JP2000321757A - Image forming material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an image forming material especially adapted to a direct printing plate (CTP) and superior in image quality, sensitivity, storage stability, and physical strength. SOLUTION: This image forming material contains as energy ray sensitive base generator, an infrared absorber, a base soluble resin, a base curable resin, a sensitizing dye, a photosensitive silver halide, a nonphotosensitive reducible silver salt, a reducing agent, a binder resin, and an onium salt compound. The infrared absorber has a molar absorption coefficient of >1×105 of an adsorption maximum in a wavelength region of 700-1500 nm. This image forming material has a layer containing the energy sensitive base generator and an ink repellent layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an image forming material using an energy-sensitive base generator. More specifically, the combination of an energy-sensitive base generator with an infrared absorber, a base-soluble resin, a base-curable resin, a thermosensitive material or an onium salt, or the generation of an energy-sensitive base in a so-called fountain-free lithographic printing plate Related to applied technology of agents.

[0002]

2. Description of the Related Art As an image forming material utilizing an energy-sensitive base generator, J. Org. M. J. Frechet et al., P
olym. Bull. 30, Vol. 369-375 (1993) discloses a UV curing technique in which a photosensitive polymer is combined with a 2-nitrobenzyl carbamate-based energy-sensitive base generator.

JP-A-10-7709 discloses an energy-sensitive radiation comprising an onium cation, an energy-sensitive acid generator that is an onium borate complex composed of a specific borate anion, and an energy-sensitive base generator. Sensitive composition with higher sensitivity and higher solubility in organic solvents and resins due to the active composition, so that Lewis acid produced as a by-product does not remain in the reaction system and cause corrosion of metals and the like. It is disclosed that a sensitizer, an alkali-soluble resin, a base-curable compound and the like are used in combination in the composition, and the sensitizer transfers energy between the energy-sensitive linear acid generator and the energy-sensitive acid generator. Alternatively, electron transfer occurs to effectively decompose the energy-sensitive acid generator to generate an acid, and the alkali-soluble resin reacts with a developing solution by an acid-catalyzed reaction. The wettable or solubility increases, the basic curable compounds by reaction with an amine generated from the energy-sensitive line base generator, it is disclosed that results in curing or crosslinking reaction.

Japanese Patent Application Laid-Open No. Hei 10-77257 discloses that a photobase generator for generating a secondary amine, which is considered to provide a high-performance photoresist, includes N, N-dialkylcarbamic acid 2-nitrobenzyl esters. Manufacturing methods have been proposed.

JP-A-10-77264 proposes N- (2-nitrobenzyloxycarbonyl) cyclic amines, which are novel compounds useful as photobase generators for photoresists and the like.

[0006] However, the above document does not disclose an improvement in the efficiency of decomposing the energy-sensitive base generator by infrared rays by transferring energy between the energy-sensitive base generator and the infrared absorber. There is no disclosure of the action of an energy-sensitive base generator on a lithographic printing plate.

JP-A-10-221806 discloses, in a heat-developable recording material having a non-photosensitive reducible silver salt, a super hardener, a reducing agent and a binder, a general formula as the reducing agent. A technique for providing a super-high contrast image with good storage stability of an image by using the compound is disclosed.

JP-T-10-509251 discloses a photothermographic layer on a surface containing a polyvinyl acetal binder, a non-photosensitive silver generator, a reducing agent for silver ions, and radiation-sensitive silver halide grains. A spectrally sensitized photothermographic silver halide element comprising a support,
The layer containing both silver halide and the non-photosensitive silver source improves the adhesion between the emulsion layer and the support by using an element containing an adhesion promoter that has better adhesion to polyester than polyvinyl acetal. It has been proposed to. However, the above document does not disclose a combination of a photothermographic material and an energy-sensitive base generator.

[0009]

SUMMARY OF THE INVENTION The object of the present invention is as follows.
The present invention is to provide a novel image forming material particularly suitable for a direct printing plate (CTP), and secondly, to provide an image forming material excellent in image quality, sensitivity, storage stability and physical strength. is there.

[0010]

The configuration of the present invention for achieving the above object is as follows.

(1) An image-forming material containing an energy-sensitive base generator and an infrared absorber.

(2) An image forming material containing an energy-sensitive base generator, an infrared absorber and a base-soluble resin.

(3) An image-forming material containing an energy-sensitive base generator, an infrared absorber and a base-curable resin.

(4) An image-forming material containing an energy-sensitive base generator, an infrared absorber and an onium salt compound.

(5) The infrared absorbent has a molar absorption coefficient of 1 × 1 having a maximum absorption at a wavelength of 700 nm or more and 1500 nm or less.
0 ⁵ in which it exceeds the above (1) image-forming material according to any one of - (4).

(6) Energy-sensitive base generator, sensitizing dye, photosensitive silver halide, non-photosensitive reducible silver salt,
An image forming material containing a reducing agent and a binder resin.

(7) An image-forming material having a layer containing an energy-sensitive base generator and an ink repellent layer.

According to the present invention, energy is transferred between the infrared absorbent and the energy-sensitive base generator by using the energy-sensitive base generator together with the infrared absorber, and the energy-sensitive base is generated by infrared rays. It is based on the finding that the decomposition of the agent can be promoted. Further, by applying this effect to an image forming layer containing an energy-sensitive base generator and a base-soluble resin, and to an image forming layer containing an energy-sensitive base generator and a base-curable resin, the image quality is improved. This is based on the finding that an image forming material having excellent sensitivity, storage stability and physical strength can be obtained. It is also based on the finding that the development reaction can be enhanced by including an energy-sensitive base generator in the image forming layer of a known photothermographic material. It is also based on the finding that the coexistence of an energy-sensitive base generator and an onium salt has an effect of increasing the base generation efficiency. Furthermore, it is based on the finding that the development reaction can be enhanced by using an energy-sensitive base generator in combination with the photosensitive layer of a known lithographic printing plate requiring no fountain solution.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The energy-sensitive base generator contained in the image forming material used for the image forming layer according to the invention according to claims 1 to 7,
It is a compound that can generate an amine by energy rays (radiation), and examples thereof include compounds represented by the following general formulas (1) to (9).

General formula (1)

[0021]

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In the general formula (1), A ¹ represents an optionally substituted aryl group having 6 to 20 aromatic ring carbon atoms;
R ¹ and R ² each represent a hydrogen atom, an optionally substituted alkyl group having 1 to 18 carbon atoms or an optionally substituted aryl group having 6 to 20 aromatic ring carbon atoms, and R ³ represents a hydrogen atom or Represents an optionally substituted alkyl group having 1 to 18 carbon atoms, and R ⁴ is an optionally substituted alkyl group having 1 to 18 carbon atoms or an optionally substituted aryl group having 6 to 20 aromatic ring carbon atoms. Represents a group. R ³ and R ⁴ may form a nitrogen-containing heterocycle having 5 to 6 carbon atoms, and the nitrogen-containing heterocycle may be substituted with a methyl group or an ethyl group.

[0023] In the general formula ^{(2) R 1 -O-CO} -NR 3 R 4 formula (2), and R ^1, R ³ and R ⁴ are R ^1, R ³ and R ⁴ in the general formula (1) Each is synonymous.

Formula (3) A ¹ -CO-CH ₂ -A ^2-
O-CO-NR ³ R ⁴ in formula ^{(3), A 1, R} 3 and R ⁴ are the general formula A ^1, R ³ and R ⁴ of (1) the same meanings.

[0025] R ¹ in the general formula ^{(4) R 1 R 2 N} -O-CO-NR 3 R 4 in formula (4), R ^1, R ^2, R ³ and R ⁴ are the general formula (1), Each has the same meaning as R ² , R ³ and R ⁴ .

General formula (5)

[0027]

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[0028] In the general formula (5), R ^1, R ^2, R ³ and R ⁴ are the general formula R ^1, R ^2, R ³ and R ⁴ of (1) the same meanings.

General formula (6)

[0030]

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In the general formula (6), A ¹ , R ³ and R ⁴
Has the same meaning as A ¹ , R ³ and R ⁴ in the general formula (1), respectively.

Formula (7)

[0033]

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[0034] In general formula (7), R ¹ and R ⁴ are R ¹ and R ⁴ in the general formula (1) respectively the same.

General formula (8) R ¹ —CO—NR ² —CH ＝ CH—A ^{1 In} general formula (8), A ¹ , R ¹ and R ² represent general formula (1)
A ¹ , R ¹ and R ² have the same meanings as above.

[0036] In the general formula (9) A ¹ -NH-COH general formula (9), A ¹ has the same meaning as A ¹ in formula (1).

Here, each substituent in the general formulas (1) to (9) will be described. Examples of the optionally substituted alkyl group having 1 to 18 carbon atoms include fluorine, chlorine, bromine, a hydroxyl group, a carboxyl group, a mercapto group, a cyano group, a nitro group, and an optionally substituted alkyl group having 1 carbon atom. To 18 linear, branched, or cyclic alkyl groups, specifically, methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl, octadecyl Group, isopropyl group, isobutyl group, sec-butyl group, t-butyl group, cyclopentyl group, cyclohexyl group, decylcyclohexyl group, fluoromethyl group, chloromethyl group, bromomethyl group, trifluoromethyl group, trichloromethyl group, tribromo Methyl group, hydroxymethyl group, carboxymethyl group, mercaptomethyl group, cyanomethyl group Nitromethyl group, azidomethyl group and the like.

The optionally substituted aryl group having 6 to 20 aromatic ring carbon atoms includes fluorine, chlorine, bromine,
A hydroxyl group, a carboxyl group, a mercapto group, a cyano group, a nitro group, a monocyclic ring having 6 to 20 carbon atoms and a condensed polycyclic aryl group which may be substituted with an azide group, specifically, phenyl Group, 1-naphthyl group, 2-naphthyl group, 9-anthryl group, 9-phenanthryl group,
1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azulenyl group, 1-acenaphthyl group, 9-fluorenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,3-xylyl Group, 2,5-xylyl group, mesityl group, p-cumenyl group, p-dodecylphenyl group, p-
Cyclohexylphenyl group, 4-phenyl group, o-fluorophenyl group, m-chlorophenyl group, p-bromophenyl group, p-hydroxyphenyl group, m-carboxyphenyl group, o-mercaptophenyl group, p-cyanophenyl group, m-nitrophenyl group, m-azidophenyl group and the like.

The optionally substituted arylene group having 6 to 20 aromatic ring carbon atoms includes fluorine, chlorine, bromine, hydroxyl group, carboxyl group, mercapto group,
Monocyclic and condensed polycyclic arylene groups having 6 to 20 aromatic rings, which may be substituted with a cyano group, a nitro group or an azide group, include 1,2-phenylene group, 1,3
-Phenylene group, 1,4-phenylene group, 1,4-naphthylene group, 2,6-naphthylene group, 9,10-anthrylene group, 1,2-acenaphthylene group, 1,1'-biphenylene group, 3-fluoro -1,2-phenylene group, 2-
Bromo-1,4-phenylene group and the like.

The amine generated from these energy-sensitive base generators preferably has a structure sufficient to prevent substantial loss of the amine by evaporation during the heating step, and has a boiling point of 60 ° C. under normal pressure. The temperature is preferably at least 80 ° C. As such a method, an amine compound having 4 or more carbon atoms is used,
Alternatively, it is preferable to adopt a method such as a method of obtaining a high molecular weight amine.

Preferred examples of the energy ray base generator include compounds having the following structures.

[0042]

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Further, as exemplified below, the energy-sensitive base generator may be a polymer compound.

[0044]

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Further, as exemplified below, dendrimers and the like, which are starburst oligomers produced by a Michael addition reaction of a diamine and an acrylate ester, can also be used as an energy-sensitive base generator.

[0046]

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The above-mentioned energy-sensitive base generators are described, for example, in J. Am. F. Cameron et al. M, J .; Fre
chet, J.M. Photochem. Photobio
l. , A: Chem. 59, 105 (1991).
Year), J.M. F. Cameron et al. Am. Che
m. Soc. 113, p. 4303 (1991).
Year), J. F. Cameron et al. Org. Che
m. 55, 5919 (1990); E. FIG.
Beecher et al., Polym. Mat. Sci. En
g. 64, 71 (1991); M. J.
Frechet et al., Polym. Bull. Thirtieth
Volume, p. 369 (1993), C.I. Kutal et al.
Electrochem. Soc. , Vol. 134, 22
The method described in a known document such as page 80 (1987) can be referred to. Furthermore, Yoshida et al., 4th Polymer Material Forum, p. 105 (1995)
And the like can also be used as an energy-sensitive base generator.

The amount of the energy-sensitive base generator to be added is preferably in the range of 0.1 to 20% by weight based on the image forming layer comprising the photosensitive composition containing the energy-sensitive base generator.

The infrared absorbent used in the invention according to claims 1 to 5 is characterized in that the infrared energy received by the infrared absorbent is transferred to an energy-sensitive base generator.
The composition containing the energy-sensitive base generator is made sensitive to infrared light, and a base is generated from the energy-sensitive base generator by exposing to a laser emitting in the infrared region. It acts on a soluble resin, a base-curable resin, an onium salt or the like to form an image. The infrared absorbing agent refers to a substance that absorbs light having a wavelength of 700 to 1500 nm. As the substance, for example, a wavelength of 700 nm to 1500 n
It is preferable to use an infrared absorbing dye, carbon black, magnetic powder or the like having an absorption in the range of m. Particularly preferred infrared absorbers have a maximum absorption at 700 nm or more and 1200 nm or less, and have a peak molar extinction coefficient ε of more than 1 × 10 ⁵ .

Examples of the infrared absorbing dye include cyanine dyes, squarium dyes, croconium dyes, azurenium dyes, phthalocyanine dyes, naphthalocyanine dyes, polymethine dyes, naphthoquinone dyes, thiopyrylium dyes, and dithiol metal complex dyes. Dyes, anthraquinone dyes, indoaniline metal complex dyes, intermolecular CT dyes and the like can be mentioned. Also, JP-A-63-13
Nos. 9191 and 64-33547, JP-A-1-160
No. 683, No. 1-280750, No. 1-293342
No. 2-2074, No. 3-26593, No. 3-3
No. 0991, No. 3-34891, No. 3-36093
No. 3-36094, No. 3-36095, No. 3-
Compounds described in Nos. 42281 and 3-103476.

When a semiconductor laser is used as a light source for image exposure, the infrared absorber has a wavelength of 750 to 900 nm.
When an AG laser is used, those having an absorption peak at 900 to 1200 nm and having a molar absorption coefficient of ε> 1 × 10 ⁵ are preferable. Further, one or more infrared absorbers belonging to the above two systems may be used in combination. The amount of the infrared absorber added is preferably in the range of 0.5 to 20% by weight in the composition containing the energy-sensitive base generator.
When the amount exceeds 20% by weight, the developability of the non-image area and the like decrease, and when the amount is less than 0.5% by weight, the sensitivity decreases.

The image forming material according to the first aspect of the present invention contains an energy-sensitive base generator and an infrared absorber in a state where the energy absorbed by the infrared absorber can be transmitted to the energy-sensitive base generator. What is necessary is just to have a layer.
Preferably, the support has a layer made of a composition containing an energy-sensitive base generator and an infrared absorber. The layer containing the energy-sensitive base generator and the layer containing the infrared absorber may be present as an adjacent layer on the same side of the support as the adjacent layer. The layer may be a layer containing an infrared absorber, or a support, a layer containing an infrared absorber, or a layer containing an energy-sensitive base generator. The compounding ratio of the energy-sensitive base generator to the infrared absorber is suitably such that the weight ratio of the energy-sensitive base generator to the infrared absorber is in the range of 0.1 to 2 mol, preferably 0.5 to 1 mol. Range of moles.

The base-soluble resin which can be used in the invention according to the second aspect is not particularly limited, and is, for example, a novolak resin, a vinyl polymer having a phenolic hydroxyl group, and JP-A-55-57841. A condensation resin of the polyhydric phenol and aldehyde or ketone described can be used. Examples of the novolak resin include phenol-formaldehyde resin, cresol-formaldehyde resin, phenol-cresol-formaldehyde copolymer resin described in JP-A-55-57841, and p-substituted phenol described in JP-A-55-127553. And phenol or cresol and formaldehyde. The molecular weight (polystyrene standard) of the novolak resin is preferably such that the number average molecular weight Mn is 3.00 × 10 ^{2 to} 7.50 × 10 ³ and the weight average molecular weight Mw is 1.00 × 10 ^{3 to} 3.00 × 1.
0 ^4, more preferably Mn of 5.00 × 10 ² 4.00
× 10 ³ and Mw are 3.00 × 10 ^{3 to} 2.00 × 10 ⁴ .

The vinyl polymer having a phenolic hydroxyl group is a copolymer having a unit having the phenolic hydroxyl group in the molecular structure, and is represented by the following general formula (10):
A polymer containing at least one structural unit represented by formulas (14) to (14) is preferable.

[0055]

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In the general formulas (10) to (14), R ₁
And R ₂ each represents a hydrogen atom, an alkyl group or a carboxyl group, and is preferably a hydrogen atom. R ₃ represents a hydrogen atom, a halogen atom or an alkyl group, preferably a hydrogen atom, an alkyl group such as a methyl group or an ethyl group.

R ₄ represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, and is preferably a hydrogen atom.
A represents an optionally substituted alkylene group which connects a nitrogen atom or an oxygen atom to an aromatic carbon atom;
Represents an integer of 10 to 10, and B represents a phenylene group which may have a substituent or a naphthylene group which may have a substituent.

The vinyl polymer having a phenolic hydroxyl group preferably has a copolymer type structure having the structural units represented by formulas (1) to (5).
As monomers to be copolymerized, for example, ethylene, propylene, isobutylene, butadiene, ethylenically unsaturated olefins such as isoprene, for example, styrene, α-methylstyrene, p-methylstyrene, styrenes such as p-chlorostyrene, Acrylic acid, acrylic acid such as methacrylic acid, for example, itaconic acid, maleic acid, unsaturated aliphatic dicarboxylic acids such as maleic anhydride, for example, methyl acrylate, ethyl acrylate, n-butyl acrylate,
Esters of α-methylene aliphatic monocarboxylic acids such as isobutyl acrylate, dodecyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, α-methyl methyl acrylate, methyl methacrylate, ethyl methacrylate and ethyl ethacrylate For example, nitriles such as acrylonitrile and methacrylotrile, and amides such as acrylamide and methacrylamide, for example, anilides such as acrylanilide, p-chloroacrylanilide, m-nitroacrylanilide and m-methoxyacrylanilide, for example, acetic acid Vinyl, vinyl propionate,
Vinyl esters such as vinyl butyrate and vinyl benzoate,
For example, methyl vinyl ether, ethyl vinyl ether,
Vinyl ethers such as isobutyl vinyl ether and β-chloroethyl vinyl ether, vinyl chloride, vinylidene chloride, vinylidene cyanide, for example, 1-methyl-1-
Methoxyethylene, 1,1-dimethoxyethylene, 1,
Ethylene derivatives such as 2-dimethoxyethylene, 1,1-dimethoxycarbonylethylene, 1-methyl-1-nitroethylene, for example, N-vinylpyrrole, N-vinylcarbazole, N-vinylindole, N-vinylpyrrolidene, N-vinyl monomers such as vinylpyrrolidone.

These monomers are present in the polymer compound in a structure in which the unsaturated double bond is cleaved. Of the above monomers, esters and nitriles of aliphatic monocarboxylic acids exhibit excellent performance and are preferred. These monomers may be bonded to the polymer used in the present invention in either a block or random state. The vinyl polymer having a phenolic hydroxyl group is contained in the photosensitive composition in an amount of 0.5 to 70%.
It is preferred that the content be contained by weight. As the vinyl polymer having a phenolic hydroxyl group, the above polymers may be used alone or in combination of two or more. Further, it can be used in combination with another polymer compound or the like.

One kind of the base-soluble resin may be used,
Two or more kinds may be used in combination. The base-soluble resin is preferably contained in the photosensitive composition containing the resin in an amount of 5 to 95% by weight.

It is desirable that a polymer binder is further mixed with the image forming composition. Although there is no particular limitation on such a polymer binder, it has compatibility with the energy-sensitive base generator or infrared absorber used in the present invention, and can be dissolved and applied by a suitable solvent and applied. Desirably, any thermoplastic polymer compound can be used without any particular problem.

Specific examples of the polymer binder include:
Polystyrene, styrene / acrylate copolymer, styrene / methacrylate copolymer, polyacrylates such as polymethyl acrylate and polyethyl acrylate, and polymethacryls such as polymethyl methacrylate and polyethyl methacrylate Acid esters, polyvinyl acetate, ethylene / vinyl acetate copolymer, polyurethane, bisphenol A (or tetrabromobisphenol A, bisphenol F, bisphenol S, etc.) type epoxy resin, novolak type epoxy resin, cellulose acetate, cellulose acetate sac Nitrate, methyl cellulose, cellulose derivatives such as ethyl cellulose, polyvinyl butyral, polyvinyl formal, polyamide resin, polyester resin, alkyd resin and the like. It can be. Further, in the image forming composition of the present invention, it is also possible to use a mixture of the above-mentioned compounds curable by the generated basic compound.

The mixing ratio of the composition for image formation used in the invention according to claim 2 is not particularly limited, but is preferably in the range of 1 to 50 g of a base-soluble resin per 1 g of an energy-sensitive base generator in the composition. Is suitable, preferably 5 to 10
g. The content of the infrared absorbent is 0.1 to 40.
% By weight, and the content of the polymer binder is 10%.
９５95% by weight. Further, when further mixing the base-soluble resin or the base-curable resin, the compounding ratio of the compound is 1/10 to 5 with respect to the compounding amount of the polymer binder.
It can be blended in a weight ratio in the double range.

When the image forming composition having the above-mentioned mixing ratio is used as an image forming medium having a film formed on a sheet-like substrate, the image forming composition is dissolved in a solvent and An application method can be adopted. The solvent used here is not particularly limited, but for example, MEK, MIB
K, ketone solvents such as cyclohexanone and cyclopentanone, ethyl acetate, amyl acetate (or isoamyl), acetate solvents such as butyl acetate, lactate esters such as methyl lactate and ethyl lactate, 1,1,2,2
-Halogen solvents such as tetrachloroethane and ethylene dichloride, and glycol derivatives such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monomethyl ether. System solvents, aromatic solvents such as toluene and xylene, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide and the like are preferable, and these solvents are used alone or in combination. In addition, a method in which an image forming medium once formed on a base material is transferred to another base material by a thermal transfer method or the like to form an image forming medium can be selected.

Further, additives such as a surfactant, an antihalation agent, an antistatic agent, a leveling agent and an antifoaming agent can be appropriately mixed and used in the above-mentioned solvent.

The solution containing the composition for image formation prepared as described above is applied to a sheet-like substrate using a roll coater, a spin coater, a gravure coater, a bar coater, or the like, and then dried. A film can be formed. As the sheet-shaped substrate, there is no limitation, but a porous substrate such as paper, nonwoven fabric, fabric, or porous glass sheet, or a substrate such as synthetic paper, coated paper, polymer film, or metal foil is used. It is possible.
These substrates may be used alone or in the form of a laminated composite substrate. Further, for the purpose of protecting the film of the image forming medium thus formed, a protective film such as a polymer film can be further provided.

In forming an image using the curable or positive-type sensitive composition as described above, a substrate (eg, a silicon / silicon dioxide coating) used in the production of precision integrated circuit devices, Substrates used for printed circuits (eg, copper clad laminates), glass plates (or plastic plates) used for color filters,
Alternatively, it is applied on a substrate (eg, anodized Al plate) used for a lithographic printing plate by an appropriate application method such as a spinner or a coater, and then prebaked under a controlled condition, and (Or electron beam) irradiation through a mask or laser (or electron beam)
After the direct drawing by the method described above, a favorable pattern image can be formed by developing and selectively removing the irradiated area under controlled conditions.

Examples of the developing solution used in the above-mentioned developing process include the following inorganic or organic base solutions. Specifically, sodium hydroxide, potassium hydroxide,
Inorganic alkalis such as sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia; primary amines such as ethylamine and n-propylamine; secondary amines such as diethylamine and di-n-butylamine; triethylamine and methyldiethylamine Tertiary amines such as
Use aqueous solutions of alkali amines such as alcoholamines such as dimethylethanolamine and triethanolamine, quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, and cyclic amines such as pyrrole and piperidine. Is desirable. Furthermore, alcohols,
Surfactants can also be used after being added in an appropriate amount.

The base-curable compound preferably used in the invention according to claim 3 includes an epoxy compound.

Examples of the epoxy compound include conventionally known aromatic epoxy compounds, alicyclic epoxy compounds, aliphatic epoxy compounds, epoxide monomers and episulfite monomers. Examples of the aromatic epoxy compound include a monofunctional epoxy compound such as phenylglycidyl ether and a polyglycidyl ether of a polyhydric phenol having at least one aromatic nucleus or an alkylene oxide adduct thereof, such as bisphenol A. Glycidyl ethers, novolak type produced by reacting bisphenol compounds such as tetrabromobisphenol A, bisphenol F, bisphenol S or alkylene oxide (for example, ethylene oxide, propylene oxide, butylene oxide, etc.) adducts of bisphenol compounds with epichlorohydrin Epoxy resins (for example, phenol novolak epoxy resin, cresol novolak epoxy resin, brominated phenol novolak epoxy resin ),
And trisphenol methane triglycidyl ether.

The alicyclic epoxy compounds include 4-vinylcyclohexene monoepoxide, norbornene monoepoxide, limonene monoepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, bis- (3,4 -Epoxycyclohexylmethyl) adipate, 2- (3,4-
Epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexanone-meta-dioxane, bis (2,3-epoxycyclopentyl) ether, 2-
(3,4-epoxycyclohexyl-5,5-spiro-
3,4-epoxy) cyclohexane-meta-dioxane, 2,2-bis [4- (2,3-epoxypropoxy) cyclohexyl] hexafluoropropane, BHP
E-3150 (manufactured by Daicel Chemical Industries, Ltd., alicyclic epoxy resin (softening point: 71 ° C.)) and the like.

Examples of the aliphatic epoxy compound include 1,4-butanediol dicricidyl ether, 1,6
-Hexanediol diglycidyl ether, ethylene glycol diglycidyl ether, ethylene glycol monoglycidyl ether, propylene glycol diglycidyl ether, propylene glycol monoglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether , Neopentyl glycol monoglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane diglycidyl ether,
Examples include trimethylolpropane monoglycidyl ether, trimethylolpropane triglycidyl ether, diglycerol triglycidyl ether, sorbitol tetraglycidyl ether, allyl glycidyl ether, and 2-ethylhexyl glycidyl ether.

Other base-curable compounds include isophorone diisocyanate, tolylene diisocyanate,
Xylylene diisocyanate, water-added xylylene diisocyanate, hexamethylene diisocyanate, diisocyanomethylnorbornene, paraphenylene diisocyanate, tetramethyl xylylene diisocyanate, triphenylmethane triisocyanate, tris (isocyanatephenyl) thiophosphate, 2-chloro-
1,4-phenyl diisocyanate, 1,5-naphthalenediisocyanate, diphenylmethane diisocyanate, 3,3-dimethyl-4,4-biphenylene diisocyanate, 3,3-dimethyl-4,4-diphenylmethane diisocyanate, 3,3-dimethoxy-4 , 4-biphenylenediisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, Aliphatic, alicyclic or aromatic isocyanate compounds such as trimethylhexanemethylene diisocyanate, blocked polyisocyanates, and polyols and polyethers It may be used, such as triol or polyester polyol with an isocyanate-terminated oligomer or polymer obtained from a polyisocyanate compound.

Further, compounds which cross-link with amines, for example, chloroprene rubber, epichlorohydrin rubber, polyvinyl chloride, polyvinylidene chloride, poly (vinylidene chloride) described in Shinzo Yamashita et al., Handbook of Crosslinking Agent, p34 (Taiseisha) / Acrylonitrile) copolymer, chlorinated polymer such as poly (vinyl chloride / β-chloroethyl vinyl ether) copolymer, vinylidene fluoride / perfluoropropylene copolymer, Lumiflon (manufactured by Asahi Glass Co., Ltd.), Cefral Coat (Central Glass Co., Ltd.) Polymer), chlorosulfonated polyethylene, carboxyl group-containing polymer such as (meth) acrylic acid and its copolymer with (meth) acrylate, styrene /
Examples of a compound capable of causing a cross-linking reaction with an amine, such as an acid anhydride-containing polymer such as a maleic anhydride copolymer, include, but are not limited to.

The curable sensitive composition of the third aspect of the present invention, if it is liquid at room temperature, can be directly applied to a substrate by a coater or the like, dropped by a dispenser or an injector, or sprayed by an inkjet nozzle or the like. And can be used for various purposes. Furthermore, it is also possible to use a binder such as a high molecular weight polymer together. If the polymer is solid, it is mixed in a solvent and mixed with various substrates such as a glass plate, an aluminum plate, a copper plate, a metal plate such as a steel plate, a polymer film such as polyethylene terephthalate, polycarbonate and polyolefin, or a plastic plate. It is also possible to apply it on a material and use it.

Binders which can be used by mixing with the curable composition of the invention according to claim 3 include polyacrylates, poly-α-alkyl acrylates, polyamides, polyvinyl acetals, polyformaldehydes, polyurethanes. , Polycarbonates, polystyrenes, polymers such as polyvinyl esters, copolymers, and more specifically, polymethacrylate, polymethyl methacrylate, polyethyl methacrylate, polyvinyl carbazole, polyvinyl pyrrolidone, polyvinyl butyral, and polyvinyl acetate. , Novolak resin, phenolic resin, epoxy resin, alkyd resin,
Siloxane polymer and others, supervised by Kiyoshi Akamatsu, "Practical technology of new photosensitive resin", (CMC, 1987) and "10
188 ", pages 657 to 767 (Kagaku Kogyo Nippo, 1988).

The onium compound of the invention according to claim 4 includes various known compounds and mixtures. For example, diazonium, phosphonium, sulfonium and iodonium BF ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , SiF ₆ ²⁻ , C
lO ₄ ^- can be used salts such as, alkyl-onium salts described in JP-A-4-42158, diazo compounds described in JP-A-7-244378 or a diazo resin.

Preferably, a condensation resin of an aromatic diazonium compound and a carbonyl compound is used. In this condensation resin, it is preferable to use a diazo resin having a structure represented by the following general formula (15) or (16).

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In the general formula (15), R represents a hydrogen atom, an alkyl group or a phenyl group, and R ₁ , R ₂ and R
₃ represents a hydrogen atom, an alkoxy group or an alkyl group, X represents a counter anion, Y represents -NH-, -O- or -S-, and n represents an integer.

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In the general formula (16), A represents a condensable aromatic group, and R, R ₁ , R ₂ , R ₃ , X, Y and n are all used in the general formula (15). It is synonymous with what was given.

In the above formula (16), specific examples of the aromatic compound which can be used to give the aromatic group represented by A include m-chlorobenzoic acid, diphenylacetic acid, phenoxyacetic acid, -Methoxyphenylacetic acid, p-methoxybenzoic acid, 2,4-dimethoxybenzoic acid, 2,4-dimethylbenzoic acid, p-phenoxybenzoic acid, 4-anilinobenzoic acid, 4- (m-methoxyanilino) benzoic acid , 4- (p-methylbenzoyl) benzoic acid, 4- (p-methylanilino) benzoic acid, phenol, cresol, xylenol, resorcin, 2-methylresorcin, methoxyphenol, ethoxyphenol, catechol, phloroglucin, p-hydroxyethylphenol , Naphthol, pyrogallol, hydroquinone, p-hydroxyben Alcohol, 4-chloro resorcinol, biphenyl-4,4'-diol, 1,2,
4-benzenetriol, bisphenol A, 2,4-
Dihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, p-hydroxyacetophenone,
4,4'-dihydroxydiphenyl ether and the like can be mentioned.

As the aromatic diazonium compound as a structural unit of the diazo resin represented by the general formula (15) or (16), for example, a diazonium salt as described in JP-B-49-48001 can be used. Although it is possible, diphenylamine-4-diazonium salts are particularly preferable. Diphenylamine-4-diazonium salts are
It is derived from aminodiphenylamines, and such 4-aminodiphenylamines include 4-aminodiphenylamine, 4-amino-3-methoxydiphenylamine, 4-amino-2-methoxydiphenylamine, and 4'-amino-2-amine. Methoxydiphenylamine,
4'-amino-4-methoxydiphenylamine, 4-amino-3-methyldiphenylamine, 4-amino-3-
Ethoxydiphenylamine, 4-amino-3- (β-hydroxyethoxy) diphenylamine, 4-aminodiphenylamine-2-sulfonic acid, 4-aminodiphenylamine-2-carboxylic acid, 4-aminodiphenylamine-2′-carboxylic acid, and the like. be able to. Of these, particularly preferred are 4-aminodiphenylamine and 4-amino-3-methoxydiphenylamine. In addition, 4,4'-dimethoxydiphenyl ether, 4,4'-dihydroxydiphenylamine, 4,4'-dihydroxydiphenyl sulfide, cumylphenol, chlorophenol, bromophenol, salicylic acid, p-hydroxybenzoic acid,
-Methyl-4-hydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 3,5
-Dihydroxybenzoic acid, 4-chloro-2,6-dihydroxybenzoic acid, 4-methoxy-2,6-dihydroxybenzoic acid, gallic acid, phloroglysin carboxylic acid, N-
(4-hydroxyphenyl) methacrylamide, N-
(4-hydroxyphenyl) acrylamide, cinnamic acid,
Methyl cinnamate, ethyl cinnamate, p-hydroxycinnamic acid,
Styrene, hydroxystyrene, stilbene, 4-hydroxystilbene, 4,4'-dihydroxystilbene, 4-carboxystilbene, 4,4'-dicarboxystilbene, diphenyl ether, diphenylamine, diphenylthioether, 4-methoxydiphenylether, 4-methoxydiphenylether Methoxydiphenylamine, 4-methoxydiphenylthioether and the like can be mentioned.

Among these diazo compounds contained in the photosensitive composition of the invention according to the fourth aspect, a diazo compound having a carboxyl group in the molecule is particularly preferably used. Preferred examples of the diazo compound having a carboxyl group in the molecule include A in the general formula (7).
And a diazo resin having a structure containing a carboxyl group in the aromatic group represented by In this case, preferred specific examples of the aromatic compound that can be used to give the aromatic group represented by A include p-hydroxybenzoic acid, p-methoxybenzoic acid, p-hydroxycinnamic acid and phenoxyacetic acid. Is mentioned.

The above diazo resin can be prepared by a known method, for example,
Photographic Science and Engineering (Photo. Sci. Eng.) Vol. 17, p. 33 (1973); U.S. Pat. No. 2,063,631.
No. 2,679,498, JP-B-49-
In accordance with the method described in JP-A-48001, an aromatic diazonium salt in sulfuric acid, phosphoric acid or hydrochloric acid, an aromatic compound providing an aromatic group represented by A in the above general formula (16) if necessary, and active carbonyl It can be obtained by polycondensing a compound such as paraformaldehyde, acetaldehyde, benzaldehyde, acetone, or acetophenone. The aromatic compound giving an aromatic group represented by A in the general formula (16), the aromatic diazo compound, and the active carbonyl compound can be freely combined with each other. It is also possible.

In the condensation, the number of moles of the charged aromatic compound which gives the aromatic group represented by A is preferably 0.1 to 1 with respect to the number of moles of the aromatic diazonium compound.
It is 0 times, more preferably 0.2 times to 2 times, and still more preferably 0.2 times to 1 time. Further, in this case, the active carbonyl compound is usually preferably 0.5 to 1.5 times by mole relative to the total number of moles of the aromatic compound giving the aromatic group represented by A and the aromatic diazonium compound. The diazo resin is obtained by charging the mixture at a ratio of preferably 0.6 to 1.2 times and reacting at a low temperature for a short time, for example, about 3 hours.

In the invention according to the fourth aspect, any means for synthesizing a diazo resin having a carboxyl group in the molecule, which can be more preferably used, is optional. A typical means is (A) an aromatic diazonium Polycondensation reaction of salt, aromatic carboxylic acid and active carbonyl compound,
(B) a polycondensation reaction between an aromatic diazonium salt having a carboxyl group and an active carbonyl compound; and (C) a polycondensation reaction between an aromatic diazonium salt and an active carbonyl compound having a carboxyl group. Among these methods, the method (A) is preferable from the viewpoint of the synthesis technique and the availability of synthesis raw materials.

The counter anion of the diazo resin is preferably an anion which forms a salt with the diazo resin stably and makes the resin soluble in an organic solvent. Examples of the acid forming such an anion include organic carboxylic acids such as decanoic acid and benzoic acid, organic phosphoric acids such as phenylphosphoric acid, and organic sulfonic acids.Typical examples include methanesulfonic acid, chloroethanesulfonic acid, Aliphatic sulfonic acids such as dodecanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, mesitylenesulfonic acid, anthraquinonesulfonic acid, naphthylsulfonic acid, alkyl-substituted naphthylsulfonic acid, and aromatic sulfonic acids, hexafluorophosphoric acid, tetrafluoroboric acid, etc. And perhalic acids such as perchloric acid and periodic acid. However,
However, it is not limited to this. Among them, particularly preferred are hexafluorophosphoric acid and tetrafluoroboric acid. In the invention according to claim 4, the molecular weight of the diazo resin used is not particularly limited. For example, the molecular weight of the diazo resin can be set to an arbitrary value by changing the molar ratio of each monomer and the condensation conditions. In general, in the present invention, those having a molecular weight of about 400 to 10,000 can be used effectively, and those having a molecular weight of about 800 to 5,000 are more suitable.

The amount of these diazo compounds contained in the photosensitive composition of the present invention is preferably 0 to 30% by weight, more preferably 0.5 to 20% by weight.
It is.

The above diazo resin is suitably used as the onium compound used in the image forming material according to the fourth aspect of the present invention, and the compounding ratio with the infrared absorbing agent is in the range of 0.1 to 100 g per 1 g of the infrared absorbing agent. Is suitable, and preferably in the range of 1 to 50 g.

The invention according to claim 4 is characterized in that the onium salt is easily decomposed by the base generated from the energy-sensitive ray base generator. Therefore, a known method using an onium salt as an acid generator is known. It can be applied to image forming materials.

The image-forming material according to the first aspect of the present invention can transfer energy or electrons between the energy-sensitive base generator and the infrared absorber to promote the decomposition of the energy-sensitive base generator. The image-forming material according to any one of claims 2 to 5 may cause a reaction between a base generated by decomposition of the energy-sensitive base generator and a base-soluble resin, a base-curable resin, or an onium salt compound. Any configuration may be used. Accordingly, a preferred embodiment includes an embodiment having a layer of a composition containing an energy-sensitive base generator, an infrared absorber, and a base-soluble resin, a base-curable resin, or an onium salt compound on a substrate.

The image forming material of the invention according to claim 6 forms a photographic image by using a known heat development processing method. Such heat developable image forming materials are described, for example, in U.S. Pat. Nos. 3,152,904 and 3,457,075, and by Morgan and B.C. Shelley
y) Thermally ProcessedS by
ilver Systems) ”(Imaging Processes and Materials (Imaging)
Processes and Materials) N
Eblette Eighth Edition, Sturge,
V. Walworth, A .; Shepp, 2nd page, 1969) and the like.

The image forming material according to the sixth aspect of the present invention forms a photographic image by using a heat development process, and comprises an energy-sensitive base generator, a sensitizing dye, a photosensitive silver halide,
A photothermographic material containing a non-photosensitive reducible silver salt and a reducing agent dispersed in a binder resin. The heat-developable image-forming material of the invention according to claim 6 is stable at room temperature, but is heated to a high temperature (for example, 60 ° C. or higher, preferably 80 ° C. or higher, and more preferably 120 ° C. or lower) without supplying a post-exposure processing liquid. Developed by heating.
Heating produces silver through a redox reaction between a non-photosensitive reducible silver salt (which functions as an oxidizing agent) and a reducing agent. This oxidation-reduction reaction is promoted by the catalytic action of the latent image generated by the exposure. The silver formed by the reaction of the silver salt in the exposed areas provides a black image, which contrasts with the unexposed areas, resulting in the formation of an image.

Another embodiment of the heat-developable image forming material of the invention according to claim 6 is a heat recording material. The thermal recording material contains a sensitizing dye which is a heat ray conversion dye in an image forming layer, and records an image by drawing with infrared light and generating heat.

The heat-developable image-forming material of the invention according to claim 6 has at least one image-forming layer containing the above-mentioned components, that is, a photosensitive layer or a heat-recording layer, on a support. The image forming layer may be formed alone on the support, but it is preferable to form at least one layer other than the image forming layer (for example, a non-photosensitive layer) on these layers.

In the heat-developable image forming material, the photosensitive layer (emulsion layer)
A filter layer may be formed on the same side as or opposite to the photosensitive layer to control the amount or wavelength distribution of light passing through the photosensitive layer, or a dye or pigment may be included in the photosensitive layer.

The photosensitive layer may be composed of a plurality of layers, and the sensitivity may be changed to a high-sensitive layer / low-sensitive layer or a low-sensitive layer / high-sensitive layer for adjusting the gradation.

In the present invention, various additives include a photosensitive layer,
It may be added to any of the thermal recording layer, the non-photosensitive layer, and other forming layers.

For the heat-developable image-forming material, for example, a surfactant, an antioxidant, a stabilizer, a plasticizer, an ultraviolet absorber, a coating aid and the like may be used.

Suitable binder resins are transparent or translucent, generally colorless, and include natural polymer synthetic resins, polymers and copolymers, other film-forming media,
For example, gelatin, gum arabic, poly (vinyl alcohol), hydroxyethyl cellulose, cellulose acetate, cellulose acetate butyrate, poly (vinyl pyrrolidone), casein, starch, poly (acrylic acid), poly (methyl methacrylic acid), poly (methyl methacrylic acid) Vinyl), poly (methacrylic acid), copoly (styrene-maleic anhydride), copoly (styrene-acrylonitrile), copoly (styrene-butadiene), poly (vinyl acetal) s [eg, poly (vinyl formal) and poly (vinyl) Butyral)], poly (ester)
, Poly (urethane) s, phenoxy resins, poly (vinylidene chloride), poly (epoxides), poly (carbonates), poly (vinyl acetate), cellulose esters, and poly (amides). The binder may be coated from water or an organic solvent or emulsion.

An aqueous dispersion of a thermoplastic resin can be used as the binder resin of the invention according to the sixth aspect. The thermoplastic resin is a thermoplastic resin at a drying temperature so that it can be applied on a support and form a film by heating and drying. The drying temperature is usually between room temperature and about 100 ° C., and drying is performed at a temperature in this range. Examples of thermoplastic resins used include polyvinyl alcohol, cellulose acetate butyrate, cellulose acetate propionate, styrene-butadiene copolymer, polyvinyl acetals (eg, polyvinyl formal, polyvinyl butyral), polyurethanes, polyvinyl acetate and acrylic resins (Including acrylic rubber) and the like are preferable. The average molecular weight of such a polymer is about 1,000 to 100,000 in terms of weight average molecular weight Mw.

An aqueous dispersion of a thermoplastic resin can be prepared by a known dispersion method. For example, to these resin powders, 5 to 80 wt% of a plasticizer (for example, a saturated or unsaturated higher fatty acid ester or the like) and 1 to 30 wt% of an alkylaryl sulfonate as a dispersant are added.
After dissolving by heating to a temperature of Tg or higher, water is added while stirring with an emulsifying and dispersing machine, and water-in is performed.
-After once forming a resin-type dispersion, water is further added to cause phase transition, and resin-in-wa
A ter-type dispersion is formed. The particle size of the dispersion is preferably as small as possible, and is controlled by the viscosity of the resin solution phase and the shearing force of the disperser. Preferably, the average particle size is reduced to 1 μm or less, usually to 0.01 μm or more.

As a commercially available aqueous dispersion, for example, Butva
An aqueous dispersion of polyvinyl butyral such as r Dispersion FP or BR (both are trade names of Monsanto Co., Ltd.) can be preferably used. The homopolymer or copolymer of polyvinyl butyral is
The weight average molecular weight Mw is preferably about 1,000 to 100,000. Further, the ratio of the polyvinyl butyral component in the copolymer is preferably 30% by weight or more.

Other commercially available aqueous dispersions include Adecabon Titer HUX-350, 232, 55
1, 290H, 401 (Asahi Denka Kogyo Co., Ltd.)
Water dispersions of anionic polyurethane such as
KR-120, KR-134, KC- of Koyo Sangyo Co., Ltd.
1, aqueous vinyl urethane-based aqueous dispersions such as KR-2060 and KR-173, and aqueous vinyl urethane-based aqueous dispersions such as Marca UV Bond # 10, # 31, and # 50 of Seiden Chemical Co., Ltd. be able to. The polyurethane homopolymer or copolymer has a weight average molecular weight M
It is preferable that w is about 1,000 to 100,000. The ratio of the polyurethane component in the copolymer is 3
It is preferably at least 0% by weight.

Also, the styrene-butadiene copolymer is an unified product number of # 1500, # 1502, and # 150.
Sumitomo S of various brands such as 7, # 1712, # 1778
BR latex (Sumitomo Chemical Co., Ltd.), JSR latex (Nippon Synthetic Rubber Co., Ltd.) and Nipol latex (Nippon Zeon Co., Ltd.) can be used.

In the invention according to claim 6, the addition of a toning agent is very desirable. Examples of suitable toning agents are disclosed in Research Report No. 17029, and include: imides (eg, phthalimide); cyclic imides, pyrazolin-5-ones, and quinazolinones (eg, succinimide, 3-phenyl-2-pyrazolin-5-one, 1-phenylurazole, quinazoline and 2,4-
Thiazolidinedione); naphthalimides (for example,
N-hydroxy-1,8-naphthalimide); cobalt complexes (e.g., hexane trifluoroacetate of cobalt), mercaptans (e.g., 3-mercapto-
1,2-, 4-triazole); N- (aminomethyl) aryldicarboximides (eg, N- (dimethylaminomethyl) phthalimide); blocked pyrazoles, isothiuronium.
m) Combinations of derivatives and certain photobleaches (e.g. N, N'hexamethylene (1-carbamoyl-3,
5-dimethylpyrazole), 1,8- (3,6-dioxaoctane) bis (isothiuronium trifluoroacetate), and 2- (tribromomethylsulfonyl)
Benzothiazole combinations); merocyanine dyes (e.g., 3-ethyl-5-((3-ethyl-2-benzothiazolinylidene (benzothiazoliny)
lidene))-1-methylethylidene) -2-thio-2,4-oxazolidinedione (oxazolidi)
nedone)); phthalazinone, a phthalazinone derivative or a metal salt of these derivatives (for example, 4- (1-
Naphthyl) phthalazinone, 6-chlorophthalazinone,
5,7-dimethyloxyphthalazinone, and 2,3-
Dihydro-1,4-phthalazinedione); a combination of phthalazinone and a sulfinic acid derivative (eg, 6-chlorophthalazinone + sodium benzenesulfinate or 8-methylphthalazinone + sodium p-trisulfonate); phthalazine + phthalic acid Combinations of phthalazine (including adducts of phthalazine) and maleic anhydride,
And phthalic acid, 2,3-naphthalenedicarboxylic acid or o-phenylene acid derivative and its anhydride (for example,
A combination with at least one compound selected from phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid and tetrachlorophthalic anhydride; quinazolinediones, benzoxazine, naloxazine derivatives; benzoxazine-2,4-dione (Eg, 1,3-benzoxazine-2,4-dione); pyrimidines and asymmetric-triazines (eg, 2,4-dihydroxypyrimidine), and tetraazapentalene derivatives (eg, 3,6- Dimercapto-1,4-diphenyl-1
H, 4H-2,3a, 5,6a-tetraazapentalene. The preferred toning agent is phthalazone.

In the heat-developable image forming material according to the preferred embodiment of the present invention, the photosensitive silver halide useful as a photocatalyst having a catalytic activity is any photosensitive silver halide (eg, silver bromide, iodine). Silver chloride, silver chloride, silver chlorobromide, silver iodobromide, silver chloroiodobromide, etc., but preferably contains iodide ions. The silver halide may be added to the image forming layer (recording layer) by any method, and the silver halide is arranged so as to be close to the reducible silver source. Generally, it is preferred that the silver halide contains 0.75 to 30% by weight based on the reducible silver salt. Silver halide may be prepared by conversion of the silver soap portion by reaction with a halide ion, may be preformed and added during the generation of the soap, or a combination of these methods is possible. Of these, the latter is preferred. The photosensitive silver halide will be described later in detail.

Non-photosensitive reducible silver salts (silver sources) are silver salts of organic and heteroorganic acids containing a reducible silver ion source, especially long chains (10-30, preferably 15-25 carbon atoms). (Atoms) aliphatic carboxylic acids are preferred. Organic or inorganic silver salt complexes wherein the ligand has a total stability constant for silver ions of 4.0 to 10.0 are also useful. An example of a suitable silver salt is Research Disclosur.
e Nos. 17029 and 29996, and include: Salts of organic acids (eg, gallic acid, oxalic acid, behenic acid, stearic acid, palmitic acid, lauric acid, etc.); carboxylalkylthiourea salts of silver (eg, 1- (3-carboxypropyl) thiourea, 1-
(3-carboxypropyl) -3,3-dimethylthiourea and the like); silver complexes of polymer reaction products of aldehydes and hydroxy-substituted aromatic carboxylic acids (for example, aldehydes (formaldehyde, acetaldehyde, butyraldehyde), hydroxy-substituted acids) (Eg, salicylic acid,
Benzoic acid, 3,5-dihydroxybenzoic acid, 5,5-thiodisalicylic acid), silver salts or complexes of thioenes (for example, 3- (2-carboxyethyl) -4-hydroxymethyl-4- (thiazoline-2) -Thioene, and 3-carboxymethyl-4-thiazoline-2-thioene), imidazole, pyrazole, urazole, 1,2,4-thiazole and 1H-tetrazole, 3-amino-5-
Complexes or salts of silver and a nitrogen acid selected from benzylthio-1,2,4-triazole and benzotriazole; silver salts such as saccharin and 5-chlorosalicylaldoxime; and silver salts of mercaptides. The preferred silver source is silver behenate. The reducible silver salt is preferably used in an amount of 5 g / m ² as an amount of silver per m ² of the heat-developable image forming material.
Or less, and more preferably 0.3 to 3.0 g / m ^2.
It is.

The reducing agent is a substance capable of reducing silver ions to metallic silver, preferably an organic substance. Conventional photographic developers such as, for example, methyl gallate, hydroquinone, substituted hydroquinone, sterically hindered phenols, catechol, pyrogallol, ascorbic acid and ascorbic acid derivatives are useful. Further, a compound represented by the general formula (1) described in JP-A-10-221806 can also be used.

The heat-developable image forming material of the invention according to claim 6 may contain an antifoggant. The most effective antifoggant was mercury ion. The use of mercury compounds as antifoggants in thermally developed imaging materials is disclosed, for example, in U.S. Pat. No. 3,589,903. However, mercury compounds are environmentally unfriendly. As the non-mercury antifoggant, for example, antifoggants disclosed in U.S. Pat. Nos. 4,546,075 and 4,452,885 and JP-A-59-57234 are preferable.

Particularly preferred non-mercury antifoggants are described in US Pat. Nos. 3,874,946 and 4,756,993.
No.9, -C (X ¹ )
(X ² ) (X ³ ) wherein X ¹ and X ² are halogen (eg, F, Cl, Br or I) and X ³ is hydrogen or halogen. It is a cyclic compound. Examples of suitable antifoggants include:

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Still more suitable antifoggants are disclosed in US Pat. No. 5,028,523 and British Patent Application No. 92221.
Nos. 383.4, 9300147.7 and 93117
No. 90.1.

The heat-developable image forming material of the invention according to claim 6 includes, for example, JP-A-63-159814 and JP-A-60-1.
No. 40335, No. 63-231437, No. 63-25
Nos. 9651, 63-304242, 63-152
No. 45, U.S. Pat. Nos. 4,639,414 and 4,74.
0,455, 4,741,966, 4,75
The sensitizing dyes described in 1,175 and 4,835,096 can be used.

The useful sensitizing dye used in the invention according to claim 6 is, for example, RESEARCH DISCLOSURE.
It is described in the literature described or cited in Item 17643 IV-A (p. 23, December 1978) and Item 1831X (p. 437 in August 1978).

In particular, a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of various scanner light sources can be advantageously selected.

For example, A) Japanese Patent Application Laid-Open No. 60-162247 and Japanese Patent Application Laid-Open No.
No. 3, U.S. Pat. No. 2,161,331, West German Patent No. 9
No. 36,071 and simple merocyanines described in Japanese Patent Application No. Hei 3-189532. B) For helium-neon laser light sources, see JP-A-50-62425 and JP-A-54-1.
Nos. 8726 and 59-102229; trinuclear cyanine dyes; Japanese Patent Application No. 6-103272; merocyanines; C) LED light sources and red semiconductor lasers; Id. 51-96
09, 55-39818, JP-A-62-2843.
Thiacarbocyanines described in JP-A-43-105, JP-A-2-105135, and D) Infrared semiconductor laser light sources are disclosed in JP-A-59-191032 and JP-A-60-8084.
Tricarbocyanines described in No. 1;
No. 192242 and JP-A-3-67242.
a), dicarbocyanines containing a 4-quinoline nucleus described in formula (IIIb) and the like are advantageously selected.

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used particularly for supersensitization. In addition to the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization.

For the image forming layer of the image forming material of the invention according to claim 6, a technique using a super-high contrast agent described in JP-A-10-221806 can be applied.

The exposure of the heat-developable image forming material, which is a preferred embodiment of the invention according to claim 6, is performed by using an Ar laser (488n).
m), a He-Ne laser (633 nm), a red semiconductor laser (670 nm), and an infrared semiconductor laser (780
nm, 830 nm).

In the heat-developable image forming material according to the preferred embodiment of the present invention, a layer containing a dye can be provided as an antihalation layer. Ar laser,
400 for He-Ne laser and red semiconductor laser
exposure wavelength in the range of at least 0.1 nm to 750 nm.
The dye is added so as to have an absorption of 3 or more, preferably 0.8 or more. 750nm-1 for infrared semiconductor laser
The dye is added so as to absorb at least 0.3 or more, preferably 0.8 or more at the exposure wavelength in the range of 500 nm. One or more dyes may be used in combination.

Such a dye can be added to a dye layer near the support on the same side as the photosensitive layer (emulsion layer) or a dye layer opposite to the photosensitive layer.

The support used in the invention according to claim 6 is paper, synthetic paper, paper laminated with synthetic resin (eg, polyethylene, polypropylene, polystyrene), plastic film (eg, polyethylene terephthalate, polycarbonate, polyimide, nylon) , Cellulose triacetate), a metal plate (for example, aluminum, an aluminum alloy, zinc, iron, or copper), paper or a plastic film on which the above-described metal is laminated or vapor-deposited, or the like.

On the other hand, when the plastic film is passed through a heat developing machine, the dimensions of the film expand and contract. When used as a printing photosensitive material, this expansion and contraction is a serious problem when performing precision multicolor printing. Therefore, in the present invention, it is preferable to use a film having small dimensional change. For example, there are a styrene-based polymer having a syndiotactic structure and a heat-treated polyethylene. Those having a high glass transition point are also preferable, and polyether ethyl ketone, polystyrene, polysulfone, polyethersulfone, polyarylate and the like can be used.

The image forming material of the invention according to claim 6 includes a mercapto compound and a disulfide compound for suppressing or accelerating the development, controlling the spectral sensitization, and improving the storage stability before and after the development. , A thione compound.

When a mercapto compound is used in the invention according to claim 6, it may have any structure,
Those represented by SM and Ar-SS-Ar are preferred.
Wherein M is a hydrogen atom or an alkali metal atom;
r is an aromatic or fused aromatic group having one or more nitrogen, sulfur, oxygen, selenium or tellurium atoms. Preferably, the heteroaromatic ring in these groups is benzimidazole, naphthymidazole, benzothiazole, naphthothiazole, benzoxazole, naphthoxazole, benzoselenazole, benzotellurazole, imidazole, oxazole, pyrazole, triazole, thiadiazole, tetrazole, Triazine,
Pyrimidine, pyridazine, pyrazine, pyridine, purine, quinoline or quinazolinone. The heteroaromatic ring includes, for example, halogen (eg, Br and Cl),
Hydroxy, amino, carboxy, alkyl (eg,
One or more carbon atoms, preferably having 1 to 4 carbon atoms) and alkoxy (for example, having one or more carbon atoms, preferably having 1 to 4 carbon atoms)
And a substituent selected from the group consisting of:
Examples of the mercapto-substituted heteroaromatic compound include 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-mercapto-5-methylbenzimidazole, 6-ethoxy-
2-mercaptobenzothiazole, 2,2'-dithiobis-benzothiazole, 3-mercapto-1,2,4-
Triazole, 4,5-diphenyl-2-imidazolethiol, 2-mercaptoimidazole, 1-ethyl-
2-mercaptobenzimidazole, 2-mercaptoquinoline, 8-mercaptopurine, 2-mercapto-4
(3H) -quinazolinone, 7-trifluoromethyl-4
-Quinolinethiol, 2,3,5,6-tetrachloro-
4-pyridinethiol, 4-amino-6-hydroxy-
2-mercaptopyrimidine monohydrate, 2-amino-5-mercapto-1,3,4-thiadiazole, 3-
Amino-5-mercapto-1,2,4-triazole,
4-hydroxy-2-mercaptopyrimidine, 2-mercaptopyrimidine, 4,6-diamino-2-mercaptopyrimidine, 2-mercapto-4-methylpyrimidine hydrochloride, 3-mercapto-5-phenyl-1,
Examples include, but are not limited to, 2,4-triazole, 2-mercapto-4-phenyloxazole, and the like.

The addition amount of these mercapto compounds is preferably in the range of 0.001 to 1.0 mol per mol of silver in the emulsion layer, more preferably 0.01 to 0.3 mol per mol of silver. Is the amount of

The method for forming photosensitive silver halide in the invention according to claim 6 is well known in the art, and is described in, for example, Research Disclosure, June 1, 1978.
No. 7029 and U.S. Pat. No. 3,700,458. Specific methods that can be used in the present invention include a method of converting a part of the silver of the organic silver salt to a photosensitive silver halide by adding a halogen-containing compound to the prepared organic silver salt, gelatin. Alternatively, a method of preparing a photosensitive silver halide grain by adding a silver supply compound and a halogen supply compound to another polymer solution and mixing the resultant with an organic silver salt can be used. In the present invention, the latter method can be preferably used. The grain size of the photosensitive silver halide is preferably small for the purpose of suppressing white turbidity after image formation, specifically 0.20 μm or less, more preferably 0.01 μm or more and 0.15 μm or less, and still more preferably. Is preferably 0.02 μm or more and 0.12 μm or less. Here, the grain size means the length of the edge of the silver halide grain when the silver halide grain is a cubic or octahedral so-called normal crystal. In the case where the silver halide grains are tabular grains, the diameter refers to a diameter when converted into a circular image having the same area as the projected area of the main surface. In the case of other than normal crystals, for example, in the case of spherical particles, rod-like particles, etc., the diameter refers to the diameter of a sphere equivalent to the volume of silver halide grains.

The shape of the silver halide grains is cubic,
Octahedral, tabular particles, spherical particles, rod-like particles, potato-like particles and the like can be mentioned. In the present invention, cubic particles and tabular particles are particularly preferable. When tabular silver halide grains are used, the average aspect ratio is preferably 100: 1 to 2: 1, more preferably 50: 1 to 3:
1 is good. Further, grains having rounded corners of silver halide grains can also be preferably used. The surface index (mirror index) of the outer surface of the photosensitive silver halide grains is not particularly limited. However, the spectral sensitization efficiency when the spectral sensitizing dye is adsorbed is high. preferable. The ratio is preferably 50% or more.
% Or more, more preferably 80% or more. The ratio of the {100} plane of the Miller index is determined by the T.M. Tani; Imaging Sci. , 29,
165 (1985). The halogen composition of the photosensitive silver halide is not particularly limited and partially described above, but may be any of silver chloride, silver chlorobromide, silver bromide, silver iodobromide, silver iodochlorobromide, and silver iodide. In the present invention, silver bromide or silver iodobromide can be preferably used. Particularly preferred is silver iodobromide, and the silver iodide content is preferably from 0.1 mol% to 40 mol%, more preferably from 0.1 mol% to 20 mol%. The distribution of the halogen composition in the grains may be uniform, the halogen composition may be changed stepwise, or may be changed continuously, but as a preferred example, the silver iodide content inside the grains is High silver iodobromide grains can be used.
Preferably, silver halide grains having a core / shell structure can be used. As the structure, core / shell particles having preferably a 2- to 5-layer structure, more preferably a 2- to 4-layer structure, can be used.

The photosensitive silver halide grain of the invention according to claim 6 preferably contains at least one complex of a metal selected from rhodium, rhenium, ruthenium, osmium, iridium, cobalt or iron. One type of these metal complexes may be used, or two or more types of complexes of the same metal and different metals may be used in combination. The preferred content is in the range of 1 nmol to 10 mmol per 1 mol of silver, more preferably 10 nmol to 100 µmol. The structure of a specific metal complex is described in JP-A-7-225.
No. 449, etc. can be used. As the compound of cobalt and iron, a hexacyano metal complex can be preferably used. As a specific example,
Examples include, but are not limited to, ferricyanate ion, ferrocyanate ion, and hexacyanocobaltate ion. The content of the metal complex in the silver halide may be uniform, may be contained at a high concentration in the core portion, or may be contained at a high concentration in the shell portion, and there is no particular limitation.

The photosensitive silver halide grains can be desalted by washing with a method known in the art such as a noodle method or flocculation method, but in the present invention, it may or may not be desalted. .

The photosensitive silver halide grains are preferably chemically sensitized. As a preferred chemical sensitization method, a sulfur sensitization method, a selenium sensitization method, and a tellurium sensitization method are well known in the art. Further, a noble metal sensitization method or a reduction sensitization method of a gold compound, platinum, palladium, an iridium compound or the like can be used. As the compound preferably used in the sulfur sensitization method, the selenium sensitization method, and the tellurium sensitization method, known compounds can be used, and the compounds described in JP-A-7-128768 can be used. Examples of tellurium sensitizers include diacyl tellurides, bis (oxycarbonyl) tellurides, bis (carbamoyl) tellurides, diacyl tellurides, bis (oxycarbonyl) ditellurides, bis (carbamoyl)
Ditellurides, compounds having a P = Te bond, tellurocarboxylates, Te-organyltellurocarboxylates, di (poly) tellurides, tellurides, tellurols, telluroacetals, tellurosulfonates, P
Compounds having a -Te bond, Te-containing heterocycles, tellurocarbonyl compounds, organic tellurium compounds, colloidal tellurium, and the like can be used. Compounds preferably used in the noble metal sensitization method include, for example, chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide, gold selenide, and US Pat. No. 2,448,0
No. 60 and British Patent No. 618061 can be preferably used. As specific compounds of the reduction sensitization method, in addition to ascorbic acid and thiourea dioxide, for example, stannous chloride, aminoiminomethanesulfinic acid, hydrazine derivatives, borane compounds, silane compounds, polyamine compounds and the like can be used. . Further, reduction sensitization can be achieved by ripening the emulsion while maintaining the pH of the emulsion at 7 or more or the pAg at 8.3 or less.
Further, reduction sensitization can be achieved by introducing a single addition portion of silver ion during grain formation.

The amount of the photosensitive silver halide to be used is preferably 0.01 mol or more and 0.5 mol or less with respect to 1 mol of the non-photosensitive reducible silver salt.
2 mol or more and 0.3 mol or less are more preferable, and 0.03 mol or more and 0.25 mol or less are particularly preferable. It is preferable that the silver halide emulsion layer contains a non-photosensitive reducible silver salt. When the above silver salt is contained in the silver halide emulsion layer, the method of mixing and the mixing conditions of the separately prepared photosensitive silver halide and non-photosensitive reducible silver salt are described below. Preparation was completed at any timing during the method of mixing the particles and the silver salt with a high-speed stirrer, a ball mill, a sand mill, a colloid mill, a vibration mill, a homogenizer or the like, or during the preparation of a non-photosensitive reducible silver salt. There is a method of mixing the photosensitive silver halide to prepare the silver salt, but there is no particular limitation as long as the effects of the present invention are sufficiently exhibited.

As described above, the heat-developable image-forming material according to the sixth aspect of the present invention has at least one photosensitive layer containing a silver halide emulsion (emulsion layer) on one side of the support, and the other side. It is preferably a so-called single-sided photosensitive material having a backing layer (back layer) on the side.

The image forming material of the invention according to claim 6 includes:
A matting agent may be added to improve transportability. The matting agent is generally fine particles of an organic or inorganic compound insoluble in water. Any matting agent can be used. For example, U.S. Patent Nos. 1,939,213 and 2,701,
No. 245, No. 2,322,037, No. 3,539,3
No. 44, 3,767, 448, etc., organic matting agents described in each specification, 1, 260, 772, 2, 19
2,241, 3,257,206, 3,37
0,951, 3,523,022, 3,76
Inorganic matting agents well-known in the art, such as the inorganic matting agent described in each specification such as 9,020, can be used. For example, specifically, examples of organic compounds that can be used as a matting agent include polymethyl acrylate, polymethyl methacrylate, polyacrylonitrile, acrylonitrile-α-methylstyrene copolymer, and polystyrene as examples of a water-dispersible vinyl polymer. , Styrene-divinylbenzene copolymer, polyvinyl acetate, polyethylene carbonate, polytetrafluoroethylene, etc., examples of cellulose derivatives such as methylcellulose, cellulose acetate, cellulose acetate propionate, and starch derivatives such as carboxy starch, carboxynitrophenyl Such as starch, urea-formaldehyde-starch reactant, and the like, gelatin hardened with a known hardener, and hardened gelatin coacervate hardened into microcapsule hollow granules. It can be used Mashiku. Examples of inorganic compounds include silicon dioxide, titanium dioxide, magnesium dioxide, aluminum oxide, barium sulfate, calcium carbonate, silver chloride desensitized by known methods, and silver bromide,
Glass, diatomaceous earth and the like can be preferably used. The above matting agents can be used by mixing different types of substances as necessary. The size and shape of the matting agent are not particularly limited, and those having an arbitrary particle size can be used.
In the practice of the present invention, it is preferable to use one having a particle size of 0.1 μm to 30 μm. Further, the particle size distribution of the matting agent may be narrow or wide. On the other hand, since the matting agent greatly affects the haze of the coating film and the surface gloss, the particle size, the shape, and the particle size distribution can be changed as necessary during the preparation of the matting agent or by mixing a plurality of matting agents. preferable.

In the invention according to claim 6, the matting degree of the backing layer is such that the Bekk smoothness is preferably 250 seconds or less and 10 seconds or more, more preferably 180 seconds or less and 50 seconds or more.

In the invention according to claim 6, the matting agent is preferably contained in the outermost surface layer of the heat-developable recording material, a layer functioning as the outermost surface layer, or a layer close to the outer surface. It is preferably contained in a layer acting as a layer.

In the invention according to claim 6, suitable binders for the backing layer are transparent or translucent, generally colorless, and include natural polymers, synthetic resins, polymers and copolymers, and other film-forming media such as gelatin and Arabic. Rubber, poly (vinyl alcohol), hydroxyethyl cellulose, cellulose acetate, cellulose acetate butyrate, poly (vinyl pyrrolidone), casein, starch, poly (acrylic acid), poly (methyl methacrylic acid), poly (vinyl chloride), poly (vinyl chloride) (Methacrylic acid), copoly (styrene-maleic anhydride), copoly (styrene-acrylonitrile), copoly (styrene-butadiene), poly (vinyl acetal)
[Eg, poly (vinyl formal) and poly (vinyl butyral)], poly (esters), poly (urethanes), phenoxy resins, poly (vinylidene chloride),
There are poly (epoxides), poly (carbonates), poly (vinyl acetate), cellulose esters, and poly (amides). The binder may be coated from water or an organic solvent or emulsion.

In the heat-developable image forming material which is a preferred embodiment of the invention according to claim 6, the backing layer preferably has a maximum absorption in a desired wavelength range of 0.3 or more, more preferably 0.1 or less. It is preferably infrared absorption of 5 or more and 2 or less, and absorption in the visible region is preferably 0.001 or more and less than 0.5, and more preferably antihalation having an optical density of 0.001 or more and less than 0.3. It is preferably a layer.

When an antihalation dye is used, it is desirable that such a dye has a desired absorption in a desired wavelength range, has a sufficiently low absorption in the visible region, and has a desirable absorbance spectrum shape of the back layer. Any compound may be used. For example, compounds described in JP-A-7-13295, U.S. Pat. No. 5,380,635, JP-A-2-685
No. 39, page 13, lower left column, line 1 to page 14, lower left column, line 9; and JP-A-3-24539, page 14, lower left column, page 16, lower right column. The invention is not limited to these.

A backside resistive heating layer as shown in US Pat. Nos. 4,460,681 and 4,374,921.
The thinning layer can also be used in a photothermographic image system as in the present invention.

The heat-developable image-forming material of the invention according to claim 6 can be provided with a surface protective layer for the purpose of preventing adhesion of the image-forming layer. Any anti-adhesion material may be used as the surface protective layer. Examples of anti-adhesion materials include:
Examples include waxes, silica particles, styrene-containing elastomeric block copolymers (eg, styrene-butadiene-styrene, styrene-isoprene-styrene), cellulose acetate, cellulose acetate butyrate, cellulose propionate, and mixtures thereof.

The emulsion layer (photosensitive layer) or the protective layer of the emulsion layer in the heat-developable image-forming material according to a preferred embodiment of the invention according to claim 6, is provided with US Pat. No. 3,253,921.
No. 2,274,782, No. 2,527,58
Light absorbing materials and filter dyes as described in US Pat. No. 3,956,879 and No. 2,956,879 can be used. See also, for example, U.S. Pat. No. 3,282,699.
The dye can be mordanted as described in the item.

The image forming layer or the protective layer of this layer in the invention according to claim 6 may have a matting agent such as starch,
Titanium dioxide, zinc oxide, silica, U.S. Pat.
Polymer beads including beads of the type described in 2,101 and 2,701,245 can be contained. The matting degree of the recording surface (e.g., emulsion surface) may be any value as long as stardust failure does not occur, but the Beck smoothness is preferably from 200 seconds to 10,000 seconds, and particularly preferably from 300 seconds to 10,000 seconds.

In the invention according to claim 7, a silicone rubber layer is suitably used as the ink repellent layer. As the silicone rubber layer, a hydroxyl group or a carbon-carbon unsaturated bond (for example, vinyl) having a repeating unit represented by the following general formula (S) in a main chain having a molecular weight of thousands to hundreds of thousands or at a terminal of the main chain. A layer composed of a silicone rubber composition containing, as a main component, a linear organic polysiloxane having two or more groups (aryl groups).

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In the general formula (S), n is an integer of 2 or more, R is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group, an alkoxy group, a hydroxyl, a phenyl group or a carbon-carbon unsaturated bond. It is preferable that 60% or more of R is a methyl group. The hydroxyl group or carbon-carbon unsaturated bond may be present in the main chain or at the terminal of the main chain, but is preferably at the terminal.

Specific examples of the linear organic polysiloxane include α, ω-dihydroxypolydimethylsiloxane,
α, ω-bis (dimethylvinylsilyl) polydimethylsiloxane and the like.

The silicone rubber layer is obtained by a condensation reaction or an addition reaction between the above-mentioned linear organic polysiloxanes or with a crosslinking agent. Preferably, a reactive crosslinking agent is added to form a crosslinked silicone rubber by a condensation reaction or an addition reaction.

Examples of the crosslinking agent include a reactive silane compound represented by the following general formula (17) and two or more S
A polyvalent hydrogen polysiloxane having an iH bond is preferably used.

Formula (17) R ¹⁴ _-n SiX _{n In the} formula, n is an integer of 1 to 4, and R ¹ is an alkyl group, an aryl group, an alkenyl group, or a monovalent group obtained by combining them. Or a group represented by a halogen atom, an amino group, a hydroxyl group, an alkoxy group, an aryloxy group, a thiol group, a glycidyl group, a (meth) acryloxy group, or another functional group such as an isocyanurate group substituted with a vinyl group. You may have. X is -OH, -R ^2, -A
^{c, -O-N = CR 3} , represents -Cl, -Br, substituents such as -I. Here, R ² and R ³ are the same as R ¹ described above, and Ac represents an acetyl group.

Specific examples of the crosslinking agent include trimethoxymethylsilane, triacetoxymethylsilane, γ-aminopropyltrimethoxysilane, methyltris (dimethylketoxime) silane, and 1- [3- (trimethoxysilyl) propyl]. -3,5-diallyl diallyl isocyanurate, 1,3,5-tris [3- (trimethoxysilyl) propyl] isocyanurate, N, N-bis [3- (trimethoxysilyl) propyl] methacrylamide, N- Glycidyl-N, N-bis [3- (trimethoxysilyl) propyl] amine, N, N-bis [3-
(Trimethoxysilyl) propyl] amine, α, ω-bis (trimethylsilyl) poly (methyl hydrogen)
(Dimethyl) siloxane copolymer, α, ω-bis (dimethylhydrogensilyl) polydimethylsiloxane,
1,3,5,7-tetramethyl-1-glycidoxypropylcyclotetrasiloxane and the like.

These crosslinking agents are used alone or as a mixture of two or more kinds.
30 parts by weight, preferably 2 to 10 parts by weight.

Further, a small amount of an organotin compound (eg, dibutyltin dilaurate, tin (II) octoate), an organic cobalt compound (eg, cobalt naphthenate), platinum alone,
Platinum chloride, chloroplatinic acid, olefin-coordinated platinum and the like are used.

For the purpose of controlling the curing rate of the silicone rubber composition, a crosslinking inhibitor such as an organopolysiloxane having a vinyl group such as tetracyclo (methylvinyl) siloxane or an alcohol having a carbon-carbon triple bond is added. It is also possible. In order to improve the strength of the silicone rubber layer and obtain a silicone rubber layer that can withstand the frictional force generated during the printing operation, a filler can be mixed. The filler may be of any material, regardless of whether it is an inorganic compound or an organic compound.

The silicone rubber layer is preferably formed by dissolving the silicone rubber composition in a suitable solvent, coating the photosensitive layer on the photosensitive layer, drying and heat-curing, and has a thickness of about 0.1 to 20 μm. Suitable, preferably 1-4
μm.

The substrate used for the image forming material according to the seventh aspect of the present invention is not particularly limited, and paper, plastic (eg, polyethylene, polypropylene, polystyrene, etc.) laminated paper, aluminum (including aluminum alloy), zinc, copper Metal plates, such as cellulose diacetate, cellulose triacetate, cellulose propionate, polyethylene terephthalate, polyethylene, polypropylene, polycarbonate, plastic films such as polyvinyl acetal, paper or the like on which the metal is laminated or vapor-deposited or Examples include a plastic film, aluminum or a chrome-plated copper plate.

In the image forming material of the present invention, a layer containing an energy-sensitive base generator and an ink repellent layer can be provided on a substrate in this order or in the reverse order. A primer layer can be provided between the substrate and the layer containing the energy-sensitive base generator or the ink repellent layer.

Examples of the primer layer include the following resin compositions.

(1) Epoxy Resin and Resin Composition Containing Epoxy A typical example of the epoxy resin used for the primer layer is a reaction product of epichlorohydrin and a polyhydric phenol such as bisphenol A. The epoxy resin may be mixed with other components to be three-dimensional, or may be modified by other components. The usage examples are as follows.

A thermosetting resin composition containing an epoxy resin obtained by mixing one or two or more thermosetting resins such as a phenol resin, a urea resin and a melamine resin, amines, polyamides, acid anhydrides, etc. Room temperature or heat-curable resin composition containing an epoxy resin obtained by adding as a curing agent, phenol, melamine, urea or these resins,
Epoxy resins obtained by precondensation with one or more of amines, polyesters, polyamides, polysulfides, etc., and epoxy resin esters obtained by esterification with fatty acids.

These epoxy resins can be used by mixing as appropriate, or can be further used as long as compatibility with a vinyl resin, an acrylic resin, an amino resin, an alkyd resin, a urethane resin or the like is permitted. is there.
When curing the curable resin containing these epoxy resins, a curing reaction accelerator such as p-toluenesulfonic acid and boron trifluoride monoethylamine can be appropriately added and used as necessary.

(2) Composition composed of a resin obtained by photocuring a layer composed of a photoduplex type photocurable resin As the photoduplex type photocurable resin, a polymer having a main chain or a side chain

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And the like. Polyesters, polycarbonates, polyamides, polyacrylic esters, polyvinyl alcohol derivatives and the like, and the molecular weight thereof are not limited as long as they are soluble in a solvent.
It is advantageous to select from a range of 0 to tens of thousands. Particularly preferred such polymers are, for example, U.S. Pat. Nos. 3,030,208 and 3,707,373.
No. 2,956,878 and the like, a photosensitive polymer containing a photosensitive group in the polymer main chain, such as a photosensitive polyester composed of p-phenylenediacrylic acid and a diol, as described in the specifications of U.S. Pat. No. 3,173,78
7, a photosensitive polyester derived from a photosensitive polymer such as a 2-propylidenemalonic acid compound such as cinnamylidenemalonic acid and a difunctional glycol, U.S. Pat. 2,690,96
No. 6, No. 2, 752, 372, No. 2, 732, 3
No. 01, such as cinnamate esters of hydroxyl-containing polymers such as polyvinyl alcohol, starch, cellulose and the like, which are insolubilized by the action of actinic rays. Etc. are included.

A pigment or dye is added to the above-mentioned polymer as a colorant. For example, phthalocyanine blue (C.I.
I. 74160), Carmine 6B (CI. 1585)
0) and pigments such as Rhodamine B lake (C.I. 45170) are preferred, but oil blue BO (C.I.
Dyes such as 50) can also be used. The amount of addition naturally varies depending on conditions such as the amount of application, but it is 1 to 1 with respect to the polymer.
50% by weight, a particularly preferred range is 2 to 15% by weight.

It is preferable that the above-mentioned polymer contains a sensitizer. Such sensitizers include, for example, U.S. Pat. Nos. 2,610,120, 2,670,285, 2,670,286, 2,670,287, 2,690,966, 2,732,301, 2,835,656, 2,956,878, 3,023,100, 3,066,177, 3,141,770, and 3 No. 3,173,787, No. 3,357,831, No. 3,409,593, No. 3,418,295, No. 3,453,110, No. 3,475,617, No. 3,561. , 969, 3,575,929, 3,582,327, 3,647,470, 3,721,566, 3,737,319, etc. Is included. Specific examples of particularly useful sensitizers include 2-benzoylmethylene-1-methyl-β-naphthothiazoline,
Nitroacenaphthene, β-chloroanskinone, 1,2
-Benzal anthraquinone, p, p'-tetraethyldiaminodiphenyl ketone, p, p'-dimethylaminobenzophenone, 4-nitro-2-chloroaniline and the like. The use ratio of the sensitizer was 0.5 to the polymer.
The range is preferably from 15 to 15% by weight, and a particularly preferred range is from 2 to 8% by weight.

(3) Use of Gelatin as Binder As gelatin, so-called photographic gelatin obtained from beef bone or skin by acid treatment or alkali treatment is mainly used. In addition, it is represented by the following general formula. Any gelatin can be used as long as it is a natural polymer compound in which various amino acids are condensed.

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The following hardening agents are used for hardening (ie, cross-linking) gelatin.

(A) Inorganic hardener Chromium alum, aluminum alum, etc. (B) Organic hardener Compounds described in JP-A-63-305360, page 4, lower right column to page 5, lower right column (B-1) to (B-12).

The amino acids in the gelatin that can be used for the hardening reaction differ depending on the type of hardener used, and the composition of the amino acids differs depending on the gelatin used. Therefore, the optimum amount of the hardener to be added varies depending on the kind of the gelatin used and the kind of the hardener, but generally, 1 to 200 mmol, preferably 5 to 100 mmol of the hardener is added to 100 parts by weight of gelatin. Is good.

(4) Composition Containing Diazo Resin and / or Photopolymerizable Photosensitive Composition The diazo resin includes various ones.
A diazo resin represented by a condensate of diazodiphenylamine and formaldehyde, which is insoluble in water and soluble in an organic solvent, and is preferably described in JP-B Nos. 47-1167 and 57-43890. Such water-insoluble and ordinary organic solvent-soluble materials are used. Particularly preferred is a diazo resin represented by the following formula (D).

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(Wherein, R ¹ , R ² and R ³ each represent a hydrogen atom, an alkyl group or an alkoxy group, R ⁴ represents a hydrogen atom, an alkyl group or a phenyl group. X represents PF ₆ or BF ₄ And Y represents -NH-, -S- or -0-.) Examples of the diazo monomer in the above diazo resin include 4-diazo-diphenylamine and 1-diazo-4-
N, N-dimethylaminobenzene, 1-diazo-4-
N, N-diethylaminobenzene, 1-diazo-4-N
-Ethyl-N-hydroxyethylaminobenzene, 1-
Diazo-4-N-methyl-N-hydroxyethylaminobenzene, 1-diazo-2,5-diethoxy-4-benzoylaminobenzene, 1-diazo-4-N-benzylaminobenzene, 1-diazo-4-N , N-dimethylaminobenzene, 1-diazo-4-morpholinobenzene,
1-diazo-2,5-dimethoxy-4-p-tolylmercaptobenzene, 1-diazo-2-ethoxy-4-N,
N-dimethylaminobenzene, p-diazo-dimethylaniline, 1-diazo-2,5-dibutoxy-4-morpholinobenzene, 1-diazo-2,5-diethoxy-4-
Morpholinobenzene, 1-diazo-2,5-dimethoxy-4-morpholinobenzene, 1-diazo-2,5-diethoxy-4-p-tolylmercaptobenzene, 1-diazo-4-N-ethyl-N-hydroxyethyl Aminobenzene, 1-diazo-3-ethoxy-4-N-methyl-N
-Benzylaminobenzene, 1-diazo-3-chloro-
4-N, N-diethylaminobenzene, 1-diazo-3
-Methyl-4-pyrrolidinobenzene, 1-diazo-2-
Chloro-4-N, N-dimethylamino-5-methoxybenzene, 1-diazo-3-methoxy-4-pyrrolidinobenzene, 3-methoxy-4-diazodiphenylamine,
3-ethoxy-4-diazodiphenylamine, 3- (n
-Propoxy) -4-diazodiphenylamine, 3-
(Isopropoxy) -4-diazodiphenylamine and the like.

Examples of the aldehyde used as a condensing agent with the diazo monomer include formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, and benzaldehyde.

Further, a water-soluble diazo resin can be obtained by using chlorine ion or tetrachlorozinc acid as an anion. Boron tetrafluoride, hexafluorophosphoric acid, triisopropylnaphthalenesulfonic acid, , 4 '
Obtaining a diazo resin soluble in an organic solvent by using -biphenyldisulfonic acid, 2,5-dimethylbenzenesulfonic acid, 2-nitrobenzenesulfonic acid, 2-methoxy-4-hydroxy-5-benzoyl-benzenesulfonic acid, or the like. Can be. Particularly preferably, a diazo resin composed of hexafluorophosphoric acid is used.

The diazo resin is a film-forming resin such as a polyester resin, a vinyl chloride-vinyl acetate copolymer, an acrylic resin, a vinyl chloride resin, a polyamide resin, a polyvinyl butyral resin, an epoxy resin, an acrylate copolymer, and a vinyl acetate resin. It is used as a mixture with a copolymer, a phenoxy resin, a polyurethane resin, a polycarbonate resin, polyacrylonitrile butadiene, polyvinyl acetate, and the like, but it is particularly preferable to use a mixture with a lipophilic polymer compound having a hydroxyl group. Examples of such a lipophilic polymer compound include a monomer having an aliphatic hydroxyl group in a side chain, for example, a copolymer of 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate with another copolymerizable monomer. In addition to these, a polyvinyl butyral resin, a polyurethane resin, a polyamide resin, an epoxy resin, a novolak resin, a natural resin, and the like may be added as necessary.

As the binder used in combination with the diazo resin, various polymer compounds can be used, but preferably a simple compound having an aromatic hydroxyl group as described in JP-A-54-98613 is used. Monomers such as N- (4-hydroxyphenyl) acrylamide, N- (4-hydroxyphenyl) methacrylamide, o-, m-, or p-
Copolymers of -hydroxystyrene, o-, m- or p-hydroxyphenyl methacrylate with other monomers, hydroxyethyl acrylate as described in U.S. Pat. No. 4,123,276 Unit or a polymer containing a hydroxyethyl methacrylate unit as a main repeating unit, shellac, natural resins such as rosin, polyvinyl alcohol, US Pat. No. 3,751,
No. 257, a linear polyurethane resin described in US Pat. No. 3,660,097, a phthalated resin of polyvinyl alcohol, an epoxy resin condensed from bisphenol A and epichlorohydrin Examples of the alkali-soluble resin include a novolak resin, a vinyl polymer having a phenolic hydroxyl group, and a condensation resin of a polyhydric phenol and an aldehyde or ketone described in JP-A-55-57841. Novolak resins include, for example, phenol-formaldehyde resin, cresol-formaldehyde resin, phenol-cresol-formaldehyde copolycondensation resin as described in JP-A-55-57841, and JP-A-55-127553. Copolycondensation resins of p-substituted phenol and phenol or cresol and formaldehyde as described are mentioned.

These binders are contained in the resin composition in an amount of 10 to 95% by weight, preferably 40 to 80% by weight, based on the solid content. The diazo resin is 5 to 80% by weight, preferably 1%.
The content is 5 to 60% by weight.

The photopolymerizable photosensitive composition is preferably
It comprises (a) a vinyl monomer having at least two terminal vinyl groups, (b) a photopolymerization initiator, and (c) a polymer compound as a binder.

Examples of the vinyl monomer of component (a) include JP-B-35-5093, JP-B-35-14719, and JP-B-44-719.
For example, those described in the respective publications of No. 28727 are used, for example, acrylic acid or methacrylic acid esters of polyols, that is, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate,
Such as trimethylolpropane tri (meth) acrylate,
Alternatively, bis (meth) acrylamides such as methylenebis (meth) acrylamide and ethylenebis (meth) acrylamide, or an unsaturated monomer containing a urethane group, for example, di- (2'-methacryloxyethyl)-
Reaction products of diol mono (meth) acrylate and diisocyanate such as 2,4-tolylene diurethane, di- (2-acryloxyethyl) trimethylene diurethane and the like can be mentioned.

As the photopolymerization initiator of the component (b),
For example, J. Examples include carbonyl compounds, organic sulfur compounds, superfluids, redox compounds, azo and diazo compounds, halogen compounds, photoreducible dyes and the like as described in Chapter 5 of "Light Sensitive Systems" by Kosar. More specifically, British Patent No. 1,45
No. 9,563.

Further, as the binder of the component (c),
Various known polymers can be used as well as the binder resin which can be used in combination with the diazo resin. Details of specific binders are described in U.S. Pat. No. 4,072,527.

The components (a), (b) and (c) comprise (a) 20 to 80% by polymerization in the solid content of the photopolymerizable composition;
It is preferable that (b) is contained in 0.1 to 20% by weight, and (c) is contained in 20 to 80% by weight.

Further, these photopolymerizable compositions may contain a thermal polymerization inhibitor, a plasticizer, a dye, a pigment, and the like.

The primer layer containing the above resins (1) to (4) may optionally contain a sensitizer, a surfactant, an organic acid, an acid anhydride, a compound capable of generating an acid upon exposure, Additives such as a plasticizer, an anchoring agent (silane coupling agent, silicone primer, organic titanate, etc.), a dye such as a dye, a pigment, etc. are added. 0.01 to 20% by weight, preferably 0.05 to 10% by weight of the hydrophilic composition
Suitably, it is added by weight%.

A protective layer can be provided on the ink repellent layer of the image forming material of the invention. As the protective layer, a material that can transmit ultraviolet rays and has transparency, such as a polypropylene film, is preferably used, and its thickness is preferably 1 to 20 μm, more preferably 1 to 10 μm.

A preferred embodiment of the image forming material of the invention according to claim 6 is an embodiment in which a primer layer, a layer containing an energy-sensitive base generator, and an ink repellent layer are provided on a substrate in this order. Then, a protective film is laminated on the film if necessary.

The image forming material of the invention according to claim 6 is, if necessary, after image exposure, peeling off the protective film and immersing it in a developing solution. As a developing solution and a developing method, those known as a developing solution and a developing method of a plate material requiring no dampening solution can be used. For example, reference can be made to JP-A-4-147261.

[0194]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples, but it goes without saying that the present invention is not limited to these Examples. In the following embodiments, Embodiment 1 is Claim 1, 2 or 6, and Embodiments 2 and 3 are Claim 1, 3 or 6 and Embodiment 4.
Is a fifth, sixth or seventh embodiment, and the fifth and sixth embodiments are embodiments of the invention according to the fourth embodiment.

Example 1 An aluminum plate having a thickness of 0.24 mm was immersed in an aqueous solution containing 5 g / l of sodium hydroxide at 50 ° C.
Degreased by rinsing with deionized water. The aluminum plate is then electrochemically polished in an aqueous solution containing 4 g / l hydrochloric acid, 4 g / l boric acid and 5 g / l aluminum ions using an alternating current at a temperature of 35 ° C. and a current density of 1200 A / m ^2. To form a surface topology with an average centerline roughness of 0.5 μm. After rinsing with deionized water, the aluminum plate was then etched with an aqueous solution containing 300 g / l sulfuric acid at 60 ° C. for 180 seconds and rinsed with deionized water at 25 ° C. for 30 seconds.

Subsequently, the aluminum was subjected to anodization in an aqueous solution containing 200 g / l of sulfuric acid at a temperature of 45 ° C., a voltage of about 10 V and a current density of 150 A / m ² for about 300 seconds to give 3.00 g / m 2. forming an anodic oxide layer of ² of Al ₂ O _3, then rinsed with deionized water, using a solution containing sodium carbonate 20 g / l, treated after 30 seconds at 40 ° C., followed by deionized water Used, 120 ° C at 20 ° C
Rinse for 2 seconds and dry. The polished, anodized lithographic base is then placed in an aqueous solution containing 5% by weight citric acid.
Submerged for 0 second, adjusted to pH 7 for 60 seconds using a 2N aqueous solution of sodium hydroxide, rinsed with deionized water, and dried at 25 ° C to obtain a hydrophilic support for a printing plate. An image forming layer coating solution having the following composition is applied to the hydrophilic support using a wire bar so that the dry film thickness becomes 2.0 g / m ² , and dried at 90 ° C. for 3 minutes to form an image forming layer. Was applied to obtain a lithographic printing plate material.

Image forming layer coating solution Infrared absorbing dye (CY10, molar absorption coefficient at 787 nm 3.4 × 10 ⁵ , manufactured by Nippon Kayaku Co., Ltd.) 0.9 parts by weight Base generator (PBG-1) 0.9 Parts by weight Base-soluble resin (m-cresol novolak resin, weight average molecular weight 2,000) 9.0 parts by weight Ethylene glycol monomethyl ether 90.0 parts by weight The above lithographic printing plate material was exposed to an exposure machine (Trendsetter 3244) manufactured by Cleo Products. ; Semiconductor laser output 10
W, 240 channel machine) and image exposure (170-200)
mJ / cm ² ), the plate surface was rubbed with a sponge while washing with tap water at 20 ° C., and the image forming layer in the exposed area was removed to obtain a printing plate. When this printing plate was attached to the cylinder of the printing machine and printing was performed by supplying a fountain solution and printing ink, 100,000 good printed matters were obtained. The lithographic printing plate material was stored for 7 days in a dry thermo at a temperature of 55 ° C. and a hydrotherm at a temperature of 40 ° C. and a humidity of 80%, and the same operation was carried out. I couldn't. It was confirmed that this printing plate was excellent in image quality, sensitivity, storability, and printing durability (physical strength).

Example 2 An image forming layer coating solution having the following composition was applied to the hydrophilic support prepared in Example 1 using a wire bar to give a dry film thickness of 2.0.
g / m ² and dried at 90 ° C. for 3 minutes to apply an image forming layer to obtain a lithographic printing plate material.

Image forming layer coating solution Infrared absorbing dye (CY10, molar absorption coefficient at 787 nm 3.4 × 10 ⁵ , manufactured by Nippon Kayaku Co., Ltd.) 0.9 parts by weight Base generator (PBG-2) 0.9 Parts by weight Base crosslinkable resin (resin in which a part of the hydroxyl group of m-cresol novolak resin having a weight average molecular weight of 2,000 was epoxidized with glycidyl methacrylate) 9.0 parts by weight Ethylene glycol monomethyl ether 90.0 parts by weight Example 1 After performing image exposure in the same manner as above, using a developing solution having the following composition, a developing process was performed at room temperature for 20 seconds.
The unexposed portions of the image forming layer were removed, and a printing plate was obtained.
Evaluation was performed in the same manner as in Example 1, and similar results were obtained. It was confirmed that the image quality, sensitivity, storage stability, and printing durability were excellent.

Developer 10% by weight of benzyl alcohol 5% by weight of sodium carbonate 5% by weight of sodium naphthalenesulfonate 100% by weight of water Example 3 A coating solution for an image forming layer having the following composition was coated on the hydrophilic support prepared in Example 1. Using a wire bar, dry film thickness 2.0
g / m ² and dried at 90 ° C. for 3 minutes to apply an image forming layer to obtain a lithographic printing plate material.

Image forming layer coating solution Infrared absorbing dye (CY17, molar absorption coefficient at 787 nm 2.5 × 10 ⁵ , manufactured by Nippon Kayaku Co., Ltd.) 0.9 parts by weight Base generator (PBG-2) 0.9 Parts by weight Base crosslinkable resin (resin in which a part of the hydroxyl group of m-cresol novolak resin having a weight average molecular weight of 2,000 is epoxidized with glycidyl methacrylate) 9.0 parts by weight diazo resin (formaldehyde condensation resin PF ₆ salt of diazodiphenylamine) 0.9 parts by weight ethylene glycol monomethyl ether 90.0 parts by weight After image exposure was performed in the same manner as in Example 1, development processing was performed for 20 seconds at room temperature using the developing solution of Example 2.
The unexposed portions of the image forming layer were removed, and a printing plate was obtained.
Evaluation was performed in the same manner as in Example 1, and similar results were obtained. It was confirmed that the image quality, sensitivity, storage stability, and printing durability were excellent.

Example 4 On a degreased smooth aluminum plate having a thickness of 0.3 mm,
10% by weight of the solid component of the primer layer composition having the following composition
The propylene glycol monomethyl ether solution contained was applied and dried for 5 minutes in hot air at 100 ° C. to a thickness of 15
It was a coating film of μm. Thereafter, the entire surface was exposed to 1 J / cm ² using a 3 kW ultra-high pressure mercury lamp and cured to obtain a primer layer.

Primer layer composition Byron UR-8300 (polyester polyurethane, manufactured by Toyobo Co., Ltd.) 100 parts by weight Pentaerythritol triacrylate 150 parts by weight 2,4-diethylthioxanthone 6 parts by weight p-dimethylaminobenzoic acid ethyl ester 6 parts by weight Part 3 parts by weight of γ-methacryloxypropyltrimethoxysilane Next, propylene glycol monomethyl ether / methyl cellosolve containing 10% by weight of a solid component of the photosensitive layer composition having the following composition on the cured primer layer (weight ratio: 60/40) ) The mixed solution was applied and dried in hot air at 80 ° C for 2 minutes to form a 0.4 µm-thick photosensitive layer.

Photosensitive layer composition Diazo resin 50 parts by weight 2-hydroxyethyl methacrylate, N- (4-hydroxyphenyl) methacrylamide Copolymer resin in a molar ratio of 30/70 50 parts by weight Victoria Pure Blue BOH (dye, Hodogaya Chemical 1 part by weight Infrared light absorbing dye (CY17, molar absorption coefficient at 787 nm 2.5 × 10 ⁵ , manufactured by Nippon Kayaku Co., Ltd.) 0.9 part by weight Base generator (PBG-2) 0 9.9 parts by weight A silicone rubber layer coating solution having the following composition was applied on the photosensitive layer so that the film thickness after drying was 2 μm.

Silicone rubber layer coating liquid α, ω-divinylpolydimethylsiloxane 100 parts by weight Polymethylhydrogensiloxane 10 parts by weight Complex of chloroplatinic acid and vinylsiloxane 150 ppm n-hexane 1400 parts by weight Then, a 5 μm thick one-side matted polypropylene film was laminated to obtain a photosensitive lithographic printing plate requiring no dampening water. The lithographic printing plate material was exposed to an exposure machine (Trendsetter 324) manufactured by Creo Products.
4: Semiconductor laser output 10W, 240 channel machine)
After image exposure (170 to 200 mJ / cm ² ), the laminate film was peeled off. Next, after immersing in a developing solution having the following composition at 27 ° C. for 1 minute, development is performed by rubbing the surface of the plate material with a pad impregnated with the developing solution to remove the unexposed portions of the silicone rubber layer and the photosensitive layer. As a result, a printing plate in which halftone dots were well reproduced was obtained. The image area of the printing plate was vividly dyed by applying a dyeing solution having the following composition to a cloth, gently rubbing the plate, and washing with water. The printing plate was attached to a cylinder of a printing press, and printing was performed by supplying printing ink. As a result, 100,000 good printed matters were obtained. The lithographic printing plate material was stored for 7 days in a dry thermo at a temperature of 55 ° C. and a hydrotherm at a temperature of 40 ° C. and a humidity of 80%, and the same operation was carried out. I couldn't. This printing plate was confirmed to be excellent in image quality, sensitivity, storability, and printing durability (physical strength).

Developer β-anilinoethanol 0.5 part by weight Propylene glycol 1.0 part by weight p-tert-butylbenzoic acid 1.0 part by weight Potassium hydroxide 1.0 part by weight Polyoxyethylene lauryl ether 0.1 Parts by weight Potassium sulfite 2.0 parts by weight Potassium metasilicate 3.0 parts by weight Water 91 parts by weight Dyeing solution Solfit (solvent, manufactured by Kuraray Isoprene Chemical Co., Ltd.) 20 parts by weight Leodol TW-O120 (surfactant, Kao) 0.5 parts by weight Benzyl alcohol 5.0 parts by weight Victoria Pure Blue BOH (dye, manufactured by Hodogaya Chemical Co., Ltd.) 1.0 parts by weight Water 100 parts by weight Example 5 (Preparation of organic acid silver emulsion) ) Behenic acid (840 g) and stearic acid (95 g) were added to 12 l of water, and the mixture was maintained at 90 ° C. Free 63g 1.5
One dissolved in 1 liter of water was added. After stirring for 30 minutes 5
0 ° C. and 1% aqueous solution of N-bromosuccinimide 1.1
was added, and then 2.3 l of a 17% aqueous solution of silver nitrate was gradually added with stirring. Further, the liquid temperature was set to 35 ° C., and 1.5 l of a 2% aqueous solution of potassium bromide was added over 2 minutes with stirring, followed by stirring for 30 minutes, and 2.4 l of a 1% aqueous solution of N-bromosuccinimide were added. To this aqueous mixture was added 3300 g of a 1.2% by weight solution of polyvinyl acetate in butyl acetate with stirring, and the mixture was allowed to stand for 10 minutes to separate into two layers, the aqueous layer was removed, and the remaining gel was washed twice with water. did. The thus-obtained gel-like mixture of behenic acid / silver stearate and silver bromide was dispersed in 1800 g of a 2.6% isopropyl alcohol solution of polyvinyl butyral (Denka Butyral # 3000-K, manufactured by Denki Kagaku Kogyo Co., Ltd.) Furthermore, polyvinyl butyral (Electrical Chemical Industry Co., Ltd.)
The dispersion was dispersed together with 600 g of Denka Butyral # 4000-2) and 300 g of isopropyl alcohol to obtain an organic acid silver salt emulsion (acicular particles having an average minor axis of 0.05 μm, an average major axis of 1.2 μm, and a variation coefficient of 25%).

(Preparation of Emulsion Layer Coating Solution) The following chemicals were added to the above-obtained organic acid silver emulsion in the following amounts per mole of silver. At 25 ° C., 10 mg of sodium phenylthiosulfonate, 70 mg of sensitizing dye a, 2-mercapto-5
-Methylbenzimidazole 2 g, 4-chlorobenzophenone-2-carboxylic acid 21.5 g and 2-butanone 58
0 g and dimethylformamide 220 g were added with stirring, and the mixture was left for 3 hours. Next, 8 g of 5-tribromomethylsulfonyl-2-methylthiazole, 6 g of 2-tribromomethylsulfonylbenzothiazole, 5 g of 4,6-ditrichloromethyl-2-phenyltriazine, 2 g of disulfide compound a, reducing agent R-1 Is 0.3 mol per mol of silver, and super hardener I is 6.5 × 10 5 per mol of silver.
^-3 mol, 2 parts of energy-sensitive base generator (PBG-3)
g, 5 g of tetrachlorophthalic acid, 1.1 g of Megafax F-176P (fluorinated surfactant manufactured by Dainippon Chemical Co., Ltd.), 590 g of 2-butanone, and 10 g of methyl isobutyl ketone were added with stirring.

(Emulsion Surface Protective Layer Coating Solution) CAB171-1
75 g of 5S (cellulose acetate butyrate manufactured by Eastman Chemical Co., Ltd.), 5.7 g of 4-methylphthalic acid, 1.5 g of tetrachlorophthalic anhydride, 12.5 g of phthalazine,
0.3g of Megafax F-176P, Sildex H31 (average size of pearl silica manufactured by Dokai Chemical Co., Ltd. 3μm)
2 g, 7 g of sumidur N3500 (a polyisocyanate manufactured by Sumitomo Bayer Urethane Co., Ltd.) is added to 2-butanone 30
A solution dissolved in 70 g and 30 g of ethyl acetate was prepared.

(Preparation of Support Having Back Surface) The back surface and the back surface surface protective layer were simultaneously coated with an aqueous solution on a polyethylene terephthalate film having an undercoat containing vinylidene chloride on both surfaces so that the coating amount was 1 m ² or less. Multi-layer coating was performed. Back layer coating amount is 1.5g gelatin, p
-Sodium dodecylbenzenesulfonate 30 mg,
1,2-bis (vinylsulfonylacetamide) ethane 100 mg, dye a 50 mg, dye b 100 mg, dye c 30 mg, dye d 50 mg, proxel 1 mg, back surface surface protective layer 1.5 g of gelatin, polymethyl having an average particle size of 2.5 μm Methacrylate 20 mg, p-
15 mg of sodium dodecylbenzenesulfonate, 15 mg of sodium dihexyl-α-sulfosuccinate, 50 mg of sodium acetate, and 1 mg of proxel.

After coating the emulsion layer coating solution on the support prepared as described above so that the silver content was 1.6 g / m ² , the emulsion surface protective coating solution was dried to a dry thickness of 2 μm on the emulsion surface. Was applied as follows.

The structural formulas of the compounds used above are shown below.

[0212]

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[0213]

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The following evaluation was performed on the samples of the photothermographic material prepared as described above.

(Evaluation of photographic performance) 633 nm He-Ne
After exposing the photosensitive material with a laser photometer (700 nm / interference filter), the photosensitive material was processed (developed) at 115 ° C. for 30 seconds, and the obtained image was evaluated by a densitometer. The result of the measurement is that the exposure amount and the gradation that give a density 3.0 higher than the sensitivity (Dmin) are 0.3 and 3.0 in the characteristic curve.
It is shown as the slope of a straight line connecting the zero points. The higher the value, the higher the contrast and the better. As a result, the sensitivity is 25
mJ / cm ² , gradation was 15.5. Further, this sample was stored in a dry thermo at a temperature of 55 ° C. and a hydrotherm at a temperature of 40 ° C. and a humidity of 80% for 7 days, and the same evaluation was carried out. . When the physical strength of the photosensitive material was evaluated, a scratch strength of 450 g was obtained, and it was found that the material was a printing photosensitive material having high sensitivity, high gradation, good storability, and high physical strength.

The scratch strength was measured using a sapphire needle having a diameter of 0.2 mm with a continuous load type scratch strength tester Type-HEIDON-18 manufactured by Shinto Chemical Co., Ltd.
Was applied to apply a scratch, and the minimum load at which the scratch could be visually identified was taken as the scratch strength. The higher the value, the better the scratch strength.

Example 6 (Preparation of silver halide grains) 23 g of phthalated gelatin and 30 mg of potassium bromide were dissolved in 700 ml of water, the pH was adjusted to 5.0 at a temperature of 35 ° C., and 18.6 g of silver nitrate was obtained.
An aqueous solution containing 159 ml of an aqueous solution containing gwo and an aqueous solution containing potassium bromide and potassium iodide at a molar ratio of 92: 8 were added over 10 minutes by a control double jet method while maintaining the pAg at 7.7. Then, 476 ml of an aqueous solution containing 55.4 g of silver nitrate, an aqueous solution containing 6 μmol / l of dipotassium hexachloroiridate and 1 mol / l of potassium bromide were added to pAg.
Controlled by the control double jet method while keeping at 7.7
Added over 0 minutes. Thereafter, the pH was lowered to perform coagulation sedimentation and desalting treatment, 0.1 g of phenoxyethanol was added to adjust the pH to 5.9 and pAg 8.2, and silver iodobromide grains (iodine content core 8 mol%, average 2 mol%) Cubic grains having an average size of 0.05 μm, a variation coefficient of projected area of 8%, and a (100) face ratio of 92%).

The silver halide grains thus obtained were heated to 60 ° C., and 85 μmol of sodium thiosulfate and 11 μmol of 2,3,4,5,6-pentafluorophenyldiphenylphosphine selenide per mol of silver. 15 μmol of the following tellurium compound, 3 μmol of chloroauric acid and 240 μmol of thiocyanic acid were added, and after aging for 120 minutes, 30
The mixture was quenched to give a silver halide emulsion.

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(Preparation of photosensitive emulsion A containing silver salt of organic acid) 1.3 g of stearic acid, 0.5 g of arachidic acid, 8.5 g of behenic acid, and 300 ml of distilled water were mixed at 90 ° C. for 15 minutes and stirred vigorously. 1N NaOH aqueous solution 3
1.1 ml was added, and after 15 minutes, the temperature was lowered to 30 ° C. Next, after adding 7 ml of a 1N phosphoric acid aqueous solution, the above silver halide emulsion was added so that the amount of silver halide was equivalent to 2.5 mmol. In addition, 25m of 1N silver nitrate aqueous solution
was added over 2 minutes and stirring was continued for 90 minutes. Thereafter, the solid content was separated by suction filtration, and the solid content was washed with water until the conductivity of the filtrate reached 30 μS / cm.

This aqueous dispersion was filtered to remove excess salt. SBR latex LAC is added to the obtained wet dispersion.
A STAR 3307B (trade name of Dainippon Ink and Chemicals, Inc.) has an AEX solid content of 5 per gram of silver behenate.
g, and re-dispersed by an ultrasonic disperser. The average particle size in such an aqueous dispersion was 0.3 μm.

(Preparation of Coated Sample) Undercoated 1
It was applied as follows on a polyethylene terephthalate support having a thickness of 00 μm.

Coating on Back Side The aqueous coating solution having the following composition was coated with 5 g of polyvinyl alcohol.
/ M ² .

Polyvinyl alcohol 6.0 g Water 100 ml Boric acid 0.2 g Mixture of dyes e, f and g in a weight ratio of 25: 65: 1 0.2 g Silica particles (average particle size 5 μm) 0.3 g For this coating solution The compounds used are shown below.

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(Coating on the Sensitive Layer Side) A sensitive layer and a surface protective layer were simultaneously coated in multiple layers.

Sensitive layer: An aqueous coating solution having the following composition was applied so that the coated silver amount was 1.6 g / m ² .

Photosensitive emulsion A 73 g Sensitizing dye b (0.05% methanol solution) 2 ml Sensitizing dye c (0.05% methanol solution) 1 ml Antifoggant a (0.01% methanol solution) 3 ml Antifoggant b (0.01% methanol solution) 8 ml Antifoggant c (2.4% DMF solution) 5 ml Mixed water dispersion of phthalazine and the following reducing agent R-2 (solid content 18 wt%) 10 g In a 01% methanol solution, 2.1 × 10 ⁻³ mol per mol of silver was added, and 0.5 g of an energy-sensitive base generator (PBG-1) dissolved in dimethylformamide was added.

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The same evaluation as in Example 5 was performed for the above photosensitive material sample. As a result, a sensitivity of 20 mJ / cm ² , a gradation of 16.0, and a scratching strength of the photosensitive material of 430 g were obtained. This is a printing photosensitive material having high sensitivity, high gradation, strong physical strength, and excellent storage performance. I understand.

Comparative Example 1 An experiment was conducted in the same manner as in Example 5 except that the energy-sensitive base generator was not added to the emulsion layer coating solution.
The sensitivity is 50 mJ / cm ² , the gradation is 11.2, and the scratching strength of the photosensitive material is 280 g. For the preserved sample, blackening that is visually recognized is observed in the non-blackened portion, and the original is printed on a printing plate. Had a problem. It was found that the sensitivity, storage stability and physical strength were inferior to those of the light-sensitive material of the present invention.

Comparative Example 2 An experiment was conducted in the same manner as in Example 6 except that the energy-sensitive base generator was not added to the emulsion layer coating solution.
The sensitivity was 40 mJ / cm ² , the gradation was 10.2, and the scratching strength of the photosensitive material was 250 g. Regarding the preserved sample, blackening was visually observed in the non-blackened portion, and the original was printed on a printing plate. Had a problem. It was found that the sensitivity, storage stability, and physical strength were inferior to those of the printing photosensitive material of the present invention.

Comparative Example 3 In place of the infrared absorbing dye CY-17 in Example 1, I
RG-002 (molar extinction coefficient at 900 nm is 2.5 × 1
0 ³ (manufactured by Nippon Kayaku Co., Ltd.), the same experiment as in Example 1 was carried out. As a result, the image forming layer in the exposed area was also removed, and no printing plate was obtained.

Comparative Example 4 In place of the infrared absorbing dye CY-17 in Example 3, N
K-3027 (molar extinction coefficient at 839 nm is 6.1 × 1
0 ^4, Japan where the photosensitive dye Co.) outside used was subjected to the same experiment as in Example 3, the image forming layer in the exposed portion is not removed, the printing plate was not obtained.

By using an infrared ray absorbent together with the energy ray base generator, energy or electrons can be transferred between the energy ray ray base generator and the infrared ray absorber,
Decomposition of the energy-sensitive base generator can be promoted.

By the above action, the present invention is applied to an image-forming material having a layer of a composition using a combination of an energy-sensitive base generator and a base-soluble resin to give an image excellent in image quality, sensitivity, storage stability and physical strength. A forming material is obtained.

By the action described above, an image-forming material having a layer of a composition using a combination of an energy-sensitive base generator and a base-curable resin is excellent in image quality, sensitivity, storability and physical strength. Is obtained.

The development reaction can be enhanced by including an energy-sensitive base generator in the image forming layer of a known photothermographic material.

The combination of an energy-sensitive base generator and an onium salt can provide both the effect of increasing the efficiency of base generation and the above-mentioned effects.

The development reaction can be enhanced by using an energy-sensitive base generator together with the photosensitive layer of a lithographic printing plate requiring no dampening solution.

[0242]

According to the present invention, there is provided a novel image forming material particularly suitable for a direct printing plate (CTP). Further, an image forming material having excellent image quality, sensitivity, storage stability and physical strength is provided.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03F 7/004 506 G03F 7/06 7/06 B41M 5/26 SF term (Reference) 2H023 CA06 CD00 2H025 AA01 AA13 AB04 AC08 BE00 CA15 CA48 CB00 CB52 CC11 CC20 2H096 AA11 BA11 BA16 BA17 BA20 EA04 2H111 HA14 HA35 2H123 AB00 AB03 AB23 AD00 AD01 BA00 BA14 BB00 BB02 BB22 BB39 CA22 EA07

Claims (7)

[Claims] 1. An image-forming material comprising an energy-sensitive base generator and an infrared absorber. 2. An image-forming material containing an energy-sensitive base generator, an infrared absorber and a base-soluble resin. 3. An image-forming material containing an energy-sensitive base generator, an infrared absorber and a base-curable resin. 4. An image-forming material containing an energy-sensitive base generator, an infrared absorber and an onium salt compound. 5. An infrared absorbent having a wavelength of 700 nm or more.
Molar extinction coefficient of absorption maximum of 500 nm or less is 1 × 10 ⁵
The image forming material according to any one of claims 1 to 4, wherein 6. An energy-sensitive base generator, a sensitizing dye,
An image-forming material containing a photosensitive silver halide, a non-photosensitive reducible silver salt, a reducing agent and a binder resin. 7. An image-forming material comprising a layer containing an energy-sensitive base generator and an ink repellent layer.