JPH06222503A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the silver halide photographic sensitive material small in fluctuation of sensitivity by the lapse of time, residual dye stains, deterioration of enlargebility, and fog by the lapse of line by forming on a support at least one layer containing a specified dye and a latex stabilized with a gelatin. CONSTITUTION:The silver halide photographic sensitive material has at least one layer containing a latex stabilized a gelatin and at least one of the dyes represented by formulae I-IV and the like, and in these formulae, each of A and A' is an acidic nucleus; B is a basic nucleus; each of X and Y is an electron-attractive group; R is H or an alkyl; each of R1 and R2 is an alkyl, aryl, or the like; each of R3 and R6 is H, OH, or the like; each of R4 and R5 is H or the like; each of L1-L3 is a methine group; (m) is 0 or 1; each of (n) and (q) is 0, 1, or 2; and (p) is 0 or 1.

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, and more specifically, to a silver halide photographic light-sensitive material which is less susceptible to fluctuations in sensitivity with time, deterioration in residual color property, stretchability, and fog over time ( Hereinafter, also referred to as a photosensitive material).

[0002]

BACKGROUND OF THE INVENTION In recent years, commonly used black-and-white light-sensitive materials (for X-ray, for plate making, for micro) are developed by an automatic processor (automatic developing machine, hereinafter the same) in 1 minute to 5 minutes. However, in order to cope with the increase in the number of photographed images, it is desired to finish the development processing as quickly as possible. In addition, a medical X-ray light-sensitive material, such as an X-ray photosensitive material, which is photographed during surgery and used for feeding back the result to the surgery, must be processed in the shortest possible time.
Due to such social conditions, the development processing time of the light-sensitive material is shifting to less than 1 minute.

Higher image quality of the light-sensitive material is required for improving diagnostic accuracy in the medical X-ray light-sensitive material. In the photosensitive material for plate making, due to the nature of undergoing the returning process many times,
If the light-sensitive material does not have a sufficient resolution, there is a problem that the image is blurred every time the returning process is performed. Therefore, higher image quality is desired. In recent years, the photosensitive material for plate-making is often exposed to laser light, and it is required for the photosensitive material to maintain high image quality even under high illuminance. Higher image quality is required for micro-photosensitive materials because the photographic image is not directly viewed but magnified, and it is necessary to have legal evidence. As described above, in black-and-white light-sensitive materials, rapid processing in less than 60 seconds and high image quality are required.

For the purpose of improving the image quality of light-sensitive materials, photographic emulsion layers or other layers are colored to absorb light of a specific wavelength. When incident light passes through or after passing through the photographic emulsion layer, the light scattered is reflected at the interface between the emulsion layer and the support or at the surface of the light-sensitive material opposite to the emulsion layer and re-enters the photographic emulsion layer. A coloring layer is provided between the photographic emulsion layer and the support or on the side of the support opposite to the photographic emulsion layer for the purpose of preventing blurring of the image based on the above, that is, halation. Such a colored layer is called an antihalation layer. Further, in the X-ray photosensitive material, a colored layer may be provided as a crossover cut layer for reducing crossover light in order to improve sharpness.

These layers to be colored are often composed of hydrophilic colloids and therefore dyes are usually incorporated in the layers for their coloring. This dye is required to satisfy the following conditions. (1) It has a proper spectral absorption according to the purpose of use. (2) It is photographic-chemically inactive, that is, it does not adversely affect the performance of the silver halide photographic emulsion layer in a chemical sense, such as reduction in sensitivity, latent image regression, or fog. (3) No detrimental residual color is left on the processed light-sensitive material by being decolorized or dissolved and removed in the course of development processing.

As a method of providing a dye layer, there is a method of dissolving a soluble dye in a hydrophilic colloid layer, and British Patents 1,414,456, 1,477,638 and 1,477,639 are known. Etc. The disadvantage of this method is that when the water solubility of the dye is increased to improve the residual color, the degree of immobilization of the dye decreases, the dye diffuses to the adjacent layer, and the desensitization and transfer of the dye to other photosensitive materials occur. Is to occur. Also, a method in which a hydrophilic polymer having a charge opposite to that of the dissociated anionic dye is allowed to coexist in the layer as a mordant to localize the dye in a specific layer by the interaction between the dye molecule and the polymer is disclosed in US Pat. No. 2,548. , 564, and 4,
Nos. 124,386 and 3,625,694. However, in this method, when an anionic substance other than the dye is present in the same layer, the localization of the dye is not successful, or the coating solution is agglomerated, which adversely affects the production suitability.

As a method for improving these obstacles, a method in which a dye dispersed in a microcrystalline state is present in a layer between a support and an emulsion layer is disclosed in US Pat. No. 4,803,150, WO8.
It is disclosed in, for example, 8/04794. This method is an excellent technique for achieving high image quality without desensitization. However, this technique has problems in suitability for rapid processing of less than 60 seconds, which is required in recent years, and suitability for manufacturing. First, the problems in rapid processing will be described. When a new layer is provided as an antihalation layer, the antihalation layer is usually formed of a hydrophilic colloid, so that the total amount of the hydrophilic colloid is increased. When the amount of hydrophilic colloid increases, the amount of water absorbed by the light-sensitive material in the processing step increases and the drying property deteriorates. This is a fatal problem for rapid processing of less than 60 seconds. Also, medical X-r
Since the ay light-sensitive material and the micro-light-sensitive material are stored for a long period of time, it is necessary that the amount of residual hypo (sodium thiosulfate) in the light-sensitive material after development is small. At this time, if the amount of the hydrophilic colloid is large, the amount of hypo absorbed in the fixing solution also increases, and in order to wash it out, it is necessary to prolong the washing time with water, which also poses a problem in suitability for rapid processing.
In addition, it is complicated to unnecessarily increase the number of layers, and there is a manufacturing problem such as a coating failure.

In order to solve such inconveniences and problems, JP-A-4-14038 discloses in a light-sensitive material having at least one silver halide photographic emulsion on a support, a hydrophilic material containing no dye on the support. Having a polymer layer containing a hydrophilic colloid and a hydrophilic colloid layer containing a solid disperse dye, and the hydrophilic colloid in the dye-containing layer is 0.5 g / m 2.
Techniques of ² or less have been proposed. According to such a proposed technique, the object of improving the residual color property, the high image quality, and the rapid processability was achieved. However, according to the research by the present inventor, it has been found that the proposed technique has a new problem that deterioration of photographic performance with time, particularly desensitization with time and fog with time occur.

[0009]

DISCLOSURE OF THE INVENTION The object of the present invention is to provide good color retention, high image quality (excellent in stretchability), rapid processability and photographic performance over time (especially sensitivity and fog). ) Is to provide a light-sensitive material with less deterioration.

[0010]

The above object of the present invention has at least one layer containing a dye selected from the compounds represented by the following general formulas [I] to [VII] on a support, and It is achieved by a light-sensitive material characterized in that the layer comprises a latex stabilized with gelatin.

[0011]

[Chemical 2]

(In the formula, A and A'may be the same or different and each represents an acidic nucleus, B represents a basic nucleus, and X represents
And Y may be the same or different and each represents an electron-withdrawing group. R represents a hydrogen atom or an alkyl group, R ₁ and R ₂ each represent an alkyl group, an aryl group, an acyl group or a sulfonyl group, and R ₁ and R ₂ may be linked to form a 5- or 6-membered ring. Good. R ₃ and R ₆ each represent a hydrogen atom, a hydroxy group, a carboxyl group, an alkyl group, an alkoxy group or a halogen atom, and R ₄ and R ₅ each represent a hydrogen atom or R ₁ and R ₄ or R ₂ and R ₅ are linked. Then 5 or 6
Represents a group of non-metal atoms necessary for forming a member ring. L ₁ ,
L ₂ and L ₃ each represent a methine group. m represents 0 or 1, n and q each represent 0, 1 or 2, and p is 0 or 1.
When p is 0, R ₃ represents a hydroxy group or a carboxyl group, and R ₄ and R ₅ represent hydrogen atoms.
B'represents a heterocyclic group having a carboxyl group, a sulfamoyl group, or a sulfonamide group. Q represents a heterocyclic group. However, the compounds represented by the general formulas [I] to [VII] have a dissociative group having a pKa in the range of 4 to 11 in a mixed solution of water and ethanol in a volume ratio of 1: 1 in one molecule. Have at least one. ) In a preferred embodiment of the present invention, the coating amount of all hydrophilic colloids (including gelatin in the latex of the present invention) is preferably 3 g / m ² or less per side, more preferably 2.5 g / m ² or less, It is preferably 2 g / m ² or less.

The present invention will be described below. First, the compounds represented by the general formulas [I] to [VII] will be described.

The acidic nucleus represented by A or A'is preferably 2-pyrazolin-5-one, rhodanine, hydantoin, thiohydantoin, 2,4-oxazolidinedione, isoxazolidinone, barbituric acid, thiobarbituric acid. , Indandione, pyrazolopyridine or hydroxypyridone.

The basic nucleus represented by B preferably represents pyridine, quinoline, indolenine, oxazole, benzoxazole, naphthoxazole or pyrrole.

Examples of B'heterocycle include pyrrole,
Indole, thiophene, furan, imidazole, pyrazole, indolizine, quinoline, carbazole, phenothiazine, phenoxazine, indoline, thiazole, pyridine, pyridazine, thiadiazine, pyran, thiopyran, oxadiazole, benzoquinolidine, thiadiazole, pyrrolothiazole, pyrrolo Examples include pyridazine and tetrazole.

The heterocyclic ring represented by Q is preferably a 5-membered heterocyclic ring which may be benzo-condensed, and preferably a 5-membered nitrogen-containing heterocyclic ring which may be benzo-condensed. . Examples of the heterocycle of Q include pyrrole, indole, pyrazole, pyrazolobilimidone, benzoindole and the like.

The group having a dissociative proton having a pKa (acid dissociation constant) in the range of 4 to 11 in a mixed solution of water and ethanol in a volume ratio of 1: 1 is a dye molecule at pH 6 or less than pH 6. Water insoluble to pH 8 or pH
There are no particular restrictions on the type and substitution position on the dye molecule as long as it substantially renders the dye molecule water-soluble when it exceeds 8, but is preferably a carboxyl group, a sulfamoyl group, a sulfonamide group or a hydroxy group. The more preferable one is a carboxyl group. The dissociative group may be directly substituted on the dye molecule, or may be substituted via a divalent coupler (for example, an alkylene group or a phenylene group). Examples via a divalent coupler include 4-carboxyphenyl, 2-methyl-3-carboxyphenyl, 2,4-dicarboxyphenyl, 3,5-dicarboxyphenyl,
3-carboxyphenyl, 2,5-dicarboxyphenyl, 3-ethylsulfamoylphenyl, 4-phenylsulfamoylphenyl, 2-carboxyphenyl,
2,4,6-trihydroxyphenyl, 3-benzenesulfonamidophenyl, 4- (p-siamibenzenesulfonamido) phenyl, 3-hydroxyphenyl, 2-
Hydroxyphenyl, 4-hydroxyphenyl, 2-hydroxy-4-carboxyphenyl, 3-methoxy-4
-Carboxyphenyl, 2-methyl-4-phenylsulfamoylphenyl, 4-carboxybenzyl, 2-carboxybenzyl, 3-sulfamoylphenyl, 4-
Sulfamoylphenyl, 2,5-disulfamoylphenylcarboxymethyl, 2-carboxyethyl, 3-
Carboxypropyl, 4-carboxybutyl, 8-carboxyoctyl and the like can be mentioned.

The alkyl group represented by R, R ₃ or R ₄ is preferably an alkyl group having 1 to 10 carbon atoms, and examples thereof include methyl, ethyl, n-propyl, isoamyl and n-octyl groups. it can.

The alkyl group represented by R ₁ and R ₂ is an alkyl group having 1 to 20 carbon atoms (for example, methyl, ethyl, n-
Propyl, n-butyl, n-octyl, n-octadecyl, isobutyl, isopropyl) are preferable, and substituents (for example, halogen atom such as chlorine and bromine, nitro group, cyano group, hydroxy group, carboxy group, alkoxy group,
(Eg, methoxy, ethoxy), alkoxycarbonyl group (eg, methoxycarbonyl, i-propoxycarbonyl), aryloxy group (eg, phenoxy group), phenyl group, amide group (eg, acetylamino, methanesulfonamide), carbamoyl It may have a group (eg, methylcarbamoyl, ethylcarbamoyl) or a sulfamoyl group (eg, methylsulfamoyl, phenylsulfamoyl).

The aryl group represented by R ₁ or R ₂ is preferably a phenyl group or a naphthyl group. Substituents [As the substituents, the alkyl groups represented by R ₁ and R ₂ above are listed. Groups and alkyl groups (eg methyl, ethyl) are included. ] May be included.

The acyl group represented by R ₁ or R ₂ is preferably an acyl group having 2 to 10 carbon atoms, and examples thereof include groups such as acetyl, propionyl, n-octanoyl, n-decanoyl, isobutanoyl and benzoyl. it can.
Examples of the alkylsulfonyl group or arylsulfonyl group represented by R ₁ or R ₂ include methanesulfonyl, ethanesulfonyl, n-butanesulfonyl, n-octanesulfonyl, benzenesulfonyl, p-toluenesulfonyl, o-carboxybenzenesulfonyl and the like. A group can be mentioned.

The alkoxy group represented by R ₃ or R ₄ is preferably an alkoxy group having 1 to 10 carbon atoms, such as methoxy, ethoxy, n-butoxy, n-octoxy, 2-ethylhexyloxy, isobutoxy and isopropoxy. A group can be mentioned. Examples of the halogen atom represented by R ₃ or R ₆ include chlorine, bromine and fluorine.

Examples of the ring formed by connecting R ₁ and R ₄ or R ₂ and R ₅ include a julolidine ring.

5 or 6 formed by connecting R ₁ and R ₂
Examples of the member ring include a piperidine ring, a morpholine ring, and a pyrrolidine ring.

The methine group represented by L ₁ , L ₂ or L ₃ is a substituent (for example, methyl, ethyl, cyano, phenyl,
It may have a chlorine atom, hydroxypropyl).

The electron-withdrawing groups represented by X or Y may be the same or different, and are a cyano group, a carboxy group, an alkylcarbonyl group (an optionally substituted alkylcarbonyl group, such as acetyl, propionyl and heptanoyl. , Dodecanoyl, hexadecanoyl, 1-oxo-
7-chloroheptyl), an arylcarbonyl group (an optionally substituted arylcarbonyl group, for example, benzoyl, 4-ethoxycarbonylbenzoyl, 3-chlorobenzoyl), an alkoxycarbonyl group (an optionally substituted alkoxycarbonyl group, , For example, methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl,
t-amyloxycarbonyl, hexyloxycarbonyl, 2-ethylhexyloxycarbonyl, octyloxycarbonyl, decyloxycarbonyl, dodecyloxycarbonyl, hexadecyloxycarbonyl, octadecyloxycarbonyl, 2-butoxyethoxycarbonyl, 2-methylsulfonylethoxycarbonyl, Two
-Cyanoethoxycarbonyl, 2- (2-chloroethoxy) ethoxycarbonyl, 2- [2- (2-chloroetokin) ethoxy] ethoxycarbonyl), an aryloxycarbonyl group (an optionally substituted aryloxycarbonyl group, for example, Phenoxycarbonyl, 3-ethylphenoxycarbonyl, 4-ethylphenoxycarbonyl, 4-fluorophenoxycarbonyl, 4-nitrophenoxycarbonyl, 4-methoxyphenoxycarbonyl, 2,4-di- (t-amyl) phenoxycarbonyl), carbamoyl group (A carbamoyl group which may be substituted, for example, carbamoyl, ethylcarbamoyl, dodecylcarbamoyl, phenylcarbamoyl, 4
-Methoxyphenylcarbamoyl, 2-bromophenylcarbamoyl, 4-chlorophenicarbamoyl, 4-ethoxycarbonylphenicarbamoyl, 4-propylsulfonylphenylcarbamoyl, 4-cyanophenylcarbamoyl, 3-methylphenylcarbamoyl, 4-hexyloxyphenylcarbamoyl, 2,4-di- (t
-Amyl) phenylcarbamoyl, 2-chloro-3-
(Dodecyloxycarbamoyl) phenylcarbamoyl, 3- (hexyloxycarbonyl) phenylcarbamoyl, sulfonyl group (for example, methylsulfonyl, phenylsulfonyl), sulfamoyl group (which may be substituted sulfamoyl group, for example, sulfamoyl, methylsulfamoyl) Represents

Next, specific examples of the dye used in the present invention will be given.

[0029]

[Chemical 3]

[0030]

[Chemical 4]

[0031]

[Chemical 5]

[0032]

[Chemical 6]

[0033]

[Chemical 7]

[0034]

[Chemical 8]

[0035]

[Chemical 9]

In addition to the above, JP-A-4-14038, No. 8 to
The exemplified compounds described on page 16 can be mentioned. Further, the present invention is not limited to the dyes shown above. The dye used in the present invention is the international application publication WO88 / 04794.
Issue, European Patent Publication (EPO) 274,723A1
No. 276, 556, 299, 435, JP-A Nos. 52-92716, 55-155350, 55.
-155351, 61-205934, 48-
68623, US Pat. Nos. 2,527,583 and 3,
No. 486,897, No. 3,746,539, No. 3,9
33,798, 41-30,429, 4,04
0,841, Japanese Patent Application Nos. 1-50874 and 1-103.
It can be easily synthesized according to the method described in No. 751, No. 1-307363 and the like. The dye in the present invention is called a solid disperse dye,
This means that the solubility of the dye itself is insufficient, so that it cannot exist in the molecular state in the intended colored layer, and it exists as a solid of a size that is substantially impossible to diffuse in the layer. .

Regarding the preparation method, International Application Publication (WO)
88/04797, European Patent Publication (EPO) 27
6566A1 and JP-A-63-197943, a method of ball-milling and stabilizing with a surfactant and gelatin, and a method of dissolving a dye in an alkaline solution and then lowering the pH to precipitate are preferably used. To be
However, the present invention is not limited to these preparation methods.

Next, the latex dispersion-stabilized with gelatin will be described. In the present invention, the object of the present invention can be achieved by using a latex stabilized with gelatin. That is, the ordinary latex is dispersed in water by a surfactant, but the latex that can be used in the present invention is characterized in that the surface and / or the inside of the polymer latex is dispersed and stabilized by gelatin. The polymer constituting the latex and gelatin may have some kind of bond. In this case, the polymer and gelatin may be bound directly or may be bound via a crosslinking agent. Therefore, the monomers constituting the latex include carboxyl group, amino group, amide group, epoxy group, hydroxyl group, aldehyde group,
It is desirable to include those having a reactive group such as an oxazoline group, an ether group, an ester group, a methylol group, a cyano group, an acetyl group, and an unsaturated carbon bond. When a cross-linking agent is used, those known as ordinary gelatin cross-linking agents can be used. For example, an aldehyde-based, glycol-based, triazine-based, epoxy-based, vinyl sulfone-based, oxazoline-based, acrylic-based, or other crosslinking agent can be used.

The gelatin-stabilized polymer latex of the present invention (referred to as the latex of the present invention) is characterized in that at least a part of the polymerization reaction of the polymer is carried out in a solvent containing at least gelatin. . The present inventor has found that, in the course of continuing the examination of the above problems, the ratio of the addition amount of gelatin and latex at the time of synthesis has a preferable range. The weight ratio of gelatin (Gel) and polymer (Poly) at the time of synthesis (finally obtained as latex) was Gel / Poly = 1/100.
To 2/1 are preferable, and 1/50 to 1/2 are particularly preferable.
Is.

The effects of the present invention give particularly preferable results when the amount of the polymer component of the latex added is 20% or more based on the gelatin in the layer to which the latex is added. The polymer latex used in the present invention can change the MFT (minimum film forming temperature) depending on the composition of the monomer, but the MFT is particularly effective at 60 ° C. or lower, and more preferably 50 ° C. or lower. Further, in the present invention, the particle size of the latex is preferably 0.3 μm or less. If the particle size is large, the devitrification property after treatment increases, so that the preferred particle size is 0.01 to 0.27 μm.

Examples of gelatin used for stabilizing the latex of the present invention include gelatin and gelatin derivatives, cellulose derivatives, graft polymers of gelatin and other polymers,
Other hydrophilic colloids such as proteins, sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymer substances such as single or copolymers can also be used in combination.

Examples of gelatin include lime-processed gelatin, acid-processed gelatin, and Bulletin of Society of Japan (Bull. Soc. Sci. Pho).
t. Japan) No. Acid-processed gelatin as described on pages 16 and 30 (1966) may be used, or a hydrolyzate or enzymatic hydrolyzate of gelatin may also be used. As the gelatin derivative, various compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic acid, alkane sultones, vinyl sulfonamides, maleinimides, polyalkylene oxides and epoxy compounds are added to gelatin. What is obtained by reaction is used. Specific examples thereof are U.S. Pat. Nos. 2,614,928, 3,132,945, 3,186,846, 3,312,553, British Patents 861,414 and 1,033,189. No. 1,005,784, and Japanese Examined Patent Publication No. 42-26845.

Proteins include albumin and casein;
As the cellulose derivative, hydroxyethyl cellulose, carboxymethyl cellulose, or a sulfuric acid ester of cellulose; or as the sugar derivative, sodium alginate or a starch derivative may be used in combination with gelatin.

Examples of the graft polymer of gelatin and other polymers include gelatin and acrylic acid, methacrylic acid,
Those obtained by grafting derivatives thereof such as esters and amides, and homopolymers or copolymers of vinyl monomers such as acrylonitrile and styrene can be used. In particular, a graft polymer of a polymer having a certain compatibility with gelatin, for example, a polymer such as acrylic acid, acrylamide, methacrylamide, hydroxyalkyl methacrylate or the like is preferable. Examples of these are described in US Pat. Nos. 2,763,625, 2,831,767, 2,956,884, and the like.

The latex used in the present invention may be added to any other layer (a plurality of non-photosensitive hydrophilic colloid layers and / or other non-photosensitive hydrophilic colloid layers) as long as it is added to at least one hydrophilic colloid layer containing the dye of the present invention. Alternatively, it may be added in the photosensitive hydrophilic colloid layer). It may be contained on only one side of the support, or may be contained on both sides.

A conventionally known latex may be added to the layer to which the latex of the present invention is added and / or not added. When contained on both sides of the support, the type and / or amount of the polymer latex contained on each side may be the same or different.

Examples of the polymer component of the latex contained in the light-sensitive material of the present invention include, for example, US Pat.
72,166, 3,325,286, 3,41
No. 1,911, No. 3,311,912, No. 3,52
5,620, Research Disclosure (RD)
No. There are hydrates of vinyl polymers such as acrylic acid ester, methacrylic acid ester and styrene as described in 19551 and the like. Specifically, acrylic acid, methacrylic acid or salt, maleic acid or salt, fumaric acid or salt, acrylic acid alkyl ester such as methyl acrylate and ethyl acrylate, methacrylic acid alkyl ester such as methyl methacrylate and ethyl methacrylate, styrene and styrene sulfone. Any compound having a double bond such as an acid or a salt, N-substituted or unsubstituted acrylamide, vinyl alcohols, hydroxyalkyl methacrylates, butadiene and the like can be selected as a homopolymer or a copolymerization component.

Specific examples of preferable monomers are given below. As the latex of the present invention, any combination (type, composition ratio) of these monomers can be adopted. Of course, the invention is not limited to these monomers.

[0049]

[Chemical 10]

[0050]

[Chemical 11]

[0051]

[Chemical 12]

The silver halide used in the light-sensitive material of the present invention can be various silver halides without any particular limitation. The average grain size of the silver halide grains is from 0.05 to
The range of 0.5 μm is preferable, but 0.06 is particularly preferable.
It is preferably about 0.40 μm. The grain size distribution of the silver halide grains is arbitrary, but the monodispersity value defined below is preferably from 1 to 30, and more preferably from 5 to 2.
It is in the range of 0. Here, the monodispersity is defined as a value obtained by multiplying the value obtained by dividing the standard deviation of the particle diameter by the average particle diameter by 100, and multiplying the value by 100. The grain size of the silver halide grains is
For convenience, cubic grains are represented by edge lengths, and other grains (octahedral, tetradecahedral, etc.) are calculated by the square root of the projected area.

When the present invention is carried out, for example, the silver halide grains may be of a single layer type or of a type having a multi-layered laminated structure of at least two layers. Further, the silver halide can be sensitized with various chemical sensitizers. The silver halide grain used in the present invention can be applied to a grain having a surface sensitivity higher than that of the internal sensitivity, that is, a silver halide grain giving a so-called negative image. Therefore, the performance is improved by treating with the above chemical sensitizer. be able to.

The silver halide emulsion used in the present invention includes mercaptos (1-phenyl-5-mercaptotetrazole, 2-mercaptobenzthiazole) and benzotriazoles (5-bromobenzotriazole-5-).
Methylbenzotriazole), benzimidazoles (6-nitrobenzimidazole), indazoles (5-nitroindazole) and the like can be used for stabilization or fog suppression.

The photosensitive silver halide emulsion layer or its adjacent layer is provided with Research Disclosure (Research) for the purpose of increasing sensitivity, increasing contrast or promoting development.
Disclosure) No. 17463 XXI term B
~ The compounds described in the section D can be added. A sensitizing dye, a plasticizer, an antistatic agent, a surfactant, a hardener and the like can be added to the silver halide emulsion.
Examples of the support that can be used in the practice of the present invention include cellulose acetate, cellulose nitrate, and polyester films such as polyethylene terephthalate. These supports are appropriately selected depending on the intended use of the silver halide photographic light-sensitive material.

Next, the processing method of the silver halide photographic light-sensitive material of the present invention will be described. The main processing steps adopted in such a processing method are composed by appropriately combining development, fixing, washing, stabilizing, etc., for example, development → fixing → washing, developing → fixing → stable, developing → fixing → washing → stable. Etc.

In the present invention, the total processing time of developing, fixing, washing with water, stabilizing and drying is preferably less than 60 seconds, more preferably within 45 seconds. In this case, the film includes the transfer time from the developing solution to the fixing solution and from the fixing solution to the washing solution (stabilizing solution).

[0058]

EXAMPLES Examples will be given below, but the embodiments of the present invention are not limited thereto. JP-A-59-19
No. 941 silver halide emulsion layer on one side of the undercoated polyethylene terephthalate film described in Example (1),
The protective layer was applied, and the backing layer / protective layer was applied to the other side.

(Gelatin-stabilized latex synthesis method) Water 4
To 0 liter of 0.125 kg of gelatin and 0.05 kg of ammonium persulfate was added 7.5 g of sodium dodecylbenzenesulfonate, and the mixture of the following monomers ( Any one of (a) to (e) was added at a rate such that the finished average particle size was 0.10 μm, the mixture was stirred for another 3 hours, and then 0.005 kg of ammonium persulfate was added to obtain 1.
Stir for 5 hours. After completion of the reaction, the residual monomer was further removed by steam distillation for 1 hour, then cooled to room temperature, and the pH was adjusted to 6.0 with aqueous ammonia. The obtained latex liquid was adjusted to 75.0 kg with water. Lx- (a) to Lx- (e) were obtained as described above. <Monomer mixture> (a) Butyl acrylate 4.51 kg Styrene 5.49 kg Acrylic acid 0.10 kg (b) Ethyl acrylate 3.52 kg Methyl methacrylate (two-component system) 5.10 kg (c) Ethyl acrylate 3.52 kg Methyl methacrylate 4.90 kg Ethylene glycol 0.20 kg (d) Ethyl acrylate 3.52 kg Methyl methacrylate 4.90 kg Styrene 0.10 kg (e) Ethyl acrylate 3.00 kg Methyl methacrylate 4.00 kg Styrene 3.00 kg 2-Acrylamido-2-methylpropane Sulfonic acid 0.80kg

(Comparative Latex Synthetic Method) In the above-mentioned gelatin-stabilized latex synthetic method, except that 0.25 kg of Meito Sangyo KMDS (dextran sulfate ester sodium salt) was added in place of gelatin to the system before polymerization, except that Comparative latex Lx-R was synthesized in the same manner as the above latex synthesis method. The monomer mixture is (e)
Was used.

(Formulation of Silver Halide Emulsion Layer) [Preparation Method of Emulsion (A)] A silver chlorobromide emulsion was prepared using the following solutions A, B and C. <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 .4 g Rhodium trichloride trihydrate 28 μg Polyisopropyleneoxy disuccinate sodium salt 10% ethanol solution 3 ml Ocein gelatin 11 g Distilled water 407 ml Sodium chloride so that the EAg value becomes 160 mV after keeping solution A at 40 ° C. Was added.

Next, as disclosed in JP-A-57-92523 and 57-
Solution B and solution C were added by the double jet method using the mixing stirrer described in No. 92524. As shown below, the addition flow rate was such that the addition flow rate was gradually increased and the EAg value was kept constant over the entire addition time of 80 minutes. EAg value was added from 160 mV, and after 5 minutes, 3
The EAg value was controlled using a ml / l sodium chloride aqueous solution.

Addition time Solution B Solution C (min) (ml / min) (ml / min) 0 1.13 1.11 10 1.13 1.11 20 2.03 1.99 30 3.17 3.11 40 4.57 4.48 50 6.22 6.10 60 8.13 7.97 70 10.29 10.01 80 12.74 12.49

For the measurement of the EAg value, a metallic silver electrode and a double junction type saturated Ag / AgCl reference electrode were used (the double junction disclosed in JP-A-57-197534 was used as the electrode structure). ). In addition, a variable flow rate roller tube metering pump was used to add solutions B and C. 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. After the addition of 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), the following compound [A] [ B] 1% aqueous solution of the mixture of [C] 15
ml was added and dispersed by stirring at 55 ° C. for 30 minutes, and then adjusted to 750 ml.

After the emulsion (A) was sensitized with gold and sulfur, potassium bromide was added in an amount of 500 m per mol of silver halide.
g, and then sensitizing dye A was added at 300 mg per mol of silver halide contained in the emulsion, and after stagnant for 10 minutes, 4-hydroxy-6-methyl-1, as a stabilizer,
3,3a, 7-Tetrazaindene was added, and Sensitizing Dye B was added in an amount of 100 mg per mol of silver halide contained in the emulsion.

[0066]

[Chemical 13]

Then, to this emulsion, 30 mg of tetrazolium compound T was added per mol of silver halide, and p-
Sodium dodecyl benzene sulfonate 300mg, styrene - maleic acid copolymer 2g, the latex of the present invention in addition amounts shown in Table 1, Ag4.0g / m ^2, so that the amount of gelatin 1.8 g / m ^2, the emulsion A coating liquid was prepared.

[0068]

[Chemical 14]

(Emulsion protective layer formulation) Gelatin amount 0.7 g /
bis spreading agent such that m ² (2-ethylhexyl) sulfosuccinate 10 mg / m ^2, added in an amount shown following compound [D] 100 mg / m ^2, the latex and the dye of the present invention of the present invention in Table 1 Then, formalin 15 mg / m ² and glyoxal 8 mg / m ² were added as a hardener to prepare an emulsion protective layer coating solution.

[0070]

[Chemical 15]

[0071]

[Chemical 16]

Gelatin 2.5 g / m ² Surfactant: Saponin 0.1 g / m ² Latex of the present invention Amount shown in Table 1 Dye of the present invention Amount shown in Table 1 Hardener: Glyoxal 0.01 g / m ² Sodium dodecylbenzenesulfonate 0.01 g / m ^{2 A} coating solution for the backing layer was prepared using the above-mentioned additive materials. (Backing protective layer formulation) Gelatin 1.0 g / m ² Matting agent: Polymethylmethacrylate having an average particle diameter of 3.0 to 5.0 μm 50 mg / m ²

[0073]

[Chemical 17]

Latex of the present invention Amount shown in Table 1 Dye of the present invention Amount shown in Table 1 Hardener: Glyoxal 25 mg / m ^{2 A} coating solution for a backing protective layer was prepared by using the additive materials shown above. The obtained sample was evaluated by the following method,
The results are shown in Table 1.

(Evaluation Method) <Evaluation of Sensitivity and Fog> The obtained sample was exposed to 3200K tungsten light for 5 seconds with a step wedge in close contact with the sample and treated with the following processing solution to measure sensitivity and fog.

The sensitivity was measured by measuring the density of the obtained sample with an optical densitometer Konica PDA-65, and measuring the sample N before thermoprocessing.
o. The sensitivity was shown as relative sensitivity with the sensitivity at a concentration of 2.5 of 1 being 100.

<Evaluation of stretched image quality> (1) Preparation of manuscript Using a scanner SG808 (II) manufactured by Dainippon Screen Co., Ltd. and a dedicated photosensitive material RSDII manufactured by Konica Corporation, the transmission image and halftone percentage of a person consisting of halftone dots are graded. Created a step wedge that was changed. The screen ruling at this time is 1
Performed at 50 lines / inch. (2) Photographing The above document was set on a Fine Zoom C-880F manufactured by Dainippon Screen Co., Ltd. so that the stretching magnification was 120% and exposed.

At this time, exposure was performed so that 95% of the step wedge of the original became 5%, and the processing was performed with the following processing solution. (3) From the sample obtained by adjusting the exposure amount, which has good halftone dot reproducibility (hardness of halftone dots) in the shard area of the sample in which the halftone dot% on the small dot side (highlight portion) is combined 10 in order
A graded evaluation (10 to 1) was performed.

<Evaluation of Residual Color> After the unexposed film was subjected to the following automatic development processing, a sample in which 5 sheets were stacked was visually evaluated in 10 steps. 5 or more: Usable level (10: best) 1 to 4: Unusable <Thermo treatment> Thermo treatment was performed at 23 ° C. for 4 hours at an unexposed sample.
After adjusting the humidity at 8% RH for 2 hours, put it in a moisture-proof bag and keep it at 50 ° C.
Heat was applied for 3 days to prepare a sample for historical use. For this, the same evaluation as before the thermotreatment was performed.

The sample was processed using a developing solution and a fixing solution having the following formulations. <Development processing conditions> (Process) (Temperature) (Time) (Tank capacity) Development 28 ° C 30 seconds 201 Fixing 28 ° C 30 seconds 201 Washing 18 ° C 20 seconds 151 Drying 40 ° C 20 seconds Each step is a so-called transition to the next step Including transportation time. D
The ry 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 30 mg Silver potassium bromide 4.5 g Potassium hydroxide Amount to bring the pH of the working solution to 10.4

(Composition B) Pure water (ion exchanged water) 3 ml Diethylene glycol 50 g Ethylenediaminetetraacetic acid disodium salt 25 mg Acetic acid (90% aqueous solution) 0.3 ml 5-Nitroindazole 110 mg 1-Phenyl-3-pyrazolidone 700 mg Use of developer Sometimes the above composition A and composition B in 500 ml of water
Were melted in this order and finished to 1 liter before use.

<Fixer Formulation> (Composition A) Ammonium thiosulfate (72.5% w / v aqueous solution) 240 ml Sodium sulfite 17 g Sodium acetate trihydrate 6.5 g Boric acid 6 g Sodium citrate dihydrate 2 g Acetic acid (90 % W / v aqueous solution) 13.6 ml (Composition B) Pure water (ion exchanged water) 17 ml Sulfuric acid (50% w / v aqueous solution) 4.7 g Aluminum sulphate (Al ₂ O ₂ conversion content is 8.1% w
/ V aqueous solution) 26.5 g Water 500 ml when using fixer
The above composition A and composition B were dissolved in this order and finished to 11 for use. The pH of this fixer was about 4.3. The evaluation results are shown in Table 1.

[0084]

[Table 1] Note: All addition amounts in the table are shown in mg / m ² .

[0085]

As is apparent from Table 1, according to the present invention, the residual color property is good, the image quality is high (extension suitability is excellent), the rapid processing property is excellent, and the photographic performance with the passage of time. It is possible to provide a light-sensitive material with less deterioration in sensitivity (fog in particular).

Claims (1)

[Claims] 1. A structure represented by the following general formulas [I] to [VII] on a support.
A silver halide photographic light-sensitive material having at least one layer containing a dye selected from compounds represented by the formula (1), and the layer containing a latex stabilized with gelatin. [Chemical 1] (In the formula, A and A ′ may be the same or different, each represents an acidic nucleus, B represents a basic nucleus, X and Y may be the same or different, and each represents an electron-withdrawing group. . R
Represents a hydrogen atom or an alkyl group, R ₁ and R ₂ each represent an alkyl group, an aryl group, an acyl group or a sulfonyl group, and R ₁ and R ₂ may be linked to form a 5- or 6-membered ring. Good. R ₃ and R ₆ are each a hydrogen atom, a hydroxy group,
It represents a carboxyl group, an alkyl group, an alkoxy group or a halogen atom, and R ₄ and R ₅ are each a hydrogen atom or necessary for R ₁ and R ₄ or R ₂ and R _{5 to} be linked to each other to form a 5- or 6-membered ring. Represents a non-metallic atomic group. L ₁ , L ₂ and L
Each ₃ represents a methine group. m represents 0 or 1, n and q each represent 0, 1 or 2, p represents 0 or 1, p
When is 0, R ₃ represents a hydroxy group or a carboxyl group, and R ₄ and R ₅ represent hydrogen atoms. B'represents a heterocyclic group having a carboxyl group, a sulfamoyl group, or a sulfonamide group. Q represents a hetero ring group. However, the compounds represented by the general formulas [I] to [VII] are 1
The molecule has at least one dissociative group having a pKa in the range of 4 to 11 in a mixed solution of water and ethanol in a volume ratio of 1: 1. )