JPS6275445A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve the self stability by incorporating a specified cyan coupler into the red-sensitive silver halide emulsion layer and a specified magneta coupler into the green-sensitive silver halide emulsion layer. CONSTITUTION:This silver halide photographic sensitive material contains a cyan coupler represented by formula I in the red-sensitive silver halide emulsion layer and a magenta coupler represented by formula II in the green- sensitive silver halide emulsion layer. The amount of the cyan coupler represented by the formula I in the red-sensitive silver halide emulsion layer is preferably regulated to >=50% of the total amount of the cyan coupler and other cyan coupler used in the layer. The amount of the magenta coupler represented by the formula II in the green-sensitive silver halide emulsion layer is preferably regulated to >=50% of the total amount of the magenta coupler and other magenta coupler used in the layer. The cyan and magenta couplers are dispersed by a solid dispersion method, a latex dispersion method, an oil-in- water type emulsion dispersion method or other method.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide photographic light-sensitive material with excellent image storage properties, and more specifically, to a silver halide photographic material with excellent image storage properties, and more specifically, to a silver halide photographic material with excellent image storage properties, and more particularly, to a silver halide photographic material with excellent image storage properties, and more particularly, to a silver halide photographic material with excellent image storage properties. This invention relates to a silver halide photographic material with excellent properties.

[Background of the invention 1] Generally, silver halide color photographic light-sensitive materials contain three types of photographic silver halide that are selectively spectrally sensitized to have sensitivity to blue light, green light, and red light on a support. An emulsion layer is coated. For example, in silver halide photographic materials for color negatives, generally a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer are coated in this order from the exposed side. A bleachable yellow filter layer is provided between the blue-sensitive silver halide emulsion layer and the green-sensitive silver halide emulsion layer to absorb the blue light that passes through the blue-sensitive silver halide emulsion layer. It is provided. Furthermore, each emulsion layer is provided with other intermediate layers for various special purposes, and with an outermost layer containing 1tJI. Furthermore, for example, in a silver halide photographic light-sensitive material for color photographic paper, a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a blue-sensitive silver halide emulsion layer are generally arranged in this order from the exposed side. As with silver halide photographic materials for color negatives, intermediate layers such as an ultraviolet absorbing layer, protective layers, etc. are provided for each specific purpose. It is also known that each of these silver halide emulsion layers is provided in a different arrangement from the above, and furthermore, each silver halide emulsion layer is sensitive to substantially the same wavelength range for each color light. It is also known to use a photosensitive silver halide emulsion layer consisting of two layers. In these silver halide color photographic materials, for example, aromatic monomers are used as color developing agents.
The exposed silver halide grains are developed using a grade amine color developing agent, and a dye image is formed by the reaction between the oxidation product of the color developing agent and the dye-forming coupler. In this method, phenolic or naphtholic cyan couplers, 5-pyrazolones, pyrazolinobenzimidazoles, pyrazolotriazoles, indacylones or cyanocoupler couplers, 5-pyrazolones, pyrazolinobenzimidazoles, pyrazolotriazoles, indacylones or cyanocouplers are typically used to form cyan, magenta and yellow dye images, respectively. An acetyl magenta coupler and an acylacetamide yellow coupler are used.

Generally, the selection of couplers is determined by the rate at which they form a dye through a coupling reaction with the oxidation product of the color developing agent when developing with a color developing solution containing a color developing agent such as a p-phenylenediamine derivative as a main component. The coupling speed should be as high as possible, the dye formed should have good hue and stability against light, heat, moisture, etc., and various types of photography, including sensitizing dyes that coexist in silver halide photographic materials. This is done based on requirements such as not deteriorating photographic properties due to interaction with additives, good storage stability, and cheap and easy synthesis of the coupler. However, it is extremely difficult to select a coupler that satisfies all of these requirements, and some relatively good couplers have been found within the range of individual light-sensitive emulsion layers containing yellow couplers, magenta couplers, and cyan couplers. It is extremely difficult to find a material that satisfies the overall requirements for a silver halide color photographic light-sensitive material arranged in combination with other light-sensitive emulsion layers.

Color photographic materials for printing generally consist of a blue-sensitive silver halide emulsion layer containing a yellow coupler, a non-light-sensitive first intermediate layer, and a green-sensitive halogen-sensitive halogen containing magenta coupler on a reflective support. It is formed by coating a silver emulsion layer, a non-photosensitive second intermediate layer, a red-sensitive silver halide emulsion layer containing a cyan coupler, and a non-photosensitive protective layer in this order.

In order to particularly suppress fading of the dye image due to light, an ultraviolet absorber is added to the first intermediate layer and/or the second intermediate layer.

However, such conventional photosensitive materials for printing,
It is still unsatisfactory in terms of image storage stability, especially light fastness, and there is a disadvantage that the dye image is significantly faded by light. In particular, among the dye images formed by each coupler, the fading speed increases in the order of cyan, yellow, and magenta, and the difference between them is extremely large, resulting in a disadvantage that the color balance is greatly disrupted by light irradiation. . This is what the British Journal of
7 Otography (British Journal
Alof Photography) 128 (63
29) 1170-1171 (1981), etc.

Furthermore, conventional color photosensitive materials for printing have the disadvantage that they are not stable even at high temperatures, and even if they are stored in an album, their color will fade significantly over a long period of time. The rate of color fading during long-term storage in a dark place increases in the order of magenta, yellow, and cyan, and because the difference in the rate of fading is large, the color balance is impaired.

A combination of a yellow coupler, a magenta coupler, and a cyan coupler that reduces the color balance is disclosed in JP-A-60-117249.

Although some of the combinations disclosed in the above-mentioned publications improve the color balance loss to some extent during storage, they are still insufficient and further improvements are required.

[Object of the Invention] The first object of the present invention is to provide a silver halide photographic material which has excellent image storage stability against light and moist heat.

A second object of the present invention is to provide a silver halide photosensitive material which has excellent storage stability and is resistant to loss of color balance from low density to high density during long-term storage.

[Structure of the Invention] The above object of the present invention is to provide a silver halide photographic material having at least a red-sensitive silver halide emulsion layer and a green-sensitive silver halide emulsion layer on a support. A silver halide photographic photosensitive material, characterized in that the layer contains a cyan coupler represented by the following general formula [I], and the green-sensitive silver halide emulsion layer contains a magenta coupler represented by the following general formula [I]. This was achieved by providing materials.

[In the formula, R represents an alkyl group having 2 to 4 carbon atoms, J represents an alkylene group, and X represents a halogen atom, an alkoxy group, or an aryloxy group. ] General formula [II] [In the formula, R5 represents a substituent, and R6 and R7 each represent a halogen atom, a hydroxy group, an alkyl group, an alkoxy group, or an aryl group. However, R6 and R7
At least one of them represents an alkoxy group. AI'
represents an aryl group, and Y represents a halogen atom or an alkoxy group.

2 and K each represent an integer from O to 4.

When 2 is 2-4, R5 may be the same group or different groups, and when K is 2-4, R7 may be the same group or different groups. ] [Specific Structure of the Invention] The cyan coupler represented by the general formula [I] will be explained.

In general formula [I], the number of carbon atoms in the alkyl group is
When these alkyl groups have a substituent, the number of carbon atoms does not include the substituent.

Examples of the alkyl group having 2 to 4 carbon atoms represented by R include ethyl group, propyl group, 1so-propyl group, butyl group, t-butyl group, and ethyl group is preferable.

The alkylene group represented by J is, for example, -CR2
CR2-1-CH2-CH2-CH2-1R' (-C-1 is particularly preferred). Here, R' represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, and a t-butyl group. R' is preferably a hydrogen atom. Further, RH represents a hydrogen atom or an alkyl group having 1 to 16 carbon atoms, and the alkyl group is preferably an alkyl group having 2 to 12 carbon atoms.
Examples include ethyl group, butyl group, t-butyl group, pentyl group, octyl group, decyl group, dodecyl group, and the like.

Further, the alkyl groups represented by R, R' and Rn each include those having a substituent.

X represents a halogen atom, an aryloxy group, or an alkoxy group that can be separated during a coupling reaction with an oxidized color developing agent; examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, etc. but,
A chlorine atom is preferred.

Examples of the alkoxy group include methoxy group, ethoxy group, β-methoxyethylcarbamoylmethoxy group, and examples of the aryloxy group include phenoxy group and p-methoxyphenoxy group.

Next, typical examples of couplers of general formula [I] included in the present invention will be listed, but the couplers used in the present invention are not limited thereto.

The following margin is ■-1g and the following margin is L I-1'I t The cyan coupler of general formula [I] used in the present invention can be synthesized, for example, according to the method described in Japanese Patent Application No. 59-67033.

Next, the magenta coupler represented by the general formula [■] will be explained.

In general formula [I], examples of the substituent represented by R5 include a halogen atom (specifically a chlorine atom, a bromine atom, etc.), an alkyl group (specifically a methyl group, a t-butyl group, a tetradecyl group, trifluoromethyl group, etc.), alkoxy group (specifically methoxy group, ethoxy group, tetradecyloxy group, etc.), acylamino group [specifically acetamido group, benzamide group, butanamide group, α-(2
゜4-di-t-amylphenoxy)acetamido group, α
-(2,4-di-t-amylphenoxy)butyramide group, etc.], sulfonamide group (specifically methanesulfonamide group, benzenesulfonamide group, p-toluenesulfonamide group, etc.), sulfamoyl group (specifically N for
-methylsulfamoyl group, N-hexadecylsulfamoyl group, N-methyl-N-tetradecylsulfamoyl group, etc.), carbamoyl group (specifically N-methylcarbamoyl group, N-octadecylcarbamoyl group, N-methyl-N-tetradecylcarbamoyl group, etc.), diacylamino group (specifically N-succinimide group, N-7 talimide group, 2.5-dioxo-1-oxazolidinyl group, 3-dodecyl-2,5 -dioxo-1-hydantoynyl group, etc.), alkoxycarbonyl group (specifically, methoxycarbosol group, tetradecyloxycarbonyl group, etc.), alkoxysulfonyl group (specifically, methoxysulfonyl group, tetradecyloxysulfonyl group, etc.) ), aryloxysulfonyl groups (specifically phenoxysulfonyl group, 2,4-di-t-amylphenoxysulfonyl group, etc.), alkylsulfonyl groups (specifically methylsulfonyl group, ocdylsulfonyl group, hexadecanesulfonyl group) etc.), arylsulfonyl groups (specifically, penzelsulfonyl groups, etc.), alkylthio groups (specifically, nibruthio group, hexylthio group, tetradecyl group, etc.),
Arylthio group (specifically, phenylthio group, etc.), alkoxycarbonylamino group (specifically, ethoxycarbonylamino group, hexadecyloxycarbonylamino group, etc.), alkylureido group (specifically, N-methylureido group, N -Methyl-N-dodecylureido group, N, N
-dioctadecylureido group, etc.), an acyl group (specifically, an aticel group, a benzoyl group, etc.), a nitro group, a carboxy group, etc.

The halogen atom represented by R6 and R7 includes, for example, a chlorine atom, a bromine atom, etc., and the alkyl group is preferably an alkyl group having 1 to 22 carbon atoms, such as a methyl group, an ethyl group, a t-butyl group, etc. , 1.1.3.
Examples of the alkoxy group include a 3-tetramethylbutyl group, and preferable alkoxy groups having 1 to 22 carbon atoms include methoxy, butoxy, and hexadecyloxy groups. Examples of the aryl group include, for example, Examples include phenyl group and p-methylphenyl group. However, R
At least one of 6 and R7 is an alkoxy group.

The aryl group represented by Ar includes, for example, a phenyl group, and in particular, a halogen atom (for example, a chlorine atom, etc.)
, alkyl groups (e.g. methyl group, t-butyl group, etc.), alkoxy groups (e.g. methoxy group, octyloxy group, etc.)
A phenyl group substituted with is preferred, and a phenyl group substituted with chlorine atoms at the 2,4 and 6 positions is most preferred.

The halogen atom represented by Y includes, for example, a chlorine atom, a bromine atom, a fluorine atom, etc., and the alkoxy group is preferably an alkoxy group having 1 to 22 carbon atoms, such as a methoxy group, a dodecyloxy group, etc. It will be done.

Typical specific examples of the magenta coupler represented by the general formula [II] of the present invention are shown below, but the present invention is not limited thereto.

Margin: H25 Ct: Margin: The magenta coupler of general formula [I] used in the present invention can be synthesized, for example, by the method described in JP-A-57-35858.

The silver halide photographic material of the present invention has at least a red-sensitive silver halide emulsion layer containing a cyan coupler of general formula [I] and a green-sensitive halogen emulsion layer containing a magenta coupler of general formula [n] on a support. It suffices to have a silver oxide emulsion layer, and may also have other layers.

In the red-sensitive silver halide emulsion layer, a cyan coupler other than the general formula [I] may be used in combination, but the cyan coupler of the general formula [I] accounts for at least 50% of the cyan couplers used in the layer. It is preferable that The total amount of cyan coupler used in the layer ranges from 2 x 10-3 moles to 5 x 10 moles per mole of silver halide.
−'Mole.

As a magenta coupler in the green-sensitive silver halide emulsion layer, a magenta coupler other than the general formula [n] may be used in combination, but the magenta coupler of the general formula [II] accounts for 50% or more of the magenta couplers used in the layer. Things are good. The total amount of magenta coupler used in the layer is between 2X10-3 and 5X10 moles per mole of silver halide.
-”It is a mole.

The magenta coupler and cyan coupler used in the present invention can be added to the silver halide photographic material using the solid dispersion method, similar to the general method of adding hydrophobic compounds.
Dispersion can be carried out using various methods such as a latex dispersion method and an oil-in-water emulsion dispersion method, which can be appropriately selected depending on the chemical structure of the hydrophobic compound such as the coupler. The oil-in-water type emulsification dispersion method can be applied by dispersing a hydrophobic compound such as a coupler, and usually a high boiling point solvent with a boiling point of about 150°C or higher is used, and if necessary, a low boiling point and/or water soluble organic compound is added. Dissolve using a combination of solvents and use a surfactant in a hydrophilic binder such as an aqueous geladine solution to create a stirrer, homogenizer, colloid mill, flow jet mixer,
After being emulsified and dispersed using a dispersing means such as an ultrasonic device, it may be added to the desired hydrophilic colloid layer. A step of removing the low boiling point organic solvent may be included simultaneously with the dispersion or dispersion.

Examples of high-boiling organic solvents include phenol derivatives, phthalate esters, phosphate esters, citrate esters, benzoate esters, alkylamides, fatty acid esters, trimesate esters, etc. that do not react with the oxidized form of the developing agent. Organic solvents are used.

The high boiling point organic solvent that can be preferably used in the present invention is a compound with a dielectric constant of 6.0 or less, such as esters such as phthalates and phosphates with a dielectric constant of 6.0 or less, organic acids, etc. These include amides, ketones, and hydrocarbon compounds.

Preferably, the dielectric constant is 6.0 or less and 1.9 or more and the vapor pressure at 100°C is 0. It is a high boiling point organic solvent with a boiling point of 5 mmH Q or less. Even more preferred are phthalic esters or phosphoric esters in the high-boiling organic solvent. Furthermore, the high boiling point organic solvent may be a mixture of two or more kinds.

Note that the dielectric constant in the present invention refers to the dielectric constant at 30°C.

The photosensitive material according to the present invention can be applied to, for example, color negative and positive films, color photographic paper, etc.
The effects of the present invention are particularly effective when applied to color photographic paper intended for direct viewing.

The photosensitive material according to the present invention, including this color photographic paper, may be one for monochrome use or one for multicolor use. In the case of multicolor silver halide color photographic materials, in order to perform subtractive color reproduction, silver halide emulsion layers containing magenta, yellow, and cyan couplers are usually used as photographic couplers, as well as non-silver halide emulsion layers containing magenta, yellow, and cyan couplers. Although the photosensitive layer has a structure in which the photosensitive layer is laminated on the support in an appropriate number and order of layers, the number and order of layers may be changed as appropriate depending on the important performance and the purpose of use.

The silver halide emulsion used in the light-sensitive material of the present invention includes silver bromide, silver iodobromide, silver iodochloride, silver halide,
Any of those used in conventional silver halide emulsions such as silver chlorobromide and silver chloride can be used.

The silver halide grains used in the silver halide emulsion may be obtained by any one of the acid method, neutral method, and ammonia method. The particles may be grown all at once, or may be grown after seed particles are produced. The method of creating and growing the seed 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 the presence of the other. In addition, while considering the critical growth rate of silver halide crystals, we added halide ions and silver ions to
)H. +1 A! It may also be produced by controlling and sequentially adding II. After growth, a conversion method may be used to change the halogen composition of the particles.

When producing a silver halide emulsion, the grain size, grain shape, grain size distribution, and grain growth rate of silver halide grains can be controlled by using a skewer using a silver halide solvent as necessary.

Silver halide grains used in silver halide emulsions are produced by cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts, rhodium salts or complex salts, iron salts, etc. Metal ions can be added to the inside of the particles and/or on the surface of the particles using complex salts, etc., and by placing them in an appropriate reducing atmosphere, reduction can be increased inside the particles and/or on the surface of the particles. It can give you a feeling of emotion.

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 as they are contained. In the case of removing the salts, it can be carried out based on the method described in Research Disclosure No. 11643.

The silver halide grains used in the silver halide emulsion may consist of uniform layers inside and on the surface, or may consist of different layers.

The silver halide grains used in the silver halide emulsion may be grains in which a latent image is mainly formed on the surface, or grains in which a latent image is mainly formed inside the grains.

The silver halide grains used in the silver halide emulsion may have a regular crystal shape or may have an irregular crystal shape such as a spherical or plate shape. In these particles, any ratio of the (100) plane to the (111) 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 silver halide emulsion may be a mixture of two or more silver halide emulsions formed separately.

The silver halide emulsion is chemically sensitized by conventional methods. Namely, sulfur sensitization using a compound containing sulfur that can react with silver ions or active gelatin, selenium sensitization using a selenium compound, reduction sensitization using a reducing substance, and noble metal using gold or other noble metal compounds. Sensitization methods and the like 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. The sensitizing dyes may be used alone or in combination of two or more. Along with the sensitizing dye, the emulsion contains a dye that itself does not have a spectral sensitizing effect, or a supersensitizer, which is a compound that does not substantially absorb visible light and enhances the sensitizing effect of the sensitizing dye. Also good.

Silver halide emulsions are used during the manufacturing process of photosensitive materials, during storage,
Alternatively, a silver halide emulsion is applied during and/or at the end of chemical ripening and/or after the end of chemical ripening for the purpose of preventing capri during photographic processing and/or keeping photographic performance stable. By now, compounds known in the photographic industry as anticapri agents or stabilizers can be added.

As a binder (or protective colloid) for silver halide emulsions, gelatin is advantageously used, but gelatin derivatives, graft polymers of gelatin and other polymers, proteins, sugar derivatives, cellulose derivatives, single Alternatively, hydrophilic colloids such as synthetic hydrophilic polymer substances such as copolymers can also be used.

The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material according to the present invention are hardened by using alone or in combination with a hardening agent that crosslinks binder (or protective colloid) molecules and increases film strength. It is desirable to add the hardening agent in an amount that can harden 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 a hardening agent to the processing solution.

A plasticizer can be added for the purpose of increasing the flexibility of the silver halide emulsion layer and/or other hydrophilic colloid layer of the photosensitive material according to the present invention.

The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material according to the present invention may contain a dispersion (latex) of a water-insoluble or poorly soluble synthetic polymer for the purpose of improving dimensional stability.

In the emulsion layer of the light-sensitive material according to the present invention, a dye is formed by a coupling reaction with an oxidized form of an aromatic primary amine developer (for example, a p-phenylenediamine derivative or an aminophenol derivative) in the color development process. A dye-forming coupler is used. The dye-forming coupler is
Typically, each emulsion layer is selected to form a dye that absorbs light in the emulsion layer's sensitive spectrum, with a yellow coupler in the blue light-sensitive emulsion layer and a yellow coupler in the green light-sensitive emulsion layer. A magenta coupler is used in the red light-sensitive emulsion layer, and a cyan coupler is used in the red light-sensitive emulsion layer.

In the present invention, the following general formula [II
From the viewpoint of color balance, it is preferable to combine a yellow coupler represented by [1] with the cyan coupler and magenta coupler of the present invention.

General formula [I[1] In the formula, R8 is -NHCOR++, -NH3O2Rn, -GOOR++ or -S○2
represents N-Rt+ (R+1 and RI2 each represent an alkyl group); R9 represents an alkyl group, and Rho represents an argyl group.

The alkyl group represented by R9 includes those having substituents, such as methyl group, ethyl group, 1so-propyl group, butyl group, t-butyl group, benzyl group, phenethyl group, etc. An alkyl group having no is preferred.

The alkyl group represented by Rho includes those having substituents, such as methyl group, ethyl group, 1so-propyl group, butyl group, t-butyl group, benzyl group, phenethyl group, etc. and an alkyl group substituted with a phenyl group such as a phenyl group.

Examples of the alkyl groups represented by R11 and R12 include ethyl group, 1so-propyl group, butyl group, t-butyl group, and hexyl group, but these alkyl groups also include those having substituents. Examples of this substituent include aryloxy groups (specifically, phenoxy groups 8), alkoxycarbonyl groups (specifically, methoxycarbonyl groups, etc.), alkylsulfonyl groups (specifically, ethylsulfonyl groups, etc.), sulfonic acid groups, etc. group, aryl group (specifically phenyl group etc.), alkylamide M (
Specific examples include diethylamide group, etc.).

Specific examples of the yellow coupler represented by the general formula [11] are shown below, but the present invention is not limited thereto.

Below Margin Below Margin The oxidized form of the developing agent or the electron transfer agent may migrate between the emulsion layers of the light-sensitive material according to the present invention (between the same color-sensitive layers and/or between different color-sensitive layers), causing color turbidity. Color antifogging agents are used to prevent deterioration of sharpness and noticeable graininess.

The color antifoggant may be used in the emulsion layer itself, or in an intermediate layer provided between adjacent emulsion layers.

In the hydrophilic colloid layers such as the protective layer and intermediate layer of the photosensitive material according to the present invention, an ultraviolet absorber is added to prevent fogging due to discharge caused by charging of the photosensitive material due to friction, etc., and to prevent image deterioration due to UV light. May contain.

Although the layer structure of the silver halide photographic light-sensitive material according to the present invention may have any number of layers and any order of layers, it is preferable that
A yellow coupler-containing silver halide emulsion layer, a magenta coupler-containing silver halide emulsion layer, and a cyan coupler-containing silver halide emulsion layer are coated from the support side in the order of ■-■-〇. - An intermediate layer is provided between 〇, a non-photosensitive layer is provided on the side farther from ■ when viewed from the support side, and
It is preferable to contain an ultraviolet absorber in the intermediate layer between and (2) and the non-photosensitive layer adjacent to (2), and when the ultraviolet absorber is contained in the non-photosensitive layer adjacent to (2) above, the layer adjacent to (2) Preferably, a protective layer is further applied.

The photosensitive material according to the present invention may be provided with auxiliary layers such as a filter layer, an antihalation layer, and/or an antiirradiation layer, if necessary.

These layers and/or the emulsion layer may contain dyes that flow out of the color light-sensitive material or are bleached during development.

A matting agent is added to the silver halide emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material according to the present invention with the aim of reducing the gloss of the light-sensitive material, increasing the ease of writing, and preventing mutual scratching of the light-sensitive materials. I can do it.

A lubricant can be added to reduce the sliding friction of the photosensitive material according to the present invention.

An antistatic agent for the purpose of preventing static electricity can be added to the photosensitive material according to the present invention. Antistatic agents are sometimes used in the antistatic layer on the side of the support on which the emulsion is not laminated, or they are used to protect the emulsion layer and/or the side other than the emulsion layer on which the emulsion layer is laminated with respect to the support. It may also be used in a colloid layer.

゛ The photographic emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material according to the present invention may be used to improve coating properties, prevent static electricity, improve slipperiness, emulsification dispersion, prevent adhesion, and (promote development, increase contrast,
Various surfactants are used for the purpose of improving photographic properties (such as sensitization).

The photographic emulsion layer and other layers of the light-sensitive material of the present invention include a baryta layer or a flexible reflective support such as paper laminated with an α-olefin polymer, synthetic paper, cellulose acetate, cellulose nitrate, polystyrene, polyester, etc. It can be applied to films made of semi-synthetic or synthetic polymers such as vinyl chloride, polyethylene terephthalate, polycarbonate, and polyamide, as well as rigid bodies such as glass, metal, and ceramics.

The photosensitive material according to the present invention can be produced by subjecting the surface of the support to corona discharge, ultraviolet irradiation, flame treatment, etc., if necessary, and then directly or It may be coated with one or more subbing layers (to improve abrasion resistance, hardness, antihalation, frictional properties and/or other properties).

When coating the photographic material according to the present invention, a thickener may be used to improve coating properties. The application method is 2.
Particularly useful are ex-dulsion coatings and curtain coatings in which more than one layer can be applied simultaneously.

The photosensitive material according to the present invention can be exposed using electromagnetic waves in a spectral region to which the emulsion layer constituting the photosensitive material according to the present invention is sensitive. As a light source, natural light (sunlight),
Tungsten electric lamps, fluorescent lamps, mercury lamps, xenon arc lamps, carbon arc lamps, xenon flash lamps, cathode ray tube flying spots, various laser lights, light emitting diode lights,
Any known light source can be used, such as light emitted from a phosphor excited by electron beams, X-rays, γ-rays, α-rays, or the like.

The exposure time is of course 1 millisecond to 1 second, which is normally used with a camera, but it is also possible to use an exposure shorter than 1 microsecond, for example, an exposure of 100 microseconds to 1 microsecond using a cathode ray tube or xenon arc lamp. Exposures longer than 1 second are also possible. The exposure may be performed continuously or intermittently.

The photosensitive material according to the present invention can form a color image by performing color development as known in the art.

The aromatic primary amine color developing agent used in the color developing solution in the present invention includes known ones that are widely used in various color photographic processes.

These developers include aminophenol and p-phenylenediamine derivatives. These compounds are
Since it is more stable than the rl-isolated state, it is generally used in the form of a salt, such as a hydrochloride or a sulfate. In addition, these compounds are generally used in color developing solution 1! About o, ig ~ about 30
( ) Preferably about 1 g per color developer 12
Use at a concentration of ~15 g.

Examples of the amine phenol developer include 0-aminophenol, p-aminophenol, 5-amino-2-
Oxytoluene, 2-amino-3-oxytoluene, 2
-oxy-3-7 minnow 1°4-dimethylbenzene, etc.

Particularly useful primary aromatic amine color developers are N, N'
-Dialkyl-〇-phenylenediamine type compound, and the alkyl group and phenyl group may be substituted with any substituent. Among them, examples of particularly useful compounds include N,N'-diethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, N,N'-diethyl-p-phenylenediamine hydrochloride,
, N'-dimethyl-p-phenylenediamine hydrochloride,
2-amino-5-(N-ethyl-N-dodecylamino)
-Toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline fA M
m, N-ethyl-N-β-hydroxyethylaminoaniline, 4-amino-3-methyl-N.

N'-diethylaniline, 4-amino-N-(2-methoxyethyl)-N-ethyl-3-methylanione-〇-
Examples include toluene sulfonate.

In addition to the above-mentioned aromatic primary amine color developer, the color developer used in the process of the present invention further contains various components normally added to color developers, such as sodium hydroxide and sodium carbonate. , an alkali agent such as potassium carbonate, an alkali metal sulfite, an alkali metal bisulfite, an alkali metal thiocyanate, an alkali metal halide, benzyl alcohol, a water softener and a thickening agent. The pH value of this coloring Jp imager is usually 7 or more, most commonly about 10
〜about 13.

In the present invention, coloring f! A: After the image processing, the image is processed with a processing liquid having fixing ability, but the processing liquid having fixing ability is a fixing liquid, and before that, bleaching is performed. As the bleaching agent used in the bleaching process, a metal complex salt of V'1 is used, and the metal 18 salt oxidizes the gold film produced by development and converts it into silver halide, and at the same time removes the uncolored part of the color former. It has the effect of developing color, and its composition is that metal ions such as iron, cobalt, copper, etc. are coordinated with aminopolycarboxylic acid or organic acids such as oxalic acid and citric acid. The most preferred m-acids used to form such metal complexes of organic acids include polycarboxylic acids or aminopolycarboxylic acids. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts.

Specific representative examples of these include the following.

[1] Ethylenediaminetetraacetic acid [2] Nitrilotriacetic acid [3] Iminodiacetic acid [4] Ethylenediaminetetraacetic acid disodium salt [5] Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt [6] Ethylenediaminetetraacetic acid tetrasodium salt [7] ] Nitrilotriacetic acid sodium salt The bleaching agent used contains the above-mentioned metal complex salt of acid as a bleaching agent, and may also contain various additives. As additives, it is particularly desirable to include rehalogenating agents, metal salts, and chelating agents such as alkali halides or ammonium halides, such as potassium bromide, sodium bromide, sodium chloride, and ammonium bromide.

Also, borate, oxalate, acetate, carbonate, phosphorus vL salt, etc.
Those known to be added to ordinary bleaching solutions, such as H buffering agents, alkylamines, and polyethylene oxides, can be added as appropriate.

Furthermore, the fixer and bleach-fixer contain ammonium sulfite,
Sulfite M salts such as potassium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, sodium metabisulfite, boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate , potassium carbonate, sodium bisulfite, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide, and the like.

When carrying out the process of the present invention while replenishing the bleach-fix solution (bath) with a bleach-fix replenisher, the bleach-fix solution (bath) may contain thiosulfate, thiocyanate, sulfite, etc. These salts may be added to the bleach-fixing replenisher to replenish the processing bath.

In the present invention, in order to increase the activity of the bleach-fix solution, air or oxygen may be blown into the bleach-fix bath and the bleach-fix replenisher storage tank, if desired, or an appropriate oxidizing agent may be added. For example, hydrogen peroxide, bromine II salt, persulfate, etc. may be added as appropriate.

[Examples] Examples of the present invention will be described in detail below, but the present invention is not limited to these embodiments.

Example 1 Samples Nos. 31 to 8 of multicolor silver halide photographic light-sensitive materials were prepared by sequentially coating the following layers on a support made of polyethylene-coated paper from the support side.

1st layer: blue-sensitive silver halide emulsion layer as a yellow coupler α-bivalyl-α-°(1-benzyl-2,4-dioxo-imidazolidin-3-yl)-2-chloro-5-[γ-( 8 m of 2゜4-di-t-amylphenoxy)butylamitoco-acetanilide
Q/di”, 3 when converting blue-sensitive silver chlorobromide emulsion into silver.
mQ/did', dinonyl phthalate at 3 mO/
dx" and gelatin were coated to give a coating amount of 16 m (1/dx2).

2nd layer: Intermediate layer gelatin was coated to a thickness of 4 m (+/dl coated m).

Third notification = 8! Sensitive silver chlorobromide emulsion layer contains the above exemplary magenta coupler (Table 1) at 4 mQ/d1
2. 3 m of the following antifading agents A-1 and A-2.

/di”, green-sensitive silver chlorobromide emulsion converted to silver, 2 m (1
/di', dioctyl phthalate 4. mQ/dm'
And gelatin was coated at a coating rate of 16 mg/dt'.

4th layer: middle layer UV absorber 2-(2'-hydroxy-3'.

5′-di[-amylphenol)-benzotriazole in 3 m(1/df12-(2′-hydroxy-
3', 5'-di[-butylphenol)-benzotriazole 3 mg/df, dioctyl phthalate 4
ma/di' and gelatin were coated to give a coating of 14 mg/df.

5th layer: red-sensitive silver chlorobromide emulsion layer containing the above-mentioned exemplary cyan coupler (Table 1) at 4 mQ/d12
, dioctyl phthalate was applied in an amount of 2 mg/(Is' and the red-sensitive silver chlorobromide emulsion was converted into silver to give a coating amount of 31 B/df).

Layer 6: Middle layer UV absorber 2-(2'-hydroxy-3'.

5'-di-t-amylphenol)-benzotriazole with 3IO/df, 2-(2'-hydroxy-3'
, 5'-di-t-butylphenol)-benzotriazole at 211 (1/df, dioctyl phthalate at 2
mG/dm' and gelatin were coated at a coating amount of 6 mg/d, 2.

7th layer: Protective layer Gelatin was coated in an amount of 9111 g/d11'.

The following margins were obtained using a sensitometer (Roku Konishi Photo Industry) for samples 1 to 8.
After exposure to white light was carried out using a KS-7 model (manufactured by Co., Ltd.), the following processing steps were carried out.

Processing steps (1) Color development 38°C 3 minutes 30 seconds (2) Bleach fixing 33°C 1 minute 30 seconds (3) Washing with water 25
~30℃ 3 minutes (4) Drying 75~80℃
Approximately 2 minutes processing solution composition (color developer) Benzyl alcohol 15 ethylene glycol 15 potassium sulfite
2.0g sodium chloride
0.2g potassium carbonate 3
0.0g Hydroxylamine ItiliM Salt
4.1g polyphosphoric acid (TPPS) 2
．． 5g 3-Methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl)-aniline sulfate 585g Optical brightener (4,4'-diaminostilbenzsulfonic acid derivative) 1.0 (1 water Add 2.0 g of potassium oxide to make the total set 12, and adjust the pH to 10.20.

(Bleach-fix solution) Ferric ammonium ethylenediaminetetraacetate dihydrate 60g ethylenediaminetetraacetic acid M3 (1 ammonium diosulfate (10% solution) 100d ammonium sulfite (40% solution) 27.51112p with potassium carbonate or glacial acetic acid) -17.1, and add water to bring the total volume to 12.

The image density obtained by the above processing and the sample obtained by this processing were
Image density after 0 hour exposure to sunlight, relative humidity 40%
The densities of the images after aging for 15 days under conditions of 77° C. and humidity were measured using a microdensitometer PDM-5, and the results are shown in Table 1. However, in Table 1, G is the density for green light, and R is the density for red light.

Margin below M-1.

Ct CsHn(j) Ct C~2 C5HI+ (From the results in Table 1, Samples N0116 and 2 using the comparative magenta coupler and the comparative cyan coupler have a particularly large deterioration in color balance after storage over time. Test F using the invented mazen coupler and the comparative cyan coupler
Although the color balance of I No. 3 after storage over time was considerably improved compared to samples No. 11 and 2,
The color balance after using sunlight is slightly distorted.

On the other hand, Samples Nos. 014 to 8 using the magenta coupler of the present invention and the cyan coupler of the present invention show very little loss of color balance even after meditation in sunlight and after storage over time; This holds true in all regions from high concentration to high concentration.

Patent applicant Konishiroku Photo Industry Co., Ltd. Representative Patent Attorney Ichinose Miyakushi-・Husband e:! nautical mile Undertake

Claims (1)

[Scope of Claims] In a silver halide photographic material having at least a red-sensitive silver halide emulsion layer and a green-sensitive silver halide emulsion layer on a support, the red-sensitive silver halide emulsion layer has the following general formula [ A silver halide photographic light-sensitive material comprising a cyan coupler represented by the following general formula [II], and a magenta coupler represented by the following general formula [II] in the green-sensitive silver halide emulsion layer. General Formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, R represents an alkyl group having 2 to 4 carbon atoms, J represents an alkylene group, and X represents a halogen atom, an alkoxy group, or an aryloxy group. ] General formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_5 represents a substituent, R_6 and R_7
are a halogen atom, a hydroxy group, an alkyl group, and
Represents an alkoxy group or an aryl group. However, R_6
and R_7, at least one of which represents an alkoxy group. Ar represents an aryl group, and Y represents a halogen atom or an alkoxy group. l and K each represent an integer from 0 to 4. When l is 2 to 4, R_5 may be the same group or different groups, and when K is 2 to 4, R_7 may be the same group or different groups. ]