JPS61248042A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To form the titled material having an excellent preservation of a green sample, and suitable for a continous replenish treatment by incorporating a specific compd. to the photographic constituting layer. CONSTITUTION:The compd. shown by formula I is comprised is at least one of the photographic constituting layer. The concrete example of the compd. shown by formula I comprises the compd. shown by formula 1. The compd. may be compounded to the titled material as the solution or the dispersion thereof by dissolving it to water, or an org. solvent miscible to water optionally, such as methanol and ethanol, or by dissolving it an org. solvent (un-necessary to miscible to water) followed by dispersing the solution into a hydrophilic colloid. The compounding amount of the compd. is preferably 1.0X10<-5>-1.0 moles, further preferably 1.2X10<-4>-1.0X10<-1> moles per 1mol of the silver halide.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a silver halide photographic material that is subjected to color development using an aromatic primary amine developing agent. The present invention relates to a silver halide color photographic material which has excellent properties and is suitable for continuous replenishment processing.

[Background of the Invention] Silver halide photographic materials are placed in various environments from the time they are shipped until they are delivered to users and exposed. The most preferable option is to store the product at a low temperature in a freezer or refrigerator, but in reality, it is rather rare that the product is stored in such conditions, and it is often exposed to harsh environments of high temperature and high humidity. For example, color films can be stored in air-conditioned photo shops, but they are often kept in harsh temperature and humidity conditions for long periods of time, such as in shops at tourist spots. Furthermore, although color photographic paper is normally required to be stored at low temperatures (e.g., below 13°C), due to reasons such as product transportation and user convenience, this is not kept and storage at high temperatures (e.g., 30°C or lower) is not possible for color photographic paper. 40℃).

Therefore, silver halide photographic materials (hereinafter referred to as "raw samples") that have not yet been exposed to light have been shipped.
It is called. ) has poor storage stability over time, resulting in variations in photographic quality and deterioration of overall photographic quality.

For this reason, many studies have been conducted on techniques to improve the preservation of raw samples, but most of them have focused on suppressing the increase in fog during storage over time, and are concerned with suppressing changes in sensitivity during storage over time. Although it has a large effect on photographic quality, there is little research into its improvement.Among these, the method described in JP-A-58-176637 has the effect of improving sensitivity changes during storage over time. Although this method has less adverse effects on other photographic performance, it has been found that it has the following drawbacks.

That is, color development is carried out using a color developer containing an aromatic primary amine color developing agent (for example, a p-phenylenediamine derivative, etc.), which is typified by color vapor, color reversal vapor, color negative film, color reversal film, etc. For silver halide color photographic light-sensitive materials that produce colored dye images, continuous replenishment processing is generally used, in which a self-help developing machine is used to replenish the processing solution according to the amount of processing of the light-sensitive material. has been adopted.

However, it has been found that when this continuous replenishment process is applied to photosensitive materials using the raw sample preservation improvement technology described above, it causes softening of the tone and discoloration of the white background of the print (hereinafter referred to as stain).

This phenomenon is particularly strongly recognized in low-replenishment processing systems that are recently implemented for purposes such as cost reduction and environmental pollution reduction.

As a result of intensive studies to improve the above-mentioned drawbacks, the present inventors have found that 1,2-dihydroxybenzene derivatives having a certain substituent have a particularly excellent effect of improving raw sample storage stability, and also have the above-mentioned drawbacks. The present invention has been completed based on the discovery that the present invention does not have the following properties.

By the way, adding 1,2-dihydroxybenzene or its derivatives to silver halide photographic materials and color developing solutions is a well-known technique in the art, and is described in Japanese Patent Application Laid-Open No. 58-176637 and Japanese Patent Application No. No. 59-214578,
In addition to Japanese Patent Application No. 59-22550, for example, British Patent No. 2,054,187 and U.S. Patent No. 3,236,652
No. 3,582,333, No. 3,671,24
No. 8, No. 3,671, 258, No. 3,522,0
No. 53, No. 3,902,905, No. 4,264,
No. 716, West German Patent Publication No. 1,171,266, each Mei 411, Japanese Unexamined Patent Publication No. 56-52743, No. 58-2874
No. 1, No. 56-32140, No. 59-160142 @
However, in all of them, 1
, there is no description regarding the effect of substituents on 2-dihydroxybenzene.

Therefore, it was completely unexpected from the known literature that a silver halide color photographic light-sensitive material having excellent raw sample storage stability and excellent suitability for continuous replenishment processing could be obtained by the present invention.

[Object of the Invention 1 Accordingly, the first object of the present invention is to provide a silver halide photographic light-sensitive material that has excellent raw sample storage stability and is suitable for continuous replenishment processing.

The second object is to provide a silver halide photosensitive material which has excellent storage stability for raw samples and excellent suitability for low-replenishment development processing.

The third object is to provide a silver halide #color photographic light-sensitive material with stable finishing quality and little change in performance due to storage of raw samples over time or continuous replenishment processing.

[Structure of the Invention] The above aspects of the present invention include a photographic constituent layer comprising at least one light-sensitive silver halide emulsion layer and at least one non-light-sensitive layer on a support, and After imagewise exposure,
In a silver halide photographic material in which a dye image is formed by color development in the presence of an aromatic primary amine color developing agent, at least one of the photographic constituent layers is represented by the following general formula [I]. This is achieved using a silver halide photographic material containing the compound.

The following 7j Mihaku general formula [In the eco formula, X and ×2 are each a halogen atom or
Carboxylic acid group (including its salts), sulfonic acid group (including its salts), mercapto group, alkylthio group, acyl group,
Carbamoyl group, acylamine group, acyloxy group, alkyloxycarbonyl group, sulfonamide group, aminosulfonyl group, alkylsulfonyl group, alkylsulfinyl group, 2Yf and Yr are hydrogen atom, halogen atom, amide L, respectively.
Represents a hydroxyl group, a carboxylic acid group (including its salts), or a sulfonic acid group (or in situ), Yl %
Y2, Y3, Yg and YJ- cannot all be hydrogen atoms. n<z represents an integer from 0 to 3.

11i1[i represents a group selected from ], R represents a halogen atom or a group 11ii. nl and nl
are integers from O to 4, n3 is an integer from O to 3, and the sum of n, and 02 is an integer from 1 to 4,
The sum of nl, nl and n3 represents an integer from 1 to 4.

[Specific structure of the invention] Hereinafter, the configuration of the present invention will be specifically explained.

In the compound represented by the general formula [E] according to the present invention, examples of the halogen atom represented by X and x2 include a chlorine atom and a bromine atom.

When x7 and x2 represent a monovalent group, the carboxylate is, for example, potassium carboxylate, the sulfonate is, for example, sodium sulfonate, and the alkylthio group is, for example, a methylthio group, an ethylthio group, etc. Examples of the acyl group include formyl group, acetyl group, propionyl group, etc.; examples of the carbamoyl group include ethylcarbamoyl group, phenylcarbamoyl group, etc.; examples of the acylamino group include acetylamino group, propionylamino group, etc.; is, for example, an acetyloxy group, a butyryloxy group, etc., an alkyloxycarbonyl group is, for example, a methyloxycarbonyl group, an ethyloxycarbonyl group, etc., an example of a sulfonamide group is an ethylsulfonamide group, etc., and an aminesulfonyl group is, for example, For example, a methylaminosulfonyl group, etc., an alkylsulfonyl group such as a methylsulfonyl group, an alkylsulfinyl group such as a butylsulfinyl group, etc., Y2' -CHZ CHOHl-CH2COOH1-CH280
3H, -CH2CH2CF3 and the like.

Particularly preferred as x1 and x2 are carboxylic acid groups (including their salts), sulfonic acid groups (including their salts), acyl groups, and alkyloxy groups. Also Xl
Or, when x2 represents a sulfonic acid group or a salt thereof, it is more preferred that two or more of the substituents represented by x1 and x2 are sulfonic acid groups or salts thereof.

Next, the halogen atom represented by R includes, for example, a chlorine atom, a bromine atom, etc., and the monovalent group represented by R includes a carboxylic acid group or a salt thereof (for example, sodium carboxylate salt, etc.), a sulfone atom, etc. Acid group or its salt (
For example, sulfonic acid sodium salt, etc.), hydroxyl group,
Cyano group, amino group, alkyl group (e.g. methyl group,
ethyl group, butyl group, etc.), cycloalkyl group (e.g. cyclohexyl group, etc.), aryl group (e.g. phenyl group,
tolyl group, etc.), alkoxy group (e.g., methoxy group, ethoxy group, etc.), cycloalkyloxy group (e.g., cyclohexyloxy group, etc.), aryloxy group (e.g., phenoxy group, naphthoxy group, etc.), acyloxy group (e.g.,
acetyloxy group, etc.), acyl group (e.g., formyl group, acetyl group, propionyl group, butyryl group, oxalyl group, benzoyl group, etc.), aminocarbonyl group (e.g., methylaminocarbonyl group, ethylaminocarbonyl group, etc.), alkyloxy Carbonyl group (e.g. methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, etc.), aryloxycarbonyl group (
For example, phenoxycarbonyl group, etc.), acylamino group (for example, acetylamino group, benzoylamino group, etc.)
, sulfonamide group (e.g., methylsulfonamide group, ethylsulfonamide group, etc.), i!i g f
! A group (e.g. furyl group, thiazolyl group, imidazolyl group, succinimide group, benzoxacylyl group, phthalimide group, etc.), alkylthio group (e.g. methylthio group, ethylthio group, propylthio group, etc.), arylthio group (e.g. phenylthio group, naphthylthio group) etc.). The monovalent group represented by R may optionally have a substituent (for example, a hydroxyl group, a carboxyl group, etc.) as long as it is substitutable.

When the monovalent group represented by R represents an alkyl group, the number of carbon atoms is preferably 5 or less, more preferably 3 or less.

Although it is possible for X+, Xz and R to form a condensed ring with each other, in order to further enhance the effects of the present invention, it is preferable that they do not form a condensed ring.

Specific examples of the compound represented by the general formula [I] according to the present invention are listed below, but the present invention is not limited thereto.

The following is 5OsNa NMb
ffi to U* Some of the compounds represented by the general formula [I] according to the present invention (hereinafter referred to as "compounds of the present invention") are known to be contained in photosensitive materials. There is. For example, West German Patent Publication No. 1,171,
No. 266 describes carboxylate or sulfonate salts of dihydroxybenzene; U.S. Pat.
No. 3,671.258 describes a technique for incorporating 1,2-dihydroxybenzene substituted with a sulfone oxygen base (or its salt) into a light-sensitive material, but the effects of the present invention have not been demonstrated. There is no description of a color photographic material that is color developed using an aromatic primary amine color developing agent.

It is also a known technique to add the compound of the present invention to a color developing solution. For example, U.S. Patent No. 4,264,
No. 716, Japanese Unexamined Patent Publication No. 59-160142@publication, etc., 1
．． There is a description of a technique for improving the stability of a color developer by adding 2-dihydroxybenzene or a derivative thereof to the color developer, but there is no description that suggests the effect of the present invention when it is included in a light-sensitive material. do not have.

Also, JP-A-56-32140, JP-A No. 58-17663
In the specifications of No. 7, etc., a technique is described in which a silver halide color photographic light-sensitive material is subjected to color development in the presence of 1,2-dihydroxybenzene or a derivative thereof. There is no description suggesting the effects of the present invention obtained by silver halide color photographic materials containing 1,2-dihydroxybenzene derivatives.

Therefore, it has been difficult to predict techniques for achieving the object of the present invention from known documents.

In order to incorporate the compound of the present invention into a silver halide color photographic light-sensitive material, it can be dissolved in water or an organic solvent miscible with water (for example, methanol, ethanol, etc.), or dissolved in an organic solvent (miscible with water). After dissolution in a hydrophilic ioroid (which may or may not be possible), it can be dispersed in a hydrophilic yoloid and added as a solution or dispersion. The amount added is preferably 1.0X10' to 1.0 mole, more preferably 1.2X10' to 1.0 mole per mole of silver halide. OX
10 moles. The addition may be made at any time from the time of production of the silver halide emulsion to the time of coating, but preferably from the end of chemical ripening of the silver halide emulsion to the time of coating. The compound of the present invention may be added to any layer of the light-sensitive silver halide emulsion layer and/or the non-light-sensitive hydrophilic colloid layer. It is sufficient if it is contained in the light-sensitive silver halide emulsion layer that should receive the effect of improving storage stability.

The silver halide composition of the silver halide emulsion used in the present invention may be silver halide commonly used in light-sensitive materials, such as silver chloride, silver bromide, silver iodide, silver chlorobromide, and silver iodobromide. , silver chloroiodobromide and the like. These silver halide grains may be coarse or fine, and the grain size distribution may be narrow or wide. Preferably, a monodisperse emulsion with a narrow particle size distribution is used.

"Monodisperse silver halide grains" preferably used in this specification mean that the shape of each silver halide grain appears uniform when the emulsion is observed using an electron micrograph;
The particle sizes are uniform and the standard deviation of the particle size distribution is S.
and average particle diameter F is preferably 0.22 or less, more preferably 0.15 or less. Here, the standard deviation S of the particle size distribution is determined according to the following formula.

In addition, the average grain size referred to here refers to the diameter of spherical silver halide grains, or the diameter when the projected image is converted to a circular image of the same area in the case of grains with shapes other than cubic or spherical. the average value of the diameter, the individual particle size is ri;
When the number is ni, 7 is defined by the following formula.

-Σn1ri r-Σni The above particle size can be measured by various methods commonly used in the technical field for the above purpose. A typical method is Loveland's [Particle Size Analysis Method JA.

S, T, M, Symposium on Light Microscopy, 1955, pp. 94-122 or Chapter 2 of ``The Theory of the Photographic Process'' by Mies and James, 3rd edition, Macmillan Publishing Co., Ltd. (1966). Are listed. The particle size can be measured using the particle's projected area or diameter approximation. If the particles are of substantially uniform shape, the particle size distribution can be described fairly accurately as diameter or projected area.

The relationship between grain size distribution is described in "Empirical Relationship between Sensitometric Distribution and Particle Size Distribution in Photographic Emulsions," The Photographic Journal, Vol. LXXIX, (1949) 33.
0-338 True This can be determined using the method described in the Trivelli and Smith paper.

The average grain size of the monodisperse silver halide grains preferably used in the present invention is not particularly limited in view of the nature of the invention;
When measured according to the above method, 0.1 to 2.0 μ■
It is preferable that it is, more preferably 0.2 to 1.
It is within the range of 6 μ garden.

The silver halide grains used in the present invention have DAQ, temperature,
It can be adjusted by controlling the addition rate or by selecting various particle generation conditions, and can be adjusted by the usual single jet method or double jet method. Any of the acidic method, neutral method, ammonia method, etc. may be used, and methods for reacting soluble silver salts with soluble halogen salts include single-ill mixing method, simultaneous mixing method,
Any combination thereof may be used. It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method). E) All in a solution of silver halide produced as a form of simultaneous mixing method
It is also possible to use a method in which l is kept constant, ie, the so-called Chondral double jet method. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

In the present invention, after forming a silver salt with a higher IF than silver bromide as disclosed in U.S. Pat. No. 2,592,250, at least a portion of the grains are converted to a silver bromide salt. A so-called conversion method may also be used.

However, it is particularly preferred to use silver chlorobromide emulsions formed without using the conversion methods described above.

Alternatively, two or more silver halide emulsions formed separately may be mixed and used. In the process of silver halide grain formation or physical ripening, cadmium salts, zinc salts, lead salts, thallium salts, iridium salts, or complex salts thereof, rhodium salts or complex salts thereof, iron salts or complex salts thereof, etc. may be present.

In the silver halide emulsion used in the present invention, unnecessary soluble salts may be removed after the growth of silver halide grains is completed, or they may be left contained. When removing the salts, please refer to Research Disclosure 17643.
This can be done based on the method described in the issue.

The silver halide grains used in the present invention may consist of uniform layers inside and on the surface, or may consist of uneven layers.

The silver halide grains used in the present invention 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 grain.

The silver halide grains used in the present invention may have a regular crystal shape or may have an irregular crystal shape such as a spherical or plate shape. In these particles, (1
Any ratio between the 00) plane and the (111) plane can be used. Also, it may have a composite form of these crystal forms,
Particles of various crystal forms may be mixed. .

The silver halide emulsion used in the present invention may be a mixture of two or more separately formed silver halide emulsions.

The silver halide emulsion used in the present invention 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 can be used alone or in combination.

The silver halide emulsion used in the present invention can be optically sensitized to a desired wavelength range using a dye known as a sensitizing dye in the photographic industry.

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.

As the sensitizing dye, cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxanol dyes are used.

Particularly useful dyes include cyanine dyes, merocyanine dyes,
and a complex merocyanine pigment. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, and a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei: and these. A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus, that is, an indolenine nucleus,
Benzindolenine cough, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus,
These include naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, and quinoline nucleus. These nuclei are
May be substituted on carbon atoms.

Merocyanine dyes or complex merocyanine dyes include a pyrazolin-5-one nucleus, thiohydantoin, 2-thioxazolidine-2 as a nucleus having a ketomethylene structure.
, 4-dione nucleus, thiazolidine-2,4-dione nucleus, a
- 5- to 6-membered heterocyclic nuclei such as danine and thiobarbic acid solutions can be applied.

Examples of useful sensitizing dyes used in blue-sensitive silver halide emulsion layers include West German Patent No. 929,080, US Pat. No. 2,231,658, US Pat. No. 2,519,001, No. 2
, No. 912,329, No. 3.656,959, No. 3
, No. 672,897, No. 3,694,217, No. 4
, No. 025,349, No. 4,046,572, British Patent No. 1,242.588, Japanese Patent Publication No. 14030/1973,
Examples include those described in No. 52-24844. Also, useful sensitizing dyes used in green-sensitive silver halide emulsions include, for example, U.S. Pat.
No. 201, No. 2.072,908, No. 2,739,
No. 149, No. 2,945,763, British Patent No. 505
Typical examples include cyanine dyes, merocyanine dyes, and composite cyanine dyes such as those described in No. 1, No. 979, and the like. Furthermore, useful sensitizing dyes used in red-sensitive silver halide emulsions include:
For example, Shuin Patent No. 2,269,234, Patent No. 2,270,
No. 378, No. 2,442,710, No. 2,454,6
Typical examples include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in No. 29, No. 2,776.280, and the like. Furthermore, U.S. Patent Nos. 2,213,995 and 2,493,
No. 748, 2,519,001@, West German Patent No. 929,
Cyanine dyes, merocyanine dyes or composite cyanine dyes such as those described in No. 080 can be advantageously used in green-sensitive silver halide emulsions or red-sensitive silver halide emulsions.

These sensitizing dyes may be used alone or in combination. Combinations of sensitizing dyes are often used, especially for the purpose of supersensitization. Typical examples are Special Publications No. 43-4932, No. 43-4933, No. 4
No. 3-4936, No. 44-32753, No. 45-25
No. 831, 45-26474@, 46-11627
No. 46-18107, No. 47-8741, No. 4
No. 7-11114, No. 47-25379, No. 47-3
No. 7443, No. 48-28293, No. 48-3840
No. 6, No. 48-38407, No. 48-38408,
48-41203, 48-41204, 4
No. 9-6207, No. 50-40662, No. 53-12
No. 315, No. 54-34535, No. 55-1569, JP-A No. 50-33220, No. 50-33828,
No. 50-38526, No. 51-107127, No. 51-115820, No. 51-135528,
No. 51-151527, No. 52-23931, No. 5
No. 2-51932, No. 52104916 9, No. 52
-104917, 52-109925, 52
-110618, 54-80118, 56-2
No. 5728, No. 57-1483, No. 58-10753
No. 58-91445, No. 58-153926,
No. 59-114533, No. 59-1166454
No. 59-116647, U.S. Patent No. 2,688,54
No. 5, No. 2.977.229, No. 3,397,06
No. 0, No. 3,506,443 No. 3,578,447
No. 3,672,898, No. 3,679,428, No. 3,769,301, No. 3,814,609,
It is described in No. 3,837.862.

Examples of dyes that do not themselves have a spectral sensitizing effect, or compounds that do not substantially absorb visible light and exhibit supersensitization, are used with sensitizing dyes, such as aromatic organic acid formaldehyde condensates ( (e.g., those described in U.S. Pat. No. 3,437,510), cadmium salts, azaindene compounds, aminostilbene compounds substituted with nitrogen-containing heterocyclic groups (e.g., U.S. Pat. No. 2,933)
, No. 390, No. 3,635, No. 721)
and so on. Red stamp patent No. 3.615,613, No. 3,6
No. 15,641, No. 3,617,295, No. 3,6
The combinations described in No. 35.721 are particularly useful.

The silver halide emulsion used in the present invention may contain chemical additives during chemical ripening and/or chemical treatment for the purpose of preventing capri during the manufacturing process, storage, or photographic processing of light-sensitive materials and/or maintaining stable photographic performance. At the end of the ripening and/or after the end of the chemical ripening and before coating the silver halide emulsion, compounds other than the compounds of the invention known in the photographic industry as anti-capri agents or stabilizers can be added. .

Emulsion 1 of the silver halide color photographic light-sensitive material of the present invention undergoes a coupling reaction with an oxidized form of an aromatic primary amine developing agent (for example, p-phenylenediamine derivatives, aminophenol derivatives, 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 to form a dye for each emulsion layer that absorbs light in the emulsion layer's sensitive spectrum, with a yellow dye-forming dye forming for the blue light sensitive emulsion layer. 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.

It is desirable that these dye-forming couplers have a group called a ballast group in the molecule, which makes the force non-diffusive and has 8 or more carbon atoms. Moreover, these dye-forming couplers contain only one molecule! ! Either a 4-equivalent type, in which four silver ions need to be reduced to form an element, or a 2-equivalent type, in which only two silver ions need to be reduced, may be used.

Dye-forming couplers can be used as development accelerators, bleach-accelerating detergents, developing agents, silver halide solvents, toning agents, hardeners, capry agents, anti-capri agents, and chemical thickeners by coupling with oxidized forms of developing agents. Compounds that release photographically useful fragments such as sensitizers, spectral sensitizers, and desensitizers can be included.

Colored couplers that have a color correction effect on these dye-forming couplers, or DIR that releases a development inhibitor during development and improves image sharpness and image graininess.
A coupler may also be used in combination. In this case, it is preferable that the dye formed from the DIR coupler is of the same type as the dye formed from the dye-forming coupler used in the same emulsion layer, but if the color turbidity is not noticeable, a different dye may be used. It may also be one that forms different types of pigments.

Instead of the DIR coupler, a DIR compound may be used which, when used with or in combination with the coupler, undergoes a coupling reaction with the oxidized form of the main agent to produce a colorless compound and at the same time releases a development inhibitor.

'The DIR couplers and DIR compounds used include:
one in which the inhibitor is directly bound to the coupling position, and one in which the inhibitor is bound to the coupling position via a divalent group;
Includes those bound in such a way that the inhibitor is released by an intramolecular nucleophilic reaction or an intramolecular electron transfer reaction at the base separated by the coupling reaction (referred to as timing DIR couplers and timing DIR compounds). . Furthermore, inhibitors that are diffusible after release and those that are not so diffusible can be used alone or in combination depending on the purpose. A colorless coupler that undergoes a coupling reaction with an oxidized form of an aromatic primary amine developing agent but does not form a dye can also be used in combination with a dye-forming coupler.

Typical yellow dye-forming couplers are acylacetamide type and benzoylmethane type 4-equivalent or 2-equivalent couplers, such as those disclosed in U.S. Pat. No. 2,186,
No. 849, No. 2,322,027, No. 2.728
, No. 658, No. 2,875,057, No. 3,26
No. 5,506, No. 3,277.155, No. 3,4
No. 08,194, No. 3,415,652, No. 3,
No. 447,928, No. 3,664.841, No. 447,928, No. 3,664.841, No.
No. 3,770,446, No. 3,778,277, No. 3,849,140, No. 3,894,875,
British Patent No. 778,089, British Patent No. 808,276,
The specifications of the same No. 875,476, the same No. 1,402,511, the same No. 1,421,126, and the same No. 1.513.832, and the Japanese Patent Publication No. 13576/1989, ? @ Kaisho No. 48-29432, No. 48-68834, No. 49-
No. 10736, No. 49-122335, No. 50-2
No. 8834, No. 50-132926, No. 50-13
No. 8832, No. 51-3631, No. 51-17438
No. 51-260313, No. 5t-26039,
No. 51-50734, No. 51-53825, No. 51
-75521, 51-89728, 51-10
No. 2636, No. 51-107137, IQJ 5
l-1t7031, 51-122439, same
No. 51-143319, No. 53-9529, No. 53
No.-82332, No. 53-135625, No. 53
-145619.

No. 54-23528, No. 54-48541, No. 54
-65035, 54-133329, 55-5
It is described in various publications such as No. 98.

Typical magenta dye-forming couplers include 4-equivalent or 2-equivalent magenta dye-forming couplers such as 5-pyrazolone, pyrazolotriazole, pyrazolinobenzimidazole, indasilone, and cyanoacetyl. U.S. Patent Nos. 1,969,479, 2,213,986, 2,294,909, 2,338,677, 2,340,763,
Same No. 2,343,703, Same No. 2,359,33
No. 2, No. 2,411,951, No. 2,435,5
No. 50, No. 2,592.303@, No. 2,600,
No. 788, No. 2,618,641, No. 2,619
, No. 419, No. 2,673,801, No. 2.69
No. 1.659, No. 2,803,554, No. 2,8
No. 29,975, No. 2,866, 706, No. 2,
No. 881,167, No. 2.895.826, No. 3
, No. 062,653, No. 3,127,269, No. 3,214,437, No. 3,253,924, No. 3,311.476, No. 3,419,391 ,
No. 3,486,894, No. 3,519,429, No. 3,558,318, No. 3,617.291
No. 3,684,514, No. 3,705,89
No. 8, No. 3,725,067, No. 3,888,6
80, British Patent No. 720,284, British Patent No. 737,7
No. 00, No. 813,866, No. 892,886, No. 918.128M, No. 1,019,111,
No. 1,042,832, No. 1,047,612, No. 1,398,828 and No. 1,398,97
9 specifications, West German Patent Publication No. 814,996, West German Patent Publication No. 1.070,030, Belgian Patent Publication No. 724,42
No. 7, JP 46-60479@, JP 49-29639
No. 49-111631, No. 49-12953
No. 8, No. 50-13041, No. 50-116471, No. 50159336, No. 51-3232, No. 51
-3233, 51-10935, 51-169
No. 24, No. 51-20826, No. 51-26541, No. 51-30228, No. 51-36938, No. 5
No. 1-37230, No. 51-37646, No. 51-3
No. 9039, No. 51-44927, No. 51-104
No. 344, No. 51-105820, No. 51-10
No. 8842, No. 51-112341, No. 51-112
No. 342, No. 51-112343, No. 51-1123
No. 44, No. 51-117032, No. 51-12683
No. 1, No. 52-31738, No. 53-9122, No. 53-55122, No. 53-75930, No. 53-8
No. 6214, No. 53-125835, No. 53-12
No. 3129, No. 54-56429 and No. 57-35
Publications No. 858 and Research Disclosure magazine (
June 1984) Vol. 242, Sections 24, 220 and 24, 230, etc.

Typical cyan dye-forming couplers are phenolic and naphthol-based 4-equivalent or 2-equivalent type cyan dye-forming couplers, and are disclosed in U.S. Pat. No. 2,306,410.
No. 2,356,475, No. 2, 362.5
No. 98, No. 2,367.531, No. 2,369,
No. 929, No. 2,423,730, No. 2,474
, No. 293, No. 2,476.008, No. 2,49
No. 8,466, No. 2,545,687 No. 2,72
No. 8,660, No. 2,772,162, No. 2.8
No. 95.826, No. 2,976.146, No. 95.826, No. 2,976.146, No.
No. 3,002,836, No. 3,419,390, No. 3,446,622, No. 3,476.563@, No. 3,737,316, No. 3,758,308 British Patent No. 3,839,044, British Patent No. 478,991, British Patent No. 945.542, British Patent No. 1,084,480,
Same No. 1,377.233, Same No. 1,373g, 024
No. 1,543,040, and JP-A-47-37425J! , No. 50-40135, No. 50-25228, No. 50-112038, No. 50-112038, No. 50-112038, No. 50-112038, No.
No. 50-117422, No. 50-130441, No. 5
No. 1-6551, No. 51-37647, No. 51-52
No. 828, No. 51-108841, No. 53-1096
No. 30, No. 54-48237, No. 54-66129, No. s<-1smt, and No. 55-32071.

As a colored coupler, for example, British Patent No. 937.
No. 621, No. 1,035,959, No. 1,255
, No. 111, JP-A-48-22028, JP-A No. 52-42
No. 121, Special Publication No. 38-22335, No. 44-201
No. 5, No. 44-15754M, U.S. Patent No. 2.449,
No. 966, No. 2,521,908, No. 2,543
, No. 691, No. 2,801,171, No. 2,983,
No. 608, No. 3,005,712, No. 3,034,
No. 892, No. 3,061,432, No. 3,419.3
No. 91, No. 3,476.560, No. 3,476.5
No. 63, No. 3.481,741, No. 3,519,42
No. 9, No. 3,583,971, No. 3,622,328
No. 3,684,514, No. 4,004,929, No. 4,070.191, No. 4.138.258, No. 4,138.264, No. 4,163.670
No. 4,292,400, No. 4.369,248
4 etc. can be used.

As a DIR coupler, for example, British Patent No. 953.4
54@, U.S. Patent No. 3,227,554, U.S. Patent No. 3,61
5.506, 3,617,291, 3,7
No. 01,783, No. 3.933,500, No. 4,0
No. 95,984, No. 4,149,886, No. 4,2
No. 86,054, No. 4,359,521, Japanese Unexamined Patent Publication No. 1973
-90932, 56-116029, 51-1
51944@ etc. and U.S. Patent No. 4,2
No. 48,962, 4.409.323@, JP-A-57
-154234, 58-162949, 58-
No. 205150, No. 59-195643, No. 59-2
No. 06834, No. 59-20683θ, No. 59-21
Timing DIR couplers described in No. 0440, No. 60-7429, etc. can be preferably used.

Examples of DIR compounds include those described in US Pat. No. 3,632.
No. 345, No. 3,928,041, No. 3,938,9
No. 96, No. 3.958,993, No. 3,961,9
No. 59, No. 4,046,574, No. 4,052,2
No. 13, 4,111,223@, 4.18e, j1
No. 2, JP-A-52-65433, JP-A No. 52-13032
Compounds described in No. 7, No. 51-128335, etc. can be preferably used.

As colorless couplers, U.S. Patent No. 2,998,314, British Patent No. 1,284,649, and West German Patent No. 1,168,769 are used to prevent gradation, color turbidity, and capri.
The so-called Weiss coupler described in No. 1 can be used.

Between the emulsion layers of the color photographic light-sensitive material of the present invention (between the same color-sensitive layers and/or between different color-sensitive layers), the oxidized form of the developing agent or the electron transfer agent may migrate, causing 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.

An image stabilizer that prevents deterioration of dye images can be used in the color light-sensitive material of the present invention.

A UV absorber is 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 UV light. It may be included.

Hydrophobic compounds such as dye-forming couplers that do not need to be adsorbed onto the silver halide crystal surface can be treated with various methods such as solid dispersion, latex dispersion, and oil-in-water emulsion dispersion. can be appropriately selected depending on the chemical structure of the hydrophobic compound, etc. The oil-in-water emulsion dispersion method can be applied by dispersing a hydrophobic compound such as a coupler, and is usually mixed with a high-boiling organic solvent with a boiling point of about 150°C or higher, and if necessary with a low-boiling point and/or water-soluble organic solvent. and emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution using a surfactant and a dispersion means such as a stirrer, homogenizer, colloid mill, flow jet mixer, or ultrasonic device. It may be added to the 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, phthalates, phosphates, citric esters, benzoic esters, alkylamides, fatty acid esters, and trimesic esters that do not react with the oxidized form of the developing agent. The above lrR solvent is used.

Anionic surfactants, nonionic surfactants, Cationic surfactants can be used.

A silver halide color photographic light-sensitive material of the present invention.

As the inder (or protective colloid), it is advantageous to use gelatin, but it is also possible to use gelatin derivatives, graft polymers of gelatin and other polymers, proteins, sugar derivatives, cellulose derivatives, single or copolymers. Hydrophilic colloids such as synthetic hydrophilic polymeric substances such as the like can also be used.

The photographic emulsion layer and other hydrophilic colloids of the silver halide color photographic light-sensitive material of the present invention can be hardened by crosslinking binder (or protective colloid) molecules and using a hardening agent alone or in combination to increase film strength. be done. ! i! The membrane agent is
Although it is desirable to add an amount of the photosensitive material that can be hardened to such an extent that it is not necessary to add a hardening agent to the processing solution, it is also possible to add a hardening agent to the processing solution.

Examples of hardening agents include aldehyde type and aziridine type (for example, PB Report No. 19,921, US Patent No. 2.
No. 950,197, No. 2,964,404, No. 2
, No. 983,611, No. 3,271,175, Japanese Patent Publication No. 46-40898, and Japanese Patent Publication No. 50-91
315), isoxazole systems (for example, those described in U.S. Pat. No. 331.609, published by Ming Peng), and epoxy systems (for example, U.S. Pat. No. 3,047,3).
No. 94 1. Specifications of West German Patent No. 1.085,663 and British Patent No. 1,033,518, Japanese Patent Publication No. 1973-35
495), vinyl sulfone type (for example, Pa Report No. 19,920, West German Patent No. 1)
, No. 100,942, No. 2,337,412, No. 2.
No. 545,722, No. 2,635,518, No. 2
, 742,308, 2,749,260, British Patent No. 1,251,091, Japanese Patent Application No. 45-54236, Japanese Patent Application No. 48-110996, U.S. Patent No. 3,539.6
No. 44 and No. 3,490,911), acryloyl type (for example, Japanese Patent Application No. 48-279)
No. 49, U.S. Pat. No. 3,640.720), carbodiimides (e.g., U.S. Pat. No. 2,938,892, U.S. Pat. No. 4,043,818, U.S. Pat.
, 061,499, Japanese Patent Publication No. 46-3871
5, Japanese Patent Application No. 49-15095), triazine type (for example, West German Patent No. 2,410,
No. 973, No. 2,553,915, U.S. Patent No. 3.3
25,287, those described in JP-A-52-12722), polymer type (examples).

For example, British Patent No. 822,061, U.S. Patent No. 3,6
No. 23.878, No. 3,396,029@, No. 3,22
Specifications of No. 6,234, Japanese Patent Publication No. 47-18578,
18579 and 47-48896), maleimide-based, acetylene-based, methanesulfonic acid ester-based, and (N-methylol-based) hardening agents can be used alone or in combination. Useful combination techniques include, for example, West German Patent Nos. 2,447,587, 2,505,746, 2,514,245,
U.S. Patent Nos. 4,047,957 and 3,832,18
Specifications of No. 1 and No. 3,840,370, JP-A-1978
-43319, 50-63062, 52-12
Examples include combinations described in Japanese Patent Publication No. 7329 and Japanese Patent Publication No. 48-32364.

Among these hardening agents, the effects of the present invention are even more exhibited when a hardening agent represented by the following general formula [II] or general formula [I11] is used.

General formula [I[] In the formula, R+ is a chlorine atom, a hydroxy group, an alkyl group, an alkoxy group, an alkylthio group, -0MI (M represents a monovalent metal atom), -NR'R'' group (R' and R
"represents a hydrogen atom, an alkyl group, or an aryl group, respectively) or -NHCOR"'(R"' represents a hydrogen atom, an alkyl group, or a general formula [I] % formula % In the formula, R3 and Ra each represent a chlorine atom. , hydroxy group, alkyl group, alkoxy group, or -OM group (M represents a monovalent metal atom).Q%Q' is a linking group selected from -〇-1-S-1-NH-, respectively. , L
represents an alkylene group or an arylene group. A and ■ represent 0 or 1.

Typical specific examples of hardeners preferably used in the present invention are listed below in the margins, but the present invention is not limited thereto.

OK OK (H-16) (H-17) (H-18) (H719) (H-20) (H-21) (H-22) (H-23) The following margin is the general formula HII or []Ir ] The hardening agent represented by the following formula may be used alone or may be used in combination with other hardening agents such as vinyl sulfone type hardeners.

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 silver halide color photographic light-sensitive material of the present invention.

The photographic emulsion layer and other hydrophilic colloid layers of the silver halide color photographic light-sensitive material of the present invention may contain a dispersion (latex) of a water-insoluble or Nm-based synthetic polymer for the purpose of improving dimensional stability. .

The silver halide color photographic material of the present invention may be provided with auxiliary layers such as a single filter layer, an antihalation layer and/or an antiirradiation layer. One of these and/or the emulsion layer may contain dyes that flow out of the color light-sensitive material or are bleached during development.

The silver halide emulsion layer and/or other hydrophilic colloid layer of the silver halide color photographic light-sensitive material of the present invention is matted with the aim of reducing the gloss of the light-sensitive material, increasing the ease of writing, preventing mutual sticking of the light-sensitive materials, etc. Agents can be added.

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

An antistatic agent for the purpose of preventing static electricity can be added to the silver halide color photographic light-sensitive material of 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 silver halide color photographic light-sensitive material of 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 silver halide color photographic light-sensitive material of the present invention has a photographic emulsion layer, and other layers include a baryta layer or a flexible reflective support such as paper laminated with an α-olephne polymer, synthetic paper, cellulose acetate, cellulose nitrate, It can be applied to films made of semi-synthetic or synthetic polymers such as polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, and polyamide, as well as rigid bodies such as glass, metal, and ceramics.

The silver halide color photographic light-sensitive material of the present invention can be produced by subjecting the surface of the support to corona discharge, ultraviolet irradiation, flame treatment, etc. as necessary, and then directly or (adhesiveness, antistatic property, dimensional stability of the support surface) (to improve wear resistance, wear resistance, hardness, antihalation properties, friction properties and/or other properties)
It may be applied through one or more subbing layers.

When coating the silver halide color photosensitive material of the present invention, a thickener may be used to improve coating properties. Particularly useful coating methods are ex-dulsion coating and curtain coating, which allow two or more layers to be applied simultaneously.

The light-sensitive material of the present invention can be exposed using electromagnetic waves in a spectral region to which the emulsion layer constituting the light-sensitive material of the present invention is sensitive. Light sources include 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, electron beams,
Any known light source can be used, such as light emitted from a phosphor excited by X-rays, γ-rays, α-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, and exposures longer than 1 second are also possible. The exposure may be performed continuously or intermittently.

The silver halide color photographic light-sensitive material of the present invention can form an image by color development known in the art. The effects of the present invention are particularly noticeable when continuous replenishment processing is carried out using.

The aromatic primary amine color developing agents used in the color developing solution of the present invention include known ones that are 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 generally have a concentration of about 0.1 g to about 30 g per color developer;
Preferably, about 1 g to about 15 a of III is used for the color development liquid 11.

'Aminophenol-based developers include, for example, O-aminophenol, p-7 minophenol, 5-amino-2
-oxytoluene, 2-amino-3-oxytoluene,
Includes 2-oxy-3-amino-1°4-dimethylbenzene.

Particularly useful primary aromatic amino coloring agents include 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'-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-(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 process of the present invention further contains various components that are 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 dibasic salt, an alkali metal thiocyanate, an alkali metal halide, benzyl alcohol, a water softener, a thickening agent, etc. may be optionally contained. . The pH value of this color developer is usually 7 or higher, most commonly about 10 to
It is about 13.

Further, a boron compound described in JP-A-56-32140 can also be added to the color developing solution.

In the present invention, after color development processing, processing is performed 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. The bleaching agent used in the bleaching process is a metal complex salt of an organic acid, and the metal complex oxidizes the metallic silver produced by the phenomenon and converts it into silver halide, and at the same time, it has the effect of coloring the uncolored part 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.

[I] 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] The bleaching agent used in the nitrile sodium acetate salt contains the above-mentioned metal complex salt of an organic 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, OH such as borate, oxalate, acetate, carbonate, phosphate, etc.
Those known to be added to ordinary bleaching solutions, such as M buffer, alkylamines, and polyethylene oxides, can be added as appropriate.

Furthermore, the fixing solution and bleach-fixing solution contain sulfites such as ammonium sulfite, potassium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, sodium metabisulfite, boric acid, Single or two types of DHIlIi agents consisting of various salts such as borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bisulfite, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide, etc. or more.

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, bromate, persulfate, etc. may be added as appropriate.

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

Example 1 In the presence of inert gelatin, under conditions such that no new grains are generated during the growth of silver halide grains, the amounts of silver and halide aqueous solutions added were controlled by the Chondral double jet method. , 90 mol% silver bromide,
Three types of monodisperse silver chlorobromide emulsions with uniform grain size and crystal habit of silver halide compositions of 80 mol % and 70 mol % were prepared, and each emulsion was subjected to chemical ripening and spectral sensitization by conventional methods. A blue-sensitive emulsion, a green-sensitive emulsion and a red-sensitive emulsion were prepared.

The above three emulsions all have a grain size distribution (i.e., S/T'
≦0.15).

Next, the surface was coated with polyethylene containing anatase-type titanium dioxide using the three types of spectrally sensitized silver chlorobromide emulsions and exemplary hardener (H-2). Sample 1 was obtained by coating each layer on a paper support as shown in Table 1.

Next, Comparative Compounds-1 to 5, which are raw sample storage improvers not included in the present invention, were added to the first layer, third layer, and fifth layer containing silver halide emulsions in an amount of 1 mol of silver halide. Hit,
Sample-1 except that it was added in an amount of 7 x 10 moles.
Samples 2 to 6 were prepared in the same manner as above.

Next, samples of the present invention were prepared in the same manner as Samples-2 to 6, except that Exemplary Compounds-3, 5, 6, 14, 17, and 29°35 of the present invention were used as raw sample storage improvers. Samples 7 to 13 were prepared.

Margin Table 1 (Comparative Compound-3) (Comparative Compound-4) The 13 types of samples obtained in this way were evaluated for raw sample storage stability and continuous replenishment treatment (hereinafter referred to as
We evaluated gradation changes and stains in the process (referred to as running processing). The results are shown in Table-2.

(1) Evaluation of raw sample storage stability Raw sample storage stability is evaluated by the change in sensitivity before storage and after being left at 40°C and 40% (relative humidity) for one month, and is expressed as the rate of change in sensitivity expressed by the following formula. Ta.

Sensitivity was determined by the method shown below.

Margins Below First, the photographic element was exposed to white light through a photoelectric current using a sensitometer (Model KS-7, manufactured by Konishiroku Photo Industry Co., Ltd.), and then processed according to the following processing steps.

[Processing process] During processing lI! IvA color development
3.5 minutes 33℃ bleach fixing 1.5 minutes 33℃ washing with water 3 minutes drying at 33℃
Drying at 80°C [Bleach-fixing solution composition] The density of each sample obtained was measured using a photoelectric densitometer (Model PDA-60, manufactured by Konishiroku Photo Industry Co., Ltd.) to determine the sensitivity.

Margin below (2) Evaluation of gradation changes due to running processing Among the above samples, each of the 12 samples (excluding sample-6) was printed using a color negative film photographed with a standard scene, and then the color developer was CI] was used as the starting solution, and the color developer replenisher (A) with the following composition was added to the samples 1 and 2.
Running treatment was performed while replenishing at a rate of 's2amQ per treatment. The end point of the run is the point when the cumulative value of the replenishment amount becomes equal to the amount of the starting solution. Color development was carried out using the above-mentioned running completion solution, and processing and density measurements were then carried out in the same manner as in section (1) above. The gradation is expressed by a gradient of concentration from 0.5 to 1.5, and the gradation difference between the processing solutions before and after running was determined by conducting a running processing experiment using each sample, and compared with the case of comparative sample-1. It was expressed as

[Composition of color developer replenisher (A)] (3) Evaluation of stain by running treatment ゛ An unexposed sample was treated in the same manner as in (1) above using the start solution and each running end solution in section 2) above. Development processing was performed. The spectral reflection density of the obtained sample was measured using a Hitachi model 607 color analyzer. The magnitude of stain was expressed as the difference in spectral reflection density of 450 rv before and after running. In this case, normally, if the increase in concentration is within 0.01, there is no problem in practical use.

As shown in Table 2 below, in Samples 1 to 6 using compounds not included in the present invention, samples with excellent raw sample storage stability and without softening or staining during running treatment cannot be obtained. For example, sample-4 has a substituent, but
There was no improvement in the suitability for running processing, and in Sample 3, the stain was slightly reduced, but the tone became softer. Furthermore, Samples-5 and -6 did not satisfy the object of the present invention, such as having a small improvement effect on raw sample storage stability.

On the other hand, Samples-7 to 13 using the compounds of the present invention not only have an excellent effect of improving raw sample storage stability, but also show almost no gradation change or staining during running treatment. It is surprising that such a dramatic improvement effect can be obtained by selecting the substituents on the benzene ring, and this could not have been predicted from the prior art.

Therefore, it can be seen that, according to the present invention, a silver halide color photographic light-sensitive material with very stable quality, which exhibits little change in performance even when a raw sample is stored over time and during running processing, can be obtained.

Example-2 Example-1 to examine suitability for low replenishment treatment according to the present invention
A running process was performed using a low replenishment processing system using the sample prepared in . The method was to use the following color developer (I) as the starting solution of the color developer and the following color developer replenisher (B) as the color developer replenisher, the temperature during color development was 38°C, and the amount of replenishment was 1 m of the sample. The gradation change and stain in the running process were evaluated in the same manner as in Example 1 except that the distance was 182 m. Table 3 shows the results.
Shown below.

[Composition of color developer (If)] [Composition of color developer replenisher (8)] Samples 2 to 5 using a raw sample storage improver not included in the present invention are shown below in Table 3 with white space below. It can be seen that the low replenishment type running process further softens the tone and/or increases the stain.

In contrast, samples-7 to 13 using the compound of the present invention
Similar to Example 1, almost no gradation change and staining were observed. Therefore, it can be seen that the effects of the present invention are even more pronounced when the light-sensitive material is subjected to low replenishment processing.

Example-3 Comparative compound-1, exemplary compound-6, and exemplary compound-1
No. 7 in Table 1 as a raw sample storage improver.
Sample-2 was prepared in the same manner as Sample-2 in Example 1, except that instead of adding it to the third layer and fifth layer, it was added to the fourth layer, and the amount added was as shown in Table-4. 14 to 25 were produced.

The above 12 types of samples and sample-1 prepared in Example "1" were evaluated for raw sample storage stability, gradation change during running treatment, and stain in the same manner as in Example 1.The results are shown in Table-- 4.

As shown in Table 4 below, exemplary compounds -6 and -17, which are compounds of the present invention, can be added directly to a silver halide emulsion layer or to a non-photosensitive hydrophilic colloid layer such as the fourth layer in Table 1. It can be seen that even when added to any layer, the effect of improving raw sample storage stability and behavior during running processing are both excellent, and the same effect can be obtained no matter which layer it is added to.

Also, from Table 4, Comparative Compound-1 and Exemplary Compound-6
Looking at the effect of the addition amount of -17, the tendency for raw sample preservation to improve slightly as the addition amount increases is the same for both cases, but regarding the effect on running processing, comparative compound -1 It can be seen that, while both softening and staining increase as the amount increases, with the compound of the present invention, almost no gradation change or staining occurs even when the amount added is increased.

Therefore, the compound of the present invention can be added to any photographic layer on the side having a light-sensitive silver halide emulsion layer of the support of the color photographic light-sensitive material according to the present invention, and raw sample storage stability is allowed! ! ! It can be seen that any addition amount can be selected as long as it is within the range.

i'1: Applicant Roku Konishi photo, -;: Gyo Co., Ltd. procedural amendment (own ship July 19, 1985)

Claims (1)

[Scope of Claims] A support has a photographic constituent layer composed of at least one light-sensitive silver halide emulsion layer and at least one light-insensitive layer, and after imagewise exposure, aromatic In a silver halide photographic material in which a dye image is formed by color development in the presence of a primary amine color developing agent, at least one of the photographic constituent layers contains a compound represented by the following general formula [I]. A silver halide photographic material comprising: General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, X_1 and X_2 are each a halogen atom, a carboxylic acid group (including its salts), a sulfonic acid group (including its salts), a mercapto group, an alkylthio group, acyl group, carbamoyl group, acylamino group, acyloxy group,
Alkyloxycarbonyl group, sulfonamide group, aminosulfonyl group, alkylsulfonyl group, alkylsulfinyl group, ▲Mathematical formula, chemical formula, table, etc.▼[Y_
1, Y_2, Y_3, Y_4, and Y_5 each represent a hydrogen atom, a halogen atom, an amino group, a hydroxyl group, a carboxylic acid group (including a salt thereof), or a sulfonic acid group (or a salt thereof), and Y_1, Y_2 , Y_3,
Not all of Y_4 and Y_5 are hydrogen atoms. n_4 represents an integer from 0 to 3. ] represents a monovalent group selected from R represents a halogen atom or a monovalent group. n_1 and n_2 each represent an integer from 0 to 4, n_3 represents an integer from 0 to 3, and n_1 and n_2
The sum of is an integer from 1 to 4, n_1, n_2 and n_3
The sum represents an integer from 1 to 4.