JPH0572684A - Silver halide color photographic sensitive material and method for processing same - Google Patents

Abstract

PURPOSE:To enhance color reproduction performance, sharpness, rapid processing aptitude, and storage stability of a color image by incorporating a pyrazoloazole type compound for releasing a development inhibitor in at least one layer. CONSTITUTION:This silver halide color photographic sensitive material has each at least one of red-sensitive, green-sensitive, and blue-sensitive silver halide emulsion layers formed on a support and the total silver amount of 1.0-4.9g/m<2>, and at least cane layer contains the compound represented by formula I in which R is H or a substituent; Z is a nonmetallic atomic group necessary to form a 5-membered optionally substituted azole ring having 2-4 N atoms: and X is an atomic group to be allowed to release the development inhibitor or its precursor by coupling with the oxidation product of a developing agent or to release a compound to be allowed to release the develop-ment inhibitor or its precursor after being released by the first coupling and the second coupling with the oxidation product car to do so further after the third coupling.

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, and more specifically, a halogen which is excellent in sharpness and rapid processing property, color reproducibility and color image storability after processing. The present invention relates to a silver halide color photographic light-sensitive material.

[0002]

2. Description of the Related Art Silver halide color photographic light-sensitive materials, particularly color photographic materials for photography, have good color reproducibility and sharpness, excellent desilvering property, and can be shortened in processing time. There is a demand for a light-sensitive material having excellent image storability afterward. Development inhibitor releasing compound (DIR compound) for the purpose of improving photographic performance such as sharpness and color reproducibility
Is used. The dye formed from these compounds preferably has an excellent hue with less unnecessary absorption in color reproduction, and a pyrazoloazole-type compound is particularly preferable as a magenta coloring compound that is chemically stable and improves color reproducibility. Kai 61-28947, 62-24252,
It is disclosed in Japanese Patent Application Laid-Open No. 3-142447. However, the use of these compounds alone has not been sufficiently satisfactory in terms of sharpness and suitability for rapid processing.

On the other hand, photographic materials having a low silver content are disclosed in JP-A-62-89963, 63-226651 and 63.
-228151, JP-A-1-96652, 2-1.
9842, 2-20859 and 2-27349.
However, since these patents do not use the compound of the present invention, these patents have drawbacks such as poor color reproducibility and storability of sensitive material and poor storability of color image after processing. Was there. Further, a light-sensitive material having a thin dry film is disclosed in JP-A-61-1.
73248, 62-166334 and 62-
No. 166342, etc., the compounds of the present invention are not used in these patents, or a large amount of DIR compound must be used due to the large silver content, color image fastness, rapid processing suitability, The storage stability of the light-sensitive material was not sufficient, and the cost was high, which was a problem.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to firstly provide a light-sensitive material having excellent color reproducibility and sharpness, and secondly to provide a light-sensitive material having excellent magenta image storability. The third is to provide a light-sensitive material having sufficient color developability even in a short-time development processing, and fourth, a light-sensitive material having a small amount of residual silver even in a short-time desilvering processing and suitable for rapid processing. To provide.

[0005]

The above problems have been solved by the following silver halide color photographic light-sensitive material. In a silver halide color photographic light-sensitive material having at least one blue-sensitive silver halide emulsion layer, green-sensitive silver halide emulsion layer and red-sensitive silver halide emulsion layer on a support, the total content of silver contained in the light-sensitive material is contained. Amount 1.0g / m ² or more 4.9
A silver halide color photographic light-sensitive material having a g / m ² or less and containing a compound represented by the following general formula (I) in at least one layer. General formula (I)

[0006]

[Chemical 4]

In the formula, R represents a hydrogen atom or a substituent. Z represents a non-metal atom group necessary for forming a 5-membered azole ring containing 2 to 4 nitrogen atoms, and the azole ring may have a substituent. X is a group that is released by a coupling reaction with an oxidized product of a developing agent to become a development inhibitor or a precursor thereof, or, after the group is removed, reacts with another molecule of an oxidized product of a developing agent to develop a development inhibitor or a precursor thereof. Represents the body group.

The compound of the general formula (I) used in the present invention is described in detail below. Among the coupler skeletons represented by the general formula (I), a preferable skeleton is 1H-imidazo [1,2-b] pyrazole, 1H-pyrazolo [1,5-
b] [1,2,4] triazole, 1H-pyrazolo [5,1-c] [1,2,4] triazole and 1H
-Pyrazolo [1,5-d] tetrazole having the formulas [P-1], [P-2], [P-3] and [P-
4].

[0009]

[Chemical 5]

The substituents R ₁₁ , R ₁₂ , R in these formulas
₁₃ and X will be described in detail. R ₁₁ is a hydrogen atom,
Halogen atom, alkyl group, aryl group, heterocyclic group,
Cyano group, hydroxyl group, nitro group, carboxyl group, amino group, alkoxy group, aryloxy group, acylamino group, alkylamino group, anilino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino Group, sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonylamino group, imide group, heterocyclic thio group , A sulfinyl group, a phosphonyl group,
It represents an aryloxycarbonyl group, an acyl group or an azolyl group, and R ₁₁ may be a divalent group to form a bis form.

More specifically, R ₁₁ is each a hydrogen atom, a halogen atom (eg, chlorine atom, bromine atom), an alkyl group (eg, a straight chain or branched chain alkyl group having 1 to 32 carbon atoms, an aralkyl group, an alkenyl). Group, alkynyl group,
A cycloalkyl group or a cycloalkenyl group, more specifically,
For example, methyl, ethyl, propyl, isopropyl, t-
Butyl, tridecyl, 2-methanesulfonylethyl, 3
-(3-Pentadecylphenoxy) propyl, 3- {4
-{2- [4- (4-hydroxyphenylsulfonyl)
Phenoxy] dodecanamide} phenyl} propyl, 2
-Ethoxytridecyl, trifluoromethyl, cyclopentyl, 3- (2,4-di-t-amylphenoxy) propyl),

Aryl groups (eg phenyl, 4-t-
Butylphenyl, 2,4-di-t-amylphenyl, 4
-Tetradecanamidophenyl), heterocyclic groups (e.g. 2-furyl, 2-thienyl, 2-pyrimidinyl, 2
-Benzothiazolyl), cyano group, hydroxyl group, nitro group, carboxyl group, amino group, alkoxy group (for example, methoxy, ethoxy, 2-methoxyethoxy, 2
-Dodecylethoxy, 2-methanesulfonylethoxy),

Aryloxy groups (eg phenoxy,
2-methylphenoxy, 4-t-butylphenoxy, 3
-Nitrophenoxy, 3-t-butyloxycarbamoylphenoxy, 3-methoxycarbamoylphenoxy), an acylamino group (for example, acetamide, benzamide, tetradecanamide, 2- (2,4-di-t-).
Amylphenoxy) butanamide, 4- (3-t-butyl-4-hydroxyphenoxy) butanamide, 2-
{4- (4-hydroxyphenylsulfonyl) phenoxy} dodecanamide),

Alkylamino groups (eg methylamino, butylamino, dodecylamino, diethylamino,
Methylbutylamino), anilino groups (eg, phenylamino, 2-chloroanilino, 2-chloro-5-tetradecaneaminoanilino, 2-chloro-5-dodecyloxycarbonylanilino, N-acetylanilino, 2-chloro- 5- {α- (3-t-butyl-4-hydroxyphenoxy) dodecanamide} anilino),

A ureido group (eg phenylureido,
Methylureido, N, N-dibutylureido), sulfamoylamino group (for example, N, N-dipropylsulfamoylamino, N-methyl-N-decylsulfamoylamino), alkylthio group (for example, methylthio, octylthio) , Tetradecylthio, 2-phenoxyethylthio, 3-phenoxypropylthio, 3- (4-t-butylphenoxy) propylthio), arylthio groups (eg, phenylthio, 2-butoxy-5-t-octylphenylthio, 3 -Pentadecylphenylthio, 2-carboxyphenylthio, 4-tetradecanamidophenylthio),

Alkoxycarbonylamino groups (eg
Methoxycarbonylamino, tetradecyloxycarbonylamino), sulfonamide group (for example, methanesulfonamide, hexadecanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, octadecanesulfonamide, 2-methyloxy-5-t-butylbenzene) Sulfonamide),

A carbamoyl group (for example, N-ethylcarbamoyl, N, N-dibutylcarbamoyl, N- (2-
Dodecyloxyethyl) carbamoyl, N-methyl-N
-Dodecylcarbamoyl, N- {3- (2,4-di-t
-Amylphenoxy) propyl} carbamoyl), a sulfamoyl group (for example, N-ethylsulfamoyl,
N, N-dipropylsulfamoyl, N- (2-dodecyloxyethyl) sulfamoyl, N-ethyl-N-dodecylsulfamoyl, N, N-diethylsulfamoyl),

A sulfonyl group (eg, methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl), an alkoxycarbonyl group (eg, methoxycarbonyl, butyloxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl),
A heterocyclic oxy group (for example, 1-phenyltetrazole-5-oxy, 2-tetrahydropyranyloxy),

Azo groups (eg phenylazo, 4-methoxyphenylazo, 4-pivaloylaminophenylazo, 2-hydroxy-4-propanoylphenylazo), acyloxy groups (eg acetoxy), carbamoyloxy groups (eg , N-methylcarbamoyloxy, N-phenylcarbamoyloxy), silyloxy group (eg, trimethylsilyloxy, dibutylmethylsilyloxy), aryloxycarbonylamino group (eg, phenoxycarbonylamino),

Imido groups (eg N-succinimide,
N-phthalimide, 3-octadecenylsuccinimide), heterocyclic thio group (for example, 2-benzothiazolylthio, 2,4-di-phenoxy-1,3,5-triazole-6-thio, 2-pyridylthio) ), A sulfinyl group (for example, dodecanesulfinyl, 3-pentadecylphenylsulfinyl, 3-phenoxypropylsulfinyl), a phosphonyl group (for example, phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), an aryloxycarbonyl group (for example, Phenoxycarbonyl),

It represents an acyl group (eg acetyl, 3-phenylpropanoyl, benzoyl, 4-dodecyloxybenzoyl) and an azolyl group (eg imidazolyl, pyrazolyl, 3-chloro-pyrazol-1-yl, triazolyl). Among these substituents, the group capable of further having a substituent may further have an organic substituent or a halogen atom linked by a carbon atom, an oxygen atom, a nitrogen atom or a sulfur atom.

Of these substituents, preferred R ₁₁ is hydrogen atom, alkyl group, aryl group, alkoxy group, aryloxy group, alkylthio group, ureido group,
A urethane group and an acylamino group can be mentioned.

R ₁₂ is a group similar to the substituents exemplified for R ₁₁ , and is preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, a sulfinyl group, an acyl group. A group and a cyano group.

R ₁₃ is a group having the same meaning as the substituent exemplified for R ₁₁ , and preferably a hydrogen atom, an alkyl group,
An aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkoxycarbonyl group, a carbamoyl group and an acyl group, more preferably an alkyl group, an aryl group, a heterocyclic group, an alkylthio group and an arylthio group. It is a base.

X is preferably a group represented by the following general formula (X-1). Formula (X-1) - {( L 1) a - (B) m} p - (L 2) in _n -DI formula, L ₁ is a bond to the left of L ₁ in formula (X-1) Represents a group in which the bond on the right side (bond with (B) _m ) is cleaved after the cleavage, and B reacts with the oxidized product of the developing agent to give a compound of the general formula (X-
1) represents a group in which the bond on the right side of B is cleaved,
L ₂ is Formula right side of the join after binding of the left L ₂ is cleavage of (X-1) (binding with DI) represents a group which cleaves,
DI represents a development inhibitor, a, m and n each represent 0 or 1, and p represents an integer of 0 to 2. Here, when p is plural, p (L ₁ ) _a- (B) _m represent the same or different.

The reaction process in which the compound represented by the general formula (X-1) releases DI during development is represented by, for example, the following reaction formula. An example when p = 1 is shown.

[0027]

[Chemical 6]

In the formula, L ₁ , a, B, m, L ₂ , n and DI have the same meanings as described in the general formula (X-1), and QDI ⁺ means an oxidized product of a developing agent. A represents a pyrazoloazole magenta coupler residue described above, that is, a moiety other than X in the general formula (I).

In the general formula (X-1), L ₁ and L ₂
The linking group represented by is, for example, US Pat. No. 4,146,39.
6, a group utilizing the cleavage reaction of hemiacetal described in No. 4,652,516 or No. 4698297, a timing group causing the cleavage reaction utilizing an intramolecular nucleophilic reaction described in US Pat. No. 4,248,962, US Pat. No. 4,409,323 or US Pat. No. 4,421,845, a timing group for causing a cleavage reaction utilizing an electron transfer reaction, and a hydrolysis reaction of an imino ketal described in US Pat. No. 4,546,073 for causing a cleavage reaction. Or a group capable of causing a cleavage reaction by utilizing a hydrolysis reaction of an ester described in West German Laid-Open Patent No. 2626317. L ₁ and L ₂ are each a hetero atom contained therein, preferably an oxygen atom, a sulfur atom or a nitrogen atom, and A or A- (L ₁ ) _a
-(B) _Combines with _m, etc.

When the groups represented by L ₁ and L ₂ are used, preferable groups include the following. (1) Group utilizing cleavage reaction of hemiacetal For example, US Pat. No. 4,146,396, JP-A-60-
249148 and 60-249149, which are groups represented by the following general formula. Here, the * mark represents a bond on the left side of L ₁ or L ₂ of the group represented by the general formula (X-1), and the ** mark represents L ₁ or L of the group represented by the general formula (X-1). _Represents the right-hand bond of ₂ . General formula (T-1)

[0031]

[Chemical 7]

In the formula, W is an oxygen atom, a sulfur atom or-
Represents an NR ₆₇ -group, R ₆₅ and R ₆₆ represent a hydrogen atom or a substituent, R ₆₇ represents a substituent, and t represents 1 or 2. When t is 2, two -W-CR ₆₅ (R ₆₆ )
− Represents the same or different. When R ₆₅ and R ₆₆ represent a substituent and typical examples of R ₆₇ are R ₆₉ group, R ₆₉ CO— group, R ₆₉ SO ₂ — group and R ₆₉ NR _{70, respectively.}
CO- group or R ₆₉ NR ₇₀ SO ₂ -, etc. group. Here, R ₆₉ represents an aliphatic group, an aromatic group or a heterocyclic group, and R ₇₀ represents an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom. Each of R ₆₅ , R ₆₆ and R ₆₇ represents a divalent group and is also included when they are linked to each other to form a cyclic structure. The following groups may be mentioned as specific examples of the group represented by formula (T-1).

[0033]

[Chemical 8]

(2) Group that causes a cleavage reaction utilizing an intramolecular nucleophilic substitution reaction. For example, a timing group described in US Pat. No. 4,248,962 can be mentioned. It can be represented by the following general formula. General formula (T-2) * -Nu-Link-E-**

In the formula, * and ** are general formulas (T-
It has the same meaning as described in 1), Nu represents a nucleophilic group, an oxygen atom or a sulfur atom is an example of a nucleophilic species, E represents an electrophilic group, and is subjected to a nucleophilic attack from Nu * Link is a group capable of cleaving the bond with *, and Link represents a linking group that sterically relates Nu and E so that they can undergo an intramolecular nucleophilic substitution reaction. Specific examples of the group represented by formula (T-2) are as follows.

[0036]

[Chemical 9]

(3) A group that causes a cleavage reaction by utilizing an electron transfer reaction along a conjugated system. For example, U.S. Pat. No. 4,409,323 or 4,4
No. 21,845, which is a group represented by the following general formula. The general formula (T-3) * -W- ( V 1 = V 2) t -CH 2 - **

In the formula, V ₁ and V ₂ represent = CR ₆₅ -or a nitrogen atom. * Mark, ** mark, W, R ₆₅ and t have the same meanings as described for (T-1). Specific examples include the following groups.

[0039]

[Chemical 10]

(4) A group which utilizes a cleavage reaction by hydrolysis of an ester. For example, the following groups are the connecting groups described in West German Published Patent No. 2,626,315. In the formula, asterisks and asterisks have the same meanings as described for the general formula (T-1). General formula (T-4) General formula (T-5) * -O-CO-** * -S-CS-**

(5) A group which utilizes a cleavage reaction of an imino ketal. For example, it is a linking group described in US Pat. No. 4,546,073, and is a group represented by the following general formula. Formula (T-6) * -W- C (= NR 68) - **

In the formula, *, ** and W are general formulas (T
-1) has the same meaning as described above, and R ₆₈ is R
It has the same meaning as ₆₇ . Specific examples of the group represented by formula (T-6) include the following groups.

[0043]

[Chemical 11]

The group represented by B in the general formula (X-1) is specifically described by the following general formulas (B-1), (B-2),
It is represented by (B-3) or (B-4). (B-1)

[0045]

[Chemical formula 12]

In the formula, * indicates B in the general formula (X-1).
Represents the position to be bonded to the left side of, and the ** symbol indicates the general formula (X-
In 1), it represents the position at the right side of B. X ₁ and X ₄ are each an oxygen atom or —N (—SO ₂ R ₇₁ ) —
(R ₇₁ represents an aliphatic group, an aromatic group or a heterocyclic group)
X ₂ and X ₃ each represent a methine group or a nitrogen atom, and b represents an integer of 1 to 3. However, b
At least one of X ₂ and b X ₃ represents a methine group having a bond indicated by **. When b is plural, b x ₂ and b x ₃ are the same or different. When X ₂ and X ₃ are methine groups having a substituent, the case where they are linked to each other to form a cyclic structure (for example, a benzene ring or a pyridine ring) and the case where they are not included are included. The group represented by the general formula (B-1) is Kendall-Pelz rule after cleavage at the bond marked with *.
(“The Theory of the Photographic Proce” by TH James
ss ”, 4th ed., 29 of Macmillan Publishing Co., Inc.
It becomes a compound that applies to (see page 9) and is oxidized by reacting with the oxidized product of the developing agent.

Specific examples of the group represented by (B-1) include the following groups.

[0048]

[Chemical 13]

[0049]

[Chemical 14]

In the formula, * and ** have the same meanings as described in (B-1), and R ₇₂ , R ₇₃ and R ₇₄ are respectively (B-2) and (B-3). The group shown represents a group for functioning as a coupler having a coupling-off group at the ** mark after cleavage at the * mark. d represents an integer of 0 to 4, and when d is plural, a plurality of R _72's are the same or different. In addition, they may combine to form a cyclic structure (for example, a benzene ring).
Examples of R ₇₂ include an acylamino group, an alkyl group and a halogen atom, examples of R ₇₄ include an acylamino group, an alkyl group, an anilino group, an amino group and an alkoxy group, and examples of R ₇₃ include a phenyl group or an alkyl group. Is mentioned.

Specific examples of the groups represented by (B-2) and (B-3) include the followings.

[0052]

[Chemical 15]

(B-4)

[0054]

[Chemical 16]

In the formula, * mark and ** mark have the same meanings as described in (B-1), R ₇₅ , R ₇₆ and R ₇₇ each represent a substituent, and R ₇₇ and R ₇₆ are linked to each other. And R ₇₇ and R ₇₅ are linked to each other to form a nitrogen-containing heterocycle. (B-
The group represented by 4) becomes a coupler having a coupling-off group at ** after cleavage at *.

Specific examples of the group represented by (B-4) include the followings.

[0057]

[Chemical 17]

25 The group represented by DI in formula (X-1) is, for example, a tetrazolylthio group, a thiadiazolylthio group, an oxadiazolylthio group, a triazolylthio group, a benzimidazolylthio group, a benzthiazolylthio group, Examples thereof include a tetrazolylseleno group, a benzoxazolylthio group, a benzotriazolyl group, a triazolyl group, and a benzimidazolyl group. Examples of these groups include U.S. Pat. Nos. 3,227,554, 3,384,657, 3,615,506, 3,617,291 and 3,733.
01, 3933500, 3958993, 3961959, 4149886, 42594.
No. 37, No. 4095984, No. 4477563, No. 4782012 or British Patent No. 1450479.

Specific examples of the group represented by DI include the following. In the following, * indicates a general formula (X-
It represents the position bonded to the left side of the group represented by DI in 1).

[0060]

[Chemical 18]

[0061]

[Chemical 19]

[0062]

[Chemical 20]

Of the groups represented by the general formula (X-1),
Particularly preferred are the following general formulas (X-2) and (X-3)
And (X-4). Formula (X-2) - (L 1) - (B) -DI Formula (X-3) - (L 2) -DI Formula (X-4) -DI wherein, L _1, L _2, B and DI have the same meanings as L ₁ , L ₂ , B and DI in formula (X-1). In the compound represented by the general formula (I), when X is a group capable of splitting off with an oxygen atom, R is a hydrogen atom, an alkyl group or an aryl group from the viewpoint of the coupling reaction rate with the oxidized form of the developing agent. Preferably, further, X is the general formula (B-1).
In the case of leaving with a group represented by, it is necessary for the leaving group to have a substituent having a Hammett's σ _p value of 0.3 or more in order to improve the storage stability in the light-sensitive material. Particularly preferred.

As the substituent having a Hammett's σ _p value of 0.3 or more, a halogenated alkyl group (eg, trichloromethyl, trifluoromethyl, heptafluoropropyl), a cyano group, an acyl group (eg, formyl, acetyl, Benzoyl), an alkoxycarbonyl group (for example,
Methoxycarbonyl, propyloxycarbonyl), an aryloxycarbonyl group (eg, phenoxycarbonyl), a carbamoyl group (eg, N-methylcarbamoyl, N-propylcarbamoyl), a sulfamoyl group (eg, N, N-dimethylsulfamoyl), Sulfonyl group (eg, methanesulfonyl, benzenesulfonyl), thiocyanato group, nitro group, phosphinyl group (eg, diethylphosphinyl, dimethylphosphinyl), heterocyclic group (eg, 1-pyrrolyl, 2-benzoxazolyl) ) And the like. Below is Hammett's σ
Specific examples of the group having _ap value of 0.3 or more are shown below, but the present invention is not limited thereto. The numerical value in parentheses indicates the σ _p value of the substituent. The σ _p value was quoted from “Structure-Activity Relationship of Drugs” (Chemical Science Special Issue No. 122, Nankodo). −CO ₂ C ₂ H ₅ (0.45) −CONHCH ₃ (0.36) −CF ₂ CF ₂ CF ₂ CF ₃ (0.52) −C ₆ F ₅ (0.41) −COCH ₃ (0.50) −COC ₆ H ₅ (0.43) −P (O) (OCH ₃ ) ₂ (0.53) −SO ₂ NH ₂ (0.57) −SCN (0.52) −CO ₂ C ₆ H ₅ (0.44) −CO ₂ CH ₃ (0.45) −CONH ₂ (0.36) − (CF ₂ ) ₃ CF ₃ (0.52) −CN (0.66)

In the compound represented by the general formula (I), when X is a group capable of leaving at a nitrogen atom or a sulfur atom, R is preferably an alkoxy group or an aryloxy group, and further represented by Z. It is particularly preferable to have a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group as a substituent of the azole ring portion, from the viewpoint of storage stability in the light-sensitive material.

General formulas (P-1), (P-2), (P-
Among the compounds represented by 3) and (P-4), those particularly preferable in terms of the hue of the magenta dye formed are represented by formulas (P-1), (P-2) and (P-3). And those represented by formula (P-2) or (P-3) are more preferred.

Further, the compound represented by the general formula (I) forms a dimer or higher multimer through the divalent or divalent or higher group in the substituent of the azole ring represented by the substituent R or Z. You may. When the compound represented by the general formula (I) forms a multimer, a homopolymer or a copolymer of the addition-polymerizable ethylenically unsaturated compound (color-forming monomer) having the above compound residue is typical. In this case the multimer contains repeating units of general formula (V). One or more types of color-forming repeating units may be contained in the multimer, and the copolymer may be a copolymer containing one or more non-color-forming ethylene-like monomers. General formula (V)

[0068]

[Chemical 21]

In the formula, R ₃₄ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a chlorine atom, and E represents —CONH—, —
CO ₂ -or a substituted or unsubstituted phenylene group, G represents a substituted or unsubstituted alkylene group, a phenylene group or an aralkylene group, T represents -CONH-,
_{-NHCONH -, - NHCO 2 -,} - NHCO -, -
OCONH -, - NH -, - CO 2 -, - OCO -, -
CO -, - O -, - SO 2 -, - NHSO 2 - or -
Representing the SO ₂ NH-. Although e, g and t represent 0 or 1, none of e, g and t are 0. Q
Q represents a compound residue in which a hydrogen atom is removed from the compound represented by the general formula (I).

As the multimer, a copolymer of a compound monomer giving the compound unit of the general formula (V) and the following non-color forming ethylene-like monomer is preferable. As the non-color-forming, ethylenic monomer that does not couple with the oxidation product of the aromatic primary amine developing agent, acrylic acid, α-chloroacrylic acid, α-alacrylic acid (for example, methacrylic acid) is derived from these acrylic acids. Ester or amide (eg, acrylamide, methacrylamide, n
-Butyl acrylamide, t-butyl acrylamide,
Cyacetone acrylamide, methylene bis acrylamide, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl acrylate, iso-butyl acrylate, 2-
Ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and β-hydroxymethacrylate), vinyl esters (eg vinyl acetate, vinyl propionate and vinyl laurate), acrylonitrile, methacryloyl. Nitriles, aromatic vinyl compounds (eg styrene and its derivatives such as vinyltoluene, divinylbenzene, vinylacetophenone and sulfostyrene) itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ethers (eg vinyl ethyl ether) malein Acid esters, N-vinyl-2-pyrrolidone, N-vinyl pyridine, and the like. Acrylic acid esters, methacrylic acid esters, and maleic acid esters are particularly preferable. Two or more kinds of the non-color-forming ethylenic monomers used here can 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.

As is well known in the field of polymer couplers,
When synthesizing the polymer coupler containing the repeating unit represented by the general formula (V), the non-color forming ethylene-like monomer copolymerized with the ethylene-like monomer having the coupler residue of the present invention is formed. The physical and / or chemical properties of the copolymer, such as solubility, compatibility with the binder of the photographic colloid composition, such as gelatin, its plasticity, thermal stability, etc. may be selected to be favorably affected. it can. A polymer compound used in the present invention (a lipophilic polymer compound obtained by polymerization of a vinyl-based monomer which gives a compound unit represented by the general formula (V)) dissolved in an organic solvent is added to an aqueous gelatin solution. It may be emulsified and dispersed in the form of latex, or may be directly emulsified. The method of emulsion-dispersing a lipophilic polymer compound in an aqueous gelatin solution in the form of a latex is described in US Pat. No. 3,451,820, and the emulsion polymerization is described in US Pat. Nos. 4,080,211 and 3,37.
The method described in No. 0,952 can be used. Specific examples of the compound represented by formula (I) used in the present invention are shown below, but the present invention is not limited thereto.

[0072]

[Chemical formula 22]

[0073]

[Chemical formula 23]

[0074]

[Chemical formula 24]

[0075]

[Chemical 25]

[0076]

[Chemical formula 26]

[0077]

[Chemical 27]

[0078]

[Chemical 28]

[0079]

[Chemical 29]

[0080]

[Chemical 30]

[0081]

[Chemical 31]

[0082]

[Chemical 32]

[0083]

[Chemical 33]

[0084]

[Chemical 34]

[0085]

[Chemical 35]

[0086]

[Chemical 36]

[0087]

[Chemical 37]

[0088]

[Chemical 38]

[0089]

[Chemical Formula 39]

[0090]

[Chemical 40]

[0091]

[Chemical 41]

The compounds represented by the general formula (I) are described in US Pat. Nos. 4,500,630 and 4,540,654.
No. 4,705,863, JP-A-61-65245.
No. 62-209457 and 62-249155.
No. 3,725,067, JP-A-60-33.
No. 552, No. 61-28947, No. 63-28415.
9, JP-A-2-59584, US Pat. No. 4,659,
It can be synthesized by the method described in No. 652 or the like or a method analogous thereto.

The synthesis examples of the compound of the present invention are shown below. Synthesis Example 1 [Synthesis of Exemplified Compound (4)]

[0094]

[Chemical 42]

1.95 g (0.04 g) of sodium hydride in 100 ml of 1,3-dimethylimidazolidin-2-one
9 mol) was added, and the mixture was stirred while cooling in an ice water bath. To this, 7.18 g of 5,6-dimethylbenzotriazole
(0.049 mol) was added in several portions over 20 minutes.
After further stirring for 10 minutes, 19.2 g of compound (A)
(0.020 mol) was added, and the mixture was stirred at 80 ° C. for 40 minutes. After cooling, 300 ml of ethyl acetate, 300 ml of water and 8 ml of concentrated hydrochloric acid were added and extraction was performed. The organic layer was washed successively with water, saturated aqueous sodium hydrogen carbonate solution and saturated brine, and then dried over anhydrous magnesium sulfate. The oily substance obtained by concentration was dispersed by silica gel column chromatography (eluent: chloroform / ethyl acetate) to prepare Exemplified Compound (4) 14.
1 g (yield 69%) was obtained as a glassy solid. This is dissolved in 20 ml of ethyl acetate while heating and 80% of hexane is added.
ml was added and left to stand. The precipitated crystals were collected by filtration, 10.9
g of the exemplary compound (4) was obtained as colorless crystals. Melting point 13
1-133 ° C

¹ H-NMR spectrum (200 MHz, CDCl ₃ ) δ1
2.92 (brs, 1H), 7.67 (d, 1H, J = 2.2Hz),
7.5-7.3 (m, 4H), 7.26 (s, 1H), 7.08
(brs, 1H), 6.90 (d, 1H, J = 8.7Hz), 6.81 (d,
1H, J = 8.8Hz), 5.66 (brs, 1H), 4.39 (q, 2H,
J = 7.1Hz), 4.15 (t, 2H, J = 6.7Hz), 4.00 (brs,
2H), 3.4-3.1 (m, 3H), 2.36 (s, 3H),
2.30 (S, 3H), 2.0-1.8 (m, 5H), 1.60
(S, 2H), 1.5-1.2 (m, 32H), 0.85 (m, 6
H), 0.51 (S, 9H).

Synthesis Example 2 [Synthesis of Exemplified Compound (14)]

[0098]

[Chemical 43]

4-phenyl-3-mercapto-1,2,
4.4 g (0.025 mol) of 4-triazole was added to 50 ml of dichloromethane, and the mixture was stirred while cooling with water at 18 ° C. To this, 2.2 ml (0.027 mol) of sulfuryl chloride was added dropwise over 10 minutes, and stirring was continued for another 15 minutes. Dichloromethane was distilled off under reduced pressure to obtain the compound (C) as pale yellow crystals. Compound (B) 15.0 g
(0.017 mol) of N, N-dimethylformamide 3
It was added to 0 ml and stirred at room temperature. Crystals of the previously synthesized compound (C) were added to this in several batches over 1 hour. After leaving it overnight, 150 ml of ethyl acetate and 150 water
ml was added for extraction. The organic layer was washed twice with saturated aqueous sodium bicarbonate solution and once with saturated brine, and then dried over anhydrous magnesium sulfate. The oily substance obtained by concentration was dispersed by silica gel column chromatography (eluent: chloroform / ethyl acetate) to obtain Exemplified Compound (14) as a glassy immobilization. Dissolve this while heating in 20 ml of ethyl acetate,
40 ml of hexane was added and left to stand. The precipitated crystals were collected by filtration to obtain 13.8 g (yield 77%) of Exemplified compound (14) as colorless crystals. Melting point 158-162 ° C

¹ H-NMR spectrum (200 MHz, CDCl ₃ ) δ1
3.89 (brs, 1H), 8.39 (S, 1H), 7.65
(D, 1H, J = 2.3Hz), 7.6-7.3 (m, 11H), 7.2
-7.0 (m, 3H), 6.77 (m, 2H), 4.1-3.9
(M, 7H), 1.84 (m, 4H), 1.6-1.3 (m, 31
H), 0.86 (m, 6H), 0.46 (S, 9H).

Synthesis Example 3 [Synthesis of Exemplified Compound (15)]

[0102]

[Chemical 44]

11.7 g (11.5 mmol) of intermediate (D) was dissolved in 100 ml of chloroform and cooled in a water bath with stirring. N-bromosuccinimide 2.
05 g (11.5 mmol) was added and stirred for 10 minutes. The reaction mixture was washed twice with 100 ml of water, then dried over anhydrous sodium sulfate and concentrated. Crystallization from a mixed solvent of ethyl acetate / hexane gave 10.4 g of intermediate (E). 1,3-Dimethylimidazolidin-2-one (D
1.14 g (28.5 mmol) of sodium hydride (dispersed in mineral oil, content 60% by weight) was added to 50 ml of MI), and the mixture was cooled in an ice-water bath with stirring. Intermediate to this (F)
8.31 g (28.5 mmol) were added portionwise over 10 minutes. After removing the ice-water bath and stirring for further 10 minutes, the intermediate (E) synthesized above was added, and the mixture was heated at 100 ° C. for 2 minutes.
Stir for hours. After cooling, the reaction mixture was diluted with ethyl acetate 150
ml and 150 ml of water were added for extraction. The organic layer was washed twice with 150 ml of saturated aqueous sodium hydrogen carbonate, once with 150 ml of dilute hydrochloric acid, and further with 150 ml of saturated saline. The organic layer was dried over anhydrous magnesium sulfate, concentrated, and purified by silica gel column chromatography (eluent: hexane / ethyl acetate mixed solvent) to give 5.0 g of the exemplified compound (15) (yield 40%).
Was obtained as a pale yellow-orange glassy solid. Mass spectrum (FAB, Negative) m / e = 1302 ([M−H]
^- )

Synthesis Example 4 [Synthesis of Exemplified Compound (18)]

[0105]

[Chemical 45]

25.0 g (23.7 mmol) of intermediate (G) was dissolved in 150 ml of chloroform and cooled in a water bath with stirring. N-bromosuccinimide 4.
18 g (23.5 mmol) was added and stirred for 25 minutes. The reaction mixture was washed twice with 100 ml of water, dried over anhydrous magnesium sulfate and concentrated to give intermediate (H). 1,3-Dimethylimidazolidin-2-one (DM
I) 2.96 g (74.1 mmol) of sodium hydride (dispersed in mineral oil, content 60% by weight) was added to 80 ml, and the mixture was cooled in an ice-water bath with stirring. Intermediate to this (F)
21.6 g (74.1 mmol) were added portionwise over 20 minutes. After removing the ice-water bath and stirring for 10 minutes, a solution of the intermediate (H) synthesized above in 40 ml of DMI was added, and the mixture was stirred at 45 ° C for 0.5 hours and further at 55 ° C for 1.5 hours. .. After cooling, the reaction mixture was extracted with 400 ml of ethyl acetate and 500 ml of water. The organic layer was washed twice with 300 ml of saturated aqueous sodium hydrogen carbonate, once with 300 ml of dilute hydrochloric acid, and further washed with 300 ml of saturated saline. The organic layer was dried over anhydrous magnesium sulfate, concentrated, and purified by silica gel column chromatography (eluent: hexane / ethyl acetate mixed solvent) to give Exemplified compound (18) 16.2 g (yield 50%). Obtained as a pale yellow-orange glassy solid. Mass spectrum (FAB, Negative) m / e = 1300
([MH] ^- )

Synthesis Example 5 [Synthesis of Exemplified Compound (44)]

[0108]

[Chemical 46]

Synthesis of Intermediate (R) To 150 ml of 1,3-dimethyl-2-imidazolidone, 6.00 g of sodium hydride (dispersed in mineral oil, content 60% by weight) was added, and the mixture was cooled in a water bath with stirring. 82.9 g of the intermediate (Q) was added in several batches over about 10 minutes, then the water bath was removed and the mixture was stirred for 10 minutes. Intermediate (P) 3
After adding 1.9 g and stirring at room temperature for 10 minutes, 120
Heat to ~ 130 ° C and stir for about 1 hour. After stopping heating and returning to room temperature, 400 ml of ethyl acetate and 400 ml of water
Then, 6 ml of concentrated hydrochloric acid was added and the mixture was extracted. 400 organic layer
After washing with ml, wash twice with 400 ml of saturated saline,
It was dried over anhydrous magnesium sulfate. After concentrating under reduced pressure,
The residue was subjected to silica gel column chromatography (eluent:
Purified by a mixed solvent of hexane / ethyl acetate), 18.7
Obtained g (34%) of the intermediate (R) as an amorphous solid.

Synthesis of Exemplified Compound (44) 14.4 g of the intermediate (R) was dissolved in 45 ml of trifluoroacetic acid. 2.25 ml of water was added and the mixture was stirred at 50 ° C for 16 hours. After cooling, 200 ml of ethyl acetate and 200 ml of water were added for extraction, and the organic layer was washed twice with 150 ml of saturated sodium bicarbonate water and once with 150 ml of saturated saline. The organic layer was dried over anhydrous magnesium sulfate and then concentrated under reduced pressure. The residue was purified by silica gel column chromatography (eluent: hexane / ethyl acetate / ethanol mixed solvent),
8.1 g (66%) of the exemplified compound (44) was obtained as an amorphous solid.

¹ H-NMR spectrum (CDCl ₃ ) δ11.5 (br), 7.84 (d, 1H), 7.9-7.6
(Br), 7.50 (m, 6H), 6.94 (d, 1H), 6.8
4 (brs, 1H), 5.75 (br, 1H), 4.10 (m, 4
H), 3.18 (m, 3H), 2.08 (brs, 3H), 1.9-
1.2 (m, 25H), 0.80 (m, 6H), 0.70 (S
, 9H).

Synthesis Example 6 [Synthesis of Exemplified Compound (56)]

[0113]

[Chemical 47]

Synthesis of Intermediate (T) 166 g of Intermediate (Q) was dissolved in 500 ml of 1,3-dimethyl-2-imidazolidone and cooled in an ice-water bath. With vigorous stirring, 12.0 g of sodium hydride (dispersed in mineral oil, content 60% by weight) was added in several portions, and the ice-water bath was removed and the mixture was stirred for 30 minutes. Intermediate (M) 37.
After adding 4 g and stirring at room temperature for 10 minutes, 130-1
The mixture was stirred at 40 ° C for 2 hours. After cooling, ethyl acetate 1.21
Then, 1.01 of water and 10 ml of concentrated hydrochloric acid were added for extraction. The organic layer was washed with water 1.01 and then saturated brine 1.01
It was washed twice with. The organic layer was dried over anhydrous magnesium sulfate and then concentrated under reduced pressure. The residue was purified by silica gel column chromatography (eluent: chloroform / ethyl acetate mixed solvent) to obtain 27.6 g (33%) of intermediate (T).

Synthesis of Intermediate (U) 27.6 g of Intermediate (T) was dissolved in a mixed solvent of 150 ml of isopropyl alcohol and 50 ml of acetonitrile,
3.16 ml of hydrazine hydrate was added, and the mixture was stirred at room temperature for 4 hours. After standing at room temperature once, 20 ml of ethyl acetate was added and the solvent was distilled off under reduced pressure. 150 ml of ethyl acetate as the residue
Was added and dissolved, and the mixture was washed twice with 150 ml of saturated sodium bicarbonate water and once with 150 ml of saturated saline solution. Crystals precipitated upon standing and were collected by filtration. The crystals obtained were dissolved in a mixed solvent of 100 ml of ethyl acetate and 20 ml of N, N-dimethylacetamide and stirred at room temperature. 2-octyloxy-5
-Tert-octylbenzenesulfonyl chloride 7.
92 g was added, followed by 1 of 2.65 ml of triethylamine.
It was dripped in 0 minutes. After stirring at room temperature for 1 hour, 50 ml of ethyl acetate, 150 ml of water and 2 ml of concentrated hydrochloric acid were added for extraction. The organic layer was washed with saturated saline and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, purification by silica gel column chromatography (eluent: hexane / ethyl acetate mixed solvent) was performed, and 16.8 g (4) of the intermediate (U) was obtained.
7%) as an amorphous solid.

Synthesis of Exemplified Compound (56) 16.2 g of intermediate (U) was dissolved in 32 ml of trifluoroacetic acid, 1.6 ml of water was added, and the mixture was stirred at 50 ° C. for 10 hours.
After standing at room temperature once, 100 ml of ethyl acetate and 100 ml of water were added for extraction. The organic layer is 2 with 100 ml of saturated heavy soup water.
After washing once with 100 ml of saturated saline, it was dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was crystallized from a mixed solvent of ethyl acetate / hexane to give the exemplified compound (56)
8.2 g (59%) were obtained as colorless crystals. Melting point 15
0-152 ° C

¹ H-NMR spectrum (CDCl ₃ ) δ11.5 (br, 1H), 8.5 (br), 7.84 (d, 1
h), 7.6-7.4 (m, 6H), 7.33 (S, 1H), 6.
99 (S, 1H), 6.92 (d, 1H), 5.71 ((brs,
1H), 4.07 (m, 4H), 3.19 (m, 3H), 1.9
-1.2 (m, 25H), 0.79 (m, 6H), 0.65 (S,
9H).

The compound represented by the general formula (I) of the present invention can be added to any layer for use.
It is preferably added to the green-sensitive emulsion layer and / or its adjacent layer or intermediate layer. The compounds may be used alone or in combination of two or more. Further, the compound and a compound which reacts with one or two molecules of the developing agent oxidant other than that of the present invention to release the development inhibitor or its precursor can be mixed and used. When the compounds other than the present invention are used together in the same layer, the ratio of the added amount is
1 to 200 mol% relative to 1 mol of the compound of the present invention,
It is preferably 5 to 100 mol%. When added in a separate layer, the ratio may be arbitrary, but in that case, the addition amount is 1 × 10 ^-4 to 1 mol of silver halide in the same layer or an adjacent layer.
It is 1 mol%.

The total amount of the compound represented by formula (I) of the present invention added to the light-sensitive material is 0.001 to 0.85 g / m ^2.
By weight, preferably 0.005~0.65g / m ^2, more preferably 0.02~0.45g / m ^2. Further, the compound of the present invention can be added to a light-sensitive material by the same method as a usual dispersing method for couplers described below.

The silver content of the light-sensitive material of the present invention is 1.0 g /
m ² or more and 4.9 g / m ² or less, preferably 1.0 g
/ M ² or more and 4.7 g / m ² or less, more preferably 1.5 g /
m ² or more and 4.5 g / m ² or less, more preferably 2.0 g /
It is not less than m ^{2 and not} more than 4.3 g / m ² . Sufficient sharpness and color reproducibility were obtained with a light-sensitive material having a low silver content as in the present invention, because it exhibited an excellent hue with less unnecessary absorption and improved storage stability in a light-sensitive material. By using the compound of the present invention. Since the conventional magenta color-forming DIR compound is not sufficiently stable in a light-sensitive material, a light-sensitive material having a low silver content such as that of the present invention cannot provide sufficient color density, resulting in remarkable sensitivity and sharpness. However, there is a problem in that the hue of the resulting dye is unnecessarily absorbed, and the tailing of long waves is poor, so that the apparent interlayer color correction effect is reduced and the color reproducibility is insufficient.
On the other hand, since the compound of the present invention exhibits an excellent hue and has improved storage stability in a light-sensitive material, it is possible to realize sufficient sharpness and color reproducibility even in a low silver light-sensitive material such as the present invention. Became possible.

The silver content referred to here is the content of all silver such as silver halide and metal converted. Several methods are known for analyzing the content of silver in the light-sensitive material, and any method may be used. For example, the fluorescent X-ray method is convenient.

In the present invention, the total dry film thickness is preferably 22 μm or less, more preferably 10 μm to 2
The thickness is 0 μm, more preferably 12 μm to 18 μm, and particularly preferably 14 μm to 16 μm. From the viewpoint of sharpness and desilvering property, the thickness from the outermost surface of the light-sensitive material to the lower end of the light-sensitive silver halide emulsion layer closest to the support, which is closer to the support, is preferably 16 μm or less. To 14 [mu] m is preferable from to the outermost surface of the color-sensitive layer closest to the support.

Here, the total dry film thickness means a temperature of 25 ° C. and a humidity of 5
It is displayed as the value measured by a commercially available contact-type film thickness meter (Anritsu Electric Co. Ltd. K-402BSTAND) under the condition that the humidity is controlled under 5% for 2 days. The total dry film thickness of all hydrophilic colloid layers on the side having the emulsion layer (that is, the total dry film thickness) is
It is determined by the difference between the thickness of the dried sample and the thickness after removing the coating layer on the support having the emulsion layer.

The film thickness of each layer of the multilayer silver halide color light-sensitive material can be measured by enlarging and photographing the cross section using a scanning electron microscope. In the measurement of a scanning electron microscope, the sample usually has to be placed under a vacuum, and the condition of the sample that has been humidity-controlled and dried cannot be maintained. There may be a loss and the film thickness may not be measured correctly. Therefore, sample preparation methods such as the freeze-drying method have been tried, but they are not sufficient. The measurement by the cross-section photography of the scanning electron microscope is used as a measuring means for calculating the thickness of each layer of the dried sample based on the value of the film thickness by the contact-type film thickness meter.

In the present invention, the specific photographic sensitivity as detailed and defined below is adopted as the sensitivity of the photographic light-sensitive material for the following reasons.

That is, ISO sensitivity, which is an international standard, is generally used as the sensitivity of a photographic light-sensitive material. With the ISO sensitivity, the light-sensitive material is developed on the fifth day after exposure, and the development treatment is a process designated by each company. According to the present invention, the time until the development processing after exposure is shortened (0.
The specific photographic sensitivity as described below was adopted so that the sensitivity can be determined by a constant developing process for 5 to 6 hours).

The specific photographic sensitivity of the light-sensitive material in the present invention is determined according to the following test method according to ISO sensitivity. (According to JIS K 7614-1981)

(1) Test Conditions The test is carried out in a room at a temperature of 20 ± 5 ° C. and a relative humidity of 60 ± 10%, and the photosensitive material to be tested is left in this state for 1 hour or more before use.

(2) Exposure The relative spectral energy distribution of the reference light on the exposure surface is shown in Table A.

[0130] Note (1) It is a value determined by standardizing the value at 560 nm to 100.

The illuminance change on the exposed surface is performed by using an optical wedge, and the optical wedge used has a spectral transmission density variation of 400 at a wavelength range of 360 to 700 nm in any part.
An area of less than 10 nm is used within 10%, and an area of 400 nm or more is used within 5%. The exposure time is 1/100 second.

(3) Development Processing From exposure to development processing, the photosensitive material to be tested is kept at a temperature of 20 ± 5 ° C. and a relative humidity of 60 ± 10%. The development process is completed within 30 minutes or more and 6 hours after exposure. The development process is performed as follows. 1 color development 3 minutes 15 seconds, 38.0 ± 0.1 ° C. 2 bleaching 6 minutes 60 seconds, 38.0 ± 3.0 ° C. 3 water washing 3 minutes 15 seconds, 24 ± 41 ° C. 4 fixing 6 minutes 30 Second, 38.0 ± 3.0 ° C 5 water wash 3 minutes 15 seconds, 24 ± 41 ° C 6 stability 3 minutes 15 seconds, 38.0 ± 3.0 ° C 7 dry 5 minutes or less

The composition of the processing liquid used in each step is shown below. Color developer Diethylenetriaminepentaacetic acid 1.0 g 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 g Sodium sulfite 4.0 g Potassium carbonate 30.0 g Potassium bromide 1.4 g Potassium iodide 1.3 mg Hydroxylamine sulfate 2 0.4 g 4- (N-ethyl-N-β-hydroxyethylamine) -2-methylaniline sulfate 4.5 g Water was added to 1.0 liter pH 10.0

Bleaching Solution Ethylenediaminetetraacetic acid ferric ammonium salt 100.0 g Ethylenediaminetetraacetic acid disodium salt 10.0 g Ammonium bromide 150.0 g Ammonium nitrate 10.0 g Water was added to 1.0 liter pH 6.0

Fixing Solution Ethylenediaminetetraacetic acid disodium salt 1.0 g Sodium sulfite 4.0 g Ammonium thiosulfate aqueous solution (70%) 175.0 ml Sodium bisulfite 4.6 g Water was added to 1.0 liter pH 6.6

Stabilizer Formalin (40%) 2.0 ml Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 g Water was added to 1.0 liter.

(4) Concentration measurement Concentration is expressed by log ₁₀ (Φ ₀ / Φ). Φ ₀ is an illumination light flux for density measurement, and Φ is a transmitted light flux of the measured portion. The geometric condition for density measurement is that the illumination light flux is a parallel light flux in the normal direction, and the standard is to use the total light flux that is transmitted as a transmitted light flux and diffused in a half space, and standard when other measurement methods are used. Correct with density strips. Also, when measuring
The emulsion film surface shall face the light receiving device side. Density measurement is performed with blue, green, and red status M densities, and its spectral characteristics are those shown in Table 1 as the overall characteristics of the light source, optical system, optical filter, and light receiving device used in the densitometer.

[0138]

[Table 1]

(5) Determination of specific photographic sensitivity Using the results of processing and density measurement under the conditions (1) to (4), the specific photographic sensitivity is determined by the following procedure. Blue, green, for the minimum concentration of each of the red, respectively H _B represents an exposure amount corresponding to 0.15 higher concentrations lux · sec, H _G, and H _R. The larger value (lower sensitivity) of H _B and H _R is designated as H _S. The specific photographic sensitivity S is calculated according to the following formula.

[Equation 1]

The specific photographic sensitivity of the light-sensitive material of the present invention determined by the above method is preferably 80 or more and less than 800, more preferably 100 or more and 640 or less. If the specific photographic sensitivity is less than 80, the aperture will open during normal shooting, and the out-of-focus probability, the probability of camera shake due to a slow shutter speed, the probability of underexposure increase, and the failure rate increases. In addition, many recent cameras have an automatic sensitivity setting function by reading a DX code, but among them, inexpensive cameras called so-called compact cameras often have a sensitivity setting of less than ISO 100 and cannot be set as an ISO sensitivity display. The camera cannot be applied to these cameras unless it is 100 or more and at least 80 or more with the specific sensitivity of this photograph.
Further, when the specific photographic sensitivity is set to 800 or more as disclosed in JP-A-63-226651, deterioration in graininess is conspicuous especially when the magnification is increased, which is not preferable.

The light-sensitive material of the present invention has at least one red-sensitive silver halide emulsion layer, green-sensitive silver halide emulsion layer, and blue-sensitive silver halide emulsion layer, but any emulsion layer having the same color sensitivity. Is preferably composed of two or more emulsion layers having different sensitivities, and more preferably a method of further improving the graininess in a three-layer structure. These techniques are described in British Patent No. 923,045 and Japanese Patent Publication No. 49-154, respectively.
No. 95.

In a color negative photographic light-sensitive material, when an emulsion layer having the same color sensitivity is composed of two or more emulsion layers having different sensitivities, the so-called grain disappearing effect is utilized to make the silver layer in the emulsion layer having a higher sensitivity. It was common knowledge to design a high content of color negative photographic light-sensitive material. However, in a high-speed color negative photographic light-sensitive material having a specific photographic speed of 80 or more and less than 800, increasing the content of silver in the emulsion layer having a higher sensitivity is more effective than increasing the content of silver in the emulsion layer having a low sensitivity. It was found to have an unexpected determination that the aging was large. Therefore, it is preferable not to increase the silver content in the emulsion layer having the highest sensitivity among the emulsion layers having the same color sensitivity. The silver content in the most sensitive emulsion layer of each of the red-sensitive layer, the green-sensitive layer and the blue-sensitive layer is preferably 0.3 g / m ² or more.
5 g / m ² or less, more preferably 0.3 g / m ² or more and 1.2 g / m ² or less, still more preferably 0.3 g / m ²
It is 1.0 g / m ² or less.

Various inventions concerning the order of layer arrangement have been made in order to achieve both high sensitivity and high image. These techniques may be used in combination. Inventions relating to the order of layer arrangements are described, for example, in US Pat. No. 4,184,876.
No. 4,129,446, 4,186,016
No., UK 1,560,965, US Pat. No. 4,18
6,011, 4,267,264, 4,17
3,479, 4,157,917, 4,16
5,236, British Patent No. 2,138,962, JP-A-59-177552, British Patent No. 2,137,37.
No. 2, JP-A-59-180556 and JP-A-59-2040.
No. 38 and the like.

A non-photosensitive layer may be present between two or more emulsion layers having the same color sensitivity. A sensitivity layer may be improved by providing a reflective layer of fine grain silver halide under the high sensitivity layer, particularly the high sensitivity blue sensitive layer. This technique is disclosed in JP-A-59-
160135.

Generally, a cyan-forming coupler is contained in the red-sensitive emulsion layer, a magenta-forming coupler is contained in the green-sensitive emulsion layer, and a yellow-forming coupler is contained in the blue-sensitive emulsion layer. You can also For example, a combination of infrared-sensitive layers may be used for pseudo color photography or semiconductor laser exposure. Also, US Pat.
497, 350 or JP-A-59-214853, the color sensitivity of the emulsion layer and the color image-forming coupler are appropriately combined, and this layer is provided at the farthest position from the support. You can

Any one of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride is used as silver halide in the photographic emulsion layer of the silver halide photographic light-sensitive material of the present invention. Good. A preferred silver halide is silver iodobromide containing 30 mol% or less of silver iodide. Preferred is silver iodobromide containing 2 to 20 mol% of silver iodide. In the present invention, in order to achieve high image quality at a low silver content, it is particularly preferable that the silver halide content of all emulsion layers be 5.6 mol% or more.

In the present invention, the average silver iodide content of silver halide in all emulsion layers means the total iodine amount based on the total silver halide amount (excluding metallic silver) present in the light-sensitive material. It is a value obtained by multiplying by 100 excluding. In the present invention, the average silver iodide content is preferably 5.6 mol% or more,
The amount is more preferably 6.0 mol% or more and 15 mol% or less, and further preferably 7.0 mol% or more and 12 mol% or less.

It is known that the graininess can be improved by increasing the average silver iodide content of silver halide, but on the contrary, there are drawbacks such as a slow developing speed, desilvering and a slow fixing speed. (For example, as described in JP-A-62-89963). However, the present inventor found that the total dry film thickness of the light-sensitive material and the amount of silver contained were reduced as in the present invention, and the sensitivity was specified, and that the use of the coupler of the present invention did not cause these problems. It was

The light-sensitive material of the present invention can be used in the color development processing step of performing color development processing containing an aromatic primary amine developing agent, desilvering processing, followed by washing and / or stabilization processing. It is particularly preferable that the processing time is 150 seconds or less in order to shorten the total development processing steps. Conventional light-sensitive materials have problems such as a reduction in color density and a decrease in color reproducibility when the time of color development step is shortened, but these drawbacks are caused by using the coupler of the present invention and reducing the total dry film thickness. I was able to solve it by setting it.

The color developing solution used in the present invention contains a known aromatic primary amine color developing agent. A preferable example is a p-ferrenine diamine derivative, and representative examples thereof are shown below, but the present invention is not limited thereto. D-1 N, N-diethyl-p-ferrenine diamine D-2 2-amino-5-diethylaminotoluene D-3 2-amino-5- [N-ethyl-N-laurylamino) toluene D-4 4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline D-5 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline D-6 4-amino-3- Methyl-N-ethyl-N-
[Β- (Methanesulfonamide) ethyl] aniline D-7 N- (2-amino-5-diethylaminophenylethyl) methanesulfonamide D-8 N, N-dimethyl-p-ferreninediamine D-9 4-amino -3-Methyl-N-ethyl-N-methoxyethylaniline D-10 4-amino-3-methyl-N-ethyl-N-β
-Ethoxyethylaniline D-11 4-amino-3-methyl-N-ethyl-N-β
-Butoxyethylaniline

Of the above p-ferrenine diamine derivatives, Exemplified Compound D-5 is particularly preferable. Further, these p-ferrenin diamine derivatives may be salts such as sulfates, hydrochlorides, sulfites, p-toluenesulfonates and the like.

The above color developing agent is color developing solution 1
It is used in the range of 0.013 mol to 0.065 mol per liter, but 0.016 mol to 0.06 mol from the viewpoint of speeding up.
48 mol is preferable, and especially 0.019 mol to 0.03
2 mol is preferred. Further, as a preservative, a sulfite salt such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite, potassium metasulfite, or a carbonyl sulfite adduct is added to the color developer as necessary. be able to. The preferable addition amount of the preservative is 0.5 to 1 per liter of the color developing solution.
It is 0 g, more preferably 1 to 5 g.

Further, various hydroxylamines (for example, JP-A Nos. 63-5341 and 63-63) are used as compounds for directly preserving the aromatic primary amine color developing agent.
The compounds described in No. 106655, especially the compounds having a sulfo group or a carboxy group are preferable. ), JP-A-63-
Hydroxamic acids described in No. 43138, 63-146.
No. 041 hydrazines and hydrazides, 63-
44657 and 63-58443, α-hydroxyketones and α-aminoketones and 63-362 and 63-362.
It is preferable to add various sugars described in No. 44. Also,
In combination with the above compound, JP-A Nos. 63-4235 and 6-6.
No. 3-24254, No. 63-21647, No. 63-1
46040, 63-27341 and 63-25.
No. 654, etc., monoamines, 63-30845.
Nos. 63-14640, 63-43139, and the like, diamines, 63-21647, and 63-2.
6655 and 63-46655, polyamines described in 63-53551, nitroxy radicals described in 63-53551, alcohols described in 63-43140 and 63-53549, oximes described in 63-56654. And the tertiary amines described in JP-A-63-239447 are preferably used.

Other preservatives are disclosed in JP-A-57-441.
Various metals described in No. 48 and No. 57-53749,
Salicylic acids described in JP-A-59-180588, alkanolamines described in JP-A-54-3582, polyethyleneimines described in JP-A-56-94349, and aroma described in US Pat. No. 3,746,544. A group polyhydroxy compound or the like may be contained if necessary. It is particularly preferable to add an aromatic polyhydroxy compound.

In the present invention, the pH of the color developing solution is set in the range of 9.5 to 12, but from the viewpoint of speeding up,
It is preferably 10.2 or more, and particularly preferably 10.5-11.5. By increasing the pH, it is possible to accelerate both the silver development and the color development reaction, and it is particularly effective for promoting the color development of the cyan dye. In order to raise the pH, it is preferable to increase the addition amount of an alkali metal hydroxide such as potassium hydroxide or sodium hydroxide and to increase the amount of an alkali buffering agent such as potassium carbonate or trisodium phosphate.
The amount of such a buffer is 0.2 per liter of the developing solution.
Mol to 1.0 mol, preferably 0.3 mol to 0.
The amount is 8 mol, particularly preferably 0.35 mol to 0.5 mol.

The developing step may be carried out in two or more baths having different pHs. For example, the first bath is treated with a developer having a pH of 9 or less for a very short time, and then a high pH of 10.5 or more is applied.
By processing with the H developing solution, the development progress balance of the upper layer and the lower layer can be adjusted.

In order to maintain the above pH, it is preferable to use various buffers. Specific examples of the buffer include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, Sodium tetraborate (borax),
Potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), 5-sulfo-
2-hydroxybenzoic acid potassium (potassium 5-sulfosalicylate) etc. can be mentioned. However, the present invention is not limited to these compounds.
The amount of the buffering agent added to the color developing solution is preferably 0.1 mol / liter or more, and particularly preferably 0.1 to 0.4 mol / liter.

In addition, various chelating agents can be used in the color developing solution as an agent for preventing the precipitation of calcium or magnesium, or for improving the stability of the color developing solution. The chelating agent is preferably an organic acid compound, and examples thereof include aminopolycarboxylic acids, organic phosphonic acids, and phosphonocarboxylic acids. As typical examples of these, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ', N'-
Tetramethylenephosphonic acid, transcyclohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid, hydroxyethyliminodiacetic acid, glycol etherdiaminetetraacetic acid, ethylenedisimine orthohydroxyphenylacetic acid, 2-phosphonobutane-1,2,4- Examples thereof include tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid and N, N'-bis (2-hydroxybenzyl) ethylenediamine-N, N'-diacetic acid. Two or more of these chelating agents may be used in combination, if necessary. The amount of these chelating agents added may be an amount sufficient to block the metal ions in the color developing solution, for example, 1
It is about 0.1 g to 10 g per liter.

A bromide of 0.02 mol / liter or less is added to the color developing solution in order to prevent fog and gradation adjustment, but preferably 0.015 mol / l for rapid development. It is preferably less than or equal to liter.
As the above bromide, alkali metal bromides such as potassium bromide, sodium bromide, lithium bromide and the like can be preferably used.

Various antifoggants can be used in order to suppress fog and improve discrimination. Preferred examples of the antifoggant include benzotriazole, 5-methylbenzotriazole, 6-nitrobenzimidazole, 5-phenyltetrazole, 1-phenyl-5-mercaptotetrazole, and the like, LFA Mason, Photographic Processing Chemistry No. 1. 2nd edition (published in 1975), the organic antifoggants described on pages 39 to 42 can be mentioned, and the amount thereof is also preferably the amount described in the same publication. See also TH James, The Theory of Photographic Process 4th Edition 398 pages-39.
4-hydroxy-6-methyl-1, described on page 9
3,3a, 7-Tetraazaindene and the like are also preferable, and the amount thereof is the same as the above organic antifoggant.

In order to speed up the development, it is also preferable to use various development accelerators in the color developing solution. Examples of these development accelerators include the compounds described in LFA Mason's book, pages 41 to 44, and the same book, pages 15 to 29.
The various black-and-white developing agents described on the page may be used in combination. Among them, pyrazolidones such as 1-phenyl-3-pyrazolidone, p-aminophenols, tetramethyl-p-phenylenediamine and the like are particularly preferable. The amount of these development accelerators used is preferably 0.001 g to 0.1 g per liter of the developing solution, and particularly preferably 0.1.
It is 003 g to 0.05 g.

The color developing solution used in the present invention may contain a fluorescent whitening agent. As the optical brightener, 4,
A 4'-diamino-2,2'-disulfostilbene compound is preferable. The addition amount is 0 to 5 g / liter, preferably 0.1 g to 4 g / liter. If necessary, various surfactants such as alkyl sulfonic acid, aryl sulfonic acid, fatty acid carboxylic acid, aromatic carboxylic acid may be added.

The processing temperature of the color developing solution in the present invention is 20 to 50 ° C, preferably 30 to 45 ° C. The processing time is 20 seconds to 5 minutes, preferably 30 seconds to 3 minutes and 20 seconds, and more preferably 1 minute to 2 minutes and 30 seconds. The present invention is preferably carried out with a color development time of 150 seconds or less. Here, the development time is the time from the first immersion of the light-sensitive material to the color developing solution to the first immersion in the processing solution of the next step, and includes the aerial time for moving between steps. To do. Generally, air time is 1 to 3 seconds
It is 0 seconds, but for the purpose of speeding up the present invention,
The air time is preferably short, specifically 15 seconds or less, and particularly preferably 10 seconds or less.

The effect of the present invention is remarkable in the treatment for a shorter time. From this point, it is more preferably 120 seconds or less, and most preferably 100 seconds or less. If necessary, the color developing bath may be divided into two or more baths, and the color developing replenisher may be replenished from the frontmost bath or the last bath to shorten the development time or the replenishing amount.

The processing method of the present invention can also be used for color reversal processing. The black-and-white developing solution used at this time is called a black-and-white first developing solution which is generally used for reversal processing of color light-sensitive materials, and it is used for black-and-white silver halide light-sensitive material processing solutions. Various well-known additives that are used by being added to the liquid can be contained. Typical additives include a developing agent such as 1-phenyl-3-pyrazolidone, metol and hydroquinone, a preservative such as sulfite, and an accelerator composed of an alkali such as sodium hydroxide, sodium carbonate or potassium carbonate. , Inorganic or organic inhibitors such as potassium bromide, 2-methylbenzimidazole and methylbenzthiazole, water softeners such as polyphosphates, development inhibitors consisting of trace amounts of iodides and mercapto compounds. You can

When processing with the above-mentioned developing solution in an automatic developing machine, it is preferable that the area (opening area) where the developing solution comes into contact with air is as small as possible. For example, opening area (cm
^When the value obtained by dividing ² ) by the volume (cm ³ ) of the developer is taken as the aperture ratio, the aperture ratio is preferably 0.01 or less, more preferably 0.005 or less. Further, in order to correct the concentration of the developing solution due to evaporation, it is preferable to add water corresponding to the amount of evaporation. The present invention is also effective when the developer is regenerated and used.

The color developing solution in the invention is preferably used continuously by supplying a replenishing solution. The replenisher contains an amount necessary for compensating for components that are consumed in development or consumed with time. Therefore, it usually contains a slightly larger amount of components than the developing mother liquor. The ratio is generally 10 to 50% larger than that of the mother liquor. However, since the bromide is eluted from the light-sensitive material with the development, the content of the replenisher is preferably set smaller than that of the mother liquor, and it is more preferable to reduce the replenisher. For example, when the replenishment amount per 1 m ^{2 of} the light-sensitive material is set to 700 ml or less, the bromide content is preferably 0.004 mol or less per liter, and when the replenishment amount is 500 ml or less, 0.03 mol or less. It is preferable that the amount is less than or equal to mol. When the replenishment amount is further reduced, it is also preferable not to include bromide.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. 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 may 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. Typical bleaching agents are organic complex salts of iron (III), such as aminoamines such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid and glycol etherdiaminetetraacetic acid. Polycarboxylic acids or complex salts of citric acid, tartaric acid, malic acid and the like can be used. Of these, aminopolycarboxylic acid iron (III) complex salts including ethylenediaminetetraacetic acid iron (III) complex salts and 1,3-diaminopropanetetraacetic acid iron (III) complex salts are preferable from the viewpoint of rapid treatment 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 a bleaching solution or a bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 4.0 to 8, but a lower pH may 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 bleaching accelerators are described in the following specifications: US Pat. No. 3,893,858, West German Patents 1,290,812, 2,059,988, JP No. 53-32736, No. 53-57831, No. 53
-37418, 53-72623, 53-95.
No. 630, No. 53-95631, No. 53-10423.
No. 2, No. 53-124424, No. 53-141623.
No. 53-28426, Research Disclosure No. 17129 (July 1978), and the like, compounds having a mercapto group or a disulfide group; thiazolidine derivatives described in JP-A-50-140129; JP-B-45. -8506, JP-A-52-20832
No. 53-32735, U.S. Pat. No. 3,706,5
Thiourea derivatives described in No. 61; West German Patent No. 1,12
No. 7,715, iodide salts described in JP-A-58-16235; West German Patent Nos. 966,410 and 2,748,4.
Polyoxyethylene compounds described in No. 30; Japanese Patent Publication No. 4
Polyamine compounds described in JP-A-5-8836; Others, JP-A-49-40943, JP-A-49-59644, and JP-A-53-
94927, 54-35727, 55-265.
Compounds described in No. 06 and No. 58-163940; bromide ions and the like can be used. Among them, a compound having a mercapto group or a disulfide group is preferable from the viewpoint of a large accelerating effect, and particularly, U.S. Pat. No. 3,893,858, West German Patent No. 1,290,812, and JP-A-53-95630.
Compounds described in US Pat. Furthermore, US Pat.
The compounds described in No. 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. A particularly preferred organic acid has an acid dissociation constant (p
Ka) is a compound 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. Use of thiosulfates Is most commonly used, with ammonium thiosulfate being the most widely used. 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 European Patent No. 294769A are preferable. Further, it is preferable to add various aminopolycarboxylic acids and organic phosphonic acids to the fixing solution and the bleach-fixing solution for the purpose of stabilizing the solution.

In the present invention, the fixer or the bleach-fixer contains a compound having a pKa of 6.0 to 9.0, preferably imidazole, 1-methylimidazole, 1-ethylimidazole, 2-methyl for adjusting the pH. It is preferable to add 0.1 to 10 mol / liter of imidazole such as imidazole.

The total time of the desilvering process is preferably as short as possible so long as no desilvering failure occurs. Preferred time is 1 to 3 minutes
Minutes, more preferably 1 minute to 2 minutes. The processing temperature is 25 ° C to 50 ° C, preferably 35 ° C to 45 ° C. In the preferred temperature range, the desilvering rate is improved,
In addition, the occurrence of stains after the treatment is effectively prevented.

In the desilvering step, it is preferable that the stirring is strengthened as much as possible. As a concrete method for strengthening the stirring, there is a method described in JP-A-62-183460, in which a jet of a processing solution is made to collide with the emulsion surface of a light-sensitive material, and JP-A-6-63.
No. 2-183461, a method of enhancing the stirring effect, and further moving the photosensitive material while bringing the wiper blade provided in the liquid into contact with the emulsion surface to make the emulsion surface turbulent, thereby further stirring. There are a method of improving the effect and a method of increasing the circulation flow rate of the entire processing liquid. Such a stirring improving means is effective in any of a bleaching solution, a bleach-fixing solution and a 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.

Automatic developing machines used for processing the light-sensitive material of the present invention are disclosed in JP-A-60-191257 and 60-19.
It is preferable to have a means for transporting the light-sensitive material described in Nos. 1258 and 60-191259. As described in JP-A-60-191257, such a conveying means can significantly reduce the carry-in of the treatment liquid from the front bath to the rear bath and has a high effect of 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 desilvering. The amount of rinsing water in the rinsing process depends on the characteristics of the photosensitive material (for example, depending on the material used such as couplers), the application, and the temperature of the rinsing water, the number of rinsing tanks (number of stages), replenishment method such as countercurrent, forward flow, and various other 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 Pictur.
e and Television Engineers Volume 64, p. 248 ~
253 (May 1955 issue).

According to the multistage countercurrent method described in the above document,
Although the amount of washing water can be significantly reduced, the increase in the residence time of water in the tank causes problems such as bacteria breeding and adhered floating substances to the photosensitive material. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, the method of reducing calcium ion and magnesium ion described in JP-A-62-288838 can be used very effectively. In addition, JP-A-57-
Nos. 8542, isothiazolone compounds, siabendazoles, chlorinated fungicides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc. Hiroshi Horiguchi, "Chemistry of Antibacterial and Antifungal Agents" (1986) Sankyo Publishing, Sanitary Technology Association, "Microbial Sterilization, Sterilization, and Antifungal Technology" (1982)
It is also possible to use the bactericide described in "Encyclopedia of Antibacterial and Antifungal Agents" (1986) edited by Japan Society of Industrial Technology and Antifungal Society.

The pH of washing water in the processing of the light-sensitive material of the present invention is 4 to 9, preferably 5 to 8. The washing water temperature and washing time can be variously set depending on the characteristics of the light-sensitive material, the use, etc., but generally 15 to 45 ° C. for 20 seconds to 10 minutes,
A range of 30 seconds to 5 minutes at 25 to 40 ° C. is preferably 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 stabilization treatment, Japanese Patent Laid-Open No. 57-8543,
All known methods described in JP-A-58-14834 and JP-A-60-220345 can be used.

In addition, the washing treatment may be followed by a further stabilizing treatment. As an example of the stabilizing treatment, a stabilizer containing a dye stabilizer and a surfactant used as a final bath of a color light-sensitive material for photographing is used. You can mention the bath. 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 be added to this stabilizing bath. The overflow solution that accompanies the washing with water and / or the supplement of the stabilizing solution can be reused in other steps such as the desilvering step.

In the processing using an automatic processor or the like, when each processing solution described above is concentrated by evaporation, it is preferable to add water to correct the concentration.

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, US Pat.
Indoaniline compounds described in 342,597, 3,342,599, Schiff base type compounds described in Research Disclosure 14850 and 15159, aldol compounds described in 13924, U.S. Pat. No. 3,719. , 492, Metal salt complexes
The urethane type compound of 3-135628 can be mentioned.

The silver halide color light-sensitive material of the present invention comprises
In order to accelerate color development, various 1-
Phenyl-3-pyrazolidones may be incorporated. Typical compounds are disclosed in JP-A-56-64339 and JP-A-57-14.
Nos. 4547 and 58-115438.

Various processing solutions used in the present invention are 10 ° C. to 50 ° C.
Used at ° C. Usually, a temperature of 33 ° C. to 38 ° C. is standard, but a higher temperature is used to accelerate the processing to shorten the processing time, and a lower temperature is used to improve the image quality and the stability of the processing liquid. be able to.

The silver halide light-sensitive material of the present invention is described in US Pat. No. 4,500,626 and JP-A-60-1334.
No. 49, No. 59-218443, No. 61-23805.
It is also applicable to the photothermographic materials described in No. 6, European Patent No. 210,660A2 and the like.

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 preparation and types ",
And No. 18716 (November 1979), 648.
Pp. 307105 (November 1989), 863.
-865, and Graphide, Physics and Chemistry of Photography,
Published by Paul Montel (P.Glafkides, Chemie et Phisiqu
e Photographique, Paul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF Duff
in, PhotographicEmulsion Chemistry (FocalPress, 196
6)), "Manufacturing and coating of photographic emulsions" by Zelikman et al., Published by Focal Press (VL Zelikman et al. Making a
nd CoatingPhotographic Emulsion, Focal Press, 1964
) And the like.

US Pat. Nos. 3,574,628 and 3,
Monodisperse emulsions described in, for example, 655,394 and British Patent 1,413,748 are also preferable.

Also, tabular grains having an aspect ratio of about 3 or more can be used in the present invention. Tabular grains are described in Gutoff. Photographic Science and E.
ngineering), Vol. 14, pp. 248-257 (1970)
); U.S. Pat. Nos. 4,434,226 and 4,41
4,310, 4,433,048, 4,43
It can be easily prepared by the method described in 9,520 and British Patent 2,112,157.

The crystal structure may be uniform, may have different halogen compositions inside and outside, may have a layered structure, and silver halides having different compositions may be bonded by epitaxial bonding. May be
Further, it may be bonded with 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-mentioned emulsion may be either a surface latent image type in which a latent image is mainly formed on the surface, an internal latent image type in which a latent image is formed inside the grain, or a type having a latent image both on the surface and inside. It must be a negative emulsion. Among the internal latent image type emulsions, core / shell type internal latent image type emulsions described in JP-A-63-264740 may be used. This core /
A method for preparing a shell type internal latent image type emulsion is described in JP-A-59-1
No. 33542. The thickness of the shell of this emulsion varies depending on development processing and the like, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

The silver halide emulsion is usually one which has been physically ripened, chemically ripened and spectrally sensitized. The additives used in such a process are the above-mentioned Research Disclosure No. 17643, No. 18716 and No. 18716.
No. 307105, the relevant parts are summarized in the table below.

The light-sensitive material of the present invention comprises a photosensitive silver halide emulsion having a grain size, a grain size distribution, a halogen composition,
Two or more kinds of emulsions having different characteristics of at least one of grain shape and sensitivity can be mixed and used in the same layer.

The fogged silver halide grains described in US Pat. No. 4,082,553 and the fogged grains described in US Pat. No. 4,626,498 and JP-A-59-214852 are fogged. The prepared silver halide grains and colloidal silver can be preferably used in the photosensitive silver halide emulsion layer and / or the substantially non-photosensitive hydrophilic colloid layer. What is a silver halide grain whose inside or surface is fogged?
It is a silver halide grain that enables uniform (non-imagewise) development regardless of the unexposed area and exposed area of the light-sensitive material. A method for preparing a silver halide grain whose inside or surface is fogged is described in US Pat. No. 4,626,498 and JP-A-59-214852.

The silver halide forming the inner core of the fogged core / shell type silver halide grain 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. The grain size of these fogged silver halide grains is not particularly limited, but the average grain size is 0.01 to 0.7.
It is preferably 5 μm, particularly preferably 0.05 to 0.6 μm. Also,
The grain shape is not particularly limited and may be regular grains or polydisperse emulsion, but monodisperse grains (at least 95% of the weight or the number of silver halide grains are within ± 40% of the average grain size). It is preferable that the particles have a particle size of

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 silver halide grain 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.

The fine grain silver halide preferably has an average grain size (average value of the equivalent circle diameters of the projected area) of 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 optically 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.

Known photographic additives that can be used in the present invention are also described in the above-mentioned three Research Disclosures, and the related portions are shown in the following table. Types of additives RD17643 RD18716 RD307105 December 1978 November 1979 November 1989 1 Chemical sensitizer page 23 648 right column page 866 2 Sensitivity enhancer page 648 right column 3 Spectral sensitizer, pages 23-24 Page 648 Right column 866 to 868 Supersensitizer to page 649 Right column 4 Whitening agent Page 24 647 Page right column 866 Page 5 Antifoggant, Page 24 to 25 Page 649 Right column 868 to 870 Stabilizer 6 Light absorber, pages 25 to 26, page 649, right column to page 873, filter dye, page 650, left column, UV absorber 7 stain inhibitor page 25, right column, page 650, left column, page 872 to right column 8, dye image stabilizer, page 25, 650 Page left column 872 Page 9 Hardener 26 page 651 Page left column 874 to 875 page 10 Binder page 26 Same as above 873 to 874 page 11 Plasticizer and lubricant page 27 650 page right column page 876 12 Coating aid, 26 to 27 Page ibid. Page 875 to 876 surface active agent 13 static protection page 27 ibid. Page 876 to 877 stop agent 14 matting agent page 878 to 879

In order to prevent deterioration of photographic performance due to formaldehyde gas, US Pat. No. 4,411,9
It is preferable to add a compound capable of being immobilized by reacting with formaldehyde described in No. 87 and No. 4,435,503 to the light-sensitive material. The light-sensitive material of the present invention can be incorporated into U.S. Pat.
JP-A-62-18539, JP-A-1-28355
It is preferable that the mercapto compound described in No. 1 is contained. A compound described in JP-A No. 1-106052, which releases a fogging agent, a development accelerator, a silver halide solvent or a precursor thereof, to the light-sensitive material of the present invention, irrespective of the amount of developed silver produced by the development processing. Is preferably contained. In the light-sensitive material of the present invention, the international publication WO88 / 04
No. 794, Dyes dispersed by the method described in JP-A-1-502912 or EP317,308A, US Pat. No. 4,420,555, JP-A-1-259358.
It is preferable to incorporate the dyes described in No.

Various color couplers can be used in the present invention, and specific examples thereof include Research Disclosure (RD) No. 17643, VII-C to G, and No. 307105, VII-C. ~ G.

Examples of yellow couplers include US Pat. Nos. 3,933,501 and 4,022,620.
Issue No. 4,326,024, No. 4,401,75
No. 2, No. 4,248,961, Japanese Patent Publication No. 58-107.
39, British Patent Nos. 1,425,020 and 1,4
76,760, U.S. Pat. Nos. 3,973,968, 4,314,023, 4,511,649,
Those described in European Patent No. 249,473A and the like are preferable.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat. Nos. 4,310,619 and 4,351,897 are preferred.
No., EP 73,636, US Pat. No. 3,06
1,432, 3,725,067, Research
Disclosure No. 24220 (June 1984)
, JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, 61-72238, 60-.
No. 35730, No. 55-118034, No. 60-18.
Those described in US Pat. No. 5951, US Pat. No. 4,500,630, US Pat. No. 4,540,654, US Pat.

Examples of cyan couplers include phenol type and naphthol type couplers, and US Pat.
52,212, 4,146,396, and 4,
No. 228,233, No. 4,296,200, No. 2,369,929, No. 2,801,171, No. 2,772,162, No. 2,895,826,
No. 3,772,002, No. 3,758,308
No. 4,334,011, No. 4,327,17
3, West German Patent Publication No. 3,329,729, European Patent Nos. 121,365A, 249,453A, U.S. Patents 3,446,622, 4,333,999.
No. 4,775,616, No. 4,451,55
9, No. 4,427,767, No. 4,690,8
89, 4,254,212 and 4,296,4
Those described in JP-A No. 199, JP-A-61-42658 and the like are preferable. Further, JP-A 64-553 and 64-5.
54, 64-555 and 64-556, and pyrazoloazole couplers described in US Pat. No. 4,811.
The imidazole couplers described in No. 8,672 can also be used.

Typical examples of polymerized dye-forming couplers are shown in US Pat. Nos. 3,451,820 and 4,084.
No. 0,211, No. 4,367,282, No. 4,4
09,320, 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,
British Patent 2,125,570, European Patent 96,57
Those described in No. 0 and West German Patent (Publication) No. 3,234,533 are preferable.

Colored couplers for correcting unwanted absorption of color forming dyes are described in Research Disclosure No.
176-Section VII-G, No. 307105, VII-
Section G, U.S. Pat. No. 4,163,670, Japanese Patent Publication No. 57-
39413, U.S. Pat. Nos. 4,004,929, 4,138,258, and British Patent 1,146,368.
Those described in No. 10 are preferable. Also, US Pat.
A coupler for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in 4,181,
It is also preferable to use a coupler described in U.S. Pat. No. 4,777,120 having a dye precursor group capable of reacting with a developing agent to form a dye 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 RD1 described above.
7643, Item VII-F and Id. No. 307105, VII-
Patents described in paragraph F, JP-A-57-151944,
Those described in U.S. Pat. Nos. 57-154234, 60-184248, 63-37346, 63-37350, and U.S. Pat. Nos. 4,248,962 and 4,782,012 are preferable.

As a coupler which releases a nucleating agent or a development accelerator imagewise during development, there is described in British Patent 2,093.
7,140, 2,131,188, JP-A-59.
Those described in Nos. 157638 and 59-170840 are preferable. Further, JP-A-60-107029, JP-A-60-252340, JP-A-1-44940 and JP-A-1-4940.
Compounds releasing a fog agent, a development accelerator, a silver halide solvent and the like by an oxidation-reduction reaction with an oxidized product of a developing agent described in JP-A-45687 are also preferable.

Other compounds that can be used in the light-sensitive material of the present invention include US Pat. No. 4,130,427.
Couplers described in U.S. Pat. No. 4,283,4
No. 72, No. 4,338,393, No. 4,310,
No. 618 and the like, multiequivalent couplers, JP-A-60-18.
5950, DI described in JP-A-62-24252, etc.
R redox compound-releasing coupler, DIR coupler-releasing coupler, DIR coupler-releasing redox compound or DIR redox-releasing redox compound, coupler releasing a dye that recolors after separation described in European Patent Nos. 173,302A and 313,308A , RDNo.11
449, No. 24241, JP-A-61-201247.
Bleach accelerator releasing couplers described in U.S. Pat.
Examples thereof include a ligand releasing coupler described in US Pat. No. 555,477, a coupler releasing a leuco dye described in JP-A-63-75747, and a coupler releasing a fluorescent dye described in US Pat. No. 4,774,181. Be done.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods. Examples of high boiling point solvents used in the oil-in-water dispersion method are described in US Pat. No. 2,322,222.
No. 027 and the like.

Specific examples of the high-boiling 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, bis (2,4-di-t-amylphenyl) phthalate, bis (2,4-di-t-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate, etc.), phosphoric acid or Esters of phosphonic acid (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-) Diethyl dodecane amide, N, N-diethyl lauryl amide, N-tetradecyl pyrrolidone, etc.),
Alcohols or phenols (isostearyl alcohol, 2,4-di-t-amylphenol, etc.), aliphatic carboxylic acid esters (bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate) , Trioctyl citrate, etc.), aniline derivatives (N, N-dibutyl-2-butoxy-5-t-octylaniline, etc.), hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.) and the like. The auxiliary solvent has a boiling point of about 30 ° C. or higher, preferably 5
An organic solvent having a temperature of 0 ° C. or higher and about 160 ° C. or lower can be used, and typical examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate and dimethylformamide.

The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in US Pat. No. 4,199,36.
No. 3, 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-62-257747 are used.
No. 272248 and 1,2-benzisothiazolin-3-one, n-butyl p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol, 2 described in JP-A No. 1-80941. It is preferable to add various preservatives or antifungal agents such as-(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 described in, for example, RD. No. 17643, page 28, No. 18
716, right column, page 647 to left column, page 648, and No. 3 of the same.
07105, page 897. The photosensitive material of the present invention preferably has a film swelling speed T _1/2 of 30 seconds or less.
0 second or less is more preferable. The film thickness is 25 ° C, relative humidity 55
% Mean film thickness measured under humidity control (2 days), and the film swelling rate T _1/2 can be measured according to a method known in the art. For example, A Green (A. Gre
en) et al., Photographic Science and Engineering (Photogr. Sci Eng.), Volume 19,
It can be measured by using a swellometer (swelling meter) of the type described in No. 2, pages 124 to 129, and T _1/2 is the maximum reached when processed with a color developer at 30 ° C. for 3 minutes and 15 seconds. 90% of the swollen film thickness is the saturated film thickness,
It is defined as the time to reach 2.

The film swelling speed T _1/2 can be adjusted by adding a film hardening agent to gelatin as a binder, or by changing the aging condition after coating. The swelling rate is preferably 150 to 400%. The swelling rate is calculated from the maximum swollen film thickness under the above-mentioned conditions by the formula:
It can be calculated according to (maximum swollen film thickness-film thickness) / film thickness.
The light-sensitive 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 to 500%
Is preferred.

[0214]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

Example 1 On a subbed cellulose triacetate film support,
A sample 101, which is a multi-layer color light-sensitive material having the following composition, was prepared. The amount coated amount (Composition of photosensitive layer) is represented in units of g / m ² of silver for silver halide and colloidal silver, also couplers, the amount for the additives and gelatin, expressed in units of g / m ^2, The sensitizing dyes are shown by the number of moles per mole of silver halide in the same layer. The symbols indicating additives have the following meanings. However, when there are multiple effects, one of them is listed as a representative. UV: UV absorber, Solv: Light boiling organic solvent, Ex
F: Dye, ExS: Sensitizing dye, ExC: Cyan coupler, ExM: Magenta coupler, ExY: Yellow coupler, Cpd: Additive

First Layer (Antihalation Layer) Black Colloidal Silver 0.15 Gelatin 1.98 ExM-2 0.11 UV-1 3.0 × 10 ^-2 UV-2 6.0 × 10 ^-2 UV-3 7.0 × 10 ⁻² Solv-1 0.16 Solv-2 0.10 ExF-1 1.0 × 10 ⁻² ExF-2 4.0 × 10 ⁻² ExF-3 5.0 × 10 ⁻³ Cpd -6 1.0 x 10 ^-3

Second Layer (Low Sensitivity Red Sensitive Emulsion Layer) Silver iodobromide emulsion (AgI 4.0 mol%, uniform AgI type, sphere equivalent diameter 0.4 μm, variation coefficient of sphere equivalent diameter 30%, plate-like grain , Diameter / thickness ratio 3.0) coated silver amount 0.25 silver iodobromide emulsion (AgI 6.0 mol%, internal high AgI type with core-shell ratio 1: 2, sphere equivalent diameter 0.45 μm, sphere equivalent diameter Coefficient of variation 23%, plate-like particles, diameter / thickness ratio 2.0) Coating amount of silver 0.15 Gelatin 0.65 ExS-1 2.4 × 10 ^-4 ExS-2 1.4 × 10 ^-4 ExS- 5 2.3 × 10 ⁻⁴ ExS-7 4.1 × 10 ⁻⁶ ExC-1 9.0 × 10 ⁻² ExC-2 2.0 × 10 ⁻² ExC-3 4.0 × 10 ⁻² ExC− 4 2.0 × 10 ⁻² ExC-5 8.0 × 10 ⁻² ExC-6 2.0 × 10 ⁻² ExC-9 1.0 × 10 ⁻²

Third Layer (Medium Sensitivity Red Sensitive Emulsion Layer) Silver iodobromide emulsion (AgI 6.0 mol%, internal high AgI type with core-shell ratio 1: 2, equivalent sphere diameter 0.65 μm, variation in equivalent sphere diameter) Coefficient 23%, plate-like particles, diameter / thickness ratio 2.0) Coating amount of silver 0.65 Gelatin 1.24 ExS-1 2.4 × 10 ^-4 ExS-2 1.4 × 10 ^-4 ExS-5 2.4 × 10 ⁻⁴ ExS-7 4.3 × 10 ⁻⁶ ExC-1 0.19 ExC-2 1.0 × 10 ⁻² ExC-3 2.5 × 10 ⁻² ExC-4 1.6 × 10 ^-2 ExC-5 0.19 ExC-6 2.0 x 10 ^-2 ExC-7 3.0 x 10 ^-2 ExC-8 1.0 x 10 ^-2 ExC-9 3.0 x 10 ^-2

Fourth Layer (High-Sensitivity Red-Sensitive Emulsion Layer) Silver iodobromide emulsion (9.3 mol% of AgI, multi-structured grains having a core-shell ratio of 3: 4: 2, AgI content of 24, 0, 6 Mol%, equivalent sphere diameter 0.75 μm, variation coefficient of equivalent sphere diameter 23%, plate-like particles, diameter / thickness ratio 2.5) Coating silver amount 1.00 Gelatin 1.18 ExS-1 2.0 × 10 ^{− 4} ExS-2 1.1 × 10 ⁻⁴ ExS-5 1.9 × 10 ⁻⁴ ExS-7 1.4 × 10 ⁻⁵ ExC-1 8.0 × 10 ⁻² ExC-4 9.0 × 10 ^{− 2} ExC-6 2.0 x 10 ^-2 ExC-9 1.0 x 10 ^-2 Solv-1 0.20 Solv-2 0.53

Fifth layer (intermediate layer) Gelatin 0.53 Cpd-1 0.13 Polyethyl acrylate latex 8.0 × 10 ⁻² Solv-1 8.0 × 10 ⁻²

Sixth Layer (Low Sensitivity Green Sensitive Emulsion Layer) Silver iodobromide emulsion (AgI 4.0 mol%, uniform AgI type, sphere equivalent diameter 0.45 μm, variation coefficient of sphere equivalent diameter 15%, plate-like grain , Diameter / thickness ratio 4.0) amount of coated silver 0.12 gelatin 0.28 ExS-3 1.0 × 10 ⁻⁴ ExS-4 3.1 × 10 ⁻⁴ ExS-5 6.4 × 10 ⁻⁵ ExM -1 0.12 ExM-3 2.1x10 ^-2 Solv-1 0.09 Solv-4 7.0x10 ^-3

Seventh Layer (Medium-Sensitivity Green Sensitive Emulsion Layer) Silver iodobromide emulsion (AgI 4.0 mol%, uniform AgI type, sphere equivalent diameter 0.65 μm, variation coefficient of sphere equivalent diameter 18%, tabular grains , Diameter / thickness ratio 4.0) coated silver amount 0.29 gelatin 0.46 ExS-3 2.7 × 10 ^-4 ExS-4 8.2 × 10 ^-4 ExS-5 1.7 × 10 ^-4 ExM -1 0.27 ExM-3 7.2 × 10 -2 ExY-1 5.4 × 10 -2 Solv-1 0.23 Solv-4 1.8 × 10 -2

Eighth Layer (High-Sensitivity Green Sensitive Emulsion Layer) Silver iodobromide emulsion (AgI 9.8 mol%, multi-structured grains having a silver amount ratio of 3: 4: 2, AgI content of 24, 0, 3 from the inside). Mol%, equivalent sphere diameter 0.81 μm, variation coefficient of equivalent sphere diameter 23%, multiple twin plate-like particles, diameter / thickness ratio 2.5) Coating silver amount 0.45 Gelatin 0.52 ExS-4 4.3 × 10 ^-4 ExS-5 8.6 × 10 ^-5 ExS-8 2.8 × 10 ^-5 ExM-4 1.0 × 10 ^-2 ExM-5 1.0 × 10 ^-2 ExM-6 3.0 × 10 ^-2 ExY-1 0.5 × 10 ^-2 ExC-1 0.4 × 10 ^-2 ExC-4 2.5 × 10 ^-3 ExC-6 0.5 × 10 ^-2 Solv-1 0.12 Cpd-8 1.0 × 10 ^-2

Ninth layer (intermediate layer) Gelatin 0.49 Cpd-1 4.0 × 10 ^-2 Polyethyl acrylate latex 5.0 × 10 ^-2 Solv-1 3.0 × 10 ^-2 UV-4 3. ^{0x10 -2} UV-5 4.0x10 ^-2

10th layer (donor layer having a multilayer effect on the red-sensitive layer) Silver iodobromide emulsion (AgI 8.0 mol, internal high AgI type grain having a core-shell ratio of 1: 2, sphere equivalent diameter 0.72 μm, sphere) Coefficient of variation of equivalent diameter 28%, multiple twinned plate-like grains, diameter / thickness ratio 2.0) Coating silver amount 0.54 Silver iodobromide emulsion (AgI 10.0 mol, core-shell ratio 1: 3, high internal AgI) Type particles, sphere equivalent diameter 0.40 μm, variation coefficient of sphere equivalent diameter 15%, normal crystal grains) coated silver amount 0.22 gelatin 0.74 ExS-3 6.7 × 10 ⁻⁴ ExM- ⁴ Solv-10 .30 Solv-6 3.0 × 10 ^-2

Eleventh layer (yellow filter layer) Yellow colloidal silver 9.0 × 10 ^-2 gelatin 0.72 Cpd-2 0.13 Solv-1 0.13 Cpd-1 5.0 × 10 ^-2 Cpd-6 2.0 x 10 ^-3 H-1 0.25

Twelfth Layer (Low Sensitivity Blue Sensitive Emulsion Layer) Silver iodobromide emulsion (AgI 9.0 mol%, multi-structured grain, spherical equivalent diameter 0.70 μm, variation coefficient of spherical equivalent diameter 20%, tabular grain) , Diameter / thickness ratio of 7.0, and 200 kV observed by a transmission electron microscope include particles having 10 or more dislocation lines inside the particles in an amount of 50% or more of all the particles.) Silver coating amount 0.40 Iodobromide Silver emulsion (AgI 2.5 mol%, uniform AgI type, equivalent sphere diameter 0.50 μm, coefficient of variation of equivalent sphere diameter 30%, tabular grains, diameter / thickness ratio 6.0) Silver coating amount 0.28 Gelatin 1 .90 ExS-6 9.0 × 10 ^-4 ExC-1 0.05 ExC-2 0.10 ExY-2 0.05 ExY-3 0.10 ExY-5 1.00 Solv-1 0.54

Thirteenth Layer (Intermediate Layer) Gelatin 0.26 ExY-4 0.14 Solv-1 0.14

Fourteenth Layer (High Sensitivity Blue Sensitive Emulsion Layer) Silver iodobromide emulsion (AgI 10.0 mol%, internal high AgI type grains, sphere equivalent diameter 1.2 μm, variation coefficient of sphere equivalent diameter 25%, multiplex Twinned plate-like particles, diameter / thickness ratio of 2.0) Coating amount of silver 0.40 Gelatin 0.50 ExS-6 2.6 × 10 ⁻⁴ ExY-2 1.0 × 10 ⁻² ExY-3 0.20 ExC-1 1.0 × 10 ^-2 Solv-1 9.0 × 10 ^-2

Fifteenth Layer (First Protective Layer) Fine grain silver iodobromide emulsion (AgI 2.0 mol%, uniform AgI type, sphere equivalent diameter 0.07 μm) Coating amount of silver 0.09 Gelatin 0.55 UV- 4 0.11 UV-5 0.18 Solv-5 2.0 × 10 ⁻² Cpd-5 0.10 Polyethyl acrylate latex 9.0 × 10 ⁻²

Sixteenth Layer (Second Protective Layer) Fine grain silver iodobromide emulsion (AgI 2.0 mol%, uniform AgI type, sphere equivalent diameter 0.07 μm) Coating amount of silver 0.27 Gelatin 0.80 B- 1 (diameter 2.0 μm) 8.0 × 10 ⁻² B-2 (diameter 2.0 μm) 8.0 × 10 ⁻² B-3 2.0 × 10 ⁻² W-4 2.0 × 10 ⁻² H-1 0.18

In addition to the above, the samples thus prepared were
1,2-benzisothiazolin-3-one (average 200 ppm relative to gelatin), n-butyl-p-hydroxybenzoate (about 1000 ppm the same), and 2-phenoxyethanol (about 10,000 ppm the same) were added. Furthermore, B-4, B-5, B-6, F-1, F-
2, F-3, F-4, F-5, F-6, F-7, F-
8, F-9, F-10, F-11, F-12 and iron salt, lead salt, gold salt, platinum salt, iridium salt and rhodium salt are contained.

In addition to the above components, each layer contains a surfactant W.
-1, W-2, and W-3 were added as a coating aid or an emulsifying dispersant. The chemical structural formulas of the compounds used in the present invention are shown below.

[0234]

[Chemical 48]

[0235]

[Chemical 49]

[0236]

[Chemical 50]

[0237]

[Chemical 51]

[0238]

[Chemical 52]

[0239]

[Chemical 53]

[0240]

[Chemical 54]

[0241]

[Chemical 55]

[0242]

[Chemical 56]

[0243]

[Chemical 57]

[0244]

[Chemical 58]

[0245]

[Chemical 59]

[0246]

[Chemical 60]

[0247]

[Chemical formula 61]

[0248]

[Chemical formula 62]

[0249]

[Chemical 63]

[0250]

[Chemical 64]

[0251]

[Chemical 65]

[0252]

[Chemical 66]

Sample 101 had a silver content of 5.2 g / m ² and a total dry film thickness of 19.5 μm.

(Samples 102 to 104) Sample 10 was prepared by reducing the amount of silver in each layer of Sample 101 to 90%, 80% and 70%.
2, 103 and 104 were produced. (Samples 105 to 108) Samples 105 to 108 were prepared by replacing ExM-4 of the eighth and tenth layers of Samples 101 to 104 with the compound (18) of the present invention in an equimolar amount. (Samples 109 to 115) Eighth Layer and First of Sample 103
Replace ExM-4 of layer 0 as shown in Table 2 to obtain sample 109
~ 115 were produced. (Samples 116 to 118) The gelatin in each layer of Sample 115 was reduced by 20%, increased by 15% and increased by 30% to increase the amount of Samples 116 to 118.
118 was produced. Table 2 shows the silver content and the total dry film thickness of the obtained sample. When the specific photographic sensitivity defined in the present invention was determined, it was between 140 and 150 for all the samples. After subjecting these samples to green imagewise exposure, uniform blue exposure was carried out to obtain a yellow density of 1.
The following development processing is carried out by giving a color density of 6 and the value obtained by subtracting the yellow density in the green unexposed area from the yellow density at the point of giving a magenta density of 1.5 is the color turbidity (ΔD
_B ) asked as. As for sharpness, the following development processing is performed to obtain a conventional MTF (Modulation Transfer Function).
) Method, magenta image 20 cycles / mm M
The TF value was calculated.

Further, the following development processing was carried out except that the white light of 40 lux · sec was given to these samples and the bleaching time was changed to 30 seconds, 40 seconds and 2 minutes. The magenta density was measured at a point of giving 0.5. The value obtained by subtracting the density for 2 minutes from the magenta density at bleaching times of 30 seconds and 40 seconds is shown in Table 2 as the desilvering defective density (ΔD _AG ). Further, two of the same samples were exposed at the same time in a white imagewise manner and left at 25 ° C. relative humidity 65% (A condition) and 50 ° C., 30% (B condition) for 14 days, and the following development processing was performed. Table 2 shows the variation value (ΔS _0.5 ) of the relative sensitivity of the B condition represented by the logarithm of the reciprocal of the exposure amount giving the magenta density (fog + 0.5) with respect to the A condition.
In addition, regarding the processed samples, the relative humidity at 80 ℃ and 70%
The before and after storage at conditions 7 days of a change value of the magenta minimum density was evaluated as the dye stability (△ D _G). The results are also shown in Table 2. The development process for evaluating the color image storability was also performed according to the following steps.

In each processing, an automatic processor FP-560B manufactured by Fuji Photo Film Co., Ltd. was used. (Processing step) Processing time Processing temperature Replenishment amount * Tank dissolution amount Color development 3 minutes 5 seconds 38.0 ° C 600 ml 17 liters Bleach 50 seconds 38.0 ° C 140 ml 5 liters Bleach fixing 50 seconds 38.0 ° C-5 liters Fixed 50 seconds 38.0 ℃ 420 ml 5 liter Water wash 30 seconds 38.0 ℃ 980 ml 3.5 liter Stability (1) 20 seconds 38.0 ℃ −3 liter Stability (2) 20 seconds 38.0 ℃ 560 ml 3 liter Dry 1 minute 30 seconds 60 ℃ * The amount of replenishment was a countercurrent system from the stabilizing solution (2) to the solution (1) per 1 m ² of the light-sensitive material, and the overflow solution of the washing water was all introduced into the fixing bath. When replenishing the bleach-fixing bath, a cutout is provided at the top of the bleaching tank of the automatic developing machine and 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 process, the amount of bleach-fixing solution brought into the fixing process, and the amount of fixing solution brought into the water-washing process are respectively per 1 m ² of the light-sensitive material. They were 65 ml, 50 ml, 50 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 processing 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 Potassium iodide 1.3 mg-hydroxylamine sulfate 2.4 3.3 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] 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-Diaminopropaneferric 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)

(Fixer) Tank solution (g) Replenisher (g) Ammonium sulfite 19 57 Ammonium thiosulfate aqueous solution (700 g / liter) 280 mm 840 ml liter Imidazole 15 45 Ethylenediaminetetraacetic acid 15 45 Water 1.0 liter 1.0 Liter pH [prepared with ammonia water 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 / l was added. The pH of this solution is 6.5 to 7.
It was in the range of 5.

(Stabilizer) Common to tank liquid and replenisher (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

[0263]

[Table 2]

From Table 2, the sample of the present invention is excellent in color reproducibility represented by color turbidity and sharpness represented by MTF value.
There is little fluctuation in photographic performance during storage (relative sensitivity fluctuation), good desilvering property, and color image storage stability after processing is stable without causing magenta color increase unlike samples using conventional compounds. I know there is. It has also been clarified that the effect of the present invention is more preferably exhibited when the dry total film thickness is thin.

Example 2 Gamma and color turbidity were determined in the following normal treatment I and short-time treatment II. The color turbidity was determined by the same method as in Example 1. Gamma was determined as the slope of a straight line connecting the points of magenta density (fog + 0.2) and (fog + 1.2). Further, the difference in magenta density between the treatment II in which white light of 40 lux · sec was applied and the treatment III in which sufficient desilvering was performed is shown in Table 5 as the defective desilvering concentration in accordance with Example 1.

[0266]

[Table 3]

(Color developer) Mother liquor (g) Replenisher (g) Diethylenetriaminepentaacetic acid 5.0 6.0 Sodium sulfite 4.0 6.0 Potassium carbonate 30.0 37.0 Potassium bromide 1.0 0.2 Potassium iodide 1.2 mg Hydroxylamine sulfate 2.5 4.2 4- ( N-ethyl-N-β-hydroxyethylamino) -2-methylaniline 4.7 7.5 Sulfate (0.015 mol) (0.024 mol) Add water 1.0 liter 1.0 liter pH 10.00 10.20

(Bleach) Mother liquor (g) Replenisher (g) 1,3-Diaminopropanetetraacetic acid ferric salt 140 140 Ethylenediaminetetraacetic acid 4.0 5.0 Ammonium bromide 160.0 220.0 Ammonium nitrate 30.0 50.0 Ammonia water (27%) 20.0 ml 23.0 ml Acetic acid (90%) 35.0 50.0 Hydroxyacetic acid (70%) 98.0 140.0 Add water 1.0 liter 1.0 liter pH 3.9 2.5

(Fixer) Mother liquor (g) Replenisher (g) Ethylenediaminetetraacetic acid disodium salt 0.5 0.7 Ammonium sulfite 15.0 25.0 Sodium bisulfite 5.0 10.0 Ammonium thiosulfate aqueous solution (700 g / l) 270.0 ml 320.0 ml Water was added. 1.0 liter 1.0 liter pH 6.7 6.6

(Stabilizer) Mother liquor and replenisher common (unit: g) Tap water 1.0 liter Formalin (37%) 1.2 ml 5-chloro-2-methyl-4-isothiazolin-3-one 6.0 ml 2-methyl-4 - isothiazolin-3-one 3.0 ml surfactant _{[C 10 H 21 -O- (CH 2} CH 2 O) 10 -H ] 0.4 ethylene glycol 1.0 pH 7.0

[0271]

[Table 4]

(Color developer) Mother liquor (g) Replenisher (g) Diethylenetriaminepentaacetic acid 5.0 6.0 Sodium sulfite 2.0 4.0 Potassium carbonate 35.0 42.0 Potassium bromide 1.4 0.0 Potassium iodide 1.2 mg Hydroxylamine sulfate 2.0 3.8 4- ( N-ethyl-N-β-hydroxyethylamino) -2-methylaniline 6.0 8.8 Sulfate (0.019 mol) (0.028 mol) 4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 0.05 0.08 1-Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 0.005 0.01 Water added 1.0 liter 1.0 liter pH 10.55 10.80

(Bleaching solution, fixing solution, stabilizing solution) Same as Process I.

Processing III The same as processing II except that the bleaching time of processing II was 3 minutes and the fixing time was 3 minutes.

[0275]

[Table 5]

From Table 5, the sample of the present invention shows sufficient gamma and low color turbidity even in the treatment II in which the color development time is short with respect to the treatment I, and has sufficient colorability and excellent color reproducibility. I understood it. Further, desilvering was sufficiently completed even in the processing II, which had a shorter bleaching and fixing time than the processing III, and it was shown that the photosensitive material was also excellent in rapid processing suitability.

[0277]

As described above, according to the present invention, color reproducibility,
It has been shown that it is possible to provide a light-sensitive material which is excellent in sharpness and storability of magenta images, storage stability and suitability for rapid processing.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] June 8, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 2

[Correction method] Change

[Correction content]

[Chemical 2] General formula (III)

[Chemical 3] In the formula, R ₁ represents a hydrogen atom, an alkyl group or an aryl group. Z ₁ and Z ₂ are each a nitrogen atom or = C
Represents (R ₂ )-, and when Z ₁ is a nitrogen atom, Z ₂ is = C.
(R ₂ )-, when Z ₁ is = C (R ₂ )-, Z ₂ is a nitrogen atom, and R ₂ represents a hydrogen atom or a substituent. R ₃ represents a hydroxyl group or a sulfonamide group, and n
Represents 1 or 2. R ₄ has a Hammett σ _p value of 0.
And R ₅ represents a hydrogen atom or a group capable of substituting for a benzene ring. R ₆ has the same meaning as R ₁ . X ₁ and X ₂ represent a development inhibitor or its precursor.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0063

[Correction method] Change

[Correction content]

Of the groups represented by the general formula (X-1),
Particularly preferred are the following general formulas (X-2) and (X-3)
And (X-4). Formula _{(X-2) - (L} 1) - (B) -DI Formula _{(X-3) - (L} 2) -DI Formula (X-4) -DI _wherein, L _{1, L} 2, B and DI have the same meanings as L ₁ , L ₂ , B and DI in formula (X-1). In the compound represented by the general formula (I), when X is a group capable of splitting off with an oxygen atom, R is a hydrogen atom, an alkyl group or an aryl group from the viewpoint of the coupling reaction rate with the oxidized form of the developing agent. preferable. In particular, X is a general formula (B-1)
The compound represented by the general formula (II) which leaves at the group represented by is preferable. In the general formula (II), R ₁ represents a hydrogen atom, an alkyl group or an aryl group, and specifically represents a substituent having the same meaning as the alkyl group and the aryl group exemplified for R in the general formula (I). In the general formula (II), R ₂ is a hydrogen atom or a substituent, and specifically represents a substituent having the same meaning as R in the general formula (I). General formula (I
In I), R ₃ represents a hydroxyl group or a sulfonamide group, and the sulfonamide group may be further substituted with the alkyl group or aryl group exemplified for R in the general formula (I). In the general formula (II), R ₄ represents a substituent having a Hammett's σ _p value of 0.3 or more, which is particularly preferable for improving the storage stability in the light-sensitive material.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0064

[Correction method] Change

[Correction content]

As the substituent having a Hammett's σ _p value of 0.3 or more, a halogenated alkyl group (eg, trichloromethyl, trifluoromethyl, heptafluoropropyl), a cyano group, an acyl group (eg, formyl, acetyl, Benzoyl), an alkoxycarbonyl group (for example,
Methoxycarbonyl, propyloxycarbonyl), an aryloxycarbonyl group (eg, phenoxycarbonyl), a carbamoyl group (eg, N-methylcarbamoyl, N-propylcarbamoyl), a sulfamoyl group (eg, N, N-dimethylsulfamoyl), Sulfonyl group (eg, methanesulfonyl, benzenesulfonyl), thiocyanato group, nitro group, phosphinyl group (eg, diethylphosphinyl, dimethylphosphinyl), heterocyclic group (eg, 1-pyrrolyl, 2-benzoxazolyl) ) And the like. Below is Hammett's σ
Specific examples of the group having a _p value of 0.3 or more are shown below, but the present invention is not limited thereto. The numerical value in parentheses indicates the σ _p value of the substituent. The σ _p value was quoted from “Structure-Activity Relationship of Drugs” (Chemical Science Special Issue No. 122, Nankodo). _{-CO 2 C 2 H 5 (0.45} ) -CO
_{NHCH 3 (0.36) -CF 2 CF} 2 CF 2 CF 3 (0.52)
_{-C 6 F 5 (0.41) -COCH} 3 (0.50) -COC
₆ H ₅ (0.43) -P (O) (OCH ₃ ) ₂ (0.53)-
_{SO 2 NH 2 (0.57) -SCN} (0.52) -CO 2 C
₆ H ₅ (0.44) -CO ₂ CH ₃ (0.45) -CO
_{NH 2 (0.36) - (CF} 2) 3 CF 3 (0.52) -C
N (0.66) In the general formula (II), R ₅ represents a hydrogen atom or a group capable of substituting for a benzene ring, and specifically represents a substituent having the same meaning as R in the general formula (I). In the general formula (II),
X ₁ represents a development inhibitor or a precursor thereof, and specifically represents a group having the same meaning as X in formula (I).

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0065

[Correction method] Change

[Correction content]

In the compound represented by the general formula (I), when X is a group capable of leaving at a nitrogen atom or a sulfur atom, R is an alkoxy group or an aryloxy group and represented by the general formula (III). The compound is preferable in terms of the rate of coupling reaction with the oxidized product of the developing agent. In the general formula (III), R ₆ is the general formula (II).
It represents the _{R 1} group having the same meaning as, _{R 2} is the general formula (II) R
₂ represents a group having the same meaning as ₂ , and X ₂ represents a group having the same meaning as X in formula (I). However, X ₂ does not include a group represented by the general formula (B-1) in X of the general formula (I).
Further, in the general formula (III), having a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group as the substituent R ₂ of the azole ring portion is advantageous in terms of storage stability in the light-sensitive material. It is particularly preferable to have an aryl group.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Name of item to be corrected] 0066

[Correction method] Change

[Correction content]

General formulas [P-1], [P-2], [P-
Among the compounds represented by 3] and [P-4], those particularly preferable in terms of the hue of the magenta dye formed are represented by formulas [P-1], [P-2] and [P-3]. Those represented by the general formula [P-2] or [P-3] are more preferable.

[Procedure Amendment 6]

[Document name to be amended] Statement

[Correction target item name] 0073

[Correction method] Change

[Correction content]

[0073]

[Chemical formula 23]

[Procedure Amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0079

[Correction method] Change

[Correction content]

[0079]

[Chemical 29]

[Procedure Amendment 8]

[Document name to be amended] Statement

[Correction target item name] 0105

[Correction method] Change

[Correction content]

[0105]

[Chemical 45]

[Procedure Amendment 9]

[Document name to be amended] Statement

[Correction target item name] 0215

[Correction method] Change

[Correction content]

Example 1 On a subbed cellulose triacetate film support,
A sample 101, which is a multi-layer color light-sensitive material having the following composition, was prepared. The amount coated amount (Composition of photosensitive layer) is represented in units of g / m ² of silver for silver halide and colloidal silver, also couplers, the amount for the additives and gelatin, expressed in units of g / m ^2, The sensitizing dye is shown by the number of moles per mole of silver halide in the same layer. The symbols indicating additives have the following meanings. However, when there are multiple effects, one of them is listed as a representative. UV: UV absorber, Solv: High boiling organic solvent, Ex
F: Dye, ExS: Sensitizing dye, ExC: Cyan coupler, ExM: Magenta coupler, ExY: Yellow coupler, Cpd: Additive

[Procedure Amendment 10]

[Document name to be amended] Statement

[Name of item to be corrected] 0225

[Correction method] Change

[Correction content]

10th layer (donor layer having a layering effect on the red-sensitive layer) Silver iodobromide emulsion (AgI 8.0 mol, internal high AgI type grain having a core-shell ratio of 1: 2, sphere equivalent diameter 0.72 μm, sphere) Coefficient of variation of equivalent diameter 28%, multiple twinned plate-like grains, diameter / thickness ratio 2.0) Coating silver amount 0.54 Silver iodobromide emulsion (AgI 10.0 mol, core-shell ratio 1: 3, high internal AgI) Type particles, sphere equivalent diameter 0.40 μm, variation coefficient of sphere equivalent diameter 15%, normal crystal grains) coated silver amount 0.22 gelatin 0.74 ExS-3 6.7 × 10 ⁻⁴ ExM-4 0.18 Solv -1 0.30 Solv-6 3.0x10 ^-2

[Procedure Amendment 11]

[Document name to be amended] Statement

[Correction target item name] 0255

[Correction method] Change

[Correction content]

Further, the following development processing was carried out except that the white light of 40 lux · sec was given to these samples and the bleaching time was changed to 30 seconds, 40 seconds and 2 minutes. The magenta density was measured at a point of giving 0.5. The desilvering defect density (ΔD ^AG ) is the value obtained by subtracting the density for 2 minutes from the magenta density for bleaching times of 30 seconds and 40 seconds.
Is shown in Table 2. Further, two of the same samples were exposed at the same time in a white imagewise manner and left at 25 ° C. relative humidity 65% (A condition) and 50 ° C., 30% (B condition) for 14 days, and the following development processing was performed. Table 2 shows the variation value (ΔS ^0.5 ) of the relative sensitivity of the B condition represented by the logarithm of the reciprocal of the exposure amount giving the magenta density (fog + 0.5) with respect to the A condition. Also, for the samples that have undergone development processing, the relative humidity at 80 ° C is 7
The change value of the minimum density of magenta before and after storage for 7 days under the condition of 0% was evaluated as the color image storability (ΔD ^G ). The results are also shown in Table 2. The development process for evaluating the color image storability was also performed according to the following steps.

Claims (5)

[Claims] 1. A silver halide color photographic light-sensitive material having at least one blue-sensitive silver halide emulsion layer, green-sensitive silver halide emulsion layer and red-sensitive silver halide emulsion layer on a support, which is included in the light-sensitive material. Silver halide having a total silver content of 1.0 g / m ² or more and 4.9 g / m ² or less, and at least one layer containing a compound represented by the following general formula (I): Color photographic light-sensitive material. General formula (I): In the formula, R represents a hydrogen atom or a substituent. Z represents a non-metal atom group necessary for forming a 5-membered azole ring containing 2 to 4 nitrogen atoms, and the azole ring may have a substituent. X is a group that is released by a coupling reaction with an oxidized product of a developing agent to become a development inhibitor or a precursor thereof, or, after the group is removed, reacts with another molecule of an oxidized product of a developing agent to develop a development inhibitor or a precursor thereof. Represents the body group. 2. The compound contained in at least one layer,
The silver halide color photographic light-sensitive material according to claim 1, which is a compound represented by the following general formula (II) or (III). General formula (II) General formula (III): In the formula, R ₁ represents a hydrogen atom, an alkyl group or an aryl group. Z ₁ and Z ₂ are each a nitrogen atom or = C
(R ₂ )-, and when Z ₁ is a nitrogen atom, Z ₂ is = C.
(R ₂ )-, when Z ₁ = C (R ₂ )-, Z ₂ is a nitrogen atom, and R ₂ represents a hydrogen atom or a substituent. R ₃ represents a hydroxyl group or a sulfonamide group, and n
Represents 1 or 2. R ₄ has a Hammett σ _p value of 0.
And R ₅ represents a hydrogen atom or a group capable of substituting for a benzene ring. R ₆ has the same meaning as R ₁ . X ₁ and X ₂ represent development inhibitors or precursors. 3. The silver halide color photographic light-sensitive material according to claim 1, wherein the total dry film thickness of the light-sensitive material is 22 μm or less. 4. The specific photographic sensitivity of the light-sensitive material is 80 or more and 80 or more.
4. The silver halide color photographic light-sensitive material according to claim 1, which is less than 0. 5. A color obtained by subjecting the light-sensitive material according to claim 1 to color development processing containing an aromatic primary amine developing agent, desilvering processing, followed by washing and / or stabilization processing. A processing method of a silver halide color photographic light-sensitive material, characterized in that in the processing step, the processing time of the color development step is 150 seconds or less.