JPH05289262A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide a silver halide color photographic sensitive material showing high density of developed color, excellent property for rapid processing and excellent rigid property of color picture by using a coupler having high reactivity with the oxidized body of a developer. CONSTITUTION:This silver halide color photographic sensitive material contains a coupler expressed by a formula in at least one layer on a supporting body. Formula: A-(X1)i-N(R1)-X2-N(R2)-(X3)j-R3. In the formula, A is a coupler residue which can couple with the oxidizer body of a developer, each of X1, X2 and X3 is CO or SO2, each of R1 and R2 is hydrogen, a metal atom, ammonium, an alkyl group or aryl group and at least one of these is hydrogen, a metal atom or ammonium, and R3 is an alkyl group or aryl group. i and j are 0 or 1 and at least one of these is 1, however, it is not allowed in the case that i=1, X1=SO2, X2=CO and j=0.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material, more specifically, a silver halide color containing a coupler having high reactivity, excellent in rapid processing suitability, and excellent in color image fastness. It relates to a photographic light-sensitive material.

[0002]

BACKGROUND OF THE INVENTION Couplers used in color photographic light-sensitive materials require various performances, but in many cases, highly reactive couplers are desired. When the dye formation rate is high, the color density is increased, which is advantageous for high sensitivity, and the development is fast, which is advantageous for rapid processing. Further, in the case of a coupler which releases a photographically useful group (for example, a coupler which releases a development inhibitor; a DIR coupler), it is desirable that the reactivity is high because the effect is enhanced. For example,
The use of a highly reactive DIR coupler is advantageous for improving image quality such as image sharpness and color reproducibility. One of the effective means for increasing the reactivity of the coupler with the oxidized product of the developing agent is to introduce an acidic dissociative group or a highly polar group into the coupler molecule. For example, couplers introduced with a p-hydroxybenzene sulfonyl group described in JP-A-58-42045, JP-B-62-61251 and JP-A-61-
Examples thereof include couplers having an N-acyl sulfamoyl group described in No. 121054.

[0003]

The above-mentioned known couplers show some performance, but they are still insufficient, and further improvement is desired. For example, there are defects in color image fastness, and further improvements have been desired. That is, an object of the present invention is to provide a silver halide color photographic light-sensitive material excellent in rapid processing suitability and color image fastness by using a coupler having high reactivity with an oxidized product of a developing agent.

[0004]

The above object is to provide a halogen containing a coupler represented by the following general formula (1) in at least one hydrophilic colloid layer provided on a support. Achieved by silver halide color photographic light-sensitive material. Formula _{(1) A- (X 1)} i -N (R 1) -X 2 -N (R 2) - (X 3) j
-R ₃ wherein, A represents a coupler residue capable of coupling reaction with oxidized developer, X _1, X ₂ and X ₃ each represent a CO or SO _2, R ₁ and R ₂ Each represents a hydrogen atom, a metal atom, ammonium, an alkyl group or an aryl group, at least one of which represents a hydrogen atom, a metal atom or an ammonium, R ₃ represents an alkyl group or an aryl group, and i and j each represent 0 or 1 And at least one of them represents 1. However, i = 1,
Excluded when X ₁ = SO ₂ , X ₂ = CO, and j = 0.

The compound represented by the general formula (1) will be described in detail below. The coupler residue represented by A may be any coupler residue of a yellow coupler, a magenta coupler, a cyan coupler, or a non-coloring type coupler that does not substantially leave a dye in the light-sensitive material. When A represents a yellow color image coupler residue, for example, pivaloyl acetanilide type, benzoyl acetanilide type, malon diester type, malon diamide type, dibenzoyl methane type, benzothiazolyl acetamide type, malon ester monoamide type, tria type Examples thereof include azolylacetamide type, benzimidazolylacetamide type or cycloalkanoylacetamide type coupler residues. Further, US Pat. Nos. 5,021,332 and 5,021,33
It may be a coupler residue described in No. 0 or EP 421,221A. When A represents a magenta color image forming coupler residue, examples thereof include a 5-pyrazolone type, a pyrazolobenzimidazole type, a pyrazolotriazole type, a pyrazoloimidazole type or a cyanoacetophenone type coupler residue. When A represents a cyan image-forming coupler residue, examples include phenol type and naphthol type. Furthermore, US Pat. No. 4,746,6
The coupler residue described in No. 02 and EP 249,453A may be used. Further, A may be a coupler residue that does not substantially leave a color image. Examples of this type of coupler residue include indanone type and acetophenone type coupler residues, and elution type coupler residues described in European Patent Nos. 443,530A and 444,501A.

Preferred coupler residues used in the present invention are represented by the following general formulas (Cp-1), (Cp-2) and (Cp).
p-3), (Cp-4), (Cp-5), (Cp-
6), (Cp-7), (Cp-8), (Cp-9) or (Cp-10). These coupler residues are preferred because of their particularly high coupling rate.

[0007]

[Chemical 1]

[0008]

[Chemical 2]

In the above, R ₅₁ , R ₅₂ , R ₅₃ , R ₅₄ ,
R ₅₅ , R ₅₆ , R ₅₇ , R ₅₈ , R ₅₉ , R ₆₀ , R ₆₁ , R ₆₂ , R
_{If 63} or Z contains a diffusion resistant group, it is selected so that the total number of carbon atoms is 8 to 40, preferably 10 to 30, otherwise the total number of carbon atoms is preferably 15 or less. The at least one formula of these groups in one molecule of _{(1) - (X 1)} i -N (R 1) -X 2 -N (R
₂₎ - (X ₃₎ a group represented by _j -R ₃ is a group having as a substituent. Alternatively, R ₅₉ , R ₆₂ or R ₆₃ are each represented by — (X ₁ ) _i —N (R ₁ ) —X ₂ —N (R ₂ ) — (X ₃ ) _j
-R ₃ itself may represent. In the case of a bis-type, telomer-type or polymer-type coupler, the above groups (R ₅₁ to
Either R ₆₃ or Z) represents a divalent group and connects repeating units and the like. In this case, the range of carbon number may be out of regulation.

R _{51 to} R ₆₃ , Z, b, d and e will be described in detail below. In the following, R ₄₁ represents an alkyl group, an aryl group or a heterocyclic group, R ₄₂ represents an aryl group or a heterocyclic group, and R ₄₃ , R ₄₄ and R ₄₅ represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. Represents.
R ₅₁ has the same meaning as R ₄₁ . R ₅₂ and R ₅₃ have the same meanings as R ₄₃ . b represents 0 or 1. R ₅₄
Group having the same meaning as R _{41 is, R 41 CO (R 43)} N- group, R ₄₁
SO ₂ (R ₄₃ ) N-group, R ₄₁ (R ₄₃ ) N-group, R ₄₁ S-
Group, R ₄₃ O— group, or R ₄₅ (R ₄₃ ) NCON (R ₄₄ ).
Represents a group. R ₅₅ has the same meaning as R ₄₁ . R
₅₆ and R ₅₇ are each a group having the same meaning as the R ₄₃ group, R ₄₁ S-
Group, R ₄₃ O-group, R ₄₁ CO (R ₄₃ ) N-group, or R ₄₁
It represents a SO ₂ (R ₄₃ ) N-group. R ₅₈ represents a group having the same meaning as R ₄₁ . And R ₅₉ groups of the same meaning as R _41, R ₄₁ CO
(R ₄₃ ) N-group, R ₄₁ OCO (R ₄₃ ) N-group, R ₄₁ SO
₂ (R ₄₃ ) N- group, R ₄₃ (R ₄₄ ) NCO (R ₄₅ ) N-
Group, R ₄₁ O- group, R ₄₁ S- group, halogen atom, or R
₄₁ (R ₄₃ ) represents an N-group. d represents an integer of 0 to 3. When d is plural, plural R _59's represent the same substituent or different substituents. R ₆₀ has the same meaning as R ₄₁ . R ₆₁ represents a group having the same meaning as R ₄₁ . R ₆₂ is a group of the same meaning as R _41, R ₄₁ CONH- group, R ₄₁ OCONH-
Group, R ₄₁ SO ₂ NH— group, R ₄₃ (R ₄₄ ) NCONH—
Group, R ₄₃ (R ₄₄ ) NSO ₂ NH— group, R ₄₃ O— group, R ₄₁
It represents an S-group, a halogen atom or an R ₄₁ NH-group. R ₆₃
Is a group having the same meaning as R ₄₁ , R ₄₃ CO (R ₄₄ ) N-group, R ₄₃
(R ₄₄₎ NCO- _{group, R 41 SO 2 (R 43} ) N- group, R ₄₁
(R ₄₃₎ NSO ₂ - group, R ₄₁ SO ₂ - group, R ₄₃ OCO-
Represents a group, R ₄₃ O—SO ₂ — group, halogen atom, nitro group, cyano group or R ₄₃ CO— group. e represents an integer of 0 to 4, and f represents an integer of 0 to 3. Multiple R ₆₂
Or, when R ₆₃ is present, it represents the same or different.

In the above, the alkyl group has 1 to 3 carbon atoms.
2, preferably 1 to 22 saturated or unsaturated, chain or cyclic, linear or branched, substituted or unsubstituted alkyl groups. As typical examples, methyl, cyclopropyl, isopropyl, n-butyl, t-butyl, i-butyl, t-amyl, n-hexyl, cyclohexyl, 2-
Examples include ethylhexyl, n-octyl, 1,1,3,3-tetramethylbutyl, n-decyl, n-dodecyl, n-hexadecyl, or n-octadecyl. The aryl group is phenyl having 6 to 20 carbon atoms, preferably substituted or unsubstituted phenyl, or substituted or unsubstituted naphthyl. The heterocyclic group has 1 to 20 carbon atoms, preferably 1 to
7 is a substituted or unsubstituted heterocyclic group, preferably a 3- to 8-membered ring, selected from nitrogen atom, oxygen atom or sulfur atom as the hetero atom. Typical examples of the heterocyclic group are 2-pyridyl, 2-benzoxazolyl,
2-imidazolyl, 2-benzimidazolyl, 1-indolyl, 1,3,4-thiadiazol-2-yl, 1,
2,4-triazol-2-yl group or 1-indolinyl may be mentioned. When the alkyl group, aryl group and heterocyclic group have a substituent, a typical substituent is,
Halogen atom, R ₄₇ O- group, R ₄₆ S- group, R ₄₇ CO (R
₄₈ ) N-group, R ₄₇ (R ₄₈ ) NCO- group, R ₄₆ OCO (R
₄₇ ) N-group, R ₄₆ SO ₂ (R ₄₇ ) N-group, R ₄₇ (R ₄₈ ).
NSO ₂ - group, R ₄₆ SO ₂ - group, R ₄₇ OCO- group, R ₄₇
NCO (R ₄₈ ) N-group, R ₄₇ CONHSO ₂ -group, R ₄₇
(R ₄₈ ) NCONHSO ₂ — group, a group having the same meaning as R ₄₆ ,
R ₄₇ (R ₄₈ ) N-group, R ₄₆ COO-group, R ₄₇ OSO _2-
Groups, cyano groups or nitro groups. Where R ₄₆
Represents an alkyl group, an aryl group, or a heterocyclic group,
R ₄₇ and R ₄₈ each represent an alkyl group, an aryl group, a heterocyclic group or a hydrogen atom. The meaning of an alkyl group, an aryl group or a heterocyclic group has the same meaning as previously defined.

Next, preferred ranges of R _{51 to} R ₆₃ , b, d, e and f will be described. R ₅₁ is preferably an alkyl group, an aryl group or a heterocyclic group. R ₅₂ and R ₅₅ are preferably aryl groups. R ₅₃ is an aryl group when b is 1,
When b is 0, a heterocyclic group is preferred. R ₅₄ is R ₄₁ CONH
A -group or an _R41 ( _R43 ) N- group is preferable. R ₅₆ and R ₅₇ are preferably an alkyl group, R ₄₁ O— group, or R ₄₁ S— group. R ₅₈ is preferably an alkyl group or an aryl group. In the general formula (Cp-6), R ₅₉ is a chloro atom,
Alkyl groups or R ₄₁ CONH- groups are preferred. d is 1
Or 2 is preferable. R ₆₀ is preferably an aryl group. In formula (Cp-7), R ₅₉ is preferably R ₄₁ CONH-group. In general formula (Cp-7), d is preferably 1. R ₆₁ is preferably an alkyl group or an aryl group. In general formula (Cp-8), e is preferably 0 or 1.
R ₆₂ is preferably an R ₄₁ OCONH- group, an R ₄₁ CONH- group or an R ₄₁ SO ₂ NH- group, and the substitution position thereof is preferably the 5-position of the naphthol ring. In the general formula (Cp-9), R ₆₃ is R ₄₃ CONH-group, R ₄₁ SO ₂ NH
-Group, R ₄₁ (R ₄₃ ) NSO ₂ -group, R ₄₁ SO ₂ -group, R
₄₃ (R ₄₄₎ NCO- group, a nitro group, or a cyano group. In general formula (Cp-10), f is preferably 0 or 1, and R ₆₃ is preferably an R ₄₃ NHCO— group, an R ₄₃ OCO— group or an R ₄₃ CO— group.

The group represented by Z may be a hydrogen atom or a conventionally known coupling-off group. Preferable Z is a hydrogen atom, a nitrogen-containing heterocyclic group bonded to a coupling position at a nitrogen atom, an aryloxy group, an arylthio group, a heterocyclic oxy group, a heterocyclic thio group, an acyloxy group, a carbamoyloxy group, an alkylthio group or A halogen atom is mentioned. Z is a hydrogen atom or the following examples are preferable Z. When Z represents a nitrogen-containing heterocyclic group bonded to the coupling position at a nitrogen atom, it preferably has 1 to 15, preferably 1 to 10 carbon atoms and 5
Alternatively, it is a 6-membered, substituted or unsubstituted, saturated or unsaturated, monocyclic or condensed-ring heterocyclic group. The hetero atom may contain an oxygen atom or a sulfur atom in addition to the nitrogen atom. Specific preferred examples of the heterocyclic group include 1-pyrazolyl, 1-imidazolyl, pyrrino,
1,2,4-triazol-2-yl, 1,2,3-triazol-1-yl, benzotriazolyl, benzimidazolyl, imidazolidin-2,4-dione-3-yl, oxazolidin-2,4 -Dione-3-yl, 1,
2,4-triazolidine-3,5-dione-4-yl,
2-Imidazolinon-1-yl, 3,5-dioxomorpholino or 1-indazolyl are mentioned. When these heterocyclic groups have a substituent, the substituent is
The alkyl group, aryl group or heterocyclic group (for example, R
_The substituents enumerated as the substituents which ₅₁ ) may have are mentioned as examples. As a preferable substituent, one of the substituents is an alkyl group, an alkoxy group, a halogen atom, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylthio group, an acylamino group, a sulfonamide group, an aryl group, a nitro group, a carbamoyl group, or a sulfonyl group. It is when When Z represents an aromatic oxy group, it is preferably a substituted or unsubstituted aromatic oxy group having 6 to 10 carbon atoms. A substituted or unsubstituted phenoxy group is particularly preferable. When it has a substituent, examples of the substituent include the substituents listed as the substituents that the aryl group (for example, R ₅₁ ) may have. Among them, a preferred substituent is a case where at least one substituent is an electron-withdrawing substituent, and examples thereof include a sulfonyl group, an alkoxycarbonyl group, a sulfamoyl group, a halogen atom, a carboxyl group, a carbamoyl group and a nitro group. , A cyano group or an acyl group. When Z represents an aromatic thio group, it is preferably a substituted or unsubstituted aromatic thio group having 6 to 10 carbon atoms. Particularly preferred is a substituted or unsubstituted phenylthio group. When it has a substituent, examples of the substituent include the substituents enumerated as the substituents which the group represented by the aryl group (for example, R ₅₁ ) may have.
Among them, preferable at least one substituent is an alkyl group, an alkoxy group, a sulfonyl group, an acylamino group, a carbamoylamino group, an alkoxycarbonyl group, a sulfamoyl group, a halogen atom, a carbamoyl group, or a nitro group. Is. When Z represents a heterocyclic thio group, the portion of the heterocyclic group has from 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and contains 3 to 12 as a hetero atom, for example, at least one nitrogen atom, oxygen atom or sulfur atom. It is preferably a 5- or 6-membered, substituted or unsubstituted, saturated or unsaturated, monocyclic or condensed-ring heterocyclic group. Examples of the heterocyclic thio group include a tetrazolylthio group, a 1,3,4-thiadiazolylthio group,
Examples thereof include a 1,3,4-oxadiazolylthio group, a 1,3,4-triazolylthio group, a benzimidazolylthio group, a benzothiazolylthio group, and a 2-pyridylthio group. When it has a substituent, examples of the substituent include the substituents enumerated as the substituents that the group represented by the heterocyclic group (for example, R ₅₁ ) may have.
Among them, preferable substituents include at least one of the substituents such as an alkyl group, an aryl group, a carboxyl group, an alkoxy group, a halogen atom, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylthio group, an acylamino group, a sulfonamide group and a nitro group. When it is a group, a carbamoyl group, a heterocyclic group or a sulfonyl group.
When Z represents a carbamoyloxy group, it has 1 to 3 carbon atoms.
0, preferably 1-20 alkyl, aryl, heterocycle, substituted or unsubstituted carbamoyloxy groups. For example, N, N-diethylcarbamoyloxy, N-
Phenylcarbamoyloxy, morpholinocarbonyloxy, 1-imidazolylcarbonyloxy, 1-pyrrolocarbonyloxy or 1-indolinocarbonyloxy. When these have a substituent, examples of the substituent include the substituents enumerated as the substituents that the alkyl group, aryl group or heterocyclic group (for example, R ₅₁ ) may have. Among them, a preferred substituent is at least one of the substituents is an alkyl group,
This is when it is an aryl group, an alkoxy group, an aryloxy group, a halogen atom, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylthio group, an acylamino group, a sulfonamide group, a nitro group, a carbamoyl group, a heterocyclic group or a sulfonyl group. When Z represents an alkylthio group, it has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms,
It is a linear, branched, cyclic, saturated, unsaturated, substituted or unsubstituted alkylthio group. When it has a substituent, examples of the substituent include the substituents enumerated as the substituents that the group represented by the alkyl group (for example, R ₅₁ ) may have.

Next, R ₁ , R ₂ and R ₃ in the general formula (1) will be described in detail below. When R ₁ , R ₂ and R ₃ represent an alkyl group, they have 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, and are straight chain, branched, cyclic, saturated, unsaturated,
It is a substituted or unsubstituted alkyl group. R ₁ ,
When R ₂ and R ₃ represent an aryl group, the number of carbon atoms is 6 to
And 10 substituted or unsubstituted aryl groups (phenyl group or naphthyl group). When R ₁ , R ₂ and R ₃ are an alkyl group or an aryl group and they have a substituent, examples of the substituent include a group represented by the alkyl group (for example, R ₅₁ ). Substituents listed as good substituents are mentioned as examples. Among them, a particularly preferable substituent is an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a sulfonyl group, an acylamino group, an alkoxycarbonyl group or a sulfonamide group. In the general formula (1), at least one of R _{1 and} R ₂ represents a hydrogen atom, a metal atom or ammonium. Any metal atom may be used as long as it forms a cation species by forming a salt, preferably sodium, potassium,
Examples include magnesium or calcium. Particularly preferred is sodium or potassium. When i is 1, R ₁ is particularly preferably a hydrogen atom, a metal atom or ammonium. When i is 1, in the compound represented by the general formula (1), the following three cases are preferable examples. The case where X ₁ is CO is preferable. It is the case when both X ₁ and X ₂ are SO ₂ . X ₁ is SO ₂ , X ₂ is CO, and j is 1.
Is the preferred case. Of the above, the case is particularly preferable. When i is 0, R ₂ is particularly preferably a hydrogen atom, a metal atom or ammonium. The coupler represented by the general formula (1) is a preferable example when it is a diffusion resistant coupler. The diffusion-resistant type is a coupler having a group in the molecule that makes the molecular weight sufficiently large in order to immobilize it in the layer to which the molecule is added. Usually, the total carbon number is 8 to 30,
Preferably an alkyl group having 10 to 20 or a total carbon number of 4 to
An aryl group having 20 substituents is used. These diffusion resistant groups may be substituted in any of the molecules,
Moreover, you may have two or more. Next, specific examples of the coupler represented by the general formula (1) will be shown, but the couplers are not limited thereto.

[0015]

[Chemical 3]

[0016]

[Chemical 4]

[0017]

[Chemical 5]

[0018]

[Chemical 6]

[0019]

[Chemical 7]

[0020]

[Chemical 8]

[0021]

[Chemical 9]

[0022]

[Chemical 10]

[0023]

[Chemical 11]

[0024]

[Chemical 12]

(Synthesis Example) Synthesis of Exemplified Compound (1) The compound was synthesized by the following synthetic route.

[0026]

[Chemical 13]

20 of (i) in 20 ml of pyridine
g and 9 g of (ii) were mixed and reacted at 40 ° C. for 5 hours.
The reaction mixture was poured into dilute hydrochloric acid, and the precipitated crystals were collected by filtration. By drying, 21.2 g of (iii) was obtained. Isopropanol 20 containing 21.2 g of (iii), 20 g of reduced iron, 0.5 g of ammonium chloride and 10 ml of water
It was added to 0 ml and heated to reflux. After reacting for 5 hours, it was filtered while hot. 500 ml of ethyl acetate was added to the filtrate, and the mixture was washed with water using a separating funnel. The oil layer is taken, and after concentration, ethyl acetate and hexane are added to the residue to crystallize it.
18.3 g of (iv) was obtained. 15 g of ethyl pivaloyl acetate and 18.3 g of (iv) were mixed and allowed to react for 4 hours on an oil bath at 160 ° C. After cooling to room temperature, 50 ml of ethyl acetate was added, and the mixture was left overnight. The precipitated crystals were filtered out to obtain 15.3 g of (v). 15.3 g of (v) was added to 50 ml of chloroform. 4 g of bromine was added dropwise at room temperature. After reacting for 10 minutes, the mixture was concentrated under reduced pressure. Add 500 ml of acetonitrile, 5.2 ml of triethylamine and 10.0 g of (vi),
The reaction was carried out at ℃ for 3 hours. After cooling to room temperature, ethyl acetate 500
After adding ml, the mixture was transferred to a separating funnel and washed with water. The oil layer was washed with diluted hydrochloric acid and then washed with water until it became neutral. The oil layer was taken, the solvent was distilled off under reduced pressure, and ether was added to the residue for crystallization. Exemplified compound (1) by drying
12.3g was obtained.

When the coupler represented by the general formula (1) is added to the light-sensitive silver halide emulsion layer, it is added to a non-light-sensitive layer per mole of silver halide in the layer, and when it is added to the light-sensitive layer, it is adjacent to the light-sensitive layer. 1.0 × 10 ^{−3 to} 1.0 mol, preferably 1 mol, per mol of the silver halide of the photosensitive silver halide emulsion layer (silver halide having a large content when sandwiched between two photosensitive layers) Is 2.0 × 10 ^{-2 to} 5.0 × 10 ^-1 mol,
More preferably, 5.0 × 10 ^{-2 to} 4.0 × 10 ^-1 mol is added.

The light-sensitive material of the present invention may have at least one of a blue-sensitive layer, a green-sensitive layer and a red-sensitive silver halide emulsion layer provided on a support. There is no particular limitation on the number and order of layers of the silver halide emulsion layer and the non-photosensitive layer. As a typical example, a silver halide photographic light-sensitive material having at least one light-sensitive layer composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. And the photosensitive layer is blue light, green light,
And a unit light-sensitive layer having color sensitivity to red light, and in a multilayer silver halide color photographic light-sensitive material, the unit light-sensitive layers are generally arranged in order from the support side to the red-color-sensitive layer and green. The color-sensitive layer and the blue color-sensitive layer are installed in this order.
However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layers. A non-photosensitive layer such as various intermediate layers may be provided between the above-described silver halide photosensitive layers and as the uppermost layer and the lowermost layer. The intermediate layer includes JP-A Nos. 61-43748 and 59-1.
13438, 59-113440, 61-20037, 61-20038
It may contain a coupler, a DIR compound or the like as described in JP-A No. 1994-101, and may contain a color mixing inhibitor as is commonly used. The plural silver halide emulsion layers constituting each unit light-sensitive layer preferably use a two-layer constitution of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer as described in West German Patent No. 1,121,470 or British Patent No. 923,045. be able to. Usually, it is preferable that the layers are arranged so that the sensitivities are gradually lowered toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. In addition,
57-112751, 62-200350, 62-206541, 62
A low-sensitivity emulsion layer may be provided on the side farther from the support and a high-sensitivity emulsion layer may be provided on the side closer to the support as described in JP-A-206543 and the like. As a specific example, from the side farthest from the support, low-sensitivity blue photosensitive layer (BL) / high-sensitivity blue photosensitive layer (BH)
/ High sensitivity green photosensitive layer (GH) / Low sensitivity green photosensitive layer (GL) /
High-sensitivity red photosensitive layer (RH) / low-sensitivity red photosensitive layer (RL), or BH / BL / GL / GH / RH / RL, or BH / BL
It can be installed in the order of / GH / GL / RL / RH. Further, as described in JP-B-55-34932, the layers can be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the side farthest from the support. In addition, JP-A-56-25738 and 62-6
As described in Japanese Patent No. 3936, the blue-sensitive layer / GL / RL / GH / RH may be arranged in this order from the side farthest from the support. Further, as described in JP-B-49-15495, the upper layer is a silver halide emulsion layer having the highest sensitivity,
The middle layer is a silver halide emulsion layer having a lower photosensitivity, and the lower layer is a silver halide emulsion layer having a lower photosensitivity than the middle layer, and the photosensitivity is gradually decreased toward the support. An arrangement composed of three layers can be mentioned. Even when it is composed of three layers having different sensitivities, as described in JP-A-59-202464, a medium-sensitivity emulsion layer from the side distant from the support in the same color-sensitive layer. / High-speed emulsion layer / low-speed emulsion layer may be arranged in this order. In addition, they may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer. Also, in the case of four layers or more, the arrangement may be changed as described above. U.S. Pat.Nos. 4,663,271 and 4,705,744 to improve color reproduction.
No. 4,707,436, JP-A-62-160448, 63-89850
It is preferable to dispose the donor layer (CL) having a multilayer effect, which has a spectral sensitivity distribution different from that of the main photosensitive layer such as BL, GL, and RL, described in Japanese Patent Publication No. JP-A-2004-320, adjacent to or adjacent to the main photosensitive layer. As described above, various layer configurations and arrangements can be selected according to the purpose of each light-sensitive material.

The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention contains silver iodobromide, silver iodochloride, or iodochlorobromide containing about 30 mol% or less of silver iodide. It is silver. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 10 mol% silver iodide. Silver halide grains in photographic emulsions have regular crystals such as cubes, octahedra and tetradecahedrons, grains having irregular crystal forms such as spheres and plates, twin planes, etc. It may have a crystal defect of, or a composite form thereof. The grain size of silver halide is about
It may be fine particles of 0.2 μm or less or large-sized grains having a projected area diameter of up to about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion. The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (RD) No.
17643 (December 1978), pp. 22-23, "I. Emulsion production (Emulsi
on preparation and types) ”, and No. 18716 (1979)
No. 307105 (November 1989), 863-865, p. 648, p. 648.
Page and Graphide, "Physics and Chemistry of Photography", published by Paul Montel (P. Glafkides, Chimie et Physique Photo
graphique, Paul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF Duffin, Phot
ographic Emulsion Chemistry (Focal Press, 1966)),
Zelikman et al., "Production and coating of photographic emulsions", published by Focal Press (VL Zelikman et al., Making and Coat
ing Photographic Emulsion, Focal Press, 1964) and the like.

Monodisperse emulsions described in US Pat. Nos. 3,574,628 and 3,655,394 and British Patent 1,413,748 are also preferable. Further, tabular grains having an aspect ratio of about 3 or more can be used in the present invention. Tabular grains are described by Gatov, Photographic Science and Engineering.
and Engineering), Vol. 14, pp. 248-257 (1970);
U.S. Pat.Nos. 4,434,226, 4,414,310, 4,433,0
It can be easily prepared by the methods described in 48, 4,439,520 and British Patent 2,112,157. The crystal structure may be uniform, may have a different halogen composition between the inside and the outside, may have a layered structure, and may have a different composition by epitaxial bonding. Alternatively, it may be bonded to a compound other than silver halide such as silver rhodanide and lead oxide. Also, a mixture of particles having various crystal forms may be used. The above emulsion may be either a surface latent image type which forms a latent image mainly on the surface, an internal latent image type which forms a latent image inside the grain or a type which has a latent image both on the surface and inside, but a negative type emulsion. It is necessary to be. Among the internal latent image type emulsions, core / shell type internal latent image type emulsions described in JP-A-63-264740 may be used. The method for preparing this core / shell type internal latent image type emulsion is described in JP-A-59-133542. The shell thickness of this emulsion varies depending on the development process and the like, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

The silver halide emulsion is usually one which has been physically ripened, chemically ripened and spectrally sensitized. Additives used in such a process are described in Research Disclosure No. 17643, No. 18716 and No. 307105, and the corresponding portions are summarized in the table below. The light-sensitive material of the present invention comprises two or more kinds of emulsions having different characteristics of at least one of the grain size, grain size distribution, halogen composition, grain shape and sensitivity of the light-sensitive silver halide emulsion.
It can be mixed and used in the same layer. US Patent No.
No. 4,082,553, the surface of which is covered with silver halide grains, U.S. Pat. No. 4,626,498, JP-A-59-214852, the inside of which is covered with silver halide grains, and colloidal silver is light-sensitively halogenated. It can be preferably used for the silver emulsion layer and / or the substantially light-insensitive hydrophilic colloid layer. The fogged silver halide grain inside or on the surface means a silver halide grain which enables uniform (non-imagewise) development regardless of the unexposed portion and exposed portion of the light-sensitive material. .. A method for preparing a silver halide grain whose inside or surface is fogged is described in U.S. Pat.
It is described in No. 9-214852. The silver halide forming the inner nucleus of a core / shell type silver halide grain having a fogged inside may have the same halogen composition or different halogen compositions. As the silver halide having the inside or surface of the grain fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. There is no particular limitation on the grain size of these fogged silver halide grains, but as the average grain size,
0.01 to 0.75 μm, particularly 0.05 to 0.6 μm is preferable. The grain shape is not particularly limited, and may be regular grains or polydisperse emulsions, but monodisperse grains (at least 95% of the weight or the number of silver halide grains are ± 40% of the average grain size). %) Is preferable.

In the present invention, it is preferable to use a non-photosensitive fine grain silver halide. The non-photosensitive fine grain silver halide is a fine grain of silver halide which is not exposed to light during imagewise exposure for obtaining a dye image and is not substantially developed in the developing treatment, and it is preferable that the fog is not fogged in advance. .. The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may optionally contain silver chloride and / or silver iodide. Preferred is one containing 0.5 to 10 mol% of silver iodide. Fine grain silver halide has an average grain size (average diameter of circles in the projected area)
Is preferably 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm. The fine grain silver halide can be prepared in the same manner as in the case of ordinary photosensitive silver halide. In this case, the surface of the silver halide grain does not need to be chemically sensitized nor spectral sensitization. However, prior to adding this to the coating liquid, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, mercapto-based compound or zinc compound in advance. Colloidal silver can be preferably contained in the layer containing the fine grain silver halide grains. Coated silver amount of the light-sensitive material of the present invention is preferably 6.0 g / m ² or less, 4.5 g / m ² or less is most preferred.

Known photographic additives that can be used in the present invention are also described in the above three Research Disclosures, and the relevant portions are shown in the following table. Types of additives RD17643 RD18716 RD307105 1. Chemical sensitizer, page 23, page 648, right column, page 866 2. Sensitivity enhancer, page 648, right column 3. Spectral sensitizer, page 23 to 24, page 648, right column, page 866 to 868 Color sensitizer ~ page 649 right column 4.whitening agent page 24 647 page right column 868 page 5.fogging prevention page 24 ~ 25 page 649 right column 868 ~ 870 agent, stabilizer 6.light absorber, 25 ~ Page 26 Page 649 Right column Page 873 Filter ~ Page 650 Left column Dye, UV absorber 7. Stain 25 Page Right column 650 Page Left column 872 Inhibitor ~ Right column 8. Dye image Page 25 650 Page Left column 872 Stabilizer 9. Hardener 26 pages 651 left column 874 to 875 10. Binder 26 pages 651 page left columns 873 to 874 11. Plasticizer, page 27 650 pages right column 876 Lubricants 12. Coating aids , Pages 26 to 27, page 650, right column, pages 875 to 876, surfactant 13. static, page 27, page 650, right column, pages 876 to 877, inhibitors 14. matting agents, pages 878 to 879

In order to prevent deterioration of photographic performance due to formaldehyde gas, US Pat.
It is preferable to add to the light-sensitive material a compound capable of immobilizing by reacting with formaldehyde described in 4,435,503. In the light-sensitive material of the present invention, US Pat.
No. 4,788,132, JP-A-62-18539, JP-A 1-2835
It is preferable to contain the mercapto compound described in No. 51. A compound which, in the light-sensitive material of the present invention, releases a fog agent, a development accelerator, a silver halide solvent or a precursor thereof as described in JP-A 1-106052, irrespective of the amount of developed silver produced by development processing. Is preferably contained. In the light-sensitive material of the present invention, dyes dispersed by the method described in International Publication WO88 / 04794 and Japanese Patent Publication No. 1-502912 or European Patent No. 317,308A, U.S. Patent No. 4,420,555, JP-A 1-259358. It is preferable to include the dyes described in No. In the present invention, a known color coupler may be used in combination with the coupler represented by the general formula (1), and specific examples thereof include Research Disclosure No. 17643 and VII-C mentioned above.
To G, and the patents described in No. 307105, VII-C to G. Examples of yellow couplers include U.S. Pat.Nos. 3,933,501, 4,022,620, and 4,32.
No. 6,024, No. 4,401,752, No. 4,248,961, No. 58
-10739, British Patents 1,425,020, 1,476,760
U.S. Pat.Nos. 3,973,968, 4,314,023, 4,51
Those described in 1,649, European Patent No. 249,473A, etc. are preferable.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat. Nos. 4,310,619, 4,351,897 and European Patent 73,636 are preferred.
U.S. Pat. Nos. 3,061,432 and 3,725,067, Research Disclosure No. 24220 (June 1984), Japanese Patent Laid-Open No. 60-33552, Research Disclosure No. 24230.
(June 1984), JP-A-60-43659, 61-72238,
60-35730, 55-118034, 60-185951, U.S. Pat.Nos. 4,500,630, 4,540,654, 4,556,630,
Those described in International Publication WO88 / 04795 are particularly preferable.
Examples of cyan couplers include phenol-type and naphthol-type couplers, and U.S. Pat.
4,146,396, 4,228,233, 4,296,200, 2,
369,929, 2,801,171, 2,772,162, 2,89
5,826, 3,772,002, 3,758,308, 4,334,
011, 4,327,173, West German Patent Publication 3,329,729
No., European Patent Nos. 121,365A, 249,453A, U.S. Patent No.
3,446,622, 4,333,999, 4,775,616, and
4,451,559, 4,427,767, 4,690,889, 4,
254,212, 4,296,199, JP-A 61-42658 and the like are preferable. Further, JP-A-64-553 and 64-5
Pyrazoloazole couplers described in JP-A Nos. 54, 64-555 and 64-556, and imidazole couplers described in US Pat. No. 4,818,672 can also be used. Typical examples of polymerized dye-forming couplers are described in US Pat.
51,820, 4,080,211, 4,367,282, 4,40
9,320, 4,576,910, British Patent 2,102,137, European Patent 341,188A and the like.

Examples of couplers in which the color forming dye has an appropriate diffusibility include US Pat. No. 4,366,237 and British Patent 2,12.
5,570, European Patent 96,570, West German Patent (Publication) 3,
Those described in No. 234,533 are preferable. Colored couplers to correct unwanted absorption of colored dyes are
Disclosure No.17643, Item VII-G, No.30710
Item VII-G, U.S. Pat. No. 4,163,670, Japanese Patent Publication No. 57-3
Those described in 9413, U.S. Pat. Nos. 4,004,929, 4,138,258 and British Patent 1,146,368 are preferable. Also,
A coupler for correcting unnecessary absorption of a coloring dye by a fluorescent dye released upon coupling described in U.S. Pat.No. 4,774,181, and a dye precursor group capable of reacting with a developing agent described in U.S. Pat.No. 4,777,120 to form a dye. It is also preferable to use a coupler having as a leaving group. Compounds that release a photographically useful residue upon coupling are also preferably used in the present invention. DIR couplers that release development inhibitors are disclosed in the patents described in RD No. 17643, VII-F and 307105, VII-F.
57-151944, 57-154234, 60-184248, 63
-37346, 63-37350, U.S. Pat.No. 4,248,962,
Those described in 4,782,012 are preferable. RD No.11
The bleaching accelerator releasing couplers described in 449, No. 24241, JP-A-61-201247 and the like are effective for shortening the processing time having a bleaching ability, and in particular, the tabular halogenated compound described above. The effect is great when it is added to a light-sensitive material using silver particles. Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent 2,097,1
40, 2,131,188, JP-A-59-157638, 59-170
Those described in No. 840 are preferable. In addition, JP-A-60-10702
No. 9, No. 60-252340, JP-A No. 1-44940, No. 1-45687.
By the redox reaction with the oxidant of the developing agent described in No.
Compounds that release a fogging agent, a development accelerator, a silver halide solvent and the like are also preferable.

Other compounds that can be used in the light-sensitive material of the present invention include competitive couplers described in US Pat. No. 4,130,427 and US Pat. Nos. 4,283,472 and 4,33.
Multi-equivalent couplers described in Nos. 8,393 and 4,310,618,
DI described in JP-A-60-185950 and JP-A-62-24252
R redox compound releasing coupler, DIR coupler releasing coupler, DIR coupler releasing redox compound or DIR redox releasing redox compound, European Patent No.
Nos. 173,302A and 313,308A, couplers releasing a dye that recolors after separation, ligand releasing couplers described in U.S. Pat.No. 4,555,477, and leuco dyes described in JP-A-63-75747. Examples thereof include couplers and couplers releasing a fluorescent dye described in US Pat. No. 4,774,181.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods. Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027. Specific examples of the high-boiling point organic solvent having a boiling point of 175 ° C. or higher at atmospheric pressure used in the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bisyl phthalate. (2,4-di-t-amylphenyl) phthalate, bis (2,4-di-t-amylphenyl)
Isophthalate, bis (1,1-diethylpropyl) phthalate, etc., phosphoric acid or phosphonic acid esters (triphenyl phosphate, tricresyl phosphate,
2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di
-2-Ethylhexylphenylphosphonate, etc., Benzoic acid esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), Amides (N, N-diethyldodecane amide, N, N-diethyllauryl) Amides, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4-di-tert-amylphenol, etc.), aliphatic carboxylic acid esters (bis (2-ethylhexyl) sebacate, dioctylazese) Rate, glycerol tributyrate, isostearyl lactate,
Trioctyl citrate, etc., aniline derivatives (N, N-
Dibutyl-2-butoxy-5-tert-octylaniline) and hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.) and the like. The auxiliary solvent has a boiling point of about 30 ° C or higher, preferably 50 ° C.
Organic solvents with temperatures above 160 ° C can be used. Typical examples are ethyl acetate, butyl acetate, ethyl propionate,
Examples thereof include methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide and the like. The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in US Pat. No. 4,199,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.

In the color light-sensitive material of the present invention, phenethyl alcohol, JP-A-63-257747 and JP-A-62-272248,
And 1,2-benzisothiazolin-3-one described in JP-A-1-80941, n-butyl p-hydroxybenzoate,
It is preferable to add various preservatives or antifungal agents such as phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol, and 2- (4-thiazolyl) benzimidazole. The present invention can be applied to various color light-sensitive materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers.
Suitable supports that can be used in the present invention are, for example, the above-mentioned R
D. No.17643, page 28, No.18716, page 647 From right column 648
It is described on the left column of the page and on page 879 of the same No. 307105. In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is preferably 28 μm or less, more preferably 23 μm or less, further preferably 18 μm or less, particularly preferably 16 μm or less. Also, the film swelling speed T
_1/2 is preferably 30 seconds or less, more preferably 20 seconds or less.
The film thickness means a film thickness measured under a humidity condition of 25 ° C. and a relative humidity of 55% (2 days), and the film swelling rate T _1/2 can be measured according to a method known in the art. For example,
Photographic Science and Engineering (Photogr. S) by A. Green et al.
ci. & Eng.), 19 Certificates, No. 2, by using the type of Swellometer described (swelling meter) pp 124-129, can be measured, T _1/2 is 30 ° C. in a color developing solution, 3 90% of the maximum swollen film thickness reached after processing for 15 minutes is defined as the saturated film thickness, and is defined as the time required to reach 1/2 of the saturated film thickness. Membrane swelling speed T
_1/2 can be adjusted by adding a hardening agent to gelatin as a binder or changing the aging condition after coating. The swelling rate is preferably 150 to 400%. The swelling ratio can be calculated from the maximum swollen film thickness under the conditions described above according to the formula: (maximum swollen film thickness-film thickness) / film thickness. The photosensitive material of the present invention is preferably provided with a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm on the side opposite to the side having the emulsion layer. This back layer preferably contains the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, surface active agent and the like. The swelling ratio of this back layer is 150-
500% is preferred.

The color photographic light-sensitive material according to the present invention is described on pages 28 to 29 of RD No. 17643, 651 left column to right column of RD No. 18716, and pages 880 to 881 of No. 307105. Development can be carried out by a conventional method. The color developing solution used in the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. As this color developing agent,
Aminophenol compounds are also useful, but p-phenylenediamine compounds are preferably used, and typical examples thereof include 3-methyl-4-amino-N, N-diethylaniline and 3-methyl-4-amino-N, N-diethylaniline.
Methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino
-N-ethyl-β-methoxyethylaniline, 4-amino-3
-Methyl-N-methyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-ethyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-ethyl -N-
(2-hydroxypropyl) aniline, 4-amino-3-ethyl-N-ethyl-N- (3-hydroxypropyl) aniline, 4-
Amino-3-methyl-N-propyl-N- (3-hydroxypropyl) aniline, 4-amino-3-propyl-N-methyl-N- (3-
Hydroxypropyl) aniline, 4-amino-3-methyl-N
-Methyl-N- (4-hydroxybutyl) aniline, 4-amino
-3-Methyl-N-ethyl-N- (4-hydroxybutyl) aniline, 4-amino-3-methyl-N-propyl-N- (4-hydroxybutyl) aniline, 4-amino-3-ethyl-N -Ethyl -N-
(3-hydroxy-2-methylpropyl) aniline, 4-amino-3-methyl-N, N-bis (4-hydroxybutyl) aniline, 4-amino-3-methyl-N, N-bis (5-hydroxy Pentyl) aniline, 4-amino-3-methyl-N- (5-hydroxypentyl) -N- (4-hydroxybutyl) aniline, 4-amino-3-methoxy-N-ethyl-N- (4-hydroxybutyl ) Aniline, 4-amino-3-ethoxy-N, N-bis (5-hydroxypentyl) aniline, 4-amino-3-propyl-N- (4-hydroxybutyl) aniline, and their sulfates and hydrochlorides Alternatively, p-toluenesulfonate may be used.
Among these, especially 3-methyl-4-amino-N-ethyl-N
-β-hydroxyethylaniline, 4-amino-3-methyl
-N-ethyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-ethyl-N- (4-hydroxybutyl) aniline, and their hydrochlorides, p-toluenesulfonate or Sulfate is preferred. Two or more kinds of these compounds can be used in combination depending on the purpose. Color developers include alkali metal carbonates, borates or phosphates.
It is common to include a pH buffer, a chloride salt, a bromide salt, an iodide salt, a development inhibitor such as a benzimidazole, a benzothiazole or a mercapto compound, or an antifoggant. Also, if necessary, hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine, various preservatives such as catechol sulfonic acids, ethylene glycol, Organic solvents such as diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competing couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity imparting Agent, aminopolycarboxylic acid,
Aminopolyphosphonic acid, alkylphosphonic acid, various chelating agents represented by phosphonocarboxylic acid, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1- Hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and them Can be mentioned as a representative example.

When the reversal process is performed, black and white development is usually performed before color development. In this black-and-white developer, 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 are used alone. Alternatively, they can be used in combination. The pH of these color developing solution and black-and-white developing solution is generally 9-12. The replenishment amount of these developers depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per 1 m 2 of the light-sensitive material, and 500 ml or less by reducing the bromide ion concentration in the replenisher. You can also When the replenishment amount is reduced, it is preferable to prevent the liquid evaporation and air oxidation by reducing the contact area with the air in the processing tank. The contact area between the photographic processing liquid and air in the processing tank can be represented by the aperture ratio defined below. That is, aperture ratio = contact area between treatment liquid and air (cm ² ) / volume of treatment liquid (cm ² ). The above aperture ratio is preferably 0.1 or less, and 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 photographic processing liquid surface of the processing tank, a method using a movable lid described in JP-A-1-82033 is disclosed. The slit developing method described in 63-216050 can be mentioned. Reducing the aperture ratio is not limited to both the color development and black and white development steps, but also the subsequent steps such as bleaching, bleach-fixing,
It is preferably applied in all steps such as fixing, washing with water, and stabilization. Further, the amount of replenishment can be reduced by using a means for suppressing the accumulation of bromide ions in the developing solution. The color development processing time is usually set to 2 to 5 minutes, but the processing time can be further shortened by setting the temperature and high pH and using the color developing agent at a high concentration.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed at the same time as the fixing process (bleach-fixing process) or separately. Further, in order to speed up the processing, a processing method of bleach-fixing processing after bleaching processing may be used. Further, treatment with two continuous bleach-fixing baths, fixing treatment before the bleach-fixing treatment, or bleaching treatment after the bleach-fixing treatment can be optionally carried out. As the bleaching agent, compounds of polyvalent metals such as iron (III), peracids, quinones, nitro compounds and the like are used. A typical bleaching agent is an iron (III) complex salt,
For example, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid, and other aminopolycarboxylic acids, or complex salts such as citric acid, tartaric acid, and malic acid. Etc. can be used. Of these, ethylenediaminetetraacetic acid iron (III) complex salt and 1,3-diaminopropanetetraacetic acid iron (III) complex (I
II) Iron (III) complex salts of aminopolycarboxylic acids, including complex salts, are preferable from the viewpoint of rapid processing and prevention of environmental pollution. Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in both the bleaching solution and the bleach-fixing solution. The pH of the bleaching solution or bleach-fixing solution using these iron (III) aminopolycarboxylic acid complex salts is usually 4.0 to 8, but a lower pH can be used for speeding up the processing.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath.
Specific examples of useful bleach accelerators are described in the following publications: US Pat. No. 3,893,858, West German Patent 1,290,812.
No. 2,059,988, JP-A No. 53-32736, No. 53-57831
No. 53, No. 53-37418, No. 53-72623, No. 53-95630, No. 53
-95631, 53-104232, 53-124424, 53-141
623, 53-28426, Research Disclosure
No. 17129 (July 1978), etc., a compound having a mercapto group or a disulfide group; JP-A-50-140129
Thiazolidine derivatives described in JP-B-45-8506, JP-A-52-20832, JP-A-53-32735, and US Pat. No. 3,706,561.
Thiourea derivative described in Japanese Patent No. 1,127,715,
Iodide salt described in JP-A-58-16235; West German Patent No. 966,41
No. 0, No. 2,748,430, polyoxyethylene compounds; Japanese Patent Publication No. 45-8836, polyamine compounds; Others, JP-A-49-40943, 49-59644, 53-94927,
Compounds described in Nos. 54-35727, 55-26506 and 58-163940; bromide ions and the like can be used. Among them, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of a large accelerating effect, and the compounds described in U.S. Pat. No. 3,893,858, West German Patent 1,290,812 and JP-A-53-95630 are particularly preferable. Further, the compounds described in US Pat. No. 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color light-sensitive material for photographing. In addition to the above compounds, the bleaching solution and the bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach stain. Particularly preferable organic acid is a compound having an acid dissociation constant (pKa) of 2 to 5, and specifically, acetic acid, propionic acid, hydroxyacetic acid and the like are preferable. Examples of the fixing agent used in the fixing solution and the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas, and a large amount of iodide salts, but thiosulfates are generally used. In particular, ammonium thiosulfate can be used most widely. Further, the combined use of thiosulfate and thiocyanate, thioether compounds, thiourea and the like is also preferable. As a preservative for the fixing solution and the bleach-fixing solution, sulfites, bisulfites, carbonyl bisulfite adducts or sulfinic acid compounds described in EP 294,769A are preferable. Further, various aminopolycarboxylic acids and organic phosphonic acids are preferably added to the fixing solution and the bleach-fixing solution for the purpose of stabilizing the solution. In the present invention, a fixing solution or a bleach-fixing solution is used for adjusting the pH.
Compounds having a pKa of 6.0 to 9.0, preferably imidazole, 1-methylimidazole, 1-ethylimidazole, 2-
It is preferable to add 0.1 to 10 mol / liter of an imidazole such as methylimidazole.

The total time of the desilvering process is preferably short as long as no desilvering failure occurs. Preferred time is 1 to 3 minutes
Minutes, more preferably 1 minute to 2 minutes. The treatment temperature is 25 ° C to 50 ° C, preferably 35 ° C to 45 ° C. In the preferable temperature range, the desilvering rate is improved and the stain generation after the processing is effectively prevented. In the desilvering process, it is preferable that the stirring is strengthened as much as possible.
As a specific method for strengthening stirring, a method of causing a jet of a processing solution to collide with the emulsion surface of a light-sensitive material described in JP-A-62-183460, or stirring using a rotating means of JP-A-62-183461 is used. Method to increase the effect, further moving the photosensitive material while the emulsion surface is in contact with the wiper blade provided in the solution to further improve the stirring effect by making the emulsion surface turbulent, circulation of the entire processing solution There is a method of increasing the flow rate. Such a stirring improving means is effective for any of the bleaching solution, the bleach-fixing solution and the fixing solution. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film and, as a result, increases the desilvering rate. Further, the above-mentioned stirring improving means is more effective when a bleaching accelerator is used, and it is possible to remarkably increase the accelerating effect and eliminate the fixing inhibiting effect of the bleaching accelerator. The automatic processor used for the light-sensitive material of the present invention is disclosed in JP-A-60-191257.
No. 60-191258 and No. 60-191259. JP-A-60 mentioned above
As described in No. 191257, such a transportation means can significantly reduce the carry-in of the treatment liquid from the front bath to the rear bath, and is highly effective in preventing the performance deterioration of the treatment liquid. Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.

The silver halide color photographic light-sensitive material of the present invention is generally washed with water and / or stabilized after the desilvering treatment. The amount of rinsing water in the rinsing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), application, and further, the rinsing water temperature, the number of rinsing tanks (number of stages), replenishment system such as countercurrent, forward flow, and other various conditions. It can be set in a wide range.
Of these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent system is described in the Journal of the Society of Motion Picture and
Television Engineers Volume 64, pp. 248-253 (May 1955)
Monthly issue) can be obtained by the method described in. According to the multi-stage counter-current method described in the above literature, the amount of washing water can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate, and the suspended matter produced adheres to the photosensitive material, etc. Problems arise. In the processing of the color light-sensitive material of the present invention, such a problem is solved by a method described in JP
The method of reducing calcium ion and magnesium ion described in No. 62-288838 can be used very effectively. Also, isothiazolone compounds and siabendazoles described in JP-A-57-8542, chlorine-based bactericides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., Hiroshi Horiguchi "Chemistry of Antibacterial and Antifungal Agents" (1986) Sankyo Publishing Co., Ltd., Hygiene Engineering Society, "Microbial sterilization, sterilization, antifungal technology"
(1982) The sterilizing agents described in “Encyclopedia of Antibacterial and Antifungal Agents” (1986) edited by Japan Society of Industrial Technology and Antifungal Society can also be used. The pH of the washing water in the processing of the light-sensitive material of the present invention is 4 to
9, and preferably 5-8. The washing water temperature and washing time can be variously set depending on the characteristics of the light-sensitive material, application, etc., but generally 15 to 45 ° C for 20 seconds to 10 minutes, preferably 25 to 40 ° C.
A range of 30 seconds to 5 minutes is selected. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such a stabilizing process, the method disclosed in
All known methods described in Nos. 57-8543, 58-14834, and 60-220345 can be used. Further, there is a case where further stabilization treatment is carried out after the water washing treatment, and an example thereof is a stabilizing bath containing a dye stabilizer and a surfactant, which is used as a final bath of a color light-sensitive material for photographing. be able to. Examples of dye stabilizers include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts. Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow solution accompanying the above washing with water and / or supplementation of the stabilizing solution can be reused in other steps such as the desilvering step. In the processing using an automatic processor, etc., when the above processing solutions are concentrated by evaporation,
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 accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents. For example, indaniline-based compounds described in U.S. Pat. Metal salt complex described in JP-A-53-13562
The urethane compounds described in No. 8 can be mentioned. The silver halide color light-sensitive material of the present invention, if necessary,
Various 1-phenyl-3-pyrazolidones may be incorporated for the purpose of accelerating color development. Typical compounds are
56-64339, 57-144547 and 58-115438. Various treatment liquids in the present invention are 10 ℃ ~ 50
Used at ° C. Normally, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature accelerates the processing to shorten the processing time, and a lower temperature lowers the image quality to improve the stability of the processing liquid. be able to.

The silver halide color photographic light-sensitive material of the present invention is more likely to exhibit the effect when applied to the lens-fitted film unit described in JP-B-2-32615, JP-B-3-39784 and the like. It is valid.

[0049]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited thereto. Example 1 On a subbed cellulose triacetate film support,
Each layer having the composition shown below was applied in multiple layers to prepare Sample 101, which is a multilayer color light-sensitive material. (Photosensitive layer composition) The main materials used for each layer are classified as follows; ExC: Cyan coupler UV: UV absorber ExM: Magenta coupler HBS: High boiling point organic solvent ExY: Yellow coupler H: Gelatin Curing agent ExS: Sensitizing dye The numbers corresponding to the respective components indicate the coating amount expressed in g / m ² , and for silver halide, the coating amount in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown in mol unit per mol of silver halide in the same layer.

(Sample 101) First layer (antihalation layer) Black colloidal silver Silver 0.18 Gelatin 1.40 ExM-1 0.18 ExF-1 2.0 × 10 ^-3 HBS-1 0.20

[0051]

Third Layer (Low Sensitivity Red Sensitive Emulsion Layer) Emulsion A Silver 0.25 Emulsion B Silver 0.25 ExS-1 6.9 × 10 ^-5 ExS-2 1.8 × 10 ^-5 ExS-3 3.1 × 10 ^-4 ExC-1 0.17 ExC-3 0.030 ExC-4 0.10 ExC-5 0.020 ExC-7 0.0050 ExC-8 0.010 Cpd-2 0.025 HBS-1 0.10 Gelatin 0.87

Fourth Layer (Medium Sensitivity Red Sensitive Emulsion Layer) Emulsion D Silver 0.70 ExS-1 3.5 × 10 ^-4 ExS-2 1.6 × 10 ^-5 ExS-3 5.1 × 10 ^-4 ExC-1 0.13 ExC-2 0.060 ExC-3 0.0070 ExC-4 0.090 ExC-5 0.025 ExC-7 0.0010 ExC-8 0.0070 Cpd-2 0.023 HBS-1 0.10 Gelatin 0.75

Fifth layer (high-sensitivity red-sensitive emulsion layer) Emulsion E Silver 1.40 ExS-1 2.4 × 10 ^-4 ExS-2 1.0 × 10 ^-4 ExS-3 3.4 × 10 ^-4 ExC-1 0.12 ExC-3 0.045 ExC-6 0.020 ExC-8 0.025 Cpd-2 0.050 HBS-1 0.22 HBS-2 0.10 Gelatin 1.20

6th layer (intermediate layer) Cpd-1 0.10 HBS-1 0.50 gelatin 1.10

Seventh Layer (Low Sensitivity Green Sensitive Emulsion Layer) Emulsion C Silver 0.35 ExS-4 3.0 × 10 ^-5 ExS-5 2.1 × 10 ^-4 ExS-6 8.0 × 10 ^-4 ExM-1 0.010 ExM-2 0.33 ExM-3 0.086 ExY-1 0.023 HBS-1 0.30 HBS-3 0.010 Gelatin 0.73

Eighth Layer (Medium Sensitivity Green Sensitive Emulsion Layer) Emulsion D Silver 0.80 ExS-4 3.2 × 10 ^-5 ExS-5 2.2 × 10 ^-4 ExS-6 8.4 × 10 ^-4 ExM-2 0.13 ExM-3 0.030 ExY-1 0.027 HBS-1 0.16 HBS-3 8.0 × 10 ^-3 Gelatin 0.90

Ninth layer (high sensitivity green sensitive emulsion layer) Emulsion E Silver 1.25 ExS-4 3.7 × 10 ^-5 ExS-5 8.1 × 10 ^-5 ExS-6 3.2 × 10 ^-4 ExC-1 0.010 ExM-1 0.030 ExM-4 0.040 ExM-5 0.019 Cpd-3 0.040 HBS-1 0.25 HBS-2 0.10 Gelatin 1.44

10th layer (yellow filter layer) Yellow colloidal silver Silver 0.030 Cpd-1 0.16 HBS-1 0.60 Gelatin 0.60

Eleventh Layer (Low Sensitivity Blue Sensitive Emulsion Layer) Emulsion C Silver 0.18 ExS-7 8.6 × 10 ^-4 ExY-1 0.050 ExY-2 0.072 HBS-1 0.28 Gelatin 1.10

Twelfth layer (medium-speed blue-sensitive emulsion layer) Emulsion D Silver 0.40 ExS-7 7.4 × 10 ^-4 ExC-7 7.0 × 10 ^-3 ExY-2 0.150 HBS-1 0.050 Gelatin 0.78

The thirteenth layer (high-sensitivity blue-sensitive emulsion layer) Emulsion F Silver 1.00 ExS-7 4.0 × 10 ^-4 ExY-2 0.20 HBS-1 0.070 Gelatin 0.86

14th layer (first protective layer) Emulsion G Silver 0.20 UV-4 0.11 UV-5 0.17 HBS-1 5.0 × 10 ^-2 Gelatin 1.00

Fifteenth layer (second protective layer) H-1 0.40 B-1 (diameter 1.7 μm) 5.0 × 10 ^-2 B-2 (diameter 1.7 μm) 0.10 B-3 0.10 S-1 0.20 Gelatin 1.20

Further, in order to improve the storability, processability, pressure resistance, antifungal / antibacterial property, antistatic property and coating property of each layer, W-1 to W-3, B-4 to B- may be used. 6, F
-1 to F-17 and iron salt, lead salt, gold salt, platinum salt,
It contains iridium salt and rhodium salt.

[0066]

[Table 1]

In Table 1, (1) Emulsions A to F were prepared according to the examples of JP-A-2-91938.
It was reduction sensitized during grain preparation using thiourea dioxide and thiosulfonic acid. (2) Emulsions A to F were prepared according to the examples of JP-A-3-237450.
Gold sensitization, sulfur sensitization and selenium sensitization are performed in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate. (3) For the preparation of tabular grains, low molecular weight gelatin is used according to the examples of JP-A 1-158426. (4) Dislocation lines as described in JP-A-3-237450 have been observed in tabular grains and normal crystal grains having a grain structure using a high voltage electron microscope.

[0068]

[Chemical 14]

[0069]

[Chemical 15]

[0070]

[Chemical 16]

[0071]

[Chemical 17]

[0072]

[Chemical 18]

[0073]

[Chemical 19]

[0074]

[Chemical 20]

[0075]

[Chemical 21]

[0076]

[Chemical formula 22]

[0077]

[Chemical formula 23]

[0078]

[Chemical formula 24]

[0079]

[Chemical 25]

[0080]

[Chemical formula 26]

[0081]

[Chemical 27]

[0082]

[Chemical 28]

[0083]

[Chemical 29]

Next, the eleventh to thirteenth layers are added to the sample 101.
The coupler ExY-2 used in the layers is as shown in Table 2,
Application sample 1 substituting the comparative compound and the compound of the present invention
02-110 were produced. Obtained Samples 101-110
Was subjected to wedge exposure with white light and processed by the method described below using an automatic developing machine (until the cumulative replenishment amount of the developer became 3 times the tank volume).

(Treatment Method) Process Treatment time Treatment temperature Replenishment amount Tank capacity Color development 3 minutes 15 seconds 38 ° C 22 ml 20 liters Bleach 3 minutes 00 seconds 38 ° C 25 ml 40 liters Water wash 30 seconds 24 ° C 1200 ml 20 liters Settling 3 minutes 00 seconds 38 ° C 25 ml 30 liters Washing with water (1) 30 seconds 24 ° C From (2) to (1) 10 liters countercurrent piping system Washing with water (2) 30 seconds 24 ° C 1200 ml 10 liters Stability 30 Second 38 ℃ 25 ml 10 liter Dry 4 minutes 20 seconds 55 ℃ Replenishment amount is 35 mm width 1 m per length

Next, the composition of the treatment liquid will be described. (Color developer) Tank solution (g) Replenisher solution (g) Diethylenetriaminepentaacetic acid 1.0 1.1 1-Hydroxyethylidene-1,1-diphosphonic acid 3.0 3.2 Sodium sulfite 4.0 4.4 Potassium carbonate 30.0 37.0 Potassium bromide 1.4 0.3 Potassium iodide 1.5 mg-hydroxylamine sulfate 2.4 2.8 4- [N-ethyl-N-β-hydroxyethylamino] -2-methylaniline sulfate 4.5 6.2 Add water 1.0 liter 1.0 liter pH 10.05 10.15

(Bleaching solution) Tank solution (g) Replenishing solution (g) Ethylenediaminetetraacetic acid sodium ferric acid trihydrate 100.0 120.0 Ethylenediaminetetraacetic acid disodium salt 10.0 11.0 3-Mercapto-1,2,4-triazole 0.08 0.09 Ammonium bromide 140.0 160.0 Ammonium nitrate 30.0 35.0 Ammonia water (27%) 6.5 ml 4.0 ml Add water 1.0 liter 1.0 liter pH 6.0 5.7

(Fixing liquid) Tank liquid (g) Replenishing liquid (g) Ethylenediaminetetraacetic acid disodium salt 0.5 0.7 Ammonium sulfite 20.0 22.0 Ammonium thiosulfate aqueous solution (700 g / liter) 290.0 ml 320.0 ml 1.0 liter 1.0 liter pH by adding water 6.7 7.0

(Stabilizer) Common tank / replenisher (g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization: 10) 0.2 Ethylenediaminetetraacetic acid disodium salt 0.05 1,2 , 4-Triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 Water was added to 1.0 liter pH 8.5

The yellow density of each sample after the treatment was measured, and the yellow density of Sample 101 was fog +1.0.
The yellow color density (value obtained by subtracting the fog density from the yellow density) of each sample at the exposure amount is calculated as the color forming property of the blue sensitive layer. Table 2 shows the relative values when the value of Sample 101 is 100. Next, each sample was stored under the conditions of 60 ° C. and 70% RH for 4 weeks, the yellow density after storage at the point where the initial density of yellow was 2.0 was determined, and the density difference between the two was regarded as the fading property. .. Table 2 shows the relative value with the fading property of Sample 101 being 100.

[0091]

[Table 2]

From the results shown in Table 2, it was found that the compound of the present invention has high color developability and excellent color image storability under high temperature and high humidity conditions.

Example 2 As compared with the sample 101 used in Example 1, as shown in Table 3, the cyan coupler ExC-3 in the red-sensitive layer (third to fifth layers) was used.
Was changed to the compound of the present invention to prepare samples 201 to 205. The samples 101 to 110 used in Example 1 and the obtained samples 201 to 205 were subjected to wedge exposure with white light, and the following method was used using an automatic processor (the cumulative replenishment amount of the developer was Processed to 3 times the tank capacity). The treatment process and the treatment liquid composition are shown below.

(Processing step) Processing time Processing temperature Replenishment amount ^* Tank capacity Color development 3 minutes 5 seconds 38.0 ℃ 600 ml 17 liter Bleach 50 seconds 38.0 ℃ 140 ml 5 liter Bleach fixing 50 seconds 38.0 ℃ -5 liter Fixed 50 seconds 38.0 ℃ 420 ml 5 liter water wash 30 seconds 38.0 ℃ 980 ml 3.5 liter stable (1) 20 seconds 38.0 ℃ ― 3 liter stable (2) 20 seconds 38.0 ℃ 560 ml 3 liter dry 1 minute 30 seconds 60 ℃ * Replenishment amount per 1 m ² of light-sensitive material

The stabilizing solution was a countercurrent system from (2) to (1), and the overflow solution of washing water was all introduced into the fixing bath. To replenish the bleach-fixing bath, a cutout is provided at the top of the bleaching tank of the automatic processor as well as at the top of the fixing tank so that all of the overflow solution generated by supplying the replenishing solution to the bleaching tank and the fixing tank is added to the bleach-fixing bath. I was allowed to flow in. The amount of developing solution brought into the bleaching process, the amount of bleaching solution brought into the bleach-fixing step, the amount of bleach-fixing solution brought into the fixing step and the amount of fixing solution brought into the rinsing step are each 1 m ² of the photographic material. 65 ml, 50 ml, 5
It was 0 ml and 50 ml. The crossover time is 6 seconds in all cases, and this time is included in the processing time of the previous step. The composition of the treatment liquid is shown below.

(Color developer) Tank liquid (g) Replenisher (g) Diethylenetriaminepentaacetic acid 2.0 2.0 1-Hydroxyethylidene-1,1-diphosphonic acid 3.3 3.3 Sodium sulfite 3.9 5.1 Potassium carbonate 37.5 39.0 Potassium bromide 1.4 0.4 Iodine Potassium iodide 1.3 mg-Hydroxylamine sulfate 2.4 3.3 2-Methyl-4- [N-ethyl-N-β-hydroxyethylamino] aniline sulfate 4.5 6.0 Water was added to 1.0 liter 1.0 liter pH 10.05 10.15

(Bleaching solution) Tank solution (g) Replenishing solution (g) 1,3-Diaminopropanetetraacetic acid ferric ammonium monohydrate 130 195 Ammonium bromide 70 105 Ammonium nitrate 14 21 Hydroxyacetic acid 50 75 Acetic acid 40 60 Water 1.0 liter 1.0 liter pH [prepared with ammonia water] 4.4 4.4

(Bleaching Fixing Tank Solution) A 15:85 (volume ratio) mixture of the above bleaching tank solution and the following fixing tank solution. (PH 7.0)

(Fixing liquid) Tank liquid (g) Replenishing liquid (g) Ammonium sulfite 19 57 Ammonium thiosulfate aqueous solution (700 g / liter) 280 ml 840 ml imidazole 15 45 Ethylenediaminetetraacetic acid 15 45 Water 1.0 liter 1.0 liter pH [Prepared with aqueous ammonia and acetic acid] 7.4 7.45

(Washing Water) Tap water was used as an H-type strongly acidic cation exchange resin (Amberlite IR-produced by Rohm and Haas).
120B) and OH-type strongly basic anion exchange resin (Amberlite IR-400) were passed through a mixed bed column to adjust the concentration of calcium and magnesium ions to 3 mg.
/ Liter or less, followed by sodium diisocyanurate dichloride 20 mg / liter and sodium sulfate 150
mg liter was added. The pH of this liquid is 6.5 to 7.5.
Was in the range.

(Stabilizing Solution) Tank Solution and Replenishing Solution Common Unit (g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization: 10) 0.2 Ethylenediaminetetraacetic acid disodium salt 0.05 1, 2,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 Water was added to 1.0 liter pH 8.5

The treated sample thus obtained is designated as Group A. These processing steps are steps in which the oxidizing power of the oxidant in the bleaching solution is increased and accelerated as compared with the processing steps performed in Example 1. An increase in the minimum color density of the post-treatment sample is seen when processed with the accelerated processing steps. This is because the color developing solution absorbed in the light-sensitive material develops color in the bleaching solution regardless of the amount of exposure, and is called bleaching fog, which is extremely undesirable. Samples 101-110 and Samples 201-205 were processed in the processing steps (not accelerated) performed in Example 1 to evaluate this increase in minimum color density in rapid processing. The obtained sample is referred to as group B. The value obtained by subtracting the minimum color density (DminB) of yellow in the group B from the minimum color density (DminA) of yellow in the group A was calculated to estimate the suitability for rapid processing. It can be said that the smaller the value, the less the bleaching fog and the suitability for rapid processing. The results are shown in Table 3.

[0103]

[Table 3]

From Table 3, it was found that the use of the compounds of the present invention resulted in a small increase in the minimum color density in rapid processing and was excellent in rapid processing suitability.

Example 3 With respect to the sample 101 used in Example 1, the first to thirteenth samples were used.
Samples 301 to 306 were prepared by substituting the compound of the present invention for the coupler ExY-1 used in the layer as shown in Table 4. However, the amounts of the compounds of the present invention of Samples 301 to 306 were adjusted so as to match the gradation of the blue sensitive layer of Sample 101.

[0106]

[Table 4]

Obtained Samples 301 to 306 and Sample 10
1 was exposed and developed as in Example 1. When the color fading property of the sample after the treatment was evaluated by the same method as in Example 1, it was found that Samples 301 to 306 using the compound of the present invention were superior to Sample 101 in fastness under wet heat conditions. It was

[0108]

EFFECTS OF THE INVENTION By using a coupler having high reactivity with an oxidized product of a developing agent according to the present invention, a color having high color forming property, excellent suitability for rapid processing, and excellent storability of color image under high temperature and high humidity conditions. An image was obtained.

Claims (3)

[Claims] 1. A silver halide color photographic light-sensitive material characterized in that at least one hydrophilic colloid layer provided on a support contains a coupler represented by the following general formula (1). Formula _{(1) A- (X 1)} i -N (R 1) -X 2 -N (R 2) - (X 3) j
-R ₃ wherein, A represents a coupler residue capable of coupling reaction with oxidized developer, X _1, X ₂ and X ₃ each represent a CO or SO _2, R ₁ and R ₂ Each represents a hydrogen atom, a metal atom, ammonium, an alkyl group or an aryl group, at least one of which represents a hydrogen atom, a metal atom or an ammonium, R ₃ represents an alkyl group or an aryl group, and i and j each represent 0 or 1 And at least one of them represents 1. However, i = 1,
Excluded when X ₁ = SO ₂ , X ₂ = CO, and j = 0. 2. The silver halide color photographic light-sensitive material according to claim 1, wherein in the compound represented by the general formula (1), i is 1 and X ₁ is CO. 3. The silver halide color photographic light-sensitive material according to claim 1, wherein in the compound represented by the general formula (1), i is 0 and j is 1.