JPS61258249A - 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 color photographic light-sensitive material, and more particularly to prevention of discoloration of a dye image obtained by processing a silver halide color photographic light-sensitive material due to light and discoloration of uncolored areas caused by light.

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. Moreover, 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 fading 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
U.S. Pat. No. 9,262 describes pyrogallol, curlicic acid and its esters, U.S. Pat. No. 2,360,290 and U.S. Pat. 52-27
No. 534, Japanese Unexamined Patent Publication 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 dihydroxy-2,2'-bisspirocoumarones, etc. Although these compounds do have the effect of fading or discoloration of pigments, the effect is small or there is no anti-fading effect. However, these compounds also have drawbacks such as a longer wavelength hue, generation of Y-stain, and the presence of these compounds lowers the coloring properties 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 [I].

General formula (1) (In the formula, R14 represents an alkyl group or an alkyl group, and R
2 represents an alkyl group, an aryl group, an alkylamino group, an arylamino group, an acylamino group, a sulbonamide group, an alkoxy group, an alkyloxycarbonyl group, an alkylthio group, or an arylthio group, and R1 and R4 represent an alkyl group, an alkenyl group, or a cycloalkyl group. group, ryor group,
To explain in more detail R8 in general formula (1), which represents a heterocyclic group, it represents a straight or branched alkyl group having 1 to 24 carbon atoms (for example, a methyl group, an ethyl group, an isopropyl group, t-butyl group, 2-ethylhexyl group, dodecyl group, t-octyl group, cyclohexyl group, benzyl group, phenylethyl group, etc.), aryl group (e.g. phenyl group, naphthyl group, etc.)
represents.

: These groups may further have a substituent, and examples of the substituent include an alkyl group, a hydroxy group, an alkoxy group, an aryl group, an acetylamino group, a sulfonamido group, an aryloxy group, an alkylthio group, and an arylthio group. , carbamoyl group, sulfamoyl group, sulfonyl group,
Nitro group, cyano group, halogen atom, carboxyl group,
Examples include an amino group, an alkylamino group, an arylamino group, an alkoxycarbonyl group, an acyl group, and an acyloxy group.

Among these, R is particularly preferred as an aryl group.

To explain R1 in general formula (1) in more detail, it can be an alkyl group, an alkyl group, an alkylamino group (e.g., methylamino group, diethylamino group, etc.), an arylamino group (e.g., phenyl group, etc.) as defined for R1. amino group, α-naphthylamino group, etc.), acylamino group (N
(e.g., acetylamino group, benzoylamino group, etc.), sulfonamide group (e.g., methanesulfonamide group, benzenesulfonamide group, etc.), alkoxy group (e.g., ethoxy group, dodecyloxy group, etc.), alkyloxycarbonyl group (e.g., methoxycarbonyl group) , t-octadecyloxycarbonyl group, etc.), alkylthio group (e.g., methylthio group, dodecylthio group, etc.), arylthio group (e.g., phenylthio group, α-naphthylthio group, etc.),
These groups may further have a substituent, and examples of the substituent include the same substituents as in the alkyl group and aryl group of .R.

Among these, R8 is preferably an alkyl group, an alkylamino group, an arylamino group, an acylamino group,
They are an alkoxy group and an alkylthio group.

To explain R1 and R4 in general formula (1) in more detail, they are linear or branched alkyl groups having 1 to 24 carbon atoms (for example, methyl group, ethyl group, isopropyl group, t
-butyl group, 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.), cycloalkyl group having 5 to 24 carbon atoms (e.g., cyclopentyl group, cyclohexyl group, etc.)
, aryol group (e.g. phenyl group, naphthyl group, etc.), heterocyclic group (e.g. pyridyl group, imidazolyl group, tetrazolyl group, oxasilyl group, 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.).

These groups may further have a substituent, and examples of the substituent include the same substituents as in the alkyl group and aryl group of R3.

Among these, preferred as R8 are alkyl groups and aryl groups, and preferred as R4 are alkyl groups and aryl groups.

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

[Exemplary compounds]

CR2 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 (1)] (A) 3-Methyl-4-methylthio-1-phenyl-2-pyrazoline-
Synthesis of 5-one Journal of Chemical Society (J.

Cheep, Sac,) C1970, (3), 4
It was synthesized according to the method described in 45-8 (Eng).

(B) Synthesis of Exemplary Compound (1) 22.0 g of 3-methyl-4-methylthio-1-phenyl-2-pyrazolin-5-one and 100 a+ methanol
1 and 28% methanol solution of sodium methylate 2
Then, 15.6 g of methyl iodide was added and stirred for 2 hours. The precipitated solid was filtered and washed with methanol to obtain 17.3 g of white crystals (yield: 83%).
.

When this substance was identified by FD mass spectrometry and HHR, it was confirmed that it was the same as Exemplified Compound (1).

Synthesis Example 2 [Synthesis of Exemplified Compound (17)] (A) Synthesis of 3-methyl-1-phenyl-4-phenylthio-2-pyrazolin-5-one Chemical Abstract (Chew
, Abs, ) 75:98.49Of.

(B) Synthesis of Exemplary Compound (17) 28.2 g of 3-methyl-1-phenyl-4-phenylthio-2-pyrazolin-5-one and 100 mt of methanol
and sodium methylate in 28% methanol solution 20
．． 3 g, then 24.9 g of dodecyl bromide
was added and stirred for 2 hours. The precipitated solid was filtered and washed with methanol to obtain 36.5 g of white solid (yield: 81
%).

When this substance was identified by FD mass spectrometry and NMR, it was confirmed that it was the same as exemplified compound (17).

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 silane layer, and other auxiliary layers. Contained in at least 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 using color photographic paper that is intended for direct viewing, it has excellent properties. 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 do 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 order. However, the calendar number and the 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.
The silver halide emulsion used here includes any silver halide used in conventional silver halide emulsions such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride. can be used.

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 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 the presence of the other, and while taking into consideration the critical growth rate of silver halide crystals, Growth may be performed by sequentially and simultaneously adding halide ions and silver ions while controlling PR and pAg in a mixing tank.The silver halide composition of the grains may be changed using a conversion 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 using a silver halide solvent as necessary.

The silver halide grains used in Kusunoki silver halide milk are cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts, rhodium salts or complex salts during the grain formation process and/or growth process. By adding metal ions using iron salts or complex salts, they can be included inside the particles and/or on the particle surfaces, and by placing them in an appropriate reducing atmosphere, reduction sensitization can be achieved inside the particles and/or on the particle surfaces. Can give a nucleus.

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 A 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 (100) plane to the (111) plane can be used. In addition, 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 compound that does not have a spectral sensitizing effect by itself or a compound that does not substantially absorb visible light, which may be used in combination with a sensitizing dye, and a compound that enhances the sensitizing effect of the sensitizing dye. A color sensitizer may also 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 capri during the manufacturing process, storage, or photographic processing of light-sensitive materials, and/or keeping photographic performance stable. At the time and/or after the end of chemical ripening and before coating the silver halide emulsion, compounds known in the photographic industry as antifoggants or stabilizers may be added. A binder for the silver halide emulsion ( It is advantageous to use gelatin (or protective colloid), but gelatin derivatives, graft polymers of gelatin and other polymers, proteins, P! derivatives, cellulose derivatives,
Hydrophilic colloids such as synthetic hydrophilic polymeric materials such as single 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.

Plasticizing may be added for the purpose of increasing the flexibility of the silver halide emulsion layer and/or other hydrophilic colloid layer of a photosensitive 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. .

The emulsion layer of the silver halide color photographic light-sensitive material according to the present invention contains a coupling reaction with an oxidized product of an aromatic primary amine developer (for example, p-phenylenediamine derivative, aminophenol derivative, etc.) during color development treatment. A dye-forming coupler is used that performs the following steps to form 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, compounds of the penzoylacetanilide Y type and pivaloylacetanilide type are advantageous. Specific examples of yellow couplers that can be used are U.S. Pat. No. 2.875.057 and U.S. Pat.
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 Publication No. 2,219,917, No. 2,
No. 261.361, No. 2.414,006, British Patent No. 1,425,020, Japanese Patent Publication No. 51710783, Japanese Patent Publication No. 47-26133, No. 48-73147, No. 5
No. 1-102636, No. 50-6341, No. 50-1
No. 23342, No. 50-130442, No. 51-21
No. 827, No. 50-87650, No. 52-82424
No. 52-115219.

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. 2,895.826, No. 3,034,89
No. 2, No. 3,311,476, No. 3,458,315
No. 3,476.563, No. 3,583,971, No. 3,591,383, No. 3,767.411,
4, 004, 929, West German patent ratio 1ffl (o
Ls) 2.4t No. 4.830, No. 2,454,329, JP-A-48-59838, 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, biraprinobenzimidazole compounds, etc. can be used. Specific examples are U.S. Patent No. 2,600.788, U.S. Pat. No. 2,369.489, U.S. Pat.
, No. 519,429, No. 3,062,653 and No. 2
, No. 108.573.

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. Alternatively, it can be dissolved using a water-soluble organic solvent and emulsified using a dispersion means such as a stirrer, homogenizer, colloid mill, flow jet mixer, or ultrasonic device using a surfactant in a hydrophilic binder such as an aqueous gelatin solution. After dispersion, a step of removing the low-boiling organic solvent may be added at the same time as the dispersion or dispersion, which may be added to the desired hydrophilic colloid layer.

High boiling point oils that react with the oxidized form of the developing agent include knife enol derivatives, phthalate esters, phosphate esters, citric acid esters, benzoate esters, alkylamides,
Boiling point of fatty acid ester, trimesic acid ester, etc. 150
An organic solvent having a temperature of ℃ 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 antifoggant 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.

Preservation of the photosensitive material of the present invention! A hydrophilic colloid layer such as an intermediate layer may contain an ultraviolet absorber 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.

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. 2,728,659, 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. 3,457.0'19, US Pat.
No. 65, September 3,698.909, Special Publication 1977-209
p-alkoxyphenols described in U.S. Pat. No. 77 and U.S. Pat. No. 52-8623, U.S. Pat.
, No. 573.050, No. 3,574.627, No. 3,
No. 764,337, JP-A No. 52-35633, No. 52
-147434, p-oxyphenol derivatives described in US Pat. No. 52-152225, US Pat.
There are bisphenols described in No. 455.

Examples of ultraviolet absorbers include benzotriazole compounds substituted with aryl groups (for example, U.S. Pat. No. 3,533
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. 3,70o, 4ss) 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 may be provided with auxiliary layers such as a filter layer, an antihalation layer, and/or an antiirradiation 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 matting 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 for the purpose of preventing static electricity can be added to the silver halide photographic material of the present invention. 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
Other hydrophilic colloid layers may contain various additives for the purpose of improving coating properties, preventing static electricity, improving slipperiness, dispersing emulsions, preventing adhesion, and improving photographic properties (such as accelerating development, increasing contrast, and sensitizing). Surfactants are 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 to form each layer, a thickener may be used to improve the coating properties.Extrusion coating and curtain coating methods that can apply two or more layers at the same time may be used. 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 exposure include natural light (sunlight), tungsten electric lamp, fluorescent lamp, mercury lamp, xenon arc lamp, carbon arc lamp, xenon flash lamp, cathode ray tube flying spot, various laser beams, light emitting diode light, electron beam, X-ray, Any known light source or light can be used, such as light emitted from a phosphor excited by r&II, alpha radiation, 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, and exposures longer than 1 second are also 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.

When performing color development, the aromatic primary amine color developing agents used in the color developing solution include those known and widely used in various color photographic processes. These developers include aminophenol and p-phenylenediamine derivatives. These compounds are generally used in the form of salts, such as hydrochlorides or sulfates, since they are more stable than in the free state. In addition, these compounds are generally contained in an amount of about 0.1 g to
A concentration of about 30 g is used, preferably about 1 g to about 1.5 g for color developer 11.

Examples of aminophenol-based developers include O-aminophenol, 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'
-Dialkyl-p-phenylenediamine type compound, the alkyl group and phenyl group may be substituted with any substituent, among which particularly useful examples include N, N"-diethyl-p-phenylenediamine Hydrochloride, N-methyl-p-phenylenediamine hydrochloride, N,N
'-'; Methyl-p-phenylenediamine salt base salt 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-(2-methoxyethyl)-N-ethyl-3-methylaniline-p-
Examples include toluene sulfonate.

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, thickeners, etc. . The pH (a) of this color developer is usually 7 or more, 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 gold complex salt oxidizes the metallic silver produced by development and converts it into silver halide, and at the same time colors the uncolored part of the color former. Its composition is aminopolycarboxylic acid or organic acids such as oxalic acid and citric acid coordinating metal ions such as iron, cobalt and copper.Metal complex salts of organic acids such as 6.2 The most preferred organic acids used to form 4Ht' 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, the pH of borates, N# salts, acetates, carbonates, phosphates, etc.
Buffers, alkylamines, polyethylene oxides, and other substances known to be added to ordinary bleaching solutions 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 pH1li 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. , the bleach-fixing replenisher may contain these salts and be replenished into the processing bath.

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 window optical 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, and is , 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, OL 1 g/100 aJ), magenta coupler (1) shown below (6,0 mg/100 aJ)
) to 2,5-di-tart-octylhydroquinone (
After dissolving and emulsifying and dispersing dibutyl phthalate (5.0 mg/100 aJ) with dibutyl phthalate (0.8 mg/100 cd), a silver chlorobromide emulsion (silver bromide 80 mol%, coated silver amount 3.8 m) was prepared.
g/100 cd), coated, and dried to obtain sample 1.

Comparative compounds (a), M) and (C), which are conventionally known magenta color image stabilizers, were added to the coating solution of Sample 1 above.
Sample 2.3.4 was obtained in the same manner except that Magenta Coupler (1) and Magenta Coupler (1) were added in an equimolar amount.

The same procedure was followed except that exemplified compounds (2), (11), (14), (21), and (24) were added to the coating solution of Sample 1 in the same mole as the coupler (1) as color image stabilizing compounds. Sample 5
．． 6.7.8 and 9 were obtained.

In addition, Sample 10 was obtained by adding Exemplified Compound (2) and Comparative Compound (al) as a color image stabilizer in equimolar amounts to the coupler. Similarly, as a color image stabilizer, Comparative Compound (14) was added. Sample 11 was obtained using Compound (first appearance), and Exemplified Compound (24) and Comparative Compound f were used as color image stabilizers.
Sample 12 was obtained using cl.

Comparative Compound fbl Comparative Compound fcl Each sample obtained above was exposed to light through an optical model according to a conventional method, and then processed in the following steps.

[Processing process] Processing temperature Processing time Color development
33℃ 3 minutes 30 seconds Bleach constant IF 53℃
Wash with water for 1 minute and 30 seconds, dry for 3 minutes at 33℃
Drying 50-80°C 2-part treatment The components of the treatment solution are as follows.

[Color developer]

Benzyl alcohol 12ml! Diethylene glycol 10 mff1 Potassium carbonate 25 g Sodium bromide 0.6 g Anhydrous sodium sulfite 2.0 g Hydroxylamine sulfate m
2.5 g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 4.5 g water was added to make 11, and the pH was adjusted 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 Water was added to bring the pH to 6.
Adjust to 7-6.8.

The concentrations of Samples 1 to 12 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 when the density of the magenta dye image part before the test is set to 1.0 (M density change)
, 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 12 prepared using specific compounds were prepared using conventionally known dye image stabilizers. It is understood that the color change and fading of the dye image due to light is smaller than when the dye image is used, and the amount of uncolored Y-stin is also smaller. It is also understood that when the specific compound and a conventionally known color image stabilizer are used in combination, the fading of the dye image is further improved.

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 13 was obtained.

1st layer: blue-sensitive silver halide emulsion layer monopivaloyl α-(2,4
-dioxo-1-benzylimidazolidin-3-yl)
-2-chloro-5-[γ-2.4-di-t-amylphenoxy)butyramide]acetanilide at 6.8 μ/
100 aJ, blue-sensitive silver chlorobromide emulsion (containing 85 mol% silver bromide) in terms of silver: 3.2 yr/100-, dibutyl phthalate: 3.5 yr/100-, and gelatin: 13.5
The coating was applied so that the coating amount was 1/100tj.

2nd layer: Intermediate layer 2.5-di-t-octylhydroquinone 0.5μ/
100 cd, dibutyl phthalate 0.5■/100
d and gelatin were coated at a rate of 9.0 cm/100 cd.

Third layer: green-sensitive silver halide emulsion layer containing the magenta coupler (1) at 3.5+ag/100c
+! , 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. ON/100cd and gelatin 12.0mg/
It was coated so that it became 100-.

4th layer: Intermediate layer UV absorber 2-(2-hydroxy-3-5ec-butyl-5-t-butylphenyl)benzotriazole 0.7μ/100aJ, dibutyl phthalate 6.0
■/100aJ, 2,5-di-t-octylhydroquinone 0.5■/100ci and gelatin 12.0■/
It was coated so that it became 100-.

5th layer: Red-sensitive silver halide emulsion layer 2-[α-(2,4-di-t-pentylphenoxy)butanamide)-4,6-dichloro-5-ethylphenol as cyan coupler 4.2/ 100-1 red-sensitive silver chlorobromide emulsion (containing 80 mol% silver bromide) was converted to silver at 3.0 µ/100cd, tricresyl phosphate was 3.5w/100cfil, and gelatin was 11.5*/
It was coated to give a weight of 100aJ.

No. 6117 protective layer gelatin was coated at a rate of 8.0 cm/100 ci.

In the above sample 13, a dye image stabilizer selected from the specific compounds was added to the third layer in the proportions shown in Table 2 to prepare heavy H samples 14 to 22, 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 conducted.

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 color balance is good with the yellow and cyan couplers as an overall color photographic material, and the color reproducibility is extremely good.

Procedural amendment (voluntary) 10P118, 1985 Michibe Uga, Commissioner of the Patent Office 1: Indication of the case 1985 Patent Application No. 99518 2, Name of the invention Silver halide photographic light-sensitive material 3, Person making the amendment Case Relationship with Patent Applicant Address 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name (127) Konishiroku Photo Industry Co., Ltd. 4, Agent

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] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1 represents an alkyl group or an aryl group, and R
_2 is an alkyl group, aryl group, alkylamino group, arylamino group, acylamino group, sulfonamide group,
It represents an alkoxy group, an alkyloxycarbonyl group, an alkylthio group, or an arylthio group, and R_3 and R_4 represent an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, or a heterocyclic group. )