JPS61258246A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To stabilize a dye image by forming a layer contg. a specified compd. in at least one of layers. CONSTITUTION:At least one of layers for constituting a silver halide photographic sensitive material, such as a surface protective layer, silver halide emulsion layers, interlayers, an undercoat, an antihalation layer, or other subsidiary layers, preferably, a silver halide emulsion layer, most preferably, the silver halide emulsion layer contg. a magenta coupler, contains one of compds. represented by the formula shown on the right, preferably, in an amt. of 0.1-4mol per mol of said magenta coupler, thus permitting stability of a photographic image to be extremely enhanced, and discoloration and fading due to light, and yellow staining at the noncolor-formed parts due to light, heat, and humidity to be prevented satisfactorily.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a photographic light-sensitive material, and in particular to a silver halide color photograph in which color fading due to light in a dye image obtained by post-exposure development processing and discoloration due to light in uncolored areas are prevented. Regarding photosensitive materials.

In silver halide color photographic light-sensitive materials, aromatic
It is known that exposed silver halide grains are developed using a primary amine compound, and a dye image is formed by the reaction of the oxidation product of the resulting aromatic primary amine compound with a coupler to obtain a color image. ing.

In this method, a compound having an open-chain active methylene group is generally used as a yellow coupler to form a yellow dye, and a pyrazolone nucleus or a pyrazolone nucleus having a closed-chain active methylene group is generally used as a magenta coupler to form a magenta dye. Compounds having a zolinobenzimidazole nucleus or an indacylon nucleus are used, and both of these form an azomethine dye by reaction with an oxidation product of an aromatic primary amine compound. On the other hand, as a cyan coupler for forming a cyan dye, a phenol or α-naphthol compound having a phenolic hydroxyl group is generally used. Forms type pigment.

It is desired that dye images obtained from such couplers do not change color or fade even when exposed to light for long periods of time or stored under high temperature and high humidity.

However, the fastness of these dye images to mainly ultraviolet rays or visible light is not yet satisfactory, and it is well known that they easily change color and fade when irradiated with these actinic rays. In order to eliminate these drawbacks, methods include selecting and using various couplers with less fading properties than conventional ones, using ultraviolet absorbers to protect dye images from ultraviolet rays, and using anti-fading agents to prevent fading due to light. Some methods have been proposed, such as a method in which a group is used or a group that imparts light resistance is introduced into the coupler.

However, in order to provide satisfactory lightfastness to a dye image using, for example, a UV absorber, a relatively large amount of UV absorber is required, in which case the dye image is significantly contaminated due to the coloring of the UV absorber itself. There were many things that happened. Further, even if an ultraviolet absorber is used, it has no effect on preventing dye images from fading due to visible light, and there are limits to the improvement of light resistance by ultraviolet absorbers. Furthermore, a method using a dye image scarlet inhibitor having a phenolic hydroxyl group or a group that can be hydrolyzed to produce a phenolic hydroxyl group is known.
No. 31625, No. 51-30462, Japanese Unexamined Patent Publication No. 49-1
34326 and 49-134327, phenol and bisphenols, U.S. Patent No. 3.06
No. 9,262 describes pyrogallol, carlinkic acid and its esters; U.S. Pat. No. 2,360,290 and U.S. Pat. No. 4,015,990 describe Kosho 52-27
No. 534, JP-A No. 52-14751 and U.S. Pat. No. 2.735.765 disclose hydroquinone derivatives, U.S. Pat.
No. 4.627 describes 6-hydroxycoumarones, U.S. Pat. It has been proposed to use -2,2'-bisspirocoumarones and the like. These compounds do have the effect of fading or discoloration of the pigment, but their effect is small, or even though they have an anti-fading effect, they may make the hue longer wavelength or cause Y-stain, and these compounds also exist. This has resulted in drawbacks such as a decrease in the color development of the coupler.

An object of the present invention is to provide a silver halide photographic light-sensitive material containing an anti-fading agent that has an excellent anti-fading effect and does not cause a change in hue, cause Y-stain, or reduce the coloring properties of couplers. Our goal is to provide the following.

As a result of various studies, the present inventors have found that the above object can be achieved with a silver halide photographic material characterized by having a layer containing a compound represented by the following general formula (1).

General formula (r) (wherein R4 and Rt may be the same or different,
Represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, a heterocyclic group, an acyl group, and R5 is a halogen atom, an alkyl group, an aryl group, an alkylthio group, an arylthio group, an amino group, an alkylamino group, an arylamino group, represents an acylamino group, a sulfonamide group, a ureido group, an acyl group, a carbamoyl group, an alkoxycarbonyl group, a sulfonyl group, a sulfamoyl group, a nitro group, a cyano group, or a carboxyl group, m represents an integer of O to 4, General formula To explain Rt and Rt in (1) in more detail, these include a hydrogen atom, a straight chain or branched alkyl group having 1 to 24 carbon atoms (for example, a methyl group, an ethyl group, an isopropyl group, a t-butyl group, a 2- ethylhexyl group, dodecyl group, t-octyl group, benzyl group, phenylethyl group, etc.), alkenyl group having 3 to 24 carbon atoms (e.g. allyl group, 2,4-pentegenyl group, etc.), 5 to 24 carbon atoms
cyclo7) Lt-kyl group (e.g. cyclopentyl group, cyclohexyl group, etc.), oryl group (e.g. phe-1l group,
naphthyl group, etc.), heterocyclic groups (e.g. pyridyl group, imidazolyl group, tetrazolyl group, oxacylyl group, X thiazolyl group, benzimidazolyl group, benzthiazolyl group,
(benzoxasilyl group, pyrimidinyl group, indolyl group, pyrazolyl group, pyrazolyl group, purinyl group, quinolyl group, isoxasilyl group, oxadiazolyl group, thiadiazolyl group, triazolyl group, furyl group, succinimidoyl group, etc.), acyl group (For example, acetyl group, benzoyl group, etc.) These groups can further have a substituent, and examples of the substituent include an alkyl group, a hydroxy group, an alkoxy group, an aryl group, an acylamino group, a sulfonamido group, an aryloxy group, an alkylthio group, an arylthio group, and a carbamoyl group. , sulfamoyl group, sulfonyl group, nitro group, cyano group, halogen atom, carboxyl group, amino group, aryamino group, alkylamino group, alkoxycarbonyl group, acyl group, or acyloxy group.

Among these, preferred as R1 and Rt are alkyl groups and aryol groups.

-8 To explain R8 in formula (1) in more detail, these include halogen atoms (e.g. fluorine atom, chlorine atom, bromine atom, etc.), straight chain or branched chain alkyl groups having 1 to 24 carbon atoms (e.g. methyl group, Ethyl group, isopropyl group, t
-butyl group, 2-ethylhexyl group, dodecyl group, [-
octyl group, benzyl group, phenylethyl group, etc.), aryl group (e.g. phenyl group, naphthyl group, etc.), alkylthio group (e.g. methylthio group, t-dodecylthio group,
cyclohexylthio group, benzylthio group, etc.), arylthio group (e.g. phenylthio group, α-naphthylthio group, etc.), amino group, alkylamino group (e.g. methylamino group, diethylamino group, dibutylamino group, etc.), arylamino group (e.g. anilino group, α-naphthylamino group, etc.), acylamino group (e.g. acetylamino group, benzoylamino group, etc.), sulfonamide group (e.g. methanesulfonamide group, benzenesulfonamide group, etc.), ureido group (e.g. methylureido group, phenylureido group, etc.), acyl group (e.g. acetyl group, benzoyl group, etc.), carbamoyl group (e.g. methylcarbamoyl group, dimethylcarbamoyl group, etc.), alkoxycarbonyl group (
For example, methoxycarbonyl group, dodecyloxycarbonyl group, etc.), sulfonyl M (for example, methanesulfonyl group,
(benzenesulfonyl group, etc.), sulfamoyl group (eg, methylsulfamoyl group, dimethylsulfamoyl group, etc.), nitro group, cyano group, and carboxyl group.

These groups may further have a substituent,
Examples of the substituent include the same substituents as those for Rt and R3.

When m is 2 or more, R8 may be the same or different. m is preferably 0-2.

-5R and -3R can be located at any position, but are preferably at the ortho position or the rose position.

Among R8, preferred are a halogen atom, an alkyl group, an alkylthio group, an arylthio group, an alkylamino group, an acylamino group, and a sulfonamide group.

Representative examples of the compound represented by formula (I) (hereinafter referred to as "specific compound") are shown below, but the invention is not limited thereto.

[Exemplary compounds]

B CM5 8C53 11CH2CH-CH2 gCB! [17 c4Hg C101121 CJ Typical synthesis examples of exemplified compounds are shown below, but other compounds can also be easily synthesized by similar reactions.

Synthesis Example 1 [Synthesis of Exemplary Compound (4)] Toluene 3.4
- 5.6 g of dithiol, 30 ml of methanol and 14.2 g of a 28% methanol solution of sodium methylate
was added, and then 13.9 g of octyl bromide was added and stirred for 2 hours. Take out the lower layer of the reaction mixture separated into two layers, and add 100 ml of ethyl acetate and 200 ml of water to it.
The ethyl acetate layer was extracted, dried and concentrated to obtain 13.3 g of a yellow liquid.

This was purified by silica gel chromatography using hexane as a developing solvent to obtain 6.8 g of a colorless liquid (yield: 50%).

When this substance was identified by FD mass spectrum and NMR, it was found to be the same as Exemplified Compound (4)! It has been certified.

Synthesis Example 2 [Synthesis of Exemplary Compound (5)] Journal of the American Chemical Society (J, Am, Cba-, Soc,) 87.265
5 (1965), 100 ml of methanol and 30.4 g of a 28% methanol solution of sodium methylate were added, and then 20 g of butyl bromide was added.
．． 6 g was added and stirred for 2 hours. The precipitated solid was filtered and washed with methanol to obtain 13.5 g of a white solid (yield 79%).

When this substance was identified by FD mass spectrometry and LMI+, it was confirmed that it was the same as exemplified compound (5).

In the present invention, the specific compound is used in the layers constituting the silver halide photographic light-sensitive material, that is, the protective layer, the silver halide emulsion layer, the intermediate layer, the filter layer, the undercoat layer, the antihalation layer, and other auxiliary layers. (Although both are contained in one layer,
It is preferably contained in a silver halide emulsion layer, most preferably in a silver halide emulsion layer containing a magenta coupler. In this case, the amount of the specific compound added is suitably 0.1 mol to 4 mol, preferably 0.5 mol to 3 mol, per 1 mol of magenta coupler.
It is a mole.

The silver halide photographic light-sensitive material of the present invention can be, for example, color negative and positive films, color photographic paper, etc., but especially when color photographic paper used for direct verification is used, its excellent properties can be improved. The effect is effectively demonstrated.

The silver halide photographic light-sensitive materials of the present invention, including this color photographic paper, may be for single color or multicolor.In the case of multicolor silver halide photographic materials, subtractive color reproduction is possible. In order to achieve this, it usually has a structure in which a silver halide emulsion layer containing magenta, yellow and cyan couplers as photographic couplers and a non-light sensitive layer are laminated on a support in an appropriate number and layer order. However, the calendar number and layer order may be changed as appropriate depending on the important performance and purpose of use.

A silver halide emulsion is used to form the silver halide emulsion layer in the silver halide photographic light-sensitive material of the present invention. Any of those used in conventional silver halide emulsions can be used, such as silver bromide, silver iodochloride, silver chlorobromide, and silver chloride.

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 forming seed grains. The method for producing and growing the hexagonal 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, and while taking into consideration the critical growth rate of silver halide crystals, 98. The halide ions and silver ions are mixed in a pot. The silver halide composition of the grains may be changed by sequentially and simultaneously adding them while controlling pAg, or by using a converge run method after growth.

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

The silver halide grains used in the silver halide emulsion may contain cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts, rhodium salts or complex salts, iron during the grain formation process and/or grain growth process. Metal ions can be added to the interior of the particles and/or on the surface of the particles using salts or complex salts, and reduction-sensitized nuclei can be created inside the particles and/or on the surface of the particles by placing them in an appropriate reducing atmosphere. Can be granted.

In the silver halide emulsion, unnecessary soluble salts may be removed after the growth of silver halide grains is completed, or unnecessary soluble salts may be left in the emulsion. When the salts are removed, the method described in Research Disclosure No. 17643 can be used. This can be done based on the method of

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 shape or a plate shape. In these particles, any ratio of the +1001 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 that have been separately formed.

The silver halide emulsion is chemically sensitized by a conventional method.

In other words, sulfur sensitization using compounds containing sulfur that can react with silver ions or active gelatin, selenium sensitization using selenium compounds, reduction sensitization using reducing substances, and noble metal sensitization using gold or other noble metal compounds. Sensing methods and the like can be used alone or in combination.

The silver halide emulsion can be optically sensitized to a desired wavelength range using a dye known as a sensitizing dye in the photographic industry. Sensitizing dyes may be used alone, but 2
A dye that does not itself have a spectral sensitizing effect together with a sensitizing dye, or a compound that does not substantially absorb visible light, which may be used in combination with sensitizing dyes, and a strong color that enhances the sensitizing effect of the sensitizing dye. A sensitizer may be included in the emulsion.

The silver halide emulsion may be used during chemical ripening and/or at the end of chemical ripening for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of light-sensitive materials, and/or maintaining stable photographic performance. At the time and/or after chemical ripening and before coating the silver halide emulsion, compounds known in the photographic industry as antifoggants or stabilizers can be added.

As the binder (or protective colloid) for the silver halide emulsion, it is advantageous to use gelatin, but gelatin derivatives, graft polymers of gelatin and other polymers, proteins, sugar derivatives, cellulose derivatives, and monomers may also be used. Hydrophilic colloids such as synthetic hydrophilic polymeric materials such as mono- or copolymers may also be used.

a photographic emulsion layer of a light-sensitive material using the silver halide emulsion;
Other hydrophilic colloid layers 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 the 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 a light-sensitive material using the silver halide emulsion.

A dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer may be included in the photographic emulsion layer or other hydrophilic colloid layer of the photosensitive material using the silver halide emulsion for the purpose of improving dimensional stability. .

In the emulsion layer of the silver halide color photographic light-sensitive material according to the present invention, a coupling reaction of an oxidant of an aromatic primary amine developer (for example, a p-phenylene diamino derivative or an aminophenol derivative) is carried out in the color development process. A dye-forming coupler is used that forms a dye. The dye-forming couplers are typically selected for each emulsion layer to form a dye that absorbs light in the emulsion layer's sensitive spectrum, with a yellow dye-forming coupler for the blue light-sensitive emulsion layer. However, a magenta dye-forming coupler is used in the green light-sensitive emulsion layer, and a cyan dye-forming coupler is used in the red light-sensitive emulsion layer. However, depending on the purpose, silver halide color photographic materials may be produced using different combinations from the above.

As the yellow coloring coupler, a known open-chain ketomethylene coupler can be used. Among these, benzoylacetanilide and pivaloylacetanilide compounds are advantageous. Specific examples of yellow couplers that can be used are U.S. Pat. Nos. 2.875.057 and 3,265.5.
No. 06, No. 3,408.194, No. 3,551.15
No. 5, No. 3,582.322, No. 3,725.072
No. 3,891,445, West German Patent No. 1,547,8
No. 68, West German Application No. 2,219.917, No. 2,2
No. 61.361, No. 2.414,006, British Patent 1
, 425,020, JP 51-10783, JP 47-26133, JP 48-73147 and JP 51
-102636, 50-6341, 50-12
No. 3342, No. 50-130442, No. 51-218
No. 27, No. 50-87650, No. 52-82424, No. 52-115219, etc.

As the cyan coloring coupler, phenol compounds, naphthol compounds, etc. can be used. Specific examples thereof include U.S. Pat. Nos. 2,369.929 and 2.434.
No. 272, No. 2,474.293, No. 2,521,9
No. 08, No. 2, No. 895, No. 826, No. 3,034,
No. 892, No. 3,311', No. 476, No. 3,458.
No. 315, No. 3,476.563, No. 3.583.9
No. 71, No. 3,591.383, No. 3,767.41
No. 1, No. 4,004,929, West German Patent No. 11K (O
LS) No. 2,414,830, No. 2,454,329, JP-A-48-59838, JP-A No. 51-26034,
No. 48-5055, No. 51-146828, No. 52
-69624 and No. 52-90932.

Magenta coloring couplers include pyrazolone compounds,
Indacylon compounds, cyanoacetyl compounds, pyrazolinobenzimidazole compounds, etc. can be used. Specific examples are U.S. Patent Nos. 2,600.788, 2.369.489, 2.343.703, and
, No. 311,082, No. 3,152,896, No. 3,
519.429, 3,062,653 and 2,
No. 108.573.

In addition, a colored coupler having a color correction effect and a development inhibitor-releasing coupler (so-called DIR coupler) can be used together with the coupler as necessary to improve image quality.

It is desirable that these dye-synthesizing couplers have a group called a ballast group in the molecule, which makes the coupler non-diffusive and has 8 or more carbon atoms. It may be either 4-equivalence, in which 100 silver ions need to be reduced, or 2-equivalence, in which only 2 molecules of silver ions need to be reduced.

For hydrophobic compounds such as dye-forming couplers that do not need to be adsorbed onto the silver halide crystal surface, various methods such as solid dispersion, latex dispersion, and oil-in-water emulsion dispersion can be used. can be appropriately selected depending on the chemical structure of the hydrophobic compound, etc. The oil-in-water emulsion dispersion method can be applied using conventionally known methods for dispersing hydrophobic additives such as couplers, and is usually mixed with a high boiling point organic solvent having a boiling point of about 150°C or higher, and if necessary, a low boiling point and/or a high boiling point organic solvent. Or, by dissolving it in combination with a water-soluble organic solvent, using a surfactant in a wood-philic binder such as an aqueous gelatin solution, and using a dispersion means such as a stirrer, homogenizer, colloid mill, flow jet mixer, or ultrasonic device, After emulsification and dispersion, a step of removing the low-boiling organic solvent may be added at the same time as the dispersion or dispersion, which can be added to the target wood-philic colloid mill.

High-boiling point oils that react with the oxidized form of the developing agent include fL isphenol derivatives, phthalate esters, phosphate esters,
Boiling point 15 of citric acid ester, benzoic acid ester, alkyl amide, fatty acid ester, trimesic acid ester, etc.
An organic solvent having a temperature of 0° C. or higher is used.

Anionic surfactants, nonionic surfactants, cations are used as dispersion aids 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 a machine or ultrasound. A surfactant can be used.

Between the emulsion layers (between the same color-sensitive layers and/or between different color-sensitive layers) of the color photographic light-sensitive material of the present invention, the oxidized form of the developing agent or the electron transfer agent may migrate, resulting in color turbidity or sharpness. Color antifoggants are used to prevent deterioration and graininess from becoming noticeable.

The color anti-capri agent may be used in the emulsion layer itself, or in an intermediate layer provided between adjacent emulsion layers.

In the color light-sensitive material using the silver halide emulsion layer according to the present invention, an image stabilizer that prevents deterioration of the dye image can be used in addition to a specific compound.

Ultraviolet absorbers are added to the hydrophilic colloid layers such as the protective layer and intermediate layer of the photosensitive material of the present invention in order 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 light. May contain.

As the image stabilizer, for example, US Pat.
No. 0.290, No. 2.418, 613, No. 2.675
・No. 314・No. 2,701.197, No. 2,704.
No. 713, No. 2, No. 728, No. 659, No. 2,732.3
No. 00, No. 2,735.765, No. 2,710.80
No. 1, No. 2,816,028, British Patent No. 1,363,
Hydroquinone derivatives described in US Pat. No. 921, etc., gallic acid derivatives described in US Pat. No. 3,457.079, US Pat.
No. 5, No. 3,698.909, Special Publication No. 49-2097
No. 7, p-alkoxyphenols described in U.S. Pat. No. 52-6623, U.S. Pat.
, No. 573.050, No. 3.574.627, No. 3,
No. 764.337, JP-A-52-35633, JP-A No. 52
-147434, p-oxyphenol derivatives described in US Pat. No. 52-152225, US Pat. No. 3,700.
There are bisphenols described in No. 455.

As the ultraviolet absorber, for example, a benzotriazole compound substituted with an aryol group (for example, U.S. Pat. No. 3.53
3.794), 4-thiazolidone compounds (e.g., U.S. Pat. No. 3,314,794, U.S. Pat. No. 3,352)
．． 681), benzophenone compounds (e.g., those described in JP-A-46-2784), cinnamic acid ester compounds (e.g., as described in U.S. Pat. Nos. 3,705,805 and 3,707,375), ), butadiene compounds (such as those described in US Pat. No. 4,045,229), or benzoxidole compounds (such as those described in US Pat. No. 3,700,455) can be used. Furthermore, those described in US Pat. No. 3,499,762 and Japanese Patent Application Laid-Open No. 54-48535 can also be used.

The silver halide photographic material according to the present invention can be provided with auxiliary layers such as a filter layer, a haleysilane prevention layer, and/or an irradiation prevention layer. These layers and/or the emulsion layer may contain dyes that flow out of the light-sensitive material or are bleached during development.

In the photographic light-sensitive material of the present invention, the silver halide emulsion layer using a silver halide emulsion and/or other hydrophilic colloid layer may be used to reduce the gloss of the light-sensitive material, increase the ease of writing, and prevent the light-sensitive materials from sticking to each other. A mantle agent can be added for the purpose of preventing such damage.

A lubricant can be added to reduce the sliding friction of the silver halide photographic material of the present invention.

An antistatic agent can be added to the silver halide photographic material of the present invention 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, or
It may be used in an emulsion layer and/or a protective colloid layer other than the emulsion layer on the side where the emulsion layer is laminated with respect to the support.

The photographic emulsion layer and/or the silver halide photographic light-sensitive material of the present invention
Alternatively, other hydrophilic colloid layers may contain various interfaces for the purpose of improving coating properties, preventing static electricity, improving slipperiness, emulsification and dispersion, preventing adhesion, and improving photographic properties (such as promoting development, increasing contrast, and worsening contrast). An activator is used.

The photographic emulsion layer and other layers of the silver halide photographic light-sensitive material of the present invention are a baryta layer or a flexible support such as paper laminated with an α-olefin polymer, synthetic paper, etc., 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, and rigid bodies such as glass, metal, and ceramics.

The silver halide photographic material of the present invention can be improved in adhesion, antistatic properties, and dimensional stability directly or on the surface of the support after subjecting the surface of the support to corona discharge, ultraviolet irradiation, flame treatment, etc., if necessary. , may have one or more subbing layers to improve abrasion resistance, hardness, antihalation properties, friction properties, and/or other properties.

In forming the silver halide photographic material of the present invention,
When applying the material liquid for forming each layer, a thickener may be used to improve the coating properties.Extrusion coating, which can apply two or more layers at the same time, and Curtain coatings are particularly useful.

The photosensitive material of the present invention can be exposed using electromagnetic waves in a spectral region to which the emulsion layer constituting the photosensitive material is sensitive. Light sources for n-light include natural light (sunlight), tungsten lamps, fluorescent lamps, mercury lamps, xenon arc lamps, carbon arc lamps/xenon flash lamps, cathode ray tube flying spots, various laser beams, light emitting diode lights, electron beams, and X-rays. Any known light source can be used, such as light emitted from a phosphor excited by , gamma rays, alpha rays, or the like.

Exposure times include not only exposure times of 1 millisecond to 1 second commonly used in cameras, but also exposure times shorter than 1 microsecond, such as exposure times of 100 microseconds to 1 microsecond using cathode ray tubes and xenon flash lamps.
Microsecond exposures can be used, or longer exposures of 1 second or more are possible. The exposure may be performed continuously or intermittently.

An image can be formed from the silver halide photographic material of the present invention by development or color development by methods known in the art.

In the case of color development, aromatic primary amine developing agents used in the color developer include those known and widely used in various color photographic processes. These developers include aminophenol and p-phenylenediamine derivatives. Since these compounds are more stable than their free states, they are generally used in the form of salts, such as hydrochlorides or sulfates. These compounds also generally have a concentration of about 0.1 for color developer IIl.
g to about 30 g, preferably about 1 g to about 1.5 g for color developer 11.

Examples of aminophenol-based developers include 0-aminephenol, p-aminophenol, and 5-amino-2
-oxytoluene, 2-amino-3-oxytoluene,
2-oxy-3-amino-1,4-dimethylbenzene and the like are included.

Particularly useful primary aromatic amino color developers are N, N'
- A dialkyl-p-phenylenediamine compound, in which the alkyl group and phenyl group may be substituted with any substituent.Among them, a particularly useful example is N,N"-diethyl-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-aminoaniline Sulfate, N-ethyl-N-β-hydroxyethylaminoaniline, 4-amino-3-methyl-N.

N'-diethylaniline, 4-amino-N-(2methoxyethyl)-N-ethyl-3-methylaniline-p-
) luenesulfonate, etc.

In addition to the above-mentioned primary aromatic amine color developer, the color developer used in the processing of the light-sensitive material of the present invention contains various components normally added to color developers, such as sodium hydroxide and carbonate. It may optionally contain alkaline agents such as sodium and potassium carbonate, alkali metal sulfites, alkali metal bisulfites, alkali metal thiocyanates, alkali metal halides, benzyl alcohol, water softeners and thickening agents. . The pH value of this color developer is usually 7 or higher, most commonly about 10 to about 13.

After a photographic light-sensitive material is subjected to color development processing, it is processed with a processing liquid having a fixing ability, but if the processing liquid having a fixing ability is a fixing liquid, a bleaching treatment is performed before that. A metal complex salt of an organic acid is used as a bleaching agent in the bleaching process, and the metal complex salt has the effect of oxidizing the metallic silver produced during development and converting it into silver halide, and at the same time coloring the uncolored areas of the coloring agent. It has a structure in which metal ions such as iron, cobalt, and copper are coordinated with aminopolycarboxylic acid or organic acids such as oxalic acid and citric acid. The most preferred organic 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 The bleaching agent used in the sodium acetate salt contains, as a bleaching agent, a metal complex salt of an organic acid such as those mentioned above, and may also contain various additives. It is desirable to contain rehalogenating agents such as potassium chloride, sodium bromide, sodium chloride, and ammonium bromide, metal salts, and chelating agents.

Also borates, oxalates, acetates, carbonates, phosphates, etc. (7)
Those known to be added to ordinary bleaching solutions, such as pH 1l buffer, alkylamines, and polyethylene oxides, can be added as appropriate.

Furthermore, the fixer and bleach-fixer contain ammonium sulfite,
Sulfites 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, carbonic acid It may contain one or more pH1L buffers consisting of various salts such as potassium, sodium bisulfite, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide.

When processing photographic materials while replenishing the bleach-fixing solution (bath) with a bleach-fixing replenisher, the bleach-fixing solution (bath) may contain thiosulfate, thiocyanate, sulfite, etc. However, the bleach-fix replenisher may contain these salts and be replenished into the processing bath.

In addition, 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 a suitable oxidizing agent such as peroxide may be added. Hydrogen, bromate, persulfate, etc. may be added as appropriate.

[Specific effects of the invention]

Since the silver halide photographic material of the present invention has a layer containing a specific compound, the stability of the formed photographic image is very high, and it is particularly effective in color photographic materials using magenta couplers. Especially light, heat,
The fastness of magenta dye images, which generally have low fastness to humidity, can be improved, and specifically, discoloration and fading against light, and generation of Y-stin in uncolored areas against light, heat, and humidity can be effectively prevented. It has the effect of

[Specific embodiments of the invention]

The present invention will be specifically explained below with reference to Examples, but the embodiments of the present invention are not limited thereto.

Example 1 On a paper support laminated on both sides with polyethylene, gelatin (15, hg/100aj), magenta coupler (1) as shown below (6, (lI1g/100al)
i) with 2,5-di-tart-octylhydroquinone (0,hg/Loom) dibutyl phthalate<5
．． 0mg/100aj) and emulsified and dispersed, silver chlorobromide emulsion (imao bromide mol%, coated silver amount 3.8mg)
/100 cd), coated, and dried to obtain Sample 1.

Comparative compounds (a), (mountain) and (0
Sample 2, Sample 3, and Sample 4 were obtained in the same manner except that the same molar amount of magenta coupler (1) was added.

Exemplary compounds (4), (5), (8), (22), (29), (3) were added to the coating solution of Sample 1 as a color image stabilizer.
Samples 5.6.7.8.9 and 1O were obtained in the same manner except that 4) and coupler (1) were added in equimolar amounts.

In addition, as a color image stabilizer, sample 11 was obtained by adding exemplified compound (4) and comparative compound (al) in equal moles.Similarly, as a color image stabilizer, exemplified compound (8) and comparative compound (al) were added. Sample 12 was obtained using
Sample 13 was obtained using a comparative compound (C1).

Comparative Compound (Al nth Comparative Compound (g)) Comparative Compound to) Each sample obtained above was exposed through an optical model according to a conventional method, and then treated in the following steps.

[Processing process Processing temperature Processing time Color development
33℃ 3 minutes 30 seconds bleach fixing 33℃
Wash with water for 1 minute and 30 seconds at 33℃
Dry for 3 minutes 50-80℃
The components of each 2-minute treatment solution are as follows.

[Color developer]

Benzyl alcohol 12mJl diethylene glycol 10-1 potassium carbonate
25 g sodium bromide
0.6g anhydrous sodium sulfite
2.0g hydroxylamine sulfate
2.5 g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate Add 4.5 g water and lI! and adjust the pH to 10.2 with NaOH.

[Bleach-fix solution]

Ammonium thiosulfate 120 g Sodium metabisulfite 15 g Anhydrous sodium sulfite 3 g EDTA ferric ammonium salt 65 g Add water II! and pH 6.7.
Adjusted to ~6,8.

The concentrations of Samples 1 to 13 treated above were measured using a densitometer (model KD-7R manufactured by Konishiroku Photo Industry Co., Ltd.) under the following conditions.

Each of the above-mentioned processed samples was irradiated with a xenon fade meter for 10 days, and the light resistance of the dye image and the Y-stain of the uncolored area were examined. Specifically, the density change (M density change) when the density of the 7 zenta dye image area before the test is set to 1.0.
, and change in density of yellow coloring on white background (Y-stin)
I looked into it. The results obtained are shown in Table 1.

Table 1 (* is related to the present invention) As is clear from Table 1, samples 5 to 13 prepared using specific compounds showed no discoloration or fading of the dye image in the light resistance test. It can be seen that the Y-stin is small and the uncolored Y-stin is also small.

Example 2 On a paper support laminated on both sides with polyethylene, the following layers were sequentially coated from the support side to prepare a multicolor silver halide photographic light-sensitive material, and Sample 14 was obtained.

1st layer: Blue-sensitive silver halide emulsion layer α-pivaloyl-α-(2,4
-dioxo-1-benzylimidazolidin-3-yl)
-2-chloro-5-(γ-2,4-di-t-amylphenoxy)butyramide]acetanilide at 6.8 μ/1
00aJ, blue-sensitive silver chlorobromide emulsion (containing 85 mol% silver bromide) converted to silver is 3.2*/100-, dibutyl phthalate is 3.5*/100aJ and gelatin is 13.5*
The coating was applied so that the coating amount was /100 cIN.

2nd layer: middle layer 0.5sg of 2.5-di-t-octylhydroquinone
/100od, dibutyl phthalate 0.5Qr/10
0- and gelatin were coated at a rate of 9.0 cm/100 cd.

Third layer: Green-sensitive silver halide emulsion layer The magenta coupler (1) was added at 3.5 μ/100 cd;
The green-sensitive silver bromide emulsion (containing 80 mol% silver bromide) was converted into silver at 2.5 cm/100 cj, and the dibutyl phthalate was converted into silver at 3.5 cm/100 cj.
0■/l00C111 and gelatin 12.0■/10
It was coated so that it was 0 cd.

4th layer: Intermediate layer Ultraviolet absorber 2-(2-hydroxy-3-5ee-butyl-5-t-butylphenyl)benzotriazole 0.7 μ/100 cal, dibutyl phthalate 6.
0 ■/IOM, 0.5 ■/100 cd of 2.5-di-t-octylhydroquinone and 12.0 ■/1 gelatin.
00cd.

5th layer: Red-sensitive silver halide emulsion layer 2-[α-(2,4-di-t-pentylphenoxy)butanamide)-4,6-dichloro-5-ethylphenol as cyan coupler at 4.2+I1g/100 −
1 red-sensitive silver chlorobromide emulsion (containing mol% of silver bromide) converted to silver: 3.0 /IGOcj, tricresylphos 7z
) to 3.5*/100aJ and gelatin to 11.5*
/100aJ.

6th layer: Protective layer gelatin was coated at 8.0+w/100aJ.

In the above sample 14, a dye image stabilizer selected from the specific compounds was added to the third layer in the proportions shown in Table 2 to create multilayer samples 15 to 23, and exposed in the same manner as in Example 1, After treatment, a light fastness test (15 days of irradiation on a xenon fade meter) was performed.

The results are also shown in Table 2.

From the results shown in Table 2 and above, the use of the specific compound as an image stabilizer according to the present invention is effective in stabilizing the dye image produced by the magenta coupler, and the results become greater as the amount added increases. Furthermore, in the sample of the present invention, discoloration of magenta pigment,
It can be seen that the color fading is small, the overall color balance with the yellow and cyan couplers as a color photographic material is good, and the color reproducibility is extremely good.

Procedural amendment (voluntary) October 1985 Michibe Uga, Commissioner of the Patent Office, October 19851, Indication of the case, Patent Application No. 99515, filed in 19852, Name of the invention: Halogenated grudge photographic light material 3, Amendment. Patent applicant address 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name (127) Konishiroku Photo Industry Co., Ltd. 4, engraving and attached sheet of the specification originally attached to the representative application As of (
(no change in content)

Claims (1)

[Scope of Claims] 1) A silver halide photographic material characterized by having a layer containing a compound represented by the following general formula [I]. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. , R_3 is a halogen atom, an alkyl group, an aryl group, an alkylthio group,
Arylthio group, amino group, alkylamino group, arylamino group, acylamino group, sulfonamide group, ureido group, acyl group, carbamoyl group, alkoxycarbonyl group, sulfonyl group, sulfamoyl group, nitro group,
It represents a cyano group or a carboxyl group, and m represents an integer of 0 to 4. )