JPH02150840A - Silver halide color photographic sensitive material having excellent rapid processing adaptability and preservable property - Google Patents

Abstract

PURPOSE:To suppress the increase of fogging in rapid processing and to improve the preservable property with age by incorporating a specific mercapto compd. into silver halide emulsion adhesive layers and incorporating a compd. which can scavenge oxides by reacting with the oxidation product of a developing agent into hydrophilic protective colloidal layer. CONSTITUTION:This photosensitive material is formed by applying the hydrophilic protective colloidal layers contg. the photosensitive silver halide emulsion adhesive layers on a substrate. The mercapto compd. expressed by the formula I is incorporated into the silver halide emulsion adhesive layers and the compd. which can scavenge the oxides reacting with the oxidation product of the developing agent is incorporated into the hydrophilic protective colloidal layers. In the formula, R<m1> denotes -NHCOR<m3>, -NHSO2R<m4>; R<m1>, R<m4> denote an alkyl group, aryl group; R<m2> denotes a halogen atom, nitro group, cyano group, amino group, sulfo group, etc.; n denotes 0 to 4. The increase of the fogging by the rapid color development processing is decreased in this way and the preservable stability under high-temp. and high-humidity conditions is improved without degrading the 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 invention relates to a silver halide color photographic 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, in order to compensate for the shortening of the development time in the color development process, the concentration of the color developing agent is increased, the PL+ of the color developer is increased, and the color developer is further increased. Techniques such as increasing the temperature have been used. However, rapid processing using the above-mentioned technique has caused a serious problem in that fogging is more likely to occur than in the past.

In order to improve these drawbacks, it has been proposed to add various fog suppressants to light-sensitive materials. In particular, U.S. Pat. Nos. 1,758,576 and 2,304,962.
No. 2,697,040, No. 2.697.09
No. 9, No. 2.824,001, No. 2,476.5
No. 36, No. 2.843,491, No. 3,251.
691, British Patent No. 403,789, British Patent No. 893,
The mercapto compounds described in Japanese Patent Publication No. 428 and Japanese Patent Publication No. 58-9939 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 at high temperatures or under high temperature conditions.

[Purpose of the invention]

An object of the present invention is to provide a silver halide color photograph that can significantly reduce the increase in fog caused by rapid processing, particularly rapid color development processing, and has improved storage stability under high temperature conditions without decreasing sensitivity. Our purpose is to provide photosensitive materials.

[Structure of the invention]

The object of the present invention is to provide a silver halide color photographic light-sensitive material comprising a hydrophilic protective colloid layer containing a light-sensitive silver halide emulsion layer coated on a support, in which a small amount of the silver halide emulsion layer (both One layer contains at least one mercapto compound represented by the following mercapto compound [I], and at least one hydrophilic protective colloid layer reacts with the oxidation product of the developing agent to scavenge the oxide. This achievement was achieved using a silver halide color photographic light-sensitive material characterized by containing a compound capable of releasing a compound or a precursor thereof.

(In the formula, Rm+ is -NlICOR" or -N
11 S O□Ra4 is represented, and R1111 and Ra4 represent an alkyl group and an aryl group, respectively. Also, Rffl
+ represents a halogen atom, nitro group, cyano group, amino group, sulfo group, hydroxy group, alkyl group, aryl group, aralkyl group, cycloalkyl group, alkoxy group, aryloxy group 1. Alkylcarbonyloxy group, arylcarbonyloxy group, carbamoyloxy group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylaminocarbonyl group, arylaminocarbonyl group, acyl group, alkoxycarbonylamino group, acylamino group, ureido group, alkylsulfonylamino group, arylsulfonylamino group, sulfamoylamino group, alkylsulfonyl group,
Arylsulfonyl group, sulfamoyl group, imide group,
Represents an alkylthio group, an arylthio group, a heterocyclic group,
n represents O to 4. ) The present invention will be described in detail below.

First, specific examples of the mercapto compound represented by the general formula [I] to be contained in the photosensitive material of the present invention are shown below.

Examples are RIll and its substitution position, n, R1111
This is done by noting the substitution position.

■ NHCOCII:l N11COCzls NIICOCJt NlIC0CHzCI2 NHCOCII zoll -NllCOCh NIISOzCIll NIICOCIIff NlIC0Czlls NIICOCsllwa to NlIC0C1hC NlIC0CH□011 NtlCOCFi NIISO□CH4 NlC0CII+ NlIC0Czlls NlIC0C113 NlIC0CII□CQ NHCOCII□011 NIICOCF.

Nll5O□C113 NHCOClh NIICOCH:+ NlIC0CII:I NHCOCllff NlIC0CII* NlIC0CII.

NlIC0C113 NlIC0C113 Nl(COCH:l NlIC0CII:I NtlCOCIh NIICOClh NHCOCI13 NtlCOCL l NO□ N N11□ So, 11 O12 CIh 0COC113 0CONIIC113 0O11 -COOCRI CONIICI+:1 NlIC0CII:1 NIICOCHi3 NIICOCHi.

5 - C0C0゜ 5 NlIC0OCII * 5 NHCOCII:1 NIICOC113 -NHCOC) I, 1 Nll5O□CH3 NHCOCIh -NllCOC1h -SO□C113 NlIC0CHz:1 NIICOClh N (COCI+) 2 NIICOClh NIICOCHi 5C41! q NHCOCII:1 NIICOClh:+ NlIC0CIh NlIC0CII+ NlIC0CT.

NlIC0Ctl+ NlIC0CHz NIICOCHi:1 4-C1h, 4 -CH3, NO□ Cg.

NO□ Ce C++Z.

Cl1ff.

5-C1! When there are a plurality of silver halide emulsion layers, the mercapto compound represented by 5-NO-maximum [I] may be contained in at least one of the layers.

Next, in the present invention, means for incorporating a mercapto compound represented by -maximum (+) into a silver halide emulsion layer will be described.

The compound represented by formula [I] may be added to the silver halide emulsion layer at any step up to the formation of the silver halide emulsion layer. For example, before the formation of silver halide grains, during the formation of silver halide grains, after the completion of silver halide grain formation and before the start of chemical sensitization,
Any period may be mentioned, such as the start of chemical sensitization, the end of chemical sensitization during chemical sensitization, and the period between the end of chemical sensitization and the time of coating. 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 application.

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

Further, the chemical sensitization described above can be stopped by a method known in the art. Methods for terminating chemical sensitization are known, such as lowering the temperature, lowering PL+, and using a chemical sensitization stopper, but considering the stability of the emulsion, etc. A method using is preferred. Examples of chemical sensitization stoppers include halides (e.g., potassium bromide, sodium chloride, etc.), organic compounds known as antifoggants or stabilizers (e.g., 4-hydroxy-6-methyl-1,3,3a, 7-TeI Razinden, etc.) are known. These compounds may be used alone or in combination.

The mercapto compound represented by the general formula [1] may be added in the chemical sensitization termination step, but the "chemical sensitization termination step" herein refers to the step of adding the above chemical sensitization termination agent. point to In this case, the mercap 1 to compound represented by -Jlu2[I] may be added as long as it is substantially during the chemical sensitization termination step. Specifically, the addition of the chemical sensitization termination agent is sufficient. At the same time as or +61 fat I 0
This includes the timing of addition within minutes, preferably at the same time or within 5 minutes before or after.

Further, the mercapto compound represented by -maximum [I] can be added after the chemical υ) is completed and before the silver halide emulsion layer is formed.

In addition, the mercapto compound represented by -jG2[I] is
In the light-sensitive material of the present invention, preferably 1XIO-' to 5X10-3 mol, more preferably 5XIO-b to 1x1O-3 mol, most preferably 1
It is preferable that Xl0-' to 5X10-' moles are contained.

The above compound can be added to the photosensitive material as a solution in water, methanol, methyl cellosolve, acetone, or the like, or as an aqueous solution after being solubilized in an anionic surfactant.

Next, in the photographic material of the present invention, a compound or a precursor thereof that is contained in at least one of the hydrophilic protective colloid layers and is capable of reacting with the oxidation product of the developing agent and scavenging the oxide is released. (hereinafter referred to as rDS)
"R compound". ) will be explained. The DSR compound is represented by the following formula (It).

General formula (II) Coup-←Time-)7-3c In the above-maximum (II), Coup can release (Time+-TSc) by reaction with the oxidized color developing agent. Represents a coupler residue, Time represents a timing group that can release Sc after being released from Coup, and Sc undergoes a redox reaction or campling of the oxidized color developing agent after being released from Coup. It represents a scavenger of an oxidized color developing agent or its precursor that can be scavenged by reaction, and l represents 0 or 1.

To further specifically explain the compound represented by the general formula [■], the coupler residue represented by Coup is generally a yellow coupler residue, a magenta coupler residue, a cyan coupler residue, or a substantially colorless coupler residue. It is a coupler residue, preferably a coupler residue represented by the following general formula (llal to l1h).

General formula (Ila) General formula (nb) General formula (IIc) General formula (Ild) 1'' General formula (Ile:1 General formula (Iff) General formula (Ilg) General formula (nh) Above - maximum (na) In the formula, R' represents an alkyl group, an aryl group, or an amino group, and R2 represents an aryl group or an alkyl group.

In the above-maximum [■b], R3 represents an alkyl group, an aryl group, and R4 represents an alkyl group, an acylamino group,
Represents an arylamino group, phenylureido group, or alkylureido group.

In the above-maximum [■C], R4 is the general formula (Ilb)
has the same meaning as R4, and R% represents an acylamino group, a sulfonamide group, an alkyl group, an alkoxy group, or a halogen atom.

In the above maximum (Ild) and (Ice), substituent R7 represents an alkyl group, aryl group, acylamino group, arylamino group, alkoxy group, phenylureido group, or alkylureido group, and Rh represents an alkyl group or an aryl group. represent.

In the above maximum (llf), R9 represents an acylamino group, carbamoyl group, or phenylureido group, and R8 represents a halogen atom, an alkyl group, an alkoxy group, an acylamino group, or a sulfonamide group.

In the above-maximum (Ilg), R9 is of the general formula [■[]
is synonymous with RIG, and RIG represents an amine group, substituted amino group, carbonic acid amide group, sulfonamide group, or hydroxyl group.

In the above-maximum (I[h), R11 is a nitro group, an acylamino group, a succinimide group, a sulfonamide group,
Represents an alkoxy group, an alkyl group, a halogen atom, or a cyano group.

Furthermore, n in the above-mentioned maximum (nf) and [IIh] represents an integer of 0 to 2, and m in the above-mentioned maximum [g] represents an integer of 0 or 1.

Each of the above groups may have a substituent. Preferred substituents include a halogen atom, a nitro group, a cyano group, a sulfonamido group, a hydroxyl group, a carboxyl group, an alkyl group, an alkoxy group, a carbonyloxy group, an acylamino group, and an aryol group.

The lipophilicity exhibited by R1 to RI1 in each of the above-mentioned maximum values can be arbitrarily selected depending on the purpose.

In the case of conventional image-forming couplers, the total number of carbon atoms of R1 to RI+ 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 preferable that R1 to R11 have at least one carboxyl group, ary-sulfonamide group, or alkylsulfonamide group as a substituent.

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 maximum (n), the timing group represented by Time is preferably the following maximum [■i], rllj)
or Cl1k].

-Maximum (Ili) General Formula (IIj) In the formula, B represents an atomic group necessary to complete a benzene ring or a naphthalene ring, and Y is bonded to the active site of the 10-Coup (coupling component). RIS, R1 and R
b2 represents a hydrogen atom, an alkyl group or an aryl group.

R'', and the other is bonded to the above-mentioned maximum (II) Sc.

In the formula, Y, RIZ, and R'3 are each the above-maximum (I[i)
, RIS represents a hydrogen atom, an alkyl group, an aryl group, an acyl group, a sulfone group, an alkoxycarbonyl group, or a heterocyclic residue, and RI6 represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic residue, an alkoxy represents an amino group, an acid amide group, a sulfonamide group, a carboxy group, an alkoxycarbonyl group, a carbamoyl group, or a cyano group.

Further, the timing group represented by the above-mentioned -maximum (II j) is similar to the above-mentioned -maximum (lli), when Y is the above-mentioned -maximum (lli).
II) RIS of Coup (coupling component) Next, Time to release Sc by intramolecular nucleophilic substitution reaction
Examples of the group include those shown below (maximum CInk).

General formula (Uk) -Nu-D-E- In the formula, Nu represents a nucleophilic group having an electron-rich oxygen, sulfur or nitrogen atom, and the - maximum (n) Cou
It is bound to the active site of p (coupling component). E
represents an electrophilic group having an electron-poor carbonyl group, thiocarbonyl group, phosphinyl group, or thiophosphinyl group.

This electrophilic group E is bonded to the heteroatom of Sc, and D
is a steric relationship between Nu and E, and Coup
Represents a bonding group that can break intramolecular nucleophilic substitution by a reaction that involves the formation of a 3- to 7-membered ring after Nu is released from (coupling component), and thereby release Sc. .

Further, scavengers for the oxidized color developing agent represented by Sc include redox type scavengers and coupling type scavengers.

In the general formula (n), when Sc scavenges the oxidized color developing agent by a redox reaction, the Sc is a group capable of reducing the oxidized color developing agent,
For example, Angew, Chem, Int.

Ed, 17875 886 (197B), The
Theory of thePhotographic
Process 4th edition (Macmillan 197
7) Reducing agents described in Chapter 11, JP-A-59-5247, etc. are preferred, and Sc may be a precursor capable of releasing such reducing agents during development. Specifically, (in the formula,
R and R' represent a hydrogen atom, alkyl, cycloalkyl, alkenyl, or aryl group. An aryl group or a heterocyclic group having at least two of ) is preferable, an aryl group is especially preferable, and a phenyl group is more preferable. The lipophilicity of Sc is arbitrarily selected depending on the purpose, similar to the above-mentioned couplers expressed by maximum (Illa) or l1h), but in order to maximize the effects of the present invention, it is necessary to The sum of the numbers is preferably 6 to 50, more preferably 6 to 30,
More preferably, it is 6-20. When the Sc scavenges the oxidized color developing agent by a coupling reaction, the Sc is a substantially colorless coupler residue, and the Sc is a substantially colorless coupler residue, and the above-mentioned efflux dye-forming coupler, bleaching dye-forming coupler, and reactive active site. An -eiss coupler having a non-leaving substituent and not forming a dye can be used.

- Specific compounds represented by maximum (II) include, for example, British Patent No. 1,546,837, JP-A-52-150
No. 631, No. 57-111536, No. 57-1115
No. 37, No. 57-138636, No. 60-18595
No. 0, No. 60-203943, No. 60-213944
No. 60-214358, No. 61-53643,
No. 61-84646, No. 61-86751, No. 61
-102646, 61-102647, 61-
No. 107245, No. 61-113060, No. 61-2
No. 31553, No. 61-233741, No. 61-23
No. 6550, No. 61-236551, No. 61-238
No. 057, No. 61-240240, No. 6124905
2, No. 62-81638, No. 62-205346, No. 62287249, etc.

As Sc, a redox type scavenger can be preferably used, and in this case, the color developing agent can be reused by reducing the oxidized product of the color developing crude drug.

Next, DSR compounds represented by the general formula (U) will be illustrated, but the present invention is not limited to the following exemplified compounds.

SR e DS+? SR DSI? SR SR 5R-8 SR DS+? SR DSrl~15 SR DSrl-12 SR SR SR 5R DS! ? -21 DSI? DSI'l1 DS+? SR SR SR-27 5R SR SR DSr? DS! '1 DSr! SR SR DSr+-36 DSR-38 5R-37 In the photosensitive material of the present invention, the DSR compound is contained in at least one of the hydrophilic protective colloid layers, and therefore the photosensitive silver halide emulsion Although it can be added to the photosensitive silver halide emulsion layer and/or the non-photosensitive photographic constituent layer, it is preferably added to the photosensitive silver halide emulsion layer.

In the present invention, two or more types of DSR compounds can be contained in the same layer. The same DSR compound can also be used with different
It may be included in more than one layer.

When these DSR compounds are contained in an emulsion layer, they are generally contained in an amount of 2X10-' to 5X10-' per mole of silver in the emulsion layer.
-' moles are preferred, more preferably 1 x 10-3 to 1
Xl0-' moles are used.

Further, when it is contained in a non-photosensitive layer, it is preferably contained in a layer adjacent to an emulsion layer, and in this case, it is preferable to use the above amount per mole of silver in the adjacent emulsion layer.

In order to incorporate these DSR compounds into the silver halide emulsion layer constituting the light-sensitive material of the present invention or into the coating solution for other photographic constituent layers, if the DSR compound is alkali-soluble, it may be added as an alkaline solution. If it is oil-soluble, for example, U.S. Pat. No. 2,322,02
No. 7, No. 2,801.170, No. 2,801.1
No. 71, No. 2.272.191 and No. 2,304
, No. 940, it is preferable to dissolve the DSR compound in a high boiling point solvent, optionally in combination with a low boiling point solvent, disperse it in the form of fine particles, and add it to the silver halide emulsion. .

The above DSR compound is disclosed in Japanese Patent Application Laid-Open No. 57-138638,
No. 57-155537, No. 57-171334, No. 58-111941, No. 61-53643, No. 61
-84646, 61-86751, 61-10
No. 2646, No. 61-102647, No. 61-107
It can be synthesized by the method described in No. 245, No. 61-113060, etc.

The silver halide emulsions used in the present invention include conventional silver halide emulsions such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, silver chloroiodobromide, and silver chloride. Any silver bromide can be used, especially silver bromide,
Silver iodobromide and silver chlorobromide are 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 making and growing the seed particles may be the same or different.

In the silver halide emulsion, halide ions and silver ions may be mixed simultaneously, or one may be mixed in a liquid in which the other is present. Further, while taking into account the critical growth rate of silver halide crystals, halide ions and anti-silver ions may be generated by sequentially and simultaneously adding them while controlling the pH and/or pAg in the mixing pot. 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 grains.

Halogen (known silver halide solvents such as ammonia, 1,000-onythyl, and thiourea can be present during the growth of one grain).

During the process of grain formation and/or growth, silver halide grains are produced using cadmium salts, zinc salts, lead salts, thallium salts, iridium salts (including complex salts), rhodium salts (including complex salts), and iron salts ( By adding metal ions using at least one selected from the group consisting of complex salts), these metal elements can be contained inside the particles and/or on the particle surfaces, and by placing them in an appropriate reducing atmosphere. Reduction sensitizing nuclei can be provided inside the particles and/or on the particle surfaces.

Unnecessary soluble salts may be removed from the silver halide emulsion after the growth of silver halide grains is completed, or they may be left contained. 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 formed primarily on the surface (or may be such that the latent image is formed primarily within 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 (100) plane to the (111) plane can be used. Further, the particles may have a composite form of these crystal forms, or particles of various crystal forms may be mixed.

The grain size of silver genide is preferably 0.0
5 to 30 pm, more preferably 0.1 to 2 oA1 m 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). When divided by the average grain size, the value is 0.20 or less.In the case of spherical silver halide, the grain size is the diameter, and in the case of grains with shapes 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. That is, 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 enhancement effect, or a compound that does not substantially absorb visible light, and which enhances the sensitizing effect of the sensitizing dye. Good too.

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,
Alternatively, for the purpose of preventing fog during photographic processing or maintaining stable photographic performance, photographic Compounds known in the industry as antifoggants or stabilizers may 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 formed by using one or more hardeners that 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 (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), activated vinyl compounds (1,3,5-triacroyl -・\kizahydro s-triazine, 1,3-
vinylsulfonyl-2-propatol, etc.), active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine, etc.), mucohalogens Ml (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, 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 ballast group in the molecule, which makes the coupler non-diffusive and has 8 or more carbon atoms. Furthermore, even if these dye-forming couplers are tetraequivalent, in which four molecules of silver ions need to be reduced in order to form one molecule of dye, only two molecules of silver ions need to 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, capri agents, anticapri agents, 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 camping 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 bound in such a way that the inhibitor 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 that undergoes a coupling reaction with the oxidized product of an aromatic primary amine developer but does not form a dye (
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 pivalylacetanilide 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
91,445, West German Patent No. 1,547°868, West German Patent Application No. 2,219,917, West German Patent Application No. 2,261,361
No. 2,414,006, British Patent No. 1,425.0
No. 20, Special Publication No. 51-10783, Japanese Patent Publication No. 47-26
No. 133, No. 4B-73147, No. 50-6341, No. 50-87650, No. 50-123342, No. 50-130442, No. 51-21827, No. 51
-102636, 52-82424, 52-11
No. 5219, No. 5B-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
34゜908, 3,891.445, West German Patent 1
, No. 810,464, West German Patent Application (OLS) 2
, No. 408,665, No. 2,417゜945, No. 2,
No. 418,959, No. 2,424,467, Special Publication No. 4
No. 0-6031, JP-A-49-74027, JP-A No. 49-
No. 74028, No. 49-129538, No. 50-60
No. 233, No. 50-159336, No. 51-2082
6. No. 51-26541, No. 52-42121, No. 52-58922, No. 53-55122, Japanese Patent Application No. 55-110943, 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-ice 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 150°C.
The above-mentioned high-boiling point organic solvent is melted using a low-boiling point and/or water-soluble organic solvent as necessary, and a surfactant is used in a hydrophilic binder such as an aqueous gelatin solution, and a stirrer is used.
homogenizer colloid mill, flowit mixer,
After emulsifying and dispersing it using a dispersing means such as an ultrasonic device, 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 organic compounds with a boiling point of 150°C or higher, such as one phenol that does not react with the oxidized form of the developing agent, alkyl phthalates, phosphates, citric esters, benzoic esters, algylamides, fatty acid esters, and trimesic esters. A solvent is used.

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

When the dye-forming coupler, DIR coupler, colored coupler, DIR compound, image stabilizer, color antifoggant, ultraviolet absorber, fluorescent whitening agent, etc. has an acid group such as carboxylic acid or sulfonic acid, an alkaline aqueous solution is used. It can also be introduced into hydrophilic colloids as a hydrophilic colloid.

Anionic surfactants and nonionic surfactants are used as dispersion aids when dissolving a hydrophobic compound in a solvent alone or in combination with a high boiling point solvent and dispersing it in water using mechanical or ultrasonic waves. , 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 RD No. 17643, Section 2 J.

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 due to formalin 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
The compound is a compound described in Section XXI B to D of No. 17643, and the development retardant is a compound described in Section XXI E of No. 17643. A black and white developing agent and/or its precursor may be used for development acceleration and other purposes.

The emulsion layer of photographic light-sensitive materials is made of polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholines, 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 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. 17643.

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

Such dyes include oxonol dyes, hemionxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes, azo dyes, and the like.

A capping agent can be added to the silver halide emulsion layer and/or other hydrophilic colloid layer of a light-sensitive material for the purpose of reducing the gloss of the light-sensitive material, improving the ease of writing, and preventing the light-sensitive materials from sticking together. Any matting agent can be used, but examples include silicon dioxide, titanium dioxide, magnesium dioxide, aluminum dioxide, barium sulfate,
Examples include calcium carbonate, acrylic acid and methacrylic acid polymers and their esters, polyvinyl resins, polycarbonates, styrene polymers and copolymers thereof, and the like. The particle size of the cloak agent is preferably 0.05 to 10 μm. The amount added is preferably 1 to 300 mg/m.

A lubricant can be added to the photosensitive material to reduce sliding friction.

An antistatic agent can be added to the photosensitive material for the purpose of preventing static electricity. The antistatic agent may be used in the antistatic layer on the side of the support on which the emulsion is not laminated, and the protective colloid layer other than the emulsion layer on the side on which the emulsion layer is laminated with respect to the emulsion layer and/or the support. May be used for. Preferably used antistatic agents are the compounds described in RD 17643 Xm.

The photographic emulsion layer and/or other hydrophilic colloid layer of a light-sensitive material is used to improve coating properties, prevent static electricity, improve slipperiness, emulsification and dispersion, prevent adhesion, and improve photographic properties (development acceleration, hardening, sensitization, etc.). Various surfactants can be used for these purposes.

Supports used in the photosensitive material of the present invention include paper laminated with α-olefin polymers (e.g. polyethylene, polypropylene, ethylene/butene copolymers), flexible reflective supports such as synthetic paper, cellulose acetate, nitric acid Includes films made of semi-synthetic or synthetic polymers such as cellulose, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, and polyamide, flexible supports made of these films with reflective layers, glass, metals, ceramics, etc. It will be done.

After applying corona discharge, ultraviolet irradiation, flame treatment, etc. to the surface of the support as necessary, the photosensitive material can be used directly or to improve the adhesion, antistatic property, dimensional stability, abrasion resistance, hardness, etc. of the support surface. It may be applied through one or more layers 25 to improve antihalation properties, frictional 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 allow two or more types of layers to be applied simultaneously, are particularly useful, but packet coating may also be used depending on the purpose. Further, the coating speed can be arbitrarily selected.

Examples of surfactants include, but are not limited to, natural surfactants such as saponin, nonionic surfactants such as alkylene oxide, glycerin, and glycidol, higher alkylamines, quaternary ammonium salts, pyridine, and others. Cationic surfactants such as heterocycles, phosphoniums or sulfoniums, carboxylic acids, sulfonic acids,
Anionic surfactants containing acidic groups such as phosphoric acid, sulfuric esters, phosphoric esters, amino acids, aminosulfonic acids,
Ampholytic surfactants such as sulfuric or phosphoric esters of amino alcohols may also 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 water washing process, and, if necessary, a stabilizing process, but instead of the process using a bleach solution and the process using a fixer. In addition, a bleach-fixing process can be performed using a one-bath bleach-fixing solution, or a monobath processing process using a one-bath developing, bleach-fixing solution that allows color development, bleaching, and fixing to be performed in one bath. You can also do

In combination with these processing steps, a pre-hardening process, its neutralization process, a stop-fixing process, a post-hardening process, etc. may be performed. In these processes, instead of the color development process, an activator process may be performed in which a color developing agent or its precursor is contained in the light-sensitive material and the development process is performed using an activator solution, or an activator process may be performed in the monobath process. can be applied. Among these processes, typical processes are shown below. (These treatments are carried out as the final step, which is either a water washing process, a water washing process, or a stabilization process.) Color development process - Bleach process Constant fixation process - Color development process - Bleach-fixing process Process/Pre-treatment membrane treatment process - Color development process - Stop fixing process - Washing process - Bleaching process Fixing process - Washing process - Post-hardening process/Color development process - Washing process - Capture color development Development process - Stop process - Bleach process Constant fixation process/Activator process - Bleach-fix process/Activator process - Bleaching process Constant fixation process/Monobath process Processing temperature is usually preferably 10 The temperature is selected to be between 65°C and 65°C, but the temperature may be higher than 65°C. More preferably, the treatment is performed at 25°C to 45°C.

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-toluenesulfonates, and the like.

These compounds are generally used in concentrations of about 0.1 to 30 g per color developer 1β, more preferably about 1 to 15 g per color developer 11.

If the amount added is less than 0.1 g, sufficient color density may not be obtained.

Examples of the aminophenol-based developer include 0-aminophenol, p-aminophenol, 5-aminophenol, and 5-aminophenol.
These include 2-hydroxytoluene, 2-amino-3-hydroxytoluene, 2-hydroxy-3-amino-1,4-dimethylbenzene, and the like.

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

Among them, examples of particularly useful compounds include N,N-dimethyl-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-toluenesulfonate, and the like.

Further, the above color developing agents may be used alone or in combination of two or more. Furthermore, the color developing agent 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 (activator solution) instead of a color developing solution, and the bleach-fixing process is carried out immediately after the alkaline solution treatment.

The color developing solution used in the present invention may contain alkaline agents commonly used in developing solutions, such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium sulfate, sodium metaborate, or borax. It also contains various additives such as benzyl alcohol, alkali metal halides such as potassium bromide or potassium chloride, development regulators such as citrazic acid, and preservatives such as hydroxylamine or sulfites. You may.

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.
or more, and more preferably about 9 to 13.

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

Various chelating agents can be used in combination as metal ion sequestering agents in the color developing solution used in the present invention. For example, as the chelating agent, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid,
-organic phosphonic acids such as hydroxyethylidene-1,1-diphosphonic acid, aminopolyphosphonic acids such as aminotri(methylenephosphonic acid) or ethylenediamine phosphonic acid, oxycarboxylic acids such as citric acid or glyconic acid, 2-phosphonobutane 1, 2.4-) Phosphonocarboxylic acids such as ricarboxylic acids, polyphosphoric acids such as tripolyphosphoric 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 the bleaching agent, a metal complex salt of an organic acid is used, and for example, one in which a metal ion such as iron, cobalt, or copper is coordinated with an organic acid such as polycarboxylic acid, aminopolycarboxylic acid, oxalic acid, or citric acid is used. Among the above organic acids, the most preferred organic acids include polycarboxylic acids and aminopolycarboxylic acids. Specific examples of these include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediamine-N-(β-oxyethyl)-N,
N'N'-triacetic acid, propylene diamine tetraacetic acid,
Examples include nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, dihydroxyethylglycine citric acid (or tartaric acid), ethyl etherdiaminetetraacetic acid, glycol etherdiaminetetraacetic acid, ethylenediaminetetrapropionic acid, and phenylenediaminetetraacetic acid.

These polycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts. These bleaching agents are normally used preferably at 5-450 g/l, more preferably at 20-250 g/l.

In addition to the above bleaching agent, the bleaching solution may contain a sulfite as a preservative, if necessary. Alternatively, it may be a bleaching solution containing an ethylenediaminetetraacetate iron (III) complex salt bleaching agent and a large amount of a halide such as ammonium bromide. 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, Belgian Patent No. 770,9
Various bleaching accelerators described in Japanese Patent Publication No. 10, Japanese Patent Publication No. 45-8836, Japanese Patent Publication No. 53-9854, Japanese Patent Application Publication No. 54-71634 and Japanese Patent Publication No. 49-42349, etc. can be added.

The pH of the bleaching solution is usually 2.0 or higher, but is generally preferably 4.0 to 9.5, preferably 4.0 to 9.5.
5 to 8.0, most preferably 5.0 to 7.0
It is.

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 thiosulfates such as potassium thiosulfate, sodium thiosulfate, and ammonium periosulfate, and thiocyanic acid are used. Typical examples include thiocyanates such as potassium, sodium thiocyanate, and ammonium thiocyanate, thiourea, and thioether. These fixing agents are usually used in an amount of 5 g/j or more, within a soluble range, but generally preferably 70 to 250 g/j! Use with. still,
A part of the fixing agent can be contained in the bleach bath, or conversely, a part of the bleach can be contained in the fixing bath.

The bleaching solution and/or fixing solution includes various pH-reducing solutions such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide. A balancing agent may be contained alone or in combination of two or more. Furthermore, various fluorescent whitening agents, antifoaming agents, or surfactants can be contained. In addition, preservatives such as hydroxylamine, hydrazine, and bisulfite adducts of aldehyde compounds, organic chelating agents such as aminopolycarboxylic acids, stabilizers such as nitroalcohol and nitrates, hardeners such as water-soluble aluminum salts, and methanol. , dimethyl sulfamide, dimethyl sulfoxide, and other organic solvents.

The pH of the fixer is usually 3.0 or higher, but is generally preferably 4.5 to 10, preferably 5 to 9.
．． 5, most preferably 6-9.

Examples of the bleaching agent used in the bleach-fixing solution include the metal complex salts of organic acids described in the above bleaching process, and preferred compounds and concentrations in the processing solution are also the same as in the above bleaching process.

The bleach-fixing solution contains a silver halide fixing agent in addition to the above bleaching agent, and if necessary, a sulfite salt as a preservative. In addition, a bleach-fixing solution consisting of an ethylenediaminetetraacetic acid iron (lI[) complex salt bleach and a small amount of a halide such as ammonium bromide other than the silver halide fixing agent mentioned above, or conversely, a bleach-fixing solution such as ammonium bromide, etc. Bleach-fix solutions containing a large amount of halides, iron ethylenediaminetetraacetate (
[[[] A special bleach-fix solution having a composition consisting of a combination of a complex salt bleach and a large amount of a halide such as ammonium bromide can also be used. In addition to ammonium bromide, the halides include hydrochloric acid, hydrobromic acid,
Lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, and the like can also be used.

Examples of the silver halide fixing agent that can be included in the bleach-fixing agent include the fixing agents described in the above-mentioned fixing process. The concentration of the fixing agent and the pH buffering agent and other additives that can be contained in the bleach-fixing solution are the same as in the fixing process described above.

The pH of the bleach-fix solution is usually preferably used at 4.0 or higher, but for -JG, it is more preferably used at a pH of 5.0 to 9.5, preferably 6.0 to 8.5. , most preferably 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 the examples below, the amount added in the silver halide photographic light-sensitive material is expressed in grams per 1 rrf unless otherwise specified. In addition, colloidal silver halide is shown in terms of grudges.

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

Sample-1 (comparison) 1st layer; antihalation layer (HC-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 (Oi42-1) 0.20 Gelatin 1.5 2nd layer; middle layer (
IL-1) UV absorber (UV-1) 0.01 High boiling point solvent (Oil-1) 0.01 Gelatin
1.5 3rd N; low sensitivity red-sensitive emulsion layer (RI-) silver iodobromide emulsion (Em-1) 0.8
Silver iodobromide emulsion (Em-2) 0.8 sensitizing dye (
SD-1) 2.5X10-' (mol/silver 1 mol) aggravating dye (SD
-2) 2.5X10-' (mol/i 1 mol) sensitizing dye (S
D-3) 0.5xlO-' (mol/i 1 Cyan coupler (C-A) Colored cyan coupler (CC mol) 1.0 0.05 0.002 0.5 1.5 DIR compound (D-1 > High boiling point solvent (Off-1) Gelatin 4th layer; High sensitivity red-sensitive emulsion layer (RH) Silver iodobromide emulsion (Em-3) 2.0 Enhanced dye (SD-1) 2.0X10-' Enhanced dye (SD-2) 2.0X10-' Sensitizing dye (SD-3) 0.1X10-' (mol/silver 1) Cyan coupler (C-A) Cyan coupler (C-B) Colored cyan coupler (CC (mol/ 1 mol of silver) (mol/1 mol of silver) 0.20 0.05 0.015 0.05 0.2 1.5 D[? Compound (D-1) High boiling point solvent (Oif-1) Gelatin 5th layer; Intermediate layer (IL-2) Gelatin 0.5 6th N; Low-sensitivity green-sensitive emulsion layer (GL) Silver iodobromide emulsion (Em-1) 1.0 Sensitizing dye (
SD-4) 5×10-' (mol/1 mole of silver) Sensitizing dye (SD-5) ■×10-4 (mol/mol of silver) Magenta coupler (M-1) 0.1 magenta coupler (M- 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 (Oin-1) 0.3 gelatin
1.0 7th layer; Intermediate layer (IL-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) 2.5XIO-' (mol/silver 1 mol) sensitizing dye (SD
-8) 0.5X10-' (mol/i 1 mol) magenta coupler CM-2) 0.05 magenta coupler (M
-3) 0.15 colored magenta coupler (C
M-2) 0.05 DIR compound (D -, 3) 0.01 High boiling point solvent (Oij2-3) 0.5 Gelatin
1.0 9th layer; yellow filter layer (yc) yellow colloidal silver 0.1 color stain inhibitor (SC-1) 0.1 high boiling point solvent
(Oiffi-3) 0.1 gelatin
0.8 10th layer; low-speed blue-bewitching emulsion layer (B
L) Silver iodobromide emulsion (Em-1) 0.25 silver iodobromide emulsion (Em-2) 0.25 enhancing dye (S
D-10) 7 Xl0-' (mol/i 1 mol) Yellow coupler (Y-A) 0.5 Yellow coupler (Y-B
) 0.1 Antifoggant AF-1 (mercapto compound for comparison) 11th layer shown in Table 1; 12th layer; DIR compound (D-2) 0.01 High boiling point solvent (Oiffi-3) 0. 3 gelatin
1.0 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) 3X10-' (mol/1 mol of silver) Yellow coupler ('r''-A) 0.30 Yellow coupler (Y-B) 0.05 Antifogging Agent Al-1 (comparative mercapto compound) The highest boiling point solvent (O
in-3) 0.15 gelatin
1.1 First protective layer (PRO-1) Fine grain silver iodobromide emulsion average grain size 0.08 μm Ag! 2 mol% 0.4UV
Absorber (UV-1) 0.10UV absorber (
UV-2) 0.05 high boiling point solvent (Oiff
i-1) 0.1 high boiling point solvent (O4l-4)
0.1 Formalin scavenger (1-13-1) 0.5 Formalin scavenger (H3-2) 0.2 Gelatin 1.0 13th layer; 2nd
Protective layer (PRO-2) Surfactant (S U-1) 0.005 Alkali-soluble capping 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 above composition, coating aid S u2, dispersion aid 5u-3, hardening agents 1-1-1 and H-2, and stabilizer 5T-1 were added to each layer.

The emulsion used to prepare the above BsE material is as follows.

2m-1 2m 2m-3 2m Average particle size: 0.46 μm.

Average silver iodide content...7.0 mol%.

Monodisperse (width of distribution 14%) surface Emulsion containing low silver iodide (2 mol%) Average particle size: 0.30μm Average silver iodide content...2.0 mol%.

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

Average silver iodide content...7.0 mol% Monodisperse (width of distribution 14%) surface Emulsion containing low silver iodide (l, 0 mol%) Average particle size: 0.95 μm.

Average silver iodide content...8.0 mol%.

Monodisperse (width of distribution 14%) surface Emulsion containing low silver iodide (0.5 mol%) Optimal chemical sensitization was performed using Monium.

Moreover, the compounds used in the above sample are as follows.

Emulsions Em-1 to Em-4 are composed of sodium thiosulfate (hypo), silver chloride, and ammonium thiocyanate SD SD SD SD-9 SD-10 (Czlls) I+ 5 [(C1l z = Cll5O□C11□)3CCI
I□SO□(Cllz)z] zN(Cl1g)zsO
A containing u-2 a03S CIlCOOCllll + q Cl1zCOOCall+ in s in the 101st and 11th layers of the above sample.
For F-1, Y-A, and Y-B, Samples 2 to 1O were prepared using the combinations shown in Table 1, using mercapto compounds and DSR compounds represented by -maximum [I].

In addition, for the eighth layer, as shown in Table 2, AF-1 or a mercapto compound represented by general formula [I] is used, and for M-2 and M-3, the combinations shown in Table 2 are used. Samples 11 to 19 were created using the DSR compound.

Similarly, for the fourth layer, Samples 20 to 29 were created using the combinations shown in Table 3.

Table (Continued) Table 3 (Continued) Each of the samples 1 to 29 thus prepared was exposed to 7 degrees of white light, and then subjected to the following development treatment (A).

Development processing (A) Processing process (38°C) Color development 3 minutes 15 seconds Bleach 6 minutes 30 seconds Washing with water 3 minutes 15 seconds Fixation
Wash with water for 6 minutes and 30 seconds 3
Stabilization for 1 minute and 30 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 sodium sulfite 4.25 g Hydroxylamine, each sulfate 2.0 g Anhydrous potassium carbonate 37 .5 g sodium bromide
1.3g nitrilotriacetic acid trisodium salt (monohydrate) 2.5g potassium hydroxide 1.0g Add water to make if. (pH = 10.1) <Bleach solution> Ethylenediaminetetraacetic acid iron ammonium salt LOO, Og Ethylenediaminetetraacetic acid diammonium salt 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 d Add water to make 12, Adjust the pH to 6.0 using aqueous ammonia.

<Fixer> Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Add water and if
and adjust the pH to 6.0 using acetic acid.

<Stabilizer> Formalin (37% aqueous solution) 1.5 d
Konidax (manufactured by Konica Corporation) 7.5 d Add water to make IL.

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 8°C.
After conducting a forced aging test at 0%RH1 and 55°C with no humidity control, each sample was exposed to white light and processed in the development process (A), and the fog density and relative Sensitivity was measured.

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

However, Table-4 is blue density, Table-5 is green density, Table-6
is the result measured as red density.

From the table green density table-4 to 6, I) Samples of the present invention using the SR compound and the mercapto compound of the present invention-4 to 10°12
-19 and 21-29 all suppress fog in small amounts, have little increase in fog at high temperatures or under high-temperature storage conditions, and exhibit almost no decrease in sensitivity.

Similar results were also obtained when a DSR compound was added to the adjacent layer. Specifically, DSR-25 in the 8th layer of Sample-12 according to the present invention was added to the 7th layer, and Sample-30 was prepared in which the 8th layer did not contain DSR-25.
When similar evaluations were conducted, the effects of the present invention were obtained.

Example 2 Samples-1 to 29 prepared in Example 1 were exposed 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 process The composition of the processing solution used in the step was the same as that of processing (A) except for the color developing solution described below.

<Color developer> 4-amino-3-methyl-N (β-hydroxyethyl) aniline sulfate 11.1 g Anhydrous sodium sulfite 4.25 g Hydroxylamine `A 6X2 acid salt 2.0 g Anhydrous potassium carbonate 30 .0 g Sodium bromide 1.3 g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5 g
Potassium hydroxide (1.0 g) was added with water to make If. (pl+=10.2) The fog density and relative sensitivity were measured for each sample obtained.

The results are shown in Tables 7 to 9.

The relative sensitivities were each expressed as relative sensitivities with Sample-1 set as 100.

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

Table-8 green density Table-7 blue density Table-9 red density It can be seen that fog is suppressed in both cases.

〔Effect of the invention〕

According to the present invention, it is possible to provide a silver halide color photographic light-sensitive material in which the increase in fog caused by rapid processing, particularly rapid color development processing, is significantly reduced. It is possible to provide a silver halide color photographic light-sensitive material having excellent storage stability.

Claims (1)

[Scope of Claims] 1. A silver halide color photographic light-sensitive material comprising a support coated with a hydrophilic protective colloid layer containing a photosensitive silver halide emulsion layer, at least one of the silver halide emulsion layers. The layer contains at least one mercapto compound represented by the following general formula [I], and at least one hydrophilic protective colloid layer is capable of reacting with an oxidation product of a developing agent to scavenge the oxide. A silver halide color photographic material characterized by containing a compound capable of releasing a compound or a precursor thereof. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^m^1 represents -NHCOR^m^3 or -NHSO_2R^m^4, and R^m^3, R ^m
^4 each represents an alkyl group or an aryl group. In addition, R^m^2 is a halogen atom, a nitro group, a cyano group, an amino group, a sulfo group, a hydroxy group, an alkyl group,
Aryl group, aralkyl group, cycloalkyl group, alkoxy group, aryloxy group, alkylcarbonyloxy group, arylcarbonyloxy group, carbamoyloxy group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylaminocarbonyl group, arylaminocarbonyl group, acyl group, alkoxycarbonylamino group, acylamino group, ureido group, alkylsulfonylamino group, arylsulfonylamino group, sulfamoylamino group, alkylsulfonyl group, arylsulfonyl group, sulfamoyl group, imido group , represents an alkylthio group, an arylthio group, or a heterocyclic group, and n represents 0 to 4. )