JP2000122297A - Planographic printing plate material and method for developing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve surface staining in printing and fine halftone dot reproducibility in printing when a material spectrally sensitized so as to ensure the sensitization maximum is the range of 610-710 nm and forming a planographic printing plate by a silver complex salt diffusion transfer process is preserved at a high humidity and a high temperature or when the material is subjected to running processing under a reduced replenishing amount. SOLUTION: The planographic printing plate material has its sensitization maximum in the range of 610-710 nm, contains ascorbic acid or a hydrazine derivative in a constituent layer and forms a planographic printing plate by a silver complex salt diffusion transfer process. A planographic printing plate material having its sensitization maximum in the range of 610-710 nm and forming a planographic printing plate by a silver complex salt diffusion transfer process is developed in the presence of ascorbic acid or a hydrazine derivative.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lithographic printing plate material for forming a lithographic printing plate by utilizing a silver complex salt diffusion transfer method, and a developing method thereof. More specifically, the present invention relates to a lithographic printing plate material spectrally sensitized for exposure by a laser or an LED such as an image setter, and a development processing method thereof.

[0002]

2. Description of the Related Art A lithographic printing plate material capable of immediately utilizing a transferred silver image obtained by a silver complex salt diffusion transfer method (DTR method) as ink receptivity is already known. For example, a lithographic printing plate material having a subbing layer, a silver halide emulsion layer and a physical development nucleus layer on a support is disclosed in US Pat.
No. 21,559, No. 3,490,905, No. 3,
385,701, 3,814,603, 3,454,398, 3,764,323, 3,099,209, JP-B-44-27242,
48-30562, JP-A-53-9603, 5
No. 3-21602, No. 54-103104, No. 56-
No. 9750, and the like.

According to a typical silver complex salt diffusion transfer method suitable for the method of making a lithographic printing plate, a support and an undercoat layer which also serves as an antihalation layer, a silver halide emulsion layer, When a photosensitive material comprising a development nucleus layer is subjected to image exposure and development processing, silver halide on which a latent image is formed becomes blackened silver in the emulsion. At the same time, the silver halide having no latent image formed thereon is dissolved by the action of the silver halide solvent contained in the developing solution and diffuses to the surface of the photosensitive material. The dissolved and diffused silver complex is deposited as image silver on the physical development nuclei of the surface layer by the reducing action of the developing agent.

In recent years, in the field of printing plate making, plate making using an apparatus called an image setter for performing digital exposure using a He-Ne laser, a red semiconductor laser, a red LED or the like as a light source is increasing. To expose with these light sources, 6
It is necessary to have a photosensitive maximum between 10 nm and 710 nm. For this purpose, it is necessary to spectrally sensitize a silver halide emulsion, which originally has a photosensitive region only at a short wavelength, to a desired wavelength with a sensitizing dye. JP-A-60-151643 describes that a specific sensitizing dye is applied to a lithographic printing plate material utilizing the above-described silver complex salt diffusion transfer method so as to have sensitivity to the above wavelength. However, in a lithographic printing plate material using a silver complex salt diffusion transfer method, when spectral sensitization is performed so as to have a photosensitive maximum from 610 nm to 710 nm, fog of an unexposed portion increases due to storage under high humidity and high temperature. There have been drawbacks such as the occurrence of background stains during printing and the inability to reproduce fine halftone dots during printing.

[0005] In recent years, there has been a demand for reducing photographic processing waste liquid due to increasing concern about the environment. For that purpose, it is preferable to reduce the replenishment amount in the development processing. However, in the case of a lithographic printing plate material having a photosensitive maximum from 610 nm to 710 nm using the above-mentioned silver salt diffusion transfer method, when the running process is performed in a state where the replenishment amount is reduced, the gradation changes and fog of the unexposed portion is reduced. There are drawbacks, such as rising, causing soiling at the time of printing, and fine halftone dots not being reproduced at the time of printing.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a silver complex salt diffusion transfer method in which spectral sensitization is performed so as to have a photosensitive maximum from 610 nm to 710 nm. It is an object of the present invention to improve the reproducibility of background stains during printing and fine halftone dots during printing when a material for forming a lithographic printing plate is stored under high humidity and high temperature. Another object of the present invention is to improve the reproducibility of background stains during printing and fine halftone dots during printing when a running process is performed with the replenishment amount reduced in the developing process of the lithographic printing plate material. To make improvements.

[0007]

The object of the present invention is to form a lithographic printing plate having a photosensitive maximum at 610 nm to 710 nm, containing ascorbic acids in a constituent layer, and utilizing a silver complex salt diffusion transfer method. A lithographic printing plate material which has a photosensitive maximum at 610 nm to 710 nm and forms a lithographic printing plate using a silver complex diffusion transfer method in the presence of ascorbic acids. Material development processing method, development processing with a processing solution containing ascorbic acids, development processing is further performed in the presence of a hydrazine derivative, having a photosensitive maximum from 610 nm to 710 nm, and containing a hydrazine derivative in a constituent layer A lithographic printing plate material for forming a lithographic printing plate using a silver complex salt diffusion transfer method, having a photosensitive maximum from 610 nm to 710 nm, The method of developing a lithographic printing plate material in which a lithographic printing plate material is formed in the presence of a hydrazine derivative by using a lithographic printing plate, wherein the developing solution is 0.1 mol / L or more of carbonic acid It is achieved by containing a salt and using a treatment liquid substantially free of hydroquinone.

Japanese Patent Application Laid-Open No. Hei 8-234435 discloses that a lithographic printing plate material utilizing a silver complex salt diffusion transfer method contains ascorbic acid. There is no idea to improve the problem in the lithographic printing plate material spectrally sensitized for exposure, and it was completely unexpected from the description, which is completely different from the present invention.

Japanese Patent Application Laid-Open No. 9-304934 describes that a lithographic printing plate material using a silver complex salt diffusion transfer method is developed in the presence of a hydrazine derivative. Not only the idea of improving the problem in the lithographic printing plate material spectrally sensitized for exposure by laser or LED, but also the spectral sensitization to the wavelength according to the present invention is not described. Is a completely different technology.

Hereinafter, the present invention will be described in detail.

In the present invention, 610 nm to 710 n
The lithographic printing plate material having a photosensitive maximum at m preferably contains a silver halide emulsion spectrally sensitized to have a photosensitive maximum at 610 nm to 710 nm. To spectrally sensitize the silver halide emulsion to the above wavelength, a sensitizing dye is used. Spectral sensitization that can be used includes those having the following structure.

[0012]

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In the formula, Z ₁ and Z ₂ each independently represent a group of atoms necessary for completing a heterocyclic ring, and R ₁ and R ₂ each independently represent an alkyl group, an alkenyl group, an aralkyl group or an aryl group. ₃ represents an alkyl group, an aryl group, a halogen atom, an alkoxy group and a heterocyclic group. Each may be substituted, and preferably has 0 to 20 carbon atoms. m represents 0 or 1. X represents a counter ion.

[0014]

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In the formula, Z ₂₁ and Z ₂₂ each independently represent a group of atoms necessary for completing a heterocyclic ring, and R ₂₁ and R ₂₂ each independently represent an alkyl group, an alkenyl group, an aralkyl group or an aryl group. ₂₃ represents a substituted amino group, an amide group, an imino group, an alkoxy group, and a heterocyclic group. L _{1 to} L ₉ represent a methine group, m and n are 0, 1 or 2, and 1 and p are 0 or 1
Represents X represents a counter ion.

[0016]

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In the formula, Z ₃₁ and Z ₃₂ each independently represent a group of atoms necessary for completing a heterocyclic ring, and R ₃₁ , R ₃₂ and R ₃₃
Each independently represents an alkyl group, an alkenyl group, an alkynyl group, or an aryl group. Here, at least one of R ₃₁ , R ₃₂ and R ₃₃ represents any one of an alkenyl group and an alkynyl group. L _{1 to} L ₉ represent a methine group, m and n represent 0, 1 or 2, l and p represent 0 or 1, and X represents a counter ion.

[0018]

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In the formula, Z ₄₁ is a thiazoline nucleus, a thiazolidine nucleus, a selenazoline nucleus, a selenazolidine nucleus, a pyrrolidine nucleus, a dihydropyridine nucleus, an oxazoline nucleus, an oxazolidine nucleus, an imidazoline nucleus, an indoline nucleus, a tetrazoline nucleus, a benzothiazoline nucleus, and a benzoselenazoline nucleus. , A benzimidazoline nucleus, a benzoxazoline nucleus, a naphthothiazoline nucleus, a naphthoselenazoline nucleus, a naphthooxazoline nucleus, a naphthoimidazoline nucleus or a dihydroquinoline nucleus. Q is a nonmetallic atom necessary for completing a rhodanine nucleus, a 2-thiooxazoline-2,4-dione nucleus, a 2-thioselenazoline-2,4-dione nucleus, a barbituric acid nucleus or a 2-thiobarbituric acid nucleus. Represents a group. R ₄₁ and R ₄₂ each independently represent a hydrogen atom, an alkyl group or an aryl group. Y ₁ and Y ₂ each independently represent a hydrogen atom, an alkyl group or an aryl group.
p represents 0 or 1.

In the general formula [1], Z ₁ and Z ₂ may be the same or different and are necessary for forming a heterocyclic ring such as a benzothiazole ring, a benzoselenazole ring, a naphthothiazole ring or a naphthoselenazole ring. These heterocyclic rings include a halogen atom (for example, chloride, bromide, etc.), an alkyl group (for example, an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, propyl, butyl group, etc.) and an alkoxy group (for example, An alkoxy group having 1 to 4 carbon atoms such as methoxy, ethoxy, propoxy and butoxy groups; an alkoxycarbonyl group (for example, a alkoxycarbonyl group having 1 to 4 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group and butoxycarbonyl group); And a substituent such as a phenyl group.

The alkyl group represented by R ₁ and R _{2 in} the general formula [1] is preferably an alkyl group having 1 to 6 carbon atoms, and may be any of linear, branched or cyclic. The alkyl group may have a substituent, for example, methyl, ethyl, iso-propyl, cyclohexyl, allyl, trifluoromethyl, β
-Hydroxyethyl, acetoxymethyl, carboxymethyl, ethoxycarbonylmethyl, β-methoxyethyl, γ-methoxypropyl, β-benzoyloxyethyl, γ-sulfopropyl, δ-sulfobutyl and the like.

Examples of the alkenyl group include allyl group, examples of the aralkyl group include benzyl, phenethyl and sulfobenzyl, and examples of the aryl group include phenyl and
Tolyl, chlorophenyl, sulfophenyl and the like can be mentioned.

R ₃ represents an alkyl group, an aryl group, an alkoxy group, a hetero ring, a halogen atom or the like. Each may be substituted, and preferably has 0 to 20 carbon atoms.

The counter ion represented by X is an anion commonly used for cyanine dyes, for example, a chloride ion,
Bromine ion, iodine ion, thiocyanate ion, sulfate ion, perchlorate ion, p-toluenesulfonic acid ion, boron tetrafluoride ion, methyl sulfate ion, ethyl sulfate ion and the like.

When an inner salt can be formed, X is not present. When two acidic groups (sulfo, sulfate, carboxyl, etc.) are present in the molecule, an alkali metal atom, Represents a cation such as organic ammonium.

M is 0 or 1 and m is 0 when the dye forms an inner salt.

Specific examples of the compound represented by the general formula [1] are shown below, but the present invention is not limited thereto.

[0028]

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[0029]

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[0030]

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[0031]

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Next, in the general formula [2], examples of the heterocyclic ring composed of Z ₂₁ and Z ₂₂ include oxazoline, oxazole, benzoxazole, benzoisoxazole, naphthooxazole, thiazoline, thiazole, benzothiazole, naphthothiazole , Selenazoline, selenazole, benzoselenazole, naphthoselenazole, tetrazole, benzotetrazole, pyridine, quinoline, benzoquinoline, indolenine, benzoindolenine, benzimidazole, pyrroline ring and the like. Known substituents may be substituted on these heterocycles, and examples thereof include alkyl, alkoxy, aryl, hydroxy, carboxy, alkoxycarbonyl, and halogen.

The alkyl group represented by R ₂₁ and R _{22 in} the general formula [2] is preferably an alkyl group having 1 to 6 carbon atoms.
It may be branched or annular. The alkyl group may have a substituent, for example, methyl, ethyl, iso-propyl, cyclohexyl, allyl, trifluoromethyl, β
-Hydroxyethyl, acetoxymethyl, carboxymethyl, ethoxycarbonylmethyl, β-methoxyethyl, γ-methoxypropyl, β-benzoyloxyethyl, γ-sulfopropyl, δ-sulfobutyl and the like.

The alkenyl group includes, for example, an allyl group, the aralkyl group includes, for example, benzyl, phenethyl and sulfobenzyl, and the aryl group includes, for example, phenyl,
Tolyl, chlorophenyl, sulfophenyl and the like can be mentioned.

Examples of the group bonded to the nitrogen atom or oxygen atom represented by R ₂₃ include, for example, alkyl, alkenyl, aralkyl, aryl, acyl, alkylsulfonyl, heterocycle and the like. And may form a ring.

[0036] for example dimethylamino As these R _23, diethylamino, N- methylanilino, 1-piperidino, 1-morpholino, N- methyl-2-Pirijinoamino, benzylidene imino, dibenzylamino, N- acetyl methylamino, benzylamino, Acetamino, N
-Methylsulfonylamino, N-methylureido, 3-
Examples of the alkoxy group such as methylbenzothiazolideneimino include methoxy and ethoxy groups.

The counter ion represented by X is an anion usually used for a cyanine dye, for example, a chloride ion,
Bromine ion, iodine ion, thiocyanate ion, sulfate ion, perchlorate ion, p-toluenesulfonic acid ion, boron tetrafluoride ion, methyl sulfate ion, ethyl sulfate ion and the like.

When an inner salt can be formed, X is not present, and when two acidic groups (sulfo, sulfate, carboxyl, etc.) are present in the molecule, an alkali metal atom, Represents a cation such as organic ammonium.

L _{1 to} L ₉ represent a methine group, which may be substituted with alkyl, aryl, alkoxy and the like.

Hereinafter, specific examples of the compound represented by the general formula [2] will be shown, but the present invention is not limited thereto.

[0041]

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[0042]

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[0043]

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In the general formula [3], examples of the heterocyclic ring composed of Z ₃₁ and Z ₃₂ include oxazoline, oxazole, benzoxazole, benzoisoxazole,
Naphthoxazole, thiazoline, thiazole, benzothiazole, naphthothiazole, selenazoline, selenazole, benzoselenazole, naphthoselenazole, tetrazole, benzotetrazole, pyridine, quinoline, benzoquinoline, indolenine, benzoindolenine, benzimidazole, pyrroline ring, etc. Is mentioned. Known substituents may be substituted on these heterocycles, and examples thereof include alkyl, alkoxy, aryl, hydroxy, carboxy, alkoxycarbonyl, and halogen.

The alkyl group represented by R ₃₁ , R ₃₂ and R _{33 in the} general formula [3] is preferably one having 1 to 6 carbon atoms, and may be any of linear, branched or cyclic. It may further have a substituent, for example, methyl, ethyl, iso-propyl, cyclohexyl, allyl, trifluoromethyl, β
-Hydroxyethyl, acetoxymethyl, carboxymethyl, ethoxycarbonylmethyl, β-methoxyethyl, γ-methoxypropyl, β-benzoyloxyethyl, γ-sulfopropyl, δ-sulfobutyl and the like.

Examples of the alkenyl group include allyl, sulfopropenyl and sulfobutenyl, and examples of the alkynyl group include propynyl and sulfobutynyl.

Examples of the aryl group include phenyl, trichlorophenyl, sulfophenyl and the like.

The counter ion represented by X is an anion usually used for a cyanine dye, for example, a chloride ion,
Bromine ion, iodine ion, thiocyanate ion, sulfate ion, perchlorate ion, p-toluenesulfonic acid ion, boron tetrafluoride ion, methyl sulfate ion, ethyl sulfate ion and the like.

When an inner salt can be formed, X is not present, and when two acidic groups (sulfo, sulfate, carboxyl group, etc.) are present in the molecule, an alkali metal atom is present. And cations such as organic ammonium.

L _{1 to} L ₉ represent a methine group, which may be substituted by alkyl, aryl, alkoxy and the like.

Hereinafter, specific examples of the compound represented by the general formula [3] will be shown, but the present invention is not limited thereto.

[0052]

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[0053]

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[0054]

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In the general formula [4], the heterocyclic ring formed by Z ₄₁ may be substituted with at least one substituent, which may be a halogen atom (eg, fluorine, chlorine, bromine, iodine), Nitro group, alkyl group (preferably having 1 to 4 carbon atoms, for example, methyl group, ethyl group, trifluoromethyl group, benzyl group, phenethyl group), aryl group (for example, phenyl group), alkoxy group (preferably having carbon number 1 to 4, such as methoxy, ethoxy, propoxy, butoxy), carboxyl, alkoxycarbonyl (preferably having 2 to 5 carbon atoms, such as ethoxycarbonyl), hydroxy, cyano, etc. I can list them.

Here, Z ₄₁ is a thiazoline nucleus (for example,
Thiazoline, 4-methylthiazoline, 4-phenylthiazoline, 4,5-dimethylthiazoline, 4,5-diphenylthiazoline and the like, benzothiazoline nucleus (for example,
Benzothiazoline, 4-chlorobenzothiazoline, 5-
Chlorobenzothiazoline, 6-chlorobenzothiazoline, 7-chlorobenzothiazoline, 5-nitrobenzothiazoline, 6-nitrobenzothiazoline, 4-methylbenzothiazoline, 5-methylbenzothiazoline, 6-methylbenzothiazoline, 5-bromobenzo Thiazoline,
6-bromobenzothiazoline, 5-iodobenzothiazoline, 5-methoxybenzothiazoline, 6-methoxybenzothiazoline, 5-ethoxybenzothiazoline, 5-
Propoxybenzothiazoline, 5-butoxybenzothiazoline, 5-carboxybenzothiazoline, 5-ethoxycarbonylbenzothiazoline, 5-phenethylbenzothiazoline, 5-fluorobenzothiazoline, 5-chloro-6-methylbenzothiazoline, 5-trifluoromethyl Benzothiazoline, 5,6-dimethylbenzothiazoline, 5-hydroxy-6-methylbenzothiazoline,
Tetrahydrobenzothiazoline, 4-phenylbenzothiazoline, 5-phenylbenzothiazoline, etc.), naphthothiazoline nucleus (for example, naphtho [2,1-d] thiazoline, naphtho [1,2-d] thiazoline, naphtho [2,
3-d] thiazoline, 5-methoxynaphtho [1,2-
d] thiazoline, 7-ethoxynaphtho [2,1-d] thiazoline, 8-methoxynaphtho [2,1-d] thiazoline, 5-methoxynaphtho [2,3-d] thiazoline and the like, thiazolidine nucleus (for example, thiazolidine) , 4-methylthiazolidine, 4-nitrothiazolidine, etc.), an oxazoline nucleus (for example, oxazoline, 4-methyloxazoline, 4-nitrooxazoline, 5-methyloxazoline, 4-phenyloxazoline, 4,5-diphenyloxazoline, 4-ethyl) Oxazoline, etc.), benzoxazoline nucleus (benzoxazoline, 5-chlorobenzoxazoline, 5-methylbenzoxazoline, 5-
Bromobenzoxazoline, 5-fluorobenzoxazoline, 5-phenylbenzoxazoline, 5-methoxybenzoxazoline, 5-nitrobenzoxazoline, 5-trifluoromethylbenzoxazoline, 5-
Hydroxybenzoxazoline, 5-carboxybenzoxazoline, 6-methylbenzoxazoline, 6-chlorobenzoxazoline, 6-nitrobenzoxazoline, 6-methoxybenzoxazoline, 6-hydroxybenzoxazoline, 5,6-dimethylbenzoxazoline, 5- Ethoxybenzoxazoline, etc.), naphthooxazoline nucleus (for example, naphtho [2,1-d] oxazoline, naphtho [1,2-d] oxazoline, naphtho [2,3-d] oxazoline, 5-nitronaphtho [2
1-d] oxazoline, etc.), oxazolidine nucleus (eg, 4,4-dimethyloxazolidine), selenazoline nucleus (eg, 4-methyl selenazoline, 4-nitro selenazoline, 4-phenyl selenazoline, etc.), selenazolidine nucleus (eg, Selenazolidine, 4-methylselenazolidine, 4-phenylselenazolidine, etc.), benzoselenazoline nucleus (e.g., benzoselenazoline, 5-chlorobenzoselenazoline, 5-nitrobenzoselenazoline, 5-methoxybenzoselenazoline, 5-hydroxybenzoselenazoline, 6-nitrobenzoselenazoline,
5-chloro-6-nitrobenzoselenazoline, etc.), naphtho selenazoline nucleus (for example, naphtho [2,1-d] selenazoline, naphtho [1,2-d] selenazoline etc.), 3,3-dialkylindoline nucleus ( For example, 3,3
-Dimethylindoline, 3,3-diethylindoline,
3,3-dimethyl-5-cyanoindoline, 3,3-dimethyl-6-nitroindoline, 3,3-dimethyl-5
-Nitroindoline, 3,3-dimethyl-5-methoxyindoline, 3,3-dimethyl-5-methylindoline, 3,3-dimethyl-5-chloroindoline, etc.),
Imidazoline nucleus (eg, 1-alkyl imidazoline,
1-alkyl-4-phenylimidazoline, 1-arylimidazoline, etc.), benzimidazoline nucleus (for example, 1-alkylbenzimidazoline, 1-alkyl-5-
Chlorobenzimidazoline, 1-alkyl-5,6-dichloro-benzimidazoline, 1-alkyl-5-methoxybenzimidazoline, 1-alkyl-5-cyanobenzimidazoline, 1-alkyl-5-fluorobenzimidazoline, 1-alkyl -5-trifluoromethylbenzimidazoline, 1-allyl-5,6-dichlorobenzimidazoline, 1-allyl-5-chlorobenzimidazoline, 1-arylbenzimidazoline, 1-aryl-5-chlorobenzimidazoline, 1-aryl −
5,6-dichlorobenzimidazoline, 1-aryl-
5-methoxybenzimidazoline, 1-aryl-5-
Cyanobenzimidazoline, etc.), naphthoimidazoline nucleus (for example, 1-alkylnaphtho [1,2-d] imidazoline, 1-arylnaphtho [1,2-d] imidazoline, etc.), and the above-mentioned alkyl is particularly preferably a carbon atom having 1 to 8 carbon atoms. For example, an unsubstituted alkyl group such as methyl, ethyl, propyl, isopropyl, and butyl, and a hydroxyalkyl group (eg, 2-hydroxyalkyl, 3-hydroxypropyl, etc.) are desirable.

The aforementioned aryl groups include phenyl, halogen (eg, chloro) substituted phenyl, alkyl (eg, methyl) substituted phenyl, alkoxy (eg, methoxy) substituted phenyl, and the like. A pyrrolidine nucleus (e.g., 2-pyrrolidine, etc.), a dihydropyridine nucleus (e.g., 1,4-dihydropyridine, 5-methyl-1,2-dihydropyridine, 3-methyl-1,4-dihydropyridine, etc.), a dihydroquinoline nucleus (e.g., 1, 4-dihydroquinoline, 3-methyl-1,2-dihydroquinoline, 5-ethyl-1,2-dihydroquinoline, 6-methyl-1,2-
Dihydroquinoline, 6-nitro-1,2-dihydroquinoline, 8-fluoro-1,2-dihydroquinoline, 6-
Methoxy-1,2-dihydroquinoline, 6-hydroxy-1,2-dihydroquinoline, 8-chloro-1,2-dihydroquinoline, 6-ethoxy-1,4-dihydroquinoline, 6-nitro-1,4- Dihydroquinoline, 8-chloro-1,4-dihydroquinoline, 8-fluoro-1,
4-dihydroquinoline, 8-methyl-1,4-dihydroquinoline, 8-methoxy-1,4-dihydroquinoline,
Dihydroisoquinoline, 6-nitro-1,2-isoquinoline, 6-nitro-2,3-dihydroisoquinoline, etc.) and a non-metallic atomic group required to complete the tetrazoline nucleus.

Among them, preferred Z ₄₁ include thiazoline nucleus, benzothiazoline nucleus, thiazolidine nucleus, benzoxazoline nucleus, naphthooxazoline nucleus, selenazoline nucleus, selenazolidine nucleus, benzoselenazoline nucleus, benzimidazoline nucleus, pyrrolidine nucleus, dihydropyridine nucleus. , Tetrazoline nucleus. Particularly preferred examples of Z ₄₁ are a thiazoline nucleus, a thiazolidine nucleus, a selenazoline nucleus, a selenazolidine nucleus, a benzimidazoline nucleus, a pyrrolidine nucleus, and a dihydropyridine nucleus. More preferred as Z ₄₁ are a thiazoline nucleus, a thiazolidine nucleus, a benzimidazoline nucleus and a pyrrolidine nucleus.

R ₄₁ and R ₄₂ are each independently a hydrogen atom or an unsubstituted alkyl group (C 1-18, preferably 1-8
An alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, hexyl, dodecyloctadecyl, etc., a substituted alkyl group, an aralkyl group (eg, benzyl, β-phenylethyl, etc.), a hydroxyalkyl group (eg, 2- Hydroxyethyl, 3-hydroxypropyl, 2-hydroxyethoxyethyl, etc.), carboxyalkyl group (for example, carboxymethyl, 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, etc.), alkyl group substituted by sulfo group (The sulfo group may be bonded to the alkyl group via an alkoxy group, an aryl group, or the like. For example, 2-sulfoethyl, 3-sulfopropyl, 3-sulfobutyl, 4-sulfobutyl, 2- [3-sulfopropoxy] Ethyl, 2-
Hydroxy-3-sulfopropyl, 2- [2- (3-sulfopropoxy) ethoxy] ethyl, p-sulfophenethyl and the like, sulfate alkyl group (for example, 3-sulfopropylpropyl and 4-sulfobutyl),
Mercapto group, vinyl-substituted alkyl group (for example, allyl group), acyloxyalkyl group (for example, 2-acetoxyethyl group, 3-acetoxypropyl group, etc.), alkoxyalkyl group (for example, 2-methoxyethyl group, 3-methoxy Propyl group, etc.), alkoxycarbonylalkyl group (for example, 2-methoxycarbonylethyl group, 3-
A methoxycarbonylpropyl group, a 4-ethoxycarbonylbutyl group, etc., a cyanoalkyl group (eg, a 2-cyanoethyl group), a carbamoylalkyl group (eg, a 2-carbamoylethyl group), an aryloxyalkyl group (eg, 2- A phenoxyethyl group, a 3-phenoxypropyl group, a mercaptoalkyl group (eg, a 2-mercaptoethyl group, a 3-mercaptopropyl group, etc.), an alkylthioalkyl group (eg, a 2-methylthioethyl group, etc.), or an aryl group ( For example, a phenyl group, a tolyl group, a naphthyl group, a methoxyphenyl group, a chlorophenyl group, etc.). R ₄₂ is preferably a hydrogen atom or an aryl group.

Q represents a rhodanine nucleus, a 2-thiooxazoline-2,4-dione nucleus, and 2-thioselenazoline-2,4-
A dione nucleus, a barbituric acid nucleus or a thiobarbituric acid nucleus [eg, a 1-alkyl group (eg, 1-methyl, 1-ethyl, 1-propyl, 1-heptyl, etc.), a 1,3-dialkyl group (eg, 1,3 -Dimethyl, 1,3-diethyl, 1,3-dipropyl, 1,3-diisopropyl,
1,3-dicyclhexyl, 1,3-di (β-methoxyethyl) and the like, 1,3-diaryl group (for example, 1,
3-diphenyl, 1,3-di (p-chlorophenyl),
1,3-di (p-ethoxycarbonylphenyl), etc.), 1-sulfoalkyl group (for example, 1- (2-sulfoethyl), 1- (3-sulfopropyl), 1- (4-sulfobutyl)), 1 , 3-disulfoalkyl group (for example, 1,3-di (2-sulfoethyl), 1,3-di (3-sulfopropyl), 1,3-di- (4-sulfocyclohexyl, etc.), 1,3- Barbitur nucleus or thio containing di- (sulfoaryl group (eg, 1,3-di- (4-sulfophenyl) etc.) or 1-sulfoaryl group (eg, 1- (4-sulfophenyl) etc.) Barbituric acid nucleus] or thiohydantoin nucleus (provided that the substituent at the 1-position is the same as that at the 3-position (R ₄₂ ), but both may be the same or different) Represents

The heterocycle formed by Q is preferably a rhodanine nucleus or a thiohydantoin nucleus, more preferably a rhodanine nucleus.

Y ₁ and Y _{2 each} represent a hydrogen atom, an alkyl group (eg, a methyl group, an ethyl group, a propyl group, a benzyl group), an aryl group (eg, a phenyl group, an o-carboxyphenyl group, a p-carboxyphenyl group). Represents

M represents 0, 1 or 2, and p represents 0 or 1.

Next, specific examples of the general formula [4] will be given, but the present invention is not limited to these.

[0065]

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The compounds represented by the general formulas [1] to [4] are contained in the silver halide emulsion in an amount of 10 ^-5 to 10 ^-1 per mol of silver.
It is appropriate to add them in moles (preferably 10 ^-4 to 10 ^-2 moles).

The compounds represented by the general formulas [1] to [4] may be added directly to the emulsion, or dissolved in an appropriate solvent such as methanol, ethanol, dimethylformamide, etc., alone or in a mixed solvent, and then added. May be. The timing of addition may be at any time during the production process of the silver halide photographic light-sensitive material, but is preferably at any time from physical ripening to completion of chemical ripening.

In general, the sensitizing dye may be used alone,
Combinations of these may be used, and combinations of sensitizing dyes are often used particularly for supersensitization.

The following general formulas (1) and (2-
a), general formula (2-b), general formula (3), general formula (4-
a), a spectral sensitizing dye represented by the general formula (4-b) or the general formula (5) is also preferably used.

[0070]

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Where R¹¹, R¹², R¹³And R¹⁴Is each
Each represents a substituted or unsubstituted aliphatic group;¹²And R¹⁴of
At least one of which has a water-solubilizing group as a substituent,
¹¹, V ¹², V¹³, V¹⁴, V^Fifteen, V¹⁶, V¹⁷And V¹⁸Is each
Each represents a hydrogen atom or a substituent;¹¹And V¹², V¹²And V
¹³, V¹³And V¹⁴, V^FifteenAnd V¹⁶, V¹⁶And V¹⁷And V¹⁷And V
¹⁸And each may form a fused ring, provided that V¹¹~
V¹⁴And V^Fifteen~ V¹⁸Is the added Hammett σp value
Is a substituent whose sum is greater than 0.12.¹¹,
L¹², L¹³, L¹⁴And L^FifteenEach represents a methine group;
¹¹Represents the ions required to offset the total charge in the molecule.
Then l¹¹Is the ion required to offset the total charge in the molecule
Represents the number of

[0072]

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Where Y^{twenty one}, Y^{twenty two}, Y^{twenty three}And Y^{twenty four}Is each
Each independently -N (R^{twenty four}) -Group, oxygen atom, sulfur atom,
Represents a ren atom or tellurium atom,^{twenty three}And Y^{twenty four}One of
Is -N (R^{twenty four})-Group;^{twenty one}, Y^{twenty two}And Y^{twenty three}Or
Y^{twenty one}, Y^{twenty two}And Y^{twenty four}Is not simultaneously a sulfur atom, R
^{twenty one}Represents an aliphatic group having 8 or less carbon atoms substituted with a water solubilizing group.
Then R^{twenty four}, R^{twenty two}And R^{twenty three}Represents an aliphatic group and an aryl group, respectively.
Or a heterocyclic group, and R^{twenty four}, R^{twenty two}And R^{twenty three}Less of
Both groups have a water solubilizing group as a substituent, Z^{twenty one}
Represents a 5- or 6-membered nitrogen-containing heterocyclic group which may be condensed
Represents the group of non-metallic atoms required to form^{twenty one}Is an oxygen atom,
Sulfur atom, = N (AR) group, = C <(E^{twenty one}) (E^{twenty two}) Group
And AR represents an aromatic ring or a heterocyclic group;^{twenty one}, L
^{twenty two}Each independently represents a substituted or unsubstituted methine carbon;^{twenty one}
And E^{twenty two}Each independently represents an electron-withdrawing group,
L may combine to form a keto ring or an acidic heterocycle,
^{twenty one}Represents 0 or 1, and M^{twenty one}Offsets the total charge in the molecule
Represents the ions necessary for ^{twenty one}Offsets the total charge in the molecule
Indicates the number of ions required for

[0074]

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In the formula, Y ²⁵ , Y ²⁶ and Y ²⁷ each independently represent an —N (R ²⁹ ) — group, an oxygen atom, a sulfur atom, or a selenium atom, and R ²⁵ is substituted with a water solubilizing group. It represents an aliphatic group having 8 or less carbon ^{atoms, R 29, R 26, R} 27 and R ²⁸ each represent an aliphatic group, an aryl group or a heterocyclic group, and R ^29,
At least three groups of R ²⁶ , R ²⁷ and R ²⁸ have a water-solubilizing group as a substituent, and Z ²² represents a nonmetallic atom group necessary for forming a nitrogen-containing heterocyclic group which may be condensed. , L ²³ ,
L ²⁴ represents a substituted or unsubstituted methine carbon, M ²² represents an ion required to offset the total charge in the molecule, and n represents
²² represents the number of ions required to offset the total charge in the molecule.

[0076]

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In the formula, Y ³¹ , Y ³² and Y ³³ each independently represent a —N (R ³⁴ ) — group, an oxygen atom, a sulfur atom or a selenium atom, and R ³¹ is substituted with a water solubilizing group. Represents an aliphatic group having 10 or less carbon atoms, R ³⁴ , R ³² and R ³³ each represent an aliphatic group, an aryl group or a heterocyclic group, and at least two groups of R ³⁴ , R ³² and R ³³ are Substituting a water solubilizing group,
V ³¹ and V ³² each represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or a group bonded to V ³¹ or V ³² to form a condensed ring with an azole ring, and L ³¹ and L ³² each represent M ³¹ independently represents a substituted or unsubstituted methylene carbon; M ³¹ represents an ion required to offset the total charge in the molecule;
³¹ represents the number of ions required to offset the total charge in the molecule.

[0078]

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In the formula, Z ⁴¹ represents a nonmetal atom necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring which may be condensed, and Y ⁴¹ and Y ⁴² each independently represent -N ( ^R44 )-
W ⁴¹ represents a ＮN (AR) group, an oxygen atom, a sulfur atom, ＝ C
<(E ⁴¹ ) represents a (E ⁴² ) group, R ⁴¹ represents an aliphatic group having a carbon number of 8 or less substituted with a water solubilizing group, and R ⁴⁴ , R ⁴² and R
⁴³ represents an aliphatic group, an aryl group or a heterocyclic group, and at least two groups of R ⁴⁴ , R ⁴² and R ⁴³ each have a water-solubilizing group as a substituent, and E ⁴¹ and E ⁴² each represent Independently represents an electron-withdrawing group or a group of nonmetallic atoms in which E ⁴¹ and E ⁴² are bonded to each other to form an acidic heterocyclic ring, and AR represents an aromatic ring or a heterocyclic group, and L ⁴¹ , L ⁴² , L ^{42 43,} L ⁴⁴ each represents a substituted or unsubstituted methine carbon independently, l ⁴¹ is an integer of 0 or 1, M ⁴¹ represents an ion required to offset the total charge of the molecule, n ⁴¹ is Indicates the number of ions required to offset the total charge in the molecule.

[0080]

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In the formula, Z ⁴² represents a nonmetal atom necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring which may be condensed, and Y ⁴³ and Y ⁴⁴ each independently represent —N ( ^R48 )-group,
Oxygen, sulfur, selenium, tellurium,
R ⁴⁵ represents a substituted aliphatic group having 8 or less carbon water-solubilizing group, a R ^48, R ⁴⁶ and R ⁴⁷ are each an aliphatic group, an aryl group or a heterocyclic group, and R ^48, R ⁴⁶ And at least two groups of R ⁴⁷ have a water-solubilizing group as a substituent, W ⁴² represents an oxygen atom or a sulfur atom, L ⁴⁵ , L ⁴⁶ , L ⁴⁷ and L ⁴⁸ each represent a methine carbon; At least one of L ⁴⁵ , L ⁴⁶ , L ⁴⁷ and L ⁴⁸ is a substituted methine carbon, M ⁴² represents an ion necessary to offset the total charge in the molecule, and n ⁴² represents the total charge in the molecule. Indicates the number of ions required to cancel each other.

[0082]

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In the formula, R ⁵¹ represents an aliphatic group having 10 or less carbon atoms substituted with a water solubilizing group, and R ⁵² , R ⁵³ and R ⁵⁴ each represent an aliphatic group, an aryl group or a heterocyclic group; And R ⁵² ,
At least two groups of R ⁵³ and R ⁵⁴ substitute a water solubilizing group. V ⁵¹ and V ⁵² are each bonded to a hydrogen atom, an alkyl group, an alkoxy group, an aryl group or V ⁵¹ and V ⁵² to form an azole ring. And L ⁵¹ and L ⁵² each represent a substituted or unsubstituted methine carbon, and W ⁵¹ represents ＮN
(AR) group, oxygen atom, sulfur atom, = C <(E ⁵¹ ) (E
⁵² ) represents a group, AR represents an aromatic ring or a heterocyclic group,
⁵¹ and E ⁵² each independently represent an electron-withdrawing group, or may combine with each other to form a keto ring or an acidic heterocyclic ring,
M ⁵¹ represents an ion required to offset the total charge in the molecule, and n ⁵¹ represents the number of ions required to offset the total charge of the molecule.

In the general formula (1), R ¹¹ , R ¹² and R ¹³
And an aliphatic group represented by R ¹⁴ , for example, a branched or linear alkyl group having 1 to 10 carbon atoms (for example,
Each group such as methyl, ethyl, n-propyl, n-pentyl and isobutyl), a vinyl group, an alkenyl group having 2 to 10 atoms (for example, each group such as 3-butenyl and 2-propenyl) or 3 carbon atoms; To 10 aralkyl groups (for example, benzyl, phenethyl, etc.). R
The ¹² and water-solubilizing group substituting at least one of groups R ^14, a sulfo group, a carboxy group, a phosphono group, a sulfate group, a sulfino group, and the like.

Each of the aliphatic groups represented by R ¹¹ , R ¹² , R ¹³ and R ¹⁴ is a hydroxy group, a halogen atom, an alkoxy group (such as a methoxy group or an ethoxy group), an aryloxy group (a phenoxy group, a p-sulfo group). Phenoxy group), cyano group,
A carbamoyl group (carbamoyl group, N-methylcarbamoyl group, N, N-tetramethylenecarbamoyl group, etc.),
Sulfamoyl group (sulfamoyl group, N, N-3-oxapentamethyleneaminosulfonyl group, etc.), methanesulfonyl group, alkoxycarbonyl group (ethoxycarbonyl group, butoxycarbonyl group, etc.), aryl group (phenyl group, carboxyphenyl group, etc.) May be substituted with a substituent such as an acyl group (acetyl group, benzoyl group, etc.), an acylamino group (acetylamino group, etc.), and specific examples of the aliphatic group substituted with a water-solubilizing group include carboxy. Methyl, sulfoethyl, sulfopropyl, sulfobutyl, sulfopentyl, 3-sulfobutyl, 6-sulfo-
3-oxahexyl, ω-sulfopropoxycarbonylmethyl, ω-sulfopropylaminocarbonylmethyl,
3-sulfinobutyl, 3-phosphonopropyl, 4-
Sulfo-3-butenyl, 2-carboxy-2-propenyl, O-sulfobenzyl, P-sulfophenethyl, P-
Each group such as carboxybenzyl is exemplified.

[0086] ^{V 11, V 12, V 13} , V 14, V 15, V 16, V
Examples ^of the ^{substituent 17} and V ¹⁸ represent each include any groups sum of the electron donating property chosen as larger than 0.12 group or electron withdrawing Hammett σp value obtained by adding.
Specifically, a cyano group, a carboxy group, a linear or branched alkyl group (for example, each group such as methyl, ethyl, iso-propyl, t-butyl, iso-butyl, t-pentyl, hexyl, etc.), an alkoxy group ( For example, each group such as methoxy, ethoxy, propoxy, etc.), an alkylthio group (eg, methylthio group), a halogen atom, a carbamoyl group (eg, carbamoyl, N-methylcarbamoyl,
Groups such as N, N-pentamethylenecarbamoyl), sulfamoyl groups (eg, groups such as N-methylsulfamoyl, morpholinosulfonyl, piperidinosulfonyl), acylamino groups (eg, acetylamino, propionylamino, Benzoylamino, etc.), sulfonylamino group (for example, methanesulfonylamino, benzenesulfonylamino, m-chlorobenzenesulfonylamino, perfluoromethanesulfonylamino, etc.), alkoxycarbonyl group (for example, methoxycarbonyl, ethoxy) Carbonyl, butoxycarbonyl, etc.), alkylsulfonyl group (eg, methanesulfonyl, ethanesulfonyl, trifluoromethanesulfonyl, etc.), arylsulfonyl group (eg, benzenesulfonyl, etc.) An acyl group (e.g., acetyl,
Each group such as benzoyl), perfluoroalkyl group (for example, each group such as trifluoromethyl and pentafluoroethyl), perfluoroalkoxy group (for example, each group such as trifluoromethoxy and pentafluoroethoxy), and perfluoroalkylthio group (for example) , Trifluoromethylthio, pentafluoroethylthio, etc.), aryl groups (eg, phenyl, m-chlorophenyl, etc.), heterocyclic groups (eg, pyrrolyl, pyridyl, imidazolyl, furyl, thiphenyl, etc.) There is.

The Hammett's σp value is a substituent constant determined from the electronic effect of the ring group on the hydrolysis rate of benzoic acid ethyl ester by Hammett et al. The value of each group is, for example, Chemical Review (Chemical Review).
Reviews, 17, 125-136 (1935), Journal of Organic Chemistry (Jou)
rnal of Organic Chemistr
y) Volume 23, 420-427 (1958), Experimental Chemistry Course 14 (Maruzen Publishing Co., Ltd.), Physical Organic
Chemistry (Physical Organic C
hemistry; McGraw Hill Boo
k: 1940), Drug Design Volume VII (Drug)
design VII Academic Press;
New York: 1970), Structure-activity relationship of drugs (Nankodo: 1979), Substitute Constants for Correlation Analysis in Chemistry and Biology (Subst)
title Constants for Corr
elation Analysis in Chemi
try and Biology; John Wil
eye and Sons: 1979).

[0088] ^{V 11, V 12, V 13} , V 14, V 15, V 16, V
^The aryl group, the heterocyclic group, and the alkyl group represented by ¹⁷ and V ¹⁸ may have any of the above-described substituents at any positions. V ¹¹ and V ^12, V ¹² and V ^13, V ¹³ and V ^14, V
Each between ¹⁵ and V ^16, V ¹⁶ and V ¹⁷ and V ¹⁷ and V ^18, 5 to 7-membered saturated carbocycle as fused ring formed, aromatic carbon ring, ring groups heterocycles mentioned And may have any of the aforementioned substituents at any position.

Examples of the group substituted by the methine carbon represented by L ¹¹ , L ¹² , L ¹³ , L ¹⁴ and L ¹⁵ include a lower alkyl group (for example, each group such as methyl and ethyl) and a cyclic alkyl group (For example, each group such as cyclopropyl and cyclopentyl), a substituted alkyl group (for example, each group such as 2-methoxyethyl and 2-thienylmethyl), an aralkyl group (for example, each group such as benzyl and phenethyl), and a phenyl group (E.g., phenyl, carboxyphenyl, etc.),
Heterocyclic groups (eg, thienyl, furyl, imidazolyl,
And alkoxy groups (for example, methoxy, ethoxy and the like) and fluorine atoms. L ¹¹ can form a condensed ring with R ¹¹ or R ¹² , and L ¹² can form a condensed ring with R ¹³ or R ¹⁴ , respectively. M ¹¹ represents a cation or an acid anion. Specific examples of the cation include a proton, an organic yunmonium ion (for example, each ion such as triethylammonium and triethanolammonium), and an inorganic cation (for example, lithium, sodium, calcium and the like). Specific examples of the acid anion include, for example, a halogen ion (for example, chloride ion, bromine ion,
Iodine ion), p-toluenesulfonic acid ion, perchlorate ion, boron tetrafluoride ion and the like.

L ¹¹ is 0 when an internal salt is formed and the total charge is offset.

Specific examples of the sensitizing dye represented by formula (1) are shown below.

[0092]

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[0093]

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[0094]

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[0095]

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[0096]

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[0097]

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[0098]

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[0099]

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[0100]

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[0101]

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[0102]

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[0103]

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[0104]

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[0105]

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[0106]

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[0107]

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[0108]

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[0109]

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[0110]

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[0111]

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These compounds are described, for example, in FM
Hama, "Cyanine Soybeans and Related
Compounds "(1964, published by Inter Science Publishers), UK Patent No. 980,234, U.S. Patent No. 3,684,517, JP-A-61-2034.
No. 46, Ukr. Khim. Zh. , 197
The compound can be easily synthesized with reference to a conventionally known method described in 7, 43 (4) 381-4.

In the compounds represented by formulas (2-a) and (2-b), Y ²¹ , Y ²² , Y ²³ , Y ²⁴ , Y ²⁵ , and Y ²⁶
And Y ²⁷ each independently represent a —NR ²⁴ or —NR ²⁹ group, an oxygen atom, a sulfur atom, or a selenium atom.

R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R
^27, as the water-solubilizing group substituting on R ²⁸ and R ^29, a sulfo group, a carboxy group, a phosphono group, a sulfate group,
And a sulfino group.

R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R
Examples of the aliphatic group represented by ²⁷ , R ²⁸ and R ²⁹ include:
A branched or straight-chain alkyl group having 1 to 8 carbon atoms (for example, each group such as methyl, ethyl, n-propyl, n-pentyl, and isobutyl), and an alkenyl group having 3 to 8 carbon atoms (for example, 3- Examples include groups such as butenyl and 2-propenyl) and aralkyl groups having 3 to 8 carbon atoms (eg, groups such as benzyl and phenethyl).

R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R
^27, examples of the aryl group represented by R ²⁸ and R ²⁹ for example, include a phenyl group, a heterocyclic group for example,
Pyridyl group (2-, 4-), pyrazyl group, furyl group (2
-), Thienyl group (2-), sulfolanyl group, tetrahydrofuryl group, piperidinyl group, pyrrole group, imidazolyl group and the like.

R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R
²⁷ , R ²⁸ and R ²⁹ each represent a halogen atom, an alkoxy group (such as a methoxy group or an ethoxy group), an aryloxy group (such as a phenoxy group or a p-tolyloxy group), a cyano group,
A carbamoyl group (carbamoyl group, N-methylcarbamoyl group, N, N-tetramethylenecarbamoyl group, etc.),
Sulfamoyl group (sulfamoyl group, N, N-3-oxapentamethyleneaminosulfonyl group, etc.), methanesulfonyl group, alkoxycarbonyl group (ethoxycarbonyl group, butoxycarbonyl group, etc.), aryl group (phenyl group, carboxyphenyl group, etc.) And an acyl group (acetyl group, benzoyl group, etc.).

Specific examples of the aliphatic group substituted with a water-solubilizing group include carboxymethyl, sulfoethyl, sulfopropyl, sulfobutyl, sulfopentyl, 3-sulfobutyl, 6-sulfo-3-oxahexyl, and ω-sulfopropoxy. Carbonylmethyl, ω-sulfopropylaminocarbonylmethyl, N-ethyl-N-sulfopropyl, 3-sulfinobutyl, 3-phosphonopropyl,
4-sulfo-3-butenyl, 2-carboxy-2-propenyl, o-sulfobenzyl, p-sulfophenethyl,
Specific examples of the aryl group having each group such as p-carboxybenzyl and substituted with a water-solubilizing group include a p-sulfophenyl group and a p-carboxyphenyl group, and a heterocyclic ring substituted with a water-solubilizing group. Specific examples of the group include a 4-sulfothienyl group and a 3-carboxypyridyl group.

In these, R ²¹ and R ²⁵ are alkyl groups substituted with a sulfo group, and R ²² , R ²³ , R ²⁴ , R ^24
26, Izure or at least two groups of R ^27, R ²⁸ and R ²⁹ are each a is preferable carboxymethyl group.

Examples of the 5- or 6-membered nitrogen-containing heterocyclic group represented by Z ²¹ and Z ²² include a basic heterocyclic ring forming a cyanine dye, and include, for example, an oxazole ring (oxazole, benzoxazole, naphtho Oxazole, etc.), thiazole ring (thiazolidine, thiazole, benzothiazole, naphthothiazole, etc.), imidazole ring (imidazole, benzimidazole, naphthimidazole, etc.), selenazole ring (selenazole, benzoselenazole, naphthoselenazole, etc.), tetrazole ring ( And rings such as tetrazole, benzotetrazole, naphthotetrazole, pyridine ring (pyridine, quinoline, etc.), pyrrole ring (pyrrole, indole, indolenine, etc.).

As the nitrogen-containing 5-membered heterocyclic ring represented by Z ²¹ , 5-membered heterocyclic rings described above for Z ²¹ can be mentioned.

The above-mentioned heterocyclic ring represented by Z ²¹ and Z ²² may have a substituent at any position, for example, a halogen atom, a trifluoromethyl group, an alkoxy group (for example, methoxy, ethoxy, etc.) , Butoxy and other unsubstituted alkoxy groups, 2-methoxyethoxy and benzyloxy and other substituted alkoxy groups), hydroxy group, cyano group and aryloxy group (for example, substituted and unsubstituted groups such as phenoxy and tolyloxy) Or an aryl group (for example, a substituted or unsubstituted group such as phenyl, p-chlorophenyl, p-tolyl, or p-methoxyphenyl), a styryl group, or a heterocyclic group (for example, each group such as furyl or thienyl); A carbamoyl group (for example, each group such as carbamoyl and N-ethylcarbamoyl) and a sulfamoyl group (for example, sulfamoyl, N, N-dimethyl); Rusulfamoyl, etc.), acylamino group (eg, acetylamino, propionylamino, benzoylamino, etc.), acyl group (eg, acetyl, benzoyl, etc.), alkoxycarbonyl group (eg, ethoxycarbonyl, etc.) ), A sulfonamide group (for example, each group such as methanesulfonylamide and benzenesulfonamide), a sulfonyl group (for example, each group such as methanesulfonyl and p-toluenesulfonyl), a carboxy group, and an alkyl group (for example, methyl, ethyl, Arbitrary groups such as isopropyl and the like).

Examples of the group substituted on the methine carbon represented by L ²¹ , L ²² , L ²³ and L ²⁴ include a lower alkyl group (for example, each group such as methyl and ethyl) and a phenyl group (for example, Phenyl, carboxyphenyl, etc.),
There are groups such as an alkoxy group (for example, each group such as methoxy and ethoxy), an aryloxy group (for example, each group such as phenoxy and carboxyphenoxy), an aralkyl (for example, a group such as benzyl), and a fluorine atom.

These dyes generally have a high spectral sensitivity when one of the methine carbons represented by L ²¹ and L ²² is substituted, and provide a property that the dye is easily drifted in a processing bath. It is understood and preferred.

The electron-withdrawing groups represented by E ²¹ and E ²² are selected from groups having a Hammett σ _p value of more than 0.3, and specifically include a cyano group, a carbamoyl group (carbamoyl group, morpholinocarbonyl group). , N-methylcarbamoyl group, etc.), alkoxycarbonyl group (methoxycarbonyl group, ethoxycarbonyl group, etc.), sulfamoyl group (sulfamoyl group, morpholinosulfonyl group, N,
N-dimethylsulfamoyl group, etc.), acyl group (acetyl group, benzoyl group, etc.), sulfonyl group (methanesulfonyl group, ethanesulfonyl group, benzenesulfonyl group,
Toluenesulfonyl group, etc.).

The keto ring formed by E ²¹ and E ²² and the acidic heterocyclic ring include, for example, the following compounds.

[0127]

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[Wherein, R ^a and R ^b each represent a lower alkyl group, an aryl group, or a heterocyclic group, and specific examples of the lower alkyl group include methyl, ethyl, propyl, 2-hydroxyethyl, and 2-methoxyethyl. Ethyl, trifluoroethyl,
Examples include substituted and unsubstituted groups such as allyl, carboxymethyl, carboxyethyl, 2-sulfoethyl, and benzyl. The aryl group and heterocyclic group represented by R ^a and R ^b include R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , and R ^27.
And those of the content shown in R ^28.

M ²¹ and M ²² each represent a cation or an acid anion. Specific examples of the cation include a proton, an organic ammonium ion (each ion such as triethylammonium and triethanolammonium), and an inorganic cation (lithium, sodium, calcium). Etc.)
Specific examples of the acid anion include, for example, a halogen ion (chlorine ion, bromine ion, iodine ion, etc.),
p-toluenesulfonic acid ion, perchlorate ion, 4-
And boron fluoride ions. n ²¹ and n ²² form an internal salt and are 0 when the total charge in the molecule is offset.
Becomes Specific examples of the sensitizing dye represented by the general formula [2-a] or [2-b] are shown below.

[0130]

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[0131]

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[0132]

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[0133]

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[0134]

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[0135]

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[0136]

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The above-mentioned compounds are described in, for example, "Cyanine Soybeans and Related Compounds" by F.M.Hama (1964, published by Inter Science Publishers), US Pat. No. 2,454,629,
No. 2,493,748, British Patent No. 489335,
The compound can be easily synthesized with reference to a conventionally known method described in European Patent No. 730008 or the like.

In the general formula (3), Y ³¹ , Y ³² and Y
³³ represents a —N (R ³⁴ ) — group, an oxygen atom, a sulfur atom or a selenium atom.

Examples of the water-solubilizing group substituted for R ³¹ , R ³² and R ³³ include a sulfo group, a carboxy group, a phosphono group, a sulfate group, a sulfino group and the like.

As the aliphatic group represented by R ³¹ , R ³² and R ³³ , for example, a branched or linear alkyl group having 1 to 10 carbon atoms (for example, methyl, ethyl, n-propyl, n-
-Each group such as pentyl and isobutyl), having 3 to 1 carbon atoms
Examples thereof include an alkenyl group of 0 (for example, each group such as 3-butenyl and 2-propenyl) and an aralkyl group having 3 to 10 carbon atoms (for example, each group of benzyl and phenethyl).

Examples of the aryl group represented by R ³² , R ³³ and R ³⁴ include a phenyl group, and examples of the heterocyclic group include a pyridyl group (2-, 4-) and a furyl group (2
-), A thienyl group (2-), a sulfolanyl group, a tetrahydrofuryl group, and a piperidinyl group.

Each of R ³¹ , R ³² and R ³³ represents a halogen atom, an alkoxy group (such as a methoxy group or an ethoxy group), an aryloxy group (such as a phenoxy group or a p-tolyloxy group), a cyano group, or a carbamoyl group. Carbamoyl group, N
-Methylcarbamoyl group, N, N-tetramethylenecarbamoyl group, etc.), sulfamoyl group (sulfamoyl group, N, N-3-oxapentamethyleneaminosulfonyl group, etc.), methanesulfonyl group, alkoxycarbonyl group (ethoxycarbonyl group, butoxy It may be substituted with a substituent such as a carbonyl group, an aryl group (phenyl group, carboxyphenyl group, etc.), an acyl group (acetyl group, benzoyl group, etc.).

Specific examples of the aliphatic group substituted with a water-solubilizing group include carboxymethyl, sulfoethyl, sulfopropyl, sulfobutyl, sulfopentyl, 3-sulfobutyl, 6-sulfo-3-oxahexyl, and ω-sulfopropoxy. Carbonylmethyl, ω-sulfopropylaminocarbonylmethyl, 3-sulfinobutyl, 3-phosphonopropyl, 4-sulfo-3-butenyl, 2-carboxy-2-propenyl, O-sulfobenzyl, P-sulfophenethyl, P A specific example of an aryl group substituted with a water-solubilizing group, such as a p-sulfophenyl group or a p-carboxyphenyl group, and a heterocyclic group substituted with a water-solubilizing group. Specific examples include a 4-sulfothienyl group and a 5-carboxypyridyl group.

As the alkyl group represented by V ³¹ and V ³² , a linear or branched group (eg, methyl, ethyl, iso
-Propyl, t-butyl, iso-butyl, t-pentyl, hexyl, etc.). Alkoxy groups represented by V ³¹ and V ³² (for example, methoxy, ethoxy,
Groups such as propoxy).

The aryl group represented by V ³¹ and V ³² may have a substituent at any position, and examples thereof include phenyl, p-tolyl, p-hydroxyphenyl and p-methoxyphenyl. Groups. Examples of the condensed ring formed by V ³¹ and V ³² bonded together with an azole ring include benzoxazole, 4,5,6,7-tetrahydrobenzoxazole, naphtho [1,2-d] oxazole, naphtho [2, 3-d] oxazole, benzothiazole, 4,5,6,7-tetrahydrobenzothiazole, naphtho [1,2-d] thiazole, naphtho [2,3-d] thiazole, benzoselenazole, naphtho [1,2 -D] condensed rings such as selenazole;

The aforementioned substituents represented by V ³¹ and V ³² and the condensed ring formed may have a substituent at any position, for example, a halogen atom, a trifluoromethyl group, an alkoxy group (E.g., unsubstituted alkyl groups such as methoxy, ethoxy, butoxy, 2-methoxyethoxy,
Substituted alkoxy groups such as benzyloxy, etc., hydroxy groups, cyano groups, aryloxy groups (eg, substituted and unsubstituted groups such as phenoxy and tolyloxy), or aryl groups (eg, substituted with phenyl, p-chlorophenyl, etc.) , Unsubstituted groups), styryl groups, heterocyclic groups (for example,
Each group such as furyl and thienyl), carbamoyl group (for example, each group such as carbamoyl and N-ethylcarbamoyl), and sulfamoyl group (for example, sulfamoyl,
N, N-dimethylsulfamoyl, etc.), acylamino group (eg, acetylamino, propionylamino, benzoylamino, etc.), acyl group (eg, acetyl, benzoyl, etc.), alkoxycarbonyl group ( For example, a group such as ethoxycarbonyl), a sulfonamide group (for example, each group such as methanesulfonylamide, benzenesulfonamide), a sulfonyl group (for example, each group such as methanesulfonyl, p-toluenesulfonyl) and a carboxy group. The group of is mentioned.

Examples of the group substituted on the methine carbon represented by L ³¹ and L ³² include a lower alkyl group (for example, each group such as methyl and ethyl) and a phenyl group (for example, each group such as phenyl and carboxyphenyl). Groups), alkoxy groups (for example, groups such as methoxy and ethoxy), and aralkyl (for example, groups such as benzyl).

M ³¹ represents a cation or an acid anion;
Specific examples of the cation include a proton, an organic ammonium ion (for example, each ion such as triethylammonium and triethanolammonium), and an inorganic cation (for example, each cation such as lithium, sodium, and calcium). Specific examples of the acid anion include For example, halogen ions (for example, chloride ion, bromine ion, iodine ion, etc.), p-toluenesulfonic acid ion, perchlorate ion, 4-boron fluoride ion and the like can be mentioned. n ³¹ is 0 when an internal salt is formed and the total charge in the molecule is offset.
Becomes

In the above formula (3), R ³¹ is an alkyl group substituted by a sulfo group, and R ³² , R ³³ and R ³⁴
Wherein at least two of the groups are carboxymethyl.

Specific examples of the sensitizing dye represented by the general formula (3) are shown below.

[0151]

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[0152]

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[0153]

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[0154]

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[0155]

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The above compounds are described, for example, in "Cyanine Soybeans and Related Compounds" by F.M.Hama (1964, published by Inter Science Publishers), US Pat. No. 2,454,629,
The compound can be easily synthesized with reference to a conventionally known method described in JP-A-2,493,748 and the like.

In the general formulas (4-a) and (4-b),
Examples of the aliphatic group represented by R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , R ⁴⁷ and R ⁴⁸ include, for example, a branched or straight-chain alkyl group having 1 to 8 carbon atoms (eg, , Methyl, ethyl, n-
Propyl, n-pentyl, each group such as isobutyl), an alkenyl group having 3 to 8 atoms (for example, 3-butenyl, 2-
Each group such as propenyl) or an aralkyl group having 3 to 8 carbon atoms (eg each group such as benzyl and phenethyl).

The aryl group represented by R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁶ , R ⁴⁷ and R ⁴⁸ includes, for example, a phenyl group, and the heterocyclic group includes, for example, a pyridyl group (2-, 4)
-), Pyrazyl group, furyl group (2-), thienyl group (2
-), Sulfolanyl group, tetrahydrofuryl group, piperidinyl group, pyrrole group, imidazolyl group and the like.

R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , R
Each of ⁴⁷ and R ⁴⁸ is a halogen atom, an alkoxy group (such as a methoxy group or an ethoxy group), an aryloxy group (such as a phenoxy group or a p-tolyloxy group), a cyano group, a hydroxyl group, or a carbamoyl group (such as a carbamoyl group or N -Methylcarbamoyl group, N, N-tetramethylenecarbamoyl group, etc.), sulfamoyl group (sulfamoyl group, N, N
-3-oxapentamethyleneaminosulfonyl group, etc.),
Methanesulfonyl group, alkoxycarbonyl group (ethoxycarbonyl group, butoxycarbonyl group, etc.), aryl group (phenyl group, carboxyphenyl group, etc.), acyl group (acetyl group, benzoyl group, etc.), amide group (acetamide group, methanesulfonamide) Group, benzoylamide group).

Specific examples of the aliphatic group substituted with a water-solubilizing group include, for example, carboxymethyl, sulfoethyl, sulfopropyl, sulfobutyl, sulfopentyl, 3-sulfobutyl, 6-sulfo-3-oxahexyl, ω-sulfo Propoxycarbonylmethyl, ω-sulfopropylaminocarbonylmethyl, N-ethyl-N-sulfopropyl, N-ethyl-N-sulfopropyl, 3-sulfinobutyl, 3-phosphonopropyl, 4-sulfo-3
-Butenyl, 2-carboxy-2-propenyl, o-sulfobenzyl, p-sulfophenethyl, p-carboxybenzyl, etc., and specific examples of the aryl group substituted with a water-solubilizing group include: There are p-sulfophenyl group, p-carboxyphenyl group and the like, and specific examples of the heterocyclic group substituted with a water-solubilizing group include a 4-sulfothienyl group and a 3-carboxypyridyl group.

In these, R ⁴¹ and R ⁴⁵ are alkyl groups substituted with a sulfo group, and R ⁴⁴ , R ⁴² , R ⁴³ , R
^46, or at least two groups of R ⁴⁷ and R ⁴⁸ are each a is preferable carboxymethyl group.

Examples of the 5- or 6-membered nitrogen-containing heterocyclic group represented by Z ⁴¹ and Z ⁴² include a basic heterocyclic ring forming a cyanine dye, and include, for example, an oxazole ring (eg, oxazole, benzoxazole) , A ring of naphthoxazole or the like), a thiazole ring (for example, a ring of thiazolidine, thiazole, benzothiazole, naphthothiazole or the like), an imidazole ring (for example, each ring of imidazole, benzimidazole, naphthoimidazole or the like), a selenazole ring ( For example, each ring such as selenazole, benzoselenazole, naphthoselenazole, etc., a tellurazole ring (eg, each ring such as tellurazole, benzotellurazole, naphthotellazole), a pyridine ring (eg, each ring such as pyridine, quinoline, etc.) , A pyrrole ring (e.g., pyrrole, indole, indole Each ring such as drainin).

The above-mentioned heterocyclic ring represented by Z ⁴¹ and Z ⁴² may have a substituent at any position, for example, a halogen atom, a trifluoromethyl group or an alkoxy group (for example, methoxy, ethoxy, etc.) , Butoxy and other unsubstituted alkoxy groups, 2-methoxyethoxy and benzyloxy and other substituted alkoxy groups), hydroxy group, cyano group and aryloxy group (for example, substituted and unsubstituted groups such as phenoxy and tolyloxy) Or an aryl group (for example, a substituted or unsubstituted group such as phenyl, p-chlorophenyl, p-tolyl, or p-methoxyphenyl), a styryl group, or a heterocyclic group (for example, each group such as furyl or thienyl); A carbamoyl group (for example, each group such as carbamoyl and N-ethylcarbamoyl) and a sulfamoyl group (for example, sulfamoyl and N, N-dimethyl) Rusulfamoyl, etc.), acylamino group (eg, acetylamino, propionylamino, benzoylamino, etc.), acyl group (eg, acetyl, benzoyl, etc.), alkoxycarbonyl group (eg, ethoxycarbonyl, etc.) ), A sulfonamide group (for example, each group such as methanesulfonylamide and benzenesulfonamide), a sulfonyl group (for example, each group such as methanesulfonyl and p-toluenesulfonyl), a carboxy group, and an alkyl group (for example, methyl, ethyl, Arbitrary groups such as isopropyl and the like).

L ⁴¹ , L ⁴² , L ⁴³ , L ⁴⁴ , L ⁴⁵ , L ⁴⁶ , L
The group substituted methine carbon represented by ⁴⁷ and L ^48, e.g., a lower alkyl group (e.g., each group such as methyl, ethyl), phenyl group (e.g., phenyl, carboxymethyl each group such as phenyl), An alkoxy group (for example, each group such as methoxy and ethoxy), an aryloxy group (for example,
Phenoxy, carboxyphenoxy, etc.), aralkyl groups (eg, benzyl, etc.), heterocyclic groups (pyridyl, pyrrolyl, tetrahydrofuryl, thienyl, thienyl, furyl, pentahydrooxazinyl) Group)
And a fluorine atom.

These dyes generally have high spectral properties when any one of the methine carbons represented by L ⁴¹ , L ⁴² , L ⁴³ , L ⁴⁴ and L ⁴⁵ , L ⁴⁶ , L ⁴⁷ , L ⁴⁸ is substituted. It has been found that sensitivity is obtained, and that the dye gives characteristics that the dye is easily drifted in the processing bath.

W ⁴¹ and W ⁴² are an oxygen atom, a sulfur atom, and ＝ C <
(E ⁴¹ ) (E ⁴² ) or ＣC <(E ⁴³ ) (E ⁴⁴ ), and E ⁴¹ and E ⁴² or E ⁴³ and E ⁴⁴ each independently represent an electron-withdrawing group, and are bonded to each other To form a keto ring or an acidic heterocyclic ring, l ⁴¹ represents an integer of 0 or 1,
M ⁴¹ and M ^{42 each} represent a cation or an acid anion. Specific examples of the cation include a proton, an organic ammonium ion (for example, each ion such as triethylammonium and triethanolammonium), and an inorganic cation (for example, lithium, sodium, calcium, and the like). Cation). Specific examples of the acid anion include, for example, a halogen ion, a p-toluenesulfonic acid ion, a perchlorate ion,
4-boron fluoride ion and the like. n ⁴¹ and n ⁴² become 0 when an internal salt is formed to cancel the total charge in the molecule.

The electron-withdrawing group represented by E ⁴¹ , E ⁴² or E ⁴³ , E ⁴⁴ is selected from groups having a Hammett σp value of more than 0.3, and specifically includes a cyano group, a carbamoyl group (carbamoyl). Group, morpholinocarbonyl group, N-methylcarbamoyl group, etc.), alkoxycarbonyl group (methoxycarbonyl group, ethoxycarbonyl group, etc.), sulfamoyl group (sulfamoyl group, morpholinosulfonyl group, N, N-dimethylsulfamoyl group, etc.) , An acyl group (acetyl group, benzoyl group, etc.), a sulfonyl group (methanesulfonyl group, ethanesulfonyl group, benzenesulfonyl group, toluenesulfonyl group, etc.).

The keto ring formed by E ⁴¹ or E ⁴² or E ⁴³ or E ⁴⁴ and the acidic heterocyclic ring are represented by the aforementioned general formula (2-
The same as the keto ring and the acidic heterocyclic ring formed by E ²¹ and E ²² in a).

In the formula, R ^a and R ^b each represent a lower alkyl group, an aryl group, or a heterocyclic group, and specific examples of the lower alkyl group include methyl, ethyl, propyl, 2-hydroxyethyl, and 2-methoxyethyl. , Trifluoroethyl,
Examples include substituted and unsubstituted groups such as allyl, carboxymethyl, carboxyethyl, 2-sulfoethyl, and benzyl. The aryl group and the heterocyclic group represented by R ^a and R ^b include those represented by R ⁴⁴ , R ⁴² , R ⁴³ , R ⁴⁸ , R ⁴⁶ and R ⁴⁷ .

Specific examples of the sensitizing dyes represented by formulas (4-a) and (4-b) are shown below.

[0171]

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[0172]

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[0173]

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[0174]

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[0175]

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[0176]

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[0177]

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In the general formula (5), R ⁵¹ , R ⁵² , R ⁵³
And the water-solubilizing group substituted for R ⁵⁴ include a sulfo group, a carboxy group, a phosphono group, a sulfate group, and a sulfino group.

Examples of the aliphatic group represented by R ⁵¹ , R ⁵² , R ⁵³ and R ⁵⁴ include a branched or straight-chain alkyl group having 1 to 8 carbon atoms (for example, methyl, ethyl, n-propyl, n
Each group such as pentyl and isobutyl), having 3 to 8 carbon atoms
(E.g., 3-butenyl, 2-propenyl, etc.) or an aralkyl group having 3 to 8 carbon atoms (e.g., benzyl, phenethyl, etc.).

Examples of the aryl group represented by R ⁵² , R ⁵³ and R ⁵⁴ include a phenyl group, and examples of the heterocyclic group include a pyridyl group (2-, 4-), a pyrazyl group and a furyl group (2 -), Thienyl group (2-), sulfolanyl group, tetrahydrofuryl group, piperidinyl group, pyrrole group, imidazolyl group and the like.

Each of R ⁵¹ , R ⁵² , R ⁵³ and R ⁵⁴ represents a halogen atom, an alkoxy group (such as a methoxy group or an ethoxy group), an aryloxy group (such as a phenoxy group or a p-tolyloxy group), a cyano group, Carbamoyl group (carbamoyl group, N-methylcarbamoyl group, N, N-tetramethylenecarbamoyl group, etc.), sulfamoyl group (sulfamoyl group, N, N-3-oxapentamethyleneaminosulfonyl group, etc.), methanesulfonyl group, alkoxycarbonyl It may be substituted with a substituent such as a group (ethoxycarbonyl group, butoxycarbonyl group, etc.), an aryl group (phenyl group, carboxyphenyl group, etc.), an acyl group (acetyl group, benzoyl group, etc.).

Specific examples of the aliphatic group substituted with a water-solubilizing group include, for example, carboxymethyl, sulfoethyl, sulfopropyl, sulfobutyl, sulfopentyl, 3-sulfobutyl, 6-sulfo-3-oxahexyl, ω-sulfo Propoxycarbonylcarbonyl, ω-sulfopropylaminocarbonylmethyl, N-ethyl-N-sulfopropyl, 3-sulfinobutyl, 3-phosphonopropyl, 4-sulfo-3-butenyl, 2-carboxy-2
-Propenyl, o-sulfobenzyl, p-sulfophenethyl, p-carboxybenzyl and the like. Specific examples of the aryl group substituted with a water-solubilizing group include a p-sulfophenyl group and a p-carboxyphenyl. There are groups, etc.
Specific examples of the heterocyclic group substituted with a water solubilizing group include 4
-Sulfothienyl group, 3-carboxypyridyl group and the like.

In these, R ⁵² and R ⁵³ are alkyl groups substituted with a sulfo group, and those in which at least two of R ⁵¹ , R ⁵² , R ⁵³ and R ⁵⁴ are each a carboxymethyl group. preferable.

Examples of the group substituted by the methine carbon represented by L ⁵¹ and L ⁵² include a lower alkyl group (for example, each group such as methyl and ethyl) and a phenyl group (for example, phenyl and carboxyphenyl). Each group), an alkoxy group (for example, each group such as methoxy and ethoxy), an aryloxy group (for example, each group such as phenoxy and carboxyphenoxy), an aralkyl (for example, a group such as benzyl), and a group such as a fluorine atom. is there.

[0185] These dyes, when one of the methine carbon represented by L ⁵¹ and L ⁵² are substituted, generally high spectral sensitivity can be obtained, giving the likely characteristics dye is bleached by treatment bath It is understood and preferred.

W ⁵¹ is an oxygen atom, a sulfur atom, ＝ C <
L ⁵¹ and L ⁵² each represent a group represented by the formula (E ⁵¹ ) or (E ⁵² ),
Represents an unsubstituted methylene carbon; E ⁵¹ and E ⁵² each independently represent an electron-withdrawing group, which may be bonded to each other to form a keto ring or an acidic heterocyclic ring;

The electron-withdrawing groups represented by E ⁵¹ and E ⁵² are selected from groups having a Hammett σ _p value of more than 0.3, and specifically include a cyano group, a carbamoyl group (carbamoyl group, morpholinocarbonyl group). , N-methylcarbamoyl group, etc.), alkoxycarbonyl group (methoxycarbonyl group, ethoxycarbonyl group, etc.), sulfamoyl group (sulfamoyl group, morpholinosulfonyl group, N,
N-dimethylsulfamoyl group, etc.), acyl group (acetyl group, benzoyl group, etc.), sulfonyl group (methanesulfonyl group, ethanesulfonyl group, benzenesulfonyl group,
Toluenesulfonyl group, etc.).

The keto ring formed by E ⁵¹ and E ⁵² and the acidic heterocyclic ring are, for example, the same as the keto ring formed by E ²¹ and E ²² and the acidic hetero ring in the above formula (2-a). It is.

Examples of the heterocyclic group include R ⁵¹ , R ⁵² and R ^53.
And those of the content shown in R ^54.

M ⁵¹ represents a cation or an acid anion. Specific examples of the cation include a proton, an organic ammonium ion (eg, each ion such as triethylammonium and triethanolammonium), and an inorganic cation (eg, lithium, sodium, calcium, etc.). And specific examples of the acid anion include a halogen ion, a p-toluenesulfonic acid ion, a perchlorate ion, and a 4-boron fluoride ion.
n ⁵¹ becomes 0 when an internal salt is formed and the total charge in the molecule is offset.

Specific examples of the sensitizing dye represented by the general formula (5) are shown below.

[0192]

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[0193]

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[0194]

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[0195]

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[0196]

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[0197]

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[0198]

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The above compounds are described, for example, in "Cyanine Soybeans and Related Compounds" by F.M.Hama (1964, published by Inter Science Publishers), US Pat. No. 2,454,629,
No. 2,493,748, British Patent No. 489335,
The compound can be easily synthesized with reference to a conventionally known method described in European Patent No. 730008 or the like.

The amount of the sensitizing dyes represented by formulas (1) to (5) varies greatly depending on the conditions used and the type of emulsion, but is preferably 1 × per mole of silver halide.
10 ^{-6 to} 5 × 10 ^-3 mol, more preferably 2 × 10 ^-6 to
It is in the range of 2 × 10 ^-3 mol. In addition, general formulas (1) to
The sensitizing dye represented by (5) can be added to a silver halide emulsion by a conventionally known method. For example, JP
0-80826, 50-80827, U.S. Pat. No. 3,822,135.
And JP-A-50-11419, a method of dispersing and adding together with a surfactant, U.S. Pat. No. 3,676,147.
No. 3,469,987, No. 4,247,627
No., JP-A-51-59942, and JP-A-53-16624.
No. 53-102732, No. 53-102733
No. 53-137131, a method of dispersing in a hydrophilic substrate, a method of adding as a solid solution described in East German Patent No. 143324, or Research Disclosure No. 21802, Japanese Patent Publication No. 50-40659. ,
Water-soluble solvents for dissolving dyes represented by JP-A-59-148053 (low-boiling solvents such as water, methanol, ethanol, propyl alcohol, acetone and fluorinated alcohol; dimethylformamide, methyl cellosolve, phenyl cellosolve and the like) A solvent having a high boiling point) can be added to the emulsion by arbitrarily selecting or adding a method of dissolving in a single solvent or a mixed solvent thereof.

The sensitizing dyes represented by the general formulas (1) to (5) may be added at any stage during the emulsion production process from physical ripening to chemical ripening and coating. It is preferably added during the period from to the end of chemical ripening. During the physical ripening, or before the chemical sensitizer is added in the chemical ripening step, or immediately after the addition of the chemical sensitizer, the addition of the compound according to the present invention has the effect of obtaining higher spectral sensitivity. Are preferably used.

The sensitizing dyes represented by formulas (1) to (5) can be used in combination with other sensitizing dyes. In this case, the respective sensitizing dyes may be added to the emulsion simultaneously or separately at different times, and the order and time interval at that time may be arbitrarily determined depending on the purpose.

Further spectral sensitivity can be obtained by using a compound having a supersensitizing effect in combination with the sensitizing dye. Compounds having such a supersensitizing effect include, for example, U.S. Pat. Nos. 2,933,390 and 3,416,9.
No. 27, No. 3,511,664, No. 3,615,61
No. 3, 3,615,632, 3,635,721
No., JP-A-3-15042, JP-A-3-110545,
Compounds having a pyrimidinylamino group or a triazinylamino group described in JP-A-4-2555841, an aromatic organic formaldehyde condensate described in British Patent No. 1137580, JP-A-61-169833 and the like, -1
No. 84332, calixarene derivatives described in U.S. Pat. No. 4,030,927, halogenated benzotriazole derivatives, bispyridinium compounds described in JP-A-59-142541 and JP-A-59-188641, An aromatic heterocyclic quaternary salt compound described in JP-A-59-190332, an electron-donating compound described in JP-A-60-79348, and an aminoallylidenemalononitrile unit described in U.S. Pat. No. 4,307,183. Containing polymer,
Hydroxytetrazaindene derivatives described in JP-A-4-149937; 1,3-oxadiazole derivatives described in U.S. Pat. No. 3,615,633; U.S. Pat.
No. 780,404, for example, amino-1,2,3,4-thiatriazole derivatives. The timing of adding these supersensitizers is not particularly limited, and they can be arbitrarily added according to the timing of adding the sensitizing dye according to the present invention. The addition amount is selected in the range of 1 × 10 ^-6 to 1 × 10 ^-1 mol per mol of silver halide, and the sensitizing dye is used in an addition molar ratio of 1/10 to 10/1.

Ascorbic acid used in the present invention includes those represented by the following general formula (A), among which those represented by (Aa) are preferably used.

[0205]

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In the general formula (A), R ₁ and R ₂ each represent
A substituted or unsubstituted alkyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkylthio group, R _1, R ₂
May combine with each other to form a ring. k represents 0 or 1, and when k is 1, X represents -CO- or -CS-.
M ₁ and M ₂ each represent a hydrogen atom or an alkali metal atom.

In the general formula (Aa), R ₃ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, Represents a sulfo group, a carboxyl group, an amide group, a sulfonamide group, Y ₁ represents O or S,
Y ₂ represents O, S or NR ₄ . R ₄ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.
M ₁ and M ₂ each represent a hydrogen atom or an alkali metal atom.

Examples of the substituent of the alkyl group include a halogen atom (Cl, Br, etc.), a hydroxyl group, an aryl group having 6 to 20 carbon atoms (phenyl, naphthyl group, etc.), a heterocyclic group (2, 2, 6,6-tetramethylpiperidyl, quinolidinyl, N, N'-diethylpyrazolidinyl, pyridyl group, etc.) C1-C20 alkoxy group (methoxy, ethoxy group, etc.), C6-C20 aryloxy Group (such as a phenoxy group), an alkenyloxy group having 1 to 20 carbon atoms (such as an allyloxy group), an alkynyloxy group having 1 to 20 carbon atoms (such as a propargyloxy group), a heterocyclic oxy group (a pyridyloxy group), Acylamino groups (acetylamino, heptylamino, propionylamino groups, etc.) and amino groups (amino, methylamino, dimethylamino, diben) Arylamino group).

Examples of the substituent of the amino group include a halogen atom (as described above), a hydroxyl group, an aryl group having 6 to 20 carbon atoms (as described above), and an alkyl group having 1 to 20 carbon atoms (methyl, ethyl, Butyl, cyclohexyl, isopropyl, dodecyl group, etc.), heterocyclic group (same as above), carbon number 1-2
0 alkoxy group (same as above), aryloxy group having 6 to 20 carbon atoms (same as above), alkenyloxy group having 1 to 20 carbon atoms (same as before), alkynyloxy group having 1 to 20 carbon atoms (same as before) , A heterocyclic oxy group (the same as above), an acyl group having 1 to 20 carbon atoms (acetyl, heptyl, propionyl group and the like) and the like.

Examples of the substituent of the alkylthio group include a halogen atom (as described above), a hydroxyl group, and a
Aryl group (same as above), heterocyclic group (same as above), alkoxy group having 1 to 20 carbon atoms (same before), aryloxy group having 6 to 20 carbon atoms (same before), 1 to 20 carbon atoms Alkenyloxy group (same as above), alkynyloxy group having 1 to 20 carbon atoms (same as above), heterocyclic oxy group (same before), and having 1 to 2 carbon atoms
And acyl group (same as above) and amino group (same as above).

Examples of the substituent of the aryl group include a halogen atom (as described above), a hydroxyl group, and a group having 1 to 20 carbon atoms.
Alkyl group (same as above), heterocyclic group (same as above), having 1 to 1 carbon atoms
20 alkoxy groups (same as above), C6-20 aryloxy groups (same as above), C1-20 alkenyloxy groups (same as before), C1-20 alkynyloxy groups (same as before) A heterocyclic oxy group (same as above), an acylamino group having 1 to 26 carbon atoms (same as above), an amino group (same as before), and the like.

Examples of the substituent of the above alkoxy group include:
Halogen atom (same as above), hydroxyl group, 6 to 2 carbon atoms
0 aryl group (same as above), alkyl group having 1 to 20 carbon atoms (same as above), heterocyclic group (same as above), aryloxy group having 6 to 20 carbon atoms (same as above), 1 to 20 carbon atoms Alkenyloxy group (same as above), alkynyloxy group having 1 to 20 carbon atoms (same as above), heterocyclic oxy group (same as above), acylamino group having 1 to 26 carbon atoms (same as above), amino group (same as above) And the like.

Examples of the substituent of the sulfo group, carboxyl group, amide group and sulfonamide group include a halogen atom (as described above), a hydroxyl group, an alkali metal group (sodium, potassium, etc.), Aryl group (same as above), alkyl group having 1 to 20 carbon atoms (same as above), heterocyclic group (same before), alkoxy group having 1 to 20 carbon atoms (same before), aryloxy group having 6 to 20 carbon atoms (Same as above), an alkenyloxy group having 1 to 20 carbon atoms (same as above), 1 carbon atom
-20 alkynyloxy group (same as above), heterocyclic oxy group (same as above), acylamino group having 1 to 26 carbon atoms (same as above),
And an amino group (same as above).

Next, the formula (A) or the formula (A-
Examples of the compound represented by a) are shown below, but the present invention is not limited thereto.

[0215]

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[0216]

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[0219]

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[0218]

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[0219]

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These compounds are typically ascorbic acid or erythorbic acid or derivatives derived therefrom, and are commercially available or can be easily synthesized by a known synthesis method.

The hydrazine derivative used in the present invention is preferably a compound represented by the following formula [H].

[0222]

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In the formula, A represents an aryl group or a heterocyclic ring containing at least one sulfur atom or oxygen atom, and G represents-
(CO) n-, sulfonyl group, sulfoxy group, -P (=
O) R ₂ — or an iminomethylene group, n represents an integer of 1 or 2, A ₁ and A ₂ are both a hydrogen atom or one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group, or Represents a substituted or unsubstituted acyl group,
R is a hydrogen atom, a substituted or unsubstituted alkyl group,
Represents an alkenyl group, an aryl group, an alkoxy group, an alkenyloxy group, an aryloxy group, a heterocyclic oxy group, an amino group, a carbamoyl group, or an oxycarbonyl group. R ₂ represents a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aryl group, alkoxy group,
Represents an alkenyloxy group, an alkynyloxy group, an aryloxy group, an amino group, or the like.

Specific examples of the compound represented by the formula [H] are shown below.

[0225]

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[0226]

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[0227]

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[0228]

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[0229]

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[0230]

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[0231]

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Specific examples of other preferred hydrazine derivatives are (1) to (252) described in US Pat. No. 5,229,248, columns 4 to 60.

The hydrazine derivative according to the present invention can be synthesized by a known method. For example, US Pat.
229, 248, columns 59 to 80 can be referred to.

In the present invention, when a hydrazine derivative is contained in a photographic material, it is preferably contained in a silver halide emulsion layer, but it may be contained in a hydrophilic colloid layer adjacent to the silver halide emulsion layer. . Such a layer is a layer having any function, such as an undercoat layer, an intermediate layer, a filter layer, a protective layer, and an antihalation layer, as long as it does not prevent the hydrazine derivative from diffusing into the silver halide grains. Is also good. The content of the hydrazine derivative in the layer is
The appropriate content can vary over a wide range, depending on the characteristics of the silver halide emulsion used, the chemical structure of the compound and the development conditions, but will vary from about 1 × 10 ^-6 per mole of silver in the silver halide emulsion. A range of １1 × 10 ^-2 moles is practically useful.

In the present invention, the above-mentioned hydrazine derivative may be contained in a developer. In this case, 1 × 10 ⁻⁶ to 1 × 10 ⁻³ mol / l is preferable in the developer and 1 × 1 ⁻⁶ mol / l
0 ^{-5 to} 5 × 10 ^-4 mol / l is more preferred.

Also, JP-A-60-179834, JP-A-60-17934
-267759, U.S. Patent No. 5,104,769,
JP-A-4,798,780, JP-A-4,994,365, JP-A-4,998,604, JP-A-1-179939, JP-A-1-179940, JP-A-6-313937, and JP-A-7-3
It is preferable to include the amino compound described in Nos. 6139 and 10-48784 and the like in the material or the developer. Among them, JP-A-10-4878
The compounds described in Columns [0082] to [0109] of No. 4 can be preferably used.

In the present invention, the developing agent may be contained in the constituent layers of the lithographic printing plate or may be contained in the developing solution.

As the developing agent used in the present invention, the ascorbic acid according to the present invention is preferably used. From the viewpoint of the environment, it is preferable that hydroquinone, which has been conventionally used for developing a lithographic printing plate material using a silver complex salt diffusion transfer method, is not substantially contained. Here, the amount substantially not contained means 0.05 mol or less, preferably 0.02 mol / m ² per 1 m ² in the lithographic printing plate material.
m ² or less, more preferably not containing at all. In the treatment liquid, it is 0.05 mol or less per liter, preferably 0.02 mol / L or less, and more preferably it does not contain any.

In the present invention, it is preferable to add 1-phenyl-3-pyrazolidone or a derivative thereof, or a p-aminophenol-based developing agent in addition to the above-mentioned developing agent.
Specific examples include 1-phenyl-3-pyrazolidone, 1-
Phenyl-4,4-dimethyl-3-pyrazolidone, 1-
Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1-p-aminophenyl-4,4-dimethyl-3
-Pyrazolidone, 1-p-tolyl-4,4-dimethyl-
3-pyrazolidone and the like. Examples of the p-aminophenol-based developing agent used in the present invention include N-methyl-p-aminophenol, N- (β-hydroxyethyl) -p-aminophenol, N- (4-hydroxyphenyl) glycine, and 2-methyl- Examples include p-aminophenol and p-benzylaminophenol.

The developing agent is preferably used in an amount of usually from 0.06 mol / m ^{2 to} 1.5 mol / m ² in the constituent layers of the lithographic printing plate. Usually 0.06 mol / L in the developing solution
It is preferably used in an amount of .about.0.8 mol / L.

Examples of the sulfite preservative used in the present invention include sodium sulfite, potassium sulfite, sodium bisulfite, potassium metabisulfite, and sodium formaldehyde bisulfite. The amount used is not particularly limited, but is preferably 0.05 mol / L to 1.0 mol / L.
Used in the range.

The developing solution contains an alkali agent.
Known alkali agents such as hydroxides, phosphates, and carbonates are used.
It is preferable to contain L or more. More preferably 0.3
Mol / L to 1.0 mol / L.

In the developing solution, a buffer, a solubilizing agent, pH
An adjusting agent, a development accelerator, a surfactant, a hardener and the like can be contained.

The developer may further contain an antifoggant and a chelating agent.

Additives other than the above components include development inhibitors such as sodium bromide and potassium iodide, ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve, hexylene glycol, ethanol and methanol. And an organic solvent such as a color tone agent, an antifoaming agent, a water softener, and the like, if necessary.

The pH value of the developer adjusted in this manner is selected to a degree sufficient to give a desired concentration and gradation. Conventionally, however, lithographic printing using a silver complex salt diffusion transfer method using hydroquinones is used. In the development process of the plate, pH 12.0
Although it is often used at the above-mentioned high pH, it is preferable that the pH is 11 or less in the present invention from the viewpoint of safety and handling properties. What we could do was surprising. More preferred pH is 7 to 10.5
It is.

In the processing of the present invention, a commercially available automatic developing machine can be used, and the type of the automatic developing machine is not limited. Further, an automatic developing machine used for processing a lithographic printing plate material utilizing a silver complex salt diffusion transfer method can also be used.

The development processing temperature and time of the photographic material are interrelated and determined in relation to the total processing time, and are generally from about 20 to 50 ° C. for 10 seconds to 3 minutes. Is from 10 to 40 seconds at about 30-50 ° C.

As described in JP-B-57-3939, the combination of an organic compound for making the surface of the silver halide image area lipophilic and a silver halide solvent is used as described in JP-B-57-3939. Although a wide range, particularly preferred silver halide solvents are sodium iodide, potassium iodide, iodides such as ammonium iodide, sodium thiosulfate, potassium thiosulfate, ammonium thiosulfate, and the like, thiosulfate, potassium thiocyanate And thiocyanates such as sodium thiocyanate and ammonium thiocyanate; and sulfites such as potassium sulfite, sodium sulfite, sodium hydrogen sulfite and potassium hydrogen sulfite.

As the organic compound to be made lipophilic, those described in JP-B-57-3939 can be used. Preferably, it has the following structure.

[0251]

Embedded image

In the formula, R is hydrogen, an alkyl group having 12 or less carbon atoms, an aryl group, an aralkyl group, and Z is the remaining atom of a bond necessary to form a 5- or 6-membered heterocyclic ring together with N and C in the formula. Represents a group.

Specific examples of the 5- or 6-membered ring include imidazole, imidazoline, thiazole, thiazoline, oxazoline, oxazole, pyrazoline, triazole, thiadiazole, oxadiazole, tetrazole, pyridine, pyrimidine, pyridazine, pyrazine, triazine and the like. And these rings may be two or more condensed rings. Specific examples of typical compounds having the above structure include 2-mercapto-5-heptyl-1,3,4-oxadiazole,
Mercapto-5-phenyl1,3,4-oxadiazole, 2-mercapto-4-phenylimidazole, 2-
Mercapto-1-benzylimidazole, 2-mercaptobenzimidazole, 2-mercapto-1-ethyl-
Benzimidazole, 2-mercapto-1-butyl-benzimidazole, 1,3-diethyl-benzimidazoline-2-thione, 2,2′-dimethylcapto-1,
1'-Decamethylene-diimidazoline, 2-mercapto-4-phenylthiazole, 2-mercaptonaphthothiazole and the like.

The amount of the silver halide solvent effective for the purpose of the present invention is not uniform depending on the composition of the silver halide emulsion, but is in the range of 10 ^-2 mol / L to 1 mol / L. The amount of the organic compound for lipophilization is not necessarily uniform for each compound, but is 10 ^-3 mol / L to 10 ^-1 mol / L.
Used at a concentration of

The sensitizing solution containing an organic compound for lipophilicity and a silver halide solvent is used in order to improve the solubility of the organic compound, such as methanol, ethanol, propanol, ethylene glycol and diethylene glycol. It may contain a water-miscible organic solvent.

The sensitizing solution is preferably buffered between pH 4 and pH 8. As a pH buffer,
An acid having a pKa value of 4 to 8, such as acetic acid, citric acid, and phosphoric acid;
You can choose from those salts. Further, the conversion liquid may contain various other components. For example, water-soluble polymers such as hydroxyethylcellulose, surface hydrophilizing agents such as colloidal silica, and the like can be included. Further, for the purpose of preventing unevenness of the sensitization treatment, a surfactant described in JP-A-4-12353 can be used.

In the present invention, the portion used as ink receptivity is undeveloped silver halide or a developed metallic silver image portion. In the case where undeveloped silver halide is converted into an ink receiving portion, it can be obtained by performing a sensitization treatment after development as described above. When the developed metallic silver image area is converted to an ink receiving area, the silver image is fixed after development, or after a single-bath development and fixing treatment, the remaining silver image is oxidized and rehalogenated, and subjected to a sensitization treatment. can get.

When a printing plate is prepared by converting undeveloped silver halide into an ink receiving portion, a positive printing plate is used when the silver halide material to be used is a negative type, and a positive printing plate is used when the silver halide material to be used is a negative type. A negative printing plate is obtained.

The silver halide of the printing plate material used in the present invention has a halogen composition of any of silver chloride, silver chlorobromide, silver chloroiodobromide, silver bromide, silver iodobromide and silver iodide. However, silver chloride, silver chlorobromide and silver chloroiodobromide containing silver chloride in an amount of 50 mol% or more are preferred. The photographic emulsion used in the present invention is P.I. Chimi by Glafkids
e et Physique Photographi
que (Paul Montel, 1967),
G. FIG. F. Photographic by Duffin
Emulsion Chemistry (The Fo
cal Press, 1966); L. Zel
Makingand Coa by ikman et al
ting Photographic Emulsio
n (published by The Focal Press, 1964)
Etc. can be prepared. That is, any of an acidic method, a neutral method, an ammonia method, etc. may be used,
The formation of the reaction between the soluble silver salt and the soluble halogen salt may be performed by any one of a one-side mixing method, a simultaneous mixing method, and a combination thereof.

The silver halide used in the present invention preferably contains an ion or a complex ion of a metal belonging to Group 6 to Group 10 of the Periodic Table of the Elements for the purpose of improving illuminance failure and adjusting the improvement. The above metals include W, Fe, C
o, Ni, Cu, Ru, Rh, Pd, Re, Os, I
r, Pt, and Au are preferred.

These metals can be introduced into the silver halide in the form of a complex. In the present invention, the transition metal complex is preferably a six-coordinate complex or a complex ion represented by the following general formula.

In the formula [ML ₆ ] ^m , M is a transition metal selected from the elements of Groups 6 to 10 of the periodic table, L is a bridging ligand, and m is 0,-, 2- or 3-.
Represents Specific examples of the ligand represented by L include halides (fluoride, chloride, bromide and iodide), cyanide, cyanate, thiocyanate, selenocyanate, tellurocyanate, azide and aquo. Ligand, nitrosyl, thionitrosyl and the like, preferably aquo, nitrosyl and thionitrosyl. If an aquo ligand is present, it preferably occupies one or two of the ligands. L may be the same or different.

Particularly preferred examples of M are rhodium (Rh), ruthenium (Ru), rhenium (Re), iridium (Ir) and osmium (Os).

Specific examples of the transition metal coordination complex are shown below.

[0265] 1: [RhCl _6] ^3- 2: [RuCl _6] ^3- 3: [ReCl _6] ^3- 4: [RuBr _6] ^3- 5: [OsCl _6] ^3- 6: [IrCl _6] ^{2 -} 7: [Ru (NO) Cl _5] ^2- 8: [RuBr ₄ (H ₂ O)] ^2- 9: _{[Ru (NO) (H 2 O} ) Cl 4 ] ^- 10: [RhCl ₅ (H ₂ O)] ^2- 11: [Re (NO) Cl _5] ^2- 12: [Re (NO) CN _5] ^2- 13: [Re (NO) ClCN _4] ^2- 14: [Rh (NO) ₂ Cl _4] ^- 15: _{[Rh (NO) (H 2 O} ) Cl 4 ] ^- 16: [Ru (NO) CN _5] ^2- 17: [Fe (CN) _6] ^3- 18: [Rh (NS) Cl _5] ^2- 19: [Os (NO) Cl _5] ^2- 20: [Cr (NO) Cl _5] ^2- 21: [Re (NO) Cl _5] ^- 22: [Os (NS) Cl ₄ (TeCN )] ^2- 23: Ru (NS) Cl _5] ^2- 24: _{[Re (NS) Cl 4 (SeCN} ) ] ^2- 25: [Os (NS) Cl (SCN) 4 ] ^2- 26: [Ir (NO) Cl _5] ^{2 -} 27: [Ir (NS) Cl _5] ^2- these metals or complex ions may be one type, the metal of the same kind of metal or different may be used alone or in combination. The content of these metal ions or complex ions is generally from 1 × 10 ^-9 to 1 × 1 per mol of silver halide.
0 ^-2 mol are suitable, preferably 1 × 10 ^-8 ~1 × 1
^0-4 moles. The compound that provides the ion or complex ion of these metals is preferably added during silver halide grain formation and incorporated into the silver halide grains. Preparation of silver halide grains, that is, nucleation, growth, and physical ripening It may be added at any stage before and after chemical sensitization, but is particularly preferably added at the stage of nucleation, growth, and physical ripening, more preferably at the stage of nucleation and growth. Preferably, it is added at the stage of nucleation. Upon addition, it may be divided and added several times, may be uniformly contained in silver halide grains,
JP-A-63-29603, JP-A-2-306236
Nos. 3-167545, 4-76534, and 6
As described in, for example, JP-A-110146 and JP-A-5-273683, they can be contained in the particles with distribution. Preferably, a distribution can be provided inside the particles. These metal compounds can be prepared from water or a suitable organic solvent (eg, alcohols, ethers, glycols,
Ketones, esters, and amides). For example, an aqueous solution of a powder of a metal compound or an aqueous solution in which a metal compound and NaCl and KCl are dissolved together may be added to water-soluble silver during particle formation. A silver halide grain is prepared by a method in which the silver halide solution is added to a salt solution or a water-soluble halide solution, or as a third aqueous solution when a silver salt solution and a halide solution are simultaneously mixed, and a three-solution simultaneous mixing method. A method in which a required amount of an aqueous solution of a metal compound is charged into a reaction vessel during grain formation, or another silver halide grain doped with metal ions or complex ions in advance during silver halide preparation is added and dissolved. There is a method to make it. In particular, an aqueous solution of a powder of a metal compound or a metal compound and N
It is preferable to add an aqueous solution in which aCl and KCl are dissolved together to a water-soluble halide solution. When adding to the particle surface, a required amount of an aqueous solution of a metal compound can be charged into the reaction vessel immediately after the particle formation, during or at the end of physical ripening, or at the time of chemical ripening.

The photosensitive silver halide grains can be desalted by washing with water by a method known in the art such as a noodle method or a flocculation method.

The photosensitive silver halide grains in the invention are preferably chemically sensitized. Preferred chemical sensitization methods are sulfur sensitization, selenium sensitization, tellurium sensitization, noble metal sensitization such as gold compounds, platinum, palladium, and iridium compounds, and reduction sensitization as well known in the art. Sensitization can be used. Known compounds can be used as compounds preferably used in the sulfur sensitization method, the selenium sensitization method, and the tellurium sensitization method.
Compounds described in No. 8768 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, US Pat. No. 2,448,060, and British Patent No. 618061.
And the like. Specific compounds of the reduction sensitization method include, as well as ascorbic acid, thiourea dioxide, for example, stannous chloride,
Aminoiminomethanesulfinic acid, hydrazine derivatives,
Borane compounds, silane compounds, polyamine compounds and the like can be used. When the pH of the emulsion is 7 or more or pA
Reduction sensitization can be achieved by aging while keeping g at 8.3 or less. Further, reduction sensitization can be achieved by introducing a single addition portion of silver ion during grain formation.

The binder of the lithographic printing plate material is a water-soluble polymer, and among them, gelatin is preferred. A part or the whole thereof may be replaced with another colloidal substance, for example, albumin, casein, polyvinyl alcohol, polyvinyl alcohol-maleic anhydride, polyvinyl alcohol-styrene maleic anhydride, alginate, a cellulose derivative and the like. .

The weight ratio of binder, preferably gelatin, to silver halide and the absolute amount of binder are important factors in determining the quality of the printing plate of the present invention in the production thereof. The amount of binder is preferably between 0.3 and 3.0, where the weight of silver halide expressed as silver nitrate is one. When the ratio of the binder is 0.3 or less, the strength of the film as the emulsion layer is apt to be lowered, and unfavorable results are likely to be produced as the printing characteristics. On the other hand, when the ratio of the binder increases, the ink receptivity may decrease.

In the production of the printing plate of the present invention, another important factor lies in the hardening of the photosensitive silver halide emulsion layer. It must be sufficiently cured, at least before printing. A curing agent may be added to the photographic emulsion coating solution in the same manner as in the ordinary photographic emulsion layer hardening method, or it may be cured by a method such as heat treatment at a stage before or after development and plate making. You may. In order to obtain stable hardening characteristics, it is preferable to apply a silver halide emulsion containing a hardening agent, apply the coating and dry it, and then heat it appropriately. This heating treatment is a treatment for obtaining a good degree of curing, and is, for example, 80 to
150 ° C for several minutes or tens of minutes, or 30-50 ° C
For several days (about 1 to 20 days).

As the curing agent, compounds used as ordinary curing agents for photographic emulsion layers can be used. For example, aldehyde-based curing agents such as formalin, glyoxal, glutaraldehyde, and mucochromic acid, and urea-formalin condensate and melanin-formalin condensate are also effective. Known compounds as hardeners for photographic emulsions, such as organic hardeners such as organic compounds and inorganic polyvalent metal salts such as chromium, aluminum and zirconium, can be used alone or in combination.

The silver halide photographic emulsion layer has a grain size of about 2 to 2 to prevent abrasion of the colloid during printing.
Fine particles having a diameter of 10 μm are preferably contained, and silica, clay, talc, secretite, rice starch and the like can be used, but silica is particularly preferred.

The silica is added to the silver halide emulsion in an amount of 0.01 to 1 g per 1 m ² . If the silica particle concentration is excessively high, it becomes difficult to increase the ink concentration during printing, or a scumming phenomenon occurs.

It is preferable to apply a so-called antireflection dye or pigment for the purpose of improving the photographic sharpness, and finally the resolution and sharpness of the printed matter. These may be applied in the silver halide emulsion layer, or in the so-called antireflection layer between the support and the silver halide emulsion layer, or in the layer opposite the silver halide emulsion layer across the support. The purpose is achieved by.

Also, light-reflective pigments such as titanium oxide,
The object can also be achieved by using a white pigment such as barium sulfate or magnesium oxide or a yellow organic pigment in combination with a light-absorbing dye or pigment.

The most preferred embodiment of the lithographic printing plate of the present invention has a colloidal undercoat layer having an antireflection dye or pigment on a support, and a silver halide emulsion layer on the undercoat layer. .

The colloidal undercoating layer having the antireflection dye or pigment is preferably made of gelatin and contains the fine particles having a particle diameter of 2 to 10 μm as described above. A preferred microparticle is silica. The binder gelatin should harden as well as the silver halide emulsion layer at 0.5 g to 2.5 g per m ² . Also, silica is applied at between 0.1 g and ²⁰ g per m ² .

The undercoat layer containing fine particles as described above is
It has the effect of improving the abrasion of the colloid during printing and improving the printing durability. In this case, fine-particle silica is not necessarily required in the emulsion layer.

As the support for the silver halide emulsion, any support commonly used in the art such as paper coated with polyethylene on both sides, a plastic film, a metal sheet and the like can be used. , Preferably a plastic film. Examples of the plastic film used in the present invention include polyethylene terephthalate, polycarbonate, polyimide, nylon, cellulose triacetate, polyethylene naphthalate and the like.

Among them, preferred supports include polyethylene terephthalate (hereinafter abbreviated as PET), polyethylene naphthalate (hereinafter abbreviated as PEN), and
Examples of the support include a plastic (hereinafter abbreviated as SPS) support containing a styrene-based polymer having a syndiotactic structure as described in Japanese Patent No. 131843.
The thickness of the support is 80 to 400 μm, preferably 1 to 400 μm.
It is 00 to 250 μm.

A plastic support which has been heat-treated to stabilize its dimensions can also be used. The plastics to be employed include the above-mentioned plastics. The heat treatment of the support means that after forming these supports and before the photosensitive layer is coated, at a temperature higher than the glass transition point of the support by 30 ° C. or more, preferably at a temperature higher by 35 ° C. or more, More preferably, heating is performed at a temperature higher than 40 ° C. However, the effect of the present invention cannot be obtained by heating at a temperature exceeding the melting point of the support.

The method of forming a support and the method of producing an undercoat according to the present invention can be a known method, and preferably are described in paragraphs [0030] to [0] of JP-A-9-50994.
070].

In the present invention, a conductive compound such as a metal oxide and / or a conductive polymer can be contained in the constituent layer in order to improve the chargeability. These may be contained in any layer, but are preferably contained in an undercoat layer, a backing layer, a layer between the photosensitive layer and the undercoat, and the like. In the present invention, column 14 of U.S. Pat.
20 to 20 are preferably used.

In the lithographic printing plate material of the present invention, in order to utilize the silver complex salt diffusion transfer method, it is preferable to have a layer containing a physical development nucleus in the constituent layer. The physical development nuclei used are well-known examples of this kind of chemicals, and include metals such as antimony, bismuth, cadmium, cobalt, palladium, nickel, gold, silver, platinum, lead, zinc, and sulfides thereof. Can be used. The physical development nucleus layer may also contain a developer and may contain a water-soluble binder.

A typical embodiment of the silver complex salt diffusion transfer method suitable for the lithographic printing plate material of the present invention is to form at least one undercoat layer which also serves as an antihalation layer and at least one halogenated layer on a support. It comprises a silver emulsion layer and at least one physical development nucleus layer. In a preferred embodiment, the support is provided with at least one undercoat layer which also serves as an antihalation layer, at least one silver halide emulsion layer, and at least one physical development nucleus layer.

In addition, a surfactant for improving coating properties, a stabilizer for maintaining photographic light-sensitive properties, an antifoggant, a sensitizing dye, a developer, a development accelerator, and coloring a photographic emulsion layer. Dyes, pigments and the like can be optionally contained for the purpose.

The lithographic printing plate material of the present invention may contain an organic thiol compound or a thione compound imparting ink receptivity,
Alternatively, some or all of the other organic heterocyclic compounds can be added in advance. It may be a layer other than the photosensitive silver halide emulsion layer. Further, these organic compounds may be added after being dissolved in an oil agent and dispersed in the form of fine oil droplets.

[0288]

EXAMPLES The present invention will be described below in detail with reference to examples, but embodiments of the present invention are not limited thereto.

Example 1 (Preparation of Subbed Photographic Support) A commercially available biaxially stretched heat-fixed polyethylene naphthalate having a thickness of 175 μm (P
EN) Both surfaces of the film are subjected to a corona discharge treatment of 8 w / m ² · min, and one surface is coated with the following undercoating coating solution a-1 so as to have a dry film thickness of 0.8 μm and dried to undercoat. Layer A-1
On the other side, an undercoating coating solution b-1 subjected to the following antistatic treatment was applied so as to have a dry film thickness of 0.8 μm and dried to obtain an antistatic undercoat layer B-1.

<< Undercoat Coating Solution a-1 >> Co-weight of butyl acrylate (30% by weight), t-butyl acrylate (20% by weight), styrene (25% by weight), and 2-hydroxyethyl acrylate (25% by weight) Combined latex liquid (solid content 30%) 270 g (C-1) 0.6 g Hexamethylene-1,6-bis (ethylene urea) 0.8 g Polystyrene fine particles (average particle size 3 μm) 0.05 g Colloidal silica (average particle size) (90 μm) 0.1 g Finish to 1 liter with water << Undercoat coating solution b-1 >> SnO ₂ / Sb (9/1 weight ratio, average particle size 0.18 μm) Amount to become 200 mg / m ² Butyl acrylate (30% by weight) ), Styrene (20% by weight), glycidyl acrylate (40% by weight) copolymer latex liquid (solid content 30%) 270 g (C-1) 0.6 Subsequently finish 1l hexamethylene-1,6-bis (ethyleneurea) 0.8 g Water, to the undercoat layer A-1 and the upper surface undercoat layer B-1,
A corona discharge of 8 w / m ² · min. Was performed, and the following lower coating liquid a-2 was coated on the lower coating layer A-1 with a dry film thickness of 0.1 μm.
As the undercoat layer A-2, the undercoat layer B-1 is coated on the undercoat layer B-1 with the following undercoat layer coating solution b-2 so as to have a dry film thickness of 0.8 μm. Coated as B-2.

<< Undercoating upper layer coating solution a-2 >> Gelatin 0.4 g / m ² Weight (C-1) 0.2 g (C-2) 0.2 g (C-3) 0.1 g Silica particles ( (Average particle size: 3 μm) 0.1 g Finished to 1 liter with water << Lower upper layer coating solution b-2 >> (C-4) 60 g Latex solution containing (C-5) as a component (solid content: 20%) 80 g Ammonium sulfate 5 g (C-6) 12 g Polyethylene glycol (weight average molecular weight 600) 6 g Finish to 1 liter with water

[0292]

Embedded image

[0293]

Embedded image

(Heat Treatment of Support) In the undercoat drying step of the undercoated support, the support was heated at 140 ° C.
Thereafter, it was gradually cooled.

(Preparation of Emulsion A) Silver chlorobromide core particles having an average diameter of 0.09 μm and containing silver bromide and the remainder being silver bromide were prepared by the double-mixing method. At the time of mixing the core particles, K ₃ Rh (N0) ₄ (H ₂ O) ₂ was added in an amount of 7 × 10 ⁻⁸ mol per mol of silver and 1 mol of silver at the end of grain formation.
_A silver nitrate aqueous solution and a water-soluble halide solution were simultaneously mixed in the presence of 8 × 10 ⁻⁶ mol of ₃ OsCl ₆ while maintaining the pH at 40 ° C. and the silver potential (EAg) at 165 mV.
The core particles were shelled using a double jet method with EAg reduced to 125 mV with saline. At this time, K ₂ IrCl ₆ was added to the halide solution in an amount of 3 × 10 ⁻⁷ mol per mol of silver, and K ₃ R
9 × 10 ⁻⁸ mol of hCl ₆ was added. Further, KI conversion was performed using silver iodide fine grains.

The resulting emulsion was a core / shell type monodisperse (coefficient of variation: 10%) silver chloroiodobromide having an average diameter of 0.18 μm (silver chloride content: 70 mol%, silver iodobromide content: 0.2 (Mole%, the remainder being silver bromide). A cubic emulsion having a [100] face ratio of 87%. Then, JP-A-2-280139
No. 287 (3), and the salt was desalted using the exemplified compound (G-8) of the modified gelatin. The EAg after desalting was 190 mV at 50 ° C.

Further, after chemical sensitization with chloroauric acid, inorganic sulfur, thiourea dioxide and 2,3,4,5,6-pentafluorophenylphosphine selenide, the sensitizing dye according to the present invention was used for 610 nm. Spectral sensitization was performed so as to have a photosensitive maximum at ７710 nm. Table 1 shows the types of sensitizing dyes used.

(Preparation of Coating Solution) 1) Coating Solution A for Prevention of Halation Undercoat Layer Gelatin 2.5 g / m ² Carbon black 0.5 g / m ² Silica powder having an average particle diameter of 5 μm 0.5 g / m ² Formaldehyde 0.2 g / m ² this adjusted to pH4 with an amount of citric acid shown in ascorbic acids and Comparative compound table 1 invention 2) emulsion layer coating solution a emulsion a silver amount 1.0 g / m ^2, the amount of gelatin 0.8 g / m monodisperse ² to become the amount of 1-phenyl-5-mercaptotetrazole 0.05 g / m ² 2-mercapto-5-ethyl-1,3,4-oxadiazole 0.05 g / m ² average particle size 1.5μm Silica powder 0.3 g / m ² Sodium thiosulfate 0.5 g / m ² Hardener HA-1 Adjust to pH 4 with 0.1 g / m ² citric acid 3) Backing layer Gelatin 2.0 g / m ² Hardener HA-10 .2g / m ² Average particle size 0.05μm colloidal silica 0.5 g / m ² 4) of the physical development nuclei layer coating solution PdS 0.1 g / m ² carboxymethylcellulose 0.1 g / m ² Hardener HA-2 0 1 g / m ² (Preparation of lithographic printing plate material) 3) A backing layer on the antistatic undercoat side of the undercoated PEN support, and 2) an emulsion layer coating solution on the other side from the support side. A backing layer was applied at the same time. After the application, it was dried and wound up. After seasoning at 40 ° C. for 5 days in a wound state, 4) a physical development nucleus layer coating solution was applied and dried to produce a product.

(Test of storage under high temperature and high humidity) The lithographic printing plate material prepared as described above was divided into two, and one of them was stored at 55 ° C. and 80% RH for 3 days as a storage test under high temperature and high humidity. did. The other is a normal condition of 23 ° C. 48
Stored at% RH for 3 days. After exposing and developing each, the following printing performance evaluation was performed.

(Exposure of Lithographic Printing Plate Material) The lithographic printing plate material prepared as described above was obtained by using a Dreb 800V manufactured by Nippon Cytex equipped with a semiconductor laser of 650 nm to reduce halftone dots of 300 lines by 5%. Exposure to 95% in 5% increments from the point, and development using a CP-286S (Mitsubishi Paper Mills / Dainippon Screen Manufacturing Co., Ltd.) automatic developing machine 38
℃, 15 seconds, neutralization treatment 38 ℃ 15 seconds, then 45 ℃
And dried.

The developing solutions A and B and the neutralizing solution were prepared as described below.

<Developer A> EDTA.2Na 1 g Potassium carbonate 10 g Sodium carbonate 15 g Lithium hydroxide monohydrate 6 g Anhydrous sodium sulfite 50 g 2-aminoethyl-aminoethanol 10 g 1-phenyl-4-hydroxymethyl-4-methyl -3-pyrazolidone (dimesone S) 2 g Lipophilic agent: 2-mercapto-5-n heptyl oxadiazole 0.25 g hydroxyphenylstearic acid (Nippon Oil & Fats Co., Ltd., trade name Novaacid P) 1 g Add water and add 1 L And pH adjusted to 9.8.

<Developer B> To the above developer A, 6 g of ascorbic acid A-40 was added.

<Neutralizing and sensitizing solution> Phosphoric acid 1.2 g Sodium monophosphate 25 g Anhydrous sodium sulfite 2.5 g Ethylene glycol 5 g Lipophilic agent: 2-mercapto-5-nheptyloxadiazole 1 g Diethanolamine 5 g Make up to 1 L with water. pH adjusted to 6.

(Running test) 55 ° C., 80% RH
In using a 3-day storage sample, the developer 1 m ²
A 100 m ² sample that had been exposed on the entire surface was subjected to a running process under the above conditions while replenishing 180 ml per sample. The performance of the first sample at the start of running and the sample at the end of 100 m ² running were compared.

(Evaluation of Printing Performance) The planographic printing plate obtained by the development processing was mounted on an offset printing machine, and printing was performed under the following conditions using the following humidifying solution.

<Humidifier> o-phosphoric acid 10 g nickel nitrate 5 g sodium nitrite 5 g ethylene glycol 100 g colloidal silica (20% solution) 28 g Water is added to make 1 L.

The printing machine is AB Dick 350CD
(Trademark of offset printing machine manufactured by AB Dick Co., Ltd.).
When image skipping occurred due to lack of% dot and became unbearable as a printed matter, the number of printed sheets was judged according to the following evaluation criteria.

A 30001 or more B 10001 to 30000 C 5001 to 10,000 D 2001 to 5000 E 2000 or less The results are shown in Table 1.

[0310]

[Table 1]

Example 2 Using the sample 101 prepared in Example 1, a liquid obtained by adding the ascorbic acids according to the present invention and the comparative compound hydroquinone (abbreviated as HQ) to the developer A was used in the same manner as in Example. Was evaluated. Table 2 shows the results.

[0312]

[Table 2]

Example 3 The emulsion to be used was used in the following emulsion B, and the antihalation undercoat layer coating solution was used in the following antihalation undercoat layer coating solution B.
Evaluation was performed in the same manner as in Example 1 except that the emulsion layer coating solution was changed to the following emulsion layer coating solution B. Table 3 shows the results.

(Preparation of Emulsion B) A salt composed of 60 mol% of silver chloride, 2.5 mol% of silver iodide, and the balance of silver bromide having an average thickness of 0.05 μm and an average diameter of 0.15 μm was obtained by a double jet method. Silver iodobromide core grains were prepared. When mixing, K ₃ Rh (H
₂ O) Br ₅ was added 2 × 10 ^-8 mole per silver mole.
The core particles were shelled using a double jet method. At that time, 3 × 10 ⁻⁷ mol of K ₂ IrCl ₆ was added per mol of silver.

The resulting emulsion was a core / shell type monodisperse (coefficient of variation: 10%) silver chloroiodobromide (average thickness: 0.05 μm, average diameter: 0.25 μm).
(5 mol%, the balance consisting of silver bromide). Then, desalting was carried out in the same manner as in Emulsion A. EAg after desalination
Was 180 mV at 50 ° C.

To the obtained emulsion, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added at 1 × 10 ^-3 mol per mol of silver, and potassium bromide and citric acid were further added. The pH was adjusted to 5.6 and the EAg to 123 mV, and 2 × 10 ⁻⁵ mol of chloroauric acid was added.
N'-trimethyl-N'-heptafluoroselenourea was added in an amount of 3 × 10 ^-5 mol and chemically ripened at a temperature of 60 ° C. until the maximum sensitivity was obtained.

After aging, 4-hydroxy-6-methyl-
1,3,3a, 7-Tetrazaindene was added in an amount of 2 × 10 ⁻³ mol per mol of silver, 1-phenyl-5-mercaptotetrazole was added in an amount of 3 × 10 ⁻⁴ mol, and gelatin was added.

Further, the sensitizing dye according to the present invention was used at 610 nm.
Spectral sensitization was performed so as to have a photosensitive maximum at ７710 nm. Table 3 shows the types of sensitizing dyes used.

<Coating solution B for antihalation undercoat layer> Gelatin 2.5 g / m ² Carbon black 0.5 g / m ² Silica powder having an average particle size of 5 μm 0.5 g / m ² Formaldehyde 0.2 g / m ² Citric acid The antihalation undercoat layer coating liquid C adjusted to pH 4 is prepared by adding ascorbic acids A-45 0.1 to the antihalation undercoat layer coating liquid B.
g / m ² were added.

<Emulsion Layer Coating Solution B> Emulsion B An amount in which the amount of silver is 0.9 g / m ² and the amount of gelatin is 0.7 g / m ² 1-phenyl-5-mercaptotetrazole 0.04 g / m ² 2- monodisperse silica powder 0.3 g / m ² sodium thiosulfate 0.5 g / m ² hydrazine derivative sulfate mercapto-5-ethyl-1,3,4-oxadiazole 0.05 g / m ² average particle size 1.5μm table in an amount nucleation accelerator AP-1 0.05g / m ² nucleation accelerator ^AP-2 0.05g / m 2 hardener HA-1 0.1g / m ² of citric acid shown in 3 is adjusted to pH 4.

Incidentally, the developing solution A was used.

[0322]

[Table 3]

Example 4 The sample 306 prepared in Example 3 was treated with the developing solution B. As a result, as good as the result of the sample 306 in Example 3 was obtained. Further, a stable printed image was obtained from the beginning of printing.

[0324]

According to the present invention, a material for forming a lithographic printing plate using a silver complex salt diffusion transfer method is a laser or an LED.
Lithographic printing plate can be obtained by performing spectral sensitization for exposure by the above method.

Claims (8)

[Claims] 1. A lithographic printing plate material having a photosensitive maximum at 610 nm to 710 nm, containing ascorbic acids in a constituent layer, and forming a lithographic printing plate using a silver complex salt diffusion transfer method. 2. A lithographic printing plate material having a photosensitive maximum at 610 nm to 710 nm and forming a lithographic printing plate using a silver complex salt diffusion transfer method is subjected to a developing treatment in the presence of ascorbic acids. Lithographic printing plate material developing method. 3. A lithographic printing plate material which has a photosensitive maximum at 610 nm to 710 nm and forms a lithographic printing plate using a silver complex salt diffusion transfer method is developed with a processing solution containing ascorbic acids. Lithographic printing plate material. 4. A lithographic printing plate material having a photosensitive maximum at 610 nm to 710 nm, containing a hydrazine derivative in a constituent layer, and forming a lithographic printing plate by using a silver complex salt diffusion transfer method. 5. A lithographic printing plate material which has a photosensitive maximum at 610 nm to 710 nm and forms a lithographic printing plate using a silver complex salt diffusion transfer method is subjected to a developing treatment in the presence of a hydrazine derivative. Lithographic printing plate material developing method. 6. The method for developing a lithographic printing plate material according to claim 2, wherein the developing treatment is further performed in the presence of a hydrazine derivative. 7. The developing solution according to claim 2, wherein the developing solution contains 0.1 mol / L or more of a carbonate.
3. The method for developing a lithographic printing plate material according to item 1. 8. The method for developing a lithographic printing plate material according to claim 2, wherein a processing liquid containing substantially no hydroquinone is used.