JPH0486740A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain sufficient color development performance even in the case of reducing an amount of organic solvent high in boiling point to be used by incorporating a specified dye-forming coupler in a photosensitive silver halide emulsion layer and specifying a weight ratio of said solvent to said coupler. CONSTITUTION:At least one of the photosensitive silver halide emulsion layers contains at least one of the dye-forming couplers represented by formula I in which Ar is optionally substituted aryl; R1 is halogen or the like; L is -COO, -O-, or the like; R2 is a group substitutable on a benzene ring; (n) is an integer of 0 - 3; R3 is a branched alkyl, a straight chain alkyl inserted by -COO- or the like in the chain, or the like; R4 is optionally substituted aryl or such an aromatic heterocyclic group. The weight ratio of the organic solvent high in boiling point to said coupler is regulated to <= 0.3, thus permitting high color development performance to be exhibited even in the case of reducing an amount of organic solvent high in boiling point.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention relates to a silver halide color photographic light-sensitive material, and more specifically, it relates to a silver halide color photographic light-sensitive material, and more specifically, it relates to silver halide color photographic materials. This patent also relates to a silver halide color photographic material containing a coupler exhibiting high color development.

(Prior art) As a silver halide color photographic light-sensitive material, aromatic
Coupling with the oxidized product of grade amine color developing agent,
It is common to use one containing three types of color couplers that produce yellow, magenta, and cyan colors.

Among these, benzoylacetanilide couplers and pivaloylacetanilide couplers are used as yellow couplers. Because the molecular extinction coefficient of certain azomethine dyes is low, in order to obtain a certain level of color density, it is necessary to increase the coating amount of coupler and/or silver halide, which results in poor sharpness due to increased emulsion film thickness and increased costs. It had the disadvantage of being accompanied by an increase. On the other hand, although conventional benzoylacetanilide couplers exhibit high color-forming performance to some extent, they suffer from the drawback that color-forming performance drops significantly when the amount of high-boiling organic solvent used to disperse the coupler is reduced. .

On the other hand, in recent years, there has been a desire for higher image quality in color photographic materials, and improvement in sharpness has become a particularly important issue. In particular, the silver halide emulsion layer that uses a yellow coupler is often placed on the top of the photosensitive silver halide layers in a photographic material, so reducing the thickness of the core layer is important for improving the sharpness of the white layer. In addition to improving
It greatly contributes to improving the sharpness of the lower green-sensitive and red-sensitive silver halide emulsion layers.

Normally, couplers are dissolved in a high-boiling organic solvent and coated on a support after emulsification and dispersion, so in order to achieve a thin layer,
Reducing the amount of high-boiling point organic solvents used can be an effective means.

However, as mentioned above, with the conventionally used benzoylacetanilide couplers, when the amount of high-boiling point organic solvent used is reduced, the coloring performance deteriorates significantly.
It has been desired to develop a new yellow coupler that exhibits high color development even when the amount of high-boiling organic solvent used is reduced.

The inventors conducted extensive research and revealed a structure of a coupler (general formula [I]) in which the activity hardly decreases even when the amount of the high-boiling organic solvent in which the coupler is dispersed is reduced. Furthermore, it has been found that among these couplers, there are some whose activity increases when the amount of high-boiling organic solvent used is reduced.

By using these yellow couplers, a silver halide color photographic material with excellent color development could be achieved even if the amount of high-boiling organic solvents was reduced (or even without using them at all).

In addition, European Patent No. 379,309 partially describes the yellow coupler of the present invention, but this patent only describes the solubility of the coupler when dissolved in a high-boiling organic solvent, and only describes the photographic properties. Based on this patent, it is completely unexpected that the coupler shown in the present invention would exhibit high color development even when the amount of high-boiling point organic solvent used is reduced.

(Problems to be Solved by the Invention) Therefore, an object of the present invention is to provide a silver halide color photographic light-sensitive material that exhibits sufficient color development even when the amount of high-boiling organic solvent used for dispersing couplers is reduced. Our goal is to provide the following.

(Means for Solving the Problems) The above object of the present invention is to provide a silver halide color photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support. Few (
Each layer contains at least one dye-forming coupler represented by the following general formula [I], and the weight ratio of the high-boiling organic solvent to the dye-forming coupler contained in the core layer is 0.3.
This was achieved by a silver halide color photographic light-sensitive material having the following characteristics.

General formula [I] In the formula, Ar represents a substituted or unsubstituted aryl group,
R1 represents a halogen atom, a hydrogen atom, alkyl, alkoxy, aryloxy, or trifluoromethyl. L is 1000-oco--o--s--5o2 co--so□NH--5O2NR, --NH3O2-
-3o, O--oso2- represents a polygroup.

R2 represents a group that can be substituted on the benzene ring, and n is 0 to 3.
represents an integer. R8 is a branched alkyl group, or -c
oo--oco--0 Represents a straight-chain alkyl group or a branched alkyl group separated by multiple 8- groups.

R4 represents a substituted or unsubstituted aryl group or a substituted or unsubstituted aromatic heterocyclic group.

R5 represents a straight-chain alkyl group or a group having the same meaning as R2.

Here, the compound represented by general formula [I] will be described in detail.

In the general formula [■], R represents a hydrogen atom, a halogen atom (e.g. fluorine, chlorine, bromine, iodine), trifluoromethyl, an alkyl group having 1 to 30 carbon atoms (e.g. methyl, ethyl, n-propyl, is).

-propyl, n-butyl, tert-butyl, n-pentadecyl), an optionally substituted alkoxy group having 1 to 30 carbon atoms, or an optionally substituted aryloxy group having 6 to 30 carbon atoms. Substituents for these alkoxy groups and aryloxy groups include halogen atoms (e.g. fluorine, chlorine, bromine, iodine), alkoxy groups (
For example, methoxy, ethoxy, methoxyethoxy, n-butoxy, n-hexyloxy, n-octyloxy, 2
-ethylhexyloxy, n-dodecyloxine, n-tetradecyloxy, n-hexadecyloxy), nitro groups, amino groups (e.g. dimethylamino, diethylamino), carbonamide groups (e.g. acetamide, henzamide), sulfonamide groups (e.g. methylsulfonamide, phenylsulfonamide, dodecylsulfonamide), etc. Examples of R1 include hydrogen atom, halogen atom, and trifluoromethyl group, as well as methquine, nidoxy, n-butoxy, methoxyethquine, n-tetradecyl, phenoxy, 0-methylphenoxy, p-methoxyphenoquine, p- Nitrophenoxy, p-dodecylsulfonamidophenoxy, methyl, 1so-propyl, te
There is rt-butyl.

In general formula [1), R8 is a branched alkyl group, or -
It represents a straight chain alkyl group or a branched alkyl group separated by multiple coo--oco--o--s- groups,
These branched alkyl groups or straight-chain alkyl groups have 1 to 30 carbon atoms and may be substituted. Examples of substituents include halogen atoms (e.g. fluorine, chlorine, bromine, iodine), cyano groups, nitro groups, aryl groups (e.g. phenyl, p-tolyl, 2-methquinphenyl), aryloxy groups (e.g. phenoxy, p- Dodecyloxyphenoxy, 2,4-di-tert-pentylphenoxy, p-
tert-octylphenoxy), arylthio groups (eg phenylthio, p-tert-butylphenylthio), and the like.

Examples of R8 include 1so-propyl, SeC butyl, t
ert-butyl, 2-ethylhexyl, cyclohexyl, 2-hexynordenyl, 5,7°7-drimethyl-2-
(1,3,3-trimethylbutyl)octyl, methoxyethoxy, 3-todecyloxinepropyl, 3-dodecylthioethyl, 2-(2-hexyloxy)ethoxyethyl, α-dodenyloxyluponylethyl, α-dodecanoyl Oxyethyl, 2-(2-phenylthioethquin)ethyl, l-ethoxycarbonylethyl, 2-(2
-ethylhexyloxy)ethquinethyl.

In general formula [I), L is -〇〇〇 -oco--o--s--so.

-C〇--3o2NH--3o, NR.

-NHSO2--8ol○--0-SO2, R5 is a linear alkyl group having 1 to 30 carbon atoms (e.g. methyl, ethyl, n-butyl, n-dodecyl), or has the same meaning as R3. represents a group.

In the general formula [I], R2 represents a group that can be substituted on the benzene ring, and includes a halogen atom (e.g. fluorine, chlorine, bromine, iodine), an alkoxy group (e.g. methoxy, ethquine,
n-dodecyloxy), alkyl groups (e.g. methyl, 5
ee-pentyl), alkoxycarbonyl groups (e.g. methoxycarbonyl, ethoxycarbonyl, octyloxycarbonyl), alkylthio groups (methylthio, hex/
sulfonyl groups (e.g. hexadecylsulfonyl, methylsulfonyl), acyl groups (e.g. decanoyl), sulfonamide groups (methanesulfonamide, propanesulfonamide), sulfamoyl groups (N,N-diethylsulfamoyl, octadecylsulfamoyl), Moyle),
There are carbamoyl groups (propylcarbamoyl, N, N-diethylcarbamoyl), trifluoromethyl groups, carbonamide groups (n-dodecanamide, acetamide), cyano groups, nitro groups, aryl groups (phenyl, etc.), etc., where n is Represents an integer from 0 to 3, and when n is 2 or more, these may be the same or different.

In the general formula CI], Ar represents an optionally substituted aryl group having 6 to 30 carbon atoms. Substituents include halogen atoms (e.g. fluorine, chlorine, bromine, iodine),
Alkyl groups (e.g. methyl, ethyl, 1so-propyl, 5ec-butyl, tert-butyl, tert-octyl, n-dodecyl), trifluoromethyl groups, cyano groups, nitro groups, amino groups (e.g. dimethylamino, diethylamino), Examples include a carbonamide group (eg, acetamide, benzamide), a sulfonamide group (eg, methylsulfonamide, phenylsulfonamide, dodecylsulfonamide), or a group represented by LR3.

Here, L and R3 represent the general formula [
It is the same as shi and R3 in [■].

In the general formula [■], R4 represents a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted aromatic heterocycle. Examples of substituents for these aryl groups or aromatic heterocycles include halogen atoms,
Hydroxyl group, nitro group, cyano group, carbonyl group,
Carboxy group, sulfo group, alkyl group, aryl group, alkoxy group, acyloxy group, alkylthio group, arylthio group, alkylsulfonyl group, arylsulfonyl group, alkoxycarbonyl group, aryloquine carbonyl group, acyl group, acyloxy group, amine group, Examples include carbonamide group, sulfonamide group, carbamoyl group, sulfamoyl group, ureido group, alkoxycarbonylamino group, sulfamoylamino group, and trifluoromethyl group.

When R represents an aryl group, it preferably represents a benzene ring having the above substituent, and examples of R4 representing an aromatic heterocycle include a pyridine ring, pyrazine ring, triazine ring having the above substituent, Examples include oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, benzoxazole ring, benzthiazole ring, benzimidazole ring, pyrimidine ring, indole ring, and pyrazole ring.

Next, regarding the above-mentioned substituents R,, R,, R,, R,, L, and Ar, substituents preferably used in the present invention will be described.

R1 is preferably a chlorine atom, methoxy, trifluoromethyl, or a straight chain or branched alkyl group having 1 to 16 carbon atoms, and more preferably a chlorine atom.

R2 is particularly preferably a halogen atom, an alkoxycarbonyl group, or a sulfamoyl group, and n is O or l.
Or preferable.

R6 is preferably a cyano group, a nitro group, a sulfonyl group, a sulfonamide group, a carbamoyl group, a carbonyl group,
At least one group selected from a sulfonamide group and an acyl group is a benzene ring substituted at the para position.

Ar is preferably phenyl or a phenyl group substituted with a linear or branched alkyl group having 1 to 16 carbon atoms, and more preferably p-methoxyphenyl.

and particularly preferably -coo--o-1 or -S
is a group represented by -, and R1 preferably has 1 carbon number.
0 to 18 branched alkyl group or -coo--o--
It is a straight chain or branched alkyl group having 10 to 18 carbon atoms separated by s-.

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

/ / / I S OC1+H+i H NH3O2CH.

β02 So, NH2 $02 (■ I Ω CCX)CH2CH2COOC+4Hu(n)C=O H I/he, ○ \~hmm H 3o, CH.

C00CR(CH3)1 (■ n NovNHCOCH.

Flea/N CH.

Toad (■ Cedar So2NHC,H.

H (I-15) H 0NH2 j7 C, H6 /CH2CHC,H.

(■ H NO□ -OH Cf! / The amount of the coupler of the present invention used is lXl0 per mole of silver halide in the photosensitive layer in which the coupler of the present invention is used.
It is preferably added to the emulsion layer at a ratio of -'mol-2 moles, and more preferably from 2XlO-2 to 0.6 moles.

The coupler represented by the general formula [■] is disclosed in European Patent No. 37
It can be synthesized by the method described in No. 9,309A or a method analogous thereto.

Various known dispersion methods can be used to introduce the coupler represented by the general formula JI] of the present invention, couplers that can be used in the light-sensitive material of the present invention described below, and other lipophilic photographic organic compounds into the light-sensitive material. It will be done.

In the oil-in-water dispersion method described in U.S. Pat. Fatty acid esters, amides, phenols, alcohols, carboxylic acids, N, N-dialkylanilines, hydrocarbons, oligomers or polymers and/or boiling points at normal pressure of about 30°C to about 160°C
low-boiling organic solvents such as esters (e.g. ethyl acetate, butyl acetate, ethyl propionate,
β-ethquin ethyl acetate, methyl cellosolve acetate), alcohols (e.g. secondary butyl alcohol), ketones (e.g. methyl isobutyl ketone, methyl ethyl ketone, cyclohexanone), amides (e.g. dimethylformamide, N-methylpyrrolidone), ethers After a lipophilic photographic organic compound is dissolved in a solution such as tetrahydrofuran or dioxane, it is emulsified and dispersed in a hydrophilic colloid such as seratin.

The process and effects of the latex dispersion method and specific examples of latex for impregnation are described in U.S. Patent No. 4. 199. No. 363, West German Patent Application (OLS) No. 2. 541. No. 274, No. 2,541,230 and European Patent No. 294,104A
It is stated in the number etc. These high boiling point organic solvents and latexes not only function as dispersion media, but also improve the physical properties of the ceratin film by selecting their structure, promote color development, adjust the hue of the color image, and improve the fastness of the color image. Various functions such as improvements can be added. The high boiling point organic solvent may be in any form such as liquid, wax, or solid, and is preferably represented by the following formula (S-1E~: 5-91).

(R,,).

Formula: s-cg (AI),,-(A2),,---(A,),.

Formula: S-3: (Ar-CoαiR.

Formula::S-0 (R.

CO0tTR.

Formula [S~5] R,ofcOo-R,,).

In formula C3-1], R, , R, and R3 each independently represent an alkyl group, a nochloroalkyl group, or an aryl group.

In the formula JS 2), R4 and R5 each independently represent an alkyl group, a cycloalkyl group, or an aryl group, and R6 is a halogen atom (F, Cj2, Br, below), an alkyl group, an alkokino group, an aryloquine group, or It represents an alkoxycarbonyl group, and a represents an integer of 0 to 3. When a is plural, the plural Ro's may be the same or different.

In formula (S-33), Ar represents an aryl group, b represents an integer of 1 to 6, and R7 represents a b-valent hydrocarbon group or a hydrocarbon group bonded to each other through an ether bond.

In formula C8-4], R8 represents an alkyl group or a cycloalkyl group, C represents an integer of 1 to 6, and R1 represents a C-valent hydrocarbon group or a hydrocarbon group bonded to each other through an ether bond.

In formula [5-5), d represents an integer of 2 to 6, and RI
O represents a d-valent hydrocarbon group (excluding aromatic groups), and R+ represents an alkyl group, cycloalkyl group, or aryl group.

In formula 1: s-6', Rl 1, RlI and R+1 each independently represent an alkyl group, a cycloalkyl group or an aryl group. R12 and R13 or R18 and Rl
i may be bonded to each other to form a ring.

In formula C3-7), Rli represents an alkyl group, a cycloalkyl group, an alkoxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, an a+)-al group, or a cyano group, and R11 represents a halogen atom, an alkyl group, or a cycloalkyl group. group, aryl group, alkoxy group or aryloxy group, and e represents an integer of 0 to 3. When e is a plurality of R16s, the plurality of R16s may be the same or different.

In formula C3-ED, R- and RlI each independently represent an alkyl group, a cycloalkyl group, or an allyl group, R19 represents a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, or an aryloxy group, and f represents an integer from 0 to 4. When f is plural, the plural RRIs may be the same or different.

In the formula (S-9'll, A,, A3,...A. each represents a polymerized unit provided by a different non-color-forming ethylene-like monomer, and a,, a2,..., ao
represents the weight fraction of each polymerized unit, and n is 1 to 3
Represents an integer of 0.

Specific examples of the high boiling point organic solvent used in the present invention are shown below.

O-HfiOcH2CHCtHg-n)+C2H.

0=P-ZOCH! CHCH. -C. H. -t)
.

CH.

, coo-′, H〉 CH.

CH3COOCC00C2Hrn CH2C00Ct Han 2H5 2Hi C,H,CHCH,QC○(CH2>-C00CH2C
HC4Hs-n polymethyl methacrylate (average molecular weight 20.000) Poly(N-t-butylacrylamide) (average molecular weight 60,000) Chlorinated paraffin (average composition C1□H,,C1,) Polymers used in the present invention Examples of boiling point organic solvents other than those mentioned above and/or methods for synthesizing these high boiling point organic solvents are described in, for example, U.S. Pat.
No. 33,514, No. 2772.163, No. 2,
No. 835,579, No. 3,676.137, No. 3
．． 912. No. 515, No. 3,936,303,
4,080.209, 4,127,413, 4,193,802, 4. 239. 8
No. 51, No. 4,278,757, No. 4,363.
No. 873, No. 4,483,918, No. 4.745
,049, European Patent No. 276.319A, Jikai Showa No. 48-47335, European Patent No. 51149028, European Patent No. 61-
No. 84641, No. 62118345, No. 62-247
No. 364, No. 63-167357, No. 64-6874
No. 5, JP-A No. 1-101543, etc.

The amount of the high boiling point organic solvent used in the present invention is 0.3 or less by weight relative to the coupler used in each photosensitive layer. From the viewpoint of sharpness improvement effect, 0.1 is more preferable.
It is as follows. Of course, no high-boiling organic solvent may be used at all.

As magenta couplers, various pyrazolone type magenta couplers and pyrazoloazole type magenta couplers are preferably used.As pyrazolone type magenta couplers,
US Patent Tube 4. 310. No. 619, No. 4,351
, 897, European Patent No. 73.636, U.S. Patent No. 3
, No. 061,432, No. 3,725,067, JP-A No. 60-35730, No. 55-118034, No. 6
No. 0185951, U.S. Patent No. 4,556,630,
Particularly preferred are those described in International Publication No. WO38104795 and the like.

Examples of pyrazoloazole magenta couplers preferably used in the present invention include magenta couplers represented by the following general formula (I[).

General formula (■)) Zc-Zb (In the formula, R' represents a hydrogen atom or a substituent, and Y represents a hydrogen atom or a leaving group. Za, Zb, and Zc are methine, substituted methine, =N- or - Represents NH-, Za-
One of the Zb bond and the Zb-Zc bond is a double bond, and the other is a single bond.

When the Zb-Zc bond is a carbon-carbon double bond, it includes the case where it is a carbon-carbon double bond or a part of an aromatic ring.

When R1 or Y forms a multimer of dimers or more, and when Za, Zb or Zc is a substituted methine, the substituted methine also forms a multimer of dimers or more) The pyrazoloazole coupler represented by formula (II) is a known coupler, and among the pyrazoloazole couplers, it is disclosed in U.S. Pat. The imidazo[1,2b] pyrazoles described in U.S. Pat. No. 4,540.654 are preferred, and the pyrazolo E1.
5-b2CL 2,4) Triazoles are particularly preferred.

Other 2.3 or 6 branched alkyl groups or pyrazolotriazole rings as described in JP-A No. 61-65245
Pyrazolotriazole coupler directly connected to JP-A No. 6
Pyrazoloazole coupler containing a sulfonamide group in the molecule described in No. 1-65246, JP-A-61-147
The pyrazoloazole coupler having an alkoxyphenylsulfonamide ballast group described in No. 254 is disclosed in European Patent No. 2
It is preferable to use pyrazolotriazole couplers having an alkoxy group or aryloxy group at the 6-position described in No. 26.849 and No. 294,785.

Specific examples of couplers represented by general formula (n) are shown below.

/ C, H1+(j) CHl Co 813(n) Q.C., H.

CH.

C, H, □ (1) CH.

C, H, □ (1) CslL+(n) C.H.

M-14 C1゜H2 CH,,cp C6HH(n) Cyan couplers include phenolic and naphthol couplers, and are described in U.S. Patent No. 4゜052.212.
No. 4,146,396, No. 4,228,23
No. 3, No. 4. 296. No. 200, No. 2,369
, No. 929, No. 2,801.171, No. 2,77
No. 2,162, No. 2,895,826, No. 3.
772. No. 002, No. 3,758,308, No. 4,334.011, No. 4,327,173, West German Patent Publication No. 3,329,729, European Patent No. 121
．． No. 365A, No. 249,453A, U.S. Patent No. 3
, 446,622, 4,333゜999, 4,775,616, 4゜451.559, 4,427,767, 4,690,889 ,
Same No. 4. 254. No. 212, No. 4,296,19
No. 9, JP-A-6142658, etc. are preferred.

Among these, particularly preferred are the ureido type cyan coupler represented by the general formula (II[) and the 5-amidonaphthol type cyan coupler represented by the general formula (IV).

General formula (III) H (wherein, R represents a substituted or unsubstituted aryl group, R
2 represents a substituted or unsubstituted alkyl group, aryl group, cycloalkyl group, or heterocyclic residue, and Z represents a hydrogen atom or a coupling-off group. ) Specific examples of the cyan coupler represented by the general formula (I) are shown below, but the present invention is not limited thereto.

Among these, particularly preferred are the ureido type cyan coupler represented by the general formula (III) and the 5-amidonaphthol type cyan coupler represented by the general formula (IV).

General formula (I[[) (wherein, R1 represents a substituted or unsubstituted aryl group, R
2 represents a substituted or unsubstituted alkyl group, aryl group, cycloalkyl group, or heterocyclic residue, and Z represents a hydrogen atom or a coupling-off group. ) Specific examples of the cyan coupler represented by the general formula (I[I) are shown below, but the present invention is not limited thereto.

/ C-16 C-11 General formula [■] H R, NHX (In formula [IV), R1 is -CONR, R,, So,
Represents NR, R. R2 represents a group that can be substituted on the naphthalene ring, and l is an integer of 0 to 3. R8 represents an alkyl group, an aralkyl group, an anru group, an alkoxycarbonyl group, an alkylaminocarbonyl group, or an alkylsulfonyl group, and these groups may be further substituted with a halogen atom, an alkoke group, or the like. X represents a hydrogen atom or a group capable of being separated by a coupling reaction with an oxidized aromatic primary amine developing agent. However, R1 and R5 may be the same or different (
, independently represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.

When l is plural, R2 may be the same or different,
They may also be combined with each other to form a ring.

R2 and R3, or R8 and X may be bonded to each other to form a ring.

Further, R1, R2, R8, or X may form a dimer or a multimer of more than two valent groups bonded to each other via a divalent or divalent or higher valent group. ) Below is the general formula (IV
) Specific examples of couplers represented by the above are given below, but the invention is of course not limited to these.

C,H,-C NH C,R5 So, NH NH ]9 ○HC C,, R25 NH The photosensitive material of the present invention has a blue-irradiated layer, a green-sensitive layer, a red-sensitive layer on a support. It is sufficient that at least one silver halide emulsion layer is provided, and there are no particular restrictions on the number and order of the silver halide emulsion layers and the non-irradiating layers. A typical example is a silver halide photographic window having on a support at least one light-sensitive layer consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. It is a photosensitive material, and the photosensitive layer is a unit photosensitive layer that is sensitive to blue light, green light, or red light. In multilayer silver halide color photographic light-sensitive materials, generally The layers are arranged in this order from the support side: a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer. However, depending on the purpose, the order of installation may be reversed, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layer.

Non-photosensitive layers such as various intermediate layers may be provided between the above-mentioned silver halide photosensitive layers and between the uppermost layer and the lowermost layer.

The intermediate layer includes JP-A Nos. 61-43748 and 59-1.
No. 13438, No. 59-113440, No. 61-20
Coupler, DIR compound, etc. as described in No. 037 and No. 61-20038 may be included,
It may also contain a commonly used color mixing inhibitor.

The plurality of silver halide emulsion layers constituting each unit photosensitive layer are a high-temperature emulsion layer, a low-speed emulsion layer, as described in West German Patent No. 1,121,470 or British Patent No. 923□045. A two-layer configuration of layers can be preferably used.

Usually, it is preferable to arrange the halogen emulsion so that the intensity of light decreases toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer.
No. 112751, No. 62200350, No. 62-20
As described in No. 6541, No. 62-206543, etc., a low-sensitivity emulsion layer may be provided on the side far from the support, and a high-sensitivity emulsion layer may be provided on the side close to the support.

As a specific example, from the side farthest from the support: low sensitivity blue photosensitive layer (BL) / high sensitivity blue photosensitive layer (B) / high sensitivity green photosensitive layer (GH) / low sensitivity green photosensitive layer Layer (GL)/
High sensitivity red photosensitive layer (R)l) / low sensitivity red photosensitive layer (RL), or B) I/BL/GL/G)l/
R11/RL order or BH/BL/GH/GL/R
They can be installed in the order of L/RH.

Further, as described in Japanese Patent Publication No. 55-34932, from the side farthest from the support, the blue-sensitive layer/GH/R
They can also be arranged in the order of H/GL/RL. Furthermore, as described in JP-A-56-25738 and JP-A-62-63936, the blue-sensitive layer/GL/RL/GO/RI (is arranged in IIIJ [from the side farthest from the support). You can also do that.

In addition, as described in Japanese Patent Publication No. 49-15495, the upper layer is a silver halide emulsion layer with the highest sensitivity, the middle layer is a silver halide emulsion layer with lower sensitivity, and the lower layer is more sensitive than the middle layer. An example is an arrangement consisting of three layers with different photosensitivity, in which a silver halide emulsion layer with a low density is disposed and the photosensitivity gradually decreases toward the support. Even when it is composed of three layers with different photosensitivity, as described in JP-A No. 59-202464,
In the same color-sensitive layer, the medium-sensitivity emulsion layer/high-sensitivity emulsion layer/low-irradiation emulsion layer may be arranged in this order from the side remote from the support.

In addition, high-sensitivity milk layer / low-sensitivity milk layer / medium-sensitivity emulsion layer,
Alternatively, the layers may be arranged in the following order: low-temperature emulsion layer/medium-temperature emulsion layer/high-sensitivity emulsion layer.

Furthermore, even in the case of four or more layers, the arrangement may be changed as described above.

As mentioned above, various layer structures and arrangements can be selected depending on the purpose of each photosensitive material.

The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide, containing about 30 mol% or less of silver iodide. . Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mole percent to about 10 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 include, for example, Research Disclosure (RD) k17643 (
December 1978), pp. 22-23, “1. Emulsion production (
Emulsion preparation and
types)', and the same species 18716 (197
November 9), 648 pages, Dobei 307105 (19
November 1989, pages L863-865, and “Physics and Chemistry of Photography” by Grafkide, published by Paul Montell, CP, Gl.
afkides, Chemie et Ph1siq
ue Photographique, Paul M.
ontel, 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (G, F, DuffinP
Photographic Emulsion Ch
ea+1try (Focal Press19
66) ), “Production and Coating of Photographic Emulsions” by Zelikman et al.
, published by Focal Press (V, L, Zelikna
Netal、Making and Coatin
g Photographic Emul-sion,
Focal Press+ 1964).

U.S. Patent Nos. 3,574,628 and 3,655,39
Monodisperse emulsions such as those described in No. 4 and British Patent No. 1,413,748 are also preferred.

Tabular grains having aspect ratios of about 3 or greater can also be used in the present invention. Tabular grains are described in Cutoff, Photographic Science and Engineering.
ence and Engineering), Vol. 14, pp. 248-257 (1970); U.S. Patent No. 4
, 434.226, 4,414, 310, 4,
433,048, 4,439,520, and British Patent No. 2.112.157.

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. They may also be bonded with compounds other than silver halide, such as silver rhodan or lead oxide, and mixtures of particles of various crystal forms may be used.

The above-mentioned emulsions may be of the surface latent image type that forms latent images primarily on the surface, of the internal latent image type that forms inside the grains, or of the type that has latent images both on the surface and inside the grains, but negative-tone emulsions It is necessary that Among the internal latent image type emulsions, the core/shell type internal latent image type emulsion may be a core/shell type internal latent image type emulsion described in JP-A-63-264740. No. 59-133542.

The thickness of the shell of this emulsion varies depending on development processing and the like, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

The silver halide emulsion used is usually one that has been subjected to physical ripening, chemical ripening, and spectral enhancement. Additives used in such processes are subject to Research Disclosure
17643, Nα18716 and Nα3071
05, and the relevant parts are summarized in the table below.

The photosensitive material of the present invention includes grain size, grain size distribution, halogen composition, grain shape,
Two or more types of emulsions differing in at least one characteristic of sensitivity can be mixed and used in the same layer.

Silver halide grains coated with grain surfaces as described in U.S. Pat. No. 4,082,553, U.S. Pat. No. 4.626.4
Silver halide grains and colloidal silver with covered grain interiors described in No. 98 and JP-A No. 59-214852 are preferably used in a photosensitive silver halide emulsion layer and/or a substantially non-photosensitive hydrophilic colloid layer. Can be used.

Silver halide grains that have their interiors or surfaces covered are defined as - (
A method for preparing silver halide grains in which the interior or surface of silver halide grains can be developed (in a non-imagewise manner) is described in U.S. Pat. No. 4,626,498 and JP-A-59 -214852.

The silver halide forming the inner core of the core/shell type silver halide grains may have the same halogen composition or different halogen compositions. As the silver halide, any of silver chloride, silver chlorobromide, silver iodobromide, and silver chloroiodobromide can be used. Although there is no particular limitation on the grain size of these fogged silver halide grains,
The average particle size is 0. O1 to 0.75μ, particularly preferably 0.05 to 0.6μ, and the particle shape is not particularly limited and may be regular particles;
It may be a polydisperse emulsion, but it may be a monodisperse emulsion (at least 95% of the weight or number of silver halide grains is ±4 of the average grain size).
0% or less) is preferable.

In the present invention, it is preferable to use non-light-sensitive fine-grain silver halide. Non-light-sensitive fine-grain silver halide is not exposed to light during imagewise exposure to obtain a dye image, but is not exposed to light during the development process. These are fine silver halide grains that are not substantially developed and are preferably not fogged in advance.

The fine-grain silver halide has a silver bromide content of 0 to 100 mol %, and may contain silver chloride and/or silver iodide if necessary, preferably silver iodide of 0.5 mol %. It contains ~10 mol%.

The fine grain silver halide preferably has an average grain size (average diameter equivalent to a circle of projected area) of 0.01 to 0.5 g m.
More preferably 0.02 to 0.2 μm.

Fine-grain silver halide can be prepared in the same manner as ordinary photosensitive silver halide. In this case, the surface of the silver halide grains does not need to be optically sensitized (and spectral enhancement is not necessary. It is preferable to add a known stabilizer such as a benzothiazolium-based compound, a benzothiazolium-based compound, a mercapto-based compound, or a zinc compound. Colloidal silver can preferably be contained in this layer containing fine silver halide grains.

The coating silver amount of the photosensitive material of the present invention is preferably 6.0 g/n (or less), and most preferably 4.5 g/rrf or less.

Known photographic additives that can be used in the present invention are also described in the three Research Disclosures mentioned above, and the relevant descriptions are shown in the table below.

In addition, in order to prevent deterioration of photographic performance due to formaldehyde gas, US Patent No. 4,411,987 and US Pat.
It is preferable to add to the light-sensitive material a compound that can be immobilized by reacting with formaldehyde as described in No. 435.503.

The photosensitive material of the present invention includes U.S. Pat. No. 4,740,454, U.S. Pat.
It is preferable to contain a mercapto compound described in JP-A No. 1283551.

A compound that releases a fogging agent, a development accelerator, a silver halide solvent, or a precursor thereof irrespective of the amount of developed silver produced during the development process, which is described in JP-A-1-106052, is added to the light-sensitive material of the present invention. It is preferable to include.

The dye dispersed in the photosensitive material of the present invention by the method described in International Publication No. WO 38104794, Japanese Patent Application Publication No. 1-502912, or EP 317,3084, US Pat.
, 420,555 and JP-A-1-259358.

Various color couplers can be used in the present invention, and specific examples thereof include the aforementioned Research Disclosure Toru 17643, ■-C-C1, Bevel 307105,
■It is described in the patent described in -〇-G.

As the yellow coupler, in addition to those represented by the general formula [I] of the present invention, for example, U.S. Patent No. 3,933.5
No. 01, No. 4, No. 022, No. 620, No. 4.32
No. 6024, No. 4.401.752, No. 4.24
No. 8,961, Special Publication No. 5840739, British Patent No. 1
, No. 425.020, No. 1, No. 476, No. 760,
U.S. Patent No. 3,973,968, U.S. Patent No. 4,314,0
No. 23, No. 4,511.649, European Patent No. 249
, No. 473A, etc. are preferred.

Typical examples of polymerized dye-forming couplers are U.S. Pat.
No. 4.576910, British Patent No. 2.102.1
No. 37, European Patent No. 341188A, etc.

Couplers whose coloring dyes have appropriate diffusivity include U.S. Patent No. 4,366.237 and British Patent No. 2,125.
．． 570, European Patent No. 96,570 and German Patent Publication No. 3.234.533 are preferred.

Colored couplers for correcting unnecessary absorption of coloring dyes are recommended in Research Disclosure 17643.
-G section, ■-G section of N11307105, U.S. Patent No. 4,163,670, Japanese Patent Publication No. 57-39413, U.S. Patent No. 4,004,929, No. 4.138.25
No. 8, British Patent No. L146,368 are preferable, and couplers that correct unnecessary absorption of coloring dyes by fluorescent dyes released during campling are described in U.S. Pat. No. 4,774.181. , U.S. Patent No. 4,77
It is also preferred to use a coupler having as a leaving group a dye precursor group capable of reacting with a developing agent to form a dye as described in No. 7.120.

Compounds that release photographically useful residues upon coupling can also be preferably used in the present invention.

DIR couplers that release development inhibitors include the aforementioned RD
17643, ■-F term and the same Nα307105, ■-
The patent described in Section F, JP-A-57-151944,
Preferred are those described in US Pat. Nos. 57-154234, 60-184248, 63-37346, 63-37350, and US Pat.

Couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent No. 2.097,140;
Those described in JP-A No. 2.13L188, JP-A-59-157638, and JP-A-59470840 are preferred. Also, JP-A-60-107029, JP-A No. 60-252340
Compounds that release fogging agents, development accelerators, silver halide abrasions, etc. through redox reactions with oxidized developing agents described in JP-A-144940 and JP-A-1-45687 are also preferred.

Other compounds that can be used in the light-sensitive material of the present invention include competitive couplers described in U.S. Pat. No. 4,130.427, U.S. Pat. , the multi-equivalent couplers described in JP-A-60-185950, etc.
DIR redox compound releasing coupler, DIR coupler releasing coupler, D as described in JP-A-62-24252 etc.
IR coupler releasing redox compound or DIR redox releasing redox compound, European Patent No. 173302
No. A, a coupler that releases a dye that recovers color after separation as described in No. 313.308A, R, D, Ma 11449, No. 2
4241, a bleaching accelerator releasing coupler described in JP-A-61-201247, etc., a ligand-releasing coupler described in U.S. Pat. No. 4,555,477, etc., JP-A-63-757, etc.
Couplers that emit leuco dyes as described in US Pat. No. 4774, and couplers that emit fluorescent dyes as described in US Pat.

The above-mentioned coupler used in the present invention can be introduced into the photosensitive material by the same dispersion method as that for the coupler represented by the general formula (1).

The color photosensitive material of the present invention contains phenethyl alcohol and JP-A No. 53-257747, No. 62-272248
1,2-benzisothiazolin-3-one, n-butyl p-hydroxybenzoate, phenol, 4-chloro-3,5 described in JP-A-1-80941
-dimethylphenol, 2-phenoxyethanol, 2
It is preferable to add various preservatives or antifungal agents such as -(4thiazolyl)benzimidazole.

The present invention can be applied to various colored fluorescent materials. Typical examples include color negative film for general use or movies, color reversal film for slides or television, color paper, color positive 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 17643, 647 of Nα18716
From the right column of the page to the left column of page 648, and also 8 of 307105
It is described on page 79.

In the light-sensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or less, more preferably 23 μm or less, even more preferably 18 μm or less, and 16 μm or less. is particularly preferred, and the membrane swelling rate TI/□ is preferably 30 seconds or less, more preferably 20 seconds or less. The film thickness was measured at 25°C and 55% relative humidity (2
The membrane swelling rate TI/□ means the membrane thickness measured in days).
0, which can be measured according to techniques known in the art, e.g.
Photographic Science and Engineering (Photogr, Sci, Eng,)
, Vol. 19, No. 2, pp. 124-129, the T I/! The saturated film thickness is defined as 90% of the maximum swollen film thickness reached when treated with a color developing solution at 30° C. for 3 minutes and 15 seconds, and is defined as the time until the saturated film thickness reaches 172.

The membrane swelling rate T I / Z can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating. Further, the swelling rate is preferably 150 to 400%. The swelling rate can be calculated from the maximum swollen film thickness under the above-mentioned conditions according to the formula: (maximum swollen film thickness - film thickness)/film thickness.

The photosensitive material of the present invention has a hydrophilic colloid layer (with a total dry thickness of 2 μm to 20 μm) on the side opposite to the side having the emulsion layer.
It is preferable to provide a bank layer (referred to as a bank layer). This hack layer contains the aforementioned light absorbers, filter dyes, ultraviolet absorbers, anti-static agents, hardeners, binders, desensitizers,
It is preferable to contain a lubricant, a coating aid, a surface active agent, etc. The swelling ratio of this back layer is preferably 150 to 500%.

The color photographic light-sensitive material according to the present invention can be produced by the conventional method described in the aforementioned RD, pages 28-29 of Xun 17643, pages 651 left column to right column of Kaimagai 18716, and pages 880-881 of Koji 307105. It can be developed by

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-phinidinediamine compounds are preferably used, representative examples of which include 3-methyl-4-amino-N,N-diethylaniline, 3-Methyl-4-amino-N-ethyl-N-
β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-Nβ-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-β-methquinethylaniline and sulfates thereof, Examples include hydrochloride and p-toluenesulfonate. Among these, 3-methyl-4-amino-N-ethyl-
Nβ-hydroxyethylaniline sulfate is preferred. Two or more of these compounds can be used in combination depending on the purpose.

Color developers include pH buffers such as alkali metal carbonates, borates or phosphates, developing agents such as chloride, bromide, iodide salts, benzimidazoles, benzothiazoles or mercapto compounds. It is common to include inhibitors or anticapri agents. In addition, if necessary, hydroxylamine, diethylhydroxylamine, sulfites, hydrazines such as N,N-biscarboxymethylhydrazine, phenylsemicarbazides,
Various preservatives such as triethanolamine, catechol sulfonic acids, organic solvents such as ethylene glycol, diethylene glycol, development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines, dye-forming couplers, competitive couplers. , an auxiliary developing agent such as 1-phenyl-3-pyrazolidone, a viscosity imparting agent, various calcinates such as aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid, and phosphonocarboxylic acid, for example, Ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid,
Cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N,N,N-)limethylenephosphonic acid, ethylenediamine-N,N,N,N tetramethylenephosphonic acid , ethylenediaminedi(0-hydroxyphenylacetic acid) and salts thereof.

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 1-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol. Alternatively, they can be used in combination.

The pit of these color developing solutions and black and white developing solutions is 9 to 12.
It is common that The amount of replenishment of these developing solutions depends on the color photographic light-sensitive material to be processed, but it is less than 3i per square meter of light-sensitive material, and by reducing the bromide ion concentration in the replenisher,
It can also be set to 0d or less. When reducing the amount of replenishment, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the area of contact with the air in the processing tank.

The contact area between the photographic processing solution and air in the processing tank can be expressed by the aperture ratio defined below.

That is, the above aperture ratio is preferably 0.1 or less, more preferably 0.001 to 0.05. As a method for reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the surface of the photographic processing liquid in the processing tank,
Method using a movable lid described in No. 033, JP-A-63
The slit development processing method described in Japanese Patent No. 216050 can be mentioned. Reducing the aperture ratio is important not only for both color development and black and white development processes, but also for subsequent processes,
For example, it is preferable to apply it to all steps such as bleaching, bleach-fixing, fixing, washing, and stabilization.Also, the amount of replenishment can be reduced by using means to suppress the accumulation of bromide ions in the developer. .

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 carried out in two ways: bleach-fixing process after 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 that can be used include compounds of polyvalent metals such as iron (I [ Aminopolycarboxylic acids such as acetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid, or complex salts such as citric acid, tartaric acid, malic acid, etc. may be used. I can do it. Among these, ethylenediaminetetraacetic acid iron (I[I) complex salt and 1,3-diaminopropanetetraacetic acid iron (m)i! Aminopolycarboxylic acid iron (I [
[) Complex salts are particularly useful in both bleach and bleach-fix solutions. These aminopolycarboxylic acid iron (I[
[) The pH of bleach or bleach-fix solutions using complex salts is usually 4.
．． 0-8, but lower p for faster processing
It can also be processed by a.

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-53-32736, No. 53-57831, No. 53-
No. 37418, No. 53-72623, No. 53-956
No. 30, No. 53-95631, No. 53-104232
Compounds having a mercapto group or a disulfide group described in JP-A No. 53-124424, No. 53-141623, No. 53-28426, Research Disclosure No. Nα17129 (July 1978), etc.; Thiazolidine derivatives described in No.
Japanese Patent Publication No. 45-8506, Japanese Patent Publication No. 52-20832,
No. 53-32735, U.S. Patent No. 3,706.561
Thiourea derivatives described in West German Patent No. 1,127,7
No. 15, iodide salts described in JP-A-58-16,235; West German Patent Nos. 966.410 and 2,748,430
Polyoxyethylene compounds described in No. 1973-
Polyamine compounds described in No. 8836; other JP-A-49
-40,943, 49-59,644, 53-
No. 94,927, No. 54-35,727, No. 55-2
Compounds described in No. 6,506 and No. 58-163.940; 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. 3,893,858.
No., West German Patent No. 1.290.812, Japanese Unexamined Patent Publication No. 1983-9
Preferred are the compounds described in US Pat. No. 5.630, and also preferred are the compounds described in US Pat. No. 4,552,834.
These bleach accelerators may be added to the light-sensitive material, and are particularly effective when bleach-fixing color light-sensitive materials for photography.

In addition to the above-mentioned compounds, the bleaching solution and bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach staining. Particularly preferred organic acids have an acid dissociation constant (pKa) of 2.
~5, specifically acetic acid, propionic acid,
Hydroxyacetic acid and the like are preferred.

Examples of fixing agents used in fixing solutions and bleach-fixing solutions include thiosulfates, thiocyanates, 1,000-onythyl compounds, thioureas, and large amounts of iodide salts, but thiosulfates are generally used. ammonium thiosulfate is the most widely used. It is also preferable to use a combination of thiosulfate, thiocyanate, thioether compounds, thiourea, etc. As a preservative for fixing solutions and bleach-fixing solutions, sulfites, bisulfites, carbonyl bisulfite adducts, or European patented The sulfinic acid compounds described in No. 294769A are preferred. Furthermore, various aminopolycarboxylic acids and organic phosphonic acids are preferably added to the fixing solution and bleach-fixing solution for the purpose of stabilizing the solution.

In the present invention, the fixing solution or bleach-fixing solution has pH!
Compounds with pKa of 6.0 to 9.0, preferably imidazole, 1-methylimidazole, 1
It is preferable to add imidazoles such as ethylimidazole and 2-methylimidazole in an amount of 0.1 to 10 mol/i.

The total time for the desilvering process is preferably as short as possible without causing desilvering defects.The preferred time is 1 minute to 3 minutes, more preferably 1 minute to 2 minutes. In addition, the processing temperature is 25°C to 5°C.
0°C, preferably 35°C to 45°C. In a preferred temperature range, the desilvering rate is improved and the occurrence of staining after processing is effectively prevented.

In the desilvering process, it is preferable to strengthen the stirring as much as possible.A specific method for strengthening the stirring is to impinge a jet of processing liquid on the emulsion surface of a photosensitive material as described in JP-A-62-183460. Method and JP-A-62-183
No. 461, a method of increasing the stirring effect using a rotating means, and further improving the stirring effect by moving the photosensitive material while bringing the emulsion surface into contact with a wiper blade provided in the liquid to create turbulence on the emulsion surface. Examples include a method of increasing the circulation flow rate of the entire treatment liquid. Such means for improving agitation is effective for all bleaching solutions, bleach-fixing solutions, and fixing solutions. It is believed that improved stirring speeds up the supply of bleach and fixing agent into the emulsion film, and as a result increases the desilvering rate. Further, the agitation improving means described above is more effective when a bleach accelerator is used, and can significantly increase the accelerating effect and eliminate the fixing inhibiting effect caused by the bleach accelerator.

The automatic developing machine used for the photosensitive material of the present invention is
No. 0491257, No. 60-191258, No. 60-
It is preferable to have a photosensitive material conveying means described in No. 191259.As described in the above-mentioned Japanese Patent Application Laid-Open No. 191257/1983, such a conveying means prevents the carrying of processing liquid from the front bath to the rear bath. This effect is particularly effective in shortening the processing time in each step and reducing the amount of processing solution replenishment.

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 of the 5ociety of M
tion Picture and Te1svis
ion Engineers No. 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 described in the issue, Osamu Horiguchi, "Chemistry of antibacterial and fungicidal agents J (1986), Sankyo Publishing, Hygiene Technology synthesis "Sterilization, sterilization, and anti-mildew technology for microorganisms," (1982)
Industrial Technology Society, Japan Antibacterial and Antifungal Synthesis “Encyclopedia of Antibacterial and Antifungal Agents” (
It is also possible to use the fungicides described in (1986).

The washing water used in the processing of the photosensitive material of the present invention, 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 2
A range of 30 seconds to 5 minutes at 5 to 40°C is selected. Furthermore, the photosensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water.

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. For example, a stabilization bath containing a dye stabilizer and a surfactant, which is used as a final bath for a color light-sensitive material for side shadows, may be further carried out. Examples of the dye stabilizer that can be mentioned include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts.

It is also possible to add various botanical agents and antifungal agents to this stabilizing bath.

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

When each of the above-mentioned processing liquids is concentrated by evaporation in processing using an automatic processor or the like, it is preferable to correct the concentration by adding water.

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. For this purpose, it is preferable to use various precursors of color developing agents. For example, U.S. Pat. No. 3,342,59
Indoaniline compound described in No. 7, No. 3,342,
No. 599, Research Disclosure Series 14, 85
0 and 15.159 of the same publication,
Aldol compounds described in U.S. Patent No. 13,924, metal salt complexes described in U.S. Pat.
Examples include urethane compounds described in No. 135628.

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

Typical compounds are JP-A-56-64339 and JP-A No. 57-
No. 144547 and No. 58-115438.

The various processing liquids used in the present invention are used at a temperature of 10°C to 50'C, and the standard temperature is usually 33°C to 38°C, but it is possible to use a higher temperature to accelerate the processing and shorten the processing time. Conversely, it is possible to improve the image quality and the stability of the processing solution by lowering the temperature.

Further, the silver halide photosensitive material of the present invention is disclosed in U.S. Patent No. 4,
No. 500,626, JP-A-60-133449, No. 5
It can also be applied to the heat-developable photosensitive materials described in No. 9-218443, No. 61-238056, European Patent No. 210.660A2, and the like.

(Examples) The present invention will be explained in more detail below with reference to Examples, but the present invention is not limited thereto.

Example 1 On a subbed cellulose triacetate film support,
Sample 101, which is a single-layer color photosensitive material for evaluation testing, was prepared by coating two layers having the composition shown below.

(Photosensitive layer composition) The number corresponding to each component indicates the coating amount expressed in g/d units. However, for sensitizing dyes, the coating amount is expressed in moles per mole of silver halide in the same layer.

(Sample 101) 1st layer (blue-sensitive emulsion layer) Emulsion Silver 0.43 average Ag
L content: 8.9% Average particle size: 0.73 μm (coefficient of variation) (14%) Core/Shell-3/F double structure particles (AgI content: 2 trillion 5 Sensitizing dye: 3.6XlO- 'YC-
1 0.75HBS-1
0. 75W
-1 0.
10F-1
0.004B-1
0.014B-2
0.010 Seratin
2.00 2nd layer (protective layer) H-1 0.18W-2
0.10B-2
0, 01B-3 (diameter 1.
7μ) 0.05B-4 (diameter 1.7μ)
) 0.10B-5
0. 10 gelatin
1.20 The compounds used in Example 1 are described below.

B5-1 CH.

C-2 ot C2H3 Nap, 5-CH-COOCH. C.H.C. H.

CH2-C00CH2CHC. H.

C2H.

H H B-1 16 CH2-CH Chi ``PeCH2-C8 7x/y=70
/30 CH, CH.

(CHz)-S i O-65i-()To■I5i-0
St+5l(CH3)3 CH2=CH3αCHCONH-CH2CH,=CH8
O, CHCONH-CH.

CH.

CHz -i CH2-c aroma τgo CH2-C, x/y
=10/90COOHC00CH.

sensitizing dye CH.

CH3 1 CH2-C "Formula CH2-C7 x/y=4
0/60OOH 0OCH3 The coupler used (YC-
Samples 102 to 118 were prepared by changing the type of 1) and the amount of high boiling point organic solvent (HBS-1) as shown in Table 1. In addition, all couplers are YC used in sample 101.
-1 was substituted in an equimolar amount.

The above samples 101-118 were subjected to imagewise exposure through an optical wedge, and the following treatments were performed. The processing was carried out after a running process was carried out in advance using Super HG-400 manufactured by Fuji Photo Film Co., Ltd. until the cumulative replenishment amount of the color developer was three times that of the mother liquor tank.

Process Processing time Color development 2 minutes 15 seconds Bleach 50 seconds Bleach fixing 50 seconds fixing 50 seconds Water wash +1 + 30 seconds Water wash (2120 seconds Processing process Processing temperature Replenishment amount 5 38.0°C23-3860°C 38,0 °C 38,0°C 38,0°C 38,0°C34-51n! Stability 20 seconds 38.0°C20-Drying 1 minute 55°C *The amount of replenishment is the amount per meter of 35mm width. It was a countercurrent method from (2) to (1), and all the overflow of the washing water was introduced into the fixing bath.The bleach-fixing bath was refilled at the top of the bleach tank of the automatic processor, the bottom of the bleach-fix tank, and the bottom of the bleach-fix tank. The upper part of the fixing tank and the bottom part of the bleach-fixing tank were connected with a pipe so that all the overflow liquid generated by supplying replenisher to the bleaching tank and fixing tank flowed into the bleach-fixing bath. The amount of bleaching solution carried into the bleaching process, the amount of bleaching solution carried into the fixing process, and the amount of fixing solution carried into the washing process were 2.5 mC2, 0 mC2, 0 mi! per 1 meter length of 35 mm wide photosensitive material, respectively. Further, the crossover time is 5 seconds in each case, and this time is included in the processing time of the previous step.

The composition of the treatment liquid is shown below.

(Developer) 3! Mother liquor (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1-Hydroxyethythene-1,1-diphosphonic acid Sodium sulfite Potassium carbonate Potassium bromide Potassium iodide Hydroxylamine sulfate 2-Methyl-4-CN- Ethyl-N- (β-Hydroxyethyl)amine] Add aniline sulfate solution to pH (bleach solution) 1.3-Propylenethia 2.0 3.3 3.9 37.5 1.4 1.3■ 2.4 4.5 1.01 10,05 2.2 3.3 5.2 39.0 0.4 3.3 6.1 1.01 10.15 Mother liquor (g) 144,0 Replenisher (g) 206,0 Minshi Ferric ammonium acetate-hydrochlorinated ammonium bromide 84.0 Ammonium nitrate 17.5 Hydroxyacetic acid 6
3.0 Acetic acid 33.2 Add water to pH 1.0j7 [adjust with aqueous ammonia] 3.20 (bleach-fix mother liquor) Mixture of the above bleaching solution mother liquor and the following fixer mother liquor in step 5 (fixer) Mother liquor (g ) Ammonium sulfite ammonium thiosulfate aqueous solution (700g/l) Add imidazole ethylenediaminetetraacetic acid water to pH 19,0 28〇- 28,5 12,5 1, OR 7,40 120, 0 25,0 90,0 47,4 1, Ol 2.80 15:85 Replenisher (g) 57.0 84〇- 85,5 37,5 1,01 7,45 [Adjusted with aqueous ammonia and acetic acid] (Washing water) Common water supply for mother liquor and replenisher Water was mixed with an H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and an OH-type strongly basic anion exchange resin (Amberlite IRA-4 manufactured by Rohm and Haas).
Water was passed through a mixed bed column packed with 00) to reduce the concentration of calcium and magnesium ions to 3/l or less, and then 20/l of sodium isocyanurate dichloride and 150/l of sodium sulfate were added. did.

The pH of this solution is 6. 5-7. It was in the range of 5.

(Stabilizing solution) Common to mother solution and replenisher solution (Unit: g) Formalin (37%) 2. 0ml polyoxyethylene-p-0,3 monononylphenyl nityl (average degree of polymerization io) ethylenediaminetetraacetic acid di 〇,05 Add sodium brine to 1.01 pH 5,0
-8,0 The characteristics of the surface-treated samples 101 to 118 were measured using blue light, and the slopes (γ) of the tangents of the characteristic curves at the maximum concentration (Dmax) and 1/3 of the maximum concentration were determined and are shown in Table 1. Ta.

As is clear from Table 1, the comparative coupler YC-1 shows a large decrease in coloring performance when the high boiling point organic solvent is reduced. Furthermore, although YC-2 exhibits a small decrease in color development when the high boiling point organic solvent is reduced, the molecular extinction coefficient is small, so the color development density is insufficient. In contrast, the coupler of the present invention has a high D ma when the weight ratio of the high boiling point organic solvent to the coupler is in the range of 1 to 0.5.
Of course, x and γ can be given, but 0 is within the scope of the present invention.
, 3 or less, the deterioration in color development is small and sufficient color development density (Dmax) and gradation (γ) are provided.

Example 2 On a subbed cellulose triacetate film support,
Sample 201, which is a multilayer color photosensitive material, was prepared by applying layers having the compositions shown below.

(Photosensitive layer composition) The numbers corresponding to each component are g/rr? The amount of coating expressed in units is shown, and for silver halide, the amount of coating expressed in terms of silver is shown. However, for sensitizing dyes, the coating amount is expressed in moles per mole of silver halide in the same layer.

(Sample 201) First layer (antihalation layer) Black colloidal silver Silver 0.18 Gelatin 1.40 Second layer (intermediate layer) 2.5-di-t-pentadecylhydroquinone 0.18EX-1
0,070 EX-30,020 EX-122,0XIO-' U-10,060 U-20,080 U-30,10 B5-1 B5-2 Gelatin third layer (first red-sensitive emulsion layer) Emulsion A Emulsion B Sensitizing dye ■ Sensitizing dye ■ Sensitizing dye ■ X-2 X-10 B5-1 Gelatin 4th layer (second red-sensitive emulsion layer) Emulsion G Sensitizing dye I Sensitizing dye ■ 0, l 0 0 , 020 1, 04 Silver 0.24 Silver 0.25 6.9 1.00 5, lXl0-' 1, 4XIO-5 Sensitizing dye ■ X-2 X-3 X-10 Gelatin 5th layer (third red-sensitive emulsion layer) Emulsion D Sensitizing dye I Sensitizing dye ■ Sensitizing Dye ■ X-2 X-3 31 Silver 1.60 5.4X10-'1.4X10-' 2, 4X10-' 0,097 0.010 0,080 0.10 1,63 EX-5 HBS-1 Gelatin 7th layer (first green feeling Emulsion layer) Emulsion A Emulsion B Sensitizing dye ■ Sensitizing dye V Sensitizing dye ■ EX-1 EX-6 EX-7 EX-8 B5-1 B5-3 Gelatin 8th layer (second green-sensitive emulsion layer) Emulsion C Sensitizing dye ■ Sensitizing dye V 0,040 0,020 0,80 Silver 0.15 Silver 0.15 3, 0XIO-'1.0X10-'3.8X10-" 0,02 1 0,26 0, 030 0,025 0,10 0.010 0,62 Silver 0.44 2, lXl0"7.0X10-" Sensitizing dye VI 2.6xlO-'E
X-60,094 EX-70,026 EX-80,018 HBS-10,16 HBS-38,0XIO-” Seratin 0.50 9th layer (
3rd green-sensitive emulsion layer) Emulsion E Silver 1.20 Sensitizing dye IV 3 5X10-' Sensitizing dye V
8.0X10-' sensitizing dye VI
3.0X10-'EX-10,01
3 EX-110,07 EX-130,015 HBS-10,14 HBS-20,06 Seratin 1.54 No. 10
Layer (yellow filter layer) Yellow colloidal silver silver o, o s.

EX-5 B5-1 Ceratin 11th layer (first blue-sensitive emulsion layer) Emulsion A Emulsion B Emulsion F Sensitizing dye ■ EX-8 EX-9 B5-1 Ceratin 12th layer (second blue-sensitive emulsion layer) Emulsion G Sensitizing dye ■ EX-9 EX-10 B5-1 Gelatin 13th layer (third blue emulsion layer) 0,080 0,030 0,95 Silver 0.080 Silver 0.070 Silver 0.070 3, 5XlO -' 0,042 0,72 0,72 1,1 l Silver 0.46 2, lXl0-" 0, l 5 7, 0 2X10-'EX-
90,20 8BS-10,070 Seratin 0.68 14th layer (first protective layer) Emulsion I Silver 0.20U-40
,11 U-50,17 HBS-15,0xlO-' Seratin 1.00 15th layer (second protective layer) H-10,40 B-1 (diameter 1.7 μm) 5,0XIO-2B
-2 (diameter 1.7μm) 0. 10B
-30,1O 3-10,20 Seratin 1.20 Furthermore, in order to improve preservability, processability, pressure resistance, anti-fungal and anti-bacterial properties, antistatic properties and coating properties in all layers, W-1, W-2, W
-3, B-4, B-5, F-1, F-2, F-3, F-
4, F-5, F-6, F-7, F-8, F-9, F-1
0, F-11, F-12, F-13 and iron salt, lead salt,
Contains gold salt, platinum salt, iridium salt, and rhodium salt.

The emulsion and compounds used in Example 2 will be explained below.

4 (Example coupler C-20) EX-5 Co　H+5(n) I EX-2 (example coupler C-18) EX-6 EX-3 X X CH.

X 11 (Example coupler X-12 2H5 M-18) 2 H5 C2H50SO.

CH.

X-13 CH.

(DCt Hs (t) C4He (t) C4He U-4 BS Tricresyl phosphate di-n-butyl phthalate sensitizing dye ■ Sensitizing dye ■ Sensitizing dye V BS Sensitizing dye ■ (Shi M!) h S () + H −N (C+
Hs)s Sensitizing dye■ Sensitizing dye■ CH2=CH Hr CONH CH.

H2 CH So. -CH2-CONH H2 B ■ CH3 CH3 CH.

CH3 0ONa 1ncH=-CH fcH,-Ci ■ 2-4 N-T/N NHC+Hla(n) N-T/N NHC,H.

H For the obtained sample 201, as shown in Table 2, the yellow coupler EX-9 in the 11th layer was changed to the coupler of the present invention, and the amount of high boiling point organic solvent HBS-1 used was changed, and the sample was prepared. 202-216 were created.

The obtained samples 201 to 216 were subjected to wedge exposure with white light and processed in the same processing steps as in Example 1.

However, the processing time for color development was 3 minutes and 15 seconds. As in Example 1, the sample was processed after the running process was performed until the cumulative replenishment amount of the color developing solution became three times the tank liquid amount.

The treated samples 201 to 216 were measured and evaluated using blue light in the same manner as in Example 1. As a result, the same results as in Example 1 were obtained, and the comparative coupler (EX-9) reduced the high boiling point organic solvent. However, it was found that the coupler of the present invention exhibits high color development even when a small amount of a high-boiling organic solvent is used.

Table 2] Example 3 Sample 2 of Example 2 described in JP-A-2-90151
In 01, the amount of HBS-1 added in the first O layer was 0.
Sample 30 was prepared by changing the amount to 65 g/m and otherwise using the same method.
1 was created.

Samples 302 to 316 were prepared by changing the type of coupler and the amount of the high-boiling organic solvent in the 10th layer to the obtained sample 301 in the same manner as in Example 2 of the present invention.

When the obtained samples were evaluated in the same manner as in Example 2, the same results as in Example 2 were obtained.
It was found that it exhibits high color development.

Example 4 Photosensitive material 9 of Example 3 described in JP-A-1-93641
, the amount of 501v-1 added in the 12th layer was 0.8
Sample 401 was changed to 9 g/m and the other things were the same.
It was created.

Samples 402 to 416 were prepared by changing the coupler type and the amount of the high-boiling organic solvent in the 12th layer to the obtained sample 401 in the same manner as in Example 2 of the present invention.

When the obtained samples were evaluated in the same manner as in Example 2, the same results as in Example 2 were obtained.
It was found that it exhibits high color development.

Patent Applicant: Fuji Photo Film Co., Ltd. Procedural Amendment (spontaneous) 4゜ Date of amendment order spontaneous Heisei 2 years ? Tsukiko/ Day 5゜ Target of correction Specification 6゜ Contents of correction engraving of statement (No change in content) Submitted failed 1゜ Display of incidents Heisei μ Special Application No. 〃Island／　7　j vinegar.

2゜ name of invention Silver halide color photographic material residence place 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture phone

Claims (1)

[Scope of Claims] A silver halide color photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, in which the light-sensitive silver halide emulsion layer is represented by the following general formula [I]. contains a dye-forming coupler, and the weight ratio of the high-boiling organic solvent to the dye-forming coupler contained in the layer is 0.
．． A silver halide color photographic material characterized by having a silver halide color of 3 or less. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, Ar represents an aryl group, and R_1 is a halogen atom, hydrogen atom, alkyl, alkoxy, aryloxy,
or trifluoromethyl. L is -COO-, -OCO-, -O-, -S-, -SO
_2-, -CO-, -SO_2NH-, -SO_2NR
_5-, -NHSO_2-, -SO_2O-, -OSO
Represents _2-. R_2 represents a group that can be substituted on the benzene ring, and n is 0 to
Represents an integer of 3. R_3 represents a branched alkyl group, or a straight-chain alkyl group or a branched alkyl group separated by each group of -COO-, -OCO-, -O-, and -S-. R_4 represents an aryl group or an aromatic heterocyclic group. R_5 represents a straight-chain alkyl group or a group having the same meaning as R_3.