JPS62168143A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide superior sharpness to a sensitive material and to stored the material in a good state by restricting the total thickness of all the hydrophilic colloidal layers of the sensitive material on one side of the support having emulsion layers on the side to <=18mum on the dry basis and by storing the sensitive material at <=55% relative humidity. CONSTITUTION:The total thickness of all the hydrophilic colloidal layers of a silver halide color photographic sensitive material on one side of the support having emulsion layers on the side is restricted to <=18mum on the dry basis, and the sensitive material is stored at <=55% relative humidity. the lower limit of the total thickness of all the hydrophilic colloidal layers depends on materials in the layers. The preferred total thickness is 5-18mum. The sensitive material is stored at <=55% relative humidity preferably by packing in a hermetically sealed state. In order to prevent static trouble liable to occur at low humidity, a fluorine compound is preferably added.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a photographic material having a thin dry film thickness and a method for preserving the same.

[Conventional technology]

In recent years, the image quality of silver halide color photographic light-sensitive materials (hereinafter referred to as color light-sensitive materials) has improved significantly, but the sharpness is still not sufficient, especially in small format negative color films (110 film, disc film, etc.). ), the roughness (granularity) and poor sharpness of the image significantly reduce the level of print quality. This is because the sharpness of negative film is not high enough to withstand high-magnification printing.

In order to improve sharpness, polymer coupler technology described in Japanese Patent Application Laid-Open No. 58-28745, etc. or Japanese Patent Application No. 1987-1952 is used.
34, etc., it has become possible to reduce the OI or Gel and achieve thinner films, but the present inventors have found that when extremely thin films It has been discovered that when photographic materials are stored under high temperature conditions, unfavorable photographic properties deteriorate.

[Purpose of the invention]

It is an object of the present invention to provide a method for preserving a photosensitive material, particularly a packaging method, which has excellent sharpness and is suitable for this purpose.

[Structure of the invention]

As a result of extensive studies, the present inventors have found that the object of the present invention is to provide a red-sensitive silver halide emulsion layer containing a cyan color-forming coupler, a green-sensitive silver halide emulsion layer containing a magenta color-forming coupler, and a yellow color-forming coupler on a support. A silver halide color photographic light-sensitive material having a blue-sensitive silver halide emulsion layer comprising a blue-sensitive silver halide emulsion layer, in which the total dry film thickness of all hydrophilic colloid layers on the side having the emulsion layer is 18 μm or less, and the silver halide color This was achieved by using a silver halide color photographic material, which is characterized by being stored at a relative humidity of 55% or less.

The term "dry film thickness" as used herein refers to a value measured under conditions where the humidity is controlled to 23° C. and 55% RH.

In the present invention, sealed packaging is preferred as a method for keeping the relative humidity at 55% or less.

Sealed packaging as used in the present invention refers to moisture-proof packaging, which is well known in the field of ordinary packaging. Packaging materials include metals and metal foils such as aluminum plates, tin plates, and aluminum foils, and glass. Or polymers such as polyethylene, polyvinyl chloride, polystyrene, polyvinylidene chloride, polypropylene, polycarbonate, polyamide,
Composite laminated materials (laminated materials in packaging terms) made of various polymers and materials such as cellophane, paper, and aluminum foil are used.

Liquid sealing methods include adhesive methods using various adhesives,
A thermal adhesion method such as heat sealing, or a method using a cartridge case, which is common in the photographic industry, can be used. The details of these liquid sealing methods are described in "Food Packaging Technology Handbook" Japan Packaging Technology Boundary (Mg), pages 573 to 609.

Halogenation stored at relative humidity of 55% or less in the present invention! ! I Photosensitive material is the weight w measured within 30 seconds after opening the silver halide photosensitive material at 25°C and 55% relative humidity.
Weight W measured after storage for 3 days or more under the same conditions as SS! The difference from SS is Δw''=wzSS−w, which is defined as SS being greater than or equal to zero.

A preferable condition of the present invention is that the weight change ΔW30 at 25° C. relative humidity is 30% is negative, and a more preferable condition is that the weight change ΔW3s is negative at 25° C. relative humidity 35%.

In the present invention, a cartridge case made of a polymer such as polyethylene or polypropylene is preferable for roll-type photographic light-sensitive materials, and a cartridge case made of polyethylene or the like is preferable for sheet-type photographic light-sensitive materials.

These sealed packagings may be done in duplicate.

As a packaging method with a lower relative humidity as in the present invention, the silver halide photographic light-sensitive material may be packaged in a low-humidity chamber, or the material may be dried more than usual when drying. Additionally, a desiccant such as silica gel may be added to the sealed container to reduce humidity.

When implementing the present invention, static failures often occur due to low humidity. To prevent this static failure,
It is particularly preferable to add a fluorine compound, which is well known as an antistatic agent.

As a fluorine compound, for example, Japanese Patent Publication No. 48-431
Compounds described in JP-A-46-778L and JP-A-55-55052 can be used.

The dry film thickness in the present invention means the film thickness measured at 23° C. and 55% UR humidity.

Regarding the thickness of each layer, the cross section of the dried sample is photographed under magnification using a scanning electron microscope, and the thickness of each layer is measured.

The lower limit of the total dry film thickness of all the hydrophilic colloid layers on the side having the emulsion layer (hereinafter referred to as the film thickness on the emulsion side) is determined by the amount of silver halide emulsion, oil agents such as couplers, additives, gelatin, etc. There is a limit depending on the volume occupied by the binder, etc., and the preferred film thickness on the emulsion surface is 5 .mu.m to 18 .mu.m, more preferably 10 .mu.m to 16 .mu.m. Also, the distance from the outermost surface of the emulsion surface to the bottom end of the emulsion layer closest to the support is 14
The thickness is preferably 10 .mu.m or less, and the distance from the emulsion layer to the lower end of the emulsion layer next to the support, which is different in color sensitivity from the emulsion layer and closest to the support, is preferably 10 .mu.m or less.

Further, the thickness of the layer containing a magenta coupler such as pyrazolotriazole is preferably 0.5 μm to 5 μm.

The silver halide emulsions used in the present invention include conventional silver halide emulsions such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, silver chloroiodobromide, and silver chloride. Any silver bromide, silver iodobromide, and silver chloroiodobromide are particularly preferred.

The silver halide grains used in the silver halide emulsion may be obtained by any of the acidic method, neutral method, and ammonia method. The grains may be grown all at once or by growing seed grains. The method for producing and growing the zero-type particles may be the same or different.

In the silver halide emulsion, halide ions and silver ions may be mixed simultaneously, or one may be mixed in a liquid in which the other is present. Further, while taking into consideration the critical growth rate of silver halide crystals, halide ions and silver ions may be generated by sequentially and simultaneously adding them while controlling 9H and pAg in the mixing tank. By this method, silver halide grains having a regular crystal shape and a nearly uniform grain size can be obtained. Conversion methods may be used at any step in the formation of AgX to change the halogen composition of the particles.

During the growth of silver halide grains, a known tMtg halide such as ammonia, thioether, thiourea, etc. can be present.

During the process of grain formation and/or growth, silver halide grains are produced using cadmium salts, zinc salts, lead salts, thallium salts, iridium salts (including complex salts), rhodium salts (including complex salts), and iron salts ( By adding metal ions using at least one selected from the group consisting of complex salts), these metal elements can be contained inside the particles and/or on the particle surfaces, and by placing them in an appropriate reducing atmosphere. A reduction sensitizing acid can be provided inside the particles and/or on the particle surface.

Unnecessary soluble salts may be removed from the silver halide emulsion after the growth of silver halide grains is completed, or they may be left contained. When removing the salts, Research Disc
losure (hereinafter abbreviated as RD)> It can be carried out based on the method described in No. 17643, Section 3.

The silver halide grains may have a uniform silver halide composition distribution within the grain, or may be core/shell grains in which the silver halide composition differs between the inside of the grain and the surface layer.

The silver halide grains may be such that the latent image is mainly formed on the surface, or may be such that the latent image is mainly formed inside the grain.

The silver halide grains may have a regular crystal shape such as a cube, octahedron, or dodecahedron, or may have an irregular crystal shape such as a spherical shape or a plate shape. In these particles, any ratio of +1001 plane to T1111 plane can be used.

Further, the particles may have a composite form of these crystal forms, or particles of various crystal forms may be mixed.

The size of silver halide grains is 0.05 to 30μ,
Preferably, those having a diameter of 0.1 to 20μ can be used.

Silver halide emulsions having any grain size distribution may be used. An emulsion with a wide grain size distribution (referred to as a polydisperse emulsion) may be used, or an emulsion with a narrow grain size distribution (referred to as a polydisperse emulsion). When divided by the average particle size, the value is 0.20 or less (here, the particle size follows the above definition)) may be used alone or in combination of several types.

Further, a mixture of a polydisperse emulsion and a monodisperse emulsion may be used.

The silver halide emulsion may be a mixture of two or more separately formed silver halide emulsions.

Silver halide emulsions can be chemically sensitized by conventional methods. Namely, sulfur enhancement method, selenium sensitization method, reduction sensitization method,
A noble metal sensitization method using gold or other noble metal compounds can be used alone or in combination.

Silver halide emulsions can be optically sensitized to a desired wavelength range using dyes known in the photographic industry as sensitizing dyes. Aggravating pigments may be used alone, or two or more types may be used in combination. Along with the sensitizing dye, the emulsion may contain a dye that itself does not have a spectral sensitizing effect, or a superchromic enhancer, which is a compound that does not substantially absorb visible light and enhances the aggravating effect of the aggravating dye.

Sensitizing dyes include cyanine dyes, merocyanine dyes,
Complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, steryl dyes and hemioxanol dyes are used.

Particularly useful dyes include cyanine dyes, merocyanine dyes,
and a complex merocyanine pigment.

Silver halide emulsions are used during the manufacturing process of photosensitive materials, during storage,
Alternatively, for the purpose of preventing fog during photographic processing or maintaining stable photographic performance, photographs may be taken during chemical ripening, at the end of chemical ripening, and/or after chemical ripening and before coating a silver halide emulsion. Compounds known in the art as antifoggants or stabilizers can be added.

Binder (or protective colloid) for silver halide emulsions
Although it is advantageous to use gelatin, gelatin derivatives, graft polymers of gelatin and other polymers,
Hydrophilic colloids such as other proteins, sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymer substances such as single or copolymers can also be used.

The photographic emulsion layer or other hydrophilic colloid layer of a light-sensitive material using the silver halide emulsion of the present invention contains one or more hardeners that crosslink binder (or protective colloid) molecules and increase film strength. It can be used to harden the membrane. The hardening agent can be added in an amount capable of hardening the photosensitive material to such an extent that it is not necessary to add the hardening agent to the processing solution, but it is also possible to add the hardening agent to the processing solution.

For example, aldehydes (formaldehyde, glyoxal, geltaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives) (2,3-dihydroxydioxane, etc.), activated vinyl compounds (1,3,5 -triacryloyl-hexahydro-5-1-lyazine,
1.3-vinylsulfonyl-2-propatol, etc.),
Active halogen compound j! , 4-dichloro-6-hydroxy-5-)riazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxychloroic acid, etc.), and the like can be used alone or in combination.

A plasticizer can be added to the silver halide emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material for the purpose of increasing flexibility. Preferred plasticizers are the compounds described in RD 17643, item x-8.

A dispersion (latex) of a water-insoluble or a-soluble synthetic polymer can be contained in the photographic emulsion layer or other hydrophilic colloid layer of a light-sensitive material for the purpose of improving dimensional stability.

For example, alkyl (meth)acrylate, alkoxyalkyl (meth)acrylate, glycidyl (meth)acrylate, (meth)acrylamide, vinyl ester (
(e.g. vinyl acetate), acrylonitrile, olefins,
Monomer components include styrene, etc. alone or in combination, or combinations thereof with acrylic acid, methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth)acrylate, sulfoalkyl (meth)acrylate, styrene sulfonic acid, etc. Polymers can be used.

In the emulsion layer of a light-sensitive material, a dye is formed by a coupling reaction with an oxidized form of an aromatic primary amine developer (e.g., p-phenylenediamine derivative, aminophenol derivative, etc.) during color development processing. Dye-forming couplers are used. The dye-forming couplers are typically selected for each emulsion layer such that a dye is formed that absorbs light in the light-sensitive spectrum of the emulsion layer, with a yellow dye-forming coupler for the blue-sensitive emulsion layer and a dye for the green-sensitive emulsion layer. A magenta dye-forming coupler is used in the sensitive emulsion layer and a cyan dye-forming coupler is used in the red-sensitive emulsion layer. However, depending on the purpose, silver halide color photographic materials may be produced using different combinations from the above.

These dye-forming couplers preferably have a group called a ballast group in the molecule, which makes the coupler non-diffusive and has 8 or more carbon atoms. In addition, even if these dye-forming couplers are tetraequivalent, which requires reduction of four molecules of silver ions in order to form one molecule of dye, only two molecules of silver ions need to be reduced. Either bi-isomerism is acceptable. Dye-forming couplers include colored couplers that have a color correction effect and, by coupling with oxidized forms of developing agents, can be used as development inhibitors, development accelerators, bleaching accelerators, developers, silver halide solvents, and toning agents. Compounds that release photographically useful fragments such as hardeners, fogging agents, antifoggants, chemical sensitizers, spectral sensitizers, and desensitizers are included. Among these, couplers that release a development inhibitor during development and improve image sharpness and image graininess are called DIR couplers. In place of the DIR coupler, a DIR compound which undergoes a coupling reaction with the oxidized form of the developing agent to produce a colorless compound and at the same time releases a development inhibitor may be used.

The DIR couplers and DIR compounds used include those with an inhibitor directly attached to the coupling position and those with an inhibitor attached to the coupling position.
It is bonded to the coupling position via a valence group, and the inhibitor is bonded in such a way that the inhibitor is released by an intramolecular nucleophilic reaction or an intramolecular electron transfer reaction at the base circle separated by the coupling reaction ( (referred to as timing DIR couplers and timing DIR compounds). Further, depending on the purpose, inhibitors that are diffusible after release and those that are not so diffusible can be used alone or in combination. A colorless coupler (also called a competitive coupler) which undergoes a coupling reaction with an oxidized aromatic primary amine developer but does not form a dye can also be used in combination with a dye-forming coupler.

As the yellow dye-forming coupler, known acylacetanilide couplers can be preferably used.

Among these, benzoylacetanilide and pivaloylacetanilide compounds are advantageous. Specific examples of yellow coloring couplers that can be used include, for example, U.S. Patent No. 2.87.
No. 5,057, No. 3゜265, 506, No. 3,4
No. 08.194, No. 3,551.155, No. 3,
No. 582.322, No. 3,725,072, No. 3
．． 891,445, West German Patent No. 1.547.868, West German Application No. 2.219.917, West German Patent No. 2,261
, No. 361, No. 2゜414.006, British Patent No. 1
．． 425.020, JP 51-10783, JP 47-26133, JP 48-73147, JP 50-
No. 6341, No. 50-87650, No. 50-1233
No. 42, No. 50-130442, No. 51-21827
No. 51-102636, No. 52-82424,
It is described in No. 52-115219, No. 58-95346, etc.

As the magenta dye-forming coupler, known 5-pyrazolone couplers, pyrazolobenzimidazole couplers, pyrazolotriazole couplers, open-chain acylacetonitrile couplers, indacylon couplers, and the like can be used.

Specific examples of magenta color-forming couplers that can be used include, for example, U.S. Pat. No. 2,600,788, U.S. Pat.
No. 3,311゜476, No. 3,419,39
No. 1, No. 3,519,429, No. 3,558,3
No. 19, No. 3,582,322, No. 3,615.
No. 506, No. 3.834.908, No. 3,891
．． 445 West German Patent No. 1,810,464, West German Patent Application (OLS) No. 2,408.665, OLS No. 2,41
No. 7,945, No. 2.418.959, No. 2,4
No. 24,467, Japanese Patent Publication No. 40-6031, Japanese Patent Publication No. 1973
-74027, 49-74028, 49-12
No. 9538, No. 50-60233, No. 50-1593
No. 36, No. 51-20826, No. 51-26541, No. 52-42121, No. 52-58922, No. 5
Examples include those described in Japanese Patent Application No. 3-55122 and Japanese Patent Application No. 110943/1983.

Phenol or naphthol couplers are commonly used as cyan dye-forming couplers. Specific examples of cyan color-forming couplers that can be used include, for example, U.S. Patent No. 2.42.
No. 3,730, No. 2,474,293, No. 2.8
OL No. 171, OL No. 2.895,826, OL No. 3, 4
No. 76.563, No. 3,737.326, No. 3.
No. 758.308, Specification No. 3.893,044,
JP-A No. 47-37425, No. 50-10135, No. 50-25228, No. 50-112038, No. 50
Preferred are couplers described in Japanese Patent Laid-open No. 117422, Japanese Patent Laid-open No. 58-98731, and the like.

Dye-forming couplers, colored couplers, DIR couplers, DIR that do not need to be adsorbed on the silver halide crystal surface
compounds, image stabilizers, color antifoggants, ultraviolet absorbers,
Among fluorescent brighteners, hydrophobic compounds can be prepared using various methods such as solid dispersion method, latex dispersion method, and oil-in-water emulsion dispersion method. It can be selected as appropriate depending on the situation. For the oil-in-water emulsion dispersion method, conventionally known methods for dispersing hydrophobic additives such as couplers can be applied, and the boiling point is usually about 150°C.
or higher boiling point organic solvents with lower boiling points, ° and/or
Alternatively, dissolve it in combination with a water-soluble organic solvent, use a surfactant in a hydrophilic binder such as an aqueous gelatin solution, and use a dispersion means such as a stirrer, homogenizer, colloid mill, flow jet mixer, or ultrasonic device. After emulsification and dispersion.

It may be added to the desired hydrophilic colloid liquid.

A step of removing the low-boiling organic solvent may be included simultaneously with the dispersion or dispersion.

Examples of high-boiling point solvents include organic compounds with a boiling point of 150°C or higher, such as phenol derivatives, phthalate alkyl esters, phosphate esters, citric acid esters, benzoic acid esters, alkylamides, fatty acid esters, and trimesic acid esters, which do not react with the oxidized form of the developing agent. A solvent is used.

Low boiling or water-soluble organic solvents can be used in conjunction with or in place of high boiling solvents. Examples of low boiling point substantially water-insoluble aqueous solvents include ethyl acetate, propyl acetate, butyl acetate, butanol, chloroform,
Examples include carbon tetrachloride, nitromethane, nitroethane, and benzene.

When dye-forming couplers, DIR couplers, colored couplers, DIR compounds, image stabilizers, color antifoggants, ultraviolet absorbers, fluorescent whitening agents, etc. have acid groups such as carboxylic acid or sulfonic acid, an alkaline aqueous solution is used. It can also be introduced into hydrophilic colloids as a hydrophilic colloid.

Anionic surfactants, nonionic surfactants can be used as auxiliary agents when dissolving a hydrophobic compound in a low boiling point solvent alone or in combination with a high boiling point solvent and dispersing it in water using mechanical or ultrasonic waves. Agents, cationic surfactants and amphoteric surfactants can be used.

The oxidized form of the developing agent or the electron transfer agent may migrate between the emulsion layers of the light-sensitive material (between the same color-sensitive layers and/or between different color-sensitive layers), causing color turbidity or deterioration of sharpness.
A color antifoggant can be used to prevent graininess from becoming noticeable.

The color antifoggant may be contained in the emulsion layer itself, or
An interlayer may be provided between adjacent emulsion layers and contained in the interlayer.

An image stabilizer can be used in the photosensitive material to prevent deterioration of the dye image. Compounds that can be preferably used are those described in RD No. 17643, Section 2 J.

Hydrophilic colloid layers such as protective layers and intermediate layers of photosensitive materials may contain ultraviolet absorbers to prevent fogging due to discharge caused by charging of the photosensitive material due to friction, etc., and to prevent image deterioration due to ultraviolet rays. good.

In order to prevent deterioration of magenta dye-forming couplers and the like due to formalin during storage of the light-sensitive material, a formalin scavenger can be used in the light-sensitive material.

When dyes, ultraviolet absorbers, etc. are contained in the hydrophilic colloid layer of a photosensitive material, they may be mordanted with a mordant such as a cationic polymer.

Compounds that change the developability, such as development accelerators and development retardants, and bleaching accelerators can be added to the silver halide emulsion layer and/or other hydrophilic colloid layers of the light-sensitive material. A compound that can be preferably used as a development accelerator is RD17.
The compound is a compound described in Section XXI B to D of No. 643, and the development retardant is a compound described in Section E of Section XXT of No. 17643. black and white developing agents for development acceleration and other purposes, and/or
Alternatively, its precursor may be used.

The emulsion layer of a photographic light-sensitive material is made of polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholines, quaternary ammonium compounds, urethane derivatives, etc. for the purpose of increasing sensitivity, increasing contrast, or promoting development. It may also contain urea t* door bodies, imidazole derivatives, and the like.

A fluorescent whitening agent can be used in the photosensitive material for the purpose of emphasizing the whiteness of the white background and making the coloration of the white background less noticeable. Compounds which can preferably be used as fluorescent brighteners are described in section V of RD 17643.

The photosensitive material can be provided with auxiliary layers such as a filter layer, an antihalation layer, and an antiirradiation layer. These layers and/or the emulsion layer may contain dyes that are washed out of the light-sensitive material or bleached during the development process.

Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes, azo dyes, and the like.

A matting agent can be added to the silver halide emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material for the purpose of reducing the gloss of the light-sensitive material, improving the ease of writing, and preventing the light-sensitive materials from sticking together. Any matting agent can be used, but examples include silicon dioxide, titanium dioxide, magnesium dioxide, aluminum dioxide, barium sulfate, charcoal hydroxide ram, polymers of acrylic acid and methacrylic acid and their esters, and polyvinyl resin. , polycarbonate, and styrene polymers and their copolymers.The particle size of the matting agent is preferably 0.05μ to 10μ.The amount added is 1 to 300mg/n?
is preferred.

A slider can be added to the photosensitive material to reduce sliding friction.

An antistatic agent can be added to the photosensitive material for the purpose of preventing static electricity. The antistatic agent may be used in the antistatic layer on the side of the support on which the emulsion is not laminated, and the protective colloid layer other than the emulsion layer on the side on which the emulsion layer is laminated with respect to the emulsion layer and/or the support. May be used for. Preferably used antistatic agents are the compounds described in RD 17643 x■.

The photographic emulsion layer and/or other hydrophilic colloid layer of a light-sensitive material is used to improve coating properties, prevent static electricity, improve slipperiness, emulsification and dispersion, prevent adhesion, and improve photographic properties (development acceleration, hardening, sensitization, etc.). Various surfactants can be used for these purposes.

Supports used in the photosensitive material of the present invention include films made of semi-synthetic or synthetic polymers such as cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene phthalate, polycarbonate, and polyamide.

After subjecting the surface of the support to corona discharge, ultraviolet irradiation, flame treatment, etc. as necessary, the photosensitive material can be used directly or to improve the adhesion, antistatic properties, dimensional stability, abrasion resistance, hardness, etc. of the support surface. It may be applied through one or more subbing layers to improve antihalation properties, frictional properties, and/or other properties.

When coating the photosensitive material, a thickener may be used to improve coating properties. Also, for things like hardeners, which are so reactive that if added to the coating solution in advance, they will gel before coating, it is best to mix them using a static mixer or the like just before coating. preferable.

As a coating method, extrusion coating and curtain coating, which allow two or more types of layers to be applied simultaneously, are particularly useful, but depending on the purpose, basket coating may also be used. Further, the coating speed can be arbitrarily selected.

Examples of the surfactant include, but are not limited to, natural surfactants such as saponin, nonionic surfactants such as alkylene ookindo type, glycerin type, and dalicidol type, higher alkylamines, quaternary ammonium salts, and lysine. Other heterocycles, cationic surfactants such as phosphoniums or sulfoniums, carboxylic acids, sulfonic acids,
Anionic surfactants containing acidic groups such as phosphoric acid, sulfuric acid esters, and phosphoric acid esters; amphoteric surfactants such as amino acids, aminosulfonic acids, and sulfuric acid or phosphoric acid esters of amino alcohols may be added.

Moreover, it is also possible to use a fluorine-based surfactant for the same purpose.

To obtain a dye image using the photosensitive material of the present invention, after exposure,
Perform color photo processing. Color processing includes a color development process, a bleaching process, a fixing process, a water washing process, and, if necessary, a stabilizing process, but instead of the process using a bleach solution and the process using a fixer. In addition, a bleach-fixing process can be carried out using a 1-bath bleach-fixing solution, or a monobath processing process using a 1-bath developing, bleach-fixing solution that allows color development, bleaching, and fixing to be performed in one bath. You can also do

In combination with these processing steps, a pre-hardening process, its neutralization process, a stop-fixing process, a post-hardening process, etc. may be performed. In these treatments, instead of the color development process, an activator treatment process may be performed in which a color developing agent or its precursor is contained in the material and the development process is performed using an activator solution, or an activator treatment may be performed in the monobath process. can be applied. Among these processes, typical processes are shown below. (These treatments are carried out as the final step, which is either a water washing process, a water washing process, or a stabilization process.) - Color development process -
Bleaching process Fixed fixing process/Color development process - Bleach-fixing process/Pre-hardening process - Color developing process - Stop fixing process - Water washing process - Bleaching process Constant fixing process - Washing process - Post-hardening treatment process/Color development treatment process - Water washing treatment process - Supplementary color development treatment process - Stop treatment process - Bleaching treatment process Constant fixation treatment - [Process/Actichator treatment process - Bleach-fixing treatment process/Actichator treatment process - Bleaching treatment Process Fixed treatment step/monobath treatment step The treatment temperature is usually selected in the range of 10°C to 65°C, but may be set to a temperature exceeding 65°C. Preferably 25℃
Processed at ~45°C.

A color developing solution generally consists of an alkaline aqueous solution containing a color developing agent. The color developing agent is an aromatic primary amine color developing agent, and includes aminophenol type and p-phenyrezine amine type Si 8 body. These color developing agents can be used as salts of organic and inorganic acids;
For example, hydrochloric acid, sulfate, p-toluenesulfonate, sulfite, oxalate, Hensensulfonate, etc. can be used.

These compounds are generally about 0.0% in color developer 11.
A concentration of 1 to 30 g is used, more preferably a concentration of about 1 to 15 g for color development itz. If the amount added is less than 0.1 g, sufficient color density cannot be obtained.

Examples of the aminophenol-based developer include O-aminophenol, p-aminophenol, 5-aminophenol,
Included are 2-oxy-toluene, 2-amino-3-oxy-toluene, 2-oxy-3-ami/-1,4-dimethyl-hensen, and the like.

Particularly useful primary aromatic amine color developers include N, N-
A dialkyl-p-)unilene diamine compound,
Alkyl groups and phenyl groups may be substituted or unsubstituted. Among them, an example of a particularly useful compound is N.

N-dimethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, N.

N-dimethyl-p-phenylenediamine hydrochloride, 2-amino-5-(N-ethyl-N-dodecylamino)-toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-amino Aniline 6M salt, N-ethyl-7N-β-hydroxyethylaminoaniline, 4
-amino-3-methyl-N, N-diethylaniline,
Examples include 4-amino-N-(2-methoxyethyl)-N-ethyl-3-methylaniline-p-toluenesulfonate.

Further, the above color developing agents may be used alone or in combination of two or more. Furthermore, the above color developing agents may be incorporated into color photographic materials.

In this case, it is also possible to treat the silver halide color photographic light-sensitive material with an alkaline solution (activator solution) instead of a color developing solution, and the bleach-fixing process is carried out immediately after the alkaline solution treatment.

The color developing solution used in the present invention may contain alkaline agents commonly used in developing solutions, such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium sulfate, sodium metaborate, or borax. It can also contain various additives such as benzyl alcohol, alkali metal halides, such as potassium bromide or potassium chloride, development control agents such as citrazic acid, and preservatives such as hydroxylamine or sulfites. You may.

Furthermore, various antifoaming agents and surfactants, as well as organic solvents such as methanol, dimethylformamide or dimethyl sulfoxide, etc. can be appropriately contained.

The pH of the color developing solution used in the present invention is usually 7 or more,
Preferably it is about 9-13.

In addition, the color developing solution used in the present invention may contain antioxidants such as diethylhydroxyamine, tetronic acid, tetronimide, 2-anilinoethanol, dihydroxyacetone, aromatic secondary alcohol, hydroxamic acid, hendose or hexose, pyrogallol-1,
3-dimethyl ether etc. may be contained.

Various chelating agents can be used in combination as metal ion sequestering agents in the color developing solution used in the present invention. For example, as the chelating agent, amine polycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminopentaacetic acid,
-Organic phosphonic acids such as hydroxyethylidene-1,1'-diphosphonic acid, aminotri(methylenephosphonic acid)
or aminopolyphosphonic acid such as ethylenediaminetetraphosphoric acid, oxycarboxylic acid such as citric acid or gluconic acid, phosphonocarboxylic acid such as 2-phosphonobutane, 1,2.4=tricarboxylic acid, polyphosphoric acid such as tripolyphosphoric acid or hexametaphosphoric acid. etc., polyhydroquine compounds, etc.

The bleaching process may be performed simultaneously with the fixing process as described above, or may be performed separately.

As bleaching agents, metal complex salts are used, such as polycarboxylic acids, aminopolycarboxylic acids, or organic acids such as oxalic acid and citric acid, coordinated with metal ions such as iron, cobalt, and copper. It will be done.

Among the above organic acids, the most preferable m-acids include polycarboxylic acids and aminopolycarboxylic acids. Specific examples of these include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediamine-N-(β-oxyethyl)-N,N',N'-triacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, and iminodiacetic acid. ,
Dihydroxyethylglycine citric acid (or tartaric acid),
Examples include ethyl ether diamine tetraacetic acid, glycol ether diamine tetraacetic acid, ethylenediaminetetrapropionic acid, and phenylenediaminetetraacetic acid. These polycarboxylic acids are alkali metal salts,
It may be an ammonium salt or a water-soluble amine salt. These bleaches contain 5-450 g/12. More preferably, it is used at 20 to 250 g/β.

In addition to the above bleaching agent, the bleaching solution may contain a sulfite as a preservative, if necessary. Alternatively, it may be a bleaching solution containing an ethylenediaminetetraacetate iron(III) 19 salt bleaching agent and a large amount of a halide such as ammonium bromide. As the halides, in addition to ammonium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, etc. can also be used. can.

The bleaching solution used in the present invention includes JP-A-46-280, JP-B No. 45-8506, JP-B No. 46-556, Belgian Patent No. 770.910, JP-B No. 45-8836,
Various bleach accelerators described in JP-A-53-9854, JP-A-54-71634 and JP-A-49-42349 can be added.

The pH of the bleaching solution used is 2.0 or higher, but generally it is 4.
．． It is used between 0 and 9.5, preferably between 4.5 and 8.0, and most preferably between 5.0 and 7.0.

A fixer having a commonly used composition can be used. As fixing agents, compounds that react with silver halide to form water-soluble complex salts, such as those used in ordinary fixing processes, such as periosulfates such as potassium thiosulfate, sodium thiosulfate, and ammonium thiosulfate, and thiocyanic acid are used. Typical examples include thiocyanates such as potassium, sodium thiocyanate, and ammonium thiocyanate, thiourea, and thioether. These fixatives are 5
It is used in an amount of 70 to 250 g/1 or more, but is generally within the range of soluble.

Incidentally, a part of the fixing agent can be contained in the bleaching tank, or conversely, a part of the bleaching agent can also be contained in the fixing tank.

The bleaching solution and/or fixing solution may contain various pH buffers such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide. These agents may be contained alone or in combination of two or more. Furthermore, various fluorescent whitening agents, antifoaming agents, or surfactants can be contained. Also,
Preservatives such as hydroxylamine, hydrazine, bisulfite adducts of aldehyde compounds, organic chelating agents such as aminopolycarboxylic acids, stabilizers such as nitro alcohols and nitrates, hardeners such as water-soluble aluminum salts, methanol, Contains dimethyl sulfamide, dimethyl sulfoxide, etc. 8! A solvent and the like can be contained as appropriate.

The pH of the fixer is used at 3.0 or higher, but generally it is 4.
．． 5-1O, preferably 5-9.5, most preferably 6-9.

As the bleaching agent used in the bleach-fixing solution, there can be mentioned the metal complex salts having the same composition as described in the above bleaching treatment step, and the preferred compounds and concentrations in the processing solution are also the same as in the above bleaching treatment step.

The bleach-fixing solution contains a silver halide fixing agent in addition to the above bleaching agent, and if necessary, a sulfite salt as a preservative. Also, a bleach-fix solution consisting of an ethylenediaminetetraacetic acid iron(III) complex salt bleach and a small amount of a halide such as ammonium bromide other than the above-mentioned silver halide fixer, or conversely, a halide such as ammonium bromide. A bleach-fixing solution containing a large amount of iron ethylenediaminetetraacetate (I
II) A special bleach-fix solution having a composition consisting of a combination of a tiF salt bleach and a large amount of a halide such as ammonium bromide can also be used. As the halides, in addition to ammonium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, etc. can also be used. can.

Examples of the silver halide fixing agent that can be included in the bleach-fixing solution include the fixing agents described in the above fixing process. The concentration of the fixing agent, pH H11 buffer agent and other additives that can be contained in the bleach-fixing solution are the same as in the fixing process described above.

The bleach-fix solution is used at a pH of 4.0 or higher, but is generally used at a pH of 5.0 to 9.5, preferably 6.0 to 8.
5, most preferably 6.5 to 8.5.

[Examples] Specific examples of the present invention will be described below, but the manner of carrying out the present invention is not limited to these.

In all of the following Examples, the amounts added in the silver halide photographic light-sensitive materials are shown per lnf unless otherwise specified, and silver halide and colloidal silver are shown in terms of silver.

Multilayer color photographic element sample 1 was prepared by sequentially forming each layer having the composition shown below on a triacetyl cellulose film support from the support side.

Sample-1 (comparison) First layer; Haley silane prevention layer (HC-1) Gelatin layer containing black colloidal silver.

Second layer: Intermediate layer (■) Gelatin layer containing an emulsified dispersion of 2.5-di-t-octylhydroquinone.

Third layer; low sensitivity red-sensitive silver halide emulsion layer (RL-1>
Monodisperse emulsion (emulsion) consisting of 8 gBrl containing 6 mol% of Agl, average grain size (r) 0.30 μm (emulsion...Amount of silver coated: 1.8 g/A sensitizing dye!... 1 mol of silver) 6XlO-'Mole Sensitizing dye ■...1.OX per mole of silver 10-'Morsian coupler (C-1)...0% per mole of silver .06 molar colored cyan coupler (CC-1)...Silver 1
0.003 mol DIR compound (D-1) per mole 0.0015 mol DIR compound (D-2) per 1 mol silver 0.002 mol 4th layer; high intensity red-sensitive silver halide emulsion layer (RH-1)
Monodisperse emulsion (emulsion ■) consisting of AgBr1 with an average grain size (r) of 0.574 m and containing 7.0 mol% of Agl... Silver coating amount 1.3 g/nf sensitizing dye I...... Silver 3XIO-' moles per mole of sensitizing dye ■...1.0X10-' moles per 1 mole of silver .02 molar colored cyan coupler (CC-1)...s1
1 mole to 0.0015 mole DIR compound (D-2)... 0.001 mole to 1 mole of silver 5th layer; Intermediate layer (1,L,) Same as second layer, Seratin layer.

6th layer; low sensitivity green-induced silver halide emulsion layer (GL-1)
Emulsion - ■... Coated silver amount: 1.5 g/m Enhancement dye: 2.5 x 10-' mol sensitizing dye per 1 mole of silver...
... 1.2 x 10-' moles per mole of silver Magenta coupler (M-1) ...0.050 per mole of silver
Mol colored magenta coupler (CM-1)...0.009 mol DIR per 1 mol silver Compound (D-1)... 0.0010 mol DIR per 1 mol silver Compound (D-3)... 0.0030 mol per mol of silver 7th layer; High-sensitivity green-sensitive silver halide emulsion layer (GO-1)
Emulsion - ■... Coated silver amount 1.4 g/m Sensitizing dye ■... If 1.5 x 10-' mole sensitizing dye ■... - 1.0 x 10-' mole magenta coupler (M-1) per mole of silver...0.02 per mole of 811
0 mol colored magenta turnip-7- (CM 1)...
・0.002 mol DIR compound (D-3) per 1 mol of silver 0.0010 mol per mol of silver 8th layer; Yellow filter single layer (VC-1) Yellow colloidal silver 2. A gelatin layer comprising an emulsified dispersion of 5-di-t-octylhydroquinone.

9th layer; low-frequency blue-bewitching silver halide emulsion layer (BL-1
) Average particle size 0.48 μm, AgB containing 8g 16 mol%
Monodispersed emulsion (emulsion m) consisting of r1...silver coating amount 0.9 g/n (sensitizing dye ■...... 1.3 x 10-' mol yellow coupler (EY -1)...0.0% per mole of silver.
29 mol 1st O layer; high-frequency blue-sensitive emulsion layer (BH-1) average grain size 0
．． 8 μm, a monodispersed emulsion (emulsion ■) consisting of ^RBr+ containing 15 mol% of Agl...! I coating amount 0.5g/n?
Sensitizing dye V... 1.0 x 10-' mol per mol of silver Yellow coupler (Y-1) 0.08 mol per mol of ill DIR compound ( D-2) Old... 0.0015 mol per mol of silver 11th layer; 1st protective layer (Pro-1) Silver iodobromide (Ag
11 mol% average particle size 0.07 μm) Silver coating amount 0.5 g/
rd Gelatin layer containing ultraviolet absorbers UV-1 and UV-2.

12th N: Second protective layer (Pro-2) Gelatin layer containing polymethyl methacrylate particles (1.5 μm in diameter) and formalin scavenger (HS-1).

In addition to the above composition, each layer contains a gelatin hardening agent ()I-
0) and a surfactant were added.

The compounds contained in each layer of Sample I are as follows.

Exacerbating pigment■;Anhydro5+5'-';Rioo-g
-ethyl-3,3"-di(3-sulfopropyl)thiacarbocyanine hydrokit sensitizing dye H; anhydro9-ethyl-3,3°-di(
3-sulfopropyl)-4,5,4°.

51-Dihenzothialic lupocyanine hydroxide sensitizing dye ■; 9-ethyl-3,3°-di(
3-Sulfopropyl)-5,6,5',61-dibenzoxacarbocyanine hydroxide sensitizing dye V;゛□ Below margin C) 13 しμ C7! V-1 H Next, Samples 2 to 5 were prepared in the same manner as Sample 1, except that the total dry film thickness on the emulsion side was changed as shown in Table 1.

*The emulsion surface film thickness was measured using a small electric micrometer manufactured by Tokyo Seimitsu Co., Ltd. after conditioning the sample at 23° C. and 55% RH for 3 days.

(Film thickness on emulsion side) = (total) (Film thickness after emulsion side removal) In addition, emulsion ■ of sample-4 had an average grain size of 0.8 μm and an average grain size of 15.0 mo1% (A
Sample 6 was prepared in the same manner except that the content was changed to tabular grains having an aspect ratio of 10:1.

These samples were placed in the dark and had a width of 3.5 am and a length of 120 am.
It was cut into cm pieces and processed into several cartridges at the same time.

This processed sample was heated at 25°C with a relative humidity of 40%, 45%, and 50%5.
After being left under conditions of 5%, 60%, and 65% for 3 days, it was placed in a cartridge case made of polypropylene and sealed under each humidity condition. 3. Leave the samples in these cartridge cases in the cartridge case.
It was left at 5°C for 4 months. Meanwhile, the sample was left at 55°C for 2 days.

Thereafter, the above sample was exposed to white wedge light and subjected to color development processing as described below, and its photographic performance was examined.

Furthermore, when the weight of some of the samples was measured in a room at 25° C. and 55% relative humidity using a Shimadzu direct balance, the weight change per sample was +46 mg + 32 mg + 16 mg.

±0+*g, -14mg, -31mg.

In addition, samples stored at 5°C for 4 months with virtually no change over time -1 to 6. The same exposure process and wedge exposure process for MIF measurement were also performed on the film, and development process was performed in the same manner as above.

Processing steps (38°C) Color development 3 minutes 15 seconds bleaching 6 minutes 30 seconds washing 3 minutes 15 seconds fixing 6 minutes 30 seconds washing 3 minutes 15 seconds stabilization 1 minute 30 seconds drying The composition of the processing solution used in each processing step is as follows. It is as follows.

[Color developer]

4-Amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)-aniline sulfate 4.75 g Anhydrous sodium sulfite 4.25 g Hydroxylamine 1/2 sulfate 2.0 g Anhydrous potassium carbonate
37.5 g sodium bromide
1.3g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5
g Potassium hydroxide 1.0 g Add water to make 11.

[Bleach solution] (BL-1) Ethylenediaminetetraacetic acid iron ammonium salt 100g Ethylenediaminetetraacetic acid diammonium salt 10.0g Ammonium bromide 150.0g Glacial acetic acid 10.0ml 1 Add water to make 11, and use ammonia water Adjust to pH=6.0.

(Fixer) Aqueous ammonia thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Add water to make 11, and adjust to pH=6.0 using acetic acid.

[Stabilizing liquid]

Formalin (37% aqueous solution) 1.5ml
Konida Sox (manufactured by Konishiroku Photo Industry Co., Ltd.)? , 5nj! Add water to make 11.

The obtained results are shown in Table-2 and Table-3.

Margin Table-2 Table-2 shows samples 1 to 6 at 40.45, 50, 55°60.
The average value of sensitometry was taken for samples prepared at 65% and stored at 5° C. for 4 months.

(No differences due to humidity were observed between each sample).

Table 29 As is clear from Table 3, sharpness is good according to the present invention, and in particular, by forming a thin film, the effect of improving fogging and sensitivity fluctuation of the photosensitive material when stored at low humidity is remarkable. .

Patent applicant: Roku Konishi Photo Industry Co., Ltd., agent Patent attorney Takatsuki Hirate Tsuzuki Shuho Masashi (method) % formula % 1. Indication of the case 1986 Patent side No. 009805 2. Name of the invention Silver halide Color photographic light-sensitive material 3, relationship with the person making the amendment case Patent applicant address 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name
(127) Konishiroku Photo Industry Co., Ltd. 4, agent name (8397) Patent attorney Takatsuki
5. Date of amendment order: March 25, 1986 6. Subject of amendment: Specification

Claims (1)

[Claims] A silver halide color having a red-sensitive silver halide emulsion layer containing a cyan color-forming coupler, a green-sensitive silver halide emulsion layer containing a magenta color-forming coupler, and a blue-sensitive silver halide emulsion layer containing a yellow color-forming coupler on a support. In the photographic light-sensitive material, the total dry film thickness of all the hydrophilic colloid layers on the side having the emulsion layer is 18 μm or less, and the silver halide color photographic light-sensitive material is stored at a relative humidity of 55% or less. A silver halide color photographic light-sensitive material characterized by: