distance of 50 cm with a 2 KW high pressure mercury lamp. The exposed photosensitive lithographic printing plate laminate film was peeled off, heated at 120 ° C. for 5 minutes, immersed in a solution of tripropylene glycol at 40 ° C. for 1 minute, and rubbed with a developing pad in water. Then, the silicone rubber layer was peeled off to expose the photosensitive layer, and in the unexposed portion, a dampening water-free photosensitive lithographic printing plate was obtained in which the silicone rubber layer remained firmly. At that time, the number of gray scale steps in which the silicone rubber layer was completely removed was evaluated as the gray scale sensitivity. Table 3 shows the results.

[0145]

[Table 1] Table 1 Enol ether or eno photosensitizer Liquid polymer Linear thioether compound Photo acid generator Example 1 [A] -1 P-1 III-11 X-21 2 [A] -2 P-2 III- 11 X-21 3 [A] -3 P-3 III-11 X-21 4 [A] -4 P-4 III-11 X-21 5 [A] -5 P-5 III-11 X-21 6 [A] -6 P-6 III-11 X-21 7 [A] -7 P-7 III-11 X-21 8 [A] -8 P-2 III-1 X-21 9 [A] -9 P-2 III-12 X-21 10 [A] -10 P-2 V-11 X-21 11 [A] -11 P-2 V-13 X-21 12 [A] -12 P-2 III- 47 X-21 13 [A] -13 P-2 III-11 XI-34 14 [A] -14 P-2 III-11 VIII-3 15 [A] -15 P-2 III-11 IX-8 16 [A] -16 P-2 III-11 XII-10 17 [A] -17 P-2 III-11 XII-12 18 [A] -18 P-2 III-11 XIV-14 Comparative Example 1 [A ' ] -1 P-2 III-11 None 2 [A ']-2 P-2 None X-21 3 [A']-3 P'-1 III-11 X-21

The compounds shown in Table 1 are shown below. P-1: Methacrylic acid / methyl methacrylate / ethyl acrylate = 20/55/25 (wt%), molecular weight Mw =
430,000 P-2: Methacrylic acid / benzyl methacrylate / 2-
Hydroxyethyl methacrylate = 20/60/20
(% By weight), molecular weight Mw = 370000 P-3: methacrylic acid / benzyl methacrylate / 2-
Mercaptoethyl methacrylate = 20/60/20
(% By weight), molecular weight Mw = 20 million P-4: methacrylic acid / benzyl methacrylate = 30
/ 70 (% by weight), molecular weight Mw = 23,000 P-5: vinyl benzoic acid / methyl methacrylate / ethyl acrylate = 20/60/20 (% by weight), molecular weight Mw
= 37,000 P-6: p-hydroxystyrene / vinyltoluene = 5
0/50 (% by weight), molecular weight Mw = 32,000 P-7: polymer of formula a, molecular weight Mw = 30000 P′-1: 2-hydroxyethyl methacrylate / benzyl methacrylate = 20/80 (weight %), Molecular weight M
w = 43,000

[0147]

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[0148]

[Table 2] Table 2: Solubility of dry coating film Tripropylene methyl ethyl ketone dioxane toluene glycol Example 1 A A A A A 2 A A A A 3 A A A A A A 4 A A A A 5 A A A A A 6 A A A A 7 A A A A A 8 A A A A 9 A A A A A 10 A A A A A 11 A A A A A A A 12 A A A A A 13 A A A A A 14 A A A A A 15 A A A A A 16 A A A A 17 A A A A A 18 A A A A Comparative Example 1 A A A A 2 C C C C 3 A C C B

[0149]

[Table 3] Table 3 Image performance Gray scale step Example 1 Clear negative image 10 2 Clear negative image 10 3 Clear negative image 10 4 Clear negative image 10 5 Clear negative image 6 6 Clear negative image 6 7 Vivid negative image 7 8 Vivid negative image 8 9 Vivid negative image 7 10 Vivid negative image 8 11 Vivid negative image 4 12 Vivid negative image 6 13 Vivid negative image 10 14 Vivid negative image 4 15 Vivid Negative image 6 16 Vivid negative image 8 17 Vivid negative image 10 18 Vivid negative image 10 Comparative Example 1 Silicone rubber layer does not peel off in exposed and unexposed areas 2 Silicone rubber layer exposed and unexposed areas Peeling off 3 Silicone rubber layer peeled off in exposed areas, and partially peeled even in unexposed areas

Example 19 The same support and photosensitive layer as in Example 2 were used, and the following composition liquid for the silicone rubber layer was applied thereon at a dry weight of 2.0 g / m ² and the temperature was maintained at 120 ° C. for 2 hours. It was dried for a minute to obtain a silicone rubber cured layer. Polydimethylsiloxane having hydroxyl groups at both ends (polymerization degree: about 700) 9.0 g Methyltriacetoxysilane 0.3 g Dibutyltin dioctanoate 0.03 g Isopar G (manufactured by Esso Chemical Co., Ltd.) 160.0 g This printing plate was prepared in the same manner as in Example 5. When exposed, heated and developed, only the silicone rubber layer was removed in the exposed area where the exposure amount was greater than 10 steps in gray scale, and the photosensitive layer was exposed.
A highly sensitive negative-working lithographic printing plate unnecessary for fountain solution was obtained in which the silicone rubber layer remained firmly in the unexposed area.

Example 20 In the same manner as in Example 2, a printing plate having a photosensitive layer and a silicone rubber layer laminated on a support was prepared, exposed and heated. By immersing the plate surface in ethanol and rubbing it with a development pad at the same time, the photosensitive layer is dissolved and removed together with the silicone layer in the exposed area where the exposure is greater than 11 steps in gray scale, and the silicone layer and the photosensitive layer are removed in the unexposed area. A photosensitive lithographic printing plate not requiring fountain solution having a high-sensitivity and clear negative image remained was obtained.

[0152]

INDUSTRIAL APPLICABILITY The photosensitive lithographic printing plate not requiring fountain solution of the present invention has high photosensitivity and can use light of a wide wavelength range.

Claims (1)

[Claims] 1. A method for producing a photosensitive lithographic printing plate not requiring fountain solution, which comprises coating a photosensitive layer and a silicone rubber layer on a support in this order, wherein the photosensitive layer comprises: ) A compound having at least two enol ether groups represented by (II) or an enol thioether group represented by (II), (b) a linear polymer compound having an acid group and a hydroxyl group or a mercapto group, (c) an activity A coating solution containing a compound that decomposes to generate an acid upon irradiation with light rays or radiation is applied, and
A method for producing a photosensitive lithographic printing plate not requiring fountain solution, which is obtained by heating at 30 ° C. for 30 seconds to 10 minutes. ^{(R 1) (R 2)} C = C (R 3) -O- (I) (R 1) (R 2) C = C in (R ³⁾ -S- (II) formula, R ^1, R ² , R ³ each independently represent hydrogen, an alkyl group or an aryl group. Also, two of them may combine to form a saturated or olefinically unsaturated ring.