JPS62297845A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide color photographic sensitive material having excellent sharpness, developing processability and color image preservable property by providing at least one layer each of silver halide emulsion layers contg. a cyan coupler, magenta couppler and specific yellow coupler on a base. CONSTITUTION:The lipophilic 2-equiv. yellow coupler expressed by the formula and high boiling org. solvent are incorporated into the yellow coupler emulsion layer of the silver halide color photographic sensitive material having respectively one layer each of the silver halide emulsion layers contg. the cyan coupler, magenta couppler and yellow coupler on the base. In the formula, R1 is an aliphat. group, R2 is a hydrogen atom, halogen atom, aliphat. oxy group, R3 is a group (including atom) which can be substd. to a benzene ring, m is 0-4 integer, X is a group which can be eliminated by the coupling reaction with the oxidant of an arom. primary amine developing agent. The corresponding mol.wt. of the yellow coupler is 450-680. The content of the high boiling org. solvent is <=0.5 weight ratio by the total weight of the coupler.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a silver halide color photographic light-sensitive material, and more specifically, to a silver halide color photographic material that has excellent sharpness, development processability, and color image storage stability. It relates to photographic materials.

(Prior art) Using exposed silver halide as an oxidizing agent, the oxidized aromatic 7th class amine color developing agent and coupler react to form indophenol, indoaniline, indamine, azomethine, phenoxazine, phenazine and It is well known that similar pigments can be produced and color images can be formed.

Among these, in order to form a yellow image, α
-Benzoylacetanilide couplers and α-piparoylacetanilide couplers are used, but α-benzoylacetanilide couplers are more efficient in forming yellow azomethine dyes through a coupling reaction with the oxidized form of the coloring agent. , Due to the high molecular extinction coefficient of Mataso's azomethine dye, it exhibits extremely high coloring performance.
The coupler itself had a large molecular weight and the storage stability of yellow images was poor.

On the other hand, although α-pivaloylacetanilide couplers have good storage stability for yellow images, they have poor efficiency in forming azomethine dyes during color development, and the molecular extinction coefficient of the formed dyes is low. In order to obtain color density, it is necessary to increase the amount of coupler and/or silver halide applied, which has the problem of deteriorating sharpness and increasing cost due to increased emulsion film thickness. .

From the point of view of thinning the emulsion film, the method of using a polymer coupler instead of an oil-protected coupler was proposed in the
4 No. 1/3376, Tokukai Sho! However, it has become clear that polymerization deteriorates the coloring performance and requires the emulsion film to be made thicker.

In addition, for the purpose of reducing the molecular weight of each coloring unit, JP-A-J3-Jr23J2, same! Riichi/3332
R, same! ! -13θQ and the same! 6-92. Yellow couplers such as t39 having 2 to 4 color forming units in one molecule have been proposed. However, since these couplers have low solubility, a large amount of a high-boiling point organic solvent must be used, resulting in the problem that the emulsion film cannot be made very thin.

Moreover, the yellow coupler according to the present invention is produced by Tokukai Sho! 0-/j
! 22/, but this patent also states that the ratio of the high boiling point organic solvent to the yellow coupler must be 0 or more, and that the produced yellow coupler has appropriate diffusivity. Although high pH treatment as shown in the patent is performed, the present invention does not exhibit the diffusivity as in the patent.

More recently, in hopes of achieving the same effect as the present invention, molecular weight 2! The coupler of θ~4tjO is JP-A Showitsu/-
7224t3, 4/-733419, etc.
Among these, examples of couplers forming yellow dyes similar to those of the present invention were presented. It is true that these couplers have made it possible to make emulsion films thinner, improve sharpness, and shorten processing time. However, these couplers, especially yellow-2 equivalent couplers, have small molecular weights, so even if they are emulsified and dispersed, they adsorb to silver halide during storage and processing, increasing the capri and deteriorating the desilvering properties. There was a problem that the performance decreased.

Also,! - A photosensitive material containing a high boiling point organic solvent at a weight ratio of 0.0/~0.3 to the total amount of pyrazolone type magenta coupler is disclosed in JP-A-4-/4-TJ. The aim was to improve resistance, and the coloring hue and effects were completely different from those of the present invention.

(Problems to be Solved by the Present Invention) Therefore, the purpose of the present invention is, firstly, to provide a silver halide color photographic light-sensitive material with excellent sharpness, and secondly, to provide a silver halide color photographic material with excellent image preservability. Another object of the present invention is to provide a silver halide color photographic light-sensitive material, which has excellent jK development processability.

(Means for Solving the Problems) The above object of the present invention is to provide a silver halide emulsion layer containing a cyan coupler, a silver halide emulsion layer containing a magenta coupler, and a halogen emulsion layer containing a yellow coupler on a support. In the silver halide color photographic light-sensitive material each having at least one silver emulsion layer, at least seven of the yellow couplers have equivalent molecular weights of G! θ
~g/θ of a lipophilic yellow coupler represented by the following general formula [I], and containing a high boiling point organic solvent in a large amount by weight relative to the total amount of yellow coupler contained in the emulsion layer. This was achieved using a silver halide color photographic light-sensitive material characterized by containing 0.3 of both.

General formula (I) In the general formula [11, R1 is an aliphatic group, R2 is a hydrogen atom, a halogen atom, or an aliphatic oxy group, R3 is a group (including atoms) that can be substituted for a benzene ring, and m is θ An integer between 1 and 2, and X represents a group capable of being separated by a coupling reaction with an oxidized aromatic primary amine developer. However, when m is plural, (Ra)m may be the same or different. Also R1. R2, Rst or X may serve as a divalent to divalent linking group to form a dimer to a dimer of the yellow coupler.

The equivalent molecular weight of the yellow coupler in the present invention is expressed by the linear formula, where N is the number of coupling positions in the Yellow Kab2-/molecule and M is the molecular weight of the molecule, represented by the general formula [I]. It is defined by

(Equivalent molecular weight)=□ The yellow coupler of the present invention is a coequivalent coupler having an equivalent molecular weight of 4tjθ to 2θθ as defined above, preferably an equivalent molecular weight of 100 to 6jO, more preferably! ! Q~tSO.

The yellow coupler represented by the general formula (1) of the present invention does not contain a water-soluble group such as sulfonic acid or carboxylic acid.

Furthermore, it is preferable that the dye produced by the coupling of the yellow coupler represented by the general formula (1) of the present invention with the oxidized product of the aromatic primary amine crude drug is non-diffusible. 60-/! r! , DBZDA defined on pages 2 to 3 of 22 O is θ, 2! in the case of the present invention. It is preferable that it is below.

Next, each substituent in the yellow coupler represented by the general formula CD used in the present invention will be described in detail.

R1 is an aliphatic group having 7 to 30 carbon atoms, a halogen atom, an aromatic group, an aliphatic oxy group, an aromatic oxy group, an aliphatic thio group, an aromatic thio group, an acyloxy group, an aliphatic sulfonyl group, It may be substituted with an aromatic sulfonyl group or the like.

R2 is a hydrogen atom, a halogen atom (fluorine atom, chlorine atom, bromine atom), or an aliphatic oxy group having up to 2 carbon atoms.

Examples of R3 include halogen atoms (fluorine atoms, chlorine atoms,
bromine atom), aliphatic group with carbon number/~2Q, carbon number 6-2
Aromatic group with 0 carbon atoms, aliphatic oxy group with ~20 carbon atoms, aromatic oxy group with 6 to 20 carbon atoms, carbonamide group with 2 to 2 carbon atoms, sulfonamide group with ~20 carbon atoms, carbon A carbamoyl group having several θ to 2 Da, a sulfamoyl group having θ to -0 carbon atoms, and a sulfamoyl group having 2 to 2 carbon atoms. 20 acyloxy group, substituted amino group having 2 to 2 carbon atoms, aliphatic thio group having 7 to 24 carbon atoms, ureido group having θ to 2Q carbon atoms, Q~, 2 carbon atoms
θ sul 7 amoylamino group, cyan group, carbon number 2-2
Q aliphatic oxycarbonyl group, aliphatic oxycarbonylamino group with 2 to θ carbon atoms, imide group with 4t-20 carbon atoms, imide group with gu to 20 carbon atoms, aliphatic sulfonyl group with ~20 carbon atoms , an aromatic sulfonyl group having 6 to 20 carbon atoms, and a heterocyclic group having 1 to -0 carbon atoms.

X is a group that can be separated by a coupling reaction with an oxidized aromatic primary amine developer, and is represented by the following general formula [1
1), [■] and [■].

General formula (n) -0-R4 General formula [:nI:l -8-Rs General formula [■] In general formula [11], R4 is an aromatic group having 2 to 30 carbon atoms, Heterocyclic group, carbon number 2-2? an acyl group, an aliphatic sulfonyl group having 24 to 24 carbon atoms, or an aromatic sulfonyl group having 6 to 24 carbon atoms.

In the general formula (I [
represents a heterocyclic group.

In the general formula (IV:I), Y represents a nonmetallic atomic group necessary to form a monocyclic or condensed j to 7-membered heterocycle with N. Examples of heterocycles formed by N and YK include , virol, pyrazole, imidazole, /, 2
．． 4t-) lyazole, tetrazole, indole, indazole, benzimidazole, benzotriazole, tetraazaindene, succinimide, phthalimide, saccharin, oxazolidine-2,4t-dione,
Imidazolidine-2,4t-dione, thiazolidine.

Goudion, urazol, panoic acid, maleimide, nipyridone, goupyridone, pyridazone, 6
-Pyrimidone, Nipyrazone, /,! .

! - triazine-2-one, /, 2,4, one triazine-, /, 3. Dartriazin-6-one, Nioxazolone, Corchiazolone, Niimidazolone, 3
-Isoxacilone! -Tetrazolone, /, 2.4t
-) rear theta-ones, etc. These may be substituted and examples of substituents include halogen atoms, hydroxy groups, nitro groups, cyano groups, hydroxy groups, aliphatic groups,
Aromatic group, heterocyclic group, aliphatic oxy group, aromatic oxy group, aliphatic thio group, aromatic thio group, aliphatic oxycarbonyl group, carbonamide group, sulfonamide group, carbamoyl group, sulfamoyl group, ureido group , a sulfamoylamino group, an aliphatic oxycarbonylamino group, a substituted amino group, and the like.

In the present invention, the aliphatic group refers to a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group, which may be substituted. Examples of aliphatic groups include methyl group, ethyl group, isopropyl group, n-butyl group, t-
Butyl group, t-amyl group, n-hexyl group, cyclohexyl group, n-octyl group, nee-ethylhexyl group, n-
Decyl group, n-dodecyl group, n-tetradecyl group, n
-hexadecyl group, nihexyldecyl group, n-octadecyl group, allyl group, benzyl group, phenethyl group, undecenyl group, octadecenyl group, trifluoromethyl group,
Examples include chloroethyl group, cyanethyl group, /-(ethoxycarbonyl)ethyl group, methoxyethyl group, butoxyethyl group, 3-dodecyloxyprobyl group, and phenoxyethyl group.

In the present invention, the term "heterocyclic group" refers to a substituted or unsubstituted monocyclic or condensed ring heterocyclic group, such as a lysyl group, 3
-pyridyl group, derpyridyl group, niquinolyl group, oxazole-niyl group, thiazol-2-yl group, benzoxazol-2-yl group, penzothiazole-niyl group, /, 3゜9-thiadiazole-niyl group, /
, 3. There are dioxadiazole-choyl groups, etc. In the present invention, the aromatic group refers to a substituted or unsubstituted monocyclic or condensed ring aryl group, such as a phenyl group,
Examples include tolyl group, <t-10 lophenyl group, Q-methoxyphenyl group, /-naphthyl group, ninaphthyl group, g-t-butylphenoxy group, and the like.

Next, examples of preferred substituents in the coupler represented by the general formula [I] used in the present invention will be described. R1 is preferably a substituted or unsubstituted tertiary alkyl group (t-butyl group, /, /-dimethylpropyl group, /, /-dimethylbutyl group, /-methyl-/-ethylpropyl group, /',
/-dimethyl-λ-chloroethyl group, /, /-dimethyl-niphenoxyethyl group, /, /-dimethyl-niphenylthioethyl group, /-adamantyl group, etc.),
More preferred is t-butyl group. R2 is preferably a chlorine atom or an aliphatic oxy group (methoxy group, ethoxy group, methoxyethoxy group, n-octyloxy group, nee-ethylhexyloxy group, n-tetradecyloxy group, etc.). R3 is preferably an aliphatic group (methyl group,
ethyl group, n-propyl group, t-butyl group, etc.), aliphatic oxy group (methoxy group, ethoxy group, n-butoxy group,
n-dodecyloxy group, etc.), halogen atom (fluorine atom, chlorine atom, bromine atom), carbonamide group (acetamide group, n-butanamide group, n-tetradecanamide group, benzamide group, etc.) or sulfonamide group (methylsulfone Amide group, n-butylsulfonamide group,
n-octylsulfonamide group, n-dodecylsulfonamide group, toluenesulfonamide group, etc.). R2
is preferably a chlorine atom, an aliphatic oxy group (methoxy group, ethoxy group, methoxyethoxy group, n-octyloxy group, λ-ethylhexyloxy group, n-tetradecyloxy group, etc.), an aliphatic oxycarbonyl group (methoxy Carbonyl group, ethoxycarbonyl group, n-butoxycarbonyl group, n-hexyloxycarbonyl group, coethylhexyloxycarbonyl group, /-(ethoxycarbonyl)ethyloxycarbonyl group, cobutoxyethyloxycarbonyl group, 3-dodecyloxy Probyloxycarbonyl group, n-decyloxycarbonyl group, n
-dodecyloxycarbonyl group, phenethyloxycarbonyl group) or carbamoyl group (dimethylcarbamoyl group, dibutylcarnocumoyl group, dimethylcarbamoyl group, di-2-ethylhexylcarbamoyl group, n-
dodecylcarbamoyl group, etc.). m is preferably Q
~2. X is preferably R4 in the general formula [■]
is an aromatic group (4t-methoxycarbonylphenoxy group, goumethylsulfonylphenyl group, kucyanophenoxy group, kudimethylsulfamoylphenoxy group, coacetamido-guethoxycarbonylphenoxy group, gouethoxycarbo of the latter, a group represented by the following general formula [■] is more preferred.

General formula [■] In general formula [v], represents a substituted or unsubstituted methylene group or a substituted or unsubstituted imino group, and W represents an oxygen atom, a sulfur atom, a substituted or unsubstituted methylene group, or a substituted or unsubstituted imino group. . However, when V is an imino group, W is neither an oxygen atom nor a sulfur atom. Examples of the group represented by the general formula [v] are succinimide group, phthalimide group, /-methyl-imidazolidine-! , 4t-dione-3-yl group, /-benzyl-imidazolidine-2,41-dione-3-yl group, ! -ethoxy/-methylimidazolidine-2,4t-dione-
3-yl group,! -Methoxy/-methylimidazolidine-2,kudione-3-yl group,! , -t-dimethyloxazolidine-cudion-3-yl group, thiazolidine-co, terdione-3-yl group, /-pendyl-cophenyltriazolidine-3,! -dione-guyl group, /-n-propyl-cophenyldriaso I)-)
Ku 3°! -dione-gooyl group, etc.

In the yellow coupler represented by the general formula [■], any of the substituents R0, R2, R3 or Monomers or dimers are preferred. Here, when the yellow coupler represented by the general formula [I] is a dimer to a dimer, R1. The carbon number ranges listed for R2, R3 or X are not limited thereto.

Specific examples of the yellow coupler represented by the general formula [I] used in the present invention are shown below, but the couplers used in the present invention are not limited to these. The molecular weight of each coupler is shown in parentheses.

2H5 Ha 2H5 Ha (t/r) <tro)Y-74t (+34t) Y-/l The yellow coupler used in the present invention is synthesized by a conventionally known method. For example, US Patent J,
227,! ! < No. 3, 4t07.

No. 799, No. 3, 4t/j, No. 4!2, No. 3, 4
t4t7.9.2/No. 4t4tO/7!2, British Patent/.

0 da θ, 7/θ issue, JP-A No. 7-26/33, JP-A-Sho g7
-777j No.4, 4t7-733/417, 4t
J'-94t4tj, 4t/-6773Z, y? -6//3! Same number? -Otsu? ♂ No. 36, same! θ−
34t232, same! /-! Same as θ23da! /-/θ
263 Otsu issue, same! ! -! ri No. 2, same j! -/4/, 23
ri issue, same! 6-ta! No. 237, same! , < −/61j4
T3 issue, same! Otsu-/! 33 Da No. 3, same! tar/74tr
It can be synthesized by the synthesis method described in the specifications of No. 39 and No. 60-3!730.

Two or more kinds of the yellow couplers of the present invention may be used, or they may be used in combination with yellow couplers other than those of the present invention.

The yellow coupler of the present invention is contained in the light-sensitive silver halide emulsion layer and its adjacent layer.

The total amount of the couplers of the present invention added is 0.02 to 3.0
g/m2, preferably 0. ／〜／、! g/m2, preferably 0.2 to .theta.g/m2.

The amount of the high boiling point organic solvent added to the yellow coupler-containing layer of the present invention is at most 0 in terms of weight ratio to all the yellow couplers contained in the yellow coupler-containing layer.
．． ! Ashi, preferably O0/~0.3! , more preferably θ, /~0.3, but may be 0.

All of the yellow couplers mentioned above also include yellow couplers that release photographically useful groups, such as development inhibitor-releasing couplers.

The high boiling point organic solvent referred to in the present invention is /7j0C7t at normal pressure.
It is water immiscible with a score of 0.00.

As the high boiling point organic solvent added to the yellow coupler-containing layer of the present invention, known ones can be used.

For example, phosphoric acid esters (tricresyl phosphonate, triphenyl phosphate, dioctyl butyl phosphate, tri-n-hexyl phosphate, tricyclohexyl hepta-osphate, trioctyl phosphate, etc.), phthalate esters (dibutyl phosphate, etc.) phthalate, dioctyl phthalate, dicyclohexyl phthalate, didodecyl hetatalate, etc.), citric acid esters (e.g. acetyl tributyl citrate), alkylamides (e.g. diethyl laurylamide), benzoic acid esters (e.g. octyl benzoate), fatty acids Examples include esters (for example, dibutoxyethyl succinate, diethyl azelate), trimesate esters (for example, tributyl trimesate), and the like.

The method of adding these high boiling point organic solvents is to add the yellow coupler and these high boiling point organic solvents to a boiling point of 30~/jo0.
So-called low-boiling organic solvents (e.g., ethyl acetate,
Lower alkyl acetate such as butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-nidoxyethyl acetate, methylceranyl acetate) - & etc.) After dissolving in VC, emulsifying and dispersing in hydrophilic colloid. It may also be added. Alternatively, an emulsified dispersion of another high-boiling organic solvent may be prepared and added to the yellow coupler monodispersion.

When the yellow coupler of the present invention is used in combination with a yellow coupler other than the present invention, it is preferable to use the yellow coupler of the present invention in layers other than the highest sensitivity layer.

In the light-sensitive material of the present invention, it is preferable to provide a so-called protective layer group further away from the light-sensitive emulsion layer furthest from the support.

In the present invention, the following general formula (
It is particularly preferable to use compounds represented by CC-/), (CC-, z), and [CC-yo].

In the above formula, R1 is -CONR5R6, -NHCORs,
-NH8O2R7, -NH8O2R7, -NHCONR
5R.

Or it represents -NH3O2NR5R6.

R5, R6 and R7 are aliphatic groups having a carbon number of /~30,
It represents an aromatic group having 6 to 30 carbon atoms and a heterocyclic group having λ to 30 carbon atoms.

R2 is a halogen atom, hydroxy group, amino group, carboxyl group, sulfonic acid group, cyan group, aromatic group, heterocyclic group, carbonamide group, sulfonamide group, carbamoyl group, sulfamoyl group, ureido group, acyl group, acyloxy group, aliphatic oxy group, aromatic oxy group, aliphatic thio group, aromatic thio group, aliphatic sulfonyl group, aromatic sulfonyl group, sulfamoylamino group, nitro group, imido group, The number of carbon atoms included is θ to 3θ. m represents an integer from 1 to 3.

When m = , 2, an example of cyclic R2 is a dioxymethylene group.

R3 is represented by the following general formula (CC-J:).

Rs (Y)-...(CC-3:) Here, Y represents] NH, CO, fcki > S O2, n is zero or /, R8 is a hydrogen atom, the number of carbon atoms /
~3Q aliphatic group, C6-3Q aromatic group, C2-30 heterocyclic group, -OR,, -COR9, -C02
Represents R11.-8O2R11. or -8020R11. Here, R9, RIO and R11 have the same meanings as defined in R5, R6 and R7 above, respectively.

They may be combined to form a nitrogen-containing heterocycle (morpholine ring, piperidine ring, pyrrolidine ring, etc.).

R4 represents an aliphatic group having 3 to 3 carbon atoms, an aromatic group having 6 to 3 carbon atoms, or a heterocyclic group having 2 to 3 carbon atoms, preferably a tertiary alkyl group having 4 to 3 carbon atoms. Or it is a group represented by the following general formula [CC-ta] having 7 to 3 carbon atoms.

In the formula, R12 and R13 may be the same or different, and may be a hydrogen atom, an aliphatic group having a carbon number of up to 30, or a carbon number of 6.
-30 aromatic group, R14 represents a heptavalent group, and 2 represents 10-1-S-1-8O- or -502-. l is θ~! , and when l is a plurality of integers, the plurality of R14s may be the same or different. Preferred substituents include R12 and R13 having a carbon number of /~/? R14 is a halogen atom, aliphatic group, aliphatic oxy group, carbonamide group, sulfonamide group, carboxy group, sulfo group, cyan group, hydroxyl group, carbamoyl group, sulfamoyl group, aliphatic For the group oxycarbonyl group and the aromatic sulfonyl group, 2 can be 10-, respectively. Here, the number of carbon atoms in R14 is θ
~3Q, and l is preferably /~3.

Ar represents a substituted or unsubstituted aryl group, and may be a condensed ring. Typical substituents for Ar include a halogen atom, a cyano group, a nitro group, a trifluoromethyl group,
-COORIS, -COR15, -8o20R engineering 5, -
NH8R18, R15 and R16 may be the same or different and represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group, and R17 represents an aliphatic group, an aromatic group or a heterocyclic group. Ar has 6 to 30 carbon atoms, and is preferably a phenyl group having the above-mentioned substituents.

X represents a hydrogen atom or a coupling-off group (including a leaving atom; the same applies hereinafter). Typical examples of coupling-off groups include halogen atom, -〇R18, -8R 8, -0
CR18, -NH8R18, -NH8R18, aromatic azo group, heterocyclic group having carbon number/-30 and connected to the coupling active position of the coupler through the nitrogen atom (succinimide group, 7-thalimide group, hydantoinyl group, pyrazolyl group) ,
(copenzotriazolyl group, etc.). Here, R18 represents an aliphatic group having ˜30 carbon atoms, an aromatic group having 6 to 30 carbon atoms, or a heterocyclic group having 2 to 3θ carbon atoms.

As mentioned above, the aliphatic group in the present invention is saturated, unsaturated,
It may be substituted or unsubstituted, linear, branched, or cyclic, and typical examples include methyl group, ethyl group, butyl group, cyclohexyl group, allyl group, propargyl group,
Methoxyethyl group, 11-7" syl group, ")'y syl group, n-hexadecyl group, trifluoromethyl group, heptafluoropropyl group, dodecyloxypropyl group,
Included are 2,4t-di-tert-amylphenoxypropyl group and 2.11-di-tert-amylphenoxybutyl group.

Further, the aromatic group may be substituted or unsubstituted,
Typical examples include phenyl group, tolyl group, 2-tetradecyloxyphenyl group, interfluorophenyl group,
Examples include λ-chloro, monododecyloxycarbonylphenyl group, cuchlorophenyl group, glucyanophenyl group, and cuhydroxyphenyl group.

In addition, the heterocyclic group may be substituted or unsubstituted,
Typical examples include; -pyridyl group, kuhiricyl group,
Includes caufuryl group, gouchenyl group, quinolinyl group, etc.

In the above formula, R4 and X have the same meanings as described in general formula [CC-2].

Couplers of the general formula (:CC-/) may be used in the R substituent RlXR2, R3 or
The couplers represented by -, z"l and [:CC-t:] are λ-mers, oligomers, or larger amounts of λ-mers, oligomers, or more, which are bonded to each other via a covalent or divalent or more-valent group in the substituent R4 or X, respectively. In this case, the range of carbon numbers shown in each of the above substituents may be outside the specified range.

General formula (CC-/], [CC-ko] or [CC-!]
When the coupler represented by the above forms a multimer, a typical example is a single or copolymer of an addition-polymerizable ethylenically unsaturated compound (cyan color-forming monomer) having a cyan dye-forming coupler residue.

In this case, the multimer contains repeating units of the general formula [:CC-g:], and cyan coloring represented by the general formula (CC-t). It may be a copolymer containing seven or more non-color-forming ethylene monomers as a copolymerization component.

In the formula, R represents a hydrogen atom, an alkyl group having 7 to 9 carbon atoms, or a chlorine atom, A represents -CONH-1-COO- or a substituted or unsubstituted phenylene group, and B represents a substituted or unsubstituted alkylene group. group, phenylene group or aralkylene group, L is -CONH-1-NHC0NH
-1-NHCOO-1-NHC0-1-0CONH-1
-NH-1-COO-1-OCO-1-CO-1-〇-
1-S-1-so2-1-NH8O2- or -502
Represents NH-. aX b, C represents O or /. Q
is the general formula (CC-/:], []CC-co] and (CC-r
) indicates a cyan coupler residue in which a hydrogen atom other than the hydrogen atom of the hydroxyl group at position 97 has been removed.

As the multimer, a copolymer of a cyan color-forming monomer that provides a coupler unit of the general formula (CC-a) and a non-color-forming ethylene-like monomer described below is preferred.

Examples of non-chromogenic ethylene-like monomers that do not couple with the oxidation products of aromatic-grade amine developers include acrylic acid,
α-chloroacrylic acid, α-alkylacrylic acid (e.g. methacrylic acid, etc.) Esters or amides derived from these acrylic acids (e.g. acrylamide, methacrylamide, n-butylacrylamide, t-
Butyl acrylamide, diacetone acrylamide, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, a-butyl acrylate, 1SO-butyl acrylate, coethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and β-hydroxy methacrylate), vinyl esters (e.g. vinyl acetate, vinyl propionate and vinyl laurate), acrylonitrile, methacrylatrile,
Aromatic vinyl compounds (such as styrene and its derivatives, such as vinyltoluene, divinylbenzene, vinylacetophenone and sulfostyrene), itacone, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl compounds (such as vinyl ethyl ether) ,
maleic acid ester, N-vinyl-2-'rolidone,
Examples include N-vinylpyridine and 2- and -<1-vinylpyridine.

Particularly preferred are acrylic esters, methacrylic esters, aromatic vinyl compounds, and maleic esters. Two or more kinds of the non-color-forming ethylene monomers used here can also be used together. For example, methyl acrylate and butyl acrylate, butyl acrylate and styrene, butyl methacrylate and methacrylic acid, methyl acrylate and diacetone acrylamide, etc. can be used.

Next, the general formulas (CC-/), (CC-, z], [CC-!
] and (CC-a), but the couplers used in the present invention are not limited to these. In the structural formula below, (t)CsHll represents -C(CH3)2C2H5, and (t)C9H□7 represents -C
(CH3) represents 2CH2C(CH3)3, respectively.

(1-J) (1-6> (1-/j) x: y=Otsu0: Zθ (molar ratio) (1-74t) (1-,2/) (I-22) n-27 ) (■-stiffness?)■3 ν Cl2H23(1-3♂) 12H25 (1-J?) CIG)(21(1-1o) α (■-g2) COOH(1-da!) x' :y=20:JO (molar ratio) (1-Qj) The coupler represented by the general formula (CC-/) was disclosed in Japanese patent application No.
No. 3603, same! Tar2t41277 and the same! Tar J
It is synthesized by the method described in No. t6r/jj.

The coupler represented by the general formula [CC-co] is a U.S. patent (
US) No. 34 #I/ri No. 3, Tokukai Shogu♂-/! TJ 2nd issue, same! 0-//74122, same! 2-/13/J-
Same issue! λ-90ri No. 32, jJ-124t2J No.
Same J Ku4t, R232, same! Kubu 61 Kota, same! ! -3-07/issue, same! , t-6! ? ! No. 7, same! !
-10j Ko No. 26, same! 1/3/issue, same jl, -/
No. 24413, same J4-27/4T issue, same! 6-/-
Bu/No. 32 and the same j/-ta! It is synthesized by the method described in No. 34t6.

Couplers of the general formula CCC-t) are disclosed in U.S. Pat.

/ri No. 9, same j, 4tlr, /ri No. 3, British patent? /4', J07, Special Public Show J4T-37Jr-
It can be synthesized by the method described in -.

General formulas [CC-/), (CC-,2] and [CC-!
] The total amount of couplers added is at least 30 moles of all cyan couplers, preferably ! It is at least θ molar, more preferably at least 70 molar, even more preferably at least O molar.

These general formulas (CC-/:], (CC-2] and (C
It is preferable to use two or more of the couplers represented by C-t) in combination, and when the same color-sensitive layer is divided into two or more layers with different sensitivities, a monoequivalent cyan coupler is added to the high-temperature layer. It is preferable to use an equivalent cyan coupler for the sensitive layer I/C4.

In the photographic emulsion layer of the photographic light-sensitive material used in the present invention, any silver halide including silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, and silver chloride may be used. The preferred silver halide is silver iodobromide or silver iodochlorobromide containing less than about 30 moles of silver iodide. Particularly preferred is silver iodobromide containing from about 2 mole percent to about 2 j mole percent silver iodide.

The silver halide grains in the photographic emulsion may be so-called regular grains having a regular crystal structure such as a cube, octahedron, or dodecahedron, or may have an irregular crystal shape such as a spherical shape. , one with crystal defects such as twin planes, or a composite form thereof.

The grain size of the silver halide may be fine grains of about 0.1 micron or less, large grains with a projected area diameter of up to about 70 microns, a monodisperse emulsion with a narrow distribution, or a polydisperse emulsion with a congested distribution. A dispersed emulsion may also be used.

The silver halide photographic emulsion that can be used in the present invention can be produced by a known method, for example, as described in Research Disclosure (
RD), Ya12t4t3 (/97/9!! February), 22
~-3 pages, '1. Emulsion pre
A//7/G (////979), p. 64t/p.

The photographic emulsion used in the present invention is described in "Physics and Chemistry of Photography J" by Grafkide, CP, published by Beaumontel.

Glafkides, Chimie et Phys
iquePhotographique Paul M
ontel, /947), "Photographic Emulsion Chemistry" by Du Huynh, published by Focalb L/S (G, F, Du
ffin, Photographic Emulsio
n Chemistry (Focal Press.

``Production and Coating of Photographic Emulsions'' by Zelikman et al.
, published by Focal Press (V, L.

Zelikman et al., Making and
CoatingPhotographic Emul
sion, Focal Press.

It can be prepared using the method described in . That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. good. It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method). As one form of the simultaneous mixing method, a method in which PAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called Chondrald double jet method. According to this method,
A silver halide emulsion with a regular crystal shape and nearly uniform grain size can be obtained.

One or more silver halide emulsions formed separately may be used in combination.

The silver halide emulsion consisting of the regular grains described above can be obtained by controlling PAg and pH during grain formation. For more information, please see Photographic Science and Engineering.
5science and Engineering) Volume 6, /! Ri~l≦! Page (/ri aX): Journal of Photography °sign, t, (Journa
l ofPhotographic 5science
), / Volume 2, 2 Dako~, 2! ! Page (/9 Otsu 4t),
U.S. Patent No. J, 1. ! j.

No. 39g and British Patent No. 1,4t/j,? It is described in the 4t♂ issue.

Furthermore, as a monodisperse emulsion, the average grain diameter is approximately θ.

Silver halide grains larger than 7 microns, at least about ? ! Emulsions in which the weight percent is within ±4 tO of the average grain diameter are typical. The average particle diameter is approximately 0. =!
~-Miku, Ron Ashii, at least about? ! At least about the weight or quantity! Emulsions containing silver halide grains having an average grain diameter within the range of -0 can be used in the present invention. A method for making such an emulsion is described in U.S. Patent No. J,!
'74t.

6? No. J, 6! ! , 394 and British Patent No. 1.4113.71J''.

In addition, JP-A No. 4 tr-rtoo, No. 11-39022, and No. 4 TR-Rtoo! /-♂No.3022, same! ! -737/33, same! Cuda/! - / issue, same! Cooter? Da/? No. 5r-
3 tons 3! Same issue! ? - Gutata 3? Monodisperse emulsions such as those described in No.

Further, tabular grains having an ascent ratio of about 1 or more can also be used in the present invention. Tabular grains are described in Cutoff, Photographic Science and Engineering.

Photographic 5science and
Engineering), Volume 1, 2er~2
37 pages (20 years); US Patent No. 4t34t
, No. 226, 41.4t/4t, No. 310, same da,
4133, 0at issue, same da, 4'j? , No. 620 and British Patent No. 1, //2, No. 112. When tabular grains are used, there are advantages such as improved color sensitization efficiency by sensitizing dyes, improved graininess, and increased sharpness.
U.S. Patent No. g, 4t341, 2.2, cited above.
This is explained in detail in issue 6.

The crystal structure may be uniform, the inside and outside may have different halogen compositions, or it may have a layered structure. These emulsion grains are described in British Patent No. 1.027,
/ Rigo issue, US Patent No. 3. ! O! , 0 Otsu wo No., Same Da, 4
t4t4t,? No. 77 and special request! ? -24tr4t
No. 69, etc.

Further, silver halides having different compositions may be joined by epitaxial joining, and for example, silver halides, rhodan silver,
It may be bonded with a compound other than silver rodanide, such as lead oxide. These emulsion grains are described in U.S. Pat.
94t, tF¥, same, /da2. ri No. 00, same,
4tj? ,! jj, British Patent No. 2,031,79
No. 2, U.S. Patent No. 41.3 Geta, A22, Same Da, 3 Rij, 4t7! No. 4t.

4t3! , No. 101, Dohiro, 4ttJ, No. 017, No. 3, Otsu! 6. ? ≦-No. 3. ♂j2.047, Tokukai Akira! 9-/62!4tO, etc.

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

The emulsion of the present invention is usually used which has been subjected to physical ripening, chemical ripening and spectral sensitization. The additives used in these processes are research disclosure standards/7t4.
1j and &/17/6, and the relevant parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also listed in the above two Research Disclosures, and the locations listed are shown in the table below.

Additive type RD/7 t13 RD/17/l/
Chemical sensitizers, page 23, page 6, right column Sensitivity increasing agents, same as above Brighteners, pages 24 to 7 Anti-stinting agents, page 2j, right column, page 460, left to right columns? Dye image stabilizer 2! Page Hardener Page 26 Otsu! /page left column/θ
Binder, page 26 Same as above //Plasticizer, lubricant Page 27 tJ-0 right column Various color couplers can be used in the present invention, specific examples of which can be found in the Research Disclosure (RD) A/
It is described in the patents listed in 6G3, ■-〇～GK. As dye-forming couplers, couplers that provide the three subtractive primary colors (i.e., yellow, agenta, and cyan) in color development are important; specific examples of diffusion-resistant g-equivalent or 2-equivalent couplers include the aforementioned RD/744t3. ,■
- in addition to the couplers described in the patents listed in sections C and D,
The following can be preferably used in the present invention.

A representative example of the yellow coupler that can be used in the present invention is a hydrophobic acylacetamide coupler having a pallast group. A specific example is US Patent No. 2.
G07. -70, same No. 2゜17J-, 067 and same No. 3. ．． 26j-,! It is described in No. 06.

The use of a two-wheel yellow coupler is preferred for the present invention, as described in U.S. Patent No. 3.4t0! , No. 129, No. 3, 4
t4t7, ? , 2/No. 3. 33. jθ/ issue and same number 4t, 02 co.

Oxygen atom separation type yellow coupler described in Bu-0 etc. or Tokko Akira! /-10739, U.S. Patent No.
, u2j, No. 020, West German Application Publication No.
! /No. 7 and No. 7.

4t33. Typical examples include the nitrogen atom separation type yellow couplers described in No. 1/- and the like. α−
Pivaloylacetanilide couplers provide color-forming dyes with excellent longevity, particularly light fastness, while α-benzoylacetanilide couplers provide high color density.

The magenta coupler that can be used in the present invention is preferably a hydrophobic indacylon or cyanoacetyl coupler having a pallast group! - Pyrazolone and pyrazoloazole couplers may be mentioned. ! - Pyrazolone-based cazolers are preferably couplers in which the 3-position is substituted with an arylamino group or an acylamino group from the viewpoint of the hue and color density of the coloring dye.
3//, No. 012, No. 2. J4t3,703, same No.-, too, Zet No., same No. λ, ri01, j73, same No. 3.06.2, 4/3, same No. 3.7! Ko, male?
No. 6 and No. 3, ? J4.0// issue etc. Two equivalents! - U.S. Patent No. 3/θ as a leaving group for pyrazolone couplers.

No. 6/R or the nitrogen atom leaving group described in U.S. Patent No. 41. ! ! Particularly preferred are the arylthio groups described in No. 1, No. 197. It also has a pallast group as described in European Patent No. 23゜43B! - Pyrazolone couplers provide high color density. Examples of pyrazoloazole couplers include pyrazolobenzimidazoles described in U.S. Pat. No. 306/4tJ-, preferably U.S. Pat.
Pyrazolo (j,/-c) described in No. 23, No. 042
(/.

λ, 4t] Triazoles, Research Disclosure 24t Coco 0 (/ri/da June 2006) and JP-A-1983
-33! Pyrazolotetrazoles described in No. 32 and Research Disclosure Ko 4t Co. 30 (/ri 29
Examples include pyrazolopyrazoles described in JP-A No. 0-4 (April 2003) and JP-A-Shogo No. 0-4 tjtj. U.S. Patent No. 41.1 is used in view of the low yellow side absorption of the coloring dye and the light fastness.
! The imidazo(/,z-b)pyrazoles described in U.S. Pat.
Pyrazolo [/, z-b) [/, λ, 4t] described in the issue
Triazoles are particularly preferred.

Cyan couplers that can be used in the present invention include hydrophobic and diffusion-resistant naphthol and phenolic couplers, such as those described in US Pat. No. 2.4t74t.

No. 223, preferably the naphthol couplers described in U.S. Patent No. G, 0! λ,, 2/, No. 2, No. 9°/4t4
, No. 796, No. 2, 2.21, . Typical examples include the oxygen atom elimination type two-equivalent naphthol couplers described in No. 233 and No. 6,200. Further, specific examples of phenolic couplers are shown in U.S. Pat.
．． j4? , No. 929, same No. λ, ♂0/, No. 177,
Same No.-, 772, /Go No. 2, Same No. 2. /the law of nature! , T-co-Otsu issue, etc.

Couplers capable of forming humidity- and temperature-fast cyan dyes are preferably used in the present invention, exemplified by US Pat. No. J, 772.

Phenolic cyan coupler having an alkyl group equal to or higher than ethyl group at the meta-position of the phenol nucleus described in No. 002, U.S. Pat.
r, jc#, same number da, /, 2bu.

3ri No. 6, same No. 4t, 334t, 0//, same No. q.

,? , 27, No. 73, West German Patent Publication No. 3,32.

No. 729 and European Patent No. 12/3tJ, etc. 2,! -Diacylamino-substituted phenolic couplers, U.S. Pat. No. 3. Da 4tj, No. 6.22, No. 333, Tata No., No. 4t3/.

! ! It has a phenylureido group at the 11th position as described in No. 1, P, 4t Core, No. 747, etc. These include phenolic couplers having a 7-syl amino group at the -position. The seven tolls described in European Patent No. 16/626A! Cyan couplers substituted with a sulfonamide group, an amide group, etc. at the -position also have excellent fastness of colored images and can be preferably used in the present invention.

In order to correct unnecessary absorption of coloring dyes, it is preferable to use a colored coupler in combination with a color photosensitive material for photographing to perform masking. U.S. Patent No. 9. /4,? , 470 and Japanese Patent Publication No. 77-394t/3, etc., or US Pat. No. 9,00'l
, No. 92, No. DA, /31.211 and British Patent No. 1. Typical examples include the magenta-colored cyan coupler described in No. 36/4tt. Other colored couplers are described in RD/7t413.1-0 above.

Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Such a coupler is
U.S. Patent No. g, J, lG4. ．． No. 237 and British Patent No. 2. Specific examples of magenta couplers are given in European Patent No. 6,670 and West German Application Publication No. 3. Core 4t, No. 633 describes four examples of yellow, magenta or cyan couplers.

The dye-forming couplers and the special couplers described above may form dimers or more polymers. Typical examples of polymerized dye-forming couplers are U.S. Pat.
No. 20 and No. DA, Q♂θ.

It is described in No. 277. Specific examples of polymerized magenta couplers are described in British Patent No. 2,102,123 and U.S. Patent No. j, 47. ．． It is described in No. 2/-.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. The DIR coupler releasing the development inhibitor is the aforementioned RD/764t3,
The patented couplers described in sections (1) to (F) are useful.

Preferred combinations with the present invention are JP-A-77-
Developer deactivated type represented by No. /j/ri4t4; U.S. Pat.
Timing type represented by JJ4 issue; special application in Showa 7? -3
The reaction type represented by No. 963-3 is particularly preferable. ♂−
Ko/2ri No. 32, special request Akira! Day 764t74 issue, same!
? -Tko 2/4 issue, same Tada-? 22/4 and the same issue? Developer deactivated type DI described in No. 04131 etc.
R coupler and special request! This is a reactive DIR coupler described in No. 39663 and the like.

In the light-sensitive material of the present invention, a coupler that releases a nucleating agent, a development accelerator, or a precursor thereof in an image form during development can be used. A concrete example of this kind of transformation is
British Patent No. 2,097.

/DaO No. 2. /J/, /J'r issue. Couplers that release a nucleating agent or the like that has an adsorption effect on silver halide are particularly preferred, and specific examples thereof are given in JP-A-Sho! ? -/j763♂ and the same! Tar/701
It is described in 4tO, etc.

The coupler used in the present invention can be introduced into the photosensitive material by various known dispersion methods, such as a solid dispersion method, an alkali dispersion method, preferably a latex dispersion method, and more preferably an oil-in-water dispersion method. be able to. In the oil-in-water dispersion method, after dissolving either a high-boiling organic solvent with a boiling point of 77!0C or higher and a so-called auxiliary solvent with a low boiling point, either alone or in a mixture of both, water or water is dissolved in the presence of a surfactant. Finely dispersed in an aqueous medium such as an aqueous gelatin solution. Examples of high boiling point organic solvents are U.S. Pat.
2.2.027, etc.

Dispersion may be accompanied by phase inversion, and if necessary, the auxiliary solvent may be removed or reduced by distillation, noodle washing, ultrafiltration, or the like before use for coating.

The process and effects of latex dispersion methods and specific examples of latex for impregnation are described in U.S. Patent No. Q,/9? .

No. 363, West German Patent Application (OLS) No. 2. ! 4t/.

No. 224 and No. 2 of the same. ! 41/, No. 230, etc.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D-A/764'j page 2j and the same, ya/♂
It is written in the right column of page 2/6j of 2/6 to the left column of page 4t.

Force 2-Photographic material according to the present invention has the above-mentioned RD,
Thread/26g 3/2/~Kota page and same, A/? 77≦6! / It can be developed by the usual methods described in the left column to right column.

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. As this color developing agent, aminophenol compounds are also useful, but p-phinidine diamine compounds are preferably used, and representative examples thereof include 3-methyl-guamino-N,N-diethylaniline, 3- Methylder-amino-N-ethyl-N-
β-hydroxyethylaniline, 3-methyl-der-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-y-amino-N-ethyl-N-
Examples include β-methoxyethylaniline and their sulfates, hydrochlorides, and I)-)luenesulfonates. These diamines are generally more stable in their salt form than in their free form, and are therefore preferably used.

The color developer contains pH buffering agents such as alkali metal carbonates, borates or phosphates, development inhibitors or anti-capri agents such as bromides, iodides, benzimidazoles, benzothiazoles or mercapto compounds. Generally, it includes such things as Also, if necessary, preservatives such as hydroxylamine or sulfites, organic solvents such as triethanolamine, diethylene glycol,
Development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines, dye-forming couplers, competitive couplers, nucleating agents such as sodium poron hydride, auxiliary development such as /-phenyl-3-pyrazolidone. Medicines, viscosity-imparting agents, various chelating agents such as aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, and phosphonocarboxylic acids, West German Patent Application (OLS) No. λ, Otsu 2.2.9J- The antioxidant described in No. 0 may be added to the color developing solution.

In the development process for reversal color photosensitive materials, black and white development is usually performed followed by color development. This black and white developer contains dihydroxybenzenes such as hydroquinone, /-phenyl-
3-pyrazolidones such as 3-pyrazolidone N-
Known black and white developers such as amine phenols such as methyl-p-7 minophenol can be used alone or in combination.

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

The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. Furthermore, in order to speed up the processing, a bleach-fixing treatment may be performed after the bleaching treatment. Examples of bleaching agents include iron (DI), cobalt (■), and chromium (
(2), compounds of polyvalent metals such as copper (If), peracids, quinones, nitrone compounds, etc. are used. Ferricyanide as a typical bleaching agent: iron(III) dichromate
or organic complex salts of Kobal) (II[), such as aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, /, 3-diaminor-coprono-ξnortetraacetic acid, or citric acid, tartaric acid, malic acid, etc. Complex salts of organic acids; persulfates: manganates; nitrone 7-alenato can be used. Of these, iron ethylenediaminetetraacetate (I[I)
Salts, iron(III) diethylenetriaminepentaacetate salts and persulfates are preferred from the viewpoint of rapid processing and environmental pollution. Furthermore, the ethylenediaminetetraacetic acid iron(III) complexes are particularly useful both in stand-alone bleach solutions and in -bath bleach-fix solutions.

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. Patent No. 3. ? RIJ, /61, West German Patent No. 1. Ko9θ, /72, same 2. Q! the law of nature.

ri No. 22, JP-A No. 63-j, 27j No. 4, same! 3-yo2
♂No.37, No.374t7/No.j3-47732,
Same number j-3-72623, same! ! -91 Go No. 30, same!
-3-9!63/No., j3-104t23, No.6
3-/2+141 Koda issue, same! 3-74tI623,
same! 3-2r4t2/, No. 2, Research Disclosure A/7/, No. 2 (July 97r), etc. Compounds having a mercapto group or disulfite group: Described in JP-A-Kokai ShojO-/4tO/Kota No. Thiazolidine derivatives such as those listed in Japanese Patent Publication No. 4TJ-RJO, Japanese Patent Publication No. Shoj
λ-2Or32, same! 3-3273! No. 3, U.S. Patent No. 3. Thiourea derivatives described in No. 06.141: West German Patent No. 1, /27.7/! No., Tokukai Akira! ? -/623!
Iodide described in West German Patent No. 944. @/θ issue, same 2
．． 7gJ', polyethylene oxides described in No. 4t30; polyamine compounds described in Japanese Patent Publication No. 4tj-1rJt; other Tokkoma Ryōgtarg No. 24t3, Geta J94! Q issue, same j3-tada 927, same! Ku 367
No. 27, same! ! -2 Otsu! No. 06 and the same? -/Otsu39
Compounds described in No. 4tO and iodine and bromide ions can also 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 US Pat. No. 3,793.7jr and West German Patent No. 1°29θ
, No. 272, Tokukai Sho! The compounds described in No. 3-9!630 are preferred. Furthermore, U.S. Patent No. ! Compounds described in No. 2r34 are also preferred. These bleach accelerators may be added to the sensitizer. These bleach accelerators are particularly effective when bleach-fixing color photosensitive materials for photography.

Examples of the fixing agent include thiosulfates, thiocyanates, thioureas of thioether compounds, and large amounts of iodides, but thiosulfuric acid sulfate is commonly used. As the preservative for the bleach-fix solution and the fix solution, sulfites, bisulfites, or carbonyl bisulfite adducts are preferred.

After the bleach-fixing treatment or the fixing treatment, washing treatment and stabilization treatment are usually performed. Various known compounds may be added to the water washing process and stabilization process for the purpose of preventing precipitation and saving water. For example, to prevent precipitation, use water softeners such as inorganic phosphoric acid, aminopolycarboxylic acid, organic aminopolyphosphonic acid, and organic phosphoric acid, disinfectants and anti-piping agents to prevent the growth of various bacteria, algae, and mold. Agents, metal salts such as magnesium salts and aluminum salts and bismuth salts, surfactants for preventing drying load and unevenness, and various hardening agents can be added as necessary. Or Photographic Science and Engineering magazine by West (L, E, West
, Phot, Sci.

Eng, ), Volume 6, 3 days ~ 3! Compounds described in RIHA-DI(/RIOTORI) may be added. Addition of chelating agents and anti-spill agents is particularly effective.

In the washing process, it is common to use countercurrent washing in tanks larger than one to conserve water. In addition, Japanese Patent Publication No. 7
-,! A multistage countercurrent stabilization treatment step as described in No. #'13 may also be carried out. In the case of this step, a countercurrent column of a tank is required. In addition to the above-mentioned additives, various compounds are added to this stabilizing bath for the purpose of stabilizing images. Various buffers (e.g. borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, ammonia) to adjust membrane pH (e.g. pl(3-9)) Typical examples include aldehydes such as water, monocarboxylic acids, dicarboxylic acids, polycarboxylic acids, etc.) and formalin.In addition, chelating agents (inorganic phosphoric acid, aminopolycarboxylic acids, etc.) may be used as necessary. , organic phosphoric acid, organic phosphonic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), fungicides (benzointhiazolinone, irithiazolone, cutiazolinepensimitasol, halogenated phenol, sulfanilamide, benzotriazole, etc.) Various additives such as surfactants, fluorescent whitening agents, and hardening agents may be used, and two or more compounds for the same or different purposes may be used in combination.

In addition, ammonium chloride,
It is preferable to add various ammonium salts such as ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate.

In the case of color sensitive materials for photography, the normally performed post-fixing (washing-stabilization) process can be replaced with the above-mentioned stabilization process and water-washing process (water-saving treatment). At this time, if the amount of magenta coupler is 2 equivalents, formalin in the stabilizing bath may be removed.

The washing and stabilization processing time of the present invention varies depending on the type of sensitive material and processing conditions, but is usually 20 seconds to 10 minutes, preferably 2Q seconds to j minutes.

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. Patent No. 3. ．． 34t2. '! Indoaniline compounds described in No. 97, No. 3.34t2,699,
Research Disclosure/4#30 and the same/
! /! Thick base type compound described in No. 9, same/j9.2'
Aldol compound described in No. 1, U.S. Pat. No. 3,779,
Metal salt complex described in No. 4t92, JP-A-63-/3! t≦
Including the urethane compounds described in No. 2♂, JP-A-4-623! No., J4-7S733, Taro!
No. 2232, same! t-67r4t2, same j4-r37
3'! No. j4-7373! No. J4-1373, same! 6-? Ri73! Same issue! ≦−? /♂No.32, same! Otsu-ot<tJo issue, same! Otsu-106ko 4t/No., same Taro/θ7ko 3g No., same! Various salt-type precursors described in 2-Tough J3/No. J7-13JTJ and the like can be mentioned.

The silver halide color light-sensitive material of the present invention may contain various /-phenyl-
3-pyrazolidones may be incorporated. Typical compounds are those disclosed in JP-A No. 33, J-7-/4t4tj.
4t7, same 57-2///4t7, same! ! -! θ!
No. 32, same j/-30! No. 3, same! ! -! θ! No. 33, same! ? -! θ! Jllt issue, same j1-! 0! No. 36 and the same! ? -//, t4tjr issue, etc.

Various processing liquids in the present invention are used at /θ0cmto0c. A temperature of 33°C to 3♂0C is standard, but higher temperatures can be used to accelerate processing and shorten processing time, while lower temperatures can be used to improve image quality and improve the stability of the processing solution. can be achieved. Further, in order to save silver on photosensitive materials, treatment using cobalt intensification or hydrogen peroxide intensification as described in West German Patent No. 22g, 270 or U.S. Patent No. 3゜j74t, gwata may be carried out. .

Each treatment bath may be provided with a heater, temperature sensor, liquid level sensor, circulation pump, filter, floating pig, squeegee, etc., as necessary.

Further, during continuous processing, a constant finish can be obtained by using a replenisher for each processing solution to prevent fluctuations in the solution composition. The replenishment amount can be reduced to half or less than the standard replenishment amount to reduce costs.

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

EXAMPLE On a subbed cellulose triacetate film support,
A multilayer color photosensitive material 10/ was prepared by applying layers having the compositions shown below.

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

1st layer (antihalation layer) Black colloidal silver 0. -2 gelatin /, O ultraviolet absorber UV - / (7,,2 dispersion oil 0IL
−/θ, 0.2th 0. (Intermediate layer) Fine grain silver bromide (average particle size θ, 07 μ) θ, /! Gelatin /・0 3rd layer (first red-sensitive emulsion layer) Monodisperse silver iodobromide emulsion (silver iodide comolti, average grain size 0.j
μ, coefficient of variation related to particle size (hereinafter simply referred to as coefficient of variation)/
Tachi) 0.7 gelatin
0. Sensitizing dye A/,
Ox70-4 sensitizing dye B 2. ox
10-4 coupler C-10, / coupler C-xo, r coupler C-jo, co-coupler C-ri θ, 02 coupler (nee jO, 0/ dispersion oil 0IL-/ o, / dispersion oil 0IL-, zo, /G layer (second red-sensitive emulsion layer) Monodispersed silver iodobromide emulsion (silver iodide! morch, average grain size 0.2
μ, coefficient of variation //chi)/, Q gelatin /, 0 sensitizing dye AJ×10−4 sensitizing dye B 2x / o-4 coupler C-10,0/ coupler C-co 0.0! Coupler C-30,03 Coupler C-,l! ; o, oi
Coupler C-7o, o2 Coupler c-, ro, θ Cocoupler C-? o, o2 Dispersion oil 0IL-2o, / No. ! Layer (middle layer) Gelatin/・0 compound c
pti-A O,Oj-Dispersion oil 0IL-,20,Or G layer (first green-sensitive emulsion layer) Monodisperse silver iodobromide emulsion (3 molt silver iodide, average grain size 0.j
μ, coefficient of variation/9ch) 0.2 Monodisperse silver iodobromide emulsion (2 molch silver iodide, average grain size O0!
μ) o, 4t gelatin
/, 0 Sensitizing Dye C3xio-4 Sensitizing Dye D Co
3 o, o/dispersion oil 0IL-, 2
o, θ! 7th layer (green-sensitive layer) Polydispersed silver iodobromide emulsion (silver iodide 7 molt, average grain size o, t
μ, coefficient of variation/j) 0.9 gelatin
O-ta sensitizing dye C, 2X10-4 Sensitizing dye D /, zx/θ-4 coupler C-/, 2 o, or coupler C
-/4tO,Oj Dispersion oil 0IL-/o, o, r Dispersion oil 0IL-30,03 r-th layer (intermediate layer) Gelatin /・Co compound C
pd-A O, dispersion oil 0I
L-/o, 3 2nd layer (yellow filter single layer) Yellow colloidal silver 0.2 Gelatin θ・? Compound Cpd-A
O,2 dispersion oil 0IL-/
o, i 1st O layer (first blue-sensitive emulsion layer) Monodispersed silver iodobromide emulsion (silver iodide g morch, average grain size 0.3
μ, coefficient of variation, 20%) θ, 4 is a monodispersed silver iodobromide emulsion (silver iodide! Morch, average grain size o, tμ, coefficient of variation 77%) 'o, 4t gelatin
K, θ sensitizing dye E
/x10-4 Sensitizing dye Ftxio-4 Coupler C-/zo, Ta coupler C-/3 o, oj Dispersion oil 0IL-J o, q 1st/layer (2nd
f-sensitive emulsion layer) Monodispersed silver iodobromide emulsion (1 molt of silver iodide, average grain size/,!
μ, coefficient of variation 74t%) 0. ! gelatin
O-! Sensitizing dye E
! ×/θ-5 sensitizing dye F
jxlo-5 coupler C-/z
o,,z coupler C-/3 θ,Ot
Dispersion oil 0IL-j O, 0/No.
(7th protective layer) Gelatin O-! Coupler C-/l O,/Ultraviolet absorber UV-1 〇,/Ultraviolet absorber UV-j
O,2 Dispersion oil 0IL-4t 0.0/First layer (Second protective layer) Fine grain silver bromide emulsion (average grain size 0.07μ) 0.2! Gelatin (17,j polymethyl methacrylate particles (diameter/,!μ) 0.2 Formaldehyde scavenger 5-7O,! In addition, a surfactant W-/ and a hardening agent H-/ were added.

(Sample IO2~/30) C-1t in the 7th theta layer of sample 10/ was replaced with the coupler shown in Table 1 in an equimolar amount, and 0IL-3 was changed to the amount shown in Table 1, and each The amount of gelatin applied was varied in order to equalize the film quality of the raw samples.

As for the film quality! The minimum amount of gelatin was applied within a range that did not cause sweating after θ'C7o%/day.

(Sample 73/) A sample was prepared in the same manner as Sample 73/, except that C-λ in the third layer of Sample 23 was replaced with C-/ in an equimolar amount.

These samples were adjusted to ♂00°K using a color temperature conversion filter using light source A, and subjected to imagewise exposure of a maximum of 10 CMS, and the following color development was performed at 3r0c to evaluate photographic performance.

Further, exposure was carried out through a noturn for MTF measurement, color development was carried out in the same manner, and the MTF value at 0 cycles per 7 mm was measured.

Furthermore, the strips that have been subjected to imagewise exposure and development are paired with fluorescent light/! The concentration change was monitored by leaving it for 79 days under θθQ lux and 74 days at tooc and 70% relative humidity.

The results obtained are summarized in Table 1.

Color development 3 minutes/j seconds Bleach White 6 minutes 30 seconds Water Wash 2 minutes 10 seconds Fixed arrival time: 9 minutes, 20 seconds Wash with water for 3 minutes/! seconds Stability/min Oj seconds The composition of the treatment liquid used in each step was as follows.

Color developer diethylenetriaminepentaacetic acid /, Og/-hydroxyethylidene- /, /-diphosphonic acid 2.0g Sodium sulfite, og Potassium carbonate
30.0g potassium bromide
7.4tg potassium iodide
/ , j mg hydroxylamine sulfate
u, 4tg Goo (N-ethyl-N-β-hydroxyethylamino) -2-methylaniline sulfate &, jg Add water /, 01 pH/θ, 0 Bleach solution Ethylenediaminetetraacetic acid ferric ammonium salt 100. Og ethylenediaminetetraacetic acid disodium salt 10.0g ammonium bromide ijo, og ammonium nitrate 10.0g Add water
/, 0 no pH 6, Q Fixer ethylenediaminetetraacetic acid disodium salt /, 0g sodium sulfite da, θg ammonium thiosulfate aqueous solution (20 t) /ri! , θm1 Sodium bisulfite 9.6! add water
7.0! To the pH, add 6 stabilized formalin (4tQ%) a, oml polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) o, 3g water /, O1 From Table 1, sample of the present invention / //, //, 2, //9, /koθ, /23,
/λda, /kotsu, /22, /, 2ri and /30 are samples for comparison, and the ratio of 0IL-j/coupler has a higher MTF value than samples outside the present invention, and the yellow image is more robust. In addition, couplers other than the present invention have high sensitivity and MT
It can be seen that the sharpness expressed by the F value is good.

In addition, samples using the conventionally known coupler Cp-j at the high boiling point organic solvent/coupler ratio within the present invention ///, //,
It is clear that Sample No. 2 is superior in both image storage stability and sharpness compared to samples using conventionally known amounts of high boiling point organic solvents.

Furthermore, the cyan coupler used at the same time has the general formula (
It is also clear that the one represented by CC-,2,) is preferable from the viewpoint of cyan image preservation.

sensitizing dye person Same as above B Same as above C (CH2)3SO3Na sensitizing dye Same as above E (CH2)3803 (CH2)3SO3Na Same as above F Coupler C-/ Coupler C-,2 Coupler C-3 Coupler C-da Coupler C-B Coupler C-/ Coupler C-/.

Coupler C-t Coupler C-taCoupler C-72 Coupler C-73 n■τ Coupler C-74t α Coupler C-/j (JP-A-Sho!0-174!OK included coupler) Coupler-C-/Otsu interface Activator W-7 Formalin scavenger-S-/ Dispersion oil 0IL-/ 2H5 Dispersion oil 0IL-co Same as above 0IL-j Ultraviolet absorber UV-/ Same as above UV-co Ultraviolet absorber UV-3 Compound CpdAH-/ Cp-/ (Coupler Cp- of JP-A No. 0-163226
2 (Coupler Cp-j of Japanese Patent Publication No. ShojO-/!!22 (Coupler y-i/ of Japanese Patent Publication No. 722'13) Cp-4t (Coupler y-/, 2) Cp -j (Coupler y-73 of JP-A-4/-722G No. 3) Cp-B (Coupler y-/4t above) Patent applicant: Fuji Photo Film Co., Ltd. Procedural Amendment 1, Indication of Case: 1988 Poetry No. 1'7111
No. 3 No. 2, Title of the invention Silver halide color photographic light-sensitive material 3, Relationship with the case of the person making the amendment Table of patent applicants Subject of the amendment Column 5 of "Detailed Description of the Invention" of the specification, Description of the contents of the amendment The description in the "Detailed Description of the Invention" section is amended as follows.

1) The 6th line of the page “μlO~yooJ "≠SO~6tO" and correct it.

2) Row B from the bottom of page 1O “2-3oJ "t~30" and correct it.

3) Page 72, line λ "Hydroxy group" "Hydroxyl group" and correct it.

4) Page 12, line 3 "Hydroxy group," Delete.

5) Last line of page 13 [4cmt-butylphenoxy group] "≠-t-butylphenyl group" and correct it.

6) Page 1j, row 0 "Methylsulfonamide group" "Methanesulfonamide group," and correct it.

7) Page 1j, line 3 "n-butylsulfonamide group" "n-butanesulfonamide group" and correct it.

8) First! Page 3 to line V "n-octylsulfonamide group" "n-octane sulfonamide group" and correct it.

9) Page 1j Hiroyuki "n-dodecylsulfonamide group" "n-dodecanesulfonamide group" and correct it.

10) First page! The line "Hiro-methylsulfonylphenyl group" is corrected to "≠-methanesulfonylphenoxy group."

11) Page 77, line llA [Phenyldriasilidine] "Phenyltriacylidine" and correct it.

12) Correct the structural formula of compound Y-17 on page 1.

13) Correct the structural formula of compound Y-/l on page 27.

14) Correct the structural formula of compound Y-/ri on page 27.

15) Change the description of compound Y-10 on page 27 to [ ” and correct it.

16) After the structural formula of compound Y-20 on page 27, “ Insert.

17) Page 30, lines t to ri "Diethyl laurylamide" [Diethyllaurinamide] and correct it.

18) Page 30 // line Before "diethyl azelate" "Dioctyl Sepacate," Insert.

1G) Structural formula of the compound [:CC-/) on page 31] and correct it.

20) The structural formula of the compound [CC-λ] on page 32 is changed to “ ” and correct it.

21) Page 32, line 2 "Ro" R.J. and correct it.

22) Change “-CONRsRs, -NHCORs,” in the second line of page 32 to [-CON
Correct as RYRa, -NHCORv, J.

23) Page 32, line 3 r　K in front of NHCOOR7J r -8O2NRRs J Insert.

24) Page 32, line 3 “-NHCONRsRa J “-NHCONRRe J and correct it.

25) Page 32, line μ [-NH8O2NR5R6J “-NH8O2NRRe J and correct it.

26) 3rd page, row j "R5" rRJ and correct it.

27) Page 32, line 10 from the bottom "R2" "R1" and correct it.

28) Page 32, line 70 from the bottom "Hydroxy group" "Hydroxyl group" and correct it.

29) Page 32, second line from the bottom "R2" R.I.J. and correct it.

30) Page 33, line 1 "R2" rRJ and correct it.

31) Page 33, line 3 "R3" rR”J and correct it.

32) Line 33 on page 33 After r-ORsj [-3RgJ Insert ◎ 33) Line B from the bottom of page 33 "R5" rRJ and correct it.

34) Correct the entry from the bottom of page 33.
”35) Correct “R4” on the 3rd μth page/line to “R9”.

36) 3rd≠From the bottom of the page! row Before "number of carbons/~/r" "Hydrogen atom" Insert.

37) 3rd ≠ 2nd line from the bottom of the page "Carboxy group" "Carboxyl group" and correct it.

38) 1st line of page 3 rXJ "Xl" and correct it.

39) The structural formula of the compound (CC-z) on page 37 is changed to “ ” Corrected with 0 4G) Page 3r, line 1 rR4 and XJt- "Xl" and correct it.

41) Insert the description on a separate sheet after the third line on page 4.

42) Page 3r Hiroyuki rRx, R2, R3 Mayu wa X” “R11RI, R1 is XJ and correct it.

43) Page 31, line 6 “R4 is XJt- “R, Ar’ or XJ ■ and correct it.

44) What is the structural formula of compound (I-≠6) on page 33? insert.

45) Evening μ page 2nd line "Special Application Shojter No. 23603," "Machima Ryo AO-, 237≠≠," and correct it.

46) Page j4c ~ line 3 "Doyota 264L Core No. 7" "Same A/-/331. Hiro Q No." and correct it.

47) Page 74c, line 3 "JP-261133" “Same A/-/No. 1137” and correct it.

Attachment ·

Claims (1)

[Scope of Claims] A silver halide emulsion layer containing a cyan coupler on a support, a silver halide emulsion layer containing a magenta coupler,
and a silver halide color photographic material having at least one silver halide emulsion layer each containing a yellow coupler, at least one of the yellow couplers having an equivalent molecular weight of 450 to 680 and represented by the following general formula [I]. A silver halide color photographic photosensitive material which is a lipophilic two-equivalent yellow coupler and contains a high boiling point organic solvent in a weight ratio of at most 0.5 to the total amount of yellow coupler contained in the emulsion layer. material. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the general formula [I], R_1 is an aliphatic group, R_2 is a hydrogen atom, a halogen atom, or an aliphatic oxy group, and R_
3 represents a group (including atoms) that can be substituted on the benzene ring, m represents an integer of 0 to 4, and X represents a group that can be separated by a coupling reaction with an oxidized aromatic primary amine developer. However, when m is plural, (R_3)m may be the same or different. Also, R_1, R_2, R_3 or X is 2
It may serve as a valent to tetravalent linking group to form a dimer to tetramer of the yellow coupler.