JPH02148033A - Silver halide photographic sensitive material superior in rapid processing aptitude and storage stability - Google Patents

Abstract

PURPOSE:To alleviate rise of fog and to enhance storage stability by incorporating inorganic sulfur in at least one of constituent layers and a specified compound in at least one of the constituent layers. CONSTITUTION:At least optional one of the constituent layers, preferably, a silver halide emulsion layer contains the inorganic sulfur, preferably, as a simple substance of alpha-sulfur, preferably, in the form of methanol or ethanol solution, preferably, in an amount of 10<-5> - 10mg per 1mol of silver halide, and at least one of the constituent layers contains the compound capable of reacting with the oxidation product of a developing agent and releasing a compound capable of scavenging the oxidation product or the precursor of the compound, thus permitting rise of fog due to rapid color development processing to be remarkably alleviated, and storage stability under high temperature and high humidity to be ensured without inducing deterioration of sensitivity.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide color photographic light-sensitive material. In particular, the present invention relates to a silver halide color photographic light-sensitive material that suppresses the increase in fog during rapid processing and has excellent storage stability over time.

[Background of the invention]

In recent years, rapid processing of silver halide color photographic materials has been desired in this industry. Generally, the above-mentioned color photographic materials are processed on an automatic processing machine installed in each laboratory (processing laboratory), but as part of our efforts to improve our service to users, the color photographic materials are processed on the same day they are received. will be returned to the user,
Recently, it has become even more necessary to return the product within a few hours of receiving it, and it has become necessary to carry out the development process more quickly than before.

In order to enable the above-mentioned rapid processing, for example, to compensate for the shortening of the development time in the color development process, the concentration of the color developing agent is increased, the pH of the color developer is increased, and the color developer's pH is increased. Techniques such as increasing the temperature have been used.

17. However, rapid processing using the technique described in Section I has caused a serious problem in that fogging is more likely to occur than in the past.

In order to improve these defects, it has been proposed to add various fog suppressants to light-sensitive materials. In particular, U.S. Pat. No. 1,758.576υ and U.S. Pat.
No. 2,697.040, No. 2,697,099
Xshi, No. 2.824,001, No. 2,476.
No. 536, No. 2.1.143491, No. 3, 2
51.691, British Patent No. 403.789, British Patent No. 8
The mercapto compounds described in the specifications of No. 93,428-, Japanese Patent Publication No. 58-9939, etc. are effective in suppressing the above-mentioned fog. However, when this is used, undesirable problems arise, such as a decrease in sensitivity and deterioration in sensitivity, gradation, etc. due to storage under high temperature and high humidity conditions.

[Purpose of the invention]

The object of the present invention is to provide a technology that can significantly reduce the increase in fog caused by rapid processing, especially rapid color development processing, and improve storage stability under high temperature and high humidity conditions without deteriorating sensitivity. The purpose of this invention is to capture and provide a silver 1genide color photographic H material.

[Structure of the invention]

The object of the present invention is to provide a dot silver monogenide film having at least 8 photographic constituent layers containing a silver halide emulsion and at least one photographic constituent layer not containing a silver halide emulsion on a support.
In the material, at least one of the photographic constituent layers is produced by adding inorganic sulfur, and at least one of the photographic constituent layers is produced by adding oxidation l of a developing agent. This was achieved by a silver halide photosensitive material characterized by containing a compound capable of scavenging the oxide or releasing a precursor thereof by reacting with the oxide. .

The present invention will be explained below.

The silver halide color photographic light-sensitive material of the present invention comprises a photographic constituent layer containing a silver halide emulsion (hereinafter also referred to as a "silver halide emulsion layer") on a support, and a silver halide emulsion containing a silver halide emulsion. It has at least 8 constituent layers (also referred to as non-photosensitive layer 1). Each of the silver halide + ijL agent layer and the non-photosensitive layer may be one layer, or a plurality of layers may be formed.

The photographic material of the present invention is produced by adding inorganic sulfur to at least one of its photographic constituent layers. Inorganic sulfur may be added to either the silver halide emulsion layer or the non-photosensitive layer. It may be both.

Preferably, the silver halide emulsion layer is prepared with the addition of inorganic sulfur.

In the present invention, inorganic sulfur may be added during the production of any of the photographic constituent layers, and does not necessarily need to be contained as inorganic sulfur in the silver halide photographic light-sensitive material as a product. However, it goes without saying that the photosensitive material of the product 4) containing inorganic sulfur may also be used.

In the present invention, the term "inorganic sulfur" refers to so-called simple sulfur that does not form a compound with other elements. Therefore, sulfur-containing compounds known in the art as photographic additives, such as sulfides,
Sulfuric acid (or its salts), sulfurous acid (or its salts), thiosulfuric acid (or its salts), sulfonic acid (or its salts),
Inorganic sulfur-11 is not included in the present invention, such as 1,000-onythyl compounds, thiA-urea compounds, mercapto compounds, and sulfur-containing pyrocyclic compounds.

In the present invention, it is known that the simple sulfur used as [-inorganic sulfur 1] has several allotropes, and any of these allotropes may be used. Among these allotropes, α-sulfur belonging to the orthorhombic system is stable at room temperature, and although the inorganic sulfur used in the present invention is arbitrary, it is preferable to use this α-sulfur.

In the present invention, in order to obtain a photographic constituent layer manufactured by adding inorganic sulfur, inorganic sulfur may be added as a solid, but it is preferable to add it as a solution (7. Although sulfur is insoluble in water, it is known to be soluble in carbon disulfide, sulfur chloride, Hensen, diethyl ether, methanol, ethanol, etc., and it can be added to these solvents by dissolving 1 or more. Among these inorganic sulfur solvents, methanol and ethanol are particularly used due to ease of handling and adverse photographic effects.

The appropriate amount of addition of inorganic sulfur (inorganic sulfur) differs depending on the type of silver halide emulsion to be applied and the magnitude of the expected effect. The amount is preferably 10-5 to 10.If the amount is to be added, the entire amount may be added all at once, or the amount may be added in portions several times.

The photographic constituent layers produced by adding inorganic sulfur are optional, and include a photosensitive silver halide emulsion layer and a non-photosensitive wood-philic color F layer (in this case, it is supplied to the silver halide emulsion layer at the time of coating). However, preferably (-2) is added to the light-sensitive silver halide emulsion layer.

When producing a silver halide emulsion by adding inorganic sulfur, it can be added at any stage up to the formation of a silver halide emulsion layer. In other words, in the process of producing an optical silver halide emulsion, before the formation of silver halide grains, during the formation of halide root grains,
An arbitrary period selected from the period from the end of silver halide grain formation to the start of chemical sensitization, the beginning of chemical sensitization, during chemical sensitization, the end of chemical sensitization, and the period from the end of chemical sensitization to the time of coating. The time is fine. It is preferably added at the start of chemical sensitization, during chemical sensitization, at the end of chemical sensitization, or between the end of chemical sensitization and the time of coating.

The chemical sensitization starting step refers to the step of adding a chemical sensitizer, and in the second step, the time when the chemical sensitizer is added is the time to start chemical sensitization.

Further, the chemical sensitization described above can be stopped by a method known in the art. How to terminate chemical sensitization 1 ()
There are several known methods such as lowering the temperature, l) H lowering, and using a chemical sensitization stopper, but considering the stability of the emulsion, the method using a chemical sensitization stopper is preferable. Examples of the chemical sensitization stopper 2 include halogenides (e.g., potassium bromide, thorium chloride, etc.), anti-cazori agents, or organic compounds known as stabilizers (e.g., 7-hydroxy-5-methyl -1, 3, 4, 7a
TE, Razinden, etc.) are known. These compounds may be used alone or in combination.

The inorganic sulfur according to the present invention may be added in the chemical sensitization termination step, but the "chemical sensitization termination step" herein is referred to as "chemical sensitization termination step".
refers to the step of adding the chemical sensitization stopper mentioned above. In this case, the time to add inorganic sulfur may be substantially during the chemical sensitization termination step, and specifically, at the same time as the chemical sensitization termination step 1-1 or within 10 minutes before or after addition of the chemical sensitization termination agent 11. , preferably at the same time or within 5 minutes before or after.

Next, in the photographic material of the present invention, at least one of the photographic constituent layers thereof can react with an oxidation product of a developing agent to release a compound or a precursor thereof capable of scavenging the oxide. Contains compounds. Such a compound is hereinafter referred to as rDSR compound-1. This DSR compound may be contained in either the emulsion layer or the non-photosensitive layer. It can be both.

The 1) S R compound is represented by the general formula CD5R-[).

In the general formula (DSR-1) Coup- (T im e-), -S c-1 - Shipin (DSR-■), Coup is the reaction Q with the oxidized color developing agent (T 'ime→Ryo-8c represents a coupler residue capable of releasing 1'ime, and 1'ime is
Sc represents a timing group capable of releasing Sc after being released from the Coup, and Sc represents an oxidized color developing agent that can scavenge the oxidized color developing agent by a redox reaction or a coupling reaction after being released from the Coup. represents a body scavenger or its precursor, and ρ does not represent 0 or 1.

Further, to specifically explain the compound represented by the general formula (DSR-1), the coupler residue represented by Coup is generally a yellow coupler residue, a magenta coupler residue, a cyan coupler residue, or a substantially A colorless coupler residue, preferably of the following format (DSR-1a) to C
It is a coupler residue represented by DSR.

rh) General formula CD5R-ia) General formula CD5R-1b) General formula (DSR-1c) -Formula (DSR-1d)-
Salmon formula (DSR-1e) -Form CD5R-1f) -Form CDSR Ig) General formula CD5R ih) In the -Form (DSR-ia), R1 is an alkyl group, an alkyl group, or an amino group. and R2 represents an aryl group or an alkyl group.

In the above-format (DSR-II) 11, R3 represents an alkyl group or an aryl group;
Represents an alkylureido group.

In the above-format CI)SR-IC), R4 has the same meaning as the general formula CD5R-1b)(7)R', and R5 represents an acylamino group, a sulfonamido group, an alkyl group, an alkoxy group, or a halogen atom.

- General formula [DSR-■d] and [1) SR-IO3
In the formula, substituted 4R7 represents an alkyl group, aryl group, acylamino group, arylamino group, alkoxy group, phenylureido group, or alkylureido group, and R6 represents an alkyl group or an aryl group.

In the above general formula CD5R-If), R9 represents an acylamino group, a carbamoyl group, a phenylureido group,
R8 represents a halogen atom, an alkyl group, an alkoxy group, an acylamino group, or a sulfonamide group.

-1- In the general formula (DSR-1g), R9 has the same meaning as the general formula CD5R-If), and RIo is an amino group,
Represents a substituted amino group, carbonate amide group, sulfonamide group, and hydroxyl group.

In the above-format CD5R-Ih), RII represents a nitro group, an acylamino group, a succinimide group, a sulfonamide group, an alkoxy group, an alkyl group, a halogen atom, or a cyano group.

In addition, the above-format CD5R-1f) and (1') SR-
In 1h), n represents an integer of O to 2, and m in the general formula (DSR-Ig) represents an integer of 0 or 1.

The above eight groups may have a substituent. Preferred substituents include a halogen atom, a nitro group, a cyano group, a sulfonamide group, a hydroxyl group, a carboxyl group, an alkyl group, an alkoxy group, a carbonyloxy group, an acylamino group, and an aryl group.

The lipophilicity exhibited by R1 to R'' in each of the above types can be arbitrarily selected depending on the purpose.

In the case of conventional image-forming couplers, the total number of carbon atoms in R1 to R1 is preferably 10 to 60, more preferably 15 to 30. Further, in order to allow the dye produced by color development to move appropriately in the light-sensitive material, the total number of carbon atoms in R1 to R9 is preferably 15 or less. In the case of a substantially colorless coupler, the number is preferably 15 or less, and it is further preferred to have at least one carboxyl group, ary-sulfonamide group, or alkylsulfonamide group as a substituent at R' to R.

Substantially colorless coupler residues mean that they either flow out from the light-sensitive material into the processing solution after the dye-forming reaction, or react with components in the processing solution and bleach the dye, resulting in color images after development. They are known as run-off dye-forming couplers and bleaching dye-forming couplers, respectively.

In the above-mentioned format (DSR-1), if the timing represented by Time is preferably the following - Mariner (1
)SR-1i), CD5R-1j'l or (DSIg-Ik).

General formula (1) SR-Ii) In the formula, B represents an atomic group necessary to complete the benzene ring or naphthalene ring, Y represents -OR+4S- or -N-, and the -Sailor CD5R■ ] of C
Binds to the active site of oup (coupling component).

RIZ, RI3 and R- represent a hydrogen atom, an alkyl group or an aryl group.

, and the other is the aforementioned - Shipman CD5R -
1) is bonded to Sc.

-Seaman CD5R-13) In the formula, Y, R12, and R13 are the above-mentioned -Seaman (DSR-
■i], R" represents a hydrogen atom, an alkyl group, an aryl group, an acyl group, a sulfone group, an alkoxycarbonyl group, or a heterocyclic residue, and R1" represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, and Ring residue, alkoxy group, amino group, acid amide group, sulfonamide group, carboxy group,
Represents an alkoxycarbonyl group, carbamoyl group or cyano group.

In addition, the timing relationship represented by the above-mentioned -Sailor CD5R-Ij) is similar to the above-mentioned -Sailor (DSR-14), where Y is the activity of Coup (cumbling component) of the above-mentioned -Sailor CD5R-1). In addition, R'1 then releases Sc by an intramolecular nucleophilic substitution reaction 'r'
Examples of the ime group include the following - Shipman (DSR-1k).

General formula CI) SR-ik) N u-D -8 In the formula, N u represents a nucleophilic group having an electron-rich oxygen, sulfur, or nitrogen atom, and the -Sailor CD5R-[
) is bound to the active site of Coup (coupling component). E represents an electrophilic group having an electron-independent carbonyl group, thiocarbonyl group, phosphinyl group, or thiophosphinyl group. This electrophilic group E is Sc
D is bonded to the heteroatom of Nu and E, and after Nu is released from C0up (coupling component), a 3- to 7-membered ring is formed. represents a bonding group capable of breaking intramolecular nucleophilic substitution by a reaction and thereby releasing Sc.

Further, the scavenger of the oxidized color developing agent represented by Sc (if Sc is a precursor, the scavenger generated from the precursor) is of the redox type and the coupling type.

- In Senjin (DSR-1), when Sc scavenges the oxidized color developing agent through a redox reaction, the Sc is a group capable of reducing the oxidized color developing agent, such as Angew, Chem.

Int., Ed., 17875 886 (1978)
,The Theory of thePhotogr
aphic Process 4th edition (Macmilla
Preferably, the reducing agents described in Chapter 11, JP-A No. 59-5247 (1977), and the like are preferred, and Sc may be an Ai7 precursor capable of releasing the reducing agent during development. Specifically, an aryl group or a heterocyclic group having at least two of (in the formula, R, R' represents a hydrogen atom, alkyl, cycloalkyl, alkenyl, or aryl group) is preferable;
Among these, a teryl group is preferred, and a phenyl group is more preferred. The lipophilicity of Sc is as follows:
) to CD5R-1h), the total number of carbon atoms in Sc is preferably 6.
~50, more preferably 6-30, even more preferably 6-30
It is 20.

When Sc scavenges the oxidized color developing agent through a coupling reaction, the Sc! ,;L is a substantially colorless coupler residue, and utilizes the aforementioned run-off dye-forming couplers, bleaching dye-forming couplers, and Weiss couplers that have a non-leaving substituent at the reaction active site and do not form a dye. can do.

Specific compounds represented by the general formula CD5R-I) include, for example, British Patent No. 1546837, Japanese Patent Application Laid-Open No.
No. 150631, No. 57-111536, No. 57-1
No. 11537, No. 57-138636, No. 60-18
No. 5950, No. 60-203943, No. 60-213
No. 944, No. 60-214358, No. 61-536.
No. 13, No. 61-84646-, No. 61-86751
No. 61402646, No. 61-102647, No. 61-107245, No. 61-113060,
No. 61-231553, No. 61-233741, No. 61-236550, No. 6L236551-, No. 6
No. 1-238057, No. 61240240, No. 61-
No. 249052, No. 62-81638, No. 62-20
There are those described in No. 5346, No. 62-287249, etc.

A redox type scavenger can be preferably used as Sc, and in this case, the color developing agent can be used for reprinting by reducing the oxidized product of the color developing agent.

DSR compounds represented by the general formula [Y]5R-1) are exemplified below, but the present invention is not limited to the exemplified compounds below.

SR ■ SR SR e SR I) SR Cρ SR Cρ [) 8 ) Gu■ +1) SI,! In DSI S R SR SR 1) S l? Ci! I) S R e SR 0OII e SR S R SR H 5R SR SR SR p 0 ■ SR H SR "Q SR H SR D S R SR SR SR I) S R SR SR SR D S R S R SR i1 NH30 □N(C41'+9)2 In the photosensitive +A material of the present invention, i) S R compound is:
At least one arbitrary layer Q of any of the photographic constituent layers is included. Therefore, it can be added to a photosensitive silver halide emulsion layer and/or a non-photosensitive layer, but it is preferably added to a silver halide emulsion layer.

Inorganic sulfur may be added to the produced photographic constituent layer, but this need not necessarily be the case.

In the present invention, two or more types of DSR compounds can be included in the same layer. Further, the same L;DSR compound may be contained in two or more different layers.

These DSR compounds are generally preferably used in amounts of 2X10-' to 5X10-' moles, more preferably lX10-' to lX10-' moles, per mole of silver in the emulsion layer.

In order to contain these DSR compounds in the silver halide emulsion layer constituting the light-sensitive material of the present invention or in the coating solution for other photographic constituent layers, I) If the S R compound is alkali-soluble, It may be added as an alkaline solution, or if it is oil-soluble, see for example US Pat.
2.027, 2.801,170, 2.8
No. 01,171, No. 2,272.191 and No. 2
, No. 304,940 according to the methods described in each specification, D
It is preferable that the SR compound is dissolved in a high boiling point solvent, optionally in combination with a low boiling point solvent, and then dispersed in the form of fine particles and added to the silver halide emulsion.

The above DSr compounds are disclosed in JP-A-57-138638, JP-A-57-155537, and JP-A-57. -171334, 58-111941, 61-53643, 61-84646, 61-86751, 61-
No. 102646, No. 61-102647, No. 61-1
It can be synthesized by the method described in No. 07245, No. 61-113060, etc.

The silver halide emulsion used in the present invention includes conventional silver halide such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, silver chloroiodobromide, and silver chloride. Any material used in chemical root emulsions can be used, but silver bromide, silver iodobromide, and silver chlorobromide are particularly preferred.

The silver halide grains used in the silver halide emulsion may be obtained by any of the acid method, neutral method, and ammonia method. The particles may be grown all at once, or may be grown after seed particles are produced. The method of producing and growing a seed may be the same or different.

In the silver halide emulsion, halide ions and silver ions may be mixed simultaneously, or one may be mixed in a liquid in which the other is present. Alternatively, the halide ions and silver ions may be generated by sequentially and simultaneously adding the halide ions and silver ions while controlling the pH and/or pA& in the mixing pot, taking into consideration the critical growth rate of the silver halide emulsion. By this method, silver halide grains having a regular crystal shape and a nearly uniform grain size can be obtained. Conversion methods may be used at any step in the formation of silver halide grains to change the halogen composition of the proof.

Known silver halide solvents such as ammonia, thioether, and urea may be present during the growth of silver halide grains.

Silver halide grains are formed by cadmium salts, zinc salts, lead salts, thallium salts, iridium salts (including complex salts), rhodium salts (including complex salts), and iron salts during the grain formation and/or growth process. It is possible to add metal ions using at least one kind selected from salts (including complex salts) to contain these metal elements inside the particles and/or on the particle surfaces, and in an appropriate reducing atmosphere. By placing reduction sensitizing nuclei inside the particles and/or on the particle surfaces (=1
I can give.

The silver halide emulsion may be free of unnecessary soluble salts after the growth of silver halide grains is completed, or may be left uncontained. When removing the salts, Research Disclosure (Research Disclosure) is required.
closure (hereinafter abbreviated as RD) No. 17643■
It can be carried out based on the method described in Section.

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

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

The silver halide grains may have a regular crystal shape such as a cube, octahedron, or dodecahedron, or may have an irregular crystal shape such as a spherical shape or a plate shape. In these particles, any ratio of the (1001 plane to the (111) plane) can be used. Furthermore, the particles may have a composite form of these crystal forms, or particles of various crystal forms may be mixed.

The silver halide grain size is preferably 0.05
-30 micrometers, more preferably 0.1-20 micrometers can be used.

Silver halide emulsions having any grain size distribution may be used. An emulsion with a wide grain size distribution (referred to as a polydisperse emulsion) may be used, or an emulsion with a narrow grain size distribution (referred to as a monodisperse emulsion). A particle with a value of 0.20 or less when divided by the average grain size.In the case of spherical silver halide, the grain size is the diameter, and in the case of grains with a shape other than spherical, the value is the diameter. This indicates the diameter when the projected image is converted into a circular image of the same area.) may be used alone or in combination. Further, a mixture of a polydisperse emulsion and a monodisperse emulsion may be used.

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

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

Silver halide emulsions can be optically sensitized to a desired wavelength range using dyes known in the photographic industry as sensitizing dyes. The sensitizing dyes may be used alone or in combination of two or more. Along with the sensitizing dye, the emulsion contains a supersensitizer, which is a dye that itself does not have a spectral sensitizing effect, or a compound that does not substantially absorb visible light, and which enhances the sensitizing effect of the sensitizing dye. It's okay.

As the sensitizing dye, for example, cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, styryl dyes, hemioxanol dyes, etc. can be used.

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

Silver halide emulsions are used during the manufacturing process of photosensitive materials, during storage,
Or, for the purpose of preventing fog during photographic processing or keeping photographic performance stable, the photographic industry Compounds known as antifoggants or stabilizers can be added.

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

Photographic emulsion layers and other hydrophilic colloid layers of light-sensitive materials using silver halide emulsions are made by using one or more hardeners to crosslink binder (or protective colloid) molecules and increase film strength. Can be hardened.

The hardening agent can be added in an amount capable of hardening the photosensitive material to such an extent that it is not necessary to add the hardening agent to the processing solution, but it is also possible to add the hardening agent to the processing solution.

For example, aldehydes (formaldehyde, glyoxal, geltaraldehyde, etc.), N-methylol compounds (dimethylolurea, methyloldimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), activated vinyl compounds (1,3,5- ) lyacroylhexahydro-s-triazine, 1,3-vinylsulfonyl-2-propatur, etc.), active halogen compounds (2,4-dichloro-6-hydroxy S-triazine, etc.), mucohalogen acids (mucochloric acid, Mucophenoxychloroic acid, etc.) can be used alone or in combination.

A plasticizer can be added to the silver halide emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material for the purpose of increasing flexibility. Preferred plasticizers are RD17643 item A
It is a compound described in .

In photographic emulsion layers and other hydrophilic colloid layers of light-sensitive materials,
For the purpose of improving dimensional stability, etc., a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer can be included.

For example, alkyl (meth)acrylate, alkoxyalkyl (meth)acrylate, glycidyl (meth)acrylate, (meth)acrylamide 1-vinyl ester (e.g. vinyl acetate), acrylonitrile, olefin, styrene, etc. alone or in combination, or these and acrylic acid, A polymer containing a combination of methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth)acrylate, sulfoalkyl (meth)acrylate, styrene sulfonic acid, etc. as a monomer component can be used.

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

These dye-synthesizing couplers preferably have a group called a pallast group in the molecule, which makes the coupler non-diffusive and has 8 or more carbon atoms. Furthermore, these dye-forming couplers may be tetraequivalent, which requires reduction of four molecules of silver ions in order to form one molecule of dye, or two molecules of silver ions may be reduced. Either bi-isomerism is acceptable. The dye-forming coupler has a color correction effect, and by coupling with the oxidized form of the developing agent, it can be used as a development inhibitor, a development accelerator, a bleach accelerator, a developer, a silver halide solvent, and a toning agent. Compounds that release photographically useful fragments such as agents, hardeners, fogging agents, antifoggants, chemical sensitizers, spectral sensitizers, and desensitizers are included. Among these, DIR is a coupler that releases a development inhibitor during development and improves image sharpness and image graininess.
called a coupler. In place of the DIR coupler, a DIR compound which undergoes a coupling reaction with the oxidized form of the developing agent to produce a colorless compound and at the same time releases a development inhibitor may be used.

The DIR couplers and DIR compounds used include those in which the inhibitor is directly bonded to the coupling position, and those in which the inhibitor is bonded to the coupling position via a divalent group, and the group is separated by the coupling reaction. Intramolecular nucleophilic reaction,
Included are those in which the inhibitor is bonded such that it is released by an intramolecular electron transfer reaction or the like (referred to as timing DIR couplers and timing DIR compounds). Also, depending on the purpose, inhibitors that are diffusible after release and those that are not so diffusible can be used alone or in combination. A colorless coupler (
Competitive couplers) can be used in conjunction with dye-forming couplers.

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

Among these, benzoylacetanilide and pyhaylacetanilide compounds are advantageous.

Specific examples of yellow couplers that can be used include U.S. Pat. No. 2,875.057, U.S. Pat.
, No. 408.194, No. 3,551,155, No. 3,
No. 582,322, No. 3.725,072, No. 3,8
9L445, West German Patent No. 1,547°868, West German Patent Application No. 2,219.917, West German Application No. 2,261,361, West German Patent No. 2,414,006, British Patent No. 1,425,02
No. 0, Special Publication No. 5l-1o7s3, Japanese Patent Publication No. 47-261
No. 33, No. 48-73147, No. 50-6341,
No. 50-87650, No. 50-123342, No. 5
No. 0-130442, No. 51-21827, No. 51-
No. 102636, No. 52-82424, No. 52-11
No. 5219, No. 58-95346, etc.

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

Specific examples of magenta color-forming couplers that can be used include, for example, U.S. Pat.
3.062,653, 3,127,269, 3,311.476, 3,419,391, 3
, No. 519,429, No. 3,558.319, No. 3.
No. 582.322, No. 3,615,506, No. 3.8
No. 34908, No. 3,89L445, West German Patent No. 1,8
No. 10.464, West German Patent Application (OL S) 2,40
No. 8,665, No. 2.417945, No. 2,418,
No. 959, No. 2,424.467, Special Publication No. 1977-1960
No. 31, JP-A-49-74027, JP-A No. 49-740
No. 28, No. 49-129538, No. 50-60233
No. 50-159336, No. 51-20826,
No. 51-26541, No. 52-42121, No. 52
No.-58922, No. 53-55122, Patent Application No. 1983-
Examples include those described in No. 110943 and the like.

Dye-forming couplers, colored couplers, DIR couplers, DIR that do not need to be adsorbed on the silver halide crystal surface
compounds, image stabilizers, color antifoggants, ultraviolet absorbers,
Among fluorescent brighteners, hydrophobic compounds can be prepared using various methods such as solid dispersion method, latex dispersion method, and oil-in-water emulsion dispersion method. It can be selected as appropriate depending on the situation. For the oil-in-ice emulsion dispersion method, conventionally known methods for dispersing hydrophobic additives such as couplers can be applied, and the boiling point is usually about 15
Low boiling point and/or
Alternatively, it is dissolved using a water-soluble organic solvent, and a surfactant is used in a hydrophilic binder such as an aqueous gelatin solution, and a dispersion method such as a stirrer, Homosina Iser colloid mill, flow jet mixer, or ultrasonic device is used. After emulsification and dispersion, it may be added to the desired hydrophilic colloid liquid. A step of removing the low-boiling organic solvent may be included simultaneously with the dispersion or dispersion.

Examples of high-boiling point solvents include phenol derivatives that do not react with the oxidized form of the developing agent, al-4-luconister phthalate, phosphoric acid esters, citric acid esters, benzoic acid esters, alkylamides, fatty acid esters, trimesic acid esters, etc. with a boiling point of 150'c. The above organic solvents are used.

Low boiling or water-soluble organic solvents can be used in conjunction with or in place of high boiling solvents. Examples of the organic solvent having a low boiling point and substantially insoluble in water include ethyl acetate, propyl acetate-1 to butyl acetate-1, butanol, chloroform, carbon tetrachloride, nitromethane, nitroethane, benzene, and the like.

Dye-forming coupler, DIR coupler, colored coupler, DIR compound, image stabilizer, anti-color fog IL
When the agent, ultraviolet absorber, fluorescent brightener, etc. have an acid group such as carboxylic acid or sulfonic acid, they can also be introduced into the hydrophilic 2111-ide as an alkaline aqueous solution.

Anionic surfactants and nonionic surfactants are used as dispersion aids when hydrophobic compounds are dissolved in a solvent using a low boiling point solvent or a high boiling point solvent and dispersed in water using mechanical or ultrasonic waves. Agents, cationic surfactants and amphoteric surfactants can be used.

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

The antifogging agent may be contained in the emulsion layer itself, or
An interlayer may be provided in an adjacent emulsion layer and contained in the interlayer.

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

Hydrophilic colloid layers such as protective layers and intermediate layers of photosensitive materials contain ultraviolet absorbers to prevent fogging and to prevent image deterioration due to ultraviolet rays due to discharge caused by charging of photosensitive materials due to friction, etc. You can stay there.

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

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

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

The emulsion layer of photographic light-sensitive materials contains polyalkylene oxide or its derivatives such as ethers, esters, and amines, thionidel compounds, thiomorpholins, quaternary ammonium compounds, and urethane derivatives for the purpose of increasing sensitivity, increasing contrast, or accelerating development. , urea derivatives, and imidazole derivatives.

A fluorescent whitening agent can be used in the photosensitive +4 material for the purpose of emphasizing the whiteness of the white background and making the coloration of the white background less noticeable. Compounds that can be preferably used as fluorescent brighteners are described in Item 7 of RD No. 1.7643.

The photosensitive material can be provided with auxiliary layers such as a filter layer, an antihalation layer, and an antiirradiation layer. Dyes may be contained in these layers and/or in the emulsion layers that are leached from the light-sensitive material or bleached during the development process.

Examples of such dyes include oxo- and nol dyes, mion-xonol dyes, styryl dyes, merocyanine-7 dyes, cyanine dyes, and azo dyes.

In the silver halide emulsion layer and/or other hydrophilic colloid layer of the photosensitive material, it is possible to reduce the gloss of the photosensitive material, add four holes for writing, and prevent sticking of the photosensitive material from collapsing [1 and 1].
Then, Man 1~ agent can be added. Any agent can be used for Mano 1~ agent and L2, but for example, silicon oxide, titanium dioxide, magnesilano 1 dioxide, FiHIS aluminum 11, barium sulfate, calcium carbonate, polymers of acrylic acid and methacrylic acid and their esters, Examples include polyvinyl resin, polycarbonate, and styrene polymers and copolymers thereof. The particle size of the cloak agent is 0.
05 to 1011 m is preferable. The amount to add is 1~
300 .mu./M is preferred.

A lubricant can be added to photosensitive materials to reduce sliding friction.

An antistatic agent II for the purpose of preventing static electricity can be added to the photosensitive material. The antistatic LL agent is made by laminating the emulsion of the support and -C
It may be used in the antistatic layer on the other side, or in the protective colloid layer other than the emulsion layer and/or the emulsion layer on the side where the emulsion layer is laminated with respect to the support. Preferably used static protection 11 - RD17643 No.
It is a compound described in I.

Photographic emulsion layer and/or other wood-loving coil of light-sensitive material
- The layer contains various surfactants with the aim of improving coating properties, preventing static electricity, improving slipperiness, emulsifying and dispersing, and improving photographic properties (development acceleration, hardening, sensitization, etc.), etc. can be used.

The support used in the photosensitive material of the present invention includes paper laminated with α-molefin polymer (e.g., polyethylene, polypropylene, ethyl]2-butene copolymer), etc.
Flexible reflective supports such as synthetic paper, semi-synthetic or 5 such as cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate = 1, polyamide, etc. [i) Film J made of synthetic polymer, and flexible supports with reflective layers on these films, glass, metals, ceramics, etc.

If necessary, the photosensitive material can be applied to the surface of the support by applying electrical discharge, ultraviolet irradiation, flame treatment, etc., and then directly or to improve the adhesion, antistatic properties, dimensional stability, abrasion resistance, hardness, etc. of the support surface. It may be coated through one or more subbing layers to improve anti-halation properties, friction properties, and/or other properties.

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

As coating methods, extrusion coating and curtain coating, which can simultaneously apply two types of layers, are particularly useful;
Brush application is also used. Further, the coating speed can be arbitrarily selected.

Examples of the surfactant include, but are not limited to, natural surfactants such as Zabonin, nonionic surfactants such as alkylene oxide type, glycerin type, and cricidol type;
Higher alkylamines, quaternary ammonium salts, pyridine and other heterocycles, cationic surfactants such as phosphonium or sulfonyl 11, anions containing acidic groups such as carbonic acid, sulfonic acid, phosphoric acid, sulfuric acid ester, phosphoric acid ester, etc. Surfactants, amphoteric surfactants such as amino acids, aminosulfonic acids, sulfuric acid or phosphoric acid esters of amino alcohols, etc. may be added. It is also possible to use fluorine surfactants for the same purpose.

To obtain a dye image using the photosensitive material of the present invention, after exposure,
Perform color photo processing.

Color processing includes a color development process, a bleaching process, a fixing process, a washing process, and a stabilizing process if necessary. ``Instead of culm, a one-bath bleach-fixing solution can be used to perform the bleach-fixing process, or a one-bath developing, bleach-fixing solution can be used that allows color development, bleaching, and fixing to be performed in one bath. It is also possible to carry out a monohass treatment process.

These treatment steps may be combined with a pre-hardening treatment step, its neutralization step, a stop-fixing treatment step, a post-drying treatment step, etc. In these processes, instead of the color development process, an actihake process may be performed in which a color developer drug or its precursor is contained in the light-sensitive material and the development process is performed with an activator solution, or an activator process may be performed in the monolith process. can be applied.

Among these processes, typical processes are shown below. (These treatments are carried out in the final stage (6) as a culm, performing one of the water washing process, water washing process, and stabilization process 6) Color development process - Bleaching process Constant coloring process - Color development process - Bleach-fixing process/Pre-hardening process - Color development process - Stop fixing process - Washing process - Bleach process - Fixing process I - Washing process - Post-hardening process/Color development process 2 rh - Water washing process - L stage - Acquisition color development process - Stopping process] Culm - Bleaching process 2 - Upper part of culm fixation process - Lower stage of bleach-fixing process - Lower stage of actihater treatment process - Bleaching process Lower stage of fixed fixation process - Monohas treatment process The treatment temperature is usually preferably selected in the range of 10'C to 65°C, but may also be at a temperature exceeding 65°C. More preferably, the treatment is carried out at a temperature of 25'C to 45C.

A color developing solution generally consists of an alkaline aqueous solution containing a color developing agent. Color developing agents are typically aromatic primary amine color developing agents, including aminophenolic and p-phenylenediamine derivatives. These color developing agents can be used as salts of organic acids and inorganic acids, such as hydrochloric acids, sulfates, p-toluenesulfonic acid salts, and the like.

These compounds are generally used in color developers 17! usually preferably at a concentration of about 0.1 to 30 g, more preferably,
It is used in a concentration of about 1 to 15 g for color developer 1e. If the amount added is less than 0.1 g, sufficient color density may not be obtained.

”- as an aminophenol developer, for example, 0-
These include aminophenol, p-aminophenol, 5-amino-2-hydroxytoluene, 2-amino-3-hydroxytoluene, 2-hydroxy3-amino-1,4-dimethylhensen, and the like.

Particularly useful primary aromatic amine color developing solutions include N, N
- dialkyl-p-phenylenediamine compound,
Alkyl groups and phenyl groups may be substituted or unsubstituted.

Among them, particularly useful examples include N,N dimethyl-p-phenylenediamine hydrochloride, N,methyl-p-phenylenediamine hydrochloride, N,N dimethyl-p-phenylenediamine hydrochloride, 2amino-5-(N -Ethyl-
N-Decylamino)-toluene, N-ethyl-N-β
-Methanesulfonamide FH 3-methyl-4-aminoaniline 6A M salt, N-ethyl-N-β-hydroxyethylaminoaniline, 4-amino-3-methyl N
, N--diethylaniline, 4-amino-N(2-methoxyethyl)-N-ethyl-3-methylaniline-p-
1-luenesulfonate and the like can be mentioned.

Further, the above color developing agents may be used alone or in combination of two or more. Furthermore, the color developing agent mentioned above may be incorporated into the color photographic material. in this case,
It is also possible to process the silver halide color photographic light-sensitive material with an alkaline solution (actihater solution) instead of a color developing solution, and after the alkaline solution treatment, it is immediately subjected to a bleach-fixing process.

The color developing solution used in the present invention is an alkaline agent commonly used in developing solutions, such as thorium hydroxide, potassium hydroxide, ammonium hydroxide, sodium chloride carbonate, potassium carbonate, sodium sulfate, thorium metaborate, or borax. In addition, various additives such as Hensyl alcohol, alkali metal halides such as potassium bromide or potassium chloride, development regulators such as citrazic acid, and preservatives such as It may also contain hydroxylamine or sulfite.

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

The pH of the color developing solution used in the present invention is usually preferably 7.
The number is -1-, more preferably about 9-13.

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

In the color developing solution used in the present invention, various GI/-1 agents can be used in combination as metal ion sequestering agents.

For example, ethylenediaminetetraacetic acid as the chelating agent,
Aminopolycarphonic acids such as diethylenetriaminepentaacetic acid, organic phosphonic acids such as 1-hydroxyethylidene-1,1-diphosphonic acid, aminopolyphosphonic acids such as aminotri(methylenephosphonic acid) or ethylenediamine phosphonic acid, citric acid or glyconic acid Oxycarboxylic acids such as 2-phosphonobutane 1. 2. Examples include phosphocarphonic acids such as 4-1 to licarphonic acid, polyphosphoric acids such as l-ribolyphosphoric acid or hexamethalin, and polyhydroxy compounds.

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

As a bleaching agent, a metal complex salt of an organic acid is used, for example, one in which a metal ion such as iron or cobal-1-1 copper is coordinated with an organic acid such as polycarboxylic acid, aminopolycarboxylic acid, oxalic acid, or citric acid is used. It will be done. Among the above organic acids, the most preferred organic acids include polycarboxylic acids and aminopolycarphonic acids. Specific examples of these include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, and ethylenediamine-N-(β-oxyconityl)N.
, N'N' -triacetic acid 1, propylene diamine tetraacetic acid, nitrilotriacetic acid, cyclohexanecyamine tetraacetic acid, iminodiacetic acid, dihyrecoxyethylglycine citric acid (or tartaric acid), ethyl ether diamine tetraacetic acid, glycol ether diamine tetraacetic acid Examples include acetic acid, ethylenediaminetetrapropionic acid, phenylenediaminetetraacetic acid, and the like.

These polycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts. These bleaching agents are usually preferably 5 to 450 g/7! , more preferably 20 to 250 g/ff.

In addition to the above-mentioned bleaching agent, the bleaching solution contains a sulfite salt as a preservative in addition to the bleaching agent described above.

Alternatively, a bleaching solution containing a large amount of a halide such as ammonium bromide, including an ethylene diaminetetraacetate iron(m) complex salt bleaching agent may be used. As the halides, in addition to ammonium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, etc. can also be used. can.

Bleaching solutions include JP-A No. 46-280 and JP-A No. 45-85.
No. 06, No. 46-556, Helgie Patent No. 770.9
No. 10, Special Publication No. 45-8836, No. 53-9854
No., JP-A No. 54-71634 and JP-A No. 49-42349
It is possible to add various bleaching accelerators as described in No. 1, etc.

The pH of the bleaching solution is usually 2.0 or more -1-, but it is generally preferably used at a pH of 4.0 to 9.5, preferably 4.5 to 8.0, and most preferably 5.0 to 9.5. 0-7
．． It is 0.

A fixer having a commonly used composition can be used. As fixing agents, compounds that react with silver halide to form water-soluble complex salts, such as those used in ordinary fixing processes, such as sodium diosulfate, sodium periosulfate, and ammonium thiosulfate, can be used.
7) Typical examples thereof include thiosulfates such as potassium thiocyanate, thiocyanate salts such as potassium thiocyanate, sodium to lithium thiocyanate, ammonium thiocyanate, thiourea, thioether, and the like. , these fixatives usually weigh 5 g
/ (!For molds, it is used in an amount within the range that can be dissolved, but it is generally preferably used in an amount of 70 to 250 g/p.) A part of the fixing agent can be contained in the bleaching tank, and vice versa. A portion of the bleach may also be included in the fixing bath.

The bleaching solution and/or fixing solution contains boric acid, borax, sodium hydroxide, potassium hydroxide 1, sodium carbonate J1, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate 11, hydroxide. Various types of p such as ammonium
H buffering agents can be contained alone or in combination of two or more. Furthermore, various fluorescent whitening agents, antifoaming agents, or surfactants can be contained.

Also, preservatives such as hydroxylamine, hydrazine, and bisulfite additives of aldehyde compounds, organic chelating agents such as aminopolycarboxylic acids, stabilizers such as nitroalcohols and nitrates, and hardening agents such as water-soluble aluminum salts. , methanol, dimethylsulfamide, dimethylsulfamide, and other organic solvents may be appropriately contained.

p)] of the fixer is usually used at 3.0 or more, generally preferably from 4.5 to 10, preferably from 7 or 5. to 9.5, and most preferably from 6 to 9.5. It is 9.

The bleaching agent used in the bleach-fix solution is
The preferred compounds and concentrations in the treatment solution are the same as in the above bleaching treatment step.

As the bleach-fix solution, a solution containing a silver halide fixing agent (in addition to the above-mentioned bleaching agent) and, if necessary, sulfite as a preservative, is used. A bleach-fix solution consisting of an iron (nI) complex salt bleach and a small amount of a halide such as ammonium bromide J, other than the silver halide fixer mentioned above, or conversely a large amount of a halide such as ammonium bromide. Also used are bleach-fix solutions with a composition of ethylenediaminetetraacetic acid iron(II) complex salt bleach and a large amount of a halide such as ammonium bromide J. In addition to ammonium bromide, the halides include hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, etc.
Thorium iodide, potassium iodide, ammonium iodide, etc. can also be used.

Examples of the silver halide fixing agent that can be contained in the bleach-fixing agent include the fixing agents described in the fixing treatment step. Concerning the concentration of the fixing agent and the pH buffering agent and other additives that can be contained in the bleach-fixing solution, C is the same as in the above-mentioned fixing treatment step.

The pH of the bleach-fix solution is usually preferably used at 4.0 or higher, but generally it is more preferably used at a pH of 5.0 to 9.5, desirably 6.0 to 8.5, and most preferably used at a pH of 5.0 to 9.5. Preferably it is 6.5 to 8.5.

〔Example〕

Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.

In all of the following examples, silver halide photographic exposure +
The amount added in Material A indicates the number of grams per IM unless otherwise specified. Further, colloidal silver halide is shown in terms of silver.

Example 1 Multilayer color photographic sensitizer sample 1 was prepared by sequentially forming layers having the compositions shown below on a triacetyl cellulose film support from the support side.

Sample-1 (comparison) 1st layer; antihalation layer (H(,-1) black colloidal silver 0.20 UV absorber (
UV-1) 0.20 colored coupler (CC-1
) 0.05 colored coupler (CM-1)
0.05 high boiling point solvent (O i (1 − 1)
0.20 Gelatin 1.5n No.? Layer: Intermediate layer (I 1. 1> tJ V absorber (LJ V 1) High boiling point solvent (Qij!-1) Ceratin 3rd layer; Low sensitivity red-sensitive emulsion layer (R1-7) Silver iodobromide emulsion ( E m-1) Silver iodobromide emulsion (l m-2> Sensitizing dye (SD I) 2.5XlO-' (mol/silver 1) Sensitizing dye (SD-2) 2.5X10-' (mol/ Silver 1 Sensitizing dye (SD-3) 0.5xlO-' (mol, / Silver 1 Cyan coupler (C-A) Colored cyan coupler (CCD I R compound (1)-1) High boiling point solvent (Oiff-1 ) 4th gelatin layer; high-speed red-sensitive emulsion layer (RII) (), (l
1 0, former 1.5 0.8 0, ) (mol) mol) mol) 1.0 0.05 0.002 0.5 Silver iodobromide emulsion (Imi m-3) 2. (1 Sensitizing dye (SD-1) 2.0XlO-' (mol/1 mol of silver) Sensitizing dye (SD
2) 2.0X10-' (mol/silver 1 mol) sensitizing dye (SD
3) 0.1X10-' (mol/1 mol silver) Cyan coupler (C-A) 0.20 Cyan coupler (C-1
3) 0.05 colored cyan turnip sea (C
C-1) 0.015 D I I'? Compound (D-1) 0.05
High boiling point solvent (Oi I! -1) 0.2 Seratin 1.5 5th layer; intermediate layer (I
L-2) Gelatin 0.5 6th layer; low-sensitivity green-sensitive emulsion layer ((,; L) Silver iodobromide emulsion (Em-1
) 1.0 Sensitizing dye (SD-4) 5XIO-' (mol/1 mole of silver) Sensitizing dye (SD-5) I Xl0-' (mol/1 mole of silver) Magenta coupler (M-1) 0. 1 Magenta coupler (lvl-4,) 0.2 Colored magenta coupler (CM-1) 0.01 DIR compound (D-3) 0.02 DIR compound (D-4) 0.020 High boiling point solvent (
Oi 1-1) 0.3 gelatin
1.0 7th layer; intermediate layer ([L-3> gelatin 0.8 8th layer; high-sensitivity green-sensitive emulsion layer (GH) silver iodobromide emulsion (Em-3) 1.3 sensitizing dye (
SD-6) 1.5X10-' (mol/mol silver) sensitizing dye (SD
-7) 2.5XlO-' (mol/silver 1 mol) sensitizing dye (SD
-8) 0.5xlO-' (mol/mol silver) magenta coupler (M -2> 0.05 magenta coupler (M
-3> 0.15 color macenter coupler (C
M-2) 0.05 DIR compound (D-3) 0.01 High boiling point solvent (Oiff-3) 0.5 Gelatin
1.0 9th layer; yellow filter layer (YC) yellow comonoid silver 0.1
Color stain inhibitor (SC-1) 0.1 High boiling point solvent (O4ff-3) 0.1 Gelatin
0.8 10th layer; low-speed blue-sensitive emulsion layer (B
L) Silver iodobromide emulsion (Em-1) 0.25
Silver iodobromide emulsion (Em-2) 0.25 sensitizing dye (SD-10) 7 Xl0-' (mol/1 mol of silver) Yellow coupler (Y-A) 0.5 yellow coupler (Y-B) 0 .1DIR compound (D-2
) 0.01 l High boiling point solvent (Oi7!-3) 0.3 Gelatin 1,0 11th layer; High sensitivity blue-sensitive emulsion layer (BH) Silver iodobromide emulsion (Em-4) 0
．． 4 silver iodobromide emulsion (Em-1) 0.4 sensitizing dye (SD-9) I Xl0-' (mol/1 mol of silver) Sensitizing dye (SD-10) 3 mole) Yellow coupler (Y-A) 0.30 Yellow coupler (Y-B) 0.05 High boiling point solvent (Oi
ff-3) 0.15 gelatin
1.1 12th layer; 1st protective layer (PRO-1) UV absorber (UV-1) 0.10 UV absorber (UV-2) 0.05 High boiling point solvent (Oi
7! -1) 0.1 high boiling point solvent (Oi 1-4
) 0.1 formalin scavenger (T-!5-1) 0.5 8m 8m Average silver iodide content...2.0 mol%.

Monodisperse (width of distribution 14%) Silver bromide-containing emulsion Average particle size: 0.81!7m.

Average silver iodide content...7.0 mol% Surface with flower dispersion (width of distribution 14%) Emulsion containing low silver iodide (1.0 mol%) Average particle size: 0.95μm Average silver iodide content...8.0 mol%.

Monodisperse (width of distribution 14%) surface-low silver iodide (0.5 mol%) containing emulsions Em-1 to Em-3 are made of sodium thiosulfate (hypo),
Chemical sensitization was optimally performed using chloroauric acid and ammonium thiocyanate.

Formalin scavenger (H3-2) 0.2 Gelatin 1.0 13th layer; 2nd
Protective layer (PRO-2) Surfactant (SU-1) 0.005 Alkali-soluble clotting agent (average particle size 2 μm) 0.05 Polymethyl methacrylate (average particle size 3 μm) 0.05 Slip agent (W
AX-1) 0.04 gelatin
0.6 In addition to the composition mentioned above, each layer contains coating aid 5u-2 dispersion aid 5u-3. Hardener H-1 and H-2
, stabilizer 5T-1, antifoggant AF-1, AI"-2
was added.

Em-1 Average grain size 0.46 μm Average silver iodide content...7.0 mol% Monodisperse (width of distribution 14%) surface low silver iodide (2 mol%) emulsion Em -2 Average particle size 0.30 IIm SD SD (CH3)
Czlls) ++NH's SF F) (IQ C n+1 M M ■) ■) υ11 H ■) U■ C,H6 S [(CH2 CIISO2CII2) 3CCH□So 2 (Ct
l Z) 2 ]2N(CH2)zsOJ u NaO,5 CIICOOCII 2 (C1ζCF21C112C
OOCIIZ (CFzCFz) zllu NaO,5 CHCOOCall+7 C112COOC,11,7 ShiqN+q (t) Next, inorganic sulfur in the amount shown in Table-1 was added to the emulsion used for the 10th layer and 11th layer of Sample-1 above. (α-sulfur) was added by the method shown in Table 1, and/or a DSR compound (and/or coupler) not shown in Table 1 was added in place of the coupler contained in the 10th and 11th layers. Add it in the amount shown in Table-1, otherwise do the same as Sample-1, and Table-1
Samples 2 to 8 shown below were prepared.

Further, samples 9 to 13 having the 8th layer as shown in Table 2 were prepared in the same manner as above for the 8th layer.

Furthermore, samples 14 to 21 having the fourth layer shown in Table 3 were created.

Note that α-sulfur, which is inorganic sulfur, was added as a dilute methanol solution.

0i 7! Each of the samples 1 to 21 prepared in this manner was wedge exposed using bright white light, and then the following development process (A>) was performed.

Development processing (A) Processing process (38℃) Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Washing with water 3 minutes 15 seconds Fixation
6 minutes 30 seconds Wash with water 3 minutes 1
Stabilization for 5 seconds Drying for 1 minute and 30 seconds The composition of the treatment liquid used in each treatment step is as follows.

Color developer> 4-amino-3-methyl-N ethyl-N-(β-hydroxyethyl) aniline, sulfate 4.75 g Anhydrous sulfite Triu J, 4.25 g hydroxylamine, % sulfate 2.0 g Anhydrous potassium carbonate 37.5 g Sodium bromide J
, 1.3g nitrilotriacetic acid.
Trisodium salt (monohydrate) 2.5 g Potassium hydroxide 1.0 g Add water and 17! shall be. (pH = 10.1) <Bleach solution> Ethylenediaminetetraacetic acid iron ammonium salt 100.0 g Ethylenecyaminetetraacetic acid 2 Ammonium salt 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 Add water and 1
7! Close and adjust pH to 6.0 using aqueous ammonia.

Fixer> Ammonium thousand sulfate 175.0 g Anhydrous thorium sulfite 8.5 g Sodium metasulfite 2.3 g Add water to 1
p and adjust the pH to 6.0 using acetic acid.

Stabilizing solution> Formalin (37% aqueous solution) 1.5 Konidasox (manufactured by Konica Corporation) 7.5 Add water to 1
Let it be e.

The fog density and relative sensitivity were measured for each sample obtained.

In addition, each coated sample before development was tested at a temperature of 40°C and a humidity of 80°C.
%R11 and a forced aging test at 55°C with no humidity control, each sample was exposed to white light and subjected to the development process (
A), and the fog density and relative sensitivity were measured for each sample obtained.

The results are shown in Tables 4 to 6. The relative sensitivity was expressed with the sensitivity of sample size 1 as 100.

However, Table 4 shows the results measured as blue density, Table 5 shows the results measured as green density, and Table 6 shows the results measured as red density.

From Tables 4 to 6, samples of the present invention manufactured by adding the DSR compound of the present invention and inorganic sulfur 4 to 810 to 13
It can be seen that small amounts of both N[115-21 and N[115-21] suppress fog, and there is little increase in fog under high-temperature or high-humidity storage conditions, and there is almost no decrease in sensitivity.

Example 2 Sample floors 1 to 21 prepared in Example 1 were exposed in step 1) in the same manner as in Example 1, and then subjected to the following development treatment (B).

Development processing (B) Processing process (40°C) Color development 90 seconds bleaching 6 minutes 30 seconds water washing 3 minutes 15 seconds fixing 6 minutes 30 seconds water washing 3 minutes 15 seconds stabilization 1 minute 30 seconds drying Drying each processing step The composition of the processing solution used in Process (A) was the same as in Process (A) except for the color developing solution described below.

Color developer> 4-amino-3-methyl-N (beta-fluoroxethyl) aniline sulfate 11.1 g Anhydrous sodium sulfite 4.25 g Hydroxylamine %6Mt4JhX 2. Og anhydrous potassium carbonate 30.0 g sulfur bromide
- Lithium 1.3g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5g Potassium hydroxide 1.0g Water was added to make 1p. (pH=10.2) The fog density and relative sensitivity were measured for each sample obtained. The results are shown in Tables 7 to 9.

Relative sensitivity was expressed with Sample-1 as 100.

However, Table-7 is blue density, Table-8 is green density, Table-9
is the result measured as red density.

From Tables-'1 to 9, samples of the present invention in which the inorganic sulfur of the present invention was present during production and the DSR compound was added, even in rapid processing, to No. 4-8, 10-13, and 15.・21
It can be seen that fog is suppressed in both cases.

(Effects of the Invention) According to the present invention, it is possible to provide a silver halide color photographic material in which the increase in fog due to rapid processing, especially rapid color development processing, is significantly reduced. It is possible to provide a silver halide color photographic light-sensitive material that has excellent storage stability under high temperature and high humidity conditions.

Claims (1)

[Claims] 1. A photographic constituent layer containing a silver halide emulsion on a support;
In a silver halide photographic material having at least one photographic constituent layer each containing no silver halide emulsion, at least one of the photographic constituent layers is produced by adding inorganic sulfur, and A silver halide color characterized in that at least one of the constituent layers contains a compound capable of reacting with an oxidation product of a developing agent to scavenge the oxide or a compound capable of releasing a precursor thereof. Photographic material.