JPH01251032A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve the image quality and the color-reproducibility of the title material by incorporating at least one kind of three kinds of compds. of a specified compd., a pyrazoloazole type coupler and a colorless coupler in the sensitive material, respectively. CONSTITUTION:The silver halide photographic sensitive material contains the three kinds of the compds. composed of at least one kind of the compd. shown by formula I, at least one kind of the pyrazoloazole type coupler and at least one kind of the compd. (a colorless coupler) which allows it to react with the oxidant of an aromatic primary amine developing main agent, but does not form a color matter, respectively. In formula I, A is a group capable of being released a group shown by the formula [(L1)l-(B)m]a-(L2)n-DI by allowing it to react with the oxidant of an aromatic primary amine developing agent, L1 is a group capable of being released a binding at the right side of the group L1, after being released a binding at the left side of the group L1, B is a group capable of being released a binding at the right side of the group B by allowing it to react with the oxidant of a developing main agent, L2 is a group capable of being released a binding at the right side of the group L2 after being released a binding at the left side of the group L2. DI is a developing retarder, (l)-(n) are each 0 or 1, (a) is an integer of 0-3. Thus, the color-reproducibility of the sensitive material is improved, and the high image quality of the sensitive material is obtd.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a silver halide color photographic light-sensitive material, and particularly to a silver halide color photographic light-sensitive material for high-quality photography with improved color reproducibility. It is something.

(Prior Art) In recent years, photographic materials have been required not only to have excellent graininess and sharpness, but also to have excellent color reproducibility.

In order to meet these demands, many techniques have been developed to improve graininess, sharpness, and color reproducibility. Graininess and sharpness can be improved by reducing the size of the dye cloud by reducing the size of silver halide grains, using development inhibitors, adjusting coupler activity, etc., and by increasing the number of silver halide grains. Methods such as adding substances that absorb irradiation light, making the film thinner, and using inhibitors to adjust the diffusivity have been developed, but each method has drawbacks and has not been fully effective. .

Furthermore, various techniques have been conventionally proposed for color reproduction of photographic photosensitive materials. For example, yellow filters are usually installed, as well as intermediate layers with different spectral sensitivities, so that the silver halide grains, spectrally sensitized or not, in the photosensitive element exhibit favorable spectral absorption. Hydroquinone derivatives and sulfonamide phenol derivatives are used as color mixing inhibitors. Furthermore, in order to prevent color contamination due to side absorption of coloring dyes in couplers, colored couplers such as well-known yellow colored magenta couplers and magenta colored cyan couplers have been proposed and put into practical use.

However, when these colored couplers are incorporated into color light-sensitive materials, not only does the thickness of the emulsion film increase, but also the color reproducibility is not satisfactory.

Also, a compound that reacts with an oxidized form of a developing agent to release a development inhibitor or a development inhibitor precursor (DIR compound)
using the interimage effect (interlayer effect below, II
A technique for improving color reproducibility by emphasizing (abbreviated as E) is known, and as these L) IR compounds, those of rice plants are used. For example, during development, the flDIR coupler reacts with an oxidized form of a color developing agent to form a coloring dye and releases a development inhibitor. NIIDIR substances that do not form a coloring dye, those that directly release a development inhibitor by reacting with an oxidized form of a color developing agent, and those that release a development inhibitor indirectly, such as those disclosed in Japanese Patent Application Laid-open No. 14-14-14, Same 17-/jQJJ41!
Issue, same Ja! -/12W Pi No. 2, same sr-co 01/1
No. 0, same! Those described in Tar/Ri J6 Hiro No. 3, Tar Co. 04lJ No., Yo Tar Co. 206 rJt, Sai J Tar can be mentioned.

In the present invention V, those exhibiting the above-mentioned DIR effect are collectively referred to as DIR compounds.

When these DIR compounds are used in a silver halide color light-sensitive material, a development inhibitor is released from the DIR compound during development, and the effect of suppressing the development of other silver halide emulsion layers, ie, 1. It is known that DIR compounds which can obtain I, E and in particular release so-called diffusible inhibitory groups or diffusible development inhibitor precursors are particularly effective.

However, in order to improve color reproducibility using only these interlayer effects, it is necessary to improve the side absorption of the coloring dye.

Therefore, as a coupler, a pyrazolotriazole type magenta coupler with low side absorption is used, for example.
- Proposed by Ko74cll and others.

I'm sure this pyrazolotriazole type magenta coupler is a conventional one! - Compared to pyrazolone-based magenta couplers, the color reproducibility was favorable because there was less sub-absorption in the vicinity of Hiro≠onm, and the absorbance on the longer wavelength side than the main absorption was extremely small.

However, even when the couplers described in these patents were used, sufficient color reproducibility could not be obtained.

Therefore, since sufficient effects cannot be obtained using the above-mentioned techniques alone, attempts have been made to combine multiple techniques in hopes of achieving dramatic effects.

For example, JP-A No. 2013 Ko-3 uses a combination of a diffusible colored coupler and a developing agent scavenger, 4J-/JA731 uses a combination of a diffusive DIR compound and a colorless coupler, and JP-A 60-λ6 No./II describes a combination of a DIR coupler and a pyrazoloazole type coupler. However, although these combinations provide partial effects, they do not improve graininess, sharpness, or color reproducibility.

Furthermore, timing DIR compounds are described in JP-A No. 4J-373, but only the graininess and sharpness are described.
There is no description of color reproduction, and the effect as a photographic material is not sufficiently described.

(Problems to be Solved by the Invention) An object of the present invention is to provide a silver halide color photosensitive material that has excellent image quality and sufficiently improved color reproducibility.

(Means for Solving the Problems) An object of the present invention is to provide a silver halogenide photographic light-sensitive material having at least seven hydrophilic colloid layers on a support. at least one type of / pyrazoloazole coupler, and at least one type of compound (colorless coupler) that undergoes a coupling reaction with the oxidized form of the developing agent but does not form a dye. This was achieved by a silver halide photographic material characterized by containing.

In the general formula (I) A+(L1)l-(B)-Ding(L2)n-DI, A reacts with an oxidized form of an aromatic i/class amine developer,
r(Lt)z (B)m)8-(L2)n-DI cleavage group f, represented by Ll represented by general formula (I)
represents a group in which the bond on the right side (bond with (B)m) is cleaved after the bond on the left side of is cleaved; L2 represents a group in which the bond on the left side of L2 shown in general formula (Z) is cleaved and the bond on the right side (bond with DI) is cleaved; DI represents a development inhibitor. Representation, l,
m and n each represent O'' or /, and a represents an integer from O to 3. Here, when a is plural, three (L1
)l-(H)m each represent the same or different.

As mentioned above, the silver halide photographic light-sensitive material of the present invention (hereinafter abbreviated as "photosensitive material") comprises a compound of general formula (I),
It contains at least/more than three types of pyrazoloazole couplers and colorless couplers.

The silver halide emulsion layer contained in this light-sensitive material is most commonly composed of three types of emulsion layers on a support that are selectively spectrally sensitized to have sensitivity to blue light, green light, and red light. and a plurality of non-photosensitive hydrophilic colloid layers (including an intermediate layer).

The three types of photosensitive emulsion layers may be applied in any order when viewed from the support side. Further, each emulsion layer having the same color sensitivity may be separated into a plurality of emulsion layers having different sensitivities and containing diffusion-resistant couplers that develop substantially the same hue, preferably separated into λ or three emulsion layers. It is something that Examples of layer configurations include the following. High sensitivity of each light-sensitive silver halide emulsion layer in the red-sensitive silver halide emulsion layer, green-sensitive silver halide emulsion layer, and blue-sensitive silver halide emulsion layer (sequential layer configuration) coated sequentially on the support. A silver halide emulsion layer and a low-sensitivity silver halide emulsion layer are separated, and these layers are stacked adjacent to each other. Including this normal layer structure, Tokukai Sho! /-419027, Tokukai Sho! 3-
The object of the present invention can be achieved with any of the reverse layer configurations described in Tough 4t Co. A non-photosensitive hydrophilic colloid layer (intermediate layer) can be arbitrarily provided between emulsion layers having different color sensitivities, or between emulsion layers having substantially the same color sensitivity but different sensitivities. In the present invention, a compound that undergoes a coupling reaction with an oxidized developing agent but does not form a dye (referred to as a colorless coupler) may be added to any layer, but is preferably added to the most sensitive emulsion layer of each color-sensitive emulsion layer. It can be added to the emulsion layer with the highest sensitivity, or it can be added to the intermediate layer adjacent to the most sensitive emulsion layer. This intermediate layer may be located on either side far from or near the emulsion layer when viewed from the support.

Further, the addition position L of the compound of general formula (I) in the present invention
When there are a plurality of color-sensitive layers, it is sufficient to add it to one of the layers, but the effect will be even greater if it is used in a plurality of the same color-sensitive layers.

When there are a plurality of same color sensitive layers and it is added only to the - layer, it is preferable to use it in the layer with the largest amount of silver.

The amount added is /XIO'~koXl0 per mole of silver.
-2 mol is preferred.

The compounds used in the present invention will be explained below.

The compound represented by general formula (I) will be described.

(I) A+(Lx)z (B)m+T(Lz)n
In the DI formula, A reacts with the oxidized product of an aromatic primary amine developer to form {(L1)l (B)m), (Lz)
n DI represents a group that cleaves, and Ll represents the general formula (
Represents a group in which the bond on the right side (bond with (B)m) is cleaved after the bond on the left side of Ll shown in I) is cleaved, and B reacts with the oxidized product of the developing agent to form a group in the general formula (I). The bond on the right side of B shown represents a group that is cleaved, and Lz is the general formula (I)
After the bond on the left side of Lz is cleaved, the bond on the right side (
DI represents a development inhibitor, L, m and n each represent 0 or 1, and a represents an integer from O to 3. Here, when a is plural, a number of (Lx)z (B)m each represent the same thing or different things.

The reaction process in which the compound represented by the general formula (I) releases DI during development is represented by the following reaction formula, for example.

An example when 3=/ is shown.

(Lz)n-DI DI where A, Ll, B, Lz, DI, 1. m and n represent the same meanings as explained in general formula (I), and T
@ means an oxidized developing agent.

Next, the compound represented by the general formula (I) will be explained in detail below.

In general formula (I), A specifically represents a coupler residue or a redox group.

Examples of the coupler residue represented by A include yellow coupler residues (e.g., open-chain ketomethylene type coupler residues such as acylacetanilide and malondianilide), magenta coupler residues (e.g., t-pyrazolone type, pyrazolotriazole type, or pyrazolone type). cyan coupler residues (e.g. phenol type, naphthol type or imidazole type coupler residues as described in European Published Patent No. 2, Hiro! 3), and colorless coupler residues. groups such as coupler residues of the indanone or acetophenone type. Also, US Patent No. ≠, 31! , No. 070, No. 4, /1
No. 3,712, 44. /717゜ri6ri, 閤3.
ri 6/, ri 12 or the same da.

It may also be a heterocyclic coupler residue described in No. 17/, No. 223.

When A represents a redox group, the redox group is a group that can be cross-oxidized by an oxidized developing agent, such as hydroquinones, catechols, pyrogallols, /,
Hirosu-7tohydroquinones, /,-naphthohydroquinones, sulfonamide phenols, hydrazide @ or sulfonamide naphthols are mentioned.

These groups are specifically described in, for example, JP-A-4/-230/3.
! No. 62-λ! 17g No. 6, 4/- Core RTR Co., U.S. Patent 8gJ, J Otohiro, O Coco No. 3.37.

No. 122, 3.632. l/7, same≠, Arg, t
o4L issue or J, Org, Chem,,2ri,! rr
(It is described in Irit4ri.

In the general formula (I), the linking groups represented by Ll and Lz are described, for example, in U.S. Pat.
612. ! No. /B or No. ≠, Buri r, a group utilizing the hemiacetal cleavage reaction described in No. 227, US Patent WIJII, 2μ? , a timing group that causes a cleavage reaction using an intramolecular nucleophilic reaction described in No. 42,
US Patent @U.

≠No. 02,323 or Dohiro, ≠2/, a timing group that causes a cleavage reaction using an electron transfer reaction as described in US Pat. No. 4<, j≠t, No. 073 Examples include a group that causes a cleavage reaction using the hydrolysis reaction of iminoketal, or a group that causes a cleavage reaction using the hydrolysis reaction of an ester described in West German Published Patent Application No. 2.6, No. 377. . Ll and Lz are bonded to A or A (Lx)z (B)m, etc., respectively, at a heteroatom contained therein, preferably an oxygen atom, a sulfur atom, or a nitrogen atom.

- The group represented by B in Monka (I) is A-(Lt)
A group that becomes a redox group or a coupler after being cleaved from z, and these terms have the same meanings as explained above for A. The group represented by B has a group that reacts with the oxidized developing agent and leaves the group (that is, a group that is bonded to the right side of B in the -pattern hole (I)). The group represented by B is, for example, the group represented by B in JP-A J-1j j 0, the group represented by C0UP (B) in US Patent No. ≠, IAJI, /23, or the group represented by C0UP (B) in US Patent No.
,/r.

Examples include the group represented by RED in No. 17/.

B is a petro atom contained therein, preferably an oxygen atom,
It is preferable to bond to A-(Lt)z at a sulfur atom or a nitrogen atom.

- In the pattern (I), the group represented by I) is, for example, a tetrazolylthio group, a thiadiazolylthio group, an oxadiazolylthio group, a triazolylthio group, a benzimidazolylthio group, a benzthiazolylthio group, a tetrazolylseleno group. group, benzoxazolylthio group, benzotriazolyl group, triazolyl group or penzoindazolyl group. These groups are described, for example, in U.S. Patent No. J, 227.1
1≠ issue, same j, jl'l, 6!7 issue, same J, tit, r
Q6 issue, same! , 617. Kota No. 1, same j, 733゜ro
No. i, 3; ri JJ, No. J-00, 3. the law of nature! r, Tata No. 3, same 3. Rij/, Ri! No., same≠.

L geta, rtrt issue, same gu, co! ri, ≠ No. 37, same < t
, oyz, yrt issue, Douhiro,! 77, JtJ or British Patent No. 1. HirojO9 Hiro7! This is what is listed in No. P.

Next, preferred ranges for the compound represented by general formula (I) will be explained.

In the formula, a is preferably O to C.

In the formula, preferred examples of the linking groups represented by Ll and L2 include a methyleneoxy group, a Hiro-methylene-3-pyrazolyloxy group, a λ (or ≠)-methylenephenoxy group, and a λ-carbonylaminomethylphenoxy group. These oxygen atoms are connected to the left bond of Ll or L2 of -Moretsu (I). These monovalent groups may also have a substituent at a substitutable position (for example, on the methylene group or benzene ring), and typical examples of the substituent are alkyl groups (for example, methyl, ethyl, inopropyl, dodecyl ), acyl groups (e.g. hachenzoyl,
acetyl), alkoxy groups (e.g. methoxy, ethoxy), alkoxycarbonyl groups (e.g. methoxycarbonyl, butoxycarbonyl), carbamoyl groups (e.g. ethylcarbamoyl), nitro groups, carboxyl groups, sulfonyl groups (e.g. methanesulfonyl), aryl groups (e.g. , t≠-nitrophenyl, ≠-carboxyphenyl)
, a halogen atom (eg, chloro atom, furan atom), or a sulfamoyl group (eg, butylsulfamoyl).

- The compound represented by the pattern (I) is preferably a diffusion-resistant type, and particularly preferably, the diffusion-resistant group is AlLl or L
This is a place included in 2.

- Particularly preferred compounds in Monka (I) are those in which A represents all coupler residues.

- Particularly preferred compounds in Monka (I) are t=/, m
=0. When a=/ and n=/, t;/, m=/, a=
/and when 11=17, 1=o.

When m=i, a=/ and n=/, or 1=o.

m''/, when a=ko and n=o.

- Examples of the compound represented by Monana (I) and the synthesis method for the general formula (I), A, Ll, B, L2, and DI are known patents or documents cited for explanation, JP-A-63- ,? 7.7≠2 and same t/-/j
It is indicated by the tl core number.

(Compound Example) (Co) (/Co) NH8O2CH3 (Co1) rl C'(-≠) C12H25 (Co3) The pyrazoloazole coupler according to the present invention is preferably represented by the following general formula [A]. It will be done.

- Monna [Al] In the general formula [A], Ro represents a hydrogen atom or a substituent, and ■ represents a hydrogen atom or a group that can be separated by a coupling reaction with an oxidized aromatic primary amine developer. , Za, Zb and Zc represent methine, substituted methine, =N- or -NH-, and the Za-Zb bond and Z b -Z
One of the c bonds is a double bond and the other is a single bond. The case where the zb-Zc bond is a carbon-carbon double bond includes the case where it is part of an aromatic ring. It may be bonded with Ro or ■ to form a multimer of tetramer or more, and when Za, Zb or Zc is a substituted methine, it may be bonded with the substituted methine to form a multimer of dimer or more. It may be formed.

Next, a magenta dye-forming coupler coated with general formula (Al) will be described below.

- In Monna (A), the term "multimer" means one having λ or more groups represented by the general formula (A) in one molecule, and this also includes bis-forms and polymer couplers. Here, the polymer coupler may be a homopolymer consisting only of a monomer having a moiety represented by the general formula [A] (preferably one having a vinyl group, hereinafter referred to as vinyl monomer), or a homopolymer consisting only of a monomer having a moiety represented by the general formula [A] (preferably one having a vinyl group, hereinafter referred to as vinyl monomer), or A copolymer may be prepared with an oxidized product of a grade amine developer and a non-color-forming ethyl/one-like monomer that does not compile.

Among the pyrazoloazole magenta couplers represented by the general formula (A), preferred ones are as follows:
a), (I-b), (I-c), CI-d), (I-e
), CI-f) and (■-g).

CI-a) (I-b) (I-c) CI-d) (I-e) (
If) (I-g) Among the couplers represented by general formulas (I-a) to (1-g), preferred ones for the purpose of the present invention are general formula (1-a).
, (r-d) and (r-e), more preferred are those represented by general formulas (1-a) and (1-e).

- Monna (1-a) ~ (1-g) K Oite, R51
, 152 and R may be the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, an alkoxy group, an arylox group, a heterocyclic oxy group, an acyloxy group, a carbamoyloxy group. group, silyloxy group, sulfonyloxy group, acylamino group, anilino group, ureido group, imide group, sulfamoylamino group, carbamoylamino group, alkylthio group, arylthio group, heterocyclic thio group, alkoxycarbonylamino group, aryloxycarbo group Represents a dinylaξ group, a sulfonamido group, a carbamoyl group, an acyl group, a sulfamoyl group, a sulfonyl group, a sulfinyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, and ■ represents a hydrogen atom, a halogen atom, a carboxy group, or Represents a group that bonds to a carbon at a coupling position via an oxygen atom, nitrogen atom, or sulfur atom, and is a group that is decoupled. R, R, R, or V may form a divalent group, ie, a cibis form.

It may also be in the form of a polymer coupler in which the coupler residues represented by the holes (I-a) to (I-g) are present in the main chain or side chain of the polymer, particularly in the form of a vinyl having a portion represented by the holes. Polymers derived from monomers are preferred;
In this case, R%R1R53 or ■ represents a vinyl group or a linking group.

More specifically, R1R1 and R are each hydrogen atom, halogen atom (e.g. chlorine atom, bromine atom), alkyl group (e.g. methyl, isopropyl, 5eC-butyl, isobutyl, ethyl, cyclohexyl, 2-pentyl, 3
-hebutyl, propyl, t-butyl, trifluoromethyl, tridecyl, J-(2,g-di-t-amylphenoxy)propyl, λ-dodecyloxyethyl, 3-phenoxypropyl, cohexylsulfonyl-ethyl , cyclopentyl, benzyl), alkenyl groups (e.g. allyl, octadecenyl), ary-A4'(ff'll,
t, phenyl, ≠-1-butylphenyl 1.2. ≠−
di-t-amylphenyl, ≠-tetradecanamidophenyl), heterocyclic groups (e.g. cofuryl, 2-thienyl, λ-pyrimidinyl, 2-benzothiazolyl), cyan groups, alkoxy groups (e.g. methoxy, ethoxy, comethoxyethoxy , 2-dodecyloxyethoxy, 2
-methanesulfonylethoxy), aryloxy groups (e.g., phenoxy, λ-methylphenoxy, +-1-butylphenoxy), heterocyclic oxy groups (e.g., copenzimidazolyloxy), acyloxy groups (e.g.,
acetoxy, hexadecanoyloxy), carbamoyloxy groups (e.g., N-phenylcarbamoyloxy,
N-ethylcarbamoyloxy), silyloxy groups (e.g., trimethylsilyloxy), sulfonyloxy groups (e.g., eva, dodecylsulfonyloxy), acylamine groups (e.g., acedoide, benzamide, tetradecaneamide, α-(, z, IIL- di-t-amylphenoxy)butyramide, r-(j-t-butyl-hiro-hydroxyphenoxy)butyramide, α-(<=-(4t
-hydroxyphenylsulfonyl)phenoxy)decaneamide), anilino groups (e.g., phenylamino, -chloroanilino, λ-chloro-tetradecanamideanilino, λ-chloro-dodecyloxycarbonylanilino, N-acetylanilino) , λ-Kuroro-
(α-(3-t-butyl-Hiro-hydroxyphenoxy)
dodecanamide) anilino), ureido groups (e.g. phenylureido, methylureido, N,N-dibutylureido), imide groups (e.g. N-succinimide, 3
-penzylhydantoinyl, ≠-(2-ethylhexanoylamine)phthalide), sulfamoylamino group (e.g., N,N-dipropylsulfamoylamino,
N-methyl-N-f silsulfamoyl ε)), alkylthio groups (e.g. methylthio, octylthio, tetradecylthio, cophenoxyethylthio, 3-phenoxypropylthio, 3-(+-t-butylphenoxy)
propylthio), arylthio groups (e.g. phenylthio, copoxyj-1-octylphenylthio, 3
-pentadecylphenylthio, 2-rupoxyphenylthio, hiro-tetradecanamidophenylthio), heterocyclic thio groups (e.g., λ-benzoteazolylthio), alkoxycarbonylamino groups (e.g., methoxycarbonylamino, tetradecyl (oxycarbonylamino), an oxycarbonylamino group (e.g., phenoxycarbonylamino, λ).

≠-di-tert--j tylphenoxycarbonylamino), sulfonamide groups (e.g., methanesulfonamide, hexadecanesulfonamide, benzenesulfonamide, p-1 luenesulfonamide, octadecanesulfonamide, -1methylo?7 -j-1-duthylbenzenesulfonamide), carbamoyl groups (e.g., N-ethylcarbamoyl, N,N-dibutylcarbamoyl, N-(2-dodecyloxyethyl)carbamoyl, N-methyl-N-dodecylcarbamoyl, N −(3
-(2゜μm di-tert-amylphenoxy)propyl)carbamoyl), acyl groups (e.g. acetyl, (
x, p-di-tert-amylphenoxy)acetyl,
benzoyl), sulfamoyl groups (e.g. eva, N-ethylsulfamoyl, N,N-dipropylsulfamoyl,
N-(2-dodecyloxyethyl)sulfamoyl, N
-ethyl-N-dodecylcarbamoyl, N,N-diethylsulfamoyl), sulfonyl groups (fetid', methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl), sulfinyl groups (e.g., t
For example, octane sulfinyl, dodecyl sulfinyl group,
phenylsulfinyl), alkoxycarbonyl groups (e.g. methoxycarbonyl, butyloxycarbonyl,
(dodecylcarbonyl group, octadecylcarbonyl), aryloxycarbonyl group (e.g., phenyloxycarbonyl, 3-ba/tadecyloxycarbonyl), and ■ represents a hydrogen atom, a halogen atom (e.g., chlorine, bromine, iodine). ), a carboxy group, or a group linked via an oxygen atom (e.g., acetoxy, propanoyloxy, benzoyloxy, λ, <2-dichlorobenzoyloxy,
Ethoxyoxaloyloxy, pyruvinyloxy, cinnamoyloxy, phenoxy, goonanophenoxyl, t-methanesulfonamidophenoxy, μm methanesulfonylphenoquino, α-naphthoxy, 3-tadecyloxy, benzyloxycarbonyloxy , ethoxy, 2-cyanoethoxy, be/zyloxy, 2-7enethyloxy, -monophenoxyethoxy/, terphenyltetrazolyloxy, λ-benzothiazolyloxy),
Groups linked via a nitrogen atom (e.g., benzenesulfonamide, N-ethyltoluenesulfonamide, butafluorobutanamide, λ, 3゜a, r, i-<ntafluoropenzamide, octanesulfonamide, p-cyanophenyl ureido, N,N-diethylsul7amoylamino, l-piperidyl, j,j-dimethyl-2,≠-dioquine-3-oxazolidinyl, l-benzyl-ethoxy-3-hydantoinyl, 1N-/,/-dioxo-J(
,2H)-oxo-/,2-benzinotiazolyl,2
-Okin-/, J-dihydro/-pyridinyl, imidazolyl, pyrazolyl, 3゜j-diethyl-7,λ, Hiro-
triazol-1-yl, j- or t-promobenzo) l) azol-/-yl, j-methyl-/, 2,
3. ≠-triazole/-yl, benzimidazolyl, 3-benzyl-7-hydantoinyl, /-benzyl-
Yo-hexadecyloxy-3-hydantoinyl! -methyl/-tetrazolyl), arylazo groups (e.g.
dermethoxyphenylazo, ≠-pivaloylaξnophenylazo, conaphthylazo, 3-methyl-≠-hydroxyphenylazo), groups linked via a sulfur atom (e.g., phenylthio, λ-carboxyphenylthio, -1methoxyj-1- Octylphenylthio, Hiro-methanesulfonylphenylthio, ≠-octanesulfonamidophenylthio, coptoxyphenylthio, λ-(-1hexanesulfonylethyl)-1-tert-octylphenylthio, benzylthio, 2-cyanoethylthio, l
-ethoxycarbonyltridecylthio, j-phenyl-
2, 3, 4! , J-tetrazolylthio, λ-benzothiazolylthio, 2-dodecylthio-yo-thiophenylthio, l-phenyl-3-dode/ru/, 2. ≠-triazolyl-yo-thio).

In the couplers of general formulas (1-a) and (1-b), R and R may be combined to form a negative to 7-membered ring.

When R51, R52, [153 or V becomes a divalent group to form a bis body, preferably r(, R.

R53 is a substituted or unsubstituted alkylene group (e.g., methylene, ethylene, i, to-decylene, -CH2CH
2-0-CH□CH2-), substituted or unsubstituted phenylene group (e.g. /, 'A-)unicine, -NHCO
-R54-CONH- group (R54 represents a substituted or unsubstituted alkylene group or phenylene group, for example -N
HCOCH2CH2CONH-1-3-R55-3- group (R55 represents a substituted or unsubstituted alkylene group,
For example, -3-CI-12CI-12-8-1■ represents the above seven-valent group converted into a divalent group at an appropriate position.

General formula (1-a), (r-b), ([-C), (I-d
), (I-e), CI-f) and (l-g) when the vinyl monomer contains R%R1R
or V is an alkylene group (substituted or unsubstituted alkylene group, for example, methylene, ethylene, /, IO-decylene, -CH2CH20CH2
CH2-), phenylene group (substituted or unsubstituted phenylene group, examples: t, /, ≠-phenylene, /, J-
Phenylene, -N HC0-1-CONJI-1-〇-1-OCO-
and an aralkylene group (for example, includes a group formed by combining

Preferred linking groups include the following.

-NHCO-1-CH2CH2-1 -CH2CH2-0-C- -CONH-CH2CH2NHCO-1-CI-IC
H0-CH2C)12-NHCO-1 The vinyl group has the general formula (1-a), (I-b), (1-C), (1-d'
), (I-e), (1-f), or (1-g) may have substituents □, and preferred substituents are hydrogen atoms, chlorine atoms, or carbon atoms/~≠ represents a lower alkyl group (eg methyl, ethyl).

- Monen (1-a), (1-b), (1-C), (1-
d), (1-e), (I-f) and (l-g) are non-chromogenic ethylene monomers that do not couple with the oxidation products of aromatic-grade amine developers. A copolymer may be made with similar monomers.

Acrylic acid, α
- Chloroacrylic acid, α-alkylacrylic rR (such as methacrylic acid) and esters or amides derived from these acrylic acids (such as acrylamide, n-butylacrylamide, t-butylacrylamide, diacetone acrylamide, methacrylamide, methyl Acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl acrylate, 1So-butyl acrylate, coetherhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and β -hydroxymethacrylate), methylenebisacrylamide, vinyl esters (e.g. vinyl acetate,
(vinylpropionate and vinyllaurate), acrylonitrile, methacrylaterile, aromatic vinyl compounds (e.g. styrene and its derivatives, vinyltoluene, divinylbenzene, vinylacetophenone and sulfostyrene), itaconic acid, citraconic acid, crotonic acid, vinylidene chloride , vinyl alkyl ether (e.g. evavinylethyl ether), maleic e, =water maleic acid, maleic acid ester, N-vinyl-λ-pyrrolidone, N-vinylpyridine, and 2- and gouvinylpyridine. Two or more kinds of the non-color-forming ethylenically unsaturated monomers used here can also be used together. Examples include n-butyl acrylate and methyl acrylate, styrene and methacrylic acid, methacrylic acid and acrylamide, methyl acrylate and zuacetone acrylamide, and the like.

As is well known in the polymeric color coupler art, the non-chromogenic ethylenically unsaturated monomers to be copolymerized with the solid water-insoluble monomeric coupler depend on the physical and/or chemical properties of the copolymer formed, e.g. solubility, compatibility of the photographic colloidal composition with binders such as gelatin, its flexibility,
It can be selected so that thermal stability etc. are favorably influenced.

The marker coupler may be water-soluble or water-insoluble, but polymer coupler latex is particularly preferred.

As mentioned above, among the pyrazoloazole magenta couplers represented by the general formulas (1-a) to (1-g), particularly preferred are those represented by the general formulas 2N-d) and (I-e). . - Substituent R5 of pyrazoloazole magenta coupler represented by Monka (I-d) and (1-e)
1, R52 and V, R51 is preferably an alkyl group, aryl group, alkoxy group or aryloxy group, R52 is preferably an alkyl group, aryl group, alkylthio group, arylthio group or heterocyclic thio group,
(2) is preferably a halogen atom, an aryloxy group, an alkylthio group, an arylthio group or a heterocyclic group. Further, R is preferably an alkyl group, especially the following -Momona CXV
) is particularly preferred.

General formula [XV] L, R55 In the general formula [X Sulfonamido) phenyl, ≠-[2-(<'-
(≠-Hydroxyphenylsulfonyl) phenoxycotetradecanamide, Hiro-methanesulfonamidophenyl, phenyl], sulfonamide groups (e.g. [Hiro-dodecylbenzenesulfonamide, Hiro-tetradecyloxyhenzenesulfonamide, hexadecanesulfonamide,
j-(u-octyloxy-t-4-octylbenzenesulfonamide)-2-octyloxybenzenesulfonamide, toluenesulfonamide), carbonamide groups (e.g. benzamide, a-[r-(J,≠-jit)
-Nitylphenoxy)butanamide]benzamide,
3-dodecanesulfonamidobenzamide), arylsulfonyl group [e.g. ehahensensulfonyl, toluene/L/*2/l/, u-tofyloxybenzenesulfonyl, p-(≠-dodecyloxybenzenesulfonamito)benzenesulfonyl , λ-butoxyj-1
-octylbenzenesulfonyl, "F'ysylbenzenesulfonyl) or alkylsulfonyl group (e.g., t
Jf mepsulfonyl, tecansulfonyl, toticansulfonyl, tetradecanesulfonyl, hexadecanesulfonyl, octadecanesulfonyl, λ-ethylhexanesulfonyl, cohexyldecasulfonyl, 3-dodecyloxyprononesulfonyl, cyclohexanesulfonyl, λ-toticansulfonyl Ethanesulfonyl, α-
Toluenesulfonyl) ヲTable h-j.

Specific examples of the maze/dye-forming coupler represented by the general formula (A) used in the present invention are shown below, but the present invention is not limited thereto.

-j -A A-r 8-ta-8-/ / A-/, 2 A-/# A-/! A-/J A-/7 -1t A-/riA-1 DaA-kot -J7 -Jl A-2? A-30 A-3/ -JJ -ju NO□ -The magenta coupler represented by the hole [A] is produced by Tokukai Sho! Tar/6 Koj Hiro issue, same! U.S. Pat. J, No. 726,067, No. 31 3r, Oij No.
Same a,, ztIi, itr issue, around, 3j/, Iri issue 7, 4≠, 367.222 issue, same'l, j'IO, Ajl
It can be synthesized by the method described in No. 1, WO-16-IRIJ, etc., or by a method analogous thereto.

The amount of the polymer coupler synthesized through a polymerization reaction using a chain transfer agent used in the present invention and the coupler represented by the pattern (A) added to the photosensitive material is as follows: photosensitive material/m
The range is preferably from /X10 mol to lX'10-1 mol, particularly preferably from lxl0-6 mol to /x10 mol.

Further, although the above-mentioned couplers used in the present invention can be added to all layers of the light-sensitive material, it is preferable to add them to the emulsion layer. The emulsion layer may be divided into high-speed, medium-speed, low-speed, etc. layers, and they can be added to various layers in consideration of other performances. Furthermore, an inversion layer structure in which the arrangement of the high-speed layer and the low-speed layer is reversed, or a layer structure in which the high-sensitivity layers among the red-sensitive layer, green-sensitive layer, and blue-sensitive layer are arranged in the order of distance from the support may be adopted.

It is of the type. In addition, when the colorless coupler of the present invention is added to an emulsion layer, the amount is 1xio' to -0θ mol per 1 mol of the coloring coupler contained in the emulsion layer, and the amount is 1xio' to -0θ mol in a hydrophilic colloid layer other than the emulsion layer. When added to /, 0X
Preferably, it is 10 to 7.0 x 10'' mol/m2.

In the colorless coupler according to the present invention, the compound belonging to ill can be represented by the following general formula (B).

General formula (B) CO or UPl-8QL BALL In the formula, C0UPl represents a coupler core having a coupling site (asterisk), BALL binds to the coupling site of C0UP 1, and #i*COU P 1 It is a group that can be separated from pcOUPt by a reaction with an oxidized product of a color developing agent, and it is a stable group having a size and shape that makes the compound of -Moretsu (B) resistant to diffusion. And SQ
L is a solubilizing group, which binds to the non-force-spring position of C0UP 1, and allows the coupling product produced by the coupling of C0UP 1 and the oxidized color developing agent to be released from the light-sensitive material during or after color development processing. It is a group that provides mobility to flow out.

C0UP! The coupler core represented by is any compound known or used in the art that forms a colored or colorless reaction product through a coupling reaction with an oxidized color developing agent. Coupler cores can be mentioned. For example, yellow dye-forming coupler cores are acylacetanilides, such as acetoacetanilides and benzoylacetanilides, and magenta dye-forming coupler cores are pyrazolones, pyrazolotriazoles, pyrazolobenzimidazoles, and indasilones. The coupler core for cyan dye formation includes phenols and naphthols.

HALL is a stabilizing group having a molecular size and shape that makes the compound of general formula (B) diffusion resistant.
) Useful groups represented by BALL include, but are not limited to, alkyl groups having 1 to 3 carbon atoms, aryl groups, and heterocyclic groups, as long as they impart diffusion resistance to the compound. It will be done. These groups represent unsubstituted or substituted groups, and as substituents, they increase the diffusion resistance of the compound of general formula (B), and
This is a group that changes the reactivity of the compound or causes a coupling reaction and increases the diffusivity of BALL after separation. Furthermore, BALL is preferably bound to the coupling site of C0UPl via a linking group. Typical linking groups include oxy (-0-), thio (-8-), carbonyloxy (-0CO-), and sulfonyloxy (-O
SO2-), amide (-NHCO-), sulfonamide (-NH8O2), and the like.

Preferred examples of BALL include an alkoxy group having an alkyl group and/or an aryl group having a total carbon number of t to 3λ, an aryloxy group, a heterocyclic oxy group, an alkylthio group,
Arylthio group, heterocyclic thio group, arylazo group, alkoxy group, alkylsulfonyloxy group, arylsulfonyloxy group, acylamino group, alkylsulfonamide group, arylsulfonamide group, or nitrogen-containing heterocyclic group (pyrrole, pyrazole, imidazole) , triazole, tetrazole, indole, indazole,
Benzimidazole, benzotriazole, 7-talimide, succinimide, Ko, Hiro-imidazolidinedione,
, Hiro-oxazolidinedione, 2.4t-thiazolidinedione, triacylidine-J, j-dione, etc.).

The cIT solubilizing group represented by SQL is a group that imparts mobility to a coupling product generated by a coupling reaction to the extent that it can flow out of the light-sensitive material system, such as an ionizable hydroxyl group, carboxyl group, sulfo group, and amino group. sulfonyl groups, as well as ionizable salts thereof;
There are also ester groups, ether groups, etc.

It is also preferred that/or two or more of these groups are bonded to the non-coupling site of C0UP 1, or are of suitable size, e.g. an alkyl group with/-10 carbon atoms, 7-12 carbon atoms Those in which the aryl group has/or a solubilizing group having co or more of the above-mentioned ionizable groups are bonded to the non-coupling site of C0UPl are also advantageously used.

Moreover, it is also preferable to bind to the non-coupling site of the C0UP1 as a linkage valve. Typical linking groups include oxy (-0-), thio (-8-), carbonyl group, carbonyloxy group, oxycarbonyl group, amine group, carbamoyl group, aminocarbonyl group, ureido group,
Mention may be made of sulfamoyl and aminosulfonyl groups.

Although useful solubilizing groups have been listed above, particularly preferred solubilizing groups are carboxyl groups, sulfo groups, or ionizable salts thereof directly bonded to the non-coupling site of C0UP1, or to the non-coupling site of C0UP1. an alkyl group having 7 to 10 carbon atoms or 6 to/ Mention may be made of the aryl group having - carbon atoms.

Further, the compounds according to the present invention which can form yellow, magenta and cyan dyes preferably used in the present invention can be represented by the following general formulas (C) to (H).

[Yellow pigment-forming compound]

General formula [C] In the formula, R is an aryl group (e.g. phenyl group) 11: an alkyl group (particularly a tertiary alkyl group, e.g. t-butyl group)
and R2 is the above-mentioned stabilizing group (BALL) and sR5
is the above-mentioned solubilizing group (80L)9, R4 is a hydrogen atom or a halogen atom, an alkyl group or an alkoxy group, and n0m=! (However, when n9I-0, m≠θ, and n and m are 2 or more, they may be the same or different).

[Magenta dye-forming compound]

General formula (D) General formula (E) General formula (F) In the formulas (L), (E), and (F), R2 has the same meaning as R2 in general formula (C), and R5 is optional. Represents a solubilizing group (SQL), R6 is a hydrogen atom, a halogen atom,
Alkyl group, alkoxy group or amino group t-represented,
p≦! (However, when p≠0 and p is 2 or more, they may be the same or different and may be at °C.) One of R7 and R8 represents the above-mentioned solubilizing group (SQL) 2, and the other represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or an amino group. R9 and 1 (10 have the same meanings as R7 and R8 in general formula (E)).

[Cyan dye-forming compound]

In the general formulas (G) and (1()), R is - Monana (C)
has the same meaning as R2, at least one of R11 and R12 is the above-mentioned solubilizing group (SOL), and the remainder represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or an alkylamido group, and q≦3( However, qf-O)
, and R represents the solubilizing group (SQL) r described above.

Unless otherwise indicated above, alkyl, alkoxy and alkylamido groups each contain /-4 carbon atoms, aryl groups contain from 6 to 10 carbon atoms, and amino groups contain from 6 to 10 carbon atoms; Includes primary, straight and tertiary amino groups. These substituents as well as the i constant (LIA
LL) also includes those which have been preliminarily replaced with groups such as halogen atoms, hydroxy, carboxy, amino, amido, carbamoyl, sulfamoyl, sulfonamide, alkyl, alkoxy and aryl.

In the colorless coupler according to the present invention V, the above (2)
A compound belonging to this group can be represented by the following general formula (J).

In the formula, C0UP2 has the same meaning as C0UP1 in the general formula (B), and R14 is bonded to the coupling site of C0UP2, and can be released by the reaction of the coupler of -Monnae (J) with the oxidized product of the color developing agent. Represents a group that does not exist.

Examples of the coupler core represented by C0UP2 include the coupler core described in -Momonen (11).

Examples of the group represented by R14 include alkyl groups, substituted alkyl groups, aryl groups, substituted aryl groups, alkenyl groups, and cyano groups.

- The compound represented by Monna (J) is an alkyl group having 3 to 3 carbon atoms, an aryl group, and It is preferable to use a heterocyclic group to prevent diffusion. Typical linking groups include oxy (-0-),
thio (-8-), carbonyl group, carbonyloxy group,
Examples include oxycarponyl group, amine group, carbamoyl group, aminocarbonyl group, ureido group, sulfamoyl group, and yohyaminosulfonyl group.

In the colorless coupler according to the present invention, the compound belonging to the above (3) can be represented by the following general formula (K).

In the formula, C0UP3 represents a coupler core which provides a substantially colorless product by coupling reaction with the oxidized form of the color developing agent, and R is bonded to the C0UP30 force coupling site and causes the oxidation of the color developing agent. Due to the coupling reaction with the body! represents a group that can be separated from C0UP3.

Preferred leaveable groups include a halogen atom, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, a heterocyclic thio group, an 17-ruazo group, an acyloxy group, an alkylsulfonyloxy group, an arylsulfonyloxy group, Examples include nitrogen-containing heterocyclic groups.

More preferred colorless couplers represented by the general formula (K) can be represented by -mona (L) to (P).

In the formula, R16 has the same meaning as R15 in general formula (K), R16 is a hydrogen atom, an alkyl group, an aryl group, a halogen atom, an alkoxy group, an acyloxy group, or a heterocyclic group, and X is an oxygen atom , or -NR1? represents. R17 represents an alkyl group, an IJ-yl group, a hydroxy group, an alkoxy group or a sulfonyl group. 2 is a ~7-membered carbon ring (e.g. indanone, cyclopentane,
cyclohexanone, etc.) or a heterocycle (for example, Pi represents a group of nonmetallic atoms necessary to form a lydone, pyrrolidone, hydrocarbostyryl, etc.).

General formula (M) In the formula, R15, R16 and X have the same meanings as R15, R16 and X in general formula (L), and R1g is an alkyl group, aryl group, heterocyclic group, cyano group, hydroxy group, alkoxy group , an aryloxy group, a heterocyclic group, an alkylamino group, a dialkylamino group, or an anilino group.

-Momonana (N) R-CH-R'' In the formula, R15 has the same meaning as R15 in general formula (K), 119 and R2O may be the same or different, and represent an alkoxycarbonyl group, carbamoyl group, acyl group, cyano group, formyl group, sulfonyl group, sulfinyl group, sulfimoyl group, Ql together with nitrogen atom!
- Represents a group of nonmetallic atoms necessary to form a 7-membered tetero ring (e.g., phthalimide, triazole, tetrazole, etc.).

In the formula, R15 has the same meaning as R15 in general formula (K), and R
21 represents an alkyl group, aryl group, anilino group, alkylamino group or alkoxy group, C2 represents an oxygen atom, and sulfur atom and 9 represent a nitrogen atom.

Next, typical examples of the colorless coupler according to the present invention will be listed, but the invention is not limited thereto.

- Exemplary compounds belonging to Monna [B] -ill 8-+31 B" O2 8-+51 8-+81 S -+91 -QI O3Na C00H S-α~ S - (141 -an OC12H25 8H9 OCH2CONHCxsH33 0CH2CH2802C12H25 N02 0CH2CONHCH2CH20C12H,.

0CRC14Hzs Summer 0OH S- (Cobu) S- (Core) NHCOC16H33 OCHCOOC12H25 H3 NHCOOC8H17 U11H23 S- (#) S- (37) Exemplary compound belonging to general formula [J] S- (≠O) α 8- (≠l ) S-(<ri) αS-(<43) S-(4L5-(IIj) Exemplary compound belonging to general formula [K] S-(!0) υNtiL; HM25 B-<zi> 8- (!J) s-(tp) The colorless coupler according to the present invention is disclosed in Japanese Patent Application Laid-open No. 113-113-4/LO, Japanese Patent Application Publication No. 113-7/911, and Japanese Patent Application Laid-open No. 7/911.
No. 4c23, British Patent No. 1III, Fall 1
．． kot≠, 6≠2, U.S. Patent No. 7≠2゜t32, US Pat. P2r, o≠No.1,
Same 3. riit, No. 223, 3゜riotl, rijrigo, sameμ, 0hiro6. j7 μ issue, same issue, or co, co 13 issue, same μ
,/da2. It can be synthesized by the method described in rr6, etc.

In the present invention, it is preferable to use a derivative of naphthalenesulfonic acid as the surfactant used in the photosensitive material.

If the water washing step after color development is omitted or shortened as in the processing steps of the present invention, a portion of the developer will be carried into the subsequent processing steps, causing various troubles. For example, if it is carried into the bleaching solution, it may reduce the bleaching ability or cause an increase in the concentration. The carrying of such a developer into the bleaching bath usually depends on the film thickness and degree of swelling of the photosensitive material, but even with the same film thickness and amount of hardener, it also depends on the type of surfactant. The inventors discovered that.

Among the surfactants, naphthalene sulfonic acid derivatives are particularly preferred. The reason for this is thought to be related to the leaves of the developing agent incorporated into the surfactant micelles and slight differences in the swelling of the membrane containing the surfactant in the developer.
It has not been made clear. Furthermore, naphthalene sulfone-saturated derivatives generate less bubbles in the treatment liquid, and are particularly preferred when stirring is intensified for short-time treatment as in the present invention. When using sodium dodecylbenzenesulfonate as an example of a surfactant used in photosensitive materials, it foams significantly in color developing baths and bleaching baths, and the foam generated is difficult to disappear. On the other hand, the naphthalene sulfonic acid derivative of the present invention is characterized by less generation of foam and easy defoaming.

In the present invention, the surfactant used in the photosensitive material is 0. j
? It is preferred that 60% or more of the total amount of surfactants be 7-talenesulfonic acid derivatives.

The total carbon number of the substituents of naphthalene sulfonic acid is preferably / or less, and the following preferred examples are given, but the present invention is not limited thereto.

W-Co Cyanamid Aerosol 08W
-J Dupont Alkanol BMU3
Currency a W-ta w-i.

W-// W-/2 03Na w-i3 W-/4A The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is iodide containing about 30 mol% or less of silver iodide. Silver bromide, silver iodochloride, or silver iodochlorobromide. Particularly preferred is silver iodobromide containing from about 2 mole percent to about 2j mole percent silver iodide.

Silver halide grains in photographic emulsions include those with regular crystals such as cubes, octahedrons, and tetradecahedrons, those with irregular crystal shapes such as spherical and plate shapes, and those with twin planes. may have crystal defects, or a composite form thereof.

The grain size of the silver halide may be fine grains of about 0.2 microns or less, or large grains with a projected area diameter of up to about 10 microns, and may be a polydisperse emulsion or a monodisperse emulsion.

Silver halide photographic emulsions that can be used in the present invention are available from, for example, Research Disclosure (RD), Ya/76 Hiroj.
(July 1971), pages 2-3, @IL emulsion preparation and
types)'1 and 17/l (2/7/2012), Hirohiro page, graphic ``Physics and Chemistry of Photography'', published by Paul Montell (P.

G}afkides, Chemical Physiqu
ePhotographique Paul Mo
ntel, / Pt7), "Photographic Emulsion Chemistry" by Duffin
, published by Focal Press (G, F, Duffin,
Photographic Emulsion Che
Mistry (Focal Press.

/ri 44)), “Manufacturing and Coating of Photographic Emulsions” by Zelikman et al., published by Focal Press (V, L.

Zekman et al, Making and
Coating Photographic Em
ulsion.

Focal Press, /94 u).

U.S. Patent No. 3. ! 7μ, Buko wo issue, same 3. Bu! ! , 3 references and British Patent No. 1.4t13,7≠r, etc., and 9 monodispersed emulsions are also preferred.

Tabular grains having an asquid ratio of about 3 or more can also be used in the present invention. Tabular grains are described in Photographic Science and Engineering by Gutto.
ic 5science and engineering
g), Volume 14L, 24411~. 2μ7 pages (/?7
U.S. Pat. λ, //J, /!
It can be easily prepared by the method described in No. 7, etc.

The crystal structure may be --like, the inside and outside may have different halogen compositions, it may be a layered structure, or silver halides with different compositions may be joined by epitaxial bonding. It may also be bonded with a compound other than silver halide, such as rotane silver or lead oxide.

Also, mixtures of particles of various crystal forms may be used.

Nine types of silver halide emulsions are usually used which undergo physical ripening, chemical ripening and spectral sensitization. Additives used in such processes are available from Research Disclosure Shop/
7j$j and the same/ni/17/l, and the relevant faces fr are summarized in the table below.

Known photographic additives that can be used in the present invention are also listed in one of the above Research Disclosures, and the relevant sections are indicated in the table below.

Additive type 'FLD/7tlAJ RD/17/
ll Chemical sensitizer - page 3 t μr page right column Sensitivity increasing agent Same as above 3 Spectral sensitizer, 23 ~ Co ≠ 100 t ≠ page right column ~ Super sensitizer 6 wide page right column μ Brightening agent Ko≠
Page j Anti-fogging agent λhiro~λ! Page A44 page right column ~ and stabilizer 2 Original absorbent, filler λ evening ~ 2 page Hiro page right column ~
Luther dye ultraviolet Ho page left horizontal line absorber stain prevention agent Ko! Page right column tzo Page left to right column r Dye image stabilizer Page 2j ta Hardener page 26 t 1 page left column 1
0 Binder Page 2 Same as above//
Plasticizers, lubricants Core page TSO page right column 12
Coating aid, surface 26-27 Negative Same as above Activator 13 Static prevention Page 27 Same as above agent Various color couplers can be used in the present invention, specific examples of which can be found in the above-mentioned Research Disc.
RD) A/7A≠3, ■-C-GK Described in the listed patent.

Yellow couplers include, for example, U.S. Patent No. J, 93
3. ! 0/No. ≠lOλko, No. 620, No. 3
Koro, Oko Hirogo, Dodaihiro, ≠0/.

No. 7J, Tokko Sho ni '1r-1073, British patent i
/, 4ZJj, No. 020, @/, 447j, No. 740, etc. are preferred.

As magenta couplers, other than the aforementioned pyrazoloazole compounds! - A pyrazolone compound may be used in combination.

They are in US patents≠,! 10゜61ri No. ≠, 3
11. ! No. 27, European Patent No. 73,634, US Patent No. J, 041. ≠No. 32, No. 3,7λj, No. 047,
Research disclosure? -&21t220(/Y
r4c (Z month), JP-A-6O-JJjt-λ issue, Research Disclosure-A coμ230 (/ri in June 2016), JP-A-Sho tO-4tJt! No. 2, U.S. Patent No. μ, J
oo.

No. 1.30, same No. ≠,! μQ, 6! Particularly preferred are the references listed under No. 3, etc.

Cyan couplers include phenolic and naphthol couplers, and are described in U.S. Patent No. μ.

0! Ko, 2/λ issue, same issue ≠, lμ6.326 issue, same gX
≠, 2? , No. 233, Hiroshi, -226. -2oo, No. 36, Octopus No. 2, No. 2. jO/, /77
No. 2,77λ, /6-, No. J, ryz, tx
No. t, No. J, 77J, No. 00-, No. J, 711,3
No. 01, No. ≠, 33 Hiroshi, No. oii, No. ≠, 327.
/73, West German Patent Publication @3,32, No.72, European Patent No. 1J/, JtJk, US Patent No. J, 14c4,
4J Ko issue, same issue ≠, JJJ, tap issue, same issue ≠, ≠yo l
,! No. 27,747, European Patent No. 1
41. Crabs described in AJAA issue etc. are preferred.

Colored to correct unnecessary absorption of color pigments.

The coupler is Research Disclosure & 176≠
Section 3 ■-G, U.S. Patent No. 3, /l,! , No. 170, Tokko Akira! 7-32≠73, U.S. Patent No. a, oou,
Octopus No. 2, same za, i3r, art no., British Patent No. 1. /4AA, No. 341 is preferred.

Couplers whose colored dyes have appropriate diffusivity include U.S. Patent No. μ, 344,237 and British Patent No. 2. l kot
, No. 170, European Patent No. A, 770, West German Patent (Publication) No. 3,234! , No. 133 is preferred.

Typical examples of polymerized dye-forming couplers are U.S. Pat.
/ No. 1t, No. 31,7,212, British Patent No.
10, No. 773, etc.

Couplers that release all photographically useful residues upon coupling can also be preferably used in the present invention. - Monka (I)
L) IR couplers releasing development inhibitors which can be used in combination with the compounds of the invention of L) are the aforementioned RD/741/
-3, Patents described in sections ■ to F, JP-A-Shoj7-/jt
/ Ha I, same! 7-/ 1M-23 Hiroshi, same to-ir
Preference is given to those described in US Pat. No. PA4CR, US Pat.

Couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent Nos. 2,027.1110 and 2. /31,111, Tokukai Shoj! i'-/! 7
No. 631, same! 19-/70r4AO is preferred.

Turnip 2 that can be used for other uninvented photosensitive materials
- Competitive couplers as described in U.S. Pat.

ko r3. Hiro 7th issue, same Hiro! 31. jri no. 3, same no. u
, 3io, ttr, etc.; 1) IR redox compounds or DIR coupler-releasing couplers or DIR coupler-releasing couplers or redox described in JP-A No. 40-11jP10, JP-A-62-24Lcoj-, etc.; , R, D, A/
/ 4'≠2, same J$J! /, 4! Kaisho 4/-20/
Bleach accelerator releasing turnip 2-1 described in US Patent No. 2117, etc., J! ! , 4t77, and the like.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods.

Examples of high boiling point solvents used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027 and the like.

Specific examples of high-boiling organic solvents with a boiling point of 175°C or higher at normal pressure used in the oil-in-water dispersion method include phthalic acid esters (dibutyl tucrate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl tucrate, bis(2,4-di(-amylphenyl)phthalate, bis(2,4-di-t-amylphenyl)isophthalate, bis(1,1-diethylpropyl)phthalate, etc.), phosphoric acid or Phosphonic acid esters (triphel phosphate, tricresyl phosphate, 2-
ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenyl phosphonate, etc.), benzoic acid esters (2-ethylhexyl phenyl phosphate, etc.), ethylhexylbenzoate,
dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides 1j [(N,N-diethyldodecanamide, N,N-diethyllaurylamide, N-tetradecylpyrrolidone, etc.), alcohols or phenols ( Isostearyl alcohol, 2.
4-di-tert-amylphenol, etc.), aliphatic carbonyl esters (bis(2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N, N-dibutyl-2
-butoxy-5-tert-octylaniline, etc.),
Examples include hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.). Further, as the auxiliary solvent, an organic solvent having a boiling point of about 30°C or higher, preferably 50°C or higher and about 160°C or lower can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, -Ethoxyethyl acetate, dimethylformamide and the like.

Specific examples of the latex dispersion process, effects, and latex for impregnation include U.S. Pat. It is described in.

The present invention can be applied to various color photosensitive materials. Typical examples include color negative film for general use or movies, color reversal film for slides or television, color paper, color negative film, and color reversal paper.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, page 28 of Na 17643, and Na 1B
716, page 647, right column to page 648, page 1 left.

The color photographic material according to the present invention includes the above-mentioned RD,
Na 17643, pages 28-29, and the same Nil 1
Development processing can be carried out by the usual methods described in the left column to right column of 615 of B716.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Aminophenol compounds are also useful as color developing agents, but p-phenylenediamine compounds are preferably used, representative examples of which are 3-methyl-4-amino-N, N-diethylaniline, 3-methyl -4-amino-N-ethyl-N-
β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-β-
Examples include methoxyethylaniline and their sulfates, hydrochlorides, p-toluenesulfonates, and the like. Two or more of these compounds can be used in combination depending on the purpose.

The color developer may contain pH-reducing agents such as alkali metal carbonates, borates or phosphates, development inhibitors such as bromide salts, iodide salts, benzimidazoles, benzothiazoles or mercapto compounds, or It generally contains antifoggants and the like. Also, if necessary,
Hydroxylamine, diethylhydroxylamine, sub-11JJ salt hydrazines, phenyl semicarbazides,
Triethanolamine, catechol sulfonic acids, triethylenediamine (1,4-diazabicyclo(2,2,
2) Various preservatives such as octane), organic solvents such as ethylene glycol and diethylene glycol, development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, and amines, dye-forming couplers, competitive couplers, and sodium. fogging agents such as boron hydride, auxiliary developing agents such as l-phenyl-3-pyrazolidone, viscosity-imparting agents, aminopolycarboxylic acids,
Various chelating agents such as aminopolyphosphonic acid, alkylphosphonic acid, phosphonocarboxylic acid, such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid,
Hydroxyethyliminodiacetic acid, l-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N,N,N-
trimethylenephosphonic acid, ethylenediamine-N, N
, N, N-tetramethylenephosphonic acid, ethylene glycol (0-hydroxyphenylacetic acid), and salts thereof can be cited as representative examples.

Further, when performing reversal processing, black and white development is usually performed and then color development is performed. This black and white developer contains known black and white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as l-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol. Alternatively, they can be used in combination.

The pi of these color developing solutions and black and white developer α solutions is generally 9 to 12. The amount of replenishment of these developing solutions depends on the color photographic light-sensitive material being processed, but in general it is 31 or less per square meter of light-sensitive material, and by reducing the bromide ion concentration in the replenisher, it can be increased to 500 or less.
mj! You can also do the following: When reducing the amount of replenishment, it is preferable to prevent evaporation of the solution and air oxidation by reducing the contact area with the air in the processing tank, and by using means to suppress the accumulation of bromide ions in the developer. It is also possible to reduce the amount of replenishment.

The time for color development processing is usually set between 2 and 5 minutes, but the processing time can be further shortened by using high temperature, high pH, and high concentration of color developing agent.

After color development, the photographic emulsion layer is usually bleached.

The bleaching process may be carried out simultaneously with the fixing process (bleach-fixing process), or separately (bleach-fixing process), or in order to speed up the process, it may be possible to perform a bleach-fixing process after the bleaching process. Depending on the purpose, treatment may be carried out in consecutive bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment. Examples of bleaching agents include iron (■), Kobal) (I
Compounds of polyvalent metals such as [I), chromium (IV), and w4(n), peracids, quinones, and nitro compounds are used.

Typical bleaching agents include ferricyanide-dichromate; organic complex salts of iron (III) or cobalt (III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, and 1,3-diaminoacetic acid. Aminopolycarboxylic acids such as propane 4ED, glycol ether diamine 4HU, or complex salts of citric acid, tartaric acid, malic acid, etc.;
Persulfates; bromates; permanganates; nitrobenzenes and the like can be used. Among these, aminopolycarboxylic acid iron (III) complex salts and persulfates, including ethylenediaminetetraacetic acid iron (III) complex salts, are preferable from the viewpoint of rapid processing and environmental pollution prevention. ) Complex salts are particularly useful in both bleach and bleach-fix solutions. The pH of the bleaching solution or bleach-fixing solution using these aminopolycarboxylic acid iron(II[) complex salts is usually 5.5 to 8, but in order to speed up the processing, the pH may be lowered. can.

A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their prebaths, if necessary.

Specific examples of useful bleach accelerators are described in U.S. Pat. No. 3,893,858, German Pat.
．． No. 290.812, No. 2,059.988, JP-A No. 53-32736, No. 53-57831, No. 53-
No. 37418, No. 53-72623, No. 53-956
No. 30, No. 53-95631, No. 53-104232
No. 53-124424, No. 53-141623
Compounds having a mercapto group or disulfide group described in JP-A No. 53-28426, Research Disclosure No. 17129 (July 1978); Thiazolidine derivatives described in JP-A-50-140129; Japanese Patent Publication No. 45-8506 No. 52-20832, JP-A No. 53-32735, U.S. Patent No. 3.706.56
Thiourea derivatives described in No. 1; West German Patent No. 1.127.
No. 715, iodide salts described in JP-A-58-16.235; West German Patent Nos. 966.410 and 2,748.43
Polyoxyethylene compounds described in No. 0; Japanese Patent Publication No. 1973
-Polyamine compound described in No. 8836; Other JP-A No. 4
No. 9-42.434, No. 49-59.644, No. 53
-94.927, 54-35.727, 55-
Compounds described in No. 26.506 and No. 58-163.94Q; bromide ions, etc. can be used. Among these, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large promoting effect, and are particularly preferred as described in U.S. Pat. No. 3,893,85.
No. 8, West Patent No. 1゜290.812, JP-A-53-9
Preferred are the compounds described in U.S. Pat. No. 5.630, and also preferred are the compounds described in U.S. Pat.
These bleach accelerators may be added to the light-sensitive material, and are particularly effective when bleach-fixing color light-sensitive materials for photography.

Examples of fixing agents include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but thiosulfates are commonly used, with ammonium thiosulfate being the most widely used. Can be used for As the preservative for the bleach-fix solution, sulfites, bisulfites, or carbonyl bisulfite adducts are preferred.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to water washing and/or stabilization steps after desilvering treatment.

The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set over a wide range. Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is
urnal or the 5ociety of 1
lotion Picture and Televis
ion Engineers Vol. 64, P, 248~
253 (May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria will breed, and the generated suspended matter will adhere to the photosensitive material. In the processing of the color photosensitive material of the present invention, such problems can be solved by:
The method for reducing calcium ions and magnesium ions described in JP-A No. 62-288.838 can be used very effectively. Also, JP-A-57-8.542
Chlorinated disinfectants such as isothiazolone compounds, cyabendazole, chlorinated sodium isocyanurate, and other benzotriazoles listed in the issue, "Chemistry of antibacterial and fungicidal agents" by Hiroshi Horiguchi, "Microbial It is also possible to use disinfectants described in "Sterilization, Disinfection, and Anti-Mildew Techniques" and "Encyclopedia of Antibacterial and Antifungal Agents" edited by the Japan Antibacterial and Antifungal Society.

The pH of the washing water in the processing of the photosensitive material of the present invention is 4 to 4.
9, preferably 5-8. The washing water temperature and washing time can also be set variously depending on the characteristics of the photosensitive material, its use, etc., but generally it is 20 seconds to 10 minutes at 15 to 45°C, preferably 30 seconds to 5 minutes at 25 to 40''C. Furthermore, instead of washing with water, the photosensitive material of the present invention can be directly processed with a stabilizing solution.

In such stabilization treatment, Japanese Patent Application Laid-Open No. 57-854
All known methods described in No. 3, No. 58-14834, and No. 60-220345 can be used.

Further, following the water washing treatment, a further stabilization treatment may be carried out, such as a stabilizing bath containing formalin and a surfactant, which is used as a final bath for color photosensitive materials for photography. .

Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow liquid from water washing and/or replenishment of the stabilizing liquid can be reused in other processes such as the desilvering process.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing. In order to incorporate a color developing agent, it is preferable to use various precursors of the color developing agent. U.S. Patent No. 3.342.59
Indoaniline compounds described in No. 7, No. 3.342.
No. 599, Research Disclosure 14.850
Schiff base-type compounds described in No. 15.159 and aldol compounds described in No. 13.924, U.S. Patent No. 3
．． Metal salt complex described in No. 719,492, JP-A-53-1
Examples include urethane compounds described in No. 35628.

The silver halide color light-sensitive material of the present invention may optionally contain various 1-phenyl-3
- Pyrazolidones may be incorporated.

Typical compounds are JP-A-56-64339 and JP-A No. 57-
144547 and 58-115438, etc. The various processing solutions in the present invention are 10"C to 5
0 used at 0°C usually 33°C to 38°C
The temperature is standard, but higher temperatures can be used to accelerate the processing and shorten the processing time, or conversely, lower temperatures can be used to improve image quality and stability of the processing solution.

In addition, West German Patent No. 2.226.7 was issued for the purpose of saving light-sensitive materials.
70 or US Pat. No. 3,674,499 using cobalt intensification or hydrogen peroxide intensification.

Further, the halogenated 11 photosensitive material of the present invention is disclosed in US Pat.
．． The present invention can also be applied to the heat-developable photosensitive materials described in JP-A No. 500.626, JP-A No. 60-133449, JP-A No. 59-218443, JP-A No. 61-2380-6, and European Patent No. 210.66OA2.

(The following is a blank space) The present invention will be described below with reference to Examples, but the present invention is not limited thereto.

A multilayer color photosensitive material consisting of each layer having the composition shown below on a transparent triacetyl cellulose film support (
10/) was created.

1st layer; antihalation layer black colloidal silver・・・・・・・・・・・・・・・・・・
...0. /j9/m2 UV absorber U-/
・・・・・・・・・・・・・・・o, ory/m2 same
U-co ・・・・・・・・・・・・・・・0.
Gelatin layer No. 21 containing /co f/m2; Intermediate layer J, j-di-t-pentadecylhytroquinone 0.
1197m2 Coupler C-/・・・・・・・・・・・・
Gelatin layer 3j containing ......0,11117 m2; 7th red-sensitive emulsion 1- ....................................../, Jf/m2 increase Dye-sensitizing......For 1 mole of silver...
・・・・・・/, ItXlo molar sensitizing dye π
・・・・・・・・・For 1 mole of silver ・・・・・・・・・
...0. μ×10 mole same ■・・・・・・・・・
・For 1 mole of silver・・・・・・・・・J, A×
10 moles same ■・・・・・・・・・For 7 moles of silver・・・・・・・・・・・・ a, oxio-' molar coupler C-2・・・・・・・・・・・・・・・・・・・・・・・・
...0.4'jt/m2 coupler C-j...
・・・・・・River・・・・・・0.031fl/m2
Coupler C-G・・・・・・・・・・・・・・・・・・
... Gelatin layer containing 0.02jf/m2; Second red-sensitive emulsion layer.................................................................................../
, 09/m2 Sensitizing dyestuff......For 1 mole of silver...j, JX/i7 Same mole ■・・・・・・・・・For 1 mole of silver...
・・・・・・・・・/, jXlo-'molar same ■・・・・・・
・・・・For 1% silver・・・・・・・・・・・・J
, lX10 mol sensitizing dye ■・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・/, lX
10 Molar coupler C-co ・・・・・・・・・・・・
・・・・・・・・・o, ozoy1mx coupler C-j
・・・・・・・・・・・・・・・・・・0.0709
7m2 coupler C-3・・・・・・・・・・・・・・・・・・
...Jth layer of gelatin layer containing 0.03197 m2; middle layer,! -G-hantadecylhytroquinone・・・・・・・・・・・・0.
Gelatin layer 6th layer containing 0197m2: @/Green-sensitive emulsion layer 0.10
9/m2 Sensitizing dye V・・・・・・・・・For 1 mole of silver・・・・・・・・・≠, oxio mole same ■・・・・・・・・・Silver °°°°°° per mole
°°°°°°3.0×lO molar same ■・・・・・・・・・
・For 1 mole of silver...0・・・・・・・／, 0X10
Molar coupler C-≦・・・・・・・・・・・・・・・
・・・・・・・・・0.11197m2 Coupler C-
7・・・・・・・・・・・・・・・・・・・・・・・・
0,1317m2 coupler C-r・・・・・・・・・・
・・・・・・・・・・・・・・・0.0kof / FF1
2 coupler C-p・・・・・・・・・・・・・・・・・・
7th gelatin layer containing 0.01717 m2; 2nd green-sensitive emulsion layer 0.01717 m2
．． rjf/m2 sensitizing dye■・・・・・・・・・2.7×IO−' mole per mole of silver ■・・・・・・...for 1 mole of silver...
・・・・・・／, l×10 molar same ■・・・・・・
・・・・・・7 for 1 mole of silver
．． jXlo Mollyi La-C-6・・・・・・-
・-Song--・0,09j t/m2 coupler C-
7・・・・・・・・・・・・・・・・・・・・・0,0
/! ? Gelatin layer containing /m2; yellow filter layer yellow colloidal silver ・・・・・・・・・・・・・・・・・・
...0,01r? /m2ko, j-g-hantadecylhydroquinone・・・・・・・・・OlOriO
Gelatin layer containing f/m2 Second layer; First back-sensitive emulsion layer・・・・・・・・・・・・・・・・・・・・・0
．． J7f/m2 sensitizing dye■・・・・・・・・・For 1 mole of silver・・・・・・・・・≠, 4Lxio
Molar coupler C-2・・・・・・・・・・・・・
・・・・・・・・・・・・0,7/? 7m2 coupler C-
Hiroshi・・・・・・・・・・・・・・・・・・・・・
0.071! /m2 io layer; second blue-sensitive emulsion layer・・・・・・・・・・・・・・・・・・o, zz
y1mz sensitizing dye ■・・・・・・・・・・・・・・・・・・・・・・・・3.0×10 mol coupler C-ta・・・・・・・・・・・・・・・・・・・・・・3.0×10 mol coupler for 1 mol of silver・・・・・・・・・・・・
... Gelatin layer 1/layer containing O, ko3y/m2; 1st protection layer ultraviolet absorber U-/ ......
・0. /≠17m2 Same U-2,,,,,,
72nd gelatin layer containing 01,22 f/m2; second protective layer, ,,,,,,,,, o,
J jy / m2 Polymethacrylate particles (diameter /, jμ)・・・・・・・・・・・・・・・・・・
- Gelatin layer containing 0,1097 m2 In addition to the above composition, gelatin hardening agent H-7 and surfactant W-/ were applied to each layer. The total amount of W-/ is 0.397m
It was 2.

Sample 10λ Sample IO- was prepared in the same manner as Sample 101 except that coupler C-7 in Sample 10 was replaced with 2 times the mole of the pyrazoloazole Kab2-.CPM-tt of the present invention.

CPM-/(Exemplary Compound A-/Co) Samples io3, IO≠ Samples ioi and 10- in the middle layer (5th layer, 1st #) Sample 103.1 was prepared in the same manner as Sample 10/10, except that the color coupler CPM-2 was replaced with an equimolar amount.
I made 0≠.

CPM-Co (Exemplary Compound 8-(2F)) Sample 101 Sample 70μ coupler c-p was converted into compound CPM with the following structure.
Sample 10 in exactly the same way as sample IO≠ except that -3 was replaced in equal moles! made.

Sample 104 Sample 1 except that the same amount of sodium dodecylbenzenesulfonate is used as W and 2 instead of W-/ in Sample IO Hiromu
Sample iot was made in exactly the same manner as 04t.

These samples were subjected to imagewise exposure for sensitometry,
When the following color development process was carried out, the results shown in Table 7 were obtained.

The development process used here was carried out using Jr'(' in the following manner.

l For color development interval: 3 minutes/j seconds - Bleaching...between intervals: 6 minutes 30 seconds 3 Washing with water: 3 minutes l!゛Second Fixation...... for 30 seconds!
Washing: Song: 3 minutes/j seconds 6 Stable: Song: 3 minutes IJ seconds The composition of the treatment liquid used in each step is as follows.

Color Developer Sodium Nitrilotriacetate / Of Sodium Sulfite Sodium Carbonate 30. Of potassium bromide
/, +Lf hydroxylamine sulfate 2. ≠2gu(N-ethyl-N-β-hydroxyethylamine)-2-methylaniline sulfate Hiroshi, Jf add water it bleach solution ammonium bromide ito, or aqueous ammonia (21%) 2j, OCc ethylenediamine-4 Sodium iron acetate salt /! 0. Of glacial acetic acid
i4t, add 117 water / fixer sodium tetrapolyphosphate 2. Of Sodium Sulfite Section, oy Ammonium Thiosulfate (70%)/7j, 000 Sodium Bisulfite
Hiroshi, 11 Add water
lt stabilized liquid formalin lr, occ
The results are also shown in FIG. 1 and Table 7 when water was added to give a uniform blue exposure, followed by wedge exposure with green light.

The results in Table 1 show that the photosensitive material of the present invention (sample 10g, 10g
This proves that sample 1) has less color staining and better color reproducibility than the conventional samples (samples 10/-103).

Here, in the figure, the curve / represents the characteristic curve regarding the magenta color image of the green photosensitive layer, and the curve C represents the yellow color image density of the back photosensitive layer 111 due to uniform blue exposure.

Difference (a-b) between yellow density (a) in M light iA and yellow # degree (b) in the same B light (a-b) t-scale of color turbidity (multilayer effect). Here, the magenta density (1)) at exposure jlA represents the fog density, and the magenta density at exposure #B represents 2.0.

From Table 1, it can be seen that Sample 104t of the present invention has improved color turbidity without impairing sensitivity.

In sample 106, the color turbidity was improved, but the sensitivity of G and H was greatly reduced. Sample 104 had variations in sensitivity and color turbidity depending on the measurement, and it was found that the sample had mold. It has been found that this unevenness is caused by the development process and can be prevented by providing a washing process between the previous process, color development, co-bleaching, and bleaching process. Therefore, it can be seen that sample B is not preferable for K in order to simplify and shorten the processing.9.

Structure of the compound used in the examples U-/C-/U-coC-λ-J C-Hiroshi [Exemplary compound aυ] C-z OH C5 z C-r α C-taH-/W-/ Increase Dye-sensitive dye (CH2)3sO3Na 2H5 2H5 2H5 Example 1 A multilayer color photosensitive material λ0/ was prepared by coating each layer having the composition shown below on an undercoated cellulose triacetate film support.

(Photosensitive layer composition) The numbers corresponding to each component indicate the coating amount expressed in f/m2 units, and for silver halide, the coating amount is expressed in terms of silver. However, for sensitizing dyes, the coating t per mole of silver halide in the same layer is expressed in moles.

7th layer (antihalation layer) Black colloidal silver 0.2 gelatin
/, 0 UV absorber UV-
10,01 Same UV-co 0. /same
UV-, io, 7 Dispersion oil QIL-/0. 02 First layer (intermediate layer) Fine grain silver bromide (average particle size 0.07μ)
Red-sensitive emulsion #) Monodisperse emulsion (silver iodide 4 mol%, average grain size O0 Hiroμm1 coefficient of variation is%) 1.4 AI2 Gelatin 0.2 Sensitizing dye A
J, 0XIO"-'sensitizing dye B
/, oxio-'sensitizing dye CO,J
Xlo-4 cp-bO, JI Cp-cO, Orkocp-ao, 0μ7 D-10,016 HBS-10,10 HBS-20,10 7th layer (middle layer) Gelatin θ,! cp-bO
,10 HBS-10,Or 1st layer (second red-sensitive emulsion r*) Monodisperse emulsion (silver iodide 6 mol%, average grain size 0.Jμm1 variation coefficient/j%) /, Jl Gelatin /, 0 increase Sensitive dye A
i,zxio-'sensitizing dye B
2.0×10”-4 sensitizing dye CO,!×10
= Cp=b o, iz.

Cp-dO10 core D-10,0/j ) (BS-/ o, or.

HBS-2o, o&.

Sixth! - (Third red-sensitive emulsion layer) Monodisperse emulsion (silver iodide 7 mol%, average grain size /, /μm, coefficient of variation 76%) 2+ 01 Sensitizing dye A 1. JXlo-4 extra g
Dye B y, 5xto 4 sensitizing dye Co, ≠X10-' gelatin /, jCp-a
O,040 Cp-cO,02HiroCQ-dO,0JI D-10,006 8H8-io,tλ 71st-(middle layer) Gelatin /, 0Cpd-
AOL 0! HBS-λ θ, O
j-th layer (first green-sensitive layer) Monodisperse silver iodobromide emulsion (3 mol% silver iodide, average grain size O9 μm, coefficient of variation/%) O,t4L monodisperse silver iodobromide emulsion ( Silver iodide 6 mol%, average grain size 0.7 μm, coefficient of variation it%) Ha/2 gelatin /, 0 sensitizing dye D /X10-' sensitizing dye E
4tx io-'sensitizing dye F txlo-'Cp-h
θ, 20cp-f
O, otsu l cp-g o, o
rμCp-k 0
．． 03! cp-to, Q3
6D-co 0
．． 0≠0HBS-/
θ, λ! I-I B S-λ
O6μ! P% (first green-sensitive emulsion layer) Monodisperse silver iodobromide emulsion (silver iodide 7 mol%, average grain size/, 0 μm1 coefficient of variation/I%) -2.07 Gelatin 1. j Sensitizing dye D
/-jXlo-4 sensitizing dye E
, 2. JXlo-4 sensitizing dye F
/,! x10-'Cp-fo, oo7 cp-ho, oikoCp-go, oori HBS -, 20,0ft 10th layer (middle I'i! yellow colloidal silver 0.06 gelatin', 1Cpd-A
O,,i) [3S-10,j 1st/layer (1f sensitive emulsion layer) Monodisperse silver iodobromide emulsion (silver iodide 4 mol%, average grain size O0≠μm, coefficient of variation a20%) 0 ．． J/Monodispersed silver iodobromide emulsion (silver iodide j mol%, average grain size O0 μm, coefficient of variation 77%) 0.31 Gelatin
K, O sensitizing dye G
txlo-'sensitizing dye H1xto-' Cp-i θ, 43C
p-j θ, j7D-10,
02O D-30,0/! HBS-10, or 1st layer (3 blue-sensitive emulsion layers) Monodispersed silver iodobromide emulsion (silver iodide 1 mol%, average grain size /, 3 μm, coefficient of variation / 1%) 0.77 gelatin
O6! Sensitizing dye G
yoX1o=sensitizing dye Hz×1O-5 Cp-io, 10 Cp-j'o, l.

D-30,001 HBS-jOo 10 1st J/il (intermediate layer) Gelatin 0.2Cp-mO
6/ UV-10, / UV-20, / '[J■-j O6/) (B
S-/0.0rHBS-
10,0! 14th layer (protective layer) Monodisperse silver iodobromide emulsion (silver iodide damol%, average grain size 0.0jμm, coefficient of variation 10%) 0. / Gelatin /,! Polymethyl methacrylate particles (average/, jμ) 0. /S/
0.
28-2
0. 2. Gelatin hardening agent H-7 was added to the other surfactants.

Compound (9) of the present invention instead of D-/ of sample λ0/ (comparative example), CPM-/ of Example 1 instead of Cp-h,
Samples of the present invention were prepared by replacing cpct-A with the same mole of CPM-2't in Example 1.

Sample 20/1λ02 was subjected to the same treatments and operations as in Example 1, and the same results as in Example 1 were obtained.

In place of the compound (9) of the present invention (8) in 0 samples,
+71. (lυ, (13), [-Almost similar results were obtained even when the same mole was used.

Sensitizing dye Human sensitizing dye B Same C Same E Same F Same G Sensitizing dye H D-j α Cp -a p-b Cp -c p-a p-f α p-g p-h Cp - i Cp-j C,H9■ Cp-k Cp-t α Cp-m HH8-/ H13S-λ ni-1 8-/ NHCONH2 UV-/ Same as above UV-coUV-J 2H5 Compound cpct-A Dan-7 Implementation Example 3 Sample 10/ of Example/, IO6'f7r:g was exposed to light and then processed in the manner described below.

Table-C Processing method Step Processing time Processing temperature Color development 3 minutes/j seconds j r 'C bleaching 1
Minutes oo seconds J r 'c bleach fixing 3 minutes/! seconds
J I 'C water wash m + LO seconds J j
'C water washing (2) 7 minutes 00 seconds J j 'C stable ≠0 seconds j r 'C drying 1
minute it second yot'cNext, the composition of the treatment liquid will be described.

(Color developer) (Unit?) Diethylenetriaminepentaacetic acid/O7-hydroxyethylidene-l.

/-diphosphonic acid J, 0 Sodium sulfite ≠, O Potassium carbonate
30.0 Potassium Bromide
/, 44 potassium iodide
/・! ■Hydroxylamine sulfate
-1 Hirogu [N-ethyl-N-(β-hydroxyethyl)amine]---Methylaniline sulfate Hiro! add water
/, 0tpH10,0! (Bleach solution) (Units?) Ethylenediaminetetraacetic acid ferric ammonium dihydrate / co0.0 Ethylenediaminetetraacetic acid disodium salt 10.0 Ammonium bromide 100.0 Ammonium nitrate
io,.

Bleach accelerator o, oat mol ammonia water (27 liters) /! , add Od water /, 0tpHA, j (bleach-fix solution) (unit?) Ethylenediamine ferric ammonium acetate dihydrate! 0.0 Ethylenediaminetetraacetic acid disodium salt j, 0 Sodium sulfite /2,0 Ammonium thiosulfate aqueous solution (70%) λ≠θ, Od ammonia water (27%) A, Add Ord water /, 02p)i
7. (Washing liquid) Tap water was mixed with an H-type strongly acidic cation exchange resin (Amberlite IR-/JOB manufactured by Rohm and Haas) and an OH-type anion exchange resin (Amberlite IR-Hiro 00 manufactured by Rohm and Haas).
- Calcium and magnesium ion concentration f: 3 / was treated as follows by passing water through the packed hotbed column, and then 201 nf/l of sodium incyanurate dichloride and sodium sulfate/, jfat were added.

The pH of this liquid is in the range of A,j-7,j.

(Stabilizing liquid) (Unit?) Formalin (37%) 0ml polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 ethylenediaminetetraacetic acid disodium salt o, or add water /, 0tpH1,0-r
, 0 As a result, almost the same results as in Example 1 were obtained, and it was found that the present invention does not depend on the form of treatment.

It was also found that sample 104 had a larger amount of residual silver after processing than the other samples, making it unsuitable for short-term processing.

[Brief explanation of the drawing]

81! /The figure represents a characteristic curve. Curve 1 represents the characteristic curve for the magenta color image of green-sensitive I-, and curve 2 represents the yellow color image density of the blue-sensitive layer with uniform blue exposure. Curve 3 represents the theoretical yellow color image density of a blue-sensitive layer with uniform blue exposure.

Claims (1)

[Scope of Claims] A silver halide photographic material having at least one hydrophilic colloid layer on a support, comprising the following general formula (I):
At least one compound represented by the following, at least one pyrazoloazole coupler, and at least one compound that undergoes a coupling reaction with an oxidized developing agent but does not form a dye (colorless coupler). A silver halide photographic material comprising: General formula (I) A+(L_1)_l-(B)_m■_a(L_2)_n
-DI In formula, A reacts with the oxidized product of aromatic primary amine developer to form {(L_1)_l-(B)_m}_a-(L
_2) _n-DI represents a group that cleaves, L_1 represents a group in which the bond on the right side (bond with (B)_m) is cleaved after the bond on the left side of L_1 shown in general formula (I) is cleaved, B represents a group that reacts with the oxidized developing agent and cleaves the bond on the right side of B represented by the general formula (I), and L_2
represents a group whose right side bond (bond with DI) is cleaved after the left side bond of L_2 shown in general formula (I) is cleaved, DI represents a development inhibitor, and l, m and n are each 0. or 1, and a represents an integer from 0 to 3. Here, when a is plural, a number of (L_1)_l−(B)_
m represents the same or different things.