JP3451500B2 - Silver halide photographic light-sensitive material and processing method thereof - Google Patents

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 dye, and more specifically, a novel silver halide photographic light-sensitive material which has less adverse effects such as fog and desensitization and is decolorized during rapid processing and has excellent residual color. The present invention relates to a silver halide photographic light-sensitive material containing a diffusion resistant dye.

[0002]

2. Description of the Related Art Conventionally, silver halide photographic light-sensitive materials (hereinafter abbreviated as photographic light-sensitive materials) have a specific wavelength for the purpose of light absorption filter, antihalation, irradiation prevention or sensitivity adjustment of photosensitive emulsion. It is well known to incorporate a dye into a constituent layer of a photographic light-sensitive material in order to absorb the light, and dyeing a hydrophilic colloid layer with the dye has been performed.

Of the constituent layers of the photographic light-sensitive material described above, the filter layer is usually located above the light-sensitive emulsion layer or between the emulsion layer and another emulsion layer and controls incident light reaching the emulsion layer. It plays a role of changing to a preferable spectral composition. The antihalation layer is provided between the light-sensitive 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 harmful to the interface between the emulsion layer and the support or the back surface of the support. The reflected light is absorbed to improve the sharpness of the image. Further, it is also performed to improve the sharpness of the image by coloring the photosensitive emulsion layer with a dye to absorb harmful reflected light or scattered light to the silver halide grains to prevent irradiation. There is.

Recently, dyes for the purpose of substituting yellow colloidal silver in color photographic light-sensitive materials, dyeing dyes in crossover cut layers in X-ray photographic light-sensitive materials, and non-light-sensitive emulsion layers in printed photographic light-sensitive materials. Its applications such as dyes are expanding.

The dye used for such purpose has not only good absorption spectrum characteristics depending on the purpose of use but also is completely decolorized during development processing and easily eluted from the photographic light-sensitive material. , No residual color contamination by dye after processing, no adverse effect such as fog or desensitization on photosensitive emulsion, no diffusion from colored layer to other layers, in photographic light-sensitive material or coating solution In the above, it must satisfy various conditions such as excellent stability over time and no discoloration or fading.

To date, many studies have been carried out with the aim of finding dyes satisfying the above-mentioned conditions.
For example, U.S. Patents 3,540,887, 3,544,325 and 3,560,
No. 214, Japanese Patent Publication No. 31-10578 and Japanese Patent Publication No. 51-3623 disclose benzylidene dyes, and British Patent No. 506,385 and Japanese Patent Publication No.
Oxonol dyes in US Pat. No. 2,493,747 in 9-22069
No. 1,845,404, and styryl dyes are proposed in US Pat. No. 1,845,404.

Some of these conventional dyes have a relatively small effect on the emulsion performance and have the ability to be bleached / eluted / bleached in the processing step, but from the viewpoint of diffusion resistance. It was not enough to see. 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 dye from diffusing into another layer, the dye itself is made diffusion resistant, for example, US Pat. No. 2,538,008.
No. 2,539,009, 4,420,555, JP-A-61-204630
Nos. 62-32460 and 63-184749 are disclosed. Each of these dyes has a drawback that the decolorizing property and the solubility in a processing liquid are inferior, resulting in residual color contamination. Also, a dissociative dye is fixed using a mordant,
As a method for making the material resistant to diffusion, for example, US Pat.
Nos. 3,625,694 and 4,124,386 are disclosed. However, the method using a mordant is a binder in the photographic light-sensitive material constituting layer, for example, gelatin, which forms an aggregate with the mordant or increases the viscosity, which causes serious problems such as uneven coating and cissing. In addition, there are drawbacks such as inconvenience, diffusion resistance between layers is not sufficient, elution and decoloring properties during treatment are poor, a treatment bath having a high pH is required, and rapid treatment suitability is poor.

Further, as a means for preventing the diffusion of the dye, there is a method of dyeing a specific layer by using a solid fine particle dispersion of a dye which is water-insoluble and easily dissolved in a solution having a high pH, for example, US Pat. No. 4,855,221, No. 4,857,446, No. 4,948,717
No. 52-92716, No. 55-155350, No. 55-155351
No. 56-12639, No. 63-197943, JP-A-2-110453
No. 2, No. 2-1838, No. 2-1839, No. 2-119942, No. 2-2642
No. 47, No. 2-264936, No. 2-277044, No. 4-37841, and World Patent 88/04794 are disclosed. However, the method, although the effect as a means of diffusion resistance of the dye is seen, there is a drawback that a dye having a desired absorption spectrum is difficult to obtain, decolorization in rapid processing can not be said to be sufficient, There was still a problem of residual color contamination. Therefore, even in rapid processing, there is a strong demand for a diffusion resistant dye that has good decolorizing properties and does not cause residual color contamination after processing.

[0010]

SUMMARY OF THE INVENTION It is therefore an object of the present invention to meet the above requirements for diffusion resistant dyes,
It is an object of the present invention to provide a silver halide photographic light-sensitive material having less fog and improved stability over time. Yet another purpose is
It is to provide a silver halide photographic light-sensitive material having high sensitivity and excellent sharpness. Another object of the present invention is to provide a processing method of a silver halide photographic light-sensitive material which gives an image with less residual color contamination by a short-time development processing.

[0011]

The above object of the present invention has been achieved by the following constitution.

1) A silver halide photographic light-sensitive material having at least one non-photosensitive hydrophilic colloid layer containing a solid fine particle dispersion of a dye represented by the following general formula (1) on a support. material.

[0013]

[Chemical 2]

(Where D is the following general formula (I) to (V)
I) represents a photographic dye, X ₁ , X ₂ , X ₃ and X ₄ represent an alkylene group, R ₁ and R ₂ represent a hydrogen atom or a monovalent organic group, and p ₁ , p ₂ , P ₃ and p ₄ each represent an integer of 0, 1, 2 and 3. However, p ₁ +
p ₂ and p ₃ + p ₄ are integers of 1 or more. )

[Chemical B]

(In the formula, A ₁ and A ₂ may be the same or different,
Each represents an acidic nucleus, and B ₁ and B ₂ are the same or different
And each represents a basic nucleus, and Q ₁ is a heterocycle.
Represents a group, Y ₁ and Y ₂ may be the same or different.
Each represent an electron-withdrawing group, L ₁ , L ₂ and L ₃
Represents a methine group. n ₁ represents 0 or 1, n ₂ represents 0,
Represents 1 or 2, n ₃ represents 1, 2 or 3, n ₄ is
Represents 0, 1, 2 or 3. However, in A ₁ of the general formula (I) ,
The acid nuclei represented are 5-pyrazolone and barbitu.
Acid, thiobarbituric acid, rhodanine, hydantoy
, Thiohydantoin, oxazolone, isoxazolo
Indanedione, pyrazolidinedione, oxazoli
Gindione, hydroxypyridone, pyrazolopyridone
Represent ) 2) the dyes of the general formula (1) is characterized in that it is a dye having at least one carboxyl group in the molecule 1
The described silver halide photographic light-sensitive material.

3) The nitrogen atom of the general formula (1) is a divalent group selected from a carbonyl group, a sulfonyl group, an amide group, an alkylene group and a phenylene group directly on the heterocycle in the photographic dye represented by D. 3. The silver halide photographic light-sensitive material as described in 2 above, which is a dye bonded through a linking group.

4) The coating amount of the hydrophilic colloid of the non-hydrophilic colloid layer containing the solid fine particle dispersion of the dye is 0.2 g / m.
^The silver halide photographic light-sensitive material as described in 1, 2, or 3 above, wherein the content is ^{2 to} 1.4 g / m ² .

5) The non-photosensitive hydrophilic colloid layer containing the solid fine particle dispersion of the dye of the general formula (1) is an intermediate layer, a protective layer, a filter layer, an antihalation layer or a backing layer. 4. The silver halide photographic light-sensitive material as described in 1, 2 or 3 above.

6) The above-mentioned 1, wherein the average particle size of the solid fine particle dispersion is 0.01 μm to 0.5 μm,
2. The silver halide photographic light-sensitive material as described in 2 or 3.

7) A development processing method characterized in that the silver halide photographic light-sensitive material described in 1 above is processed for a development processing time of 90 seconds or less.

8) A development processing method characterized in that the silver halide photographic light-sensitive material described in 1 above is processed for a development processing time of 45 seconds or less.

9) A development processing method characterized in that the silver halide photographic light-sensitive material described in 1 above is processed for a development processing time of 30 seconds or less.

The present invention will be described in more detail below.

Examples of the photographic dye represented by D of the general formula (1) include oxonol dye, allylidene dye, merocyanine dye, cyanine dye, hemicyanine dye, hemioxonol dye, azo dye, azomethine dye, indophenol dye. , Triphenylmethane dyes, anthraquinone dyes, etc.
The dyes represented by (I) to (VI) are preferred.

[0024]

[Chemical 3]

(In the formula, A ₁ and A ₂ may be the same or different and each represents an acidic nucleus, B ₁ and B ₂ may be the same or different and each represents a basic nucleus,
Q ₁ is represents a double heterocyclic group, Y ₁ and Y ₂ may be the same or different, each represents an electron withdrawing group, L _1, L ₂
And L ₃ represents a methine group. n ₁ represents 0 or 1,
n ₂ represents 0, 1 or 2, n ₃ represents 1, 2 or 3 and n ₄ represents 0, 1, 2 or 3. ) Formula (I),
Examples of the acidic nuclei represented by A ₁ and A ₂ in (II) and (III) include 5 -pyrazolone, barbituric acid, thiobarbituric acid, rhodanine, hydantoin, thiohydantoin,
Examples thereof include oxazolone, isoxazolone, indandione, pyrazolidinedione, oxazolidinedione, hydroxypyridone and pyrazolopyridone.

The basic nucleus represented by B ₁ and B ₂ in the general formulas (III), (V) and (VI) is preferably pyridine, quinoline, oxazole, benzoxazole, naphthoxazole, thiazole, benzthiazole. , Naphthothiazole, pyrrole, indole, indolenine, imidazole, benzimidazole and the like.

Examples of the aryl group represented by Q ₁ in the general formulas (I) and (IV) include a phenyl group, a naphthyl group and a julolidyl group. In addition, general formula (I) and
Examples of the heterocyclic group represented by Q ₁ in (IV) include a pyridyl group, a quinolyl group, an isoquinolyl group, a pyrrolyl group, a pyrazolyl group, an imidazolyl group, an indolyl group, a furyl group,
Examples thereof include a thienyl group, a thiazolyl group and an oxazolyl group. The aryl group and the heterocyclic group include those having a substituent, and examples of the substituent include an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a halogen atom, an alkoxycarbonyl group, an aryloxycarbonyl group, and a carboxy group. Group, cyano group, hydroxy group, mercapto group, amino group, alkoxy group, aryloxy group,
Examples thereof include an acyl group, a carbamoyl group, an acylamino group, a ureido group, a sulfonamide group, and a sulfamoyl group, and these substituents may have two or more kinds in combination.
Preferred substituents are alkyl groups having 1 to 8 carbon atoms (for example, methyl group, ethyl group, t-butyl group, n-octyl group, 2-hydroxyethyl group, 2-methoxyethyl group, etc.),
Hydroxy group, cyano group, halogen atom (eg fluorine atom, chlorine atom, etc.), alkoxy group having 1 to 6 carbon atoms (eg methoxy group, ethoxy group, 2-hydroxyethoxy group, methylenedioxy group, n-butoxy group, etc.) ), A substituted amino group (eg, dimethylamino group, diethylamino group, di (n-butyl) amino group, N-ethyl-N-hydroxyethylamino group, N-ethyl-N-methanesulfonamidoethylamino 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.) ,
You may combine these substituents.

The electron withdrawing groups represented by Y ₁ and Y ₂ in the general formulas (IV) and (V) may be the same or different,
Substituent constant Hammett's σp value (edited by Toshio Fujita, “Special Issue on Chemistry, No. 122, Structure-Activity Relationship of Drugs”, 96-103 (1979)
It is listed in Nankodo and other places. ) Is preferably a group of 0.3 or more, for example, a cyano group, an alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group, octyloxycarbonyl group, etc.),
Aryloxycarbonyl group (eg, phenoxycarbonyl group, 4-hydroxyphenoxycarbonyl group), carbamoyl group (eg, carbamoyl group, methylcarbamoyl group, ethylcarbamoyl group, butylcarbamoyl noble,
Dimethylcarbamoyl group, phenylcarbamoyl group, 4-
Carboxyphenylcarbamoyl group etc.), acyl group (eg methylcarbonyl group, ethylcarbonyl group, butylcarbonyl group, phenylcarbonyl group, 4-ethylsulfonamidophenylcarbonyl group etc.), alkylsulfonyl group (eg methylsulfonyl group, ethylsulfonyl group) , Butylsulfonyl group, octylsulfonyl group, etc.),
Arylsulfonyl group (for example, phenylsulfonyl group,
4-chlorosulfonyl group and the like).

L ₁ , L ₂ and L _{3 of the} general formulas (I) to (VI)
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, a methyl group, an ethyl group, a hexyl group, etc.), an aryl group (for example, a phenyl group). , Tolyl group, 4-hydroxyphenyl group etc.), aralkyl group (eg benzyl group, phenethyl group etc.), heterocyclic group (eg pyridyl group, furyl group, thienyl group etc.), substituted amino group (eg dimethylamino group,
Diethylamino group, anilino group, etc.), alkylthio group (eg, methylthio group, etc.), alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, 2-
Hydroxyethoxycarbonyl group and the like) carbamoyl group (for example, carbamoyl group, methylcarbamoyl group, ethylcarbamoyl group, 2-hydroxyethylcarbamoyl group, dimethylcarbamoyl group, 4-carboxyphenylcarbamoyl group and the like).

The alkylene group represented by X ₁ , X ₂ , X ₃ and X ₄ in the general formula (1) is preferably a group having 1 to 10 carbon atoms, more preferably a group having 1 to 6 carbon atoms. Is. Specific examples thereof include a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group and the like. These alkylene groups may have a substituent, for example, a compound represented by the general formula
There are the groups mentioned as the substituents of the methine group represented by L ₁ , L ₂ and L ₃ in (I) to (VI).

The monovalent organic group represented by R ₁ and R ₂ in the general formula (1) is, for example, an alkyl group having 1 to 6 carbon atoms (for example, methyl group, ethyl group, propyl group, isopropyl group, Butyl group, hexyl group, isoamyl group, etc.),
Examples thereof include an aryl group (eg, phenyl group), an acyl group (eg, acetyl group, ethylcarbonyl group, isopropylcarbonyl group, benzoyl group, etc.), and an alkylsulfonyl group (eg, methylsulfonyl group, ethylsulphonyl group, butylsulfonyl group, etc.).

The dye according to the present invention is preferably a dye having at least one carboxy group in the molecule of the general formula (1), and more preferably at least one carboxy group in the molecule of the general formula (1). Having a nitrogen atom directly on the heterocycle in the photographic dye represented by D or a carbonyl group, a sulfonyl group, an amide group, an alkylene group (for example, a methylene group, an ethylene group, a propylene group, a butylene group, etc.) And a dye bonded through a divalent linking group selected from a phenylene group. The heterocycle also includes a benzo-condensed ring, for example, pyrrole, indole,
Examples include indolenine, imidazole, benzimidazole, pyrazole, furan, thiophene, thiazole, benzthiazole, oxazole, benzoxazole, 5-pyrazolone, isoxazolone, pyridinedione, pyridine, quinoline and the like.

Specific examples of the dye of the present invention are shown below.

[0034]

[Chemical 4]

[0035]

[Chemical 5]

[0036]

[Chemical 6]

[0037]

[Chemical 7]

[0038]

[Chemical 8]

[0039]

[Chemical 9]

[0040]

[Chemical 10]

[0041]

[Chemical 11]

[0042]

[Chemical 12]

[0043]

[Chemical 13]

[0044]

[Chemical 14]

[0045]

[Chemical 15]

The dyes used in the present invention are, for example, those described in JP-A-
52-92716, 55-120030, 55-155350, 55-155
No. 351, No. 56-12639, No. 63-197943, JP-A-2-1838
No. 2-1839, World Patent 88/04794, US Patent 4,8
It can be produced by utilizing the synthetic method described in 61,700, 4,950,586, European Patent 489,973 and the like. A specific synthesis example is shown below.

Synthesis Example 1 (Exemplary Dye I-10) (1) 200 g of furfural and 280 g of barium carbonate are added to 600 ml of dimethylformamide, stirred and cooled to 5 ° C.
140 ml of bromine was added to this suspension so that the internal temperature was maintained at 20-25 ° C.
Is added dropwise and stirred for 1 hour after the addition. The reaction solution is ice water
Pour into 1200 ml and stir, then from this aqueous layer 500 ml of ethyl acetate
Extract 3 times with. The ethyl acetate layer is washed 3 times with 10% aqueous sodium thiosulfate solution, 10% aqueous sodium carbonate solution and brine, and dried over magnesium sulfate. After adding activated carbon and filtering, ethyl acetate is distilled off. The obtained crude crystals are recrystallized from a mixed solvent of ethanol: water = 3: 2 to obtain 68.0 g of 5-bromofurfural.

(2) Bis (2-methoxyethyl) amine (58.6 g) was added to ethanol (60 ml), and 5-bromofurfural (35.0 g) was added under water cooling and the mixture was stirred for 1 hour. Start heating, 50-5
React at 5 ° C for 5 hours. After cooling the reaction mixture to below 5 ℃,
70 g of 0% aqueous sodium hydroxide solution is added dropwise and reacted for 2 hours. Ethyl acetate (300 ml) was added to the organic layer which was left standing and separated into two layers, washed with water and dried, and then ethyl acetate and bis (2-methoxyethyl) amine were distilled off to give 5-bis (2-
39.6 g of methoxyethyl) aminofurfural are obtained.

(3) 11.5 g of 1- (4-carboxyphenyl) -3-cyano-5-pyrazolone was added to 172 ml of methanol to give about 50
Dissolve by heating at ℃. The insoluble matter was filtered off, cooled to room temperature, and then 5-
11.4 g of bis (2-methoxyethyl) aminofurfural was added, and the mixture was reacted with heating under reflux for 5 hours. After cooling with water and allowing to stand overnight, the precipitate is collected by filtration and thoroughly washed with methanol. The crude crystals were put in 120 ml of methanol and suspended and stirred for 2 hours, then the crystals were collected by filtration, washed with methanol and dried to obtain 12.5 g of dye (I-10). The structure of the compound was confirmed by NMR, IR and MASS spectra.

A method for producing a solid fine particle dispersion of a dye according to the present invention is described in JP-A Nos. 52-92716 and 55-15535.
No. 0, 55-155351, 63-197943, 3-182743,
The method described in WO88 / 04794 or the like can be used. Specifically, it can be prepared by using a surfactant and using a fine disperser such as a ball mill, a vibration mill, a planetary mill, a sand mill, a roller mill, a jet mill or a disc impeller mill. Further, after dissolving the dye in a weak alkaline aqueous solution, a method of precipitating fine particulate solids by lowering the pH to weakly acidic or a weak alkaline solution of the dye and an acidic aqueous solution are simultaneously mixed while adjusting the pH. Dispersions of dyes can be obtained by the method of making finely divided solids. The dyes may be used alone or in combination of two or more. Two
When two or more species are mixed and used, they may be dispersed individually and then mixed, or may be simultaneously dispersed.

The dye dispersed in the form of solid fine particles according to the present invention is preferably dispersed so that the average particle diameter is 0.01 μm to 5 μm, more preferably 0.01 μm to 1 μm, and particularly preferably 0.01 μm. ~ 0.5 μm. Also,
The coefficient of variation of particle size distribution is preferably 50% or less, more preferably 40% or less, and particularly preferably 30% or less. Here, the variation coefficient of the particle size distribution is a value represented by the following formula.

(Standard deviation of particle size) / (average value of particle size) ×
100 A surfactant may be used when producing a solid fine particle dispersion of the dye, and examples of the surfactant include anionic surfactants, nonionic surfactants, cationic surfactants and amphoteric surfactants. Although any of these can be used, preferably, for example, alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, sulfosuccinates, sulfoalkyl polyoxyethene alkylphenyl ethers, N Anionic surfactants such as -acyl-N-alkyl taurines and nonionic surfactants such as saponins, alkylene oxide derivatives, alkyl esters of sugars.

The surfactant may be added at any position before dispersion, during dispersion, or after dispersion, but it is preferably added before the start of dispersion of the dye. Further, if necessary, it may be added to the dye dispersion liquid after the dispersion is completed. These anionic activators and / or nonionic activators may be used alone or in combination of two or more, and both activators may be used in combination. The amount of the anionic activator and / or the nonionic activator used is not uniform depending on the kind of the activator or the conditions of the dispersion liquid of the dye, etc.
It may be 0.1 to 2000 mg per 1 g of dye, preferably 0.5 to 100
It may be 0 mg, more preferably 1 to 500 mg. The concentration of the dye in the dispersion is 0.01 to 10% by weight, preferably 0.1 to 5% by weight.

To the dye dispersion of the present invention, a hydrophilic colloid used as a binder of a photographic constituent layer can be added before the start of dispersion or after the end of dispersion. As the hydrophilic colloid, it is advantageous to use gelatin, but in addition, gelatin derivatives such as phenylcarbamylated gelatin, acylated gelatin and phthalated gelatin, and gelatin and a monomer having a polymerizable ethylene group can be used. Graft polymers, carboxymethyl cellulose, hydroxymethyl cellulose, cellulose derivatives such as cellulose sulfate, polyvinyl alcohol, partially oxidized polyvinyl acetate, polyacrylamide, poly-
Synthetic hydrophilic polymers such as N, N-dimethylacrylamide, poly-N-vinylpyrrolidone and polymethacrylic acid, agar, gum arabic, alginic acid, albumin and casein can be used. You may use these in combination of 2 or more types.

The dispersion of the dye of the present invention is used for a layer constituting a photographic light-sensitive material, for example, a non-photosensitive hydrophilic colloid layer such as an emulsion layer upper layer, an emulsion layer lower layer, a protective layer, a support undercoat layer and a backing layer. be able to. The preferred amount of dye used is
Depending on the type of dye and the characteristics of the photographic light-sensitive material, it is not uniform, but the optical density in the photographic light-sensitive material may vary from 0.05 to 0.05 depending on the purpose.
Used to achieve 3.0, 1m per 1m ^{2 of} photographic light-sensitive material
g-1000 mg, more preferably 3 mg-500 mg,
Particularly preferred is 5 mg to 250 mg.

In the photographic light-sensitive material of the present invention, the solid fine particle dispersion of the dye may be contained in at least one non-photosensitive hydrophilic colloid layer. Gelatin is preferred as the hydrophilic colloid, and its coating amount is preferably
0.01 g / m was ^{2 ~2.0g} / m ^2, more preferably 0.1 g /
m ² was ~1.7g / m ^2, particularly preferably 0.2 g / m ² to 1.4
g / m ² .

The photographic light-sensitive material of the present invention may have at least one light-sensitive silver halide emulsion layer and at least one non-light-sensitive hydrophilic colloid layer on one side of the support, and A photographic light-sensitive material having the emulsion layer and the colloid layer on both sides of the support is also preferably used. Photographic materials include medical X-ray photographic materials, printing plate photographic materials, color negative photographic materials, color reversal photographic materials, color photographic paper photographic materials, direct positive photographic materials, and heat-developable color photographic materials. , Diffusion transfer type color photographic materials and the like.

The gelatin used in the photographic light-sensitive material of the present invention is generally produced from cow bone, cow hide, pig skin, etc. as a raw material. In the process of producing collagen, gelatin treated with lime or the like, and hydrochloric acid, etc. There is acid-processed gelatin accompanied by the treatment with, and any gelatin can be used in the present invention. For details of the manufacturing method and properties of these gelatins, see, for example, “T by Arthur Veis”.
he Macromolecular Chemistry of Gelatin, '' pages 187-217.
(1964) (Academic Press), TH James, The Theory
of the photographic Process '' 4th.ed, p. 55 (1977) (M
acmillan), "Nanikawa and Gelatin" Published by Japan Niwa Gelatin Industry Association (1987), "Basics of Photographic Engineering, Silver Salt Photography" 1
19 to 124 (Corona) and the like. The jelly strength of gelatin (according to the PAGI method) is preferably 250 g or more. The calcium content (according to the PAGI method) of gelatin of the present invention is preferably 4000 ppm or less, particularly preferably 3000 ppm or less.

Gelatin is hardened by a hardener, and the swelling ratio and film strength of the coating film can be adjusted by the amount of hardener in the photographic light-sensitive material. Examples of hardening agents include aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), mucohalogenoic acids (mucochloric acid, mucophenoxycycloric acid, etc.), epoxy compounds, active halogen compounds (2,4-dichloro-6-hydroxy-s). -Triazine etc.), active vinyl derivatives (1,3,5-triacryloylhexahydro-s-triazine, bis (vinylsulfonyl) methyl ether, N, N'-methylenebis (β- (vinylsulfonyl
(Propionamide) etc.) ethyleneimines, carbodiimides, methanesulfonic acid esters, organic hardeners such as isoxazoles, inorganic hardeners such as chromium alum, U.S. Patents 3,057,723, 3,396,029, 4,161,407 Polymer hardeners and the like described in No. etc. can be used,
Used alone or in combination. In the photographic light-sensitive material of the present invention, the swelling ratio of the coating film during development processing is preferably 150 to 250%, and the film thickness after expansion is preferably 70 μm or less. The swelling rate means the difference between the film thickness after swelling in each processing solution and the film thickness before the development processing, and this is divided by the film thickness before processing and multiplied by 100, and the swelling rate is 250. If it exceeds%, poor drying occurs, and if the swelling ratio is less than 150%, uneven development and residual color tend to deteriorate during development.

The halide emulsion used in the photographic light-sensitive material of the present invention includes silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide,
Although any of silver chloroiodobromide, silver chloride and the like can be used, silver bromide, silver iodobromide, silver chlorobromide and silver chloroiodobromide are particularly preferable.

The silver halide grains in the photographic emulsion are all isotropically grown crystal type such as cube, octahedron, and tetrahedron, or polyhedral crystal type such as sphere, and plane defects. It may be of a twin crystal having, or a mixed type or a composite type thereof. The grain size of these silver halide grains may be from fine grains of 0.1 μm or less to large grains of 15 μm.

The emulsion used in the photographic light-sensitive material of the present invention can be produced by a known method. See, for example, Research Disclosure (RD) No. 17643 (December 1978), pp. 22-23, 1; Emulsion Preparation and Types and No. 18716 (November, 1979), p. 648. Can be prepared by any method. See also “The theory o” by TH James
fthe photographic process ”4th edition, published by Macmillan (1
977) 38-104, GF Daufin, "Photographic Emulsion Chemistry", Focal
Published by Press (1966), P. Glafkides "Physics and Chemistry of Photography""Chimie et Physique Photographique", Paul Mo
VL Zelikman et al., “Making and Coating Photographic Emulsi,” published by ntel (1967).
on ”, published by Focal Press (1964), etc., ie, forward mixing method, back mixing method, double jet method, control under solution conditions such as neutral method, acidic method, ammonia method, etc. It can be produced using mixing conditions such as the doubly jet method, conversion methods, particle preparation conditions such as the core / shell method, and combinations thereof.

The silver halide emulsions preferably used in the present invention are, for example, JP-A-59-177535 and 61-802238.
No. 61-132943, No. 63-49751, and the like, high internal iodine type monodisperse particles are disclosed. The crystal habit may be a cube, an octahedron, a tetrahedron, or an intermediate (111) plane and (100) plane mixed arbitrarily. The monodisperse emulsion referred to here is a halogen having at least 95% of the grains by number or weight within ± 40% of the average grain size, preferably within ± 30% when the average grain diameter is measured by a conventional method. It is a silver halide grain. The grain size distribution of the silver halide grains may be either a monodisperse emulsion having a narrow distribution or a polydisperse emulsion having a wide distribution. The definition of monodispersity described here is described in JP-A-60-162244, and the coefficient of variation with respect to particle diameter is 0.2 or less.
The crystal structure of silver halide may be composed of different silver halide compositions inside and outside. For example, a core / shell type monodisperse emulsion having a two-layer structure composed of a high-iodity core portion and a low-iodity shell layer can be mentioned. A method for producing a monodisperse emulsion is well known, for example, JP-A-48-36890 and JP-A-52-1.
No. 6364, No. 55-142329, No. 58-49938,
60-14331, British Patents 1,027,146, 1,413,748,
U.S. Patents 3,505,068, 3,574,628, 3,655,394
No. 4,444,877 and the like.

The silver halide emulsion preferably used in the present invention includes tabular grains having an aspect ratio of 3 or more. The advantages of such tabular grains include improved spectral sensitization efficiency and improved image graininess and sharpness. For example, British Patent 2,112,157 and U.S. Pat.
Issue 4,433,048, Issue 4,414,310, Issue 4,434,226,
JP-A-58-113927, 58-127921, 63-138342,
No. 63-284272, No. 63-305343, etc.,
The emulsion can be produced by the methods described in these publications. The tabular silver halide grains according to the present invention are preferably monodisperse emulsions having a narrow grain size distribution, and the coefficient of variation is preferably 25% or less, more preferably 20% or less, particularly preferably 15%. % Or less. As tabular silver halide grains, at least 80% or more of the total projected area of silver halide grains contained in the emulsion should have an aspect ratio of 3.0 to 12.0 indicated by the (grain size) / (thickness) ratio. Is preferred, and more preferably the aspect ratio is 3.
0 to 8.0. The thickness of tabular silver halide grains is 0.05.
~ 1 μm is preferable, more preferably 0.05 ~
0.5 μm. When the ratio (t / l) of the longest distance (l) between two or more parallel twin planes of a tabular silver halide grain to the thickness (t) of the tabular grain is 5 or more, It is preferable that it is, more preferably 7 or more. The tabular silver halide grain preferably used is a core / shell type grain, for example, a double structure type grain having a silver halide composition in which the inside of the grain is different from the surface, and the multiple grain structure shown in JP-A-61-245151. Structural type particles and the like can be mentioned.

As a silver halide solvent, for example, ammonia, a thioether compound, a thione compound or the like can be used in order to control the growth of grains during the formation of silver halide grains. Also, during physical aging and chemical aging, zinc,
A metal salt such as lead, thallium, iridium or rhodium can coexist.

The above silver halide can be sensitized with a noble metal salt such as a sulfur compound or a gold salt. Further, reduction sensitization can be performed, and these methods can be combined for sensitization. Further, a silver halide spectrally sensitized to a desired wavelength region with a spectral sensitizing dye can be used. Dyes used include cyanine, merocyanine, complex cyanine, complex merocyanine, holopolar cyanine, hemicyanine, styryl dye, and hemioxonol dye, and particularly useful dyes are cyanine,
It is a dye belonging to merocyanine and complex merocyanine dyes.

The photographic light-sensitive material of the present invention can be obtained by coating a polyethylene terephthalate or triacetate cellulose support with an emulsion prepared by dispersing the above silver halide in a hydrophilic colloid medium, for example, gelatin.
For the cross-linking of gelatin, aldehydes such as glyoxal and mucochloric acid, cyanuric acid, aziridine, vinyl sulfones and the like can be used.

The photographic light-sensitive material may contain a hydrazine compound or a tetrazolium compound in the light-sensitive silver halide emulsion layer or a hydrophilic colloid layer adjacent thereto for the purpose of adjusting gradation. The hydrazine compound is a compound having a -N (R) N (R) CO- group (R is an arbitrary substituent) in the molecule, and examples thereof include compounds described in JP-A-3-36540. . A photographic light-sensitive material containing a hydrazine compound should have a developing time of 30 with a developer having a pH of 10.8 or less.
It is developed in less than a second, and the contrast can be 10 or more. Examples of the tetrazolium compound include compounds described in JP-A No. 3-15039.

Various techniques and additives known in the art can be used in the silver halide photographic light-sensitive material of the present invention, if necessary. For example, in addition to the photosensitive silver halide emulsion layer, a protective layer, an intermediate layer, a filter layer, an antihalation layer,
Photographic layers such as a crossover light cut layer and a backing layer can be provided, and in these layers, a supersensitizer, a coupler, a high boiling point solvent, an antifoggant, a stabilizer, a development inhibitor, and a bleaching agent can be provided. Accelerator, fixing accelerator, anti-color mixing agent, formalin scavenger, toning agent, hardener, surfactant,
A thickener, a plasticizer, a slip agent, an ultraviolet absorber, a polymer latex, an antistatic agent, a matting agent and the like can be contained by various methods. As a support that can be used in the silver halide photographic light-sensitive material of the present invention, cellulose triacetate, cellulose nitrate, polyester such as polyethylene terephthalate, polyolefin such as polyethylene, polystyrene, baryta paper, polyethylene laminated paper, etc. Glass, metal, etc. can also be used. The surface of these supports is provided with an undercoat layer to improve the adhesion of the coating layer, or is subjected to an undercoating process such as corona discharge or ultraviolet irradiation as required.

More specifically, the above-mentioned additives are described in Research Disclosure No. 17643 (December 1978).
No. 18716 (November 1979), No. 308119 (December 1989)
Month). The types of compounds shown in these Research Disclosures and their locations are shown below.

Additive RD-17643 RD-18716 RD-308119 Page Classification Page Page Classification Chemical sensitizer 23 III 648 Upper right 996 III Sensitizing dye 23 IV 648-649 996-8 IV Desensitizing dye 23 IV 998 IV B Dye 25 to 26 VII 649 to 650 1003 VIII Development accelerator 29 XXI 648 Upper right fog inhibitor / stabilizer 24 IV 649 Upper right 1006 to 7 VI Whitening agent 24 V 998 V Hardener 26 X 651 Left 1004 to 5 X Surfactant Agent 26-27 XI 650 Right 1005-6 XI Antistatic agent 27 XII 650 Right 1006-7 XIII Plasticizer 27 XII 650 Right 1006 XII Sliding agent 27 XII Matting agent 28 XVI 650 Right 1008-9 XVI Binder 26 XXII 1009 XXII Support Body 28 XVII 1009 XVII The silver halide photographic light-sensitive material of the present invention can be developed by, for example, T.W. H. The Theory of the Photographic Process, 4th Edition by James (The The
ory of the Photographic Process, fourth Edition) 29
Pages 1-334 and the Journal of the American Chemic
al Society) Vol. 73, page 3,100 (1951). As a developing agent,
Specifically, dihydroxybenzenes (eg hydroquinone), 3-pyrazolidones (eg 1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3)
-Pyrazolidone, 5,5-dimethyl-1-phenyl-3-pyrazolidone), aminophenols (eg p-aminophenol, N-methyl-p-aminophenol), ascorbic acid, etc. may be used alone or in combination. it can.
The photographic light-sensitive material according to the present invention can be developed by rapid processing in which the development processing time from development to drying is 90 seconds or less, and can also be processed by rapid processing in which the development processing time is 45 seconds or less. You can Further development processing time
Development processing can be performed even by rapid processing for 30 seconds or less. The treatment temperature is preferably 25 to 50 ° C, more preferably 30 to 40 ° C.

[0072]

EXAMPLES Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.

Example 1 (Preparation of seed emulsion-1) Seed emulsion-1 was prepared as follows.

A1 ossein gelatin 24.2 g water 9657 ml polypropyleneoxy-polyethyleneoxy-disuccinate Na salt (10% ethanol aqueous solution) 6.78 ml potassium bromide 10.8 g 10% nitric acid 114 ml B1 2.5N silver nitrate aqueous solution 2825 ml C1 potassium bromide 824 g iodination Potassium 23.5 g Water to make 2825 ml D1 1.75N potassium bromide aqueous solution Solution A1 solution B1 and solution using the mixing stirrer described in JP-B-58-58288 and 58-58289 at the following silver potential control amount of 35 ° C. 46 of each C1
Nucleation was carried out by adding 4.3 ml by the simultaneous mixing method over 1.5 minutes.

After the addition of the solutions B1 and C1 was stopped, it took 60 minutes to raise the temperature of the solution A1 to 60 ° C., adjust the pH to 5.0 with 3% potassium hydroxide, and then re-solution. 55.4 ml / each of B1 and solution C1 by the simultaneous mixing method
It was added for 42 minutes at a flow rate of min. The silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) during the temperature increase from 35 ° C. to 60 ° C. and the re-simultaneous mixing with the solutions B1 and C1 was +8 mv using the solution D1. And +
Controlled to be 16mv. After the addition was completed, the pH was adjusted to 6 with 3% potassium hydroxide, and the mixture was immediately desalted and washed with water.

In this seed emulsion, 90% or more of the total projected area of silver halide grains is composed of hexagonal tabular grains having a maximum adjacent side ratio of 1.0 to 2.0. The hexagonal tabular grains have an average thickness of 0.06 μm and an average grain size ( It was confirmed by an electron microscope that the circle diameter was 0.59 μm. The variation coefficient of thickness was 40%, and the variation coefficient of the distance between twin planes was 42%.

(Preparation of Emulsion Em-1) A tabular emulsion Em-1 having a core / shell structure was prepared using seed emulsion-1 and the following solution.

A2 ossein gelatin 11.7 g polypropyleneoxy-polyethyleneoxy-disuccinate Na salt (10% ethanol aqueous solution) 1.4 ml seed emulsion-1 0.10 mol equivalent B2 ossein gelatin 5.9 g potassium bromide 6.2 g Potassium bromide 0.8g Water to make 145ml C2 silver nitrate 10.1g Water to make 145ml D2 ossein gelatin 6.1g Potassium bromide 94g Water to make 304ml E2 Silver nitrate 137g Water to make 304ml A2 liquid vigorously stirred at 67 ℃ The solution B2 and the solution C2 were added by the double jet method in 58 minutes. Next, in the same liquid, D2
Solution and E2 solution were added by the double jet method in 48 minutes. During this time, pH was kept at 5.8 and pH was kept at 8.7 throughout.

After completion of the addition, desalting and precipitation were carried out in the same manner as in the seed emulsion-1, and the average silver iodide contents of pAg8.5 and pH5.85 were obtained at 40 ° C.
An emulsion of 0.5 mol% was obtained.

Observation of the obtained emulsion with an electron microscope revealed that tabular silver halide grains having an average aspect ratio of 4.5 with 81% of the projected area having an average grain size of 0.96 μm and a broad grain size distribution of 19%. Met. The average distance between twin planes is 0.019 μm.
And the coefficient of variation was 28%.

Next, after the emulsion (Em-1) was heated to 60 ° C., a predetermined amount of the spectral sensitizing dye was added as a solid fine particle dispersion, and then adenine, ammonium thiocyanate, chloroauric acid and sodium thiosulfate were added. Was added to the mixed solution of triphenylphosphine selenide in a mixed solvent of ethyl acetate and methanol, and after 60 minutes, a silver iodide fine grain emulsion was added, and ripening was performed for a total of 2 hours. 4-hydroxy-6-methyl-1,3,3 as a stabilizer at the end of aging
A predetermined amount of a, 7-tetrazaindene (TAI) was added.

The above-mentioned additives and their addition amounts (per mol of AgX) are shown below.

Spectral sensitizing dye (SD-1) 2.0 mg Spectral sensitizing dye (SD-2) 120 mg Adenine 15 mg Ammonium thiocyanate 95 mg Chloroauric acid 2.5 mg Sodium thiosulfate 2.0 mg Triphenylphosphine selenide 0.4 mg Silver iodide Fine particle emulsion 280 mg 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (TAI) 50 mg A solid fine particle dispersion of a spectral sensitizing dye is described in Japanese Patent Application No. 4-99437.
It was prepared according to the method described in No. That is, a predetermined amount of the spectral sensitizing dye was added to water whose temperature was adjusted to 27 ° C. in advance, and the mixture was stirred by a high-speed stirrer (dissolver) at 3,500 rpm for 30 to 120 minutes to obtain the dye.

[0084]

[Chemical 16]

The average iodine content on the outermost surface of the silver halide grains contained in the silver halide emulsion (Em-1) by the addition of the silver iodide fine grain emulsion was about 4 mol%. The following additives were added to the emulsion thus sensitized to prepare an emulsion layer coating solution, and at the same time, a protective layer coating solution was prepared.

Next, a polyethylene terephthalate film base for X-rays colored blue with a density of 0.15 (thickness: 175 μm)
Copolymer aqueous dispersion prepared by diluting so that the concentration of the copolymer consisting of three monomers of glycidyl methacrylate 50 wt%, methyl acrylate 10 wt% and butyl methacrylate 40 wt% is 10 wt% on both sides of Then, the dye layer described below was applied on both sides of the support. Further, the emulsion layer coating solution and the protective layer coating solution were simultaneously multi-layer coated in the following predetermined coating amounts and dried.

First layer (dye layer) Solid fine particle dispersion dye Amount shown in Table-1 Gelatin 0.2 g / m ² Sodium dodecylbenzenesulfonate 5 mg / m ² Compound (I) 5 mg / m ² 2,4-dichloro- 6-Hydroxy-1,3,5-triazine sodium salt 5 mg / m ² colloidal silica (average particle size 0.014 μm) 10 mg / m ² The solid fine particle dispersion of the dye is prepared by the method described in World Patent 88/04794. It was prepared according to the above. That is, in a 60 ml screw cap container, 21.7 ml of water and the surfactant Triton X.
-200 (manufactured by Rohm & Haas) and 6.7% solution 2.65g, and put into this solution 1.0g powdered dye in a mortar,
40 ml of zirconium oxide beads (2 mm diameter) were added. After the cap was closed and placed in a ball mill and dispersed at room temperature for 4 days, 8.0 g of a 12.5% gelatin aqueous solution was added and mixed well, and the zirconium oxide beads were filtered and removed to obtain a solid fine particle dispersion of the dye.

Second layer (emulsion layer) The following various additives were added to the emulsion obtained above.

Compound (G) 0.5 mg / m ² 2,6-bis (hydroxyamino) -4-diethylamino-1,3,5-triazine 5 mg / m ² t-butylcatechol 130 mg / m ² polyvinylpyrrolidone (molecular weight 10,000 ) 35 mg / m ² styrene-maleic anhydride copolymer 80 mg / m ² sodium polystyrene sulfonate 80 mg / m ² trimethylolpropane 350 mg / m ² diethylene glycol 50 mg / m ² nitrophenyl-triphenylphosphonium chloride 20 mg / m ² 1, Ammonium 3-dihydroxybenzene-4-sulfonate 500 mg / m ² 2-Mercaptobenzimidazole-5-sodium sulfonate 5 mg / m ² Compound (H) 0.5 mg / m ² nC ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 350 mg / m ² compound (M) 5 mg / m ² compound (N) 5 mg / m ² colloidal silica 0.5 g / m ² latex (L) 0.2 g / m ² dextrin (average molecular weight 1000) 0.2 g / m ² However, as gelatin 1. It was adjusted to be 0 g / m ² .

Third layer (protective layer) Gelatin 0.8 g / m ² 4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 7 mg / m ² Polymethyl methacrylate matting agent 50 mg / m ² (Area average particle size 7.0 μm) Formaldehyde 20 mg / m ² 2,4-Dichloro-6-hydroxy-1,3,5-triazine sodium salt 10 mg / m ² Bis (vinylsulfonylmethyl) ether 36 mg / m ² latex (L ) 0.2 g / m ² polyacrylamide (average molecular weight 10000) 0.1 g / m ² sodium polyacrylate 30 mg / m ² polysiloxane (SI) 20 mg / m ² compound (I) 12 mg / m ² compound (J) 2 mg / m ² compound (S-1) 7 mg / m ² compound (K) 15 mg / m ² compound (O) 50 mg / m ² compound (S-2) 5 mg / m ² C ₉ F ₁₉ -O- (CH ₂ CH ₂ O ) ₁₁ -H 3mg / m ² C ₈ F ₁₇ SO ₂ N- (C ₃ H ₇ ) (CH ₂ CH ₂ O) ₁₅ -H 2mg / m ² C ₈ F ₁₇ SO ₂ N- (C ₃ H ₇ ) _{(CH 2 CH 2 O) 4} - (CH 2) 4 SO 3 Na 1mg / m 2 Here, the additive Weight attached is single-sided component, coating amount of silver was adjusted to 1.6 g / m ² as a one-sided min.

[0091]

[Chemical 17]

[0092]

[Chemical 18]

[0093]

[Chemical 19]

Each of the samples Nos. 1 to 10 thus obtained was stored under two kinds of storage conditions (condition A: 23 ° C./55% R
H, condition B: 40 ° C./80% RH), and the photographic performance was evaluated after storage for 4 days.

[Evaluation of Photographic Performance] Samples Two samples were obtained.
It is sandwiched between sheets of intensifying screen KO-250 (made by Konica Corporation), a tube voltage of 80 kvp, a tube current of 100 mA, and an X of 0.05 seconds through an aluminum wedge.
Exposure was performed by irradiating a line. Then automatic processor SR for rapid processing
X-502 (manufactured by Konica Corp.) was used for processing with a developer and a fixer having the following formulations.

The processed sample was subjected to density measurement with an optical densitometer PDA-65 (manufactured by Konica Corp.) to evaluate sensitivity, fog and residual color. Sensitivity is the reciprocal of the exposure amount at fog density + 0.5, and the sensitivity of sample No. 1 in Table 1 immediately after coating and drying is
It was shown by the relative value. The residual color was visually evaluated by treating the obtained sample without exposing it. The best sample with no residual color was set to 5, 1 was a level where the residual color was extremely bad, and 4 or more was a practical level. The MTF was evaluated as follows. That is, an MTF chart containing a rectangular wave of 0.5 to 10 lines / mm of lead is displayed on a fluorescent screen KO-250 (Konica Corporation).
(Made by the manufacturer), the density of the part not covered by the lead chart on the film surface is about 1.
After irradiating with X-rays so as to obtain 0 and developing, the recorded rectangular wave pattern was measured with a Sakura Microdensitometer M-5 type (manufactured by Konica Corp.). At this time, the aperture size was 300 μm in the direction of the rectangular wave and 25 μm in the direction of the right angle, and the magnification was 20 times. The MTF is shown as a value at a spatial frequency of 2.0 lines / mm. The results obtained are shown in Table 1.

<Preparation of processing agent> (Developer formulation) Part-A (for 12 liter finishing) Potassium hydroxide 450 g Potassium sulfite (50% aqueous solution) 2280 g Sodium hydrogencarbonate 132 g Diethylenetetraamine pentaacetic acid 120 g 5-Methylbenzotriazole 1.2g 1-Phenyl-5-mercaptotetrazole 0.2g Hydroquinone 340g Add water to finish to 5000ml Part-B (12l finish) Glacial acetic acid 170g Triethylene glycol 185g 1-Phenyl-3-pyrazolidone 22g 5-Nitroindazole 0.4g Starter Glacial acetic acid 120 g Potassium bromide 225 g Add water to make 1000 ml Add the above Part-A and Part-B simultaneously to about 5 liters of water,
The mixture was adjusted to 12 l with water while stirring, and the pH was adjusted to 10.4 with glacial acetic acid. This is used as a development replenisher. This development replenisher 1
20 ml of the above starter was added to 1 liter, and the pH was 10.26.
To prepare a developer.

(Fixing solution formulation) Prat-A (for 18 l finishing) Ammonium thiosulfate (70 wt / vol%) 6000 g Sodium sulfite 110 g Sodium acetate trihydrate 450 g Sodium citrate 50 g Gluconic acid 70 g 1- (N, N-dimethylamino) ) -Ethyl-5-mercaptotetrazole 18g Prat-B (for 18l finishing) Aluminum sulphate (anhydrous salt equivalent) 800g Part-A and Part-B are added at the same time to about 5l of water, and water is added with stirring to make 18l. Finish and adjust pH to 4.40 with sulfuric acid and sodium hydroxide.

The processing was carried out at development 35 ° C., fixing 33 ° C., water washing 20 ° C. and drying 50 ° C., respectively, and the processing time was dry to dry for 45 seconds.

[0100]

[Table 1]

As is clear from the results shown in Table 1, the photographic light-sensitive material containing the solid fine particle dispersion of the dye of the present invention has less adverse effect on photographic characteristics such as sensitivity and fog, and has excellent sharpness. Very little residual color contamination after processing,
It can be seen that it has excellent storage stability over time.

Example 2 In the same manner as in Example 1, Samples 11 to 18 were prepared by changing the coating amount of the solid fine particle dispersion of the dye according to the present invention. The coating amount of the dye is shown in Table 2. These samples are 23 ℃ / 55% RH
After storing for 4 days under the conditions described above, the sensitivity, fog, and residual color were evaluated in the same manner as in Example 1. However, the treatment was carried out by using the developing solution and the fixing solution described in Example 1 at a developing temperature of 35 ° C., a fixing temperature of 33 ° C., a water washing temperature of 20 ° C. and a drying temperature of 50 ° C., and the processing time was dry to dry for 25 seconds. . The obtained results are shown in Table 2.

[0103]

[Table 2]

As is clear from the results shown in Table 2, the photographic light-sensitive material containing the solid fine particle dispersion of the dye of the present invention hardly adversely affects the photographic characteristics such as sensitivity and fog even in the ultra-rapid processing, It can be seen that the residual color contamination after the treatment is extremely small.

Example 3 (Preparation of silver halide emulsion) 70 mol% of silver chloride, 30 of silver bromide
A silver nitrate aqueous solution and a mixed aqueous solution of NaCl and KBr were mixed by a controlled double jet method to grow silver halide grains so as to have a mol% silver halide composition. At this time, the mixing was carried out under the conditions of 36 ° C., pH 7.8 and pH 3.0, and 2 × 10 ⁻⁷ mol of NaRhCl ₆ was added per 1 mol of silver during grain formation. After mixing, 80 mg of the following SD-3 was added per 1 mol of silver. Thereafter, desalting was carried out with modified gelatin treated with phenylisocyanate, and a bactericide consisting of a mixture of the following compounds (A) (B) (C) and ossein gelatin were added and redispersed. The obtained emulsion has an average grain size of 0.2 μm and a coefficient of variation of 10%.
The emulsion was composed of cubic grains of. The emulsion thus obtained contains 4-hydroxy-6-methyl-1, per mole of silver.
60 mg of 3,3a, 7-tetrazaindene was added, and 5 mg of chloroauric acid and 0.5 mg of sulfur flower were added to 1 mol of silver, and the pH was adjusted to 5.8 and p.
Chemical aging was carried out at 60 ° C. for 80 minutes under the condition of Ag 7.5. After completion of ripening, 900 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added per 1 mol of silver, KI300 mg, SD-4
350 mg was added.

(Preparation of silver halide photographic light-sensitive material) One of 100 μm-thick polyethylene terephthalate film having 0.1 μm-thick undercoat layer on both sides (see Example 1 of JP-A-59-19941) An antihalation layer of the following formulation (1) is coated on the undercoat layer so that the amount of gelatin is 0.5 g / m ^2, and a silver halide emulsion layer of (2) has a gelatin amount of 2.6 g / m 2.
^2, the amount of silver is coated so as to become 3.2 g / m ^2, the amount of gelatin protective layer having the following formulation on (3) was coated so as to become 1.0 g / m ² more. On the other undercoat layer on the opposite side, a backing layer having a gelatin amount of 3.1 g was prepared according to the following prescription (4).
/ M ² and the protective layer of the following formulation (5) was further applied thereon so that the amount of gelatin would be 1.0 g / m ² to prepare a sample.

Formulation (1) [Antihalation layer composition] Gelatin 0.5 g / m ² Solid fine particle dispersion dye Amount shown in Table 3 Surfactant: Sodium dodecylbenzenesulfonate 5 mg / m ² Colloidal silica (average particle size 0.014 μm 18 mg / m ² polyvinylpyrrolidone (molecular weight 10,000) 35 mg / m ² Hardener: HD 25 mg / m ² A solid fine particle dispersion of dye was prepared in the same manner as in Example 1.

Formulation (2) [Silver halide emulsion layer composition] Gelatin 2.6 g / m ² Silver halide emulsion Silver amount 3.2 g / m ² Antifoggant: 4-mercaptobenzoic acid 2 mg / m ² 5-Nitroindazole 10 mg / M ² Nucleating agent: Z-1 3 × 10 ^-5 mol / m ² Nucleating accelerator: Z-2 1 × 10 ^-4 mol / m ² Polymer latex-1 1.0 g / m ² Colloidal silica 0.5 g / m ² compound P 45 mg / m ² Water-soluble polymer: V-1 20 mg / m ² Surfactant: saponin 0.1 g / m ² sodium sulfosuccinate isopentyl normal decyl ester 8 mg / m ² Hardener: 2-hydroxy-4 , 6-Dichloro-1,3,5-triazine 60 mg / m ² formulation (3) [emulsion protective layer composition] Gelatin 1.0 g / m ² matting agent: silica having an average particle size of 3.5 μm 20 mg / m ² polymer latex 2 0.5 g / m ² Surfactant: Sodium sulfosuccinate di (2-ethylhexyl) ester 10 mg / m ² Surfactant F-12m g / m ² accelerator: hydroquinone 50 mg / m ² 1-phenyl-4-hydroxymethyl-4'-methyl-3-pyrazolidone 5 mg / m ² hardener: HD 30 mg / m ² formulation (4) [backing layer composition ] Dye (D-1) 50 mg / m ² Dye (D-2) 40 mg / m ² Dye (D-3) 30 mg / m ² Gelatin 3.1 g / m ² Surfactant: Sodium dodecylbenzenesulfonate 50 mg / m ² 1-Phenyl-5-mercaptotetrazole 5 mg / m ² colloidal silica 0.4 g / m ² Hardener: HD 60 mg / m ² Formulation (5) [Backing protective layer composition] Gelatin 1 g / m ² Matting agent: Average particle size 4.0 μm polymethylmethacrylate 50 mg / m ² Surfactant: sodium sulfosuccinate di (2-ethylhexyl) ester 10 mg / m ² Hardener: HD 25 mg / m ² 2-hydroxy-4,6-dichloro-1,3, 5-triazine 25mg / m ²

[0109]

[Chemical 20]

[0110]

[Chemical 21]

[0111]

[Chemical formula 22]

[0112] The obtained samples were evaluated by the following methods.

[Sensitivity and Gamma] The obtained sample was brought into close contact with a step wedge, exposed to a tungsten light of 3200 ° K for 3 seconds, and developed and fixed to determine the sensitivity. The sensitivity is the reciprocal of the exposure amount that gives a fog density + 3.0 transmission density, and was determined as a relative value under each condition with the sensitivity of Sample No. 1 being 100. Further, gamma was obtained from the slope of the characteristic curve at the transmission density of 1.0 to 3.0. Gamma needs to be 10 or more for practical use.

[Quality of halftone dot] A return halftone screen (1
50 lines / inch), attach the sample closely to it, expose it with a xenon light source for 5 seconds, perform the following development processing, and visually observe the halftone quality of the sample with a magnifying glass of 100 times, The sample having the best halftone dot quality was 5, 1 was an extremely poor level, and 4 or more was a practical level.

[Residual Color] The obtained sample was processed as it was without being exposed, and five sheets were stacked and visually evaluated. The best sample with little residual color was set to 5, 1 was a level where the residual color was extremely bad, and 4 or more was a practical level.

[0116] The results obtained are shown in Table 3.

Processing was performed under the following conditions with a rapid automatic developing machine using a developing solution and a fixing solution having the compositions shown below.

Developer Formulation (Composition A) Pure Water (Ion Exchanged Water) 150 ml Ethylenediaminetetraacetic Acid Disodium 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 Potassium bromide 4.5 g Potassium hydroxide Amount to make the pH of the used solution 10.4 (Composition B) Pure water (ion exchanged water) 3 ml Diethylene glycol 50 g Ethylenediaminetetraacetic acid disodium 25 mg Acetic acid (90% aqueous solution) 0.3 ml 5-nitroindazole 110 mg 1-phenyl-3-pyrazolidone 500 mg When the developer was used, the above composition A and composition B were dissolved in 500 ml of water in this order, and the solution was made up to 1 liter.

Fixer formulation (composition A) Ammonium thiosulfate (72.5% W / V aqueous solution) 240 ml Sodium sulfite 17 g Sodium acetate trihydrate 6.5 g Sodium citrate dihydrate 2 g Boric acid 6 g Acetic acid (90% 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 sulfate (Al2O3 equivalent content is 8.1% W / V aqueous solution) 26.5 g The composition A and the composition B were dissolved in this order, and the solution was finished to 1 l and used. The pH of this fixer was about 4.3.

Development processing conditions (Process) (Temperature) (Time) Development 35 ℃ 30 seconds Fixing 33 ℃ 20 seconds Rinse at room temperature for 15 seconds Dry 45 ℃ 15 seconds

[0121]

[Table 3]

As is clear from the results shown in Table 3, the photographic light-sensitive material containing the solid fine particle dispersion of the dye of the present invention has less adverse effects on photographic characteristics such as sensitivity and fog, and is excellent in halftone dot quality. It can be seen that the residual color contamination after development processing is extremely small.

[0123]

According to the present invention, a silver halide photographic light-sensitive material having less fog and improved stability over time was obtained. Also,
According to the present invention, a silver halide photographic light-sensitive material having high sensitivity and excellent sharpness was obtained. Further, according to the present invention, a processing method of a silver halide photographic light-sensitive material which gives an image with little residual color contamination by a short-time development processing has been found out.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yamato Komamura Konica Co., Ltd. 1 Sakura-cho, Hino-shi, Tokyo (56) References JP-A-2-264936 (JP, A) JP-A-4-204938 ( JP, A) JP-A-6-43586 (JP, A) JP-A-63-64044 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) G03C 1/83

Claims (9)

(57) [Claims] 1. A silver halide photographic light-sensitive material comprising at least one non-photosensitive hydrophilic colloid layer containing a solid fine particle dispersion of a dye represented by the following general formula (1) on a support. material. [Chemical 1] (In the formula, D represents a photographic dye represented by any one of the following general formulas (I) to (VI) , X ₁ , X ₂ , X ₃ and X ₄ represent an alkylene group, and R ₁ and R ₂ represents a hydrogen atom or a monovalent organic group, and p ₁ , p ₂ , p ₃ and p ₄ are 0, ₁ , ₂ respectively.
And an integer of 3. However, p ₁ + p ₂ and p ₃ + p ₄
Is an integer of 1 or more. ) [Chemical A] (In the formula, A ₁ and A ₂ may be the same or different,
Each represents an acidic nucleus, and B ₁ and B ₂ are the same or different
And each represents a basic nucleus, and Q ₁ is a heterocycle.
Represents a group, Y ₁ and Y ₂ may be the same or different.
Each represent an electron-withdrawing group, L ₁ , L ₂ and L ₃
Represents a methine group. n ₁ represents 0 or 1, n ₂ represents 0,
Represents 1 or 2, n ₃ represents 1, 2 or 3, n ₄ is
Represents 0, 1, 2 or 3. However, in A ₁ of the general formula (I) ,
The acid nuclei represented are 5-pyrazolone and barbitu.
Acid, thiobarbituric acid, rhodanine, hydantoy
Down, thio hydantoin, oxazolone, isoxazolo
Indanedione, pyrazolidinedione, oxazoli
Gindione, hydroxypyridone, pyrazolopyridone
Represent ) 2. The silver halide photographic light-sensitive material according to claim 1, wherein the dye represented by formula (1) is a dye having at least one carboxy group in the molecule. 3. A divalent nitrogen atom of the general formula (1) selected from a carbonyl group, a sulfonyl group, an amide group, an alkylene group and a phenylene group directly on the heterocycle in the photographic dye represented by D. The silver halide photographic light-sensitive material according to claim 2, wherein the dye is a dye bonded through a linking group. 4. The coating amount of the hydrophilic colloid of the non-hydrophilic colloid layer containing the solid fine particle dispersion of the dye is from 0.2 g / m ² to.
Claim 1, which is a 1.4 g / m ^2, claim 2
Alternatively, the silver halide photographic light-sensitive material according to claim 3. 5. A non-photosensitive hydrophilic colloid layer containing a solid fine particle dispersion of the dye of the general formula (1) is an intermediate layer, a protective layer,
The silver halide photographic light-sensitive material according to claim 1, 2 or 3, which is a filter layer, an antihalation layer or a backing layer. 6. The average particle size of the solid fine particle dispersion is 0.
The silver halide photographic light-sensitive material according to claim 1, 2 or 3, characterized in that it is from 01 µm to 0.5 µm. 7. A development processing method, which comprises processing the silver halide photographic light-sensitive material according to claim 1 for a development processing time of 90 seconds or less. 8. A development processing method comprising processing the silver halide photographic light-sensitive material according to claim 1 for a development processing time of 45 seconds or less. 9. A development processing method comprising processing the silver halide photographic light-sensitive material according to claim 1 for a development processing time of 30 seconds or less.