JPH0664315B2 - Silver halide photographic light-sensitive material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a silver halide photographic light-sensitive material (hereinafter abbreviated as light-sensitive material), and more particularly to preserving hydrophilic colloid used as a binder for the light-sensitive material.

(Prior Art) In general, a light-sensitive material is formed by coating at least one light-sensitive emulsion layer on a support and, if necessary, a photographic composition such as an undercoat layer, an intermediate layer, an anti-halation layer and a protective layer. It is made by applying layers.
Hydrophilic colloids used as a binder for these photographic constituent layers include gelatin, colloidal albumin, agar, gum arabic, alginic acid, hydrolyzed cellulose acetate, cellulose derivatives such as carboxymethyl cellulose, hydroxyethyl cellulose and methyl cellulose. , Synthetic binders such as polyvinyl alcohol, partially saponified polyvinyl acetate, polyacrylamide, polyN, N-dimethylacrylamide, polyN-vinylpyrrolidone, US Pat. No. 3,847,620.
Issue 3, Issue 3,655,389, Issue 3,341,332
No. 3,615,424, 3,860,428, and the like, and water-soluble polymers as described in US Pat. Nos. 2,614,928 and 2,525,753. Gelatin derivatives such as phenylcarbamylated gelatin, acylated gelatin, phthalated gelatin, etc.
US Pat. Nos. 2,548,520 and 2,831,767
Acrylic acid (ester), as described in No.
Examples thereof include those obtained by graft-copolymerizing a monomer having a polymerizable ethylene group such as methacrylic acid (ester) and acrylonitrile with gelatin. These binders can be used as a compatible mixture of two or more, if desired.

It is known that hydrophilic colloids used as binders for photosensitive materials are easily affected by microorganisms such as bacteria, yeasts and molds. In particular, when a photographic hydrophilic colloid is applied on a support, the influence of microorganisms becomes significant because it is performed at a temperature suitable for the growth of microorganisms. For example, if a hydrophilic colloid decomposes or decomposes due to microorganisms, the viscosity of the coating solution will decrease, the strength of the applied film will decrease, and bacteria etc. will agglomerate to form small clumps, resulting in a defect like a comet. In some cases, a uniform coating film may not be obtained, or microbial metabolites may adversely affect photography.

Further, if the light-sensitive material is left under high temperature and high humidity conditions, molds and the like may propagate and the quality of the light-sensitive material may be significantly impaired.

It is known to add a bactericidal agent or an antifungal agent to the light-sensitive material in order to prevent such defects of the hydrophilic colloid used in the light-sensitive material due to bacteria, yeast, mold and the like.

In general, preservatives or antifungal agents for such purpose include, for example, phenol, phenol thymol, chlorophene, dichlorophene, bromochlorophene, 2,2'-dihydroxy-5,5'-dichlorodiphenyl mono. Sulfide, 2,4,4'-trichloro-
2'-dihydroxydiphenyl ether, 3,4,5-
Aromatic hydroxy compounds such as tribromosartylanilide, 4-n-hexylresorcin, or salts thereof,
Alternatively, a compound having a carbonyl group such as formaldehyde, paraformaldehyde, chloroacetaldehyde, glutaraldehyde, chloroacetamide, methylol chloroacetamide, benzoic acid, monobromoacetic acid ester, p-hydroxybenzoic acid ester,
Carboxylic acids or esters thereof such as sorbic acid, amines such as hexamethylenetetramine, alkylguanidine, nitromethylbenzylethylenediamine, disulphides such as tetramethylthiuramdisulfide, 2-mercaptobenzthiazole, 2-
Nitrogen-containing heterocyclic compounds such as (4-thiazolyl) -benzimidazole and 2-methoxycarbonylaminobenzimidazole, or organic mercury compounds such as mercury phenylacetate, mercury phenylpropionate, and mercury phenyloleate, or neomycin and kanamycin. , Polymycin, streptomycin, flamycin and other antibiotics are known, some of which are also known for photographic use.

(Problems to be solved by the invention) However, these substances do not exhibit their effects unless they are added in a large amount to the hydrophilic colloid, or they are harmful to the living body, and only to specific bacteria. In many cases, the bactericidal effect is insufficient due to being ineffective, being photographically harmful, or interacting with other photographic additives.
For example, most often used phenols do not exhibit a sufficient antiseptic effect unless added in an amount of 2% by weight or more based on the hydrophilic colloid. Moreover, although phenol has an antiseptic effect against bacteria, it has little antiseptic and antifungal effects against mold and yeast, and is highly toxic to living organisms. Aldehydes such as formalin are effective against bacteria, but less effective against mold,
It is harmful to the living body and easily causes fog on the light-sensitive material. Further, a heterocyclic compound such as benzthiazole may sometimes exhibit a photographically harmful action, for example, a desensitizing action. Organic mercury compounds are effective against fungi but less effective against bacteria and are harmful to living organisms. Antibiotics such as neomycin and kanamycin are effective against bacteria but not against mold and yeast.

The use of a large amount of the bactericide adversely affects the physical properties of the coating solution, for example, causes the agglomeration of the binder, and deteriorates the photographic characteristics of the finished light-sensitive material.

Therefore, it is desirable that the amount of the bactericide added is as small as possible.

As described above, it has been strongly desired to develop a bactericidal agent for photographic hydrocolloids that has a remarkable bactericidal and antifungal effect against bacteria, yeasts, molds and the like in a small amount.

(Object of the Invention) A first object of the present invention is to provide a structure of a hydrophilic colloid composition for coating a photographic constituent layer of a light-sensitive material containing a hydrophilic colloid, and a novel antiseptic property during storage or after coating. To provide a method.

The second object is to provide a preservative for hydrophilic colloid which does not affect the photographic performance (sensitivity, fog, graininess, sharpness, etc.).

(Means for Solving the Problems) As a result of various investigations by the present inventors, the object of the present invention is to find that at least one compound represented by the following general formula [I] is contained in a hydrophilic colloid for a light-sensitive material. It has been found that this can be achieved by a silver halide photographic light-sensitive material characterized by containing at least one compound represented by the following general formula [II].

General formula [I] In the formula, R ₁ represents a lower alkylene group, which may be linear or branched. X is a halogen atom, a nitro group, a lower alkyl group, -COR ₂ , Represents —SO ₃ M, R ₂ represents a hydrogen atom, —OM, a lower alkyl group, a lower alkoxy group, Represents R ₃ and R ₄ may be the same or different from each other, and may be a hydrogen atom, a lower alkyl group, —COR ₇ , or —SO ₂ R ₇
R ₅ and R ₆ , which may be the same or different from each other, represent a hydrogen atom or a lower alkyl group, R ₇ represents a lower alkyl group, M represents a hydrogen atom, an alkali metal atom,
And n represents an atomic group necessary for forming a monovalent cation, and n represents 0 or an integer of 1 to 5.

General formula (II) In the formula, R ₈ represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, and the alkyl group may be cyclic. R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are each a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group, an aryl group,
Alkoxy group, aryloxy group, aralkyloxy group, carboxyl group, sulfo group, hydroxy group, Represents —SO ₂ R ₁₅ , R ₁₃ and R ₁₄ represent a hydrogen atom, an alkyl group, —COR ₁₅ and —SO ₂ R ₁₅ , and R ₁₅ represents an alkyl group and an alkoxy group. These R ₉ , R
₁₀ , R ₁₁ and R ₁₂ may be the same or different from each other.

Next, the compound of the present invention will be described in detail.

In the general formula [I], R ₁ represents a linear or branched lower alkylene group (for example, ethylene group, propylene group, methylethylene group, etc.), and an alkylene group having 1 to 6 carbon atoms is particularly preferable.

X is a halogen atom (eg, chlorine atom, bromine atom, fluorine atom, etc.), nitro group, lower alkyl group (eg, methyl group, ethyl group, iso-propyl group, tert-butyl group, etc.), —COR ₂ , Represents —SO ₃ M, R ₂ represents a hydrogen atom —OM, a lower alkyl group (eg, methyl group, n-propyl group, tert-group).
Butyl group), lower alkoxy group (eg, methoxy group, n-butoxy group, iso-propoxy group, etc.), Represents

R ₃ and R ₄ may be the same as or different from each other, and are a hydrogen atom, a lower alkyl group (eg, methyl group, n-propyl group, iso-amyl group, etc.), —COR ₇ , —SO ₂ R
₇ , R ₅ and R ₆ may be the same or different from each other, and are a hydrogen atom, a lower alkyl group (eg, methyl group, iso
-Butyl group, n-butyl group, etc.), R ₇ represents a lower alkyl group (eg, methyl group, ethyl group, iso-propyl group, n-butyl group, tert-amyl group, etc.), and M represents hydrogen. Represents an atom, an alkali metal atom (eg, sodium, potassium, etc.) and a group of atoms necessary for forming a monovalent cation (eg, ammonium cation, phosphonium cation, etc.), and n is 0 or 1 to 5
Represents an integer up to.

The preferred carbon number of the lower alkyl group and lower alkoxy group is in the range of 1 to 6.

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

These exemplified compounds are generally commercially available as reagents, and are easily available. Alternatively, the corresponding phenol compound can be easily synthesized by a reaction with ethylene oxide or the like using the corresponding phenol compound as an intermediate.

Next, the compound of the general formula [II] will be described.

R ₈ is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms (eg, methyl group, ethyl group, n-
Propyl group, tert-octyl group, n-heptadecyl group, n-octadecyl group, 2-hydroxyethyl group, 2
-Carboxyethyl group, 2-cyanoethyl group, sulfobutyl group, etc.), substituted or unsubstituted aryl group (eg, phenyl group, o-methoxyphenyl group, p-chlorophenyl group, p-iso-propylphenyl group, etc.) Cyclic Alkyl group (eg cyclohexyl group), substituted or unsubstituted aryl group (eg phenyl group, 2,4-dinitrophenyl group etc.), substituted or unsubstituted aralkyl group (eg benzyl group, p-methylbenzyl group, p- Isopropylbenzyl group) and R ₉ , R ₁₀ , R ₁₁ and R ₁₂
Is a hydrogen atom, a hydroxy group, a nitro group, a cyano group, a halogen atom (eg, chlorine atom, bromine atom, fluorine atom, etc.), a carboxyl group, a sulfo group, a substituted or unsubstituted alkyl group (eg, methyl group, ethyl group, n -Propyl group, t
ert-butyl group, n-hexyl group, etc.), substituted or unsubstituted aryl group (eg phenyl group o-methylphenyl group, p-acetamidophenyl group, m-methoxyphenyl group, p-chlorophenyl group, etc.), substituted , An unsubstituted alkoxy group (eg, methoxy group, ethoxy group, n-hexyloxy group, methoxyethoxy group, etc.), a substituted or unsubstituted aryloxy group (eg, phenoxy group, p-chlorophenoxy group, o-carboxy) Phenoxy group, m-
Methylphenoxy group, m-nitrophenoxy group, etc.),
A substituted or unsubstituted aralkyloxy group (eg, benzyloxy group, p-chlorobenzyloxy group, p-iso-propylbenzyloxy group, etc.), -COR _15, SO ₂ represents R ₁₅ R ₁₃ and R ₁₄ is a hydrogen atom, a substituted unsubstituted alkyl group (e.g. methyl, ethyl, 2-hydroxyethyl group, 2-ethoxycarbonylethyl group,
Such as 2-cyanoethyl _{group), - COR 8, -SO 2} R 8
The stands, R ₈ is a substituted, unsubstituted alkyl group (e.g. methyl, ethyl 2-hydroxyethyl group, iso- propyl, n- or butyl group), a substituted, unsubstituted alkoxy groups (e.g. methoxy group, Ethoxy group, n-butoxy group, methoxyethoxy group and the like).

The preferred carbon number of the alkyl group and the alkoxy group of R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ and R ₁₅ is 1 to 1.
It is in the range of 0. R ₉ , R ₁₀ , R ₁₁ , and R ₁₂
May be the same as or different from each other. Next, the above general formula [I
Representative specific examples of the compound represented by I] (hereinafter referred to as compound II) are shown, but the compound of the present invention is not limited thereto.

In the present invention, the hydrophilic colloid for a light-sensitive material means a binder contained in a coating liquid used for coating various photographic constituent layers of the light-sensitive material, that is, the gelatin mentioned at the beginning of the description of the prior art. Agar, natural hydrophilic macromolecules such as colloidal albumin and derivative gelatin, derivative cellulose, sol of synthetic hydrophilic polymers such as polyvinyl alcohol, gel-like hydrocolloid solution, and water used for preparing coating solution. A composition such as a coating solution that is in the process of preparing, storing or blending a solution or dispersion of various compounds that are soluble or sparingly soluble or insoluble, such as a silver halide emulsion, a coupler, a matting agent, etc. Dispersions, surface-active solutions, dye solutions and other various additives. The conditions which must be provided as a sterilizing and anti-bacterial agent for the hydrophilic colloid for light-sensitive materials are [1] no interaction with photographic additives, [2] a large amount of sterilizing and anti-bacterial effects, [3] ] No influence on photographic performance such as desensitization, fog, graininess and sharpness, [4] No influence on processing performance such as developability, desilvering property, color recovery, [5] to environmental ecosystem It is hoped that there will be no effect and that [6] there will be no adverse effect on the human body.

The combination of compounds I and II almost meets these requirements.

Bacteria, bacteria, which generally propagate in hydrophilic colloids,
The type of mold is not limited to one type, but it is common for several types to mix and reproduce.

For this reason, the complete antiseptic effect cannot be seen only by using one kind of bactericide and antifungal agent, and the purpose cannot be achieved in many cases.

As a result of a detailed study by the present inventors, the compound I and compound II were combined and added to a liquid containing a hydrophilic colloid, whereby the delayed action of the compound [II] and the “too weak bactericidal power” of the compound [I] were observed. It was possible to obtain a great effect by covering the shortcomings of "," and finding a wide range of antibacterial properties that cannot be obtained individually.

The compounds I and II of the present invention are each layer constituting a light-sensitive material containing a hydrophilic colloid, for example, a silver halide emulsion layer, an undercoat layer,
It may be applied to any of an intermediate layer, a filter layer, an anti-halation layer, a protective layer and the like.

Further, in the manufacturing process, when each of these layers is prepared by mixing two or more liquids, it can be added to each liquid.

Compounds I and II are added in an amount of 10 to 10000 ppm for compound I and 1 to 1000 pp for compound II with respect to the hydrophilic colloid.
A range of m is suitable.

The compounds I and II of the present invention may be dissolved in water or an organic solvent such as methanol, isopropanol, acetone or ethylene glycol, which does not adversely affect the photographic performance, and may be added as a solution to the hydrophilic colloid. It may be contained on the layer by coating or by immersing it in a germicide solution. Alternatively, it may be dissolved in a high-boiling solvent, a low-boiling solvent or a mixed solvent of both, and then emulsified and dispersed in the presence of a surfactant, and then added to a liquid containing a hydrophilic colloid or further coated on the protective layer. You may

The light-sensitive material using the hydrocolloid to which the antiseptic method of the present invention is applied will be described in more detail below.

The silver halide emulsion of the light-sensitive material used in the present invention may have any halogen composition such as silver iodobromide, silver bromide, silver chlorobromide and silver chloride. For example, in the case of performing rapid processing or low replenishment processing of color paper or the like, a silver chlorobromide emulsion or a silver chloride emulsion containing 60 mol% or more of silver chloride is preferable, and the silver chloride content is 80 to 100. The case of mol% is particularly preferable. When high sensitivity is required and fog during production, storage and / or processing is required to be particularly low, a silver chlorobromide emulsion containing 50 mol% or more of silver bromide or an odor is used. A silver halide emulsion (which may contain 3 mol% or less of silver iodide) is preferable, and 70 mol% or more is more preferable. For the color light-sensitive material for photography, silver iodobromide,
Silver chloroiodobromide is preferred, where the silver iodide content is 3-15.
% Is preferred.

The silver halide grains used in the present invention may have different phases in the inside and the surface layer, may have a multi-phase structure having a junction structure, or may have a uniform phase as a whole. Moreover, they may be mixed.

The average grain size of the silver halide grains used in the present invention (in the case of spherical grains or grains close to spheres, the grain diameter is represented, and in the case of cubic grains, the ridge length is represented as the grain size, and the average is represented by the projected area. In the case of particles, it is expressed in terms of a circle.) Is preferably 2 μm or less and 0.1 μm or more, and particularly preferably 1.5 μm or less and 0.15 μm.
That is all. The grain size distribution may be narrow or broad, but the value (variation rate) obtained by dividing the standard deviation value in the grain size distribution curve of the silver halide emulsion by the average grain size is 20.
It is preferred to use a so-called monodisperse silver halide emulsion in the present invention within the range of 15%, particularly preferably 15%. Further, in order to satisfy the target gradation of the light-sensitive material, two or more kinds of monodisperse silver halide emulsions having different grain sizes in the emulsion layers having substantially the same color sensitivity (the above-mentioned monodispersity is the same). It is preferable that those having a variation rate) be mixed in the same layer or multilayer-coated in different layers. Furthermore, two or more kinds of polydisperse silver halide emulsions or a combination of monodisperse emulsions and polydisperse emulsions can be mixed or laminated and used.

The silver halide grains used in the present invention may have a regular crystal such as a cube, an octahedron, a rhodohedron, and a tetradecahedron, or may have a coexisting form thereof. It may have an irregular crystal form such as a spherical shape, or may have a composite form of these crystal forms. Further, tabular grains may be used, and in particular, tabular grains having a length / thickness ratio value of 5 to 8 or 8 or more,
An emulsion which occupies 50% or more of the total projected area of grains may be used. It may be an emulsion composed of a mixture of these various crystal forms. These various emulsions may be either a surface latent image type which forms a latent image mainly on the surface or an internal latent image type which is formed inside the grain. The photographic emulsions used in the present invention are RESEARCH DISCLOSURE No. 1
70, No. 17643 (I, II, III) (December 1978).

The emulsion used in the present invention is usually one which has been physically ripened, chemically ripened and spectrally sensitized. The additives used in such a process are Research Disclosure Volume 176, No. 17643 (December 1978) and Volume 187, No. 18716 (November 1979).
The relevant parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above-mentioned two Research Disclosures, and the locations described in the table below are shown.

Examples of the photographic light-sensitive material used include various color and black-and-white light-sensitive materials.

For example, a color negative film for photography (general use, movie etc.), a color reversal film (for slide, movie etc. and sometimes not containing a coupler), color photographic paper, color positive film (movie etc.), Color reversal photographic paper, photothermographic material (see US Pat.
00,626, JP-A-60-133449, 59.
No. 218443, JP-A-61-238056), a color light-sensitive material using a silver dye bleaching method, a photographic light-sensitive material for plate making (lith film, scanner film, etc.),
X-ray photographic light-sensitive material (direct / indirect medical use, industrial use, etc.),
Examples thereof include black-and-white negative film for photographing, black-and-white photographic paper, micro light-sensitive material (for COM, micro film, etc.), color diffusion transfer light-sensitive material (DTR), silver salt diffusion transfer light-sensitive material and print-out light-sensitive material.

When applied to color light-sensitive materials, various couplers can be used.

Here, the color coupler means a compound capable of forming a dye by a coupling reaction with an oxidation product of an aromatic primary amine developing agent. Typical examples of useful color couplers are naphthol or phenol compounds, pyrazolone or pyrazoloazole compounds and open chain or heterocyclic ketomethylene compounds. Specific examples of these cyan, magenta and yellow couplers which can be used in the present invention are Research Disclosure (RD) No. 17643.
(December 1978) Item VII-D and ibid. No. 18717.
(November 1979).

The color coupler incorporated in the light-sensitive material preferably has a ballast group or is polymerized to be diffusion resistant. The coating amount of silver can be reduced in the case of a two-equivalent color coupler in which a coupling active position is substituted with a leaving group, rather than a four-equivalent color coupler in which a hydrogen atom is present. It is also possible to use couplers in which the color forming dye has a suitable diffusivity, uncolored couplers or DIR couplers which release a development inhibitor upon coupling reaction or couplers which release a development accelerator.

A typical example of the yellow coupler that can be used in the present invention is an oil protect type acylacetamide coupler. A specific example is US Pat. No. 2,40.
No. 7,210, No. 2,875,057 and No. 3,265,506. In the present invention, it is preferable to use a two-equivalent yellow coupler, and US Pat. Nos. 3,408,194 and 3,447,928 are preferred.
No. 3,933,501 and No. 4,022.
No. 620, etc., or an oxygen atom-releasing type yellow coupler or Japanese Patent Publication No. 55-10739, U.S. Pat. Nos. 4,401,752, 4,326,024, Research Disclosure No. 18053 (1979).
April, 2004), British Patent No. 1,425,020, West German Patent Application Publication Nos. 2,219,917, and 2,261,361.
No. 2,329,587 and 2,433.
Typical examples thereof include nitrogen atom-releasing yellow couplers described in JP-A No. 812. The α-pivaloyl acetanilide type coupler is excellent in the fastness, especially the light fastness, of the color forming dye, while the α-benzoyl acetanilide type coupler can obtain a high coloring density.

Examples of the magenta coupler which can be used in the present invention include oil-protection type indazolone type or cyanoacetyl type, preferably 5-pyrazolone type and pyrazoloazole type couplers such as pyrazolotriazoles. The 5-pyrazolone-based coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamino group, from the viewpoint of the hue and color density of the color forming dye, and a typical example thereof is U.S. Pat. No. 2,311,082. Same number 2,
343,703, 2,600,788, 2,908,573, 3,062,653, 3,152,896 and 3,936,015.
No. etc. As a leaving group for a 2-equivalent 5-pyrazolone-based coupler, US Pat. No. 4,310,619
Nitrogen atom leaving group described in U.S. Pat.
The arylthio groups described in 51,897 are preferred. Further, the 5-pyrazolone-based coupler having a ballast group described in EP 73,636 provides a high color density.

As a pyrazoloazole coupler, US Pat.
369,879 pyrazolobenzimidazoles, preferably pyrazolo [5,1-c] [1,2,4] triazoles described in U.S. Pat. No. 3,725,067, Research Disclosure. No. 24220
(June 1984) and pyrazolotetrazoles and Research Disclosure No. 24230 (1).
Pyrazolopyrazoles described in Jun. 984). The imidazo [1,2-b] pyrazoles described in European Patent No. 119,741 are preferable from the viewpoint of low yellow sub-absorption of the color forming dye and light fastness, and European Patent No. 1
Pyrazolo [1,5-b] [1, described in 19,860.
2,4] triazole is particularly preferred.

Cyan couplers usable in the present invention include oil-protection type naphthol type and phenol type couplers, and the naphthol type couplers described in US Pat. No. 2,474,293, preferably US Pat. No. 4,05.
No. 2,212, No. 4,146,396, No. 4,2
Representative examples thereof include oxygen atom desorption type two-equivalent naphthol couplers described in Nos. 28,233 and 4,296,200. Further, specific examples of the phenol-based coupler are described in U.S. Pat. No. 2,369,929 and No. 2,369,929.
801,171, 2,772,162, 2,895,826 and the like. Cyan couplers that are robust to humidity and temperature are preferably used in the present invention, of which typical examples are US Pat.
No. 72,022, a phenolic cyan coupler having an ethyl group or higher alkyl group at the meta position of the phenol nucleus, US Pat. Nos. 2,772,162, and 3,
758,308, 4,126,396, 4,334,011, 4,327,173, West German Patent Publication No. 3,329,729 and JP-A-59-.
2,5-diacylamino-substituted phenol-based couplers described in 166956 and the like and US Pat. No. 3,44.
No. 6,622, No. 4,333,999, No. 4,4
51,559 and 4,427,767, etc., and has a phenylureido group at the 2-position and 5-
Examples thereof include a phenol type coupler having an acylamino group at the position, and a 5-amido-1-naphthol type coupler described in JP-A No. 61-179438.

The graininess can be improved by using a coupler in which the color forming dye has an appropriate diffusibility. Such dye-diffusing couplers are exemplified by magenta couplers in U.S. Pat. No. 4,366,237 and British Patent No. 2,125,570, and also in European Patent No. 96,570 and West German Application No. No. 234,533, specific examples of yellow, magenta or cyan couplers are described.

The dye-forming coupler and the above-mentioned special coupler may form a polymer of a duplex or more. Typical examples of polymerized dye forming couplers are found in US Pat. No. 3,451,82.
0 and 4,080,211. Specific examples of polymerized magenta couplers are described in British Patent No. 2,102,173 and US Patent No. 4,367,
282.

The various couplers used in the present invention can be used in combination of two or more kinds in the same layer of the light-sensitive layer in order to satisfy the properties required for the light-sensitive material, and two or more layers in which the same compound is different. Can also be introduced.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods. Examples of the high boiling point organic solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,02.
No. 7, etc. Further, steps of the latex dispersion method, effects, and specific examples of the latex for impregnation are described in US Pat. No. 4,199,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230. No. etc.

The standard amount of the color coupler used is in the range of 0.001 to 1 mol per mol of the light-sensitive silver halide, preferably 0.01 to 0.5 mol for the yellow coupler and 0.003 for the magenta coupler. In the cyan coupler, it is 0.002 to 0.3 mol.

The photographic light-sensitive material used in the present invention is applied to a rigid support such as a commonly used plastic film (cellulose nitrate, cellulose acetate, polyethylene terephthalate, etc.), a flexible support such as paper or glass. . For details of the support and the coating method, see Research Dice Closure, Volume 176, No. 1764.
Item 3XV (P.27) X VII (P.28) (197)
(December 8 issue).

In the present invention, a reflective support is preferably used.

The "reflective support" is one which enhances the reflectivity and makes the dye image formed on the silver halide emulsion layer clear, and such a reflective support includes titanium oxide, zinc oxide, Examples include those coated with a hydrophobic resin containing a light reflecting substance such as calcium carbonate and calcium sulfate dispersed therein, and those using a hydrophobic resin containing a light reflecting substance dispersed therein as a support.

There is no particular limitation on the developing method of the silver halide photographic light-sensitive material. For example, Research Disclosure, No. 1
Any of known methods and known processing solutions such as those described in Vol. 76, pp. 28-30 can be applied. This photographic processing may be either photographic processing for forming a silver image (black and white photographic processing) or photographic processing for forming a dye image (color photographic processing) depending on the purpose.
Treatment temperature is usually selected between 18 ° C and 50 ° C, but 1
The temperature may be lower than 8 ° C or higher than 50 ° C.

Conventional methods can be applied to form a dye image. For example, the negative-positive method (for example, “Journal of the Society of
Motion Picture and Teleuision Engineers ”, 61st
Vol. (1953), pp. 667-701); developed with a developer containing a black-and-white developing agent to produce a negative silver image, then at least one uniform exposure or other suitable fog treatment. And a color reversal method for obtaining a dye positive image by subsequent color development; a silver dye bleaching method in which a photographic emulsion layer containing the dye is exposed and then developed to form a silver image, and the silver image is bleached using the bleaching catalyst as a bleach catalyst. Are used.

Color developers generally consist of an alkaline aqueous solution containing a color developing agent. Color developing agents are known primary aromatic amine developers such as phenylenediamines (eg 4-
Amino-N, N-diethylaniline, 3-methyl-4-
Amino-N, N-diethylaniline, 4-amino-N-
Ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N
-Β-methanesulfoamidoethylaniline, 4-amino-3-methyl-N-ethyl-N-β-methoxyethylaniline, etc.) can be used.

LFA Mason Photographic Processing Chemist
ry (Focal Press, 1966), pages 226-229,
U.S. Pat. Nos. 2,193,015 and 2,592,36
No. 4, JP-A-48-64933 and the like may be used.

Color developers also include pH buffers such as alkali metal sulfites, carbonates, borates, and phosphates, bromides,
A development inhibitor such as iodide and an organic antifoggant or an antifoggant can be contained. If necessary, a water softener, a preservative such as hydroxylamine,
Organic solvents such as benzyl alcohol and diethylene glycol, polyethylene glycol, quaternary ammonium salts,
Development accelerators such as amines, dye-forming couplers, competitive couplers, fogging agents such as sodium boron hydride, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, tackifiers, polycarboxylic acid chelating agents, antioxidants It may also contain agents.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process or may be performed individually. As the bleaching agent, for example, compounds of polyvalent metals such as iron (III), cobalt (III), chromium (VI) and copper (II), peracids, quinones, nitroso compounds and the like are used.

For example, ferricyanide, dichromate, iron (III)
Or an organic complex salt of cobalt (III), such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, 1,3-diamino-
Aminopolycarboxylic acids such as 2-propanoltetraacetic acid or complex salts of organic acids such as citric acid, tartaric acid and malic acid; persulfates, permanganates; nitrosphenol and the like can be used. Of these, potassium ferrocyanide, sodium iron (III) ethylenediaminetetraacetate and ammonium iron (III) ethylenediaminetetraacetate are particularly useful. The ethylenediaminetetraacetic acid iron (III) complex salt is useful both in a stand-alone bleaching solution and in a one-bath bleach-fixing solution.

As the fixer, those having a commonly used composition can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as a fixing agent can be used. The fixing solution may contain a water-soluble aluminum salt as a hardening agent.

The silver halide color photographic light-sensitive material used in the present invention is generally washed with water and / or stabilized after desilvering such as fixing or bleach-fixing.

The amount of rinsing water in the rinsing process depends on the characteristics of the light-sensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the rinsing water, the number of rinsing tanks (the number of tiers), the replenishment method such as countercurrent and forward flow, and various other conditions. It can be set in a wide range. Of these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent system is as follows: Journal of the Society of Motion Picture and Television Engineers (Journal of
the Society of Motion Picture and Televiaion Engi
neers) 64, 248-253 (May 1955). Usually, the number of stages in the multi-stage countercurrent system is preferably 2-6, particularly 2-4
Is preferred.

According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate, and the suspended matter produced adheres to the photosensitive material, etc. Problem arises. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem,
The method of reducing calcium ion and magnesium ion described in Japanese Patent Application No. 61-131,632 can be used very effectively. In addition, JP-A-57-8,542
Compounds, siabendazoles, chlorinated fungicides such as chlorinated sodium isocyanurate, and other benzotriazoles, Hiroshi Horiguchi, "Chemistry of Antibacterial and Antifungal Agents," edited by the Institute of Hygiene, "Microorganisms The sterilizing agents described in "Sterilization, Sterilization, Antifungal Technology" and "Encyclopedia of Antibacterial and Antifungal Agents" edited by Japan Society for Antibacterial and Antifungal Agents can also be used.

The pH of washing water in the processing of the light-sensitive material of the present invention is 4-9.
And preferably 5-8. The washing water temperature and washing time can be variously set depending on the characteristics and intended use of the light-sensitive material, but in general, it is 20 seconds to 10 minutes at 15 to 45 ° C, preferably 25 seconds.
A range of 30 seconds-5 minutes at -40 ° C is selected. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such stabilizing treatment, JP-A-57-8,543, 58-14,834
All known methods described in No. 60-220, 345 can be used.

Further, there is a case where a stabilizing treatment is further performed after the water washing treatment, and an example thereof is a stabilizing bath containing formalin and a surfactant, which is used as a final bath of a color light-sensitive material for photographing. . Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow solution accompanying the above washing with water and / or supplementation of the stabilizing solution can be reused in other steps such as the desilvering step.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents. For example, US Pat. No. 3,342,59
Indoaniline compounds described in No. 7, No. 3,342,
No. 599, Research Disclosure 14,850
And Schiff base type compounds described in JP-A No. 15-159, aldol compounds described in JP-A No. 13,924, metal salt complexes described in US Pat. No. 3,719,492, JP-A-53-53.
The urethane compound described in No. 135,628 can be mentioned.

The silver halide color light-sensitive material of the present invention contains various 1-phenyl-type light-sensitive materials for the purpose of promoting color development, if necessary.
You may incorporate 3-pyrazolidones. Typical compounds are JP-A-56-64,339 and JP-A-57-144,54.
7 and 58-115,438.

The developing solution used for black-and-white photographic processing may contain a known developing agent. As developing agents, dihydroxybenzenes (for example, hydroquinone), 3-
Pyrazolidones (eg 1-phenyl-3-pyrazolidone), aminophenols (eg N-methyl-p)
-Aminophenol) and the like can be used alone or in combination. The developer generally contains other known preservatives, alkali agents, pH buffers, antifoggants, etc.,
Further, if necessary, a dissolution aid, a color toning agent, a development accelerator, a surfactant, a defoaming agent, a water softener, a film hardener, a viscosity imparting agent, etc. may be contained.

A so-called "lith type" development process can be applied to the photographic emulsion of the present invention. What is "lith type" development processing? For the photographic reproduction of line images or the photographic reproduction of halftone images with halftone images, dihydroxybenzenes are usually used as the developing agent, and the development process is performed under a low sulfite ion concentration. Is a contagious development process (details are described in Mason's "Photographic Processing Chemistry" (1966), pages 163-165).

Hereinafter, the present invention will be described in more detail with reference to Examples.

Example 1 Various preservatives were added to a 6% by weight aqueous solution of gelatin to compare the inhibitory effects on biological growth.

A group of test solutions were infected at the same concentration with bacteria isolated from the degraded gelatin solution. The other groups of test solutions were similarly infected by fungi isolated from the degraded gelatin solution.

The infected test solution was kept at 37 ° C. to facilitate biological production and a 1 ml sample was taken after 24 hours and 3 weeks.

A 1 ml sample was used to infect commercial nutrient sources for bacteria and mold, respectively, which were incubated under the same environment for the development of microbial colonies.

Table 1 shows the survey results obtained. Here, (-) indicates that there was no microbiological growth, and (+) indicates that there was considerable microbiological growth.

As can be seen from the results in Table-1, the general formula [I] and the general formula [I
It is clear that the combined use of the compounds shown in I] shows a large effect with a small use amount of each.

This is suitable for the method of preserving hydrocolloids for photographic light-sensitive materials, which requires a small amount to be used due to adverse effects on photography. The example is shown below.

Example-2 A magenta coupler dispersion for color, a UV absorber dispersion, and a green-sensitive silver chlorobromide emulsion were mixed and inoculated with one strain of Pseudomanas, one strain of Entrobacter, and one strain of Acinetobacter, respectively. The preservative was added in the amount shown in Table 2. The sample was allowed to stand at 25 ° C for 1 week for storage stability test, and the number of bacteria was measured.

(E) was used as the magenta coupler and (h) was used as the UV absorber. The details of the light-sensitive material used are described below.

Front side on paper support laminated on both sides with polyethylene
A multilayer color photographic paper having the layer structure shown in 2 was prepared. The coating liquid was prepared as follows.

Preparation of coating liquid for the first layer: 19.1 g of yellow coupler (a), 4.4 g of color image stabilizer (b), 27.2 ml of ethyl acetate and solvent (c)
7.9 ml was added and dissolved, and this solution was emulsified and dispersed in 185 ml of 10% gelatin aqueous solution containing 8 ml of 10% sodium dodecylbenzenesulfonate. On the other hand, the following blue-sensitive sensitizing dyes were added to a silver chlorobromide emulsion (containing 1 mol% of silver bromide and 70 g / kg of Ag) at 5.0 × 10 ⁻⁴ mol per mol of silver chlorobromide to give a blue-sensitive emulsion. 90 g of the product was prepared. The emulsified dispersion and the emulsion were mixed and dissolved, and the gelatin concentration was adjusted so that the composition shown in Table 2 was obtained to prepare a coating solution for the first layer.

The coating solutions for the second to seventh layers were also prepared in the same manner as the coating solution for the first layer.

As a gelatin hardening agent for each layer, 1-oxy-3,5-
Dichloro-s-triazine sodium salt was used.

The following were used as the spectral sensitizer for each emulsion.

Blue-sensitive emulsion layer (5.0 × 10 ⁻⁴ mol added per mol of silver halide) Green-sensitive emulsion layer (Adding 4.0 × 10 ⁻⁴ mol per mol of silver halide) (Addition of 7.0 × 10 ⁻⁴ mol per mol of silver halide) Red-sensitive emulsion layer (Addition of 1.0 × 10 ⁻⁴ mol per mol of silver halide) For the red-sensitive emulsion layer, the following compounds were added.
2.6 × 10 ⁻³ mol was added per mol.

The following dyes were used as the anti-irradiation dye in each emulsion layer.

Green sensitive emulsion layer Red-sensitive emulsion layer Structural formulas of compounds such as couplers used in this example are as follows.

(A) Yellow coupler (B) Color image stabilizer (C) solvent (D) Color mixing inhibitor (E) Magenta coupler (F) Color image stabilizer (G) solvent 2: 1 mixture (weight ratio) (h) UV absorber 1: 5: 3 mixture (molar ratio) of (i) Color mixing inhibitor (J) Solvent (iso C ₉ H ₁₉ O ₃ P = O (k) Cyan coupler 1: 1 mixture (molar ratio) (l) Color image stabilizer 1: 3: 3 mixture (molar ratio) of (m) solvent For the third layer, the fourth layer, and the sixth layer, the coupler dispersion, the UV absorber dispersion, and the green-sensitive silver chlorobromide emulsion which had been subjected to the above-mentioned storage stability test (rot test) were used.

These samples (Nos. 8 to 12) were wet-exposed through a green filter and then subjected to the following development processing.

On the other hand, the sensitometry was similarly performed on the sample which had been stored at 25 ° C. and 60% relative humidity for 3 months after coating and drying.

The obtained color photographic paper was processed in the following processing steps in which the composition of the color developing solution was changed. Treatment process Temperature Time Color development 35 ° C 45 seconds Bleach fixing 35 ° C 45 seconds Rinse 1 35 ° C 20 seconds Rinse 2 35 ° C 20 seconds Rinse 3 35 ° C 20 seconds Dry 80 ° C 60 seconds Rinse from rinse 3 Rinsing 1 was carried out by flushing with water in 3 tanks. The treatment liquids used are as follows.

Color developer Hydroxylamine 0.04 mol Benzyl alcohol 15 ml Diethylene glycol 10 ml Sodium sulfite 0.2 g Potassium carbonate 30 g EDTA.2Na 1 g Sodium chloride 1.5 g 4-Amino-3-methyl-N-ethyl-N- [β- (methane Sulfonamido) ethyl] -p-phenylenediamine sulfate 5.0 g Whitening agent (4,4'-diaminostilbene type) 3.0 g Water was added to 1000 ml pH 10.05 Bleach-fixing solution EDTAFe (III) NH _{4 · 2H 2 O 60g EDTA · 2Na} · 2H 2 O 4g ammonium thiosulfate (70%) 120 ml sodium sulfite 16g glacial acetic acid 7g water to make 1000 ml pH 5.5 rinse solution formalin (37%) 0.1ml 1- hydroxyethylidene - 1,1-diphosphonic acid (60 %) 1.6 ml Bismuth chloride 0.35 g Ammonia water (26%) 2.5 ml Nitrilotriacetic acid.3Na 1.0 g EDTA.4H 0.5 g Sodium sulfite 1.0 g 5-chloro-2-methyl-4-isothiazoline- 3-on 50mg Water added 1000ml The sensitivity represents a relative value when the sample No. 10 is 100. As is clear from Table 3, the samples according to the combination of the present invention
Nos. 15 and 16 had no adverse effect on photographic performance and showed a strong inhibitory effect on the rearing of bacteria.

Example-3 Dispersion A was prepared as follows.

(Dispersion A) 10% bone gelatin 1000 g Emulsion EM 500 g Sodium dodecylbenzenesulfonate 5 g Water 1000 ml 5% 5% methanol solution of the compound-1 of the present invention was dissolved at 45 ° C to prepare dispersion A. Prepared the solution.

Emulsion ME was prepared by dissolving Compound EX-14 (44 g) and HBS-1 (20 ml) in ethyl acetate (100 ml), mixing with sodium dodecylbenzenesulfonate (4 g) dissolved in 10% bone gelatin (1000 g) and emulsifying with a household mixer for 10 minutes. Prepared.

(Dispersions B to F) Dispersions B to E in which the preservatives shown in Table 4 were added in place of the compound-1 of the present invention in Dispersions A and Dispersions F containing no preservatives were prepared.

These dispersions were aged at 40 ° C for 3 days and 6 days, and then the viscosity was measured.

Sample 3 was prepared by using these dispersions as a liquid for the sixth layer of a multilayer constitution coating sample composed of each layer having the composition shown below.
01-306 were produced.

(Photosensitive Layer Composition) The numbers corresponding to the respective components indicate the coating amount expressed in units of g / m ² , and for silver halide, the coating amount in terms of silver. However, for the sensitizing dye, the coating amount is shown in mol unit per mol of silver halide in the same layer. The compound will be specifically described later.

(Sample 101) First layer; anti-halation layer Black colloidal silver ...... Silver 0.18 gelatin ...... 0.40 Second layer; Intermediate layer 2,5-di-t-pentadecyl hydroquinone ...... 0.18 EX-1 ...... 0.07 EX-3 ...... 0.02 EX-16 ...... 0.004 U-1 ...... 0.08 U-2 ...... 0.08 HBS-1 ...... 0.10 HBS-2 ...... 0.02 Gelatin ...... 1.04 Third layer (first red-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 6 mol%, average grain size 0.6 µ) ...... Silver 0.55 Sensitizing dye I ...... 6.9 × 10 ^-5 sensitizing dye II ・ ・ ・ 1.8 × 10 ^-5 sensitizing dye III ・ ・ ・ 3.1 × 10 ^-4 sensitizing dye IV ・ ・ ・ 4.0 × 10 ^-5 EX- 2 ... 0.350 HBS-1 ... 0.005 EX-12 ... 0.020 Gelatin ... 1.20 Fourth layer (second red-sensitive emulsion) Layer) Silver iodobromide emulsion (silver iodide 8 mol%, average grain size 0.8 μ) ...... Silver 1.0 sensitizing dye I ...... 5.1 × 10 ^-5 sensitizing dye II ...... 1.4 × 10 ^-5 Sensitizing dye III ...... 2.3 × 10 ^-4 Sensitizing dye IV ...... 3.0 × 10 ^-5 EX-2 ...... 0.300 EX-3 ...... 0.050 EX-12 ... ... 0.015 HBS-2 ... 0.050 Gelatin ... 1.30 Fifth layer (third red sensitive emulsion layer) Silver iodobromide emulsion (16 mol% silver iodide, average grain size 1.1 µ) ... … Silver 1.60 Sensitizing dye IX …… 5.4 × 10 ⁻⁵ Sensitizing dye II …… 1.4 × 10 ⁻⁵ Sensitizing dye III …… 2.4 × 10 ⁻⁴ Sensitizing dye IV …… 3.1x10 ^-5 EX-5 ...... 0.050 EX-3 ...... 0.055 EX-4 ...... 0.060 HBS-1 ...... 0.32 Gelatin ...... 1.63 6th layer (intermediate) Layer) EX-1 ...... 0.115 HBS-1 ...... 0.057 Gelatin ...... 0.90 Seventh layer (first green-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 6 mol%, average grain size 0.6 μ) ...... Silver 0.40 Sensitizing dye V ...... 3.0 × 10 ^-5 Sensitizing dye VI ・ ・ ・ 1.0 × 10 ^-4 Sensitizing dye VII ・ ・ ・ 3.8 × 10 ^-4 EX-6 ...... 0.260 EX-1 ...... 0.021 EX-7 ...... 0.030 EX-8 ...... 0.025 EX-9 ...... 0.018 HBS-1 ...... 0.100 Gelatin ...... 0.75 Eight layers (second green-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 9 mol%, average grain size 0.7 μ) ...... Silver 0.80 Sensitizing dye V ...... 2.1 × 10 ^-5 sensitive dye VI ...... 7.0 × ^{10 -5} sensitizing dye ^{VII ...... 2.6 × 10 -4 EX-} 6 ...... 0.18 EX-8 ...... 0.010 EX-1 ...... 0.008 EX 7 ...... 0.012 EX-9 ...... 0.008 HBS-1 ・ ・ ・ 1.10 9th layer (third green sensitive emulsion layer) Silver iodobromide emulsion (12 mol% silver iodide, average grain size 1) .0 .mu.) ...... Silver 1.2 sensitizing dye V ...... 3.5 × 10 ^-5 sensitizing dye VI …… 8.0 × 10 ^-5 sensitizing dye VII ・ ・ ・ 3.0 × 10 ^-4 EX- 6 ...... 0.065 EX-13 ...... 0.030 EX-1 ...... 0.025 HBS-2 ...... 0.55 Gelatin ...... 1.74 10th layer (yellow filter layer) Yellow colloidal silver ...... Silver 0.05 EX-14 0.08 EX-15 0.03 HBS-1 0.03 Gelatin 0.95 11th layer (first blue-sensitive emulsion layer) Silver iodobromide emulsion ( silver iodide 6 mol%, average particle diameter a 0.6 micron) ...... silver 0.24 sensitizing dye ^{VIII ...... 3.5 × 10 -4 EX-} 12 ...... 0.0 5 EX-11 0.92 HBS-1 0.28 Gelatin 1.28 12th layer (second blue emulsion layer) Silver iodobromide emulsion (10 mol% silver iodide, average grain size) 0.8μ) Silver 0.45 Sensitizing dye VIII 2.1 × 10 ⁻⁴ EX-11 0.20 EX-10 0.015 HBS-1 0.03 Gelatin 0.46 Thirteenth layer (third blue-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 1 mol%, average grain size 1.3 μ) ...... Silver 0.77 Sensitizing dye VIII ...... 2.2 × 10 ^-4 EX-11 ... 0.20 HBS-1 ... 0.07 Gelatin ... 0.69 14th layer (first protective layer) Silver iodobromide emulsion (1 mol% silver iodide, average grain size) 0.07μ) ...... Silver 0.5 U-1 ...... 0.11 U-2 ...... 0.17 HBS-1 ...... 0.90 Gelatin ...... 1.00 Fifteenth Layer (second protective layer) Polymethyl acrylate particles (diameter about 1.5 μm) ...... 0.54 S-1 ...... 0.05 S-2 ...... 0.20 Gelatin ...... 0.72 Each of the above In addition to the components, gelatin hardening agent H-1 and a surfactant were added.

After subjecting these samples to imagewise exposure, color development described below was carried out to determine the relative sensitivities of the respective layers, which are shown in Table 4.

From Table 3, the dispersion of the present invention does not decrease in sensitivity,
It can be seen that it has an excellent antiseptic effect without the viscosity decreasing with time.

Color development processing was carried out at 38 ° C. according to the processing steps described below.

Color development 3 minutes 15 seconds Bleach 6 minutes 30 seconds Washing with water 2 minutes 10 seconds Fixing 4 minutes 20 seconds Washing with water 3 minutes 15 seconds Stability 1 minute 05 seconds The composition of the treatment liquid used in each step was as follows.

Color developer Diethylenetriaminepentaacetic acid 1.0 g 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 g Sodium sulfite 4.0 g Potassium carbonate 30.0 g Potassium bromide 1.4 g Potassium iodide 1.3 mg Hydroxylamine sulfate 2 .4 g 4- (N-ethyl-N-β-hydroxyethylamino) -2-methylaniline sulfate 4.5 g Water was added to 1.0 pH 10.0 Bleaching solution Ethylenediaminetetraacetic acid ferric ammonium salt 100 0.0 g Ethylenediaminetetraacetic acid dinatrium salt 10.0 g Ammonium bromide 150.0 g Ammonium nitrate 10.0 g Water added 1.0 pH 6.0 Fixing solution Ethylenediaminetetraacetic acid dinatrium salt 1.0 g Sodium sulfite 4.0 g Ammonium thiosulfate aqueous solution (70%) 175.0 ml Sodium acid 4.6 g Water added 1.0 pH 6.6 Stabilizer Formalin (40%) 2.0 ml Polyoxyethylene-p-monononylphenyl ether (average weight 10) 0.3 g Water added 1.0 Structure of the compound used in Example 3 HBS-1 Tricresyl Phosphate HBS-2 Dibutylphthalate HBS-3 Bis (2-ethylhexyl) phthalate Sensitizing dye I Sensitizing dye II Sensitizing dye III Sensitizing dye IV Sensitizing dye V Sensitizing dye VI Sensitizing dye VII Sensitizing dye VIII Sensitizing dye IX Example-4 The results of treating the multilayer color photographic paper prepared in Example-2 with a treatment liquid in which the color developer composition is changed to the following treatment liquid composition are shown in Table-5. The other treatment liquid compositions were the same as in Example-2.

Treatment process Temperature Time Color development 35 ° C 45 seconds Bleach fixing 35 ° C 45 seconds Rinse 1 35 ° C 20 seconds Rinse 2 35 ° C 20 seconds Rinse 3 35 ° C 20 seconds Dry 80 ° C 60 seconds Color developer used The composition is described below.

Color developer N, N-diethylhydroxylamine 4 g Triethanolamine 10.4 g Potassium carbonate 30 g EDTA.2Na.2H ₂ O 2 g Sodium chloride 1.0 g 4-Amino-3-methyl-N-ethyl-N- [β- (Methanesulfonamide) Ethyl] -p-phenylenediamine sulfate 5.0 g Fluorescent brightener (4,4′-diamino-stilbene system) 3.0 g Water was added to pH 1.10.

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material containing at least one compound represented by the general formula [I] and at least one compound represented by the general formula [II]. General formula [I] In the formula, R ₁ represents a lower alkylene group, X represents a halogen atom, a nitro group, a lower alkyl group, —COR ₂ , Represents —SO ₃ M, R ₂ represents a hydrogen atom, —OM, a lower alkyl group, a lower alkoxy group, Represents R ₃ and R ₄ may be the same or different from each other, and may be a hydrogen atom, a lower alkyl group, —COR ₇ , or —SO ₂ R ₇
R ₅ and R _{6, which} may be the same or different from each other, represent a hydrogen atom or a lower alkyl group, R ₇ represents a lower alkyl group, M represents a hydrogen atom, an alkali metal atom,
And n represents an atomic group necessary for forming a monovalent cation, and n represents 0 or an integer of 1 to 5. General formula (II) In the formula, R ₈ represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, and R ₉ , R ₁₀ , R ₁₁ and R ₁₂ represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group or an aryl group. Group, alkoxy group, aryloxy group,
Aralkyloxy group, carboxyl group, sulfo group, hydroxy group, Represents —SO ₂ R ₁₅ , R ₁₃ and R ₁₄ represent a hydrogen atom, an alkyl group, —COR ₁₅ and —SO ₂ R ₁₅ , and R ₁₅ represents an alkyl group and an alkoxy group. These R ₉ , R
₁₀ , R ₁₁ and R ₁₂ may be the same or different from each other.