JPH07128792A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the silver halide photographic sensitive material freed of deterioration of photographs in storage for a long period and at high temperature by packaging the silver halide photographic sensitive material containing a specified dye and a specified compound so that the temperature and relative humidity in the inside of the package are controlled to be within a specific range. CONSTITUTION:This silver halide photographic sensitive material has a photograph constituting layer containing the fine solid particle dispersion of an organic dye salt formed with the dye repressed by formula I or the like and the compound represented by formula II or III on a support, and it is packaged at a temperature of 18-30 deg.C and in a relative humidity of 10-30% in the inside of the package. In formulae II and III, each of R1-R4 is H, alkyl, alkenyl, or the like, and each may combine with each other to form a ring; each of R5-R7 is alkyl, alkenyl, aryl, or the like, or each may combine with each other to form a ring; and each of X1 and X2 is an anion.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material containing a diffusion resistant dye, and more specifically, it has improved outflow decolorization during rapid processing and improved long-term storage and high-temperature storage. , A silver halide photographic light-sensitive material.

[0002]

2. Description of the Related Art Silver halide photographic light-sensitive materials (hereinafter abbreviated as light-sensitive materials) are required to have excellent image quality characteristics such as sharpness and color reproducibility. In order to counter the property, further shortening of processing time, that is, rapid processing suitability is required.

In a light-sensitive material, a light absorption filter,
It is well known that a dye is contained in a constituent layer of a light-sensitive material in order to absorb light of a specific wavelength for the purpose of preventing halation, preventing irradiation or adjusting the sensitivity of a photosensitive emulsion. Coloring the hydrophilic colloid layer has been conventionally performed.

Of the constituent layers of the light-sensitive material described above, the filter layer is usually positioned above the light-sensitive emulsion layer or between the emulsion layer and another emulsion layer, and the incident light reaching the emulsion layer is preferable. It plays a role in changing the spectral composition. Further, the antihalation layer is provided between the photosensitive emulsion layer and the support or on the back surface of the support for the purpose of improving the sharpness of the image, and is provided at the interface between the emulsion layer and the support or the back surface of the support. The sharpness of the image is improved by absorbing harmful reflected light.

Further, the sharpness of an image is improved by coloring a light-sensitive emulsion layer with a dye to absorb harmful reflected light or scattered light to silver halide grains to prevent irradiation. Has also been done.

Recently, dyes (hereinafter referred to as "YC dyes") intended to replace yellow colloidal silver in color photographic light-sensitive materials.
Application) and dyes for dyeing a crossover cut layer in an X-ray photographic light-sensitive material, dyes for dyeing a non-light-sensitive emulsion layer in a printed photographic light-sensitive material, and so on.

The dye used for such purpose has, of course, good absorption spectrum characteristics depending on the purpose of use, and is, for example, completely decolorized during development processing and easily removed from the light-sensitive material during development processing. It does not cause residual color contamination due to dye after processing, does not adversely affect fog or desensitization on photosensitive emulsion, does not diffuse from colored layer to other layers, photosensitive material or solution. It must satisfy various conditions such as excellent stability over time and no discoloration.

To date, many studies have been conducted for the purpose of finding dyes satisfying the above-mentioned conditions, for example, US Pat. Nos. 3,540,887, 3,544,325, and 3,560,214.
Nos. 3,037,078, and JP 51-3623, and benzylidene dyes, and British Patent 506,385 and JP 39-39.
22069 proposes an oxonol dye, US Pat. No. 2,493,747 proposes a merocyanine dye, and US Pat. No. 1,845,404 proposes a styryl dye.

Some of these conventional dyes have a relatively small effect on the emulsion performance and have the ability to be bleached / eluted / erased in the processing step, but from the viewpoint of diffusion resistance. It was not enough. That is, when a specific layer of a plurality of emulsion layers is selectively colored and used as a filter layer or an antihalation layer, not only the diffusion to other layers is remarkable, but the light absorption effect is lowered,
There was a defect that it gave an unfavorable effect to other layers such as sensitivity deterioration, gradation change and fog abnormality.

As a means for preventing the diffusion and migration of the dye to another layer, the dye itself is made resistant to diffusion, for example, US Pat.
008, 2,539,009, 4,420,555, JP 61-2046
No. 30, No. 61-205934, No. 62-32460, No. 62-56958,
62-92949, 62-222248, 63-40143, 63-18
No. 4749, No. 63-316852 and the like are disclosed, but none of these dyes has a decolorizing property or solubility in a processing liquid, and thus has a drawback of increasing residual color contamination.

Further, as a method for fixing a dissociative dye using a mordant to make it resistant to diffusion, for example, US Pat. No. 2,548,564 is used.
Nos. 3,625,694 and 4,124,386 are disclosed.

However, in the method using a mordant, for example, gelatin which is a binder in the light-sensitive material constituting layer forms an aggregate with the mordant or increases the viscosity, which causes serious problems such as uneven coating and cissing. There are drawbacks that cause troubles, the diffusion between layers is not sufficiently suppressed, the elution and decolorization during processing are poor, and a high pH processing bath is required.
There was a drawback that it was inferior in suitability for rapid processing.

Further, as a method for making diffusion resistant by utilizing the association between a dye having a cationic group or an anionic group and a special ionic compound, British Patent Nos. 2,002,916 and 2,1
No. 56,373 is disclosed, but it cannot be said that the decolorization property or diffusion resistance in rapid processing is sufficient, and there is a problem that a desired effect cannot be obtained.

As a separate method, a dye whose pH has been designed so that it can be easily dissolved in a solution having a high pH is dispersed as a solid fine particle dispersion in a hydrophilic colloid layer having a low pH, for example, US Pat. No. 4,855,221. , Ibid 4,857,4
46, 4,948,717, JP-A-52-92716, 55-155350
No. 55, No. 55-155351, No. 56-12639, No. 63-197943, JP-A No. 2-110453, No. 2-1838-9, No. 2-191942, No. 2-2.
No. 64247, No. 2-264936, and World Patent No. 88/04794 are disclosed.

However, this method requires the dye molecules
Since the kind of dye is structurally limited to give pKa, there is a drawback that a dye having a desired absorption wavelength is hard to be obtained, and decolorizing property in rapid processing is not sufficient,
There is a drawback that residual color contamination occurs. Therefore, the decolorization is good,
A new technique for making a dye having a desired spectral characteristic resistant to diffusion has been strongly desired.

However, according to the conventional technique, the interlaminar migration of the dye is not sufficiently prevented during long-term storage or high-temperature storage in the summer, and a filter effect, an antihalation effect, an anti-irradiation effect, etc., obtained by adding a diffusion resistant dye, etc. However, there is a defect that deterioration of photographic performance due to deterioration of photographic performance and deterioration of photographic performance such as fog and desensitization.

When a silver halide photographic light-sensitive material containing a solid fine particle dispersion of a dye is packaged at high temperature,
It was found that during long-term storage and high-temperature storage, fog unevenness due to fine fog silver is likely to occur and black spots deteriorate, which is a problem not observed with water-soluble dyes.

On the other hand, various originals having different characters, illustrations, photographic densities of halftone dots, and different line widths are pasted in the line drawing photographing process of the printing plate making. Therefore, images having different densities and line widths are mixed in the original document, and there is a strong demand for a plate-making camera, a photosensitive material, or an image forming method for finishing these original documents with good reproducibility. Further, in catalogs and posters, so-called enlargement and contraction, such as enlargement and reduction of halftone photographs, are performed, and in plate making with enlarged halftone dots, the number of lines becomes rough and blurred dots are taken. Therefore, a photosensitive material having a wide exposure latitude is required to enhance the reproducibility of halftone, and a tetrazolium compound or a hydrazine derivative is used for improving these photographic performances. However, it has been found that the above deterioration of photographic performance is particularly remarkable in such a photosensitive material for printing, which is a superhigh-contrast silver halide photographic photosensitive material containing a tetrazolium compound or a hydrazine derivative.

Further, it has been found that the above deterioration is remarkable in the rapid processing with a developing time of 45 seconds or less, and is particularly remarkable when the developing solution is processed with a pH of 10.7 or less.

[0020]

In contrast to the above problems, the first object of the present invention is to provide a photosensitive silver halide emulsion layer or a non-photosensitive colloid layer with good absorption spectrum characteristics. And a diffusion-resistant dye containing a silver halide photographic light-sensitive material.

A second object of the present invention is to provide a silver halide photographic light-sensitive material containing a dye which is excellent in elution and decolorization during a photographic processing step and is suitable for rapid processing.

A third object of the present invention is to provide a silver halide photographic light-sensitive material which does not deteriorate in photographic performance during long-term storage or high temperature storage.

[0023]

The above object of the present invention can be achieved by the following means.

In a silver halide photographic light-sensitive material containing at least one photographic constitutional layer containing a solid fine particle dispersion of a dye, the silver halide photographic light-sensitive material is relative to a humidity inside the package of 18 ° C. to 30 ° C. A silver halide photographic light-sensitive material, which is packaged so that the humidity is 10% to 60%.

A dye represented by the above general formula [I] or [I] ′ or [I] ″ and a following general formula [I] are formed on a support.
A silver halide photographic light-sensitive material having at least one photographic constituent layer containing a solid fine particle dispersion of a dye organic salt formed with at least one of the compounds represented by I] or [III]. A silver halide photographic light-sensitive material, characterized in that the photographic light-sensitive material is packaged so that the humidity inside the package is 18% to 30 ° C and the relative humidity is 10% to 60%.

A silver halide photographic light-sensitive material having at least one photographic constituent layer containing a silver salt of a dye as a solid fine particle dispersion on a support, wherein the silver halide photographic light-sensitive material has a humidity inside the packaging of 18 Relative humidity from ℃ to 30 ℃
A silver halide photographic light-sensitive material, which is packaged so as to be 10% to 60%.

The silver halide photographic light-sensitive material preferably contains a tetrazolium compound or a hydrazine derivative.

The present invention will be specifically described below.

The dyes preferably used in the present invention according to claim 1 include compounds represented by the following general formulas [1] to [6].

[0030]

[Chemical 7]

[In the formula, A and A ′ may be the same or different and each represents an acidic nucleus, Q represents an aryl group or a heterocyclic group, B represents a basic nucleus, and B ′ represents a heterocyclic ring. Represents a group, X and Y may be the same or different and each represents an electron-withdrawing group, and L ₁ , L ₂ and L ₃ each represent a methine group. m represents 0 or 1, n represents 0, 1
Or 2 and p represents 1 or 2. However, the dyes represented by the general formulas [1] to [6] have at least one group selected from a carboxy group, a sulfonamide group and a sulfamoyl group in the molecule. Examples of the aryl group represented by Q in the general formulas [1] and [4] include a phenyl group, a naphthyl group and a julolidyl group.
The heterocyclic ring represented by Q is, for example, pyridine,
Examples thereof include quinoline, isoquinoline, pyrrole, pyrazole, imidazole and indole.

The aryl group and the heterocycle include those having a substituent, and examples of the substituent include an alkyl group, a cycloalkyl group, an aryl group, a halogen atom, an alkoxycarbonyl group, an aryloxycarbonyl group,
Carboxy group, cyano group, hydroxy group, mercapto group, amino group, alkoxy group, aryloxy group, acyl group, carbamoyl group, acylamino group, ureido group,
Examples thereof include a sulfamoyl group and a sulfonamide group, and two or more kinds of these substituents may be combined. Preferably,
Alkyl group having 1 to 6 carbon atoms (eg, methyl group, ethyl group, butyl group, 2-hydroxyethyl group, etc.), hydroxy group, halogen atom (eg, fluorine atom, chlorine atom, etc.), alkoxy group (eg, methoxy group) , Ethoxy group, methylenedioxy, 2-hydroxyethoxy group, n-butoxy group, etc.), substituted amino group (eg, dimethylamino group, diethylamino group, di (n-butyl) amino group, N-ethyl-N-hydroxy group) Ethylamino group, N-ethyl-N-methanesulfonamide ethylamino group, morpholino group, piperidino group, pyrrolidino group, etc.), carboxy group, sulfonamide group (eg, methanesulfonamide group, benzenesulfonamide group, etc.), sulfamoyl group (Eg, sulfamoyl group, methylsulfamoyl group, phenylsulfamoyl group, etc.) It may be combined.

The acidic nuclei represented by A and A'in the general formulas [1], [2] and [3] are preferably 5-pyrazolone, barbituric acid, thiobarbituric acid, rhodanine, hydantoin and thio. Hydantoin, oxazolone,
Examples include isoxazolone, indandione, pyrazolidinedione, oxazolidinedione, hydroxypyridone, and pyrazolopyridone.

The basic nucleus represented by B in the general formulas [3] and [5] is preferably pyridine, quinoline, oxazole, benzoxazole, naphthoxazole,
Examples include thiazole, benzthiazole, naphthothiazole, indolenine, pyrrole and indole.

The electron withdrawing groups represented by X and Y in the general formulas [4] and [5] may be the same or different, and for example, a cyano group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, Carboxy group, acyl group, alkylsulfonyl group, arylsulfonyl group,
A sulfamoyl group is mentioned.

The heterocycle represented by B'in the general formula [5] is
Examples include pyridine, pyridazine, quinoline, pyrrole, pyrazole, imidazole and indole.

L ₁ , L ₂ and L _{3 of the} general formulas [1] to [5]
The methine group represented by includes those having a substituent, and examples of the substituent include an alkyl group having 1 to 6 carbon atoms (for example, methyl, ethyl, propyl, isobutyl, etc.),
Aryl groups (eg phenyl, p-tolyl, p-chlorophenyl, etc.), C1-C4 alkoxy groups (eg methoxy, ethoxy, etc.), aryloxy groups (eg phenyl, etc.), aralkyl groups (eg benzyl) Groups, phenethyl groups, etc.), heterocyclic groups (eg pyridyl, furyl,
Thienyl, etc.), substituted amino groups (eg dimethylamino,
Tetramethyleneamino, anilino, etc.) and alkylthio groups (eg, methylthio group, etc.).

Specific compounds of the present invention are described in, for example, Japanese Patent Application No. 5-14.
No. 5042, pages 12 to 24, 1-1 to 6-5.

Next, the general formula [I], the general formula [I] ', the general formula [I] ", and the general formula [I] according to the present invention are described.
The compound represented by formula [III] and formula [III] will be described.

In the general formulas [I], [I] 'and [I] ", A ₁ , A ₂ , A and A ₃ represent acidic nuclei, and A ₁ and A ₂ are the same or different. Specifically, 5-pyrazolone, barbituric acid, thiobarbituric acid, rhodanine, hydantoin, thiohydantoin,
Oxazolone, isoxazolone, indandione, pyrazolidinedione, oxazolidinedione, hydroxypyridone and pyrazolopyridone are preferable.

L ₁ , L ₂ , L ₃ , L ₁₁ , L ₁₂ , L ₁₃ , L ₂₁
And the methine group represented by L ₂₂ include those having a substituent, and examples of the substituent include an alkyl group having 1 to 6 carbon atoms (eg, methyl, ethyl, propyl, isobutyl, etc.), an aryl group (eg, Phenyl, p-tolyl, p-chlorophenyl etc.), alkoxy groups having 1 to 4 carbon atoms (eg methoxy, ethoxy etc.), aryloxy groups (eg phenoxy etc.), aralkyl groups (eg benzyl, phenethyl etc.), heterocycles Examples thereof include groups (eg thienyl, furyl etc.), substituted amino groups (eg dimethylamino, tetramethyleneamino, anilino etc.), alkylthio groups (eg methylthio etc.) and the like.

Next, examples of the aryl group represented by Q in the formula [I] 'include a phenyl group and a naphthyl group. The aryl group includes those having a substituent, and examples of the substituent include an alkyl group (eg, methyl group, ethyl group, n-propyl group, i-propyl group, t-butyl group, n-hexyl group, etc.) , Halogen atoms (eg chlorine,
Each atom of bromine, iodine, fluorine, etc.), aryl group (eg phenyl group, naphthyl group etc.), cycloalkyl group (eg cyclopentyl group, cyclohexyl group), heterocyclic group (eg pyrrolidyl group, pyridyl group, furyl group, thienyl) Group, etc.), sulfinic acid group, carboxyl group, nitro group, hydroxyl group, mercapto group, amino group (for example, amino group, diethylamino group, etc.), alkyloxy group (for example, methyloxy group, ethyloxy group, n-butyloxy group,
n-octyloxy group, isopropyloxy group, etc.), aryloxy group (phenyloxy group, naphthyloxy group, etc.), carbamoyl group (for example, aminocarbonyl group, methylcarbamoyl group, n-pentylcarbamoyl group, phenylcarbamoyl group, etc.), Amido group (eg, methylamide group, benzamide group, n-octylamide group, etc.), aminosulfonylamino group (eg, aminosulfonylamino group, methylaminosulfonylamino group, anilinosulfonylamino group, etc.), sulfamoyl group (eg, sulfamoyl group, Methylsulfamoyl group, phenylsulfamoyl group, n-butylsulfamoyl group etc.), sulfonamide group (eg methanesulfonamide group, n-heptanesulfonamide group, benzenesulfonamide group etc.), sulfinyl group (eg Met Sulfinyl group, ethylsulfinyl group, phenylsulfinyl group, octyl sulfinyl group), an alkyloxycarbonyl group (e.g., methyl group, an ethyloxycarbonyl group,
2-hydroxyethyloxycarbonyl group, n-octyloxycarbonyl group etc.), aryloxycarbonyl group (eg phenyloxycarbonyl group, naphthyloxycarbonyl group etc.), alkylthio group (eg methylthio group, ethylthio group, n-hexylthio group etc.) ), An arylthio group (eg, phenylthio group, naphthylthio group, etc.), an alkylcarbonyl group (eg, acetyl group, ethylcarbonyl group, n-butylcarbonyl group, n-octylcarbonyl group, etc.), an arylcarbonyl group (eg, benzoyl group,
p-methanesulfonamidobenzoyl group, p-carboxybenzoyl group, naphthoyl group, etc.), cyano group, ureido group (for example, methylureido group, phenylureido group, etc.),
Examples thereof include thioureido group (eg, methylthioureido group, phenylthioureido group, etc.).

Further, examples of the aryl group represented by Q include a julolidyl group, a 1,2-methylenedioxyphenyl group, a benzofuryl group, an indolyl group and a tetrahydroquinolyl group. The aryl group is preferably a phenyl group having a substituted amino group, for example, 2- or 4-dimethylaminophenyl group, 2- or 4-diethylaminophenyl group, 2- or 4-dibutylaminophenyl group, 4- (N
-Ethyl-N-hydroxyethyl) aminophenyl group, 4- (N-
Ethyl-N-methanesulfonamidoethyl) aminophenyl group, 4-morpholinophenyl group, 4-piperidinophenyl group, 4-pyrrolidinophenyl group, julolidyl group and the like are preferable.

The heterocyclic group represented by Q is, for example, pyridyl, quinolyl, isoquinolyl, pyrrolyl, imidazolyl, pyrazolyl, indolyl, indolinyl, indolenyl, benzoindolyl, furyl, benzofuryl, thienyl, thianaphthenyl, pyranyl, thiopyranyl, oxazolyl, Benzoxazolyl, naphthoxazolyl, thiazolyl, benzothiazolyl, pyridazinyl, oxadiazolyl, thiadiazolyl, indolizinyl, quinolidinyl, carbazolyl, phenothiazinyl, phenoxazinyl, pyrrolothiazolyl, pyrrolopyridazinyl,
Each group such as pyrazolopyrimidonyl and the like can be mentioned. Examples of the heterocyclic group include those having a substituent, and examples of the substituent include the groups described above as the substituent of the aryl group represented by Q.

Next, B in the general formula [I] ″ represents a basic nucleus, specifically, for example, pyridine, quinoline, oxazole, benzoxazole, naphthoxazole, thiazole, benzthiazole, naphthothiazole, indolenine, Pyrrole, indole and the like are preferable.

In the general formulas [II] and [III], R _{1 to} R
_The alkyl group represented by ₁₆ , for example, methyl group, ethyl group, n-propyl group, iso-propyl group, t-butyl group,
Examples thereof include n-pentyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, n-dodecyl group, n-pentadecyl group and eicosyl group. The alkyl group includes those having a substituent, and examples of the substituent include those exemplified as the substituent of the aryl group represented by Q.

In the general formulas [II] and [III], R _{1 to} R
_{As the} alkenyl group represented by ₁₀ , for example, a vinyl group,
Examples thereof include an allyl group, a 1-propenyl group, a 1,3-butadienyl group, and the alkenyl groups include those having a substituent, and the substituent is exemplified as the substituent of the aryl group represented by Q. The ones that were done are listed.

In the general formulas [II] and [III], R _{1 to} R
_{As the} aryl group represented by ₁₆ , for example, a phenyl group,
A naphthyl group may be mentioned. The aryl group includes those having a substituent, and examples of the substituent include the groups described above as the substituent of the aryl group represented by Q.

In the general formulas [II] and [III], R _{1 to} R
Examples of the heterocyclic group represented by ₁₆ include a pyridyl group (2-
Pyridyl group, 3-pyridyl group, 4-pyridyl group, 5-carboxy-2-pyridyl group, 3,5-dichloro-2-pyridyl group, 4,6-dimethyl-2-pyridyl group, 6-hydroxy-2- Pyridyl group, 2,
3,5,6-tetrafluoro-4-pyridyl group, 3-nitro-2-pyridyl group, etc., oxazolyl group (5-carboxy-2-benzoxazolyl group, 2-benzoxazolyl group, 2- Oxazolyl group, etc.), thiazolyl group (5-sulfamoyl-2-benzthiazolyl group, 2-benzthiazolyl group, 2-thiazolyl group, etc.), imidazolyl group (1-methyl-2-imidazolyl group,
1-methyl-5-carboxy-2-benzimidazolyl group, etc.),
Furyl group (3-furyl group etc.), pyrrolyl group (3-pyrrolyl group etc.), thienyl group (2-thienyl group etc.), pyrazinyl group (2-pyrazinyl group etc.), pyrimidinyl group (2-pyrimidinyl group, 4- Chloro-2-pyrimidinyl group etc.), pyridazinyl group (2-pyridazinyl group etc.), purinyl group (8-purinyl group etc.), isoxazolyl group (3-isoxazolyl group etc.), selenazolyl group (5-carboxy-2-selenazolyl group) Etc.), sulforanyl group (3-sulfolanyl group etc.), piperidinyl group (1-methyl-3-piperidinyl group etc.), pyrazolyl group (3-pyrazolyl group etc.), tetrazolyl group (1-methyl-5-tetrazolyl group etc.) And the like. The heterocyclic group includes those having a substituent, and examples of the substituent include those exemplified as the substituent of the aryl group represented by Q.

In the general formulas [II] and [III], X ₁ , X
_The anions represented by ₂ and X ₃ include inorganic and organic anions, specifically, a halogen ion (for example, chlorine,
Bromine, iodine, etc.), organic acid anions (eg, p-toluenesulfonate, p-chlorobenzenesulfonate, methanesulfonate, etc.), tetrafluoroboron ion, perchlorate ion, methylsulfate ion, ethylsulfate ion, etc. .

In the general formula [II], R ₁ , R ₂ , R ₃ and R ₄ may optionally combine with each other to form a ring,
As the ring, a 5-membered or 6-membered heterocycle in which R ₁ or R ₂ and R ₃ or R ₄ are bonded and a condensed ring thereof are preferable.
Specifically, for example, a thiazole type (for example, thiazole,
4-methylthiazole, 4-phenylthiazole, 4,5-dimethylthiazole, 4,5-diphenylthiazole, benzothiazole, 5-fluorobenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, 5-methylbenzothiazole , 6-methylbenzothiazole, 5-bromobenzothiazole, 5-carboxybenzothiazole, 5-ethoxycarbonylbenzothiazole, 5-hydroxybenzothiazole, 5-phenylbenzothiazole, 6-phenylbenzothiazole, 5-methoxybenzothiazole, 6-
Methoxybenzothiazole, 6-ethoxybenzothiazole, tetrahydrobenzothiazole, 5,6-dimethylbenzothiazole, 5,6-dimethoxybenzothiazole, 5,6-
Dioxymethylenebenzothiazole, 6-ethoxy-5-methylbenzothiazole, 5-phenethylbenzothiazole, 6-hydroxybenzothiazole, 5-carboxymethylbenzothiazole, tetrahydrobenzothiazole,
Naphtho [1,2-d] thiazole, naphtho [2,1-d] thiazole, naphtho [2,3-d] thiazole, 5-hydroxynaphtho [1,2-d] thiazole, 8-methoxynaphtho [2, 1-d] thiazole, 7-methoxynaphtho [2,1-d] thiazole, 5-methoxythionaphtho [6,7-d] thiazole, 8,9-dihydronaphtho [1,2-d] thiazole, 4, 5-dihydronaphtho [2,1-d] thiazole etc.), thiazoline type (eg thiazoline, 4-methylthiazoline, 4-carboxythiazoline etc.), oxazole type (eg oxazole, 4-methyloxazole, 5-methyloxazole, 4 -Phenyloxazole, 5-thienyloxazole, 4,5-diphenyloxazole, 4,5-dibenzyloxazole, benzoxazole, 5-chlorobenzoxazole, 5-methylbenzoxazole, 5-phenylbenzoxazole, 5-meth Shi benzoxazole, 5-hydroxy benzoxazole, 5-ethoxycarbonyl-benzoxazole, 5,
6-dimethylbenzoxazole, 5-carboxybenzoxazole, 5-ethylsulfonamide oxazole, naphtho [1,2-d] oxazole, naphtho [2,1-d] oxazole, naphtho [2,3-d] oxazole, etc.) , Oxazoline-based (eg, oxazoline, 4,4-dimethyloxazoline, etc.), selenazole-based (4-phenylselenazole, 5-hydroxybenzoselenazole, 5-methylbenzoselenazole, tellurazole-based (eg 4-phenylterrazole, 4 -Methylterrazole, benzoterrazole, 5-hydroxybenzoterrazole, etc.), pyridine-based (eg, pyridine, 5-methylpyridine, 3-methylpyridine, 2-hydroxypyridine, 2-methoxypyridine, etc.), quinoline-based (eg, Quinoline, 6-methylquinoline, 5-ethylquinoline, 6-chloroquinoline, 6-methoxyki Phosphorus, 2,4-dihydroxyquinoline, 8-butylsulfonamidoquinoline, etc.), isoquinoline type (eg isoquinoline, 3,4-dihydroisoquinoline etc.), 3,3-dialkylindolenine type (eg 3,3-dimethylindolenine) , 3,3,5-trimethylindolenine, 3,3-diethylindolenine, 3,3-dimethyl-5- (dimethylamino) indolenine, 3,3-dimethyl-5-
(Dimethylamino) indolenine, 3,3-dimethyl-5-cyanoindolenine, 3,3-dimethyl-5-hydroxyindolenine, 3,3-dimethyl-5-cyanoindolenine, 3,3-dimethyl-5 -Methoxyindolenine, 3,3-dimethylbenz [e] indolenine and the like), imidazole series (for example, imidazole, 1-alkylimidazole, 1-alkyl-4-phenylimidazole, 1-alkyl-4,5-dimethylimidazole, 1-alkylbenzimidazole, 1-alkyl-5
-Cyanobenzimidazole, 1-alkyl-5-hydroxybenzimidazole, 1-alkyl-5-methylsulfonylbenzimidazole, 1-alkyl-5-methoxycarbonylbenzimidazole, 1-alkyl-5- (N, N-dimethylamino ) Sulfonylbenzimidazole, 1-alkylnaphtho [1,2-d] imidazole, 1-alkylnaphtho [2,1-d]
It is a core of imidazole, 1-alkylnaphtho [2,3-d] imidazole, etc.).

The above-mentioned alkyl group is an alkyl group having 1 to 10 carbon atoms (when it has a substituent, the number of carbon atoms of the substituent is not included), and an alkoxy group having 1 to 6 carbon atoms. An alkoxycarbonyl group having an alkoxy group having 1 to 4 carbon atoms, a carboxyl group, a carbamoyl group,
Those substituted with a cyano group, a halogen atom, a phenyl group, a substituted phenyl group, a vinyl group and the like are also included (specifically, for example, methyl, ethyl, cyclohexyl, butyl, decyl, 2-methoxyethyl, 3 -Butoxypropyl, 2-hydroxy-ethoxyethyl, ethoxycarbonylmethyl, carboxymethyl, 2-carboxyethyl, 2-cyanoethyl, 2-carbamoylethyl, 2-hydroxyethyl, 2-fluoroethyl, 2,2,2-trifluoro Examples include groups such as ethyl, phenethyl, benzyl, carboxybenzyl, allyl).

The nitrogen-containing heterocycle formed by Z is further an isoxazole type (for example, isoxazole, benzisoxazole, 5-chlorobenzisoxazole, 6-methylbenzisoxazole, 6-methoxybenzoxazole, 5-hydroxy). -Benzisoxazole etc.),
1,3,4-thiadiazole type (eg 5-methyl-1,3,4-thiadiazole, 5-methylthio-1,3,4-thiadiazole, etc.), thienothiazole type (eg thieno [2,3-d] thiazole) , Thieno [3,2-d] thiazole, thieno [2,3-
e] benzothiazole, thieno [3,2-d] benzothiazole, thiazolo [4,5-b] benzothiophene, etc.), tetrazole type (eg 1-alkyltetrazole), imidazoquinoxaline type (eg 1-alkylimidazo [4 , 5-b]
Quinoxaline, 6,7-dichloro-1-alkylimidazo 〔4,5
-b] quinoxaline, 6-chloro-1-arylimidazo [4,5
-b] quinoxaline etc.), imidazoquinoline type (eg 1-
Alkylimidazo [4,5-b] quinoline, 6,7-dichloro-1-
Alkylimidazo [4,5-b] quinoline, etc.), pyrrolopyridine type (eg 3,3-dialkyl-3H-pyrrolo [2,3-b] pyridine), pyrrolopyrazine type (pyrrolo [2,3-b] pyrazine ), Pyridopyridine-based (eg, pyrido [2,3-b] pyridine), quinazoline, phenazine, and imidazopyrimidine nuclei.

In the general formula [III], R ₅ , R ₆ , R ₇ and R ₈ may optionally combine with each other to form a ring,
The ring is preferably a 5- or 6-membered heterocycle. Examples thereof include pyrrolidine, piperidine, piperazine, morpholine, imidazolidine, pyrazoline, 1,2,3,4-tetrahydroquinoline and the like.

Examples of the dye represented by the general formula [I] include Japanese Patent Application No. 5-5991, pages 26 to 30, I-1 to I-55, but the present invention is not limited thereto. Not a thing.

The above dye of the present invention is, for example, Japanese Patent Publication No. 39-220.
No. 69, No. 43-13168, JP-A No. 50-91627, No. 58-1145.
No. 58, No. 58-143342, No. 59-80470, No. 59-111640,
59-111641, U.S. Pat. Nos. 2,274,782, 3,417,084 and the like, or a synthetic method similar thereto.

Examples of the dye represented by the general formula [I] 'include Japanese Patent Application No. 5-5991, pages 32 to 36, I'-1 to I'-51. It is not limited to.

The above dyes of the present invention are, for example, Japanese Patent Publication No. 31-105.
78, 45-20635, 46-42667, 48-3286, JP-A-48-68623, 50-40625, 59-206829, U.S. Patents 3,540,884, 3,544,325, etc. It can be obtained by the method described in 1 or a synthesis method similar thereto.

Next, as the dye represented by the general formula [I] ", for example, Japanese Patent Application No. 5-5991, pages 37 to 45, I" -1 to I "
However, the present invention is not limited thereto.

The above-mentioned dyes used in the present invention are, for example, Japanese Patent Publications Nos. 45-34232 and 46-18106, and US Pat. No. 2,527,583.
No. 3,148,187, No. 3,260,601, No. 3,282,699, etc., or a synthetic method similar thereto.

Next, the compounds represented by the general formulas [II] and [III] include, for example, Japanese Patent Application No. 5-5991, pages 47 to 54.
II-1 to III-15 are mentioned, but the present invention is not limited thereto.

The above compounds used in the present invention are, for example,
Edited by K. Venkataraman “The Chemistry of Synthetic Dye
s "Volume 4, pages 103-340 (Academic Press Inc., 1971)
It can be obtained according to the method described in.

The solid fine particle dispersion in the present invention means a state in which the solid particles are substantially dispersed in the layer as a solid having a size resistant to diffusion. Specifically, for example, the method described in JP-A-63-197943 can be used in which a surfactant (nonionic surfactant) is used for emulsion dispersion and stabilization with a gelatin solution. Further, a solution of the dye of the general formula [I], the general formula [I] 'or the general formula [I] "and a solution of the compound of the general formula [II] or [III] is prepared, mixed and reacted to obtain The reaction product may be used as it is, or may be isolated and used.

The solid fine particle dispersion can be prepared by a known method of forming fine particles in the presence of a dispersant, such as ball milling, sand milling, colloid milling and roller milling. The fine particles in the solid fine particle dispersion preferably have an average particle diameter of 10 μm or less,
It is particularly preferably 1 μm or less.

The preferable amount of the dye used in the present invention is not uniform depending on the kind of the dye and the characteristics of the light-sensitive material, but preferably 1 mg to 1 per 1 m ² of the light-sensitive material of the present invention.
g, particularly preferably 10 mg to 500 mg. Further, the compound represented by the general formula [II] or the general formula [III] of the present invention is preferably used in an amount equal to or more than the amount of the dye used.

The dye organic salt of the present invention can be used in a non-photosensitive hydrophilic layer on the photosensitive layer side which is a constituent layer of a silver halide photographic light-sensitive material such as a protective layer, an intermediate layer, an undercoat layer and a filter layer. . Further, it can be used for a hydrophilic layer such as a backing layer, a protective layer, and an undercoat layer on the side opposite to the photosensitive layer side. When used for the hydrophilic layer on the side opposite to the photosensitive layer side, the layer closest to the support is preferred.

In the silver halide photographic light-sensitive material of the present invention, the above-mentioned dye organic salt is present in at least one of these constituent layers, and one is formed on each of the light-sensitive layer side and the backing layer side on the back surface thereof. It may be contained in more than one layer.

The combination of the dye organic salts according to the present invention can be appropriately selected and two or more kinds of dyes are represented by the general formula [II] in order to obtain a desired absorption wavelength depending on the color sensitivity of the light-sensitive material to be used. Alternatively, it may be supported by the compound [III]. Further, if necessary, in addition to the dye organic salt of the present invention, a well-known conventional photographic dye may be used alone.

The hydrophilic colloid layer containing the organic dyestuff according to the present invention comprises various gelatins as hydrophilic binders,
It may contain synthetic or natural polymers.
For example, gelatin derivative, graft polymer of gelatin and other polymer, or polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone,
A single substance or a copolymer such as polyacrylic acid, polymethacrylic acid or polyacrylamide can be used.

Next, immobilization can be carried out with a silver salt or a silver complex formed by the reaction of the dye according to claim 3 of the present invention with silver ions. As a preferable dye capable of forming a silver salt of such a dye, for example, Japanese Patent Application No.
General formulas [I] to [V], general formulas [I '] to [V'], and general formulas [V] described on pages 6 to 58 of the specification of 3-358344
Examples thereof include compounds represented by I]. More specific compounds include pages 12 to 22 and pages 28 to 36 of the same specification.
And those described on pages 40 to 57.

The packaging material used for the light-sensitive material of the present invention is not particularly limited, and known silver halide photographic light-sensitive material packaging materials can be used. For example, a composite material of a moisture barrier material and a synthetic resin such as aluminum foil, aluminum vapor deposition, or silica vapor deposition is preferable. In the present invention, the humidity inside the packaging bag is 10 even when the external environment temperature changes from 18 ° C to 30 ° C.
Holds at ~ 60%.

As a result, the silver halide photographic light-sensitive material containing the solid fine particle dispersion of the dye of the present invention has a characteristic that the photographic performance is not deteriorated even during long-term storage or high temperature storage.

In the silver halide photographic light-sensitive material of the present invention, silver chloride, silver chlorobromide or silver chloroiodobromide having any composition can be used. The average grain size of silver halide grains is 0.025 to 1.0μ
The range of m is used, but 0.05 to 0.80 μm is more preferable.

The particles may be prepared by any of the acidic method, the neutral method and the ammonia method. The shape is arbitrary and may be cubic, octahedral, tetradecahedral, dodecahedral or tabular grains. The silver halide photographic light-sensitive material of the present invention can use various known sensitizing methods, but need not.
In the case of chemical sensitization, a sulfur sensitization method, a reduction sensitization method, a noble metal sensitization method or the like can be used alone or in combination.
Further, various sensitizers, sensitizing dyes, additives and the like known in the photographic industry can be used. Particularly when used for printing plate making, at least one kind of tetrazolium compound, hydrazine compound and the like, which are known as so-called contrast-increasing agents, may be added.

General formula [T] preferably used in the present invention
As a tetrazolium compound represented by, Japanese Patent Application No. 5-16
No. 552, pages 28 to 31 are mentioned.

Examples of the hydrazine derivative include compounds represented by the following general formula [H].

[0077]

[Chemical 8]

The hydrazine derivative represented by the general formula [H] is described, for example, in Japanese Patent Application No. 5-43861, pp. 7 to 19, and specific compounds thereof are pp. 12 to 18 in the same specification. Examples thereof include H-1 to H-40.

Further, the nucleation accelerator preferably used when a hydrazine derivative is used is described on pages 21 to 27 of the same specification, and specific compounds are described on the same page.
2-1 to 3-6 described on pages 23 to 27 are mentioned.

The processing solution used in the present invention is not particularly limited, and various processing solutions and processing devices such as various developing solutions and fixing solutions usually used in the photographic industry can be used.

[0081]

EXAMPLES Specific examples of the present invention will be given below, but the mode for carrying out the present invention is not limited to these.

Example 1 Preparation of silver halide photographic light-sensitive material A ( preparation of silver halide emulsion coating solution E1) Temperature 40 ° C., pH
In a nitric acid acidic atmosphere of 3.0, the silver potential EAg was 170 with 1N NaCl.
While maintaining at mV, Solution B, Solution C and Solution D were mixed in Solution A below for 11 minutes by the double jet method.

Solution A Gelatin 5.6 g HO (CH ₂ CH ₂ O) n (CH ₂ CH ₂ CH ₂ O) ₁₇ (CH ₂ CH ₂ O) mH (however, n + m = 6) in 10% ethanol 0.56 ml sodium chloride 0.12g Concentrated nitric acid 0.43ml Distilled water 445ml Solution B Silver nitrate 60g Concentrated nitric acid 0.208ml Distilled water 85.2ml Solution C Gelatin 3g HO (CH ₂ CH ₂ O) n (CH ₂ CH ₂ CH ₂ O) ₁₇ (CH ₂ CH ₂ O) ) mH (however n + m = 6) 10% ethanol solution 0.3 ml Sodium chloride 20.2 g Na ₃ RhCl ₆ 1% aqueous solution 0.02 ml distilled water 85.61 ml Solution D gelatin 1.4 g HO (CH ₂ CH ₂ O) n (CH ₂ CH ₂ CH ₂ O) ₁₇ (CH ₂ CH ₂ O) mH (however n + m = 6) in 10% ethanol 0.14 ml distilled water 48.8 ml The obtained silver halide grains have an average grain size of 0.12 μm and a rhodium content of The amount of monodispersion was 1.0 to 10 ^-4 mol per mol of silver halide and the monodispersity was 8 to 15%.

Solution D was added to the emulsion thus prepared, pH was adjusted to 6.0 with sodium carbonate, and then 4-hydroxy-6-methyl, 1,3,3a, 7-tetrazaindene was halogenated. 560 mg was added per mole of silver. Thereafter, each silver halide emulsion was washed with water and desalted in a conventional manner, and Solution E was added as a preservative.

Solution E 2-Methyl-5-chloroisothiazol-3-one 15 mg Water 0.3 ml 4-hydroxy-6-methyl, 1,3,3a, 7-tetrazaindene was added to the above emulsion in 1 mol of silver halide. Per 60 mg and 66 mg per mol of silver halide sodium thiosulfate was added for sulfur sensitization. After sulfur sensitization, 4-hydroxy-6 as a stabilizer
-Methyl, 1,3,3a, 7-tetrazaindene to silver halide 1
580 mg and 14 g gelatin were added per mole. Further, the following additives were added to prepare a coating solution for emulsion layer.

1-phenyl-5-mercaptotetrazole 0.2 g gallic acid propyl ester 0.5 g saponin 1.8 g 1-decyl-2- (3-isopentyl) succinate-2-sodium sulfonate 0.1 g polymer latex (ethyl acrylate and meta Copolymer of acrylic acid) 14g Citric acid 0.1g 5-Nitroindazole 0.2g Copolymer of styrene and maleic acid ester 0.32g Glyoxal 0.48g Formaldehyde 0.59g NaCl 0.007g After adding the additives, make the total amount of the coating liquid 750ml. The emulsion coating solution was prepared by adjusting with pure water.

(Preparation of Coating Liquid P1 for Protective Layer) Gelatin 60 g Water 470 ml Sodium nonadecane-10-sulfate 0.5 g NaCl 0.4 g Amorphous silica (average particle size 3 μm) 0.7 g Amorphous silica (average particle size 8 μm) 1.1 g citric acid 0.2 g resorcin 0.3 g preservative: 2-bromo-2-nitro-1,3-propanediol 4 mg cyanuric chloride 1.5 g The solid dispersed dye according to claim 1 of the present invention and the comparative dye are added, It was adjusted with pure water so that the total amount was 1029 ml.

(Preparation of Backing Layer Coating Solution BC1) Gelatin 73.3 g Water 1368 ml Dye below C 5.8 g Dye below D 1.0 g Saponin 3.6 g Butyl acrylate and vinyl chloride copolymer 2.5 g Glyoxal 0.26 g Citric acid 0.21 g Styrene and maleic acid Sodium copolymer 0.5 g After adding the additive, the total amount was adjusted to 1695 ml with pure water.

[0089]

[Chemical 9]

(Preparation of Coating Solution for Backing Layer Protective Layer) Gelatin 60 g Water 862 ml Matting agent; Methyl methacrylate 2.2 ml NaCl 3 g Dioctyl sulfosuccinate 0.9 g Glyoxal 1.8 g Pure water so that the total amount becomes 1230 ml after adding the additive I adjusted it with.

(Preparation of sample) On one side of a polyethylene terephthalate transparent support having a thickness of 100 μm, which had been previously subjected to undercoating, the above silver halide emulsion layer coating solution E1 was applied with a gelatin dry weight of 1.8 g / m ² and a silver coating amount. 3.2 g / m ² was coated, and at the same time, the above-mentioned emulsion protective layer coating solutions were separately applied so that the dry weight of gelatin was 0.8.
It was applied so as to be g / m ² . Next, the backing layer coating solution BC1 was coated on the opposite surface of the support so that the gelatin dry weight was 2.0 g / m ² , and at the same time, the backing protective layer coating solution was 1.0 g / m 2. ^It was applied so as to be ² . After coating all coating liquids at a coating liquid temperature of 35 ° C, treat them with cold air at 5 ° C for 6 seconds and set them by cooling.
The coating layers on both sides were dried for 2 minutes by sequentially controlling the conditions of keeping the dry bulb below 35 ° C and the film surface temperature below 20 ° C. Within 20 seconds after the completion of drying, the dry bulb temperature is 50 ° C and the dew point is -5 ° C.
After treating for 50 seconds, it was packaged under the temperature and humidity conditions shown in Table 1 to prepare samples 1-1 to 1-17.

Evaluation of Samples As a substitute for long-term storability and high-temperature storability in summer, a sample with a natural time of one month was stored at 55 ° C. and 20% RH for 5 days, and the following evaluations were performed.

(Evaluation of quality of blank characters) Bright room printer P-
100 from the light source side of 627F (manufactured by Dainippon Screen Co., Ltd.)
A transparent embedded base with a thickness of μm, a black line image with a line width of 80 μm, a transparent original with a thickness of 100 μm, a transparent embedded base with a thickness of 100 μm, and a 50% hard dot halftone transparent original with a thickness of 100 μm are made into four originals. After exposing the test sample, it was processed by the GR-26S automatic developing machine (manufactured by Konica Corporation) under the following conditions. Halftone dot 50
The degree of collapse of the line image at the exposure amount returning to% was measured as the width of the defect, and defined as D (μm). This D is called a blank character width and is an evaluation value of blank character quality. The larger D means the better result.

(Evaluation of Residual Color) 5 pieces of developed test pieces were used.
The sheets were piled up and the degree of coloring was visually evaluated on a scale of five. The level of the test piece without addition of the dye was set to 5, and the number of overlapped target sample pieces, which is equivalent to the overlap of the sample without addition of the dye, was ranked below. However, all the inferior ones were ranked as rank 1.

<Development processing conditions> (Process) (Temperature) (Time) Tank capacity (l) Image 28 ° C 30 seconds 20 Settling 28 ° C 30 seconds 20 Water washing 18 ° C 20 seconds 15 Drying 40 ° C 20 seconds Each The process includes so-called wading transport time until the next process.
Dry to Dry time is 100 seconds. <Developer formulation> (Composition A) Pure water (ion exchanged water) 150 ml Ethylenediaminetetraacetic acid disodium salt 2 g Diethylene glycol 50 g Potassium sulfite (55% w / v aqueous solution) 100 ml Potassium carbonate 50 g Hydroquinone 15 g 5-Methylbenzotriazole 200 mg 1- Phenyl-5-mercaptotetrazole 30mg Potassium hydroxide pH of the used solution is 10.4 Potassium bromide 4.5g (Composition B) Pure water (ion exchanged water) 3ml Diethylene glycol 50g Ethylenediaminetetraacetic acid disodium salt 25mg Acetic acid (90% aqueous solution) ) 0.3 ml 5-nitroindazole 110 mg 1-phenyl-3-pyrazolidone 700 mg When the developer was used, the above composition A and composition B were dissolved in 500 ml of water in this order to make 1 liter.

Fixer formulation (composition A) Ammonium thiosulfate (72.5% w / v) 240 ml Sodium sulfite 17 g Sodium acetate trihydrate 6.5 g Nitric acid 6 g Sodium citrate dihydrate 2 g Acetic acid (90% w / w aqueous solution) 13.6 ml (composition B) pure water 17ml sulfate (50% w / w aqueous solution) 4.7 g aluminum sulfate (Al ₂ 0 ₃ in terms of content of 8.1% w / w aqueous solution) 26.5 g fixer finish 1l with water at the time of use Using. The pH of this fixer was about 4.6.

The results are shown in Table 1.

[0098]

[Table 1]

[0099]

[Chemical 10]

[0100]

[Chemical 11]

From the results shown in Table 1, it can be seen that the sample of the present invention has excellent extracted character quality, little residual color, and good storability.

[0102] Ha androgenic halide photographic material aqueous sodium chloride solution containing prepare (Preparation of silver halide emulsion E2) aqueous silver nitrate solution and 1 mol of silver per 0.5 × 10 ^-4 mol six rhodium (III) chloride ammonium B By the double jet method, the mixture was mixed in a gelatin solution at 35 ° C. while controlling the pH to be 6.5 to prepare a monodispersed silver chloride emulsion having an average grain size of 0.10 μm. After the particles are formed, soluble salts are removed by a flocculation method known in the art, and 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene and 1-phenyl-5-mercaptotetrazole are used as stabilizers. Was added, and then the following additives were added to prepare an emulsion coating solution, and then an emulsion protective layer coating solution P-0 was prepared with the following composition.

The backing layer coating solution and the backing protective layer coating solution were prepared and coated in the same manner as in the silver halide photographic light-sensitive material A.

(Preparation of emulsion coating solution)

[0105]

[Chemical 12]

Next, polyethyl acrylate latex was added.
mg / m ² , per 1 m ² by adding 2,4-dichloro-6-hydroxy-1,3,5-triazine sodium salt as a hardening agent
A silver halide emulsion layer was coated on a polyethylene terephthalate transparent support so that the amount of silver was 3.5 g.

(Preparation of Emulsion Protective Layer Coating Solution P0) Gelatin 1.0 g / m ²

[0108]

[Chemical 13]

Stabilizer Thioctic acid 6.0 mg / m ² Matting agent Polymethylmethacrylate (average particle size 2.5 μm) 9.0 mg / m ² Dye Amount shown in Table 2 Standard processing conditions Temperature (° C) Time (sec) Development 38 20 Fixing 39 14 Washing with water Room temperature 10 Drying 40 24 Basic developer formulation Hydroquinone 35.0 g N-methyl-p-aminophenol 1/2 sulfate 0.8 g Sodium hydroxide 13.0 g Potassium triphosphate 74.0 g Potassium sulfite 90.0 g Ethylenediaminetetraacetic acid tetra Sodium salt 1.0 g Potassium bromide 4.0 g 5-Methylbenzotriazole 0.6 g 3-Diethylamino-1,2-propanediol 15.0 g Water is added to make 1 liter, and the pH is adjusted to 11.5.

Fixer formulation Ammonium thiosulfate (100% conversion) 168.2g Pure water 5.0g Sodium sulfite 5.63g Boric acid 9.78g Sodium citrate dihydrate 2.0g Sodium acetate trihydrate 27.8g Acetic acid (90% W / W %) 6.4 g Water was added to make 1 liter, pH was about 4.38.

The obtained samples 1-18 to 1-34 were evaluated in the same manner as in the silver halide photographic light-sensitive material A. The results are shown in Table 2.

[0112]

[Table 2]

From the results shown in Table 2, it can be seen that the sample of the present invention is excellent in the quality of blank characters, the residual color, and the long-term storage stability.

Preparation of silver halide photographic light-sensitive material C On the one side on the undercoated polyethylene terephthalate film described in JP-A-59-19941 on the one side, a dye-containing layer and a silver halide are arranged in this order from the support. Three layers, an emulsion layer and a protective layer, were coated, and a backing layer was coated on the other side.

[Dye-Containing Layer and Emulsion Lower Layer] The dye according to claim 1 shown in Table 3 was first alkali-dissolved in an aqueous sodium acetate solution. Next, add to this solution so that the amount of gelatin at the time of application is 0.6 g / m ² and sodium p-dodecylbenzenesulfonate as a surfactant is 10 mg / m ^2, and adjust the pH of the solution to 5.8 with citric acid. Then, the emulsion layer and the emulsion protective layer were simultaneously coated in multiple layers. The amount of dye added was 0.3 g / m ² .
At this time, the average particle size of the solid dye dispersion was 0.2 μm, and the standard deviation of the particle size distribution was 30%.

(Preparation of Silver Halide Emulsion E3) A silver chlorobromide emulsion was prepared using solutions A, B, C and D shown below.

<Solution A> Ocein gelatin 17 g Polyisopropylene-polyethyleneoxydisuccinate sodium salt 10% ethanol aqueous solution 5 ml Distilled water 1280 ml <Solution B> Silver nitrate 170 g Distilled water 410 ml <Solution C> Sodium chloride 45.0 g Potassium bromide 27.4g 6 Iridium chloride salt 200μg Polyisopropyleneoxydisuccinic acid sodium salt 10% ethanol solution 3ml Ocein gelatin 11g Distilled water 407ml After keeping solution A at 40 ℃, add sodium chloride so that the EAg value becomes 160mV. Was added. Next, as in JP-A-57-92523
Solution B and solution C were added by the double jet method using the mixing stirrer described in No. 57-92524. As shown below, the addition flow rate was gradually increased over the entire addition time of 80 minutes while the EAg value was kept constant.

EAg value was 160 mV, and 3 ml /
The EAg value was changed to 120 mV using 1 l of an aqueous sodium chloride solution, and this value was maintained thereafter until the completion of mixing.

In order to keep the EAg value constant, the EAg value was controlled using a 3 mol / l sodium chloride aqueous solution.

[0120] A metal silver electrode and a double junction type saturated Ag / AgCl reference electrode were used to measure the EAg value (the double junction disclosed in JP-A-57-197534 was used for the electrode configuration).

For addition of solutions B and C, a variable flow rate roller tube metering pump was used. During the addition, it was confirmed by observing with an electron microscope that no new grains were found in the system due to sampling of the emulsion. Further, during the addition, the pH value of the system was controlled with a 3% nitric acid aqueous solution so as to keep it constant at 3.0.

After the addition of the solutions B and C, the emulsion was ripened for 10 minutes in Ostwald, desalted and washed in a conventional manner, and then 600 ml of an aqueous solution of ossein gelatin (containing 30 g of ossein gelatin) and the compound [ 15 ml of a 1% aqueous solution of the mixture of A], [B] and [C] was added and dispersed by stirring at 55 ° C. for 30 minutes and then adjusted to 750 ml to obtain emulsion A.

[0123]

[Chemical 14]

The emulsion E3 thus obtained was sensitized with gold and sulfur, and 1 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added as a stabilizer, followed by sensitization. Dye A
300 mg per mol of silver halide contained in the emulsion,
Sensitizing dye B was added in an amount of 100 mg per mol of silver halide contained in the emulsion.

[0125]

[Chemical 15]

Then, as shown in Table 1, the tetrazolium compound T-14 of the present invention was added per mol of silver halide, 300 mg of sodium p-dodecylbenzenesulfonate, 2 g of styrene-maleic acid polymer and styrene-maleic acid copolymer were added. Add 15 g of butyl acrylate-acrylic acid copolymer latex (average particle size of about 0.25 μm) to obtain a gelatin amount of 1.8 in the emulsion layer.
g / m ^2, it was coated on the support so that the Ag amount 4.0 g / m ^2. At that time, a protective layer of bis- (2-ethylhexyl) sulfosuccinate 10 mg / m ^{2 as} a spreading agent, formalin 15 mg / m ² as a hardening agent, and a gelatin amount 1.0 g / m ² containing glyoxal 8 mg / m ² Simultaneous multilayer coating was performed. Further, the polymer latex prepared as described below was added to the protective layer.

The following (c) and (d) were used as comparative dyes.

[0128]

[Chemical 16]

The absorption spectrum of the dye is 2 × 10 ^-4 mo for each dye.
l / m ² and gelatin coverage 2.0 g / m ² (dry film thickness 1.49 mm) were coated on a polyethylene terephthalate base, and the sample was applied to a spectrophotometer UV1DEC-610 (manufactured by JASCO Engineering Co., Ltd.). Measured.

(Latex synthesis method Lx-1) To a solution prepared by adding 0.125 kg of gelatin and 0.05 kg of ammonium persulfate to 40 liters of water, 7.5 g of sodium dodecylbenzenesulfonate was added.
And stirring under a liquid temperature of 50 ° C., under a nitrogen atmosphere, the following monomers (a) to (c) (or (a),
(D)) The mixed solution (35 ° C) has a finished average particle size of 0.
The mixture was added at a rate of 10 μm and stirred for 3 hours, 0.005 kg of ammonium persulfate was added, and the mixture was stirred for 1.5 hours. After completion of the reaction, residual monomers were removed by steam distillation for 1 hour, then cooled to room temperature and adjusted to pH 6.0 with aqueous ammonia. The obtained latex liquid was adjusted to 75.0 kg with water.

The latex in Table 3 is as follows. (Unit: Kg) In Lx-1, (1) (A) Butyl acrylate 4.51 (B) Styrene 5.49 (C) Acrylic acid 0.1 (2) (A) Ethyl acrylate 3.52 (B) Methyl methacrylate (two-component system) 5.1 ( 3) (A) Ethyl acrylate 3.52 (B) Methyl methacrylate 4.9 (C) Ethylene glycol 0.2 (4) (A) Ethyl acrylate 3.52 (B) Methyl methacrylate 4.9 (C) Styrene 0.1 (5) (A) Ethyl acrylate 3.0 ( B) Methyl methacrylate 4.0 (C) Styrene 3.0 (D) 2-Acrylamido-2-methylpropanesulfonic acid 0.8 Further, the following backing layer was provided on the opposite side of the emulsion layer with the support in between.

Gelatin 60 g Dyes A to C 100 mg / m ² saponin 2 g Glyoxal 1 g Finished to 1 liter with pure water, added 2 g / m ² of gelatin, and 1 g of the same emulsion protective layer as gelatin It was applied so as to be / m ² .

[0133]

[Chemical 17]

Samples 1-35 to 1-51 were prepared in this manner.

The obtained samples 1-35 to 1-51 were evaluated by the following methods.

As a substitute for long-term storability and high-temperature storability in summer, a sample with a natural aging time of 1 month was stored at 55 ° C. and 20% RH for 5 days, and then the following evaluation was performed.

Measurement of Sensitivity and Gamma The obtained sample was brought into close contact with a step wedge, exposed to a tungsten light of 3200 ° K for 5 seconds, and developed.

Test for stretching and contraction (a) Preparation of originals Transmission of a person consisting of halftone dots using a scanner SG-808 (II) manufactured by Dainippon Screen Co., Ltd. and a photosensitive material RSDII manufactured by Konica Corporation. A step wedge in which the image and the dot% were changed stepwise was created. The screen frequency at this time was 150 lines / inch.

(B) Photographing The above document was set on a Fine Zoom C-880F manufactured by Dainippon Screen Co., Ltd. so that the magnification was 120% and exposed. At this time, the exposure was performed so that 95% of the step wedge of the original became 5%.

The exposed sample was processed in an automatic processor using a developing solution and a fixing solution having the following formulations.

(C) Evaluation of fog unevenness Only the development processing time was changed from 30 seconds to 50 seconds, and the sample was subjected to development processing without being exposed. The processing was the same as in Example 1, silver halide photographic light-sensitive material A.

(Evaluation Method) (a) Sensitivity, Gamma The obtained sample was subjected to concentration measurement with an optical densitometer Konica PDA-65,
The relative sensitivity of the comparative sample in each table at a concentration of 2.5 was defined as 100, and gamma was represented by the tangent of the concentrations of 0.1 and 2.5. If the gamma value is less than 6, it cannot be used, and if the gamma value is 6 or more and less than 10, the contrast is still insufficient. With a gamma value of 10 or more, the image becomes ultra-high contrast and can be used sufficiently.

(B) Stretched image quality In the sample obtained by adjusting the exposure amount, the gradation reproducibility of the shardy part of the sample in which the dot% on the small dot side (highlight part) is combined (the dot is difficult to be crushed) 5 grades were evaluated in descending order of goodness.

(C) Fog unevenness The obtained sample was visually evaluated on a 10-point scale. Rank 5 and below cannot be put to practical use.

The results are shown in Table 3.

[0146]

[Table 3]

[0147]

[Chemical 19]

[0148]

[Chemical 20]

From the results shown in Table 3, it can be seen that the samples of the present invention are excellent in sensitivity, gamma, stretching properties, and long-term storage stability.

Preparation of silver halide photographic light-sensitive material D ( preparation of silver halide photographic emulsion E4) A silver chloroiodobromide emulsion (0.2 mol% of silver iodide per mol of silver;
Silver chloride (65 mol%) was prepared. The mixture during the K ₂ IrCl ₆ was per mole silver 8 × 10 ^-7 mol, and Na ₃ RhCl ₆ 1 × 10 ^-7 mol was added. The obtained emulsion was an emulsion composed of cubic monodisperse grains (coefficient of variation 10%) having an average grain size of 0.20 μm. Then, it was washed with water and desalted by a conventional method. Thereafter, a mixture of the compounds [A], [B] and [C] was added, gold and sulfur sensitization was performed, and then sensitizing dyes A and B were added to the emulsion E4 at 300 mg and 100 mg, respectively, per mol of silver halide to obtain Emulsion E4. Obtained.

(Preparation of silver halide photographic light-sensitive material) One of 100 μm-thick polyethylene terephthalate films having a 0.1 μm-thick undercoat layer (see Example 1 of JP-A-59-19941) on both sides A dye-containing layer similar to the above-described silver halide photographic light-sensitive material C was coated on the undercoat layer, and a silver halide emulsion layer having the following formulation (1) was added, and the amount of gelatin was 2.0 g / m ² .
A silver amount of 3.2 g / m ² was coated, and an emulsion protective layer of the following formulation (2) was further coated thereon so that the amount of gelatin was 1.0 g / m ² . The dye-containing layer, emulsion layer and emulsion protective layer were simultaneously coated as the main layers. On the other undercoat layer on the opposite side, a backing layer having a gelatin content of 2. according to the following prescription (3).
It is coated so that it will be 4 g / m ^2, and the following formulation (4)
A backing protective layer was coated on the backing so that the amount of gelatin was 1 g / m ² to obtain a sample.

Formulation (1) (Silver Halide Emulsion Layer Composition) Gelatin Amount of 1.5 g / m ² for emulsion layer Silver halide emulsion E4 Silver amount 3.2 g / m ²

[0153]

[Chemical 21]

Stabilizer: 4-methyl-6-hydroxy-1,3,3a, 7-tetrazaindene 30 mg / m ² Antifoggant: 5-nitroindazole 1 × 10 ^-4 mol / m ² 5-sulfonic acid Sodium-2-mercaptobenzimidazole 5 mg / m ² Surfactant: saponin 0.1 g / m ²

[0155]

[Chemical formula 22]

[0156]

[Chemical formula 23]

Formulation (3) (backing layer composition)

[0158]

[Chemical formula 24]

Gelatin 2.4 g / m ² Surfactant: Saponin 0.1 g / m ² : S-1 6 mg / m ² Colloidal silica 100 mg / m ² Formulation (4) [Backing protective layer composition] Gelatin 1 g / m ² matting agent average particle size: 3.5μm monodisperse polymethyl methacrylate a cleat 40 mg / m ² surfactant: ^S-2 10mg / m 2 hardener: at glyoxal 35 mg / m ² obtained sample temperature and humidity conditions in Table 4, wherein Packaged with
Samples 1-52-1-68 were prepared.

These samples were evaluated in the same manner as the silver halide photographic light-sensitive material C under the following processing conditions.

[Developer composition 1] Potassium sulfite 50.0 g Hydroquinone 20.0 g 4-Methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidone 1.0 g Ethylenediaminetetraacetic acid disodium salt 2.0 g Potassium carbonate 12.0 g Potassium bromide 5.0 g 5-Methylbenzotriazole 0.3 g Diethylene glycol 25.0 g 5-Nitroindazole 0.1 g Compound (d) 0.1 g Water was added to make 1 liter, and pH was adjusted to 10.4 with potassium hydroxide.

[0162]

[Chemical 25]

Fixing Solution Formulation Ammonium thiosulfate (72.5% W / V aqueous solution) 200 ml Sodium sulfite 17 g Sodium acetate trihydrate 6.5 g Boric acid 6.0 g Sodium citrate dihydrate 2.0 g Pure water (ion exchange water) 17 ml Sulfuric acid ( 50% W / V aqueous solution) 2.0 g Aluminum sulphate (Al ₂ O ₃ converted content is 8.1% W / V aqueous solution) 8.5 g The fixing solution was finished to 1 liter and used. Of this fixer
The pH was adjusted to 4.8 with acetic acid.

(Development processing conditions) The time includes the time for wading.

[0165] The results are shown in Table 4.

[0166]

[Table 4]

From the results shown in Table 4, it can be seen that the samples of the present invention are excellent in sensitivity, gamma, stretchability and have good long-term storage stability.

Example 2 As shown in Table 5, the general formula [I] described in claim 2
A gelatin emulsion obtained by mixing an aqueous dye solution of [I] 'or [I] "with a solution of a compound of the general formula [II] or [III] to form a dye organic salt, and then adding it to an aqueous gelatin solution. I used a thing.

Preparation of a silver halide photographic light-sensitive material was carried out in the same manner as in A of Example 1, and samples 2-1 to 2-17 were prepared by changing only the dye part to the above dye. These samples were processed and evaluated in the same manner as the silver halide photographic light-sensitive material A. The results are shown in Table 5.

[0170]

[Table 5]

[0171]

[Chemical formula 26]

[0172]

[Chemical 27]

From the results shown in Table 5, it can be seen that the samples of the present invention are excellent in the quality of characters left out, the residual color, and the long-term storage stability.

Example 3 (Preparation Method of Dye Solid Fine Particle Dispersion) As shown in Table 3, 0.1 mol of dye and 10.1 g of triethylamine were dissolved in 1000 ml of water, and a 1 mol / liter silver nitrate aqueous solution was added dropwise under stirring. The resulting precipitate was filtered, washed with water, and dried to obtain the desired silver salt of the dye.

The silver halide photographic light-sensitive material was prepared in the same manner as in C of Example 1, except that the dye portion was changed to the above dyes to obtain samples 3-1 to 3-17. These samples were processed and evaluated in the same manner as the silver halide photographic light-sensitive material A. The results are shown in Table 6.

[0176]

[Table 6]

[0177]

[Chemical 28]

[0178]

[Chemical 29]

From the results shown in Table 6, it can be seen that the samples of the present invention are excellent in sensitivity, gamma and stretchability and have good long-term storage stability.

[0180]

According to the present invention, a photosensitive silver halide emulsion layer or a non-photosensitive colloidal layer has good absorption spectrum characteristics and is also diffusion resistant, and has no character, sensitivity, gamma, and stretch. Provided is a silver halide photographic light-sensitive material containing a dye which has excellent characteristics, is excellent in elution and decolorization during photographic processing, and is suitable for rapid processing, and has no deterioration in photographic performance during long-term storage or high temperature storage. We were able to.

Claims (5)

[Claims] 1. A silver halide photographic light-sensitive material containing at least one photographic constituent layer containing a solid fine particle dispersion of a dye, wherein the silver halide photographic light-sensitive material has a humidity inside the package of 18 ° C. to 30 ° C. A silver halide photographic light-sensitive material, which is packaged so that the relative humidity is 10% to 60%. 2. A dye represented by the following general formula [I] or [I] 'or [I] "and a general formula [I]
A silver halide photographic light-sensitive material having at least one photographic constituent layer containing a solid fine particle dispersion of a dye organic salt formed with at least one of the compounds represented by I] or [III]. A silver halide photographic light-sensitive material, characterized in that the photographic light-sensitive material is packaged so that the humidity inside the package is 18% to 30 ° C and the relative humidity is 10% to 60%. [Chemical 1] [In the formula, A ₁ and A ₂ represent acidic nuclei, L ₁ , L ₂ and L ₃ represent methine groups, and n ₁ represents 0, 1 or 2. However,
It has at least one sulfo group or carboxy group in the molecule. ] [Chemical 2] [In the formula, A represents an acidic nucleus, Q represents an aryl group or a heterocyclic group, L ₁₁ , L ₁₂ and L ₁₃ represent a methine group, and n
₂ represents 0 or 1. However, it has at least one sulfo group or carboxy group in the molecule. ] [Chemical 3] [In the formula, A ₃ represents an acidic nucleus, B represents a basic nucleus, and L
₂₁ and L ₂₂ each represent a methine group, and n ₃ represents 1 or 2. However, it has at least one sulfo group or carboxy group in the molecule. ] [Chemical 4] [Wherein R ₁ , R ₂ , R ₃ and R ₄ represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group,
R ₁ , R ₂ , R ₃ and R ₄ may optionally combine with each other to form a ring. X ₁ represents an anion. ] [Chemical 5] [Wherein R ₅ , R ₆ , and R ₇ represent an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group, R ₈ represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and R ₅ , R ₆ , R
₇ and R ₈ may optionally combine with each other to form a ring.
X ₂ represents an anion. ] 3. A silver halide photographic light-sensitive material having at least one photographic constituent layer containing a silver salt of a dye as a solid fine particle dispersion on a support, wherein the silver halide photographic light-sensitive material is a humidity inside a package. At 18 ° C to 30 ° C and relative humidity of 10
% To 60% packaged silver halide photographic light-sensitive material. 4. The silver halide photographic light-sensitive material according to claim 1, 2 or 3, which contains at least one tetrazolium compound represented by the following general formula [T]. [Chemical 6] [In the formula, preferred examples of the substituents represented by R ₁ to R ₃ are an alkyl group, an amino group, an acylamino group, a hydroxyl group, an alkoxy group, an acyloxy group, a halogen atom, a carbamoyl group, an acylthio group, an alkoxycarbonyl group and a carboxyl group. , Acyl group, cyano group, nitro group,
Examples thereof include groups such as a mercapto group, a sulfoxy group and an amino sulfoxy group. X ^- represents an anion. ] 5. The silver halide photographic light-sensitive material according to claim 1, 2 or 3, which contains at least one hydrazine derivative.