JP2000066416A - Plate making method for photopolymerizable planographic printing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a plate making method for a photopolymerizable planographic printing plate which does not generate flare, etc., in a laser direct plate making, can give a clear image and has high printing resistance. SOLUTION: A photopolymerizable planographic printing plate with a photosensitive layer contg. (a) a compd. having an addition polymerizable ethylenically unsatd. bond, (b) a photopolymn. initiator system and (c) a binder is imagewise exposed with a fixed quantity of light from a laser exposure system, developed and exposed all over the surface with at least 100 times as much light at the above light.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for making a photopolymerizable lithographic printing plate. In particular, the present invention relates to a plate making method for a photopolymerizable lithographic printing plate in which image exposure is performed using a laser beam such as Ar ⁺ or YAG-SHG.

[0002]

2. Description of the Related Art Negative type lithographic printing plates have been widely known, and various types of photosensitive layers such as a diazo resin-containing type, a photopolymerization type, and a photocrosslinking type are used for such a negative type lithographic printing plate. ing. In order to prepare such a lithographic printing plate, it is common to place a transparent negative film original (lith film) on these lithographic printing plates and expose the image using ultraviolet rays. It took time and effort. In recent years, with the development of image forming technology, a photopolymer having high photosensitivity to light in the visible region has been demanded. It is a photosensitive material suitable for, for example, non-contact type projection exposure plate making or visible light laser plate making, and a photopolymerization system has the highest sensitivity. As the visible light laser, 48 of Ar laser is used.
8, 514.5 nm light, second harmonic light of semiconductor laser (SHG-LD, 350 to 600 nm), SHG-YA
532 nm light of a G laser or the like is used. Therefore, by using a kind of high-sensitivity photopolymerizable photosensitive layer in the photosensitive layer, a laser beam with a narrow beam is scanned over the plate surface, and character documents, image documents, etc. are formed directly on the plate surface, Plate making can be performed directly without using a manuscript. For example, JP-B-61-9621 and JP-A-63-17810.
No. 5, JP-A-2-244050, etc., it is possible to directly make a plate without using a film original. However, conventional photopolymerizable printing plates have insufficient curing, and when used for high-volume printing at high speeds, solid images may be missing, thin lines or highlights may be thinned, or flying may occur. . If the intensity of the laser beam is increased to obtain a sufficient degree of curing, a phenomenon called flare occurs and the image becomes unclear. This is presumably because the increase in the intensity of the laser light causes scattering of the laser light due to dust or the like in the air. Therefore, development of a photopolymerizable lithographic printing plate or a plate making method capable of performing clear image exposure and obtaining a sufficient degree of curing has been desired.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a method for making a photopolymerizable printing plate which can obtain a clear image without causing flare or the like and has high printing durability in laser direct plate making. It is to provide.

[0004]

Means for Solving the Problems In order to achieve the above object, the present inventors have conducted intensive studies and as a result, have been able to obtain a clear image by producing a photopolymerizable lithographic printing plate by the following plate making method. It has been found that a photopolymerizable lithographic printing plate which can be obtained and has high printing durability can be obtained. That is, (a) a compound having an addition-polymerizable ethylenically unsaturated bond, (b)
A photopolymerization initiator system, and (c) image-exposing a photopolymerizable lithographic printing plate having a photosensitive layer containing a binder at a constant exposure amount with a laser exposure device, and after performing development, at least the image exposure amount The above object is achieved by a plate-making method for a photopolymerizable lithographic printing plate, wherein the entire surface is exposed at an exposure amount of 100 times. According to the method of the present invention, when a photopolymerizable lithographic printing plate is image-exposed by a laser exposure apparatus, the exposure can be performed with a low exposure amount, and a clear image can be obtained by preventing a decrease in resolution due to scattering of flare and the like. . Next, the lithographic printing plate thus obtained is developed to remove non-image portions, and then the image exposure amount is at least 10%.
By performing the entire surface exposure with the exposure amount of 0 times, it is possible to increase the degree of curing of the image area, which was insufficient with the image exposure amount. By such a plate making method, a clear image can be obtained and a photopolymerizable lithographic printing plate having high printing durability can be obtained. Further, by further heating during the entire surface exposure after the development, a photopolymerizable lithographic printing plate having higher printing durability can be obtained, which is preferable.

[0005]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The method of the present invention will be described below in detail. On a support, (a) a compound having an addition-polymerizable ethylenically unsaturated bond, (b) a photopolymerization initiator system, and
(c) Providing a photosensitive layer containing a binder, performing image exposure with a constant exposure amount by a laser exposure device, and performing development,
Post-treatment such as desensitization treatment is optionally performed. Photopolymerizable lithographic printing with a surprisingly clear image and high press life by performing a full exposure with an exposure of at least 100 times the image exposure after or before the post-processing. I was able to get a version.

As the light source for the entire surface exposure, for example, a carbon arc lamp, a mercury lamp, a metal halide lamp, a xenon lamp, a tungsten lamp, various laser beams and the like can be mentioned. The ratio of the exposure amount during image exposure before development to the exposure amount during overall exposure is at least 1: 100, and more preferably 1: 500. Furthermore, in order to obtain sufficient printing durability, the overall exposure amount should be at least 100 mJ /
cm ² or more, more preferably 150 mJ / cm ² or more, further preferably 200 mJ / cm ² or more. Heating may be performed at the same time as the entire surface exposure, and further improvement in printing durability is recognized by heating. As a heating device, a conventional convection oven, IR irradiation device,
Examples include an IR laser, a microwave device, and a Wisconsin oven. At this time, the plate surface temperature is 30 ° C
To 150 ° C., more preferably 3 ° C.
5 to 130 ° C, more preferably 40 to 120 ° C
It is.

The light source at the time of image exposure is an electromagnetic wave that is active with respect to the photopolymerization initiation system. Specifically, the light source has a wavelength in the visible region or the ultraviolet to visible region, that is, a light source having a wavelength of 3.
A light source that emits ultraviolet-visible light in the range of 10 to 700 nm, more preferably 350 to 550 nm, is used. For example, argon laser light, FD-YAG laser light, and helium-neon laser light can be given. The exposure amount at the time of image exposure can be appropriately selected and used depending on the components of the photopolymerizable composition to be used, other conditions, and the like, in a range that gives high resolution without causing flare. Suitable image exposure amount is ^{0.01mJ / cm 2 ~1mJ / cm 2} , more preferably from ^{0.02mJ / cm 2 ~0.5mJ / cm 2} .

Among the components contained in the photosensitive layer of the photopolymerizable lithographic printing plate, the compound (a) having an addition-polymerizable ethylenically unsaturated bond, preferably has at least one terminal ethylenically unsaturated bond, preferably Can be arbitrarily selected from compounds having two or more. For example, monomers,
Prepolymers, that is, those having chemical forms such as dimers, trimers and oligomers, or mixtures thereof and copolymers thereof. Examples of monomers and their copolymers include esters of unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) with aliphatic polyhydric alcohol compounds, unsaturated esters Examples include amides of a carboxylic acid and an aliphatic polyamine compound.

Specific examples of the ester monomer of the aliphatic polyhydric alcohol compound and the unsaturated carboxylic acid include acrylates such as ethylene glycol diacrylate, triethylene glycol diacrylate, and 1,3.
-Butanediol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, sorbitol Triacry Over DOO, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer.

Examples of the methacrylate include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, and 1,3-butanediol. Dimethacrylate, hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate , Bis [p- (3--methacryloxy-2-hydroxypropoxy) phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane. Examples of itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, and pentaerythritol diitaconate. And sorbitol tetritaconate.

The crotonates include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate,
Sorbitol tetradicrotonate and the like. Examples of the isocrotonic acid ester include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate. The maleic acid ester includes ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, sorbitol tetramaleate and the like. Furthermore, a mixture of the above-mentioned ester monomers can also be mentioned.

Specific examples of the amide monomer of an aliphatic polyamine compound and an unsaturated carboxylic acid include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6- Hexamethylene bis-methacrylamide,
Examples include diethylenetriaminetrisacrylamide, xylylenebisacrylamide, xylylenebismethacrylamide, and the like. Another example is JP-B-48-417.
08 polyisocyanate compound having two or more isocyanate groups in one molecule described in
A vinyl urethane compound containing two or more polymerizable vinyl groups in one molecule to which a hydroxyl group-containing vinyl monomer represented by the following general formula is added is exemplified. ^{_{CH 2 = C (Q 1)}} COOCH 2 CH (Q 2) OH ( provided that, Q ¹ and Q ² represents H or CH _3, independently.)

Also, urethane acrylates described in JP-A-51-37193,
64183, JP-B-49-43191, JP-B-52
And polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates obtained by reacting an epoxy resin with (meth) acrylic acid as described in JP-A-30490. Furthermore, the Japan Adhesion Association magazine, Vo 1.20, No. 7, 300-308
Those introduced as photocurable monomers and oligomers on page (1984) can also be used. In addition, the amount of these used is 5-70 with respect to all components.
% By weight (hereinafter abbreviated as%), preferably 10 to 50%
%.

As the component (b) photopolymerization initiator system, various photoinitiators known in patents and literatures, or a combination system of two or more photoinitiators (photoinitiation, depending on the wavelength of the light source used) System) can be appropriately selected and used. For example, when light near 400 nm is used as a light source, benzyl, benzoin ether, Michler's ketone, anthraquinone, thioxanthone, acridine, phenazine, benzophenone, and the like are widely used. Also, 400n
Various light-initiating systems have also been proposed when using visible light of m or more, an Ar laser, a second harmonic of a semiconductor laser, or a SHG-YAG laser as a light source. For example, US Pat. No. 2,850,445. A certain photoreducible dyes, such as rose bengal, eosin, erythrosine, etc., or a combination of a dye and an initiator,
For example, a complex initiation system of a dye and an amine (JP-B-44-20)
No. 189), a combination system of hexaarylbiimidazole, a radical generator and a dye (JP-B-45-37377).
No.), a system of hexaarylbiimidazole and p-dialkylaminobenzylidene ketone (JP-B-47-2528).
JP-A-54-155292), a system of a cyclic cis-α-dicarbonyl compound and a dye (JP-A-48-84183).
), A system of cyclic triazine and a merocyanine dye (Japanese Patent Application Laid-Open No. 54-115024), a system of 3-ketocoumarin and an activator (Japanese Patent Application Laid-Open Nos. 52-112681 and 58-155).
No. 03), a system of biimidazole, a styrene derivative and a thiol (JP-A-59-140203), and a system of an organic peroxide and a dye (JP-A-59-1504, JP-A-59-14).
No. 0203, JP-A-59-189340, JP-A-62
174203, JP-B-62-1641, U.S. Pat. No. 4,766,055), a system of a dye and an active halogen compound (JP-A-63-178105, JP-A-63-2589).
No. 03, JP-A-2-63054 and the like, and a system of a dye and a borate compound (JP-A-62-143044, JP-A-6-14304).
2-150242, JP-A-64-13140, JP-A-64-13141, JP-A-64-13142, JP-A-64-13143, JP-A-64-13144,
JP-A-64-17048, JP-A-1-229003
JP-A-1-298348, JP-A-1-13820
No. 4, etc.) and a system of a dye having a rhodanine ring and a radical generator (JP-A-2-179463, JP-A-2-244)
No. 050), a system of titanocene and a 3-ketocoumarin dye (JP-A-63-221110), a system of a combination of titanocene and a xanthene dye, and an addition-polymerizable ethylenically unsaturated compound containing an amino group or a urethane group (JP-A-Hei. JP-A-4-221958, JP-A-4-219756
), A system of titanocene and a specific merocyanine dye (JP-A-6-295061), and a system of titanocene and a dye having a benzopyran ring (Japanese Patent Application No. 7-164585).

The preferred photopolymerization initiator system is a photopolymerization initiator system containing at least one compound selected from the group consisting of a trihalomethyltriazine compound and a titanocene compound, and a photopolymerization initiator system represented by the following general formulas (I) and (II). Examples include photopolymerization initiator systems containing at least one compound selected from the group consisting of the compounds shown. More preferred photopolymerization initiator systems include a trihalomethyltriazine compound and / or a titanocene compound and a compound represented by the general formula (I) or (I
And those containing a combination with the dye shown in I). Further, as a sensitizer, the following formula (A),
It may contain the compounds (B) and (C). Examples of the trihalomethyltriazine compound include compounds represented by the following general formula (II
Compounds represented by I) can be mentioned.

[0016]

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(In the formula, Hal represents a halogen atom.
R ¹⁹ is _{-C (Hal) 3, -NH 2} , -NHR 21, -NR 21 2, represent -OR ^21. Here, R ²¹ represents an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group. R ²⁰ is -C (Hal)
_{3 represents} an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, or a substituted alkenyl group. ). Specifically, Wakabayashi et al., Bull. Chem. Soc. Jap
an, 42 , 2924 (1969), for example, 2-phenyl 4,6-bis (trichloromethyl)-
S-triazine, 2- (p-chlorophenyl) -4,6
-Bis (trichloromethyl) -S-triazine, 2-
(P-tolyl) -4,6-bis (trichloromethyl)-
S-triazine, 2- (p-methoxyphenyl) -4,
6-bis (trichloromethyl) -S-triazine, 2-
(2 ', 4'-dichlorophenyl) -4,6-bis (trichloromethyl) -S-triazine, 2,4,6-tris (trichloromethyl) -S-triazine, 2-methyl-4,6- Bis (trichloromethyl) -S-triazine, 2-n-nonyl-4,6-bis (trichloromethyl) -S-triazine, 2- (α, α, β-trichloroethyl) -4,6-bis (trichlor Methyl) -S-triazine and the like. In addition, British Patent No. 1388
No. 492, for example, 2-styryl-4,6-bis (trichloromethyl) -S-triazine, 2- (p-methylstyryl) -4,6-bis (trichloromethyl) -S-triazine , 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -S-
Compounds described in JP-A-53-133428, such as triazine and 2- (p-methoxystyryl) -4-amino-6-trichloromethyl-S-triazine;
(4-methoxy-naphth-1-yl) -4,6-bis-
Trichloromethyl-S-triazine, 2- (4-ethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2- [4- (2-ethoxyethyl) -naphth-1- Yl] -4,6-bis-trichloromethyl-S-triazine, 2- (4,7-dimethoxy-
Naphth-1-yl] -4,6-bis-trichloromethyl-S-triazine, 2- (acenaphth-5-yl)-
4,6-bis-trichloromethyl-S-triazine and the like,
The compounds described in DE 3337024 can be mentioned, for example, the following compounds.

[0018]

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[0019]

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Also, J. Org by FC Schaefer et al.
Chem .; 29, 1527 (1964), for example, 2-methyl-4,6-bis (tribromomethyl)
-S-triazine, 2,4,6-tris (tribromomethyl) -S-triazine, 2,4,6-tris (dibromomethyl) -S-triazine, 2-amino-4-methyl-6-tribromomethyl -S-triazine, 2-methoxy-4-methyl-6-trichloromethyl-S-triazine and the like can be mentioned. Further, JP-A-62-582
The compounds described in No. 41, for example, the following compounds may be mentioned.

[0021]

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[0022]

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Further, compounds described in JP-A-5-281728, for example,

[0024]

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And the like. As the titanocene compound, for example, known compounds described in JP-A-59-152396 and JP-A-61-151197 can be appropriately selected and used.

More specifically, di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-
Ti-bis-2,3,4,5,6-pentafluorophenyl-1-yl, di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl,
Di-cyclopentadienyl-Ti-bis-2,4,6-
Trifluorophenyl-1-yl, di-cyclopentadienyl-Ti-bis-2,6-difluorophenyl-1-yl, di-cyclopentadienyl-Ti-bis-2,4-
Difluorophenyl-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophenyl-1-yl, di-methylcyclopentadienyl-Ti-bis-2 , 3,5,6-tetrafluorophenyl-1-yl, di-methylcyclopentadienyl-T
Examples thereof include i-bis-2,4-difluorophenyl-1-yl, bis (cyclopentadienyl) -bis (2,6-difluoro-3- (pyrid-1-yl) phenyl) titanium and the like.

(B) The compounds represented by the general formula (I) or (II) used in the photopolymerization initiator system are the following compounds.

[0028]

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(Wherein R ¹ and R ² are each independently a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group, an alkoxycarbonyl group, an aryl group, a substituted aryl group A represents an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, an alkyl- or aryl-substituted nitrogen atom, or a dialkyl-substituted carbon atom, and X forms a nitrogen-containing 5-membered heterocyclic ring. Y represents a substituted phenyl group,
Represents an unsubstituted or substituted polynuclear aromatic ring, or an unsubstituted or substituted heteroaromatic ring. Z represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an aralkyl group, an alkoxy group, an alkylthio group, an arylthio group, a substituted amino group, an acyl group, or an alkoxycarbonyl group; To form a ring. )

[0030]

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(Wherein, R ^{3 to} R ⁶ are each independently
Represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a hydroxyl group, an alkoxy group or an amino group. Also, R ³
To R ⁶ may form a ring composed of a non-metallic atom together with the carbon atoms to which they can be attached. R ⁷ represents a hydrogen atom, an alkyl group, an aryl group, a heteroaromatic group, a cyano group, an alkoxy group, a carboxy group or an alkenyl group. R ⁸ is a group represented by R ⁷ or —ER ⁷ , and E represents a carbonyl group, a sulfonyl group, a sulfinyl group, or an arylenedicarbonyl group. R ⁷ and R ⁸ may together form a ring composed of a nonmetallic atom.
B ₁ represents O, S, NH or a nitrogen atom having a substituent. B ₂ is a group

[0032]

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And G ₁ and G ₂ may be the same or different and include a hydrogen atom, a cyano group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, an arylcarbonyl group, an alkylthio group, an arylthio group, an alkylsulfonyl group. Group, arylsulfonyl group or fluorosulfonyl group. However, G ₁ and G ₂ are not simultaneously hydrogen atoms. G ₁ and G ₂ may form a ring composed of a non-metal atom together with a carbon atom. Examples of the compound represented by formula (I) or (II) include JP-A-8-129257 and JP-A-8-33.
And the compounds described in JP-A-4897. Examples of the compound represented by the general formula (I) include a compound represented by the following chemical formula.

[0034]

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Preferred specific examples of R ¹ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group,
Hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, octadecyl, tridecyl, hexadecyl, octadecyl, eicosyl, isopropyl, isobutyl, s- Butyl group, t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, allyl group, 1-
Propenylmethyl group, 2-butenyl group, 2-methylallyl group, 2-methylpropenyl group, 2-propynyl group, 2
-Butynyl group, 3-butynyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-methyl-1-phenethyl group, p-methylbenzyl group, cinnamyl group, hydroxyethyl group, methoxyethyl group, phenoxyethyl group , Allyloxyethyl group, methoxyethoxyethyl group,
Ethoxyethoxyethyl, morpholinoethyl, morpholinopropyl, sulfopropyl, sulfonatopropyl, sulfobutyl, sulfonatobutyl, carboxymethyl, carboxyethyl, carboxypropyl, methoxycarbonylethyl, 2-ethylhexyl Oxycarbonylethyl group, phenoxycarbonylmethyl group, methoxycarbonylpropyl group, N-methylcarbamoylethyl group, N, N-ethylaminocarbamoylmethyl group, N-phenylcarbamoylpropyl group, N-tolylsulfamoylbutyl group, p- Toluenesulfonylaminopropyl group, benzoylaminohexyl group, phosphonomethyl group, phosphonoethyl group, phosphonopropyl group, p-phosphonobenzylaminocarbonylethyl group, phosphana Methyl group, phosphonium Juana preparative propyl, phosphate Juana preparative butyl group, and a p- phosphate Juana preparative -benzylaminocarbonyl ethyl group.

Next, the above R^TwoIs shown below. R^TwoIs-
R^{twenty three}-C (R^{twenty four}) = C (R^{twenty five}) (R ²⁶), And -R
²⁷-C≡CR²⁸A substituted or unsubstituted alkene represented by
Nilalkyl group, alkynylalkyl group, alkenyl
Or an alkynyl group. Where R^{twenty three}And
R²⁷Is a covalent bond or a straight chain having 1 to 20 carbon atoms.
Represents a chain, branched or cyclic alkylene group,
Preferably a covalent bond or one having from 1 to 6 carbon atoms
Linear, branched having 2 to 8 carbon atoms, and carbon
Represents a cyclic alkylene group having 5 to 10 atoms.
R^{twenty four}, R^{twenty five}, R²⁶, R ²⁸As a hydrogen atom, a halogen
Atoms, alkyl groups, substituted alkyl groups, aryl groups and
Represents a substituted aryl group. R^{twenty four}, R^{twenty five}, R²⁶, R²⁸No
More preferred substituents include a hydrogen atom and a halogen atom.
Linear, branched, cyclic with 1 to 10 carbon atoms
Can be mentioned. R^TwoPreferred tool
Examples of the body include an allyl group, a 2-butenyl group, and a 3-butenyl group.
Group, 2-pentenyl group, 3-pentenyl group, 4-pen
Thenyl group, 5-hexenyl group, 2-octenyl group, 7-
Octenyl group, 1-methylpropenyl group, 1,1-dimethyl
Tylpropenyl group, 2-methylpropenyl group, 2-ethyl
Lupropenyl group, 3,3-dimethylpropenyl group, 2-
Cyclohexenyl group, geranyl group (7,7,3,3-
Tramethyl-2,6-heptadienyl group), citroneni
(7,7,3-trimethyl-5-heptenyl group),
2-chloro-2-propenyl group, 3-chloro-2-pro
Phenyl group, 2-propynyl group, 2-butynyl group, 3-bu
Tinyl group, 4-pentynyl group, 1,1-dimethylpropyl
Nyl group, 1,1-diethylpropynyl group, 4,4-dimethyl
A tyl-2-butynyl group, a vinyl group, a chloroethynyl group,
1-propenyl group, 1-butenyl group, styryl group, ethyl
And a 2-phenylethynyl group.
You. R^TwoThe most preferred examples of
Lopinyl group, vinyl group, ethynyl group
You. Then R⁹, R^Ten, R¹¹And R¹²Preferred specific examples of
It is shown below.

[0037]

[Table 1]

[0038]

[Table 2]

[0039]

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Next, R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R
Preferred examples of ¹⁸ are shown below.

[0041]

[Table 3]

[0042]

[Table 4]

[0043]

[Table 5]

The partial skeleton (a) represented by the above (a-1) to (a-65) and the partial skeleton (b) represented by the above (b-1) to (b-72) are combined in a permutation to form a general Formula (I)
(R ¹ and R ^1)
2 can be arbitrarily selected from the groups described above. ).
Preferred specific examples of the compound represented by formula (I) are shown below.

[0045]

[Table 6]

[0046]

[Table 7]

[0047]

[Table 8]

[0048]

[Table 9]

[0049]

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The compounds represented by the general formula (II) include the following compounds.

[0051]

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[0052]

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[0053]

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[0054]

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[0055]

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[0056]

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[0057]

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[0058]

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[0059]

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[0060]

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[0061]

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Specific examples of the compounds of the formulas (A), (B) and (C) include the following compounds.

[0063]

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Here, Ar ¹ represents an aromatic group selected from one of the following general formulas, R ³⁰ and R ³¹ represent a hydrogen atom or an alkyl group, and R ³⁰ and R ³¹ are bonded to each other. May represent an alkylene group.

[0065]

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In the formula, R ^{32 to} R ³⁶ may be the same or different, and each represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, a substituted aryl group, a hydroxyl group, an alkoxy group, a —S- R ³⁹ groups, -SO-R
³⁹ groups represent a -SO ₂ -R ³⁹ group, provided that at least one represents an -S-R ³⁹ group or -SO-R ³⁹ group (R ³⁹ represents an alkyl or alkenyl group of R ³² to R ³⁶ Represent). R ³⁷
Represents a hydrogen atom, an alkyl group or an acyl group.

[0067]

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A ketoxime compound represented by the following general formula (B).

[0069]

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In the formula, R ⁴⁰ and R ⁴¹ are the same or different and represent a hydrocarbon group which may have a substituent or may contain an unsaturated bond, or a heterocyclic group. R ⁴² and R ⁴³ are the same or different and are a hydrogen atom, a hydrocarbon group which may have a substituent or may contain an unsaturated bond, a heterocyclic group, a hydroxyl group, a substituted oxy group, a mercapto group, a substituted Represents a thio group. Also, R ^42, R ⁴³ are bonded to each other to form a ^{ring, -0 -, - NR 44 -} , -O-CO-, -NH-CO -, - S-
And / or an alkylene group having 2 to 8 carbon atoms which may contain -SO ₂ -in the connecting main chain of the ring. R ⁴⁴ , R ⁴⁵
Represents a hydrogen atom, a hydrocarbon group which may have a substituent and may contain an unsaturated bond, or a substituted carbonyl group. A compound represented by the following general formula (C).

[0071]

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In the formula, R ^{50 to} R ⁵³ represent an alkyl group or an aryl group, and Ar ² represents an aryl group. Also R ⁵⁰ and R
⁵¹ or R ⁵² and R ⁵³ may be bonded to each other to form a ring. z represents a hydrocarbon-containing linking group which may have a divalent substituent.

[0073]

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2 containing at least one group represented by
Represents a valent linking group or a single bond. Here, R ⁵⁴ represents a hydrogen atom, a hydrocarbon group which may have a substituent or may contain an unsaturated bond, a carbonyl group or a sulfonyl group. R ^{54 to} R ⁵⁷ are the same or different from each other, and represent a hydrocarbon group which may have a substituent and may contain an unsaturated bond. T ⁻ represents a monovalent anion composed of a halogen atom or a monovalent sulfonate anion. x is
It is a group having an addition polymerizable group represented by the following formula.

[0075]

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And r ^{1 to} r ³ are the same or different from each other and represent a hydrogen atom, a methyl group, an ethyl group, a phenyl group, a halogen atom, a cyano group or —C (＝ O) —OR ⁵⁸ . n represents 0 or 1. However, when n is 0, r ^{1 to} r ³
Not all are hydrogen atoms. r ⁴ and r ⁵ are the same or different and represent a hydrogen atom, a methyl group, an ethyl group or a phenyl group. R ⁵⁸ represents an alkyl group or an aryl group.

Next, the ketone compound represented by formula (A) will be described in more detail. In the general formula (A), R ³⁰ and R ³¹ represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R ³⁰ and R ³¹ may combine to represent an alkylene group. R ^{32 to} R ³⁶ independently of each other,
Hydrogen atom, halogen atom, alkyl group having 1 to 12 carbon atoms, alkenyl group having 3 to 12 carbon atoms, aryl group, alkoxy group having 1 to 12 carbon atoms, hydroxyl group, -S
It represents -R ³⁹ group, -SO-R ³⁹ group, a -SO ₂ -R ³⁹ group,
R ³⁹ represents an alkyl group or an alkenyl group; R ³⁷ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an acyl group having 2 to 13 carbon atoms. These alkyl group, aryl group, alkenyl group, and acyl group may be further substituted with a substituent having 1 to 6 carbon atoms. Specific examples include the following compounds described in U.S. Pat. No. 4,318,791 and European Patent No. 0284561A.

[0078]

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[0079]

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[0080]

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Next, the ketoxime compound represented by the formula (B) will be described in more detail. In the general formula (B), R ⁴⁰ and R ⁴¹ are the same or different and represent a hydrocarbon group which may have a substituent and may contain an unsaturated bond, or a heterocyclic group. R ⁴² and R ⁴³ are the same or different and are a hydrogen atom, a hydrocarbon group which may have a substituent or may contain an unsaturated bond, a heterocyclic group, a hydroxyl group, a substituted oxy group, a mercapto group, a substituted Represents a thio group. R ⁴² and R ⁴³ are bonded to each other to form a ring, and —0—, —NR ⁴⁴ —, —O—CO—, —NH—CO—, —S—, and / or
Alternatively, it represents an alkylene group having 2 to 8 carbon atoms which may contain -SO ₂ -in the connecting main chain of the ring. R ⁴⁴ and R ⁴⁵ represent a hydrogen atom, a hydrocarbon group which may have a substituent or may contain an unsaturated bond, or a substituted carbonyl group. More specific compounds include the following, but are not limited thereto.

[0082]

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[0083]

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[0084]

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[0085]

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[0086]

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Next, the oxime ether compound represented by the formula (C) will be described in detail. R ⁵⁰ in general formula (C)
Examples of the alkyl group or the aryl group for R ⁵³ include the following groups. Examples of the alkyl group include a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. Group,
Hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, octadecyl, eicosyl, isopropyl, isobutyl, s-butyl, t-butyl,
Isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group,
And a 2-norbornyl group. Among these, straight-chain having 1 to 12 carbon atoms, branched having 3 to 12 carbon atoms, and 5 to 1 carbon atoms
Up to zero cyclic alkyl groups are more preferred.

These alkyl groups are substituted with an alkylene
A substituted alkyl group may be formed by bonding to the group. Substituent
As the monovalent non-metallic atomic group except hydrogen is used,
Preferred examples include a halogen atom (-F, -Br,-
Cl, -I), hydroxyl group, alkoxy group, aryl
Roxy, mercapto, alkylthio, arylthio
O group, alkyldithio group, aryldithio group, amino
Group, N-alkylamino group, N, N-dialkylamino
Group, N-arylamino group, N, N-diarylamino
Group, N-alkyl-N-arylamino group, acyloxy
Si group, carbamoyloxy group, N-alkylcarbamoy
Roxy group, N-arylcarbamoyloxy group, N,
N-dialkylcarbamoyloxy group, N, N-diali
Carbamoyloxy group, N-alkyl-N-ary
Rucarbamoyloxy group, alkylsulfoxy group, ant
Sulfoxy group, acylthio group, acylamino group, N
-Alkylacylamino group, N-arylacylamino
Group, ureido group, N'-alkylureido group, N ',
N'-dialkyl ureide group, N'-aryl ureide
Group, N ', N'-diarylureido group, N'-alkyl
Ru-N'-arylureido group, N-alkylureido
Group, N-arylureido group, N'-alkyl-NA
Alkylureido group, N'-alkyl-N-aryluree
Id group, N ', N'-dialkyl-N-alkyl urea
Group, N ', N'-dialkyl-N-arylureido
Group, N'-aryl-N-alkylureido group, N'-
Aryl-N-arylureido group, N ', N'-dia
Reel-N-alkylureido group, N ', N'-diali
Ole-N-arylureido group, N'-alkyl-N '
-Aryl-N-alkylureido groups, N'-alkyl
-N'-aryl-N-arylureido group, alkoxy
Cicarbonylamino group, aryloxycarbonylamino
Group, N-alkyl-N-alkoxycarbonylamino
Group, N-alkyl-N-aryloxycarbonylamino
Group, N-aryl-N-alkoxycarbonylamino
Group, N-aryl-N-aryloxycarbonylamino
Group, formyl group, acyl group, carboxyl group and
Role base group (hereinafter referred to as carboxylate), alkoxy
Cicarbonyl group, aryloxycarbonyl group, carbamo
Yl group, N-alkylcarbamoyl group, N, N-dial
A kill carbamoyl group, an N-aryl carbamoyl group,
N, N-diarylcarbamoyl group, N-alkyl-N
-An arylcarbamoyl group, an alkylsulfinyl group,
Arylsulfinyl group, alkylsulfonyl group, ant
Sulfonyl group, snifo group (—SO_ThreeH) and both
Role base group (hereinafter referred to as fluphonato group), alkoxys
Ruphonyl group, aryloxysulfonyl group, sulfinamo
Yl group, N-alkylsulfinamoyl group, N, N-di
Alkylsulfinamoyl group, N-arylsulfina
Moyl group, N, N-diarylsulfinamoyl group, N
-Alkyl-N-arylsulfinamoyl group, sulf
Amoyl group, N-alkylsulfamoyl group, N, N-
Dialkylsulfamoyl group, N-arylsulfamo
Yl group, N, N-diarylsulfamoyl group, N-A
Alkyl-N-arylsulfamoyl group, N-acyls
Rufamoyl group and its conjugate base group, N-alkylsulfur
Honylsulfamoyl group (-SO_TwoNHSO_Two(alky
l)) and its conjugated base group, N-arylsulfonyls
Rufamoyl group (-SO_TwoNHSO_Two(Aryl)) and
And its conjugate base group, N-alkylsulfonylcarbamoy
Group (-CONHSO_Two(alkyl)) and conjugate salts thereof
Group, N-arylsulfonylcarbamoyl group (—CO
NHSO_Two(aryl)) and its conjugated base group, alkoxy
Silicyl group (-Si (Oalkyl)_Three), Ally Loki
Silicyl group (-Si (Oaryl)_Three), Hydroxy
Ryl group (-Si (OH)_Three) And its conjugate base group, phospho
No group (-PO_ThreeH_Two) And its conjugated base group (hereinafter referred to as phospho
A dialkylphosphono group (-PO)._Three(al
kyl)_Two), A diarylphosphono group (—PO_Three(ary
l)_Two), An alkylarylphosphono group (—PO_Three(alk
yl) (aryl)), monoalkylphosphono group (-PO
_ThreeH (alkyl)) and its conjugated base group (hereinafter referred to as
A monoarylphosphono group)
(-PO_ThreeH (aryl)) and its conjugated base group (hereinafter
Later called arylphosphonato group), phosphonooxy group
(-OPO_ThreeH_Two) And its conjugated base group (hereinafter referred to as phospho-
Natoxy group), dialkylphosphonooxy group
(-OPO_Three(alkyl)_Two), Diarylphosphonooxy
Group (-OPO_Three(aryl)_Two), Alkyl aryl phos
Honoxy group (-OPO_Three(alkyl) (aryl),
Monoalkylphosphonooxy group (-OPO_ThreeH (alk
yl)) and its conjugated base group (hereinafter referred to as alkyl phosphona
Tooxy group), monoarylphosphonooxy group
(-OPO_ThreeH (aryl)) and its conjugated base group (hereinafter
Hereinafter referred to as an arylphosphonatooxy group), a cyano group,
Nitro, aryl, alkenyl, alkynyl groups
can give.

In these substituents, specific examples of the alkyl group include the aforementioned alkyl groups, and specific examples of the aryl group include phenyl, biphenyl, naphthyl, tolyl, xylyl, and mesityl groups. , Cumenyl group, fluorophenyl group, chlorophenyl group, bromophenyl group, chloromethylphenyl group, hydroxyphenyl group, methoxyphenyl group, ethoxyphenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, Phenylthiophenyl group, methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, phenoxycarbonylphenyl group, N-phenylca Ba carbamoylphenyl group, a phenyl group, nitrophenyl group, cyanophenyl group, sulfophenyl group, sulfonatophenyl group, phosphonophenyl group,
And a phosphonatophenyl group. Examples of the alkenyl group include vinyl, 1-propenyl, 1-butenyl, cinnamyl, 2-chloro-
Examples thereof include a 1-ethenyl group and the like, and examples of the alkynyl group include an ethynyl group, a 1-propynyl group, a 1-butynyl group, a trimethylsilylethynyl group, and a phenylethynyl group. Examples of the acyl group (R ⁶⁰ CO—) include a hydrogen atom for R ⁶⁰ and the above-mentioned alkyl group, aryl group, alkenyl group, and alkynyl group.

On the other hand, the alkylene group in the substituted alkyl group may be a divalent organic residue obtained by removing any one of the aforementioned hydrogen atoms on the alkyl group having 1 to 20 carbon atoms. And preferably a linear alkylene group having 1 to 12 carbon atoms, a branched alkylene group having 3 to 12 carbon atoms and a cyclic alkylene group having 5 to 10 carbon atoms. Specific examples of preferred substituted alkyl groups include a chloromethyl group, a bromomethyl group,
-Chloroethyl group, trifluoromethyl group, methoxymethyl group, methoxyethoxyethyl group, allyloxymethyl group, phenoxymethyl group, methylthiomethyl group, tolylthiomethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyl Oxymethyl group, benzoyloxymethyl group, N-cyclohexylcarbamoyloxyethyl group, N-phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-
Methylbenzoylaminopropyl group, 2-oxoethyl group, 2-oxopropyl group, carboxypropyl group, methoxycarbonylethyl group, methoxycarbonylmethyl group, methoxycarbonylbutyl group, ethoxycarbonylmethyl group, butoxycarbonylmethyl group, allyloxycarbonylmethyl Group, benzyloxycarbonylmethyl group, methoxycarbonylphenylmethyl group, trichloromethylcarbonylmethyl group, allyloxycarbonylbutyl group, chlorophenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl group,
N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, N-methyl-N
-(Sulfophenyl) carbamoylmethyl group, sulfopropyl group, sulfobutyl group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N-dipropylsulfamoylpropyl group, N
-Tolylsulfamoylpropyl group, N-methyl-N-
(Phosphonophenyl) sulfamoyloctyl group,

[0091]

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Phosphonobutyl, phosphonatohexyl, diethylphosphonobutyl, diphenylphosphonopropyl, methylphosphonobutyl, methylphosphonatobutyl, tolylphosphonohexyl, tolylphosphonatohexyl, phosphonooxy Propyl group, phosphonatoxybutyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-methyl-1-phenylethyl group, p
-Methylbenzyl group, cinnamyl group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2-methylallyl group, 2-methylpropenylmethyl group, 2-propynyl group, 2-butynyl group, 3-butynyl group, etc. Can be given. Examples of the aryl group include those in which one to three benzene rings form a condensed ring, and those in which a benzene ring and a 5-membered unsaturated ring form a condensed ring. Specific examples thereof include a phenyl group and naphthyl. Group, anthryl group, phenanthryl group, indenyl group, acenaphthenyl group, fluorenyl group, among these,
A phenyl group and a naphthyl group are more preferred.

These aryl groups can form a substituted aryl group in which a substituent is bonded to an aryl group. As the substituted aryl group, those having a monovalent nonmetallic atomic group other than hydrogen as a substituent on the ring-forming carbon atom of the aforementioned aryl group are used. Preferred examples of the substituent include the aforementioned alkyl group, substituted alkyl group, and those described above as the substituent for the substituted alkyl group. Preferred specific examples of these substituted aryl groups include biphenyl, tolyl, xylyl, mesityl, cumenyl, chlorophenyl, bromophenyl, fluorophenyl, chloromethylphenyl, trifluoromethylphenyl, Hydroxyphenyl group,
Methoxyphenyl group, methoxyethoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, methylthiophenyl group, tolylthiophenyl group, phenylthiophenyl group, ethylaminophenyl group, diethylaminophenyl group, morpholinophenyl group, acetyloxyphenyl group, Benzoyloxyphenyl, N-cyclohexylcarbamoyloxyphenyl, N-phenylcarbamoyloxyphenyl, acetylaminophenyl, N-methylbenzoylaminophenyl, carboxyphenyl, methoxycarbonylphenyl, allyloxycarbonylphenyl, chloro Phenoxycarbonylphenyl group, carbamoylphenyl group, N-methylcarbamoylphenyl group, N, N-dipropylcarbamoylphenyl group, -(Methoxyphenyl) carbamoylphenyl group, N-methyl-N- (sulfophenyl) carbamoylphenyl group, sulfophenyl group, sulfonatophenyl group, sulfamoylphenyl group, N-ethylsulfamoylphenyl group, N, N -Dipropylsulfamoylphenyl group, N-tolylsulfamoylphenyl group, N-methyl-N- (phosphonophenyl) sulfamoylphenyl group, phosphonophenyl group, phosphonatophenyl group, diethylphosphonophenyl group, Diphenylphosphonophenyl group, methylphosphonophenyl group, methylphosphonatophenyl group, tolylphosphonophenyl group, tolylphosphonatophenyl group, allylphenyl group, 1-propenylmethylphenyl group, 2-butynylphenyl group, 2
-Methylallylphenyl group, 2-methylpropenylphenyl group, 2-propynylphenyl group, 2-butynylphenyl group, 3-butynylphenyl group, and the like.

Next, the case where R ⁵⁰ and R ⁵¹ are bonded to each other to form a ring will be described. The ring in which R ⁵⁰ and R ⁵¹ are bonded to each other is -O-, -OC (= O)-, -S
Examples thereof include an alkylene group having 2 to 8 carbon atoms which may contain-, -NH-C (= O)-in the connecting main chain. Then R ⁵²
And a case where R ⁵³ is bonded to each other to form a ring. The ring in which R ⁵² and R ⁵³ are bonded to each other is-
Examples thereof include an alkylene group having 2 to 8 carbon atoms which may contain OC (= O)-, -S-, -NH-C (= O)-in the connecting main chain. Next, Ar ² in the general formula (C) will be described. Aryl group represented by Ar ² has the same meaning as those described in R ⁵⁰ to R ^53, may constitute a same substituted aryl group as R ⁵⁰ to R ^53. Next, z in the general formula (C) will be described in detail. Examples of the hydrocarbon-containing linking group which may have a divalent substituent at z in the general formula (C) include a divalent link in which one hydrogen is removed from either carbon of an alkyl group or an aryl group. Group. These alkyl groups or aryl groups have the same meanings as those described above for R ^{50 to} R ⁵³ and can form a substituted alkyl group or a substituted aryl group. Next, y will be described in detail. Examples of the divalent linking group for y include a divalent linking group obtained by removing one hydrogen from carbon on either an alkyl group or an aryl group.
Here, the alkyl group, the aryl group is the same meaning as that indicated by R ⁵⁰ to R ⁵³ described above.

Next, R ^{54 to} R ^{57 in} y will be described in detail.
Examples of the hydrocarbon group which may have a substituent of R ^{54 to} R ⁵⁷ and may contain an unsaturated bond include an alkyl group, an aryl group, an alkenyl group and an alkynyl group. Here, the alkyl group, the aryl group, the alkenyl group, and the alkynyl group have the same meanings as those described above for R ^{50 to} R ⁵³ . Further, in a substituted alkenyl group in which a substituent replaces and is bonded to a hydrogen atom of an alkenyl group, as the substituent, the substituent in the above-mentioned substituted alkyl group is used,
On the other hand, the above-mentioned alkenyl group can be used as the alkenyl group. Examples of preferred substituted alkenyl groups include

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And the like. In the substituted alkynyl group in which the substituent is replaced by a hydrogen atom of the alkynyl group and bonded, as the substituent, the substituent in the above-mentioned substituted alkyl group is used, while the alkynyl group can be the above-mentioned alkynyl group. Next carbonyl group of R ^54, and the sulfonyl group is described. As the carbonyl group (R ⁶¹ —CO—), those in which R ⁶¹ is a monovalent nonmetallic atomic group can be used. Preferred examples of the carbonyl group include a formyl group, an acyl group, a carboxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an N-alkylcarbamoyl group, an N, N-dialkylcarbamoyl group, an N-arylcarbamoyl group, , N-diarylcarbamoyl group and N-alkyl-N-arylcarbamoyl group. Examples of the alkyl group and the aryl group in these include those described above as the alkyl group and the aryl group. Of these, more preferred substituents include formyl, acyl, carboxyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, N-alkylcarbamoyl, N, N-dialkylcarbamoyl, and N-arylcarbamoyl. And even more preferred are a formyl group, an acyl group, an alkoxycarbonyl group and an aryloxycarbonyl group. Specific examples of preferred substituents include formyl, acetyl, benzoyl, carboxyl, methoxycarbonyl, allyloxycarbonyl, N-methylcarbamoyl, N-phenylcarbamoyl, N, N-diethylcarbamoyl, And a morpholinocarbonyl group.

As the sulfonyl group (R ⁶² -SO _2- ), those in which R ⁶² is a monovalent nonmetallic atomic group can be used. More preferred examples include an alkylsulfonyl group and an arylsulfonyl group. Examples of the alkyl group and the aryl group in these include those described above as the alkyl group and the aryl group. Specific examples of such a sulfonyl group include a butylsulfonyl group and a chlorophenylsulfonyl group. Next, T ^- will be described in detail. Examples of the halogen atom of T ⁻ include F, Cl, Br, and I, and examples of the sulfonate anion include a sulfonato group (—S) in any of the above-described alkyl groups and aryl groups represented by R ^{50 to} R ^56.
O ₃ ⁻ ) is linked. Preferable examples include a methylsulfonic acid anion, a trifluoromethylsulfonic acid anion, a benzenesulfonic acid anion, and a toluenesulfonic acid anion.

Next, x in the general formula (C) will be described in detail. alkyl or aryl group in R ⁵⁸ in the x have the same meanings as those shown in the above R ⁵⁰ to R ^54, may form a substituted alkyl group or a substituted aryl group. Examples of the compound represented by formula (C) are shown below, but are not limited thereto.

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[0101]

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[0102]

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[0103]

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[0104]

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[0105]

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[0106]

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[0107]

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[0108]

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[0109]

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[0110]

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[0111]

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Examples of the binder of the component (c) include an organic high molecular polymer. Examples of such an organic high molecular polymer include an organic polymer having compatibility with a photopolymerizable ethylenically unsaturated compound. Any one may be used as long as it is a high molecular polymer. Preferably, an organic polymer which is soluble or swellable in water or weakly alkaline water, which enables water development or weakly alkaline water development is selected. The organic high molecular weight polymer is used not only as a film forming agent of the composition, but also with water,
It is selected and used depending on the use as a weak alkaline water or organic solvent developer. For example, when a water-soluble organic high molecular polymer is used, water development becomes possible. Examples of such an organic high molecular weight polymer include an addition polymer having a carboxylic acid group in a side chain,
For example, JP-A-59-44615, JP-B-54-343.
No. 27, JP-B-58-12577, JP-B-54-25
957, JP-A-54-92723, JP-A-59-5
No. 3836 and JP-A-59-71048, that is, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer,
There are maleic acid copolymers, partially esterified maleic acid copolymers and the like.

Similarly, there is an acidic cellulose derivative having a carboxylic acid group in a side chain. In addition, those obtained by adding a cyclic acid anhydride to an addition polymer having a hydroxyl group are useful. In particular, among these, [benzyl (meth) acrylate / (meth) acrylic acid / optionally other addition-polymerizable vinyl monomers] copolymer and [allyl (meth) acrylate / (meth) acrylic acid / optionally And other addition-polymerizable vinyl monomers] copolymers.
In addition, polyvinyl pyrrolidone and polyethylene oxide are useful as the water-soluble organic polymer. In order to increase the strength of the cured film, an alcohol-soluble polyamide, a polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are also useful. These organic high-molecular polymers can be mixed in an arbitrary amount in the entire composition. However, when the content exceeds 90% by weight, no favorable result is obtained in view of the strength of the formed image and the like. Preferably 10-90%, more preferably 30%
~ 80%. Further, the weight ratio of the photopolymerizable ethylenically unsaturated compound and the organic polymer is preferably in the range of 1/9 to 9/1. A more preferred range is 2/8 to
8/2, and more preferably 3/7 to 7/3.

In the present invention, in addition to the above basic components, a small amount of thermal polymerization is inhibited in order to prevent unnecessary thermal polymerization of a polymerizable ethylenically unsaturated compound during the production or storage of the photosensitive composition. It is desirable to add an agent. Suitable thermal polymerization inhibitors include hydroquinone, p
-Methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4- Methyl-
6-t-butylphenol), cerium N-nitrosophenylhydroxylamine, aluminum aluminum N-nitrosophenylhydroxylamine and the like.
The amount of the thermal polymerization inhibitor added is about 0.
Preferably from 01% to about 5%. Further, if necessary, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to prevent polymerization inhibition by oxygen, and may be unevenly distributed on the surface of the photosensitive layer in a drying process after coating. . The addition amount of the higher fatty acid derivative is preferably about 0.5% to about 10% of the whole composition.

A coloring agent may be added for the purpose of coloring the photosensitive layer. Examples of the coloring agent include phthalocyanine pigments (CI Pigment Blue 15: 3, 15:15).
4, 15: 6), azo pigments, carbon black,
There are pigments such as titanium oxide, ethyl violet, crystal violet, azo dyes, anthraquinone dyes, and cyanine dyes. The amount of dye and pigment added is preferably from about 0.5% to about 5% of the total composition. In addition, additives such as inorganic fillers and plasticizers such as dioctyl phthalate, dimethyl phthalate and tricresyl phosphate may be added to improve the physical properties of the cured film. The amount of these additives is preferably 10% or less of the total composition. A surfactant can be added to the photopolymerizable composition of the present invention in order to improve the quality of the coated surface.

When the photopolymerizable composition of the present invention is coated on a support, it is used after being dissolved in various organic solvents.
As the solvent used here, acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether,
Propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetylacetone, cyclohexanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxy Ethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N N- dimethylformamide, dimethyl sulfoxide, .gamma.-butyrolactone, methyl lactate and ethyl lactate. These solvents can be used alone or as a mixture. The concentration of the solid content in the coating solution is suitably from 1 to 50% by weight. In the present invention, the coating amount of the photopolymerizable composition is about 0.1 g / m ² to about 0.1 g / m ² after drying.
A range of about 10 g / m ² is suitable. More preferably 0.3
To 5 g / m ² , more preferably 0.5 to 3 g / m ² .

As the support used in the present invention, a dimensionally stable plate is used. Examples of the dimensionally stable plate include paper, plastic (eg, polyethylene,
Paper laminated with polypropylene, polystyrene, etc.), or a metal plate such as aluminum (including aluminum alloy), zinc, copper, etc., and further, for example, cellulose diacetate, cellulose triacetate, cellulose propionate, butyric acid Cellulose, cellulose acetate butyrate,
Examples include plastic films such as cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, and the like, and paper or plastic films on which a metal is laminated or vapor-deposited as described above. Among these supports, the aluminum plate is particularly preferable because it is extremely dimensionally stable and inexpensive. Further, a composite sheet in which an aluminum sheet is bonded on a polyethylene terephthalate film as described in JP-B-48-18327 is also preferable.

In the case of a support having a surface of a metal, particularly aluminum, a surface treatment such as graining treatment, immersion treatment in an aqueous solution of sodium silicate, potassium fluorozirconate, phosphate or the like, or anodizing treatment. Is preferably performed. Further, an aluminum plate that is grained and then immersed in an aqueous solution of sodium silicate can be preferably used. After anodizing the aluminum plate as described in JP-B-47-5125,
Those immersed in an aqueous solution of an alkali metal silicate are preferably used. The anodizing treatment may be, for example, an aqueous solution or a non-aqueous solution of an inorganic acid such as phosphoric acid, chromic acid, sulfuric acid, or boric acid, or an organic acid such as oxalic acid or sulfamic acid, or a salt thereof, or an electrolytic solution in which two or more kinds are combined. It is carried out by passing a current through an aluminum plate as an anode. Also, silicate electrodeposition as described in U.S. Pat. No. 3,658,662 is effective. In addition, Tokiko Sho 4
No. 6,27,481, JP-A-52-58602 and JP-A-52-30503, a support having been subjected to electrolytic graining is subjected to a surface treatment combining the above anodic oxidation treatment and sodium silicate treatment. What is done is also useful. Further, those obtained by sequentially performing mechanical roughening, chemical etching, electrolytic graining, anodizing treatment, and sodium silicate treatment as disclosed in JP-A-56-28893 are also suitable.

Further, after these treatments, water-soluble resins such as polyvinylphosphonic acid, polymers and copolymers having a sulfonic acid group in the side chain, polyacrylic acid, and water-soluble metal salts (eg, zinc borate) ) Or those undercoated with a yellow dye, an amine salt or the like are also suitable. Furthermore,
A sol-gel treated substrate having a functional group capable of causing an addition reaction by a radical covalently disclosed in JP-A-7-159983 is also preferably used. These hydrophilic treatments are performed not only to make the surface of the support hydrophilic, but also to prevent harmful reactions of the photopolymerizable composition provided thereon and to improve the adhesion of the photosensitive layer. Etc.

A photosensitive material (for example, a photosensitive lithographic printing plate) obtained by applying the above-described photosensitive layer on the above-mentioned support.
Is directly exposed by an Ar laser, a YAG-SHG laser or the like as described above. After performing image exposure, development processing is performed. As a developing solution used for such a developing process, a conventionally known alkaline aqueous solution can be used. For example, sodium silicate, potassium, tribasic sodium, potassium, ammonium, dibasic sodium phosphate, potassium, ammonium, sodium carbonate, potassium, ammonium, sodium bicarbonate, potassium, potassium Ammonium, sodium borate, potassium, ammonium, sodium hydroxide,
And inorganic alkali agents such as ammonium, potassium and lithium. Also, monomethylamine,
Dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, ethyleneimine, ethylenediamine, Organic alkali agents such as pyridine are also used. These alkali agents are used alone or in combination of two or more.

Among the above-mentioned alkaline aqueous solutions, a developing solution in which the effect of the present invention is further exhibited is an aqueous solution containing an alkali metal silicate and having a pH of 12 or more. The aqueous solution of alkali metal silicate is silicon oxide SiO ₂ which is a component of silicate
And the ratio of alkali metal oxide M ₂ O (generally [SiO ₂ ] /
[Expressed in the molar ratio of [M ₂ O]) and the concentration can be adjusted. For example, the molar ratio of SiO ₂ / Ma ₂ O as disclosed in JP-A-54-62004 can be adjusted. Is 1.0 to
1.5 (that is, [SiO ₂ ] / [Ma ₂ O] is 1.0 to 1.5,
An aqueous solution of sodium silicate having a content of SiO ₂ of 1 to 4% by weight or [SiO ₂ ] / [M] of 0.5 to 0.75 as described in JP-B-57-7427. (Ie [SiO ₂ ]
/ [M ₂ O] is 1.0 to 1.5) and the concentration of SiO ₂ is 1 to
4% by weight and the developer is at least 20% based on gram atoms of total alkali metal present therein.
An aqueous solution of an alkali metal silicate containing potassium is preferably used.

Further, when developing the photosensitive material (for example, a photosensitive lithographic printing plate) using an automatic developing machine, an aqueous solution (replenisher) having a higher alkali strength than the developing solution is added to the developing solution. It is known that a large amount of photosensitive material can be processed without replacing the developing solution in the developing tank for a long time. This replenishment system is also preferably applied in the present invention. For example, JP-A-54-6200
No. 4 discloses a developer having a SiO ₂ / Na ₂ O molar ratio of 1.0 to 1.5 (that is, [SiO ₂ ] / [Na ₂ O] of 1.0 to 1.0.
5), wherein an aqueous solution of sodium silicate having a SiO ₂ content of 1 to 4% by weight is used, and the SiO ₂ / SiO ₂ is continuously or intermittently depending on the throughput of a positive photosensitive lithographic printing plate. Na ₂ O
Is 0.5 to 1.5 (that is, [SiO ₂ ] / [Na ₂ O] is 0.5
To 1.5) of a sodium silicate aqueous solution (replenisher), and further disclosed in JP-B-57-7427, where [SiO ₂ ] / [M] is 0.5 to 0.5. 0.75 (i.e., [SiO _2] / [M ₂ O] is 1.0 to 1.5) a, SiO ₂
An aqueous solution of an alkali metal silicate having a concentration of 1 to 4% by weight is used as a developing solution, and [SiO ₂ ] / [M] of the alkali metal silicate used as a replenisher is 0.25 to 0.75 ( That is, [SiO ₂ ] / [M ₂ O] is 0.5 to 1.5), and both the developer and the replenisher are based on gram atoms of all alkali metals present therein. At least 20
% Of potassium is preferably used.

The photosensitive lithographic printing plate thus developed is described in JP-A-54-8002 and JP-A-55-1504.
No. 5, No. 59-58431, etc., a rinsing solution containing washing water, a surfactant and the like,
It is treated with a desensitizing solution containing gum arabic and starch derivatives. For the post-processing of the photosensitive lithographic printing plate of the present invention, these processings can be used in various combinations.

After development or, optionally, post-treatments such as the desensitizing treatment described above, the entire surface is exposed by the method described above, and the lithographic printing plate thus obtained is subjected to an offset printing machine. Multiplied and used for printing many sheets.
At the time of printing, a conventionally known plate cleaner for a PS plate is used as a plate cleaner used for removing stains on a plate. For example, CL-1, CL-2, CP, CN-
4, CN, CG-1, PC-1, SR, IC (manufactured by Fuji Photo Film Co., Ltd.) and the like. Preferably, CP and CN-4 are mentioned.

[0125]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. (Preparation of Sensitive Material 1) An aluminum plate having a thickness of 0.30 mm was grained with a nylon brush and a 400-mesh aqueous suspension of pumicestone, and then thoroughly washed with water.
After being immersed in a 10% aqueous solution of sodium hydroxide at 70 ° C. for 60 seconds for etching, the film was washed with running water, neutralized and washed with a 20% aqueous solution of nitric acid, and then washed with water. This is V _A = 12.7V
Under the condition (1), an electrolytic surface roughening treatment was performed with a 1% nitric acid aqueous solution at an anode electricity of 160 coulomb / dm ² using a sinusoidal alternating current. The surface roughness was measured to be 0.6μ
(Ra display). Subsequently, after immersing in a 30% aqueous sulfuric acid solution and desmutting at 55 ° C. for 2 minutes, the thickness of the anodic oxide film is adjusted to 2.7 g / m ² at a current density of 2 A / dm ² in a 20% aqueous sulfuric acid solution. Anodizing treatment was performed for 2 minutes. Next, a liquid composition (sol solution) of the SG method was prepared by the following procedure.

[Sol Solution] Unichemical Co., Ltd .: Phosmer PE 24 parts by weight Methanol 130 parts by weight Water 20 parts by weight 85% phosphoric acid 16 parts by weight Tetraethoxysilane 50 parts by weight 3-methacryloxypropyltrimethoxysilane 48 parts by weight Were mixed and stirred. An exotherm was observed in about 5 minutes. After reacting for 60 minutes, the content was transferred to another container and 3,000 parts by weight of methanol was added to obtain a sol solution. This sol solution was diluted with methanol / ethylene glycol = 9/1 (weight ratio), applied with a wheeler so that the amount of Si on the substrate was 3 mg / m ^2, and dried at 100 ° C. for 1 minute. On the substrate thus treated, a photopolymerizable composition 1 having the following composition
Was applied to a dry coating weight of 1.4 g / m ² ,
It dried at 2 degreeC for 2 minutes, and formed the photopolymerizable photosensitive layer.

Photosensitive solution Pentaerythritol tetraacrylate 1.5 g Allyl methacrylate / methacrylic acid 2.0 g (80/20 weight ratio) Photopolymer, molecular weight 30,000 (A) Compound 1 0.15 g Compound 2 0.20 g Compound 3 0.50 g Copper phthalocyanine Pigment Blue 15: 6 / (A) = 3/2 dispersion 0.5 g Megafac F-177 (Dainippon Ink and Chemicals) 0.02 g Fluorosurfactant manufactured by N-Nitroso Phenylhydroxylamine 0.015 g Aluminum salt (manufactured by Wako Pure Chemical Industries) Propylene glycol monomethyl ether 27.5 g Methyl ethyl ketone 19.0 g On this photopolymerizable photosensitive layer, a water-soluble protective layer having the following composition was dried and weighed 2.5 g. / M ² and dried at 100 ° C. for 3 minutes. Polyvinyl alcohol (degree of saponification 98.5 mol%, degree of polymerization 550) 22 g Nonionic surfactant (EMALEX NP-10, 0.5 g, manufactured by Nippon Emulsion Co., Ltd.) Distilled water 450 g

(Preparation of Photosensitive Material 2) Photosensitive material 2 was prepared in the same manner as in Photosensitive Material 1 except that the photosensitive solution was changed to the following composition. Pentaerythritol tetraacrylate 1.7 g Allyl methacrylate / methacrylic acid 1.8 g (80/20 weight ratio) Photopolymer, molecular weight 30,000 (A) Compound 4, 0.15 g Compound 5, 0.20 g Compound 3, 0.50 g Copper phthalocyanine Pigment Blue 15: 3 / (A) = 3/2 dispersion 0.5 g Megafac F-177 (Dainippon Ink & Chemicals) 0.02 g Fluorosurfactant manufactured by N-Nitrosophenylhydroxylamine 015 g Aluminum salt (manufactured by Wako Pure Chemical Industries) Propylene glycol monomethyl ether 27.5 g Methyl ethyl ketone 19.0 g

[0129]

Embedded image

[0130]

Embedded image

(Examples 1 to 14)
Nix's XLP4000 plate setter (Air cooled Ar
⁺Laser, 488 nm), and the image exposure amount was 0.15.
mJ / cm^TwoAnd the number of lines is 175 lpi and the resolution is 40
Image exposure was performed at 00 dpi. Furthermore, the degree of film hardening
For the purpose of raising it, post heat treatment at 110 ℃ for 12 seconds
gave. In addition, the above-mentioned photosensitive material 2 is a Gut manufactured by Rhino Type Hell.
enberg plate setter (SHG-YAG, 532n
m) and the image exposure amount is 0.15 mJ / cm^TwoAnd then the line
Images with 175 lpi resolution and 2540 dpi resolution
Exposure was performed. In order to further increase the degree of film curing,
A post-heating treatment was performed at 10 ° C. for 12 seconds.

The development was carried out by Fuji Photo Film Co., Ltd. DP-4.
Using a solution obtained by diluting a developer 18-fold with water, 85
The immersion was carried out at 30 ° C. for 15 seconds using a 0NX automatic developing machine. Fuji Film Co., Ltd. FP-2W gum solution with water 1:
After gumming with the solution diluted to 1, the whole surface was exposed and heated. Table 1 shows the conditions of the overall exposure and heating.
The printing plate thus obtained was evaluated as follows. For the printing durability evaluation, SOR-KZ manufactured by Heidelberg Co. was used as a printing machine, an emerald premium MXE 2% diluent of Anchor Co., Ltd. was used as a dampening solution, and GEOS-G (N) manufactured by Dainippon Ink Co., Ltd. was used as an ink. It was used. The solid printing durability refers to the number of sheets that can be printed normally without any solid omission in the solid printing portion. Highlight durability is 17
3% of 5 lpi halftone dots indicate the number of prints reproduced on the printed matter. The results are shown in Table 10.

Comparative Examples 1 to 4 In the same manner as in Examples 1 to 14, the photosensitive materials 1 and 2 were subjected to image exposure and development. Comparative experiments were performed in cases where the entire surface exposure and the heat treatment were not performed at all (Comparative Examples 1 and 3) and cases where only the heat treatment was performed without performing the entire surface exposure (Comparative Examples 2 and 4). Table 10 shows each condition. Printing was performed on the obtained lithographic printing plate under the same conditions as in Examples 1 to 14, and the printing durability was evaluated. The results are shown in Table 10.

[0134]

[Table 10]

As is clear from Table 10, when the entire surface was exposed at an exposure amount of 100 times or more that of the image exposure after the development, a lithographic printing plate having both good solid printing durability and highlight printing durability was obtained (FIG. 10). Examples 1 to 14). When heated to 100 ° C. during the whole-surface exposure after the development, good solid printing durability and highlight printing durability were obtained as in the case where the whole-surface exposure was about 20 times (Examples 7 and 14). When the entire surface was not exposed after development, the solid printing durability and highlight printing durability were insufficient regardless of whether heating was performed or not (Comparative Examples 1 to 4).

As described above, according to the plate making method of the present invention, a clear image can be obtained without causing flare and the like, and a photopolymerizable lithographic printing plate having significantly improved printing durability can be obtained. .

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Koji Aoshima, Inventor Koji Aoshima, 4000 Kawajiri, Yoshida-cho, Haibara-gun, Shizuoka Prefecture F-term in Fujisha Shin Film Co., Ltd. HA03

Claims (2)

[Claims] 1. A photopolymerizable lithographic printing plate having a photosensitive layer containing (a) a compound having an ethylenically unsaturated bond capable of addition polymerization, (b) a photopolymerization initiator system, and (c) a binder is exposed to a laser. A plate making method for a photopolymerizable lithographic printing plate, comprising exposing an image at a constant exposure amount by an apparatus, performing development, and exposing the entire surface at an exposure amount of at least 100 times the image exposure amount. 2. A plate surface temperature of 30.degree.
The plate-making method according to claim 1, wherein the plate-making method is performed by heating at a temperature of ℃.