JPH0588316A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the silver halide color photographic sensitive material improved in color reproduction performance. CONSTITUTION:The silver halide color photographic sensitive material has at least each one of blue-sensitive, green-sensitive, and red-sensitive silver halide emulsion layers on a support. At least one of the silver halide emulsion layers contains a yellow-colored cyan coupler and a magenta coupler in a weight ratio of (0.3-2.5):1.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a silver halide color photographic light-sensitive material having improved color reproducibility.

[0002]

The use of colored couplers as a means for improving the color reproducibility of silver halide color photographic light-sensitive materials is well known. As one of them, the method of using a magenta colored cyan coupler is well known in the art. A method using a yellow-colored cyan coupler is disclosed in, for example, European Patent No. 423727A.
Nos. 436938A and 435334A. However, if these are simply used as described in the above patent, the color reproducibility of some colors is improved, but on the other hand, the color reproducibility is impaired.

For example, when a yellow colored cyan dye coupler is used in the red photosensitive layer, the interlayer effect from the red photosensitive layer to the blue photosensitive layer is increased, and the saturation of pure red color is improved to some extent. However, the color reproducibility in a broad sense is not greatly improved, and the color reproducibility in a broad sense cannot be said to have been greatly improved because the color that is a mixture of red and other colors, such as skin color, becomes terrible as it is. I couldn't use it to the fullest.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide color photographic light-sensitive material having improved color reproducibility.

[0005]

[Means for Solving the Problems] That is, a halogenated compound having at least one of a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer on a support. In a silver color photographic light-sensitive material, at least one of the silver halide emulsion layers contains both a yellow colored cyan coupler and a magenta colored cyan coupler, and the content of the yellow colored cyan coupler in the layer is magenta. The molar ratio of the color cyan dye coupler is 0.3 or more and 2.5 or more.
It was achieved by a silver halide color photographic light-sensitive material characterized by:

The present invention will be described in detail below.

The yellow-colored cyan coupler of the present invention will be described.

In the present invention, the yellow colored cyan coupler has an absorption maximum in the visible absorption region of the coupler between 400 nm and 500 nm, and has an aromatic first group.
It is a cyan coupler which forms a cyan dye having an absorption maximum in the visible absorption region between 630 nm and 750 nm by coupling with an oxidized product of a primary amine developing agent.

Among the yellow colored cyan couplers of the present invention, a water-soluble 6-hydroxy-2-pyridon-5-ylazo group and a water-soluble pyrazolone are formed by a coupling reaction with an oxidized product of an aromatic primary amine developing agent. A compound residue containing a -4-ylazo group, a water-soluble 5-amino-pyrazol-4-ylazo group, a water-soluble 2-acylaminophenylazo group or a water-soluble 2-sulfonamidophenylazo group can be released. Cyan couplers are preferably used.

The yellow colored cyan coupler of the present invention is preferably represented by the general formulas (CI) to (C) shown in the following chemical formulas 1 and 2.
IV).

[0011]

[Chemical 1]

[0012]

[Chemical 2] In the general formulas (CI) to (CIV), Cp is a cyan coupler residue (T is bonded to its coupling position),
T represents a timing group, k represents an integer of 0 or 1, and X represents N, O, or S, and represents a divalent linking group which binds (T) _k and links Q, and Q is It represents an arylene group or a divalent heterocyclic group.

In the general formula (CI), R ₁ and R ₂ are independently a hydrogen atom, a carboxyl group, a sulfo group, a cyano group, an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group, a carbamoyl group, a sulfamoyl group, A carbonamido group, a sulfonamide group or an alkylsulfonyl group, R ₃ is a hydrogen atom, an alkyl group, a cycloalkyl group,
It represents an aryl group or a heterocyclic group, respectively. However,
At least one of T, X, Q, R ₁ , R ₂ or R ₃ contains a water-soluble group (eg, hydroxyl, carboxyl, sulfo, amino, ammonium, phosphono, phosphino, hydroxysulfonyloxy).

The group represented by the following chemical formula 3 in the general formula (CI)

[0015]

[Chemical 3] It is well known that the compound can take a tautomeric structure as shown in the following chemical formulas 4 to 5, and these tautomeric structures are also included in the structure defined by the general formula (CI) of the present invention. It is a thing.

[0016]

[Chemical 4]

[0017]

[Chemical 5] In formula (CII), R ₄ represents an acyl group or a sulfonyl group, R ₅ represents a substitutable group, and j represents an integer of 0 to 4. When j is an integer of 2 or more, R ₄ may be the same or different. However, T, X, Q, R ₄ or R
_At least one of the _five is a water-soluble group (eg hydroxyl, carboxyl, sulfo, phosphono, phosphino, hydroxysulfonyloxy, amino, ammoniumyl)
Shall be included.

In the general formulas (CIII) and (CIV),
R ₉ is hydrogen atom, carboxyl group, sulfo group, cyano group, alkyl group, cycloalkyl group, aryl group, alkoxy group, cycloalkyloxy group, aryloxy group, heterocyclic group, carbamoyl group, sulfamoyl group, carbonamido group , A sulfonamide group or an alkylsulfonyl group, and R ₁₀ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group. However, at least one of T, X, Q, R ₉ or R ₁₀ contains a water-soluble group (for example, hydroxyl, carboxyl, sulfo, phosphono, phosphino, hydroxysulfonyloxy, amino, ammoniumyl). The groups represented by the following chemical formulas 6 to 7 are in the tautomeric relationship and are the same group.

[0019]

[Chemical 6]

[0020]

[Chemical 7] The compounds represented by formulas (CI) to (CIV) will be described in more detail below.

Examples of the coupler residue represented by Cp include known cyan coupler residues (for example, phenol type and naphthol type).

The timing group represented by T is a group in which the bond with Cp is cleaved by the coupling reaction between the coupler and the oxidation product of the aromatic primary amine developing agent, and then the bond with X is cleaved. It is used for various purposes such as adjusting the reactivity, stabilizing the coupler, adjusting the release timing of X and below. Examples of the timing group include known groups (T-1) to (T-7) shown in Chemical formulas 8 to 9 below. In the following, R ₄₁ represents an aliphatic group, an aromatic group or a heterocyclic group, R ₄₃ , R ₄₄ and R ₄₅ represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group, and * indicates C
The p and ** marks are connected to X, or the * mark is connected to Cp and the ** mark is connected to Q, respectively.

[0023]

[Chemical 8]

[0024]

[Chemical 9] In formulas (T-1) to (T-7), R ₁₀ represents a group capable of substituting on the benzene ring, R ₁₁ has the same meaning as described for R ₄₁ , and R ₁₂ represents a hydrogen atom or a substituent. Represent. t
Represents an integer of 0 to 4. The substituents of R ₁₀ and R ₁₂ include R ₄₁ , halogen atom, R ₄₃ O—, R ₄₃ S—, R
_{43 (R 44) NCO-, R} 43 OOC-, R 43 SO 2 -, R
₄₃ (R ₄₄ ) NSO ₂ −, R ₄₃ CON (R ₄₃ ) −, R ₄₁ S
O ₂ N (R ₄₃ )-, -R ₄₃ CO-, R ₄₁ COO-, R ₄₁
SO-, _{nitro, R 43 (R 44) NCON} (R 45) -, _{cyano, R 41 OCON (R 43)} -, R 43 OSO 2 -, R 43
(R ₄₄ ) N-, R ₄₃ (R ₄₄ ) NSO ₂ N (R ₄₅ )-, or a group represented by the following chemical formula 10

[0025]

[Chemical 10] Is mentioned.

K is an integer of 0 or 1, but it is generally preferred that k is 0, that is, Cp and X are directly bonded.

X is Cp- (T) _k depending on N, O or S.
-A divalent linking group bonded to the above, such as -O-,
-S-, -OCO-, -OCOO-, -OCOS-,-
_{OCONH -, - OSO 2 -,} - OSO 2 NH- or Cp- in N (T) _k - or a Hajime Tamaki bonded (such as pyrrolidine, piperidine, morpholine, piperazine,
Pyrrole, pyrazole, imidazole, 1,2,4-triazole, benzotriazole, succinimide, phthalimide, oxazolidine-2,4-dione, imidazolidine-2,4-dione, 1,2,4-triazolidine-3,5- Groups derived from dione and the like) or alkylene groups (for example, methylene, ethylene, propylene), cycloalkylene groups (for example, 1,4-cyclohexylene), arylene groups (for example, o-phenylene, p-phenylene), and the like. Divalent heterocyclic group (for example, a group derived from pyridine, thiophene, etc.), -CO-,-
_{SO 2 -, - COO -,} - CONH -, - SO 2 NH
_{-, - SO 2 O -,} - NHCO -, - NHSO 2 -, -
NHCONH -, - NHSO ₂ NH-, preferably a linking group that combines NHCOO-. X is more preferably represented by the general formula (I).

In the general formula (I) * -X _1- (L-X ₂ ) _m -**, in the general formula (I), * is a position at which (T) _k or more is bonded, and ** is a position at which Q is bonded. X ₁ is -O- or-
S-, L is an alkylene group, X ₂ is a single bond, -O-,
-S -, - CO -, - SO 2 -, - OCO -, - COO
-, - NHCO -, - CONH -, - SO 2 NH -, -
_{NHSO 2 -, - SO 2 O} -, - OSO 2 -, - OCO
O-, -OCONH-, -NHCOO-, -NHCON
_{H -, - NHSO 2 NH -} , - OCOS -, - SCOO
-, - OSO ₂ NH- or -NHSO ₂ O-a, m represents an integer of 0 to 3. The total number of carbon atoms of X (hereinafter referred to as C number) is preferably 0 to 12, and more preferably 0 to 8. Most preferred are -OCH ₂ CH ₂ O as X
−

Q represents an arylene group or a divalent heterocyclic group. When Q is an arylene group, the arylene group may have a substituent (for example, a halogen atom, hydroxyl, carboxyl, sulfo, nitro, cyano, amino,
Ammonium, phosphono, phosphino, alkyl, cycloalkyl, aryl, carbonamide, sulfonamide, alkoxy, aryloxy, acyl, sulfonyl, carboxyl, carbamoyl, sulfamoyl), and the C number is preferably 6 to 15 , And more preferably 6 to 10. When Q is a divalent heterocyclic group,
The heterocyclic group is a 3- to 8-membered ring containing at least one hetero atom selected from N, O, S, P, Se, and Te,
Preferably a 5- to 7-membered monocyclic or condensed-ring heterocyclic group (for example, pyridine, thiophene, furan, pyrrole, pyrazole, imidazole, thiazole, oxazole,
Benzothiazole, benzoxazole, benzofuran, benzothiophene, 1,3,4-thiadiazole,
A group derived from indole, quinoline, etc.), which is a substituent (same as the substituent when Q is an arylene group)
May be included, and the C number is preferably 2 to 15, and more preferably 2 to 10. The most preferable Q is 1,4-phenylene.

Therefore, the most preferred in the present invention-
(T) _k -X-Q- is -OCH ₂ CH ₂ -O- (1,4
-Phenylene)-.

When R ₁ , R ₂ or R ₃ is an alkyl group, the alkyl group may be linear or branched, and may contain an unsaturated bond. Atom, hydroxyl, carboxyl, sulfo, phosphono, phosphino, cyano, alkoxy, aryl,
Alkoxycarbonyl, amino, ammonium, acyl, carbonamide, sulfonamide, carbamoyl,
Sulfamoyl, sulfonyl) may be included.

When R ₁ , R ₂ or R ₃ is a cycloalkyl group, the cycloalkyl group may be a _3- to 8-membered cycloalkyl group having a bridging group and containing an unsaturated bond. Alternatively, it may have a substituent (the same as the substituent when R ₁ , R ₂ or R ₃ is an alkyl group).

When R ₁ , R ₂ or R ₃ is an aryl group, the aryl group may have a substituent (R ₁ ,
In addition to the substituent when R ₂ or R ₃ is an alkyl group, there are alkyl, cycloalkyl and the like).

When R ₁ , R ₂ or R ₃ is a heterocyclic group, the heterocyclic group is at least one N, S, O, P, Se.
Or 3 to 8 containing a hetero atom selected from Te in the ring
Membered (preferably 5 to 7 membered) monocyclic or condensed ring heterocyclic group (eg, imidazolyl, thienyl, pyrazolyl, thiazolyl, pyridyl, quinolinyl), wherein the substituent (R ₁ , R ₂ or R ₃ is aryl) In the case of a group, it may have the same as the substituent).

Here, the carboxyl group may include a carboxylate group, the sulfo group may include a sulfonate group, the phosphino group may include a phosphinate group, and the phosphono group may include a phosphonate group. At this time, the counter ion may include Li ⁺ , Na ⁺ , and K.
⁺ , Ammonium, etc.

R ₁ is preferably a hydrogen atom, a carboxyl group, an alkyl group having a C number of 1 to 10 (for example, methyl, t-butyl, carbomethyl, 2-sulfomethyl, carboxymethyl, 2-carboxymethyl, 2-hydroxymethyl,
Benzyl, ethyl, isopropyl) or C number 6-12
Is an aryl group (eg, phenyl, 4-methoxyphenyl, 4-sulfophenyl), particularly preferably a hydrogen atom, a methyl group or a carboxyl group.

R ₂ is preferably a cyano group, a carboxyl group, a carbamoyl group having a C number of 1 to 10, a sulfamoyl group having a C number of 0 to 10, a sulfo group, an alkyl group having a C number of 1 to 10 (eg methyl, sulfomethyl), A sulfonyl group having 1 to 10 C numbers (eg, methylsulfonyl, phenylsulfonyl), a carbonamido group having 1 to 10 C numbers (eg, acetamide, benzamide), or a sulfonamide group having 1 to 10 C numbers (eg, methanesulfonamide, toluenesulfone) Amido), particularly preferably cyano group, carbamoyl group or carboxyl group.

R ₃ is preferably a hydrogen atom and has a C number of 1 to 12.
An alkyl group of (for example, methyl, sulfomethyl, carboxymethyl, 2-sulfomethyl, 2-carboxymethyl,
Ethyl, n-butyl, benzyl, 4-sulfonbenzyl) or an aryl group having a C number of 6 to 15 (eg phenyl, 4-carboxyphenyl, 3-carboxyphenyl, 4-methoxyphenyl, 2,4-dicarboxyphenyl, 2 -Sulfophenyl, 3-sulfophenyl, 4-
Sulfophenyl, 2,4-disulfophenyl, 2,5-
Disulfophenyl), more preferably C number 1 to 7
Or an aryl group having 6 to 10 carbon atoms.

R ₄ is specifically an acyl group represented by the general formula (II) or a sulfonyl group represented by the general formula (III).

When the general formula (II) R ₁₁ CO-general formula (III) R ₁₁ SO ₂ -R ₁₁ is an alkyl group, the alkyl group may be a straight chain or branched chain, and an unsaturated bond. A substituent (for example, a halogen atom, hydroxyl, carboxyl, sulfo, phosphono, phosphino, cyano, alkoxy, aryl, alkoxycarbonyl, amino,
Ammoniumyl, acyl, carbonamide, sulfonamide, carbamoyl, sulfamoyl, sulfonyl).

When R ₁₁ is a cycloalkyl group, the cycloalkyl group is a 3- to 8-membered cycloalkyl group, which may have a bridging group or an unsaturated bond, and may be substituted. Group (same as the substituent when R ₁₁ is an alkyl group)
May have.

When R ₁₁ is an aryl group, the aryl group, even if it is a condensed ring, has a substituent (in addition to the substituent when R ₁₁ is an alkyl group, there are, for example, alkyl and cycloalkyl). May be.

When R ₁₁ is a heterocyclic group, the heterocyclic group is a 3- to 8-membered (preferably a heterocyclic group) containing at least one hetero atom selected from N, S, O, P, Se or Te in the ring. 5
To 7-membered) monocyclic or condensed-ring heterocyclic group (for example, imidazolyl, thienyl, pyrazolyl, thiazolyl, pyridyl, quinolinyl) having a substituent (the same as the substituent when R ₁₁ is an aryl group). You may have.

Here, the carboxyl group may include a carboxylate group, the sulfo group may include a sulfonate group, the phosphino group may include a phosphinate group, and the phosphono group may include a phosphonate group. At this time, the counter ion may include Li ⁺ , Na ⁺ , and K.
⁺ , Ammonium, etc.

R ₁₁ is preferably an alkyl group having a C number of 1 to 10 (eg, methyl, carboxymethyl, sulfoethyl,
Cyanoethyl), a C 5-8 cycloalkyl group (eg cyclohexyl, 2-carboxycyclohexyl),
Alternatively, it is an aryl group having 6 to 10 C atoms (phenyl, 1-naphthyl, 4-sulfophenyl), particularly preferably an alkyl group having 1 to 3 C atoms, and an aryl group having 6 C atoms.

R ₅ is a substitutable group, preferably an electron donating group, and particularly preferably —NR ₁₂ R ₁₃ or —OR ₁₄ . The 4-position is preferable as the substitution position. R ₁₂ , R ₁₃ and R ₁₄ are a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group. A ring may be formed between R ₁₂ and R ₁₃ , and the nitrogen heterocycle formed is preferably an alicyclic ring.

J represents an integer of 0 to 4, preferably 1 or 2, and particularly preferably 1.

When R ₉ or R ₁₀ is an alkyl group, the alkyl group may be linear or branched, may contain an unsaturated bond, and may have a substituent (eg, a halogen atom, hydroxyl, Carboxyl, sulfo, phosphono,
Phosphino, cyano, alkoxy, aryl, alkoxycarbonyl, amino, ammonium, acyl, carbonamide, sulfonamide, carbamoyl, sulfamoyl, sulfonyl).

When R ₉ or R ₁₀ is a cycloalkyl group, the cycloalkyl group is a 3- to 8-membered cycloalkyl group, which may have a bridging group or an unsaturated bond. Also may have a substituent (the same as the substituent when R ₉ or R ₁₀ is an alkyl group).

When R ₉ or R ₁₀ is an aryl group,
Even if the aryl group is a condensed ring, a substituent (R ₉ or R _9
In addition to the substituent when ₁₀ is an alkyl group, there are alkyl, cycloalkyl and the like).

When R ₉ or R ₁₀ is a heterocyclic group, the heterocyclic group is a 3 to 8 membered member containing at least one hetero atom selected from N, S, O, P, Se or Te in the ring. A (preferably 5 to 7 membered) monocyclic or condensed ring heterocyclic group (for example, imidazolyl, thienyl, pyrazolyl, thiazolyl, pyridyl, quinolinyl), which has a substituent (R ₉
Alternatively, when R ₁₀ is an aryl group, it may have the same as the substituent).

Here, the carboxyl group may include a carboxylate group, the sulfo group may include a sulfonate group, the phosphino group may include a phosphinate group, and the phosphono group may include a phosphonate group, and the counter ion may include Li ⁺ , Na ⁺ , and K.
⁺ , Ammonium, etc.

R ₉ is preferably a cyano group, a carboxyl group, a carbamoyl group having a C number of 1 to 10, an alkoxycarbonyl group having a C number of 2 to 10, an aryloxycarbonyl group having a C number of 7 to 11, and a C number of 0 to 10. Sulfamoyl group, sulfo group, alkyl group having 1 to 10 C's (eg, methyl, carboxymethyl, sulfomethyl), sulfonyl group having 1 to 10 C (eg, methylsulfonyl, phenylsulfonyl), carbonamido group having 1 to 10 C (Eg, acetamide, benzamide), C 1-10 sulfonamide group (eg, methane sulfonamide, toluene sulfonamide), alkyloxy group (eg, methoxy, ethoxy) or aryloxy group (eg, phenoxy), particularly preferably Cyano group, carbamoyl group, alkoxycarbonyl group, It is a carboxyl group.

R ₁₀ is preferably a hydrogen atom and has a C number of 1 to 12.
An alkyl group of (for example, methyl, sulfomethyl, carboxymethyl, ethyl, 2-sulfoethyl, 2-carboxyethyl, 3-sulfopropyl, 3-carboxypropyl, 5-sulfopentyl, 5-carboxypentyl, 4
-Sulfobenzyl) or an aryl group having a C number of 6 to 15 (eg, phenyl, 4-carboxyphenyl, 3-carboxyphenyl, 2,4-dicarboxyphenyl, 4-
Sulfophenyl, 3-sulfophenyl, 2,5-disulfophenyl, 2,4-disulfophenyl), more preferably an alkyl group having 1 to 7 C atoms or 6 to 10 C atoms.
Is an aryl group.

Specific examples of the yellow-colored cyan coupler of the present invention are shown in the following chemical formulas 11 to 33, but are not limited thereto.

[0056]

[Chemical 11]

[0057]

[Chemical formula 12]

[0058]

[Chemical 13]

[0059]

[Chemical 14]

[0060]

[Chemical 15]

[0061]

[Chemical 16]

[0062]

[Chemical 17]

[0063]

[Chemical 18]

[0064]

[Chemical 19]

[0065]

[Chemical 20]

[0066]

[Chemical 21]

[0067]

[Chemical formula 22]

[0068]

[Chemical formula 23]

[0069]

[Chemical formula 24]

[0070]

[Chemical 25]

[0071]

[Chemical formula 26]

[0072]

[Chemical 27]

[0073]

[Chemical 28]

[0074]

[Chemical 29]

[0075]

[Chemical 30]

[0076]

[Chemical 31]

[0077]

[Chemical 32]

[0078]

[Chemical 33] The yellow colored coupler represented by the general formula (CI) of the present invention can be generally synthesized by a diazo coupling reaction between a 6-hydroxy-2-pyridone and an aromatic diazonium salt or a heterocyclic diazonium salt containing a coupler structure. ..

The former, that is, 6-hydroxy-2-pyridones are described, for example, in Klinsberg, "Heterocyclic compounds-pyridine and derivatives thereof-Part 3" (Interscience Publishing, 1962), Journal of the American.・ Chemical Society (J. Am. Che
m. Soc. ) 1943, 65, 449, Journal of the Chemical Technology and Biotechnology (J. Chem. Tech. Biote).
chnol. 1986, 36, 410, Tetrahedron Lets
ters) 1966, vol. 22, p. 445, Japanese Patent Publication No. 61
-52827, West German Patent Nos. 2,162,612, 2,349,709, 2,902,486, and U.S. Pat. No. 3,763,170.

The latter diazonium salt can be synthesized by the method described in, for example, US Pat. Nos. 4,004,929 and 4,138,258, and JP-A 61-72244 and 61-273543. it can. The diazo coupling reaction between 6-hydroxy-2-pyridones and a diazonium salt is carried out with a solvent such as methanol, ethanol, methyl cellosolve, acetic acid, N, N-dimethylformamide, N, N-dimethylacetamide, tetrahydrofuran, dioxane, water, or the like. It can be performed in these mixed solvents. At this time, as the base, for example, sodium acetate, potassium acetate, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, sodium hydroxide, potassium hydroxide, pyridine, triethylamine, tetramethylurea,
Tetramethylguanidine can be used. The reaction temperature is generally -78 ° C to 60 ° C, preferably -20 ° C to 30 ° C.
℃.

The synthesis examples of the yellow colored coupler of the present invention are shown below. Synthesis Example 1 Synthesis of Exemplified Coupler (YC-1) The synthesis route of this example is shown in Chemical Formula 34 below.

[0082]

[Chemical 34] Synthesis of Compound a To 125.2 g of taurine and 66 g of potassium hydroxide, 500 ml of methanol was added, and the mixture was stirred with heating, and 110 g of methyl cyanoacetate was added dropwise in about 1 hour. After heating and refluxing for 5 hours, the mixture was allowed to stand overnight, the precipitated crystals were filtered, washed with ethanol,
By drying, 202.6 g of a crystal of compound a was obtained. Synthesis of compound b 11.5 g of compound a and 3.5 g of potassium carbonate in water 1
1.5 ml was added, 7.8 g of ethyl acetoacetate was added dropwise with stirring on a steel bath, and the mixture was further stirred for 7 hours. After allowing to cool, 9.2 ml of concentrated hydrochloric acid was added and the mixture was stirred to precipitate crystals. The crystals were filtered, washed with methanol and dried to obtain 10.4 g of compound b crystals. Synthesis of Exemplified Coupler (YC-1) 10.1 g of compound c synthesized by the synthetic method described in U.S. Pat. No. 4,138,258 was dissolved in 60 ml of N, N-dimethylformamide and 60 ml of methyl cellosolve,
4.3 ml of concentrated hydrochloric acid was added under ice cooling, and then a solution of 1.84 g of sodium sulfite in 5 ml of water was added dropwise to prepare a diazonium solution. Next, 60 ml of methyl cellosolve and 20 ml of water were added to 7.8 g of the compound b and 8.2 g of sodium acetate, and the diazonium solution was added dropwise while stirring under ice cooling. After dropping, the mixture was further stirred for 1 hour and at room temperature for 2 hours, and the precipitated crystals were filtered. After washing with water and drying, the crystals were dispersed in 500 ml of methanol, heated under reflux for 1 hour, and then allowed to cool. The crystals were filtered, washed with methanol, and dried to give 13.6 g of red crystals of the target exemplary coupler (YC-1).
Got The melting point of this compound is 269 to 272 ° C (decomposition)
And the structure was confirmed by ¹ H NMR spectrum, mass spectrum and elemental analysis. The maximum absorption wavelength of this compound in methanol was 457.7 nm, and the molecular extinction coefficient was 41300, showing good spectral absorption characteristics as a yellow colored coupler. Synthesis Example 2 Synthesis of Exemplified Coupler (YC-3) The synthetic route of this example is shown in Chemical Formula 35 below.

[0083]

[Chemical 35] 75 ml of N, N-dimethylformamide and 75 ml of methyl cellosolve were added to and dissolved in 19.2 g of compound d synthesized by the synthetic method described in JP-A-62-85242, and 5.6 ml of concentrated hydrochloric acid was added with stirring under ice cooling. Then, a solution of 2.5 g of sodium sulfite in 5 ml of water was added dropwise. After dropping 1
The mixture was stirred for an additional 1 hour at room temperature to prepare a diazonium solution.

10.1 g of compound b and sodium acetate 1
75 ml of methyl cellosolve and 26 ml of water were added to 0.7 g, and the diazonium solution was added dropwise while stirring under ice cooling. After dropping, the mixture was stirred for 1 hour and at room temperature for 2 hours, and the precipitated crystals were filtered. Next, the crystals were dispersed in 200 ml of methanol, a solution of 2.2 g of sodium hydroxide in 10 ml of water was added dropwise, and the mixture was stirred for 3 hours. It was neutralized with concentrated hydrochloric acid, and the precipitated crystals were washed with water, washed with methanol and dried. The obtained crude crystal was purified with hot methanol in the same manner as in Synthesis Example 1 to give the desired exemplary coupler (YC-3)
4.8 g was obtained. The melting point of this compound is 246 to 251 ° C.
(Decomposition), and the structure was confirmed by ¹ H NMR spectrum, mass spectrum and elemental analysis. The maximum absorption wavelength of this compound in methanol was 457.6 nm, and the molecular absorption coefficient was 42700, indicating good spectral absorption characteristics as a yellow colored coupler. Synthesis Example 3 Synthesis of Exemplified Coupler (YC-30) The synthesis route of this example is shown in Chemical Formula 36 below.

[0085]

[Chemical 36] Synthesis of compound e Anthranilic acid 137.1 g was added to acetonitrile 600 ml.
The mixture was added to the mixture, heated and stirred, and 92.5 g of diketene was added dropwise in about 1 hour. After heating under reflux for 1 hour, the mixture was cooled to room temperature, and the precipitated crystals were filtered, washed with acetonitrile, and dried to obtain 200.5 g of compound e crystals. Synthesis of compound f Compound e 199.1 g, ethyl cyanoacetate 89.2 g,
344 g of 28% sodium methoxide was added to methanol.
In addition to 9 liters, the mixture was reacted in an autoclave at 120 ° C for 8 hours. After standing overnight, the reaction mixture was concentrated under reduced pressure and washed with water.
00 ml was added, and hydrochloric acid was acidified with 230 ml of concentrated hydrochloric acid. The precipitated crystals were collected by filtration, and the obtained crude crystals were heated and washed with a mixed solvent of ethyl acetate and acetonitrile to give compound f152g
Got Synthesis of Exemplified Coupler (YC-30) 13.0 g of compound g synthesized according to the synthesis method described in U.S. Pat. No. 4,138,258 was dissolved in 40 ml of N, N-dimethylformamide, and concentrated under ice-cooling. 0.5 ml was added, and then a solution of 1.48 g of sodium nitrite in 5 ml of water was added dropwise to prepare a diazonium solution. Then compound f
20 ml of N, N-dimethylformamide and 15 ml of water were added to 6.0 g and 8 g of sodium acetate, and the diazonium solution was added dropwise while stirring under ice cooling. After the dropping, the mixture was further stirred at room temperature for 30 minutes. The mixture was acidified with hydrochloric acid, extracted with ethyl acetate, washed with water, concentrated under reduced pressure, and the concentrate was recrystallized with a mixed solvent of ethyl acetate and methanol to obtain 13 g of a yellow crystal of an exemplary coupler (YC-30). The melting point of this coupler (YC-30) was 154-156 ° C, and the structure was confirmed by ¹ HNMR spectrum, mass spectrum and elemental analysis. The maximum absorption wavelength of this compound in methanol was 458.2 nm, and the molecular extinction coefficient was 42800, showing good spectral absorption characteristics as a yellow colored coupler. Synthesis Example 4 Synthesis of Exemplified Coupler YC-42 Synthesis routes of this example are shown in Chemical Formulas 37 to 38 below.

[0086]

[Chemical 37]

[0087]

[Chemical 38] (1) Synthesis of Compound (iii) 445.5 g of phenyl ester compound (i) and 90.1 g of isopropanolamine (ii) were added to 600 ml of acetonitrile.
The mixture was heated under reflux for 2 hours. After cooling with water, the precipitated crystals were collected by filtration and dried to obtain 342 g of compound (iii). mp. 16
2-165 ° C. (2) Synthesis of compound (v) 341 g of hydroxyl compound (iii) and 231 g of 2-hexyldecanoyl chloride (iv) are added to 880 ml of acetonitrile.
The mixture was heated under reflux for 2 hours in the medium, cooled with water, and the precipitated crystals were collected by filtration.
It was dried to obtain 437 g of compound (v). mp. 97-1
00 ° C. (3) Synthesis of compound (vi) Nitro compound (v) 370 g, 10% Pd—C catalyst 6 g, and ethyl acetate 1 liter were charged in an autoclave and heated to 50 ° C.
It was hydrogenated for 3 hours. After completion of the reduction, the catalyst was filtered off, the filtrate was concentrated under reduced pressure, and the resulting residue was crystallized with n-hexane, and the precipitated crystals were collected by filtration and dried to obtain 327 g of amine compound (vi). mp. 95-97 ° C. (4) Synthesis of Exemplified Coupler YC-42 20.8 g of amine compound (vi) was added to dimethylformamide 60.
It was dissolved in liter and 7.6 ml of concentrated hydrochloric acid was added under water cooling. Further, an aqueous solution of 2.7 g of sodium nitrite and 10 ml of water was added dropwise over 20 minutes, and stirring was continued for 30 minutes to prepare a diazo solution.

On the other hand, 9.7 g of pyridone (vii) and 13 g of sodium acetate were added to a mixed solution of 30 ml of water and 30 ml of dimethylformamide, dissolved by heating, cooled with water, and the above diazo solution was slowly added while stirring at 10 ° C. or lower. .. After stirring was continued for further 15 minutes, the mixture was extracted with ethyl acetate and washed with water three times. The organic layer was concentrated under reduced pressure, the residue was crystallized from methanol ethyl acetate, and the precipitated crystals were collected by filtration and dried to obtain 21.2 g of Exemplified coupler YC-42. mp. 117-119 [deg.] C. Yellow-colored cyan couplers represented by the general formulas (CII) to (CIV) are described in JP-B-58-6939 and JP-A-1-6939.
It can be synthesized by the method described in the above-mentioned patents etc. as the method for synthesizing the coupler represented by -197563 and the general formula (CI).

In the present invention, the yellow colored cyan couplers represented by the general formulas (CI) and (CII) are more preferably used, and the one represented by the general formula (CI) is particularly preferably used.

[0090] The total amount of the photosensitive material in the yellow-colored cyan coupler is a 0.005~0.30g / m ^2, preferably 0.02~0.20g / m ^2, more preferably 0.03 ˜0.15 g / m ² .

The yellow-colored cyan coupler of the present invention can be added in the same manner as a usual coupler as described below.

Next, the magenta colored cyan coupler used in the present invention will be described. The magenta colored cyan coupler used in the present invention has the following formula
The general formula (MI) shown in or the general formula (MI
The compound represented by the formula (I) is preferably used, and the compound represented by the general formula (MII) is more preferably used in terms of color reproduction.

[0093]

[Chemical Formula 39] In formula (MI), R ₂₁ represents an aromatic group or a heterocyclic group, and R ₂₂ represents a group capable of substituting for a naphthol ring. A
-B-N = ND represents a coupling-off group, and A represents a carbon atom at the coupling active position of this coupler and A by the reaction between the oxidized product of the color developing agent and the coupler of the general formula (MI). Represents a divalent group capable of cleaving the bond of, B represents a divalent aromatic group or a heterocyclic group, and D represents
Represents an aromatic group or a heterocyclic group. n represents an integer of 0 to 4.

At least one of the groups represented by A, B and D in the formula (MI) has a sulfo group, a carboxyl group, an alkali metal salt, an ammonium salt, an alkylamine salt or a pyridinium salt as a substituent. .. By having such a water-soluble group, A-B-N
The coupling-off group represented by = ND is released from the coupler residue and then flows out into the developer.

Examples of the aromatic group represented by R ₂₁ include a substituted or unsubstituted aromatic group having 6 to 30 carbon atoms.
Further, examples of the heterocyclic group include a substituted or unsubstituted heterocyclic group having 2 to 30 carbon atoms, and the heteroatom in the heterocycle is
N, O, S, Se, etc., preferably an unsaturated heterocycle containing nitrogen.

R ₂₂ represents a group capable of substituting on a naphthol ring (including atoms, the same applies hereinafter), and representative examples thereof include a halogen atom, a hydroxy group, an amino group, a carboxyl group,
Sulfonic acid group, cyano group, aromatic group, heterocyclic group, carbonamide group, sulfonamide group, carbamoyl group, sulfamoyl group, ureido group, acyl group, acyloxy group, aliphatic oxy group, aromatic oxy group, aliphatic group Thio group,
Examples thereof include an aromatic thio group, an aliphatic sulfonyl group, an aromatic sulfonyl group, a sulfamoylamino group, a nitro group, and an imide group, and the carbon number contained in R ₂₂ is 0 to 30.
Is. Examples of cyclic R ₂₂ when there are two R _22, and the like dioxymethylene group. Here, the aliphatic group is an aliphatic hydrocarbon group containing an alkyl, alkenyl and alkynyl group, and may have a usual substituent.

[0097]

[Chemical 40] In formula (MII), R ₂₅ represents an aliphatic group or an alicyclic group, R ₂₆ represents a group capable of substituting for a naphthol ring, and n represents an integer of 0 to 4. A-B-N = N-D represents a coupling-off group and is the same as that shown in formula (MI).

Next, specific examples of the magenta colored cyan coupler represented by the formulas (MI) and (MII) will be shown below.
Shown at 61.

[0099]

[Chemical 41]

[0100]

[Chemical 42]

[0101]

[Chemical 43]

[0102]

[Chemical 44]

[0103]

[Chemical 45]

[0104]

[Chemical 46]

[0105]

[Chemical 47]

[0106]

[Chemical 48]

[0107]

[Chemical 49]

[0108]

[Chemical 50]

[0109]

[Chemical 51]

[0110]

[Chemical 52]

[0111]

[Chemical 53]

[0112]

[Chemical 54]

[0113]

[Chemical 55]

[0114]

[Chemical 56]

[0115]

[Chemical 57]

[0116]

[Chemical 58]

[0117]

[Chemical 59]

[0118]

[Chemical 60]

[0119]

[Chemical formula 61] The coupler represented by the formula (MI) is disclosed, for example, in JP-A-63-
23152. Further, the coupler represented by the formula (MII) is described in, for example, US Pat. No. 4,0049,29,
No. 4,138,258 and British Patent No. 1,146,368.
No.

The method of using the yellow colored cyan coupler and the magenta colored cyan coupler used in the present invention is such that at least one of the emulsion layers contains both, and the content of the yellow colored cyan coupler in the layer is the same. The molar ratio to the content of the magenta colored cyan coupler in the layer may be 0.3 or more and 2.5 or less, preferably 0.5 or more and 2.0 or less, and more preferably 0.7 or more. It is 1.5 or less.

The yellow-colored cyan coupler and the magenta-colored cyan coupler of the present invention are preferably used in the red-sensitive silver halide emulsion layer, and in the red-sensitive silver halide emulsion layer using the colored-cyan coupler of the present invention. More preferably always contains both a yellow colored cyan coupler and a magenta colored cyan coupler.

The light-sensitive material of the present invention may be provided with at least one of a silver halide emulsion layer of a blue color-sensitive layer, a green color-sensitive layer and a red color-sensitive layer on a support. There is no particular limitation on the number and order of layers of the silver halide emulsion layer and the non-photosensitive layer. As a typical example, a silver halide photographic light-sensitive material having at least one light-sensitive layer composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. And the photosensitive layer is blue light, green light,
And a unit light-sensitive layer having color sensitivity to red light, and in a multilayer silver halide color photographic light-sensitive material, the unit light-sensitive layers are generally arranged in order from the support side to the red-color-sensitive layer and green. The color sensitive layer and the blue color sensitive layer are installed in this order. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layers.

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

For the intermediate layer, JP-A-61-43748 is used.
No. 59-113438, No. 59-113440
Nos. 61-20037 and 61-20038, the couplers, the DIR compounds, etc. may be contained, and a color mixing inhibitor may be contained as is usually used.

A plurality of silver halide emulsion layers constituting each unit light-sensitive layer are composed of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer as described in West German Patent No. 1,121,470 or British Patent No. 923,045. A two-layer structure of emulsion layers can be preferably used. Usually, it is preferable that the layers are arranged so that the sensitivities are gradually lowered toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. Also,
JP-A-57-112751, JP-A-62-200350
No. 62-206541, No. 62-206543, etc., a low-sensitivity emulsion layer may be provided on the side farther from the support, and a high-sensitivity emulsion layer may be provided on the side closer to the support.

As a specific example, from the side farthest from the support,
Low sensitivity blue photosensitive layer (BL) / high sensitivity blue photosensitive layer (BH)
/ High sensitivity green photosensitive layer (GH) / Low sensitivity green photosensitive layer (G
L) / high-sensitivity red photosensitive layer (RH) / low-sensitivity red photosensitive layer (RL), or BH / BL / GL / GH / RH /
RL order or BH / BL / GH / GL / RL / RH
Can be installed in order.

Further, as described in JP-B-55-34932, the layers may be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the side farthest from the support. Also, JP-A-56-25738 and 62-6393.
As described in No. 6, it is also possible to arrange in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support.

As described in JP-B-49-15495, the upper layer is the silver halide emulsion layer having the highest sensitivity, the middle layer is the silver halide emulsion layer having a lower sensitivity, and the lower layer is the middle layer. Another example is an arrangement in which a silver halide emulsion layer having a lower photosensitivity is arranged and three layers having different sensitivities are sequentially lowered toward the support. Even when it is composed of three layers having different sensitivities, as described in JP-A-59-202464, a medium-sensitivity emulsion from the side remote from the support in the same color-sensitive layer. It may be arranged in the order of layer / high-speed emulsion layer / low-speed emulsion layer.

In addition, the layers may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer. Also, 4
In the case of more than one layer, the arrangement may be changed as described above.

In order to improve color reproducibility, US Pat. Nos. 4,663,271, 4,705,744, 4,707,436 and JP-A-62-160448 are used.
No. 63-89850, and BL, G described in the specification.
It is preferable to dispose a donor layer (CL) having a multilayer effect, which has a spectral sensitivity distribution different from that of the main photosensitive layer such as L and RL, adjacent to or in proximity to the main photosensitive layer.

As described above, various layer structures and arrangements can be selected according to the purpose of each photosensitive material.

The preferable silver halide content in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is about 30 mol%.
Silver iodobromide, silver iodochloride, or silver iodochlorobromide, including the following silver iodides. About 2 mol% is particularly preferred.
To silver iodobromide or silver iodochlorobromide containing up to about 10 mol% silver iodide.

The silver halide grains in the photographic emulsion have regular crystals such as cubes, octahedra and tetradecahedrons, grains having irregular crystal forms such as spheres and plates.
It may have a crystal defect such as a twin plane or a composite form thereof.

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

The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (RD) No.
17643 (December 1978), pp. 22-23,
"I. Emulsion preparation
ion and types) ”, and ibid. No. 1871
6 (November 1979), p. 648, ibid. 30710
5 (Nov. 1989), pp. 863-865, and "Graphics and Chemistry" by Graphide, published by P. Glafkides, Chemie et Phi.
sique Photographie, Paul
Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF Duffin,
Photographic Emulsion Che
mistry (Focal Press, 196
6)), "Production and coating of photographic emulsions" by Zelikmann et al., Published by Focal Press (VL Zelikman et.
al. , Making and Coating P
photographic Emulsion, Foca
l Press, 1964).

For example, US Pat. No. 3,574,628,
No. 3,655,394 and British Patent No. 1,413,
The monodisperse emulsion described in No. 748 is also preferable.

Further, tabular grains having an aspect ratio of about 3 or more can be used in the present invention. The tabular grains are described in Gutoff, Photographic Science and Engineering (Gutoff, Photogr), for example.
apic Science and Engineer
ing), 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, or may have a layered structure. Further, silver halides having different compositions may be joined by epitaxial joining,
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 which forms a latent image mainly on the surface, an internal latent image type which is formed inside the grain or a type which has a latent image on both the surface and the inside. Must be a type of emulsion. Among the internal latent image types, the cores described in JP-A-63-264740 /
It may be a shell type internal latent image type emulsion. The preparation method of this core / shell type internal latent image type emulsion is described in JP-A-59-13.
3542. The shell thickness of this emulsion varies depending on the development process and the like, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

The silver halide emulsion is usually one which has been physically ripened, chemically ripened and spectrally sensitized. The additives used in such a process are Research Disclosure No. 17643, ibid. 18716 and ibid.
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.
The fogged silver halide grain inside or on the surface means a silver halide grain which enables uniform (non-imagewise) development regardless of the unexposed portion and exposed portion of the light-sensitive material. .. A method for preparing a silver halide grain whose inside or surface is fogged is described in US Pat. No. 4,626,498 and JP-A-59-214852.

The silver halide forming the inner nucleus of a core / shell type silver halide grain having a fogged inside may have the same halogen composition or different halogen compositions. As the silver halide having the inside or surface of the grain fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. 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 fine grain of silver halide which is not exposed to light during imagewise exposure for obtaining a dye image and is not substantially developed in the developing treatment, and it is preferable that the fog is not fogged in advance. ..

The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and if necessary, silver chloride and / or
Alternatively, it may contain 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 diameter of circles corresponding to 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,
Also, spectral sensitization is not necessary. 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.

The silver coating amount of the light-sensitive material of the present invention was 6.0 g.
/ M ² or less is preferable, and 4.5 g / m ² or less is most preferable.

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

Types of additives RD17643 RD18716 RD307105 1. Chemical sensitizer Page 23 Page 648 Right column Page 866 2. Sensitivity enhancer Page 648, right column 3. Spectral sensitizer, pages 23 to 24, page 648, right column, pages 866 to 868, supersensitizer, page 649, right column, 4. Whitening agent Page 24 Page 647 Right column Page 868 5. Fogging prevention pages 24 to 25 pages 649 right column 868 to 870 pages agents and stabilizers 6. Light absorber, page 25-26, page 649, right column, page 873, filter dye, ~ page 650, left column, ultraviolet absorber 7. Stain page 25 right column page 650 left column page 872 Inhibitor to right column 8. Dye image Page 25 Page 650 Left column Page 872 Stabilizer 9. Hardener 26 pages 651 left column 874-875 pages 10. Binder page 26 page 651 left column 873 to 874 page 11. Plasticizers and lubricants Page 27 Page 650 Right column Page 876 12. Coating aid, pages 26 to 27, page 650, right column, pages 875 to 876, surfactant 13. Static Page 27 Page 650 Right column 876-877 Page 14 Inhibitor 14. Matting agent pp. 878-879 Further, in order to prevent deterioration of photographic performance due to formaldehyde gas, it is immobilized by reacting with formaldehyde described in US Pat. Nos. 4,411,987 and 4,435,503. It is preferable to add a compound capable of being added to the light-sensitive material.

The light-sensitive material of the present invention can be prepared according to US Pat.
0,454, 4,788,132, JP-A-62.
It is preferable to incorporate the mercapto compounds described in JP-A-18539 and JP-A-1-283551.

The light-sensitive material of the present invention can be incorporated into Japanese Patent Laid-Open No. 1-1060
It is preferable to contain a compound which releases a fogging agent, a development accelerator, a silver halide solvent or a precursor thereof, as described in No. 52, regardless of the amount of developed silver produced by the development processing.

In the light-sensitive material of the present invention, the international publication WO88 /
No. 04794, dyes dispersed by the method described in JP-A-1-502912 or EP317,308A,
U.S. Pat. No. 4,420,555, Japanese Patent Laid-Open No. 1-25935.
It is preferable that the dye described in No. 8 is contained.

Various color couplers can be used in the present invention, specific examples of which are described in Research Disclosure No. 17643, VII-CG, and N
o. 307105, VII-C to 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 EP 249,473A are preferred.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and examples thereof include US Pat. Nos. 4,310,619 and 4,351,8.
97, European Patent 73,636, US Patent 3,0.
61,432, No. 3,725,067, Research Disclosure No. 24220 (June 1984)
Mon.), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A Nos. 60-43659, 61-72238, and 60-.
No. 35730, No. 55-118034, No. 60-18.
Those described in US Pat. No. 5951, U.S. Pat. Nos. 4,500,630, 4,540,654, 4,556,630 and International Publication WO88 / 04795 are particularly preferable.

Examples of cyan couplers include phenol-type and naphthol-type couplers. For example, US Pat. Nos. 4,052,212, 4,146,396, 4,228,233, and 4 are cited. , 296,200,
No. 2,369,929, No. 2,801,171
No. 2,772,162, No. 2,895,82
No. 6, No. 3,772,002, No. 3,758,3
No. 08, No. 4,334, 011, No. 4,327,
173, West German Patent Publication 3,329,729, European Patents 121,365A, 249,453A,
U.S. Pat. Nos. 3,446,622 and 4,333,9
No. 99, No. 4,775, 616, No. 4,451,
No. 559, No. 4,427,767, No. 4,69
No. 0,889, No. 4,254,212, No. 4,2
Those described in 96,199 and JP-A No. 61-42658 are preferred. Furthermore, JP-A-64-553 and JP-A-64-553
-554, 64-555, 64-556, and pyrazoloazole couplers described in US Pat.
The imidazole couplers described in No. 18,672 can also be used.

Typical examples of polymerized dye-forming couplers are, for example, US Pat. Nos. 3,451,820, 4,080,211, 4,367,282, and 4,409. No. 320, No. 4,576,910,
British Patent 2,102,137, European Patent 341,1
88A.

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 96,570,
Those described in West German Patent (Publication) No. 3,234,533 are preferable.

Colored couplers for correcting unwanted absorption of color-forming dyes may be used in addition to those of the present invention, if necessary.
Research Disclosure No. 17643 VII
-G item, the same No. Item VII-G of 307105, U.S. Pat. No. 4,163,670, Japanese Patent Publication No. 57-39413, U.S. Pat. Nos. 4,004,929 and 4,138,25.
No. 8, British Patent No. 1,146,368 can be used. Also, U.S. Pat. No. 4,774,1
No. 81, a coupler for correcting unnecessary absorption of a coloring dye by a fluorescent dye released upon coupling, and a dye precursor capable of forming a dye by reacting with a developing agent described in US Pat. No. 4,777,120. It is also preferable to use a coupler having a group as a leaving group.

Compounds releasing 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, section VII-F and ibid. 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.

R. D. No. 11449, 24241,
The bleaching accelerator releasing coupler described in JP-A No. 61-201247 is effective for shortening the processing time having a bleaching ability, and is particularly useful for a light-sensitive material using the tabular silver halide grains described above. When added, the effect is great. Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent 2,097,140.
No. 2,131,188, JP-A-59-1576.
Nos. 38 and 59-170840 are preferable. Also, JP-A-60-107029 and JP-A-60-25
2340, JP-A-1-44940, and 1-4568.
Compounds capable of releasing a fogging 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 No. 7 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 , A ligand releasing coupler described in U.S. Pat. No. 4,555,477, a coupler releasing a leuco dye described in JP-A-63-75747, and a fluorescent dye described in U.S. Pat. No. 4,774,181. Examples thereof include releasing couplers.

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

Examples of high boiling point solvents used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027. The boiling point at atmospheric pressure used in the oil-in-water dispersion method is 17
Specific examples of the high boiling point organic solvent having a temperature of 5 ° C. or higher include phthalic acid esters (eg, 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-di-ethylpropyl) phthalate), phosphoric acid or phosphonic acid esters (for example, triphenyl phosphate, tricresyl phosphate) , 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-
2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenylphosphonate), benzoic acid esters (eg 2-ethylhexylbenzoate, dodecylbenzoate, 2
-Ethylhexyl-p-hydroxybenzoate), amides (e.g., N, N-diethyldodecane amide,
N, N-diethyllaurylamide, N-tetradecylpyrrolidone), alcohols or phenols (eg isostearyl alcohol, 2,4-di-tert)
-Amylphenol), aliphatic carboxylic acid esters (for example, bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate),
Examples thereof include aniline derivatives (eg, N, N-dibutyl-2-butoxy-5-tert-octylaniline) and hydrocarbons (eg, paraffin, dodecylbenzene, diisopropylnaphthalene). The auxiliary solvent has a boiling point of about 30 ° C or higher, preferably 50 ° C or higher and about 16 ° C.
An organic solvent at 0 ° C. or lower can be used, and typical examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide and the like.

The steps and effects of the latex dispersion method and specific examples of latex for impregnation are described in, for example, US Pat. No. 4,19.
No. 9,363, West German Patent Application (OLS) No. 2,541
274 and 2,541,230.

The color light-sensitive material of the present invention contains phenethyl alcohol, JP-A-63-257747 and JP-A-62-1257.
No. 272248, and 1,2-benzisothiazolin-3-one, n-butyl p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol 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, for example, those described in RD. No. 17643, page 28, ibid. 18
716, right column, page 647 to left column, page 648, and ibid.
307105, page 879.

In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is preferably 28 μm or less, more preferably 23 μm or less, and 18 μm or less.
m or less is more preferable, and 16 μm or less is particularly preferable.
The film swelling speed T _1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. The film thickness means a film thickness measured under a humidity condition of 25 ° C. and a relative humidity of 55% (2 days), and the film swelling rate T
_1/2 can be measured according to a method known in the art. For example, A Green (A. Gre
en) et al., Photographic Science and Engineering (Photogr. Sci. En.
g. ), Vol. 19, No. 2, pp. 124-129, the measurement can be carried out by using a swellometer (swelling meter) of the type, and T _1/2 is treated with a color developer at 30 ° C. for 3 minutes 15 seconds. 90% of the maximum swollen film thickness reached when
It is defined as the time required to reach 1/2 of the saturated film thickness.

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 photographic material of the present invention is preferably provided with a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm on the side opposite to the side having the emulsion layer. This back layer preferably contains the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, surface active agent and the like. The swelling ratio of this back layer is 150.
~ 500% is preferred.

The color photographic light-sensitive material according to the present invention can be obtained by the method described in R. D. No. 17643, pages 28-29, ibid. 1
8716, 651 left column to right column, and the same No. 30710
No. 5, 880-881 can be used for development processing.

The color developing solution used for the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. Although aminophenol compounds are also useful as the color developing agent, p-phenylenediamine compounds are preferably used, and a typical example thereof is 3-methyl-4-amino-.
N, N-diethylaniline, 3-methyl-4-amino-
N-ethyl-N-β-hydroxyethylaniline, 3-
Methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-
Examples thereof include N-ethyl-β-methoxyethylaniline and their sulfates, hydrochlorides or p-toluenesulfonates. Among these, especially 3-methyl-4-
Amino-N-ethyl-N-β-hydroxyethylaniline sulfate is preferred. Two or more kinds of these compounds can be used in combination depending on the purpose.

The color developer contains a pH buffering agent such as an alkali metal carbonate, borate or phosphate, a chloride salt,
It generally contains a development inhibitor such as a bromide salt, an iodide salt, benzimidazoles, benzothiazoles or a mercapto compound, or an antifoggant. If necessary, hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine, various preservatives such as catecholsulfonic acids, ethylene glycol, Organic solvents such as diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competing couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity imparting Agents, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, various chelating agents represented by phosphonocarboxylic acids, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclo Hexane diamine tetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene--1,
1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-
Hydroxyphenylacetic acid) and salts thereof can be mentioned as representative examples.

When the reversal process is carried out, the black and white development is usually carried out before the color development. In this black-and-white developing solution, known black-and-white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone or aminophenols such as N-methyl-p-aminophenol are used alone. Alternatively, they can be used in combination. The pH of these color developing solution and black-and-white developing solution is generally 9 to 12.
The replenishment amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per 1 square meter of the light-sensitive material, and 500 ml or less by reducing the bromide ion concentration in the replenishing solution. You can also do it. When the replenishment amount is reduced, it is preferable to prevent the liquid evaporation and air oxidation by reducing the contact area with the air in the processing tank.

The contact area between the photographic processing liquid and the air in the processing tank can be expressed by the aperture ratio defined below. That is, aperture ratio = (contact area between treatment liquid and air (cm ² )) ÷ (volume of treatment liquid (cm ³ )) The above aperture ratio is preferably 0.1 or less, more preferably 0. 0.001 to 0.05. As a method of reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the surface of the photographic processing liquid in the processing tank, JP-A-1-82
No. 033, a method using a movable lid, JP-A-63-63
-216050 can be mentioned as a slit developing treatment method. To reduce the aperture ratio, not only the steps of color development and black and white development, but also the subsequent steps,
For example, it is preferably applied in all steps such as bleaching, bleach-fixing, fixing, washing with water, stabilization and the like. Further, the amount of replenishment can be reduced by using a means for suppressing the accumulation of bromide ions in the developing solution.

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

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

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their prebaths.
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
7,715, iodide salts described in JP-A-58-16,235; West German Patent Nos. 966,410 and 2,748,
No. 430, polyoxyethylene compounds; Japanese Patent Publication No. 45-8836, polyamine compounds; Others, JP-A-49-40,943, 49-59,644, 53-94,927 54-35, 727, 5
Compounds described in Nos. 5-26,506 and 58-163,940; bromide ion and the like can be used. Among them, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of having a large accelerating effect, and in particular, US Pat. No. 3,893,
858, West German Patent 1,290,812, JP-A-5
The compounds described in 3-95,630 are preferred. Furthermore,
The compounds described in US Pat. No. 4,552,834 are also preferred. 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 agent and the bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach stain. Particularly preferred organic acids are compounds having an acid dissociation constant (pKa) of 2 to 5, and specifically acetic acid, propionic acid, hydroxyacetic acid and the like are preferred.

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. It is also preferable to use a thiosulfuric acid solution in combination with a thiocyanate, a thioether compound, thiourea or the like. 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 294769A are preferable. Further, various aminopolycarboxylic acids and organic phosphonic acids are preferably added to the fixing solution and the bleach-fixing solution for the purpose of stabilizing the solution.

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

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 preferable temperature range, the desilvering rate is improved and the stain generation after the processing is effectively prevented.

In the desilvering step, it is preferable that the stirring is strengthened as much as possible. As a specific method for strengthening the stirring, a method of causing a jet of a processing solution to collide with the emulsion surface of the light-sensitive material described in JP-A-62-183460, or stirring using a rotating means of JP-A-62-183461. Method to increase the effect, further moving the photosensitive material while contacting the emulsion surface with the wiper blade provided in the solution, to improve the stirring effect by making the emulsion surface turbulent, circulation of the entire processing solution There is a method of increasing the flow rate. Such stirring improving means includes a bleaching solution, a bleach-fixing solution,
It is effective with any of the fixing solutions. 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 or eliminate the fixing inhibiting action of the bleaching accelerator.

The automatic developing machine used in the light-sensitive material of the present invention is disclosed in JP-A-60-191257 and 60-19125.
It is preferable to have the photosensitive material conveying means described in No. 8 and No. 60-191259. JP-A-60-1
As described in No. 91257, such a conveying means can significantly reduce the carry-in of the treatment liquid from the front bath to the rear bath, and is highly effective in preventing the performance deterioration of the treatment liquid. Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.

The silver halide color photographic light-sensitive material of the present invention is generally washed with water and / or stabilized after the desilvering treatment. The amount of rinsing water in the rinsing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), application, and further, the rinsing water temperature, the number of rinsing tanks (number of stages), replenishment system such as countercurrent, forward flow, and other various conditions. It can be set in a wide range.
Among 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
y of Motion Picture and T
Evolution Engineers Volume 64,
P. 248 to 253 (May 1955 issue). According to the multi-stage counter-current method described in the above literature, the amount of washing water can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate, and the suspended matter produced adheres to the photosensitive material, etc. Problems arise. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, JP-A-62-288,838 has been proposed.
The method of reducing calcium ion and magnesium ion described in No. 10 can be used very effectively. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8,542, chlorine-based bactericides such as chlorinated sodium isocyanurate, and benzotriazole are also described by Hiroshi Horiguchi in "Bacterial and Antifungal Agents". Chemistry "(1986)
Sankyo Publishing Co., Ltd., Sanitary Technology Association, "Microbial Sterilization, Sterilization, and Antifungal Technology" (1982), Industrial Technology Association, Japan Antibacterial and Antifungal Society, "Antibacterial and Antifungal Encyclopedia" (1986). Can also be used.

Rinsing water in processing the light-sensitive material of the present invention
The pH is 4-9, preferably 5-8. The washing water temperature and washing time can be variously set depending on the characteristics of the light-sensitive material, the use, etc., but are generally in the range of 15 to 45 ° C. for 20 seconds to 10 minutes, preferably 25 to 40 ° C. for 30 seconds to 5 minutes. To be 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 stabilizing treatment, JP-A-57-8543 and 58-58
All known methods described in Nos. 14834 and 60-220345 can be used.

In addition, there is a case where further stabilization treatment is carried out after the above-mentioned water washing treatment. As an example thereof, 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.

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 No. 342,597, No. 3,342,599, Research Disclosure
No. 14,850 and the same No. Schiff base type compounds described in JP-A Nos. 15,159,159, aldol compounds described in JP-A No. 13,924, metal salt complexes described in US Pat. No. 3,719,492, and urethane compounds described in JP-A-53-135628. be able to.

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 stabilizing solution preferably used in the present invention is described below.

In the present invention, it is preferred that the stabilizing solution contains substantially no formaldehyde. The term "substantially free of formaldehyde" means that the total amount of free formaldehyde and its hydrate is 0.003 mol or less per liter of the stabilizing solution.

By using such a stabilizing solution, it is possible to suppress the scattering of formaldehyde vapor during processing.

In this case, for the purpose of stabilizing the magenta dye, it is preferable that the formaldehyde-releasing compound is present in the stabilizing solution, the bleaching solution or its prebath.

Preferred compounds as the formaldehyde-releasing compound are hexamethylenetetramine and its derivatives, formaldehyde bisulfite adduct, and N-methylol compound.

These preferred compounds not only stabilize the magenta dye but also suppress the generation of yellow stain over time.

Hexamethylenetetramine and its derivatives are described in "Beilstein Handbook Der.
Organischen Chemie "(Beilsteins
Handbuch der Organishen C
hemie) Vol. Although the compounds described in 212 can be used, hexamethylenetetramine is particularly preferable.

As the formaldehyde bisulfite addition product, sodium formaldehyde bisulfite is preferable.

As the N-methylol compound, an N-methylol compound of pyrazole and its derivative, an N-methylol compound of triazole and its derivative, and an N-methylol compound of urazole and its derivative are particularly preferable.

Of the above formaldehyde-releasing compounds,
Particularly preferred are hexamethylenetetramine, and sodium formaldehyde bisulfite, and the above-mentioned preferred N-methylol compounds.

Of these, N-methylol compounds of pyrazole and its derivatives, N-methylol compounds of triazole and its derivatives, and N-methylol compounds of urazole and its derivatives are preferable.

Specific examples of these N-methylol compounds are: 1-hydroxymethylpyrazole 1-hydroxymethyl-2-methylpyrazole 1-hydroxymethyl-2,4-dimethylpyrazole 1-hydroxymethyltriazole 1-hydroxymethyl It is urazole.

Of these, the most preferred is 1-hydroxymethylpyrazole.

The above N-methylol compound is prepared by reacting an amine compound not having a methylol group with formaldehyde or paraformaldehyde.
Can be easily synthesized.

When the above N-methylol compound is used, it is preferable that an amine compound having no methylol group is made to coexist in the treatment liquid, and it is preferable that the N-methylol compound is present at a molar concentration of 0.2 to 10 times.

The amount of the formaldehyde-releasing compound added is preferably 0.003 to 0.2 mol, and more preferably 0.005 to 0.5 mol, per liter of the treatment liquid.

These formaldehyde-releasing compounds are
You may use together 2 or more types in a bath.

[0213]

EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. (Example 1) Sample 101, which is a multilayer color light-sensitive material, was prepared by applying multiple layers of the following composition on a cellulose triacetate film support having an undercoat. (Photosensitive layer composition) The numbers corresponding to the respective components indicate the coating amount expressed in g / m ² , and for silver halide, the coating amount in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown in mol unit per mol of silver halide in the same layer. (Sample 101) First layer (antihalation layer) Black colloidal silver 0.18 Gelatin 1.40 ExM-1 0.18 ExF-1 2.0 × 10 ^-3 Second layer (intermediate layer) Emulsion G Silver 0 0.065 2,5-di-t-pentadecylhydroquinone 0.18 Compound of the present invention MII-3 0.020 UV-1 0.060 UV-2 0.080 UV-3 0.10 HBS-1 0.10 HBS-2 0.020 Gelatin 1.04 Third layer (first red-sensitive emulsion layer) Emulsion A Silver 0.25 Emulsion B Silver 0.25 ExS-1 6.9 × 10 ⁻⁵ ExS-2 1.8 × 10 ⁻⁵ ExS-3 3.1 × 10 ⁻⁴ ExC-1 0.17 ExC-3 0.017 ExC-4 0.17 ExC-7 0.020 UV-1 0.070 UV-2 0.050 UV -3 0.070 HBS-1 0.060 gelatin 0.87 Fourth layer (second red-sensitive emulsion layer) Emulsion D Silver 0.80 ExS-1 3.5 × 10 ⁻⁴ ExS-2 1.6 × 10 ⁻⁵ ExS-3 5.1 × 10 ^{− 4} ExC-1 0.20 ExC-2 0.0050 ExC-4 0.20 ExC-7 0.015 UV-1 0.070 UV-2 0.050 UV-3 0.070 Gelatin 1.30 Fifth layer (Third Red Sensitive Emulsion Layer) Emulsion E Silver 1.40 ExS-1 2.4 × 10 ⁻⁴ ExS-2 1.0 × 10 ⁻⁴ ExS-3 3.4 × 10 ⁻⁴ ExC-1 0.097 ExC-2 0.0050 ExC-3 0.065 ExC-6 0.020 HBS-1 0.22 HBS-2 0.10 Gelatin 1.63 6th layer (intermediate layer) Cpd-1 0.040 HBS-1 0.020 Gelatin 0.80 Seventh layer (first green-sensitive emulsion layer) Emulsion C Silver 0.30 ^{xS-4 2.6 × 10 -5 ExS} -5 1.8 × 10 -4 ExS-6 6.9 × 10 -4 ExM-1 0.021 ExM-2 0.26 ExM-3 0.030 ExY- 1 0.025 HBS-1 0.10 HBS-3 0.010 Gelatin 0.63 Eighth layer (second green emulsion layer) Emulsion D Silver 0.55 ExS-4 2.2 × 10 ^-5 ExS-5 1.5 × 10 ⁻⁴ ExS-6 5.8 × 10 ⁻⁴ ExM-2 0.094 ExM-3 0.026 ExY-1 0.018 HBS-1 0.16 HBS-3 8.0 × 10 ^{− 3} Gelatin 0.50 9th layer (3rd green emulsion layer) Emulsion E Silver 1.55 ExS-4 4.6 × 10 ⁻⁵ ExS-5 1.0 × 10 ⁻⁴ ExS-6 3.9 × 10 ^{-4 ExC-1 0.015 ExM-1} 0.013 ExM-4 0.065 ExM-5 0.019 HBS- 0.25 HBS-2 0.10 Gelatin 1.54 10th layer (yellow filter layer) Yellow colloidal silver 0.035 Cpd-1 0.080 HBS-1 0.030 Gelatin 0.95 11th layer (1st layer) Blue-sensitive emulsion layer) Emulsion C Silver 0.18 ExS-7 8.6 × 10 ⁻⁴ ExY-1 0.042 ExY-2 0.72 HBS-1 0.28 Gelatin 1.10 12th layer (2nd blue) Emulsion-sensitive layer) Emulsion D Silver 0.40 ExS-7 7.4 × 10 ⁻⁴ ExC-7 7.0 × 10 ⁻³ ExY-2 0.15 HBS-1 0.050 Gelatin 0.78 13th layer ( Third blue-sensitive emulsion layer) Emulsion F Silver 0.70 ExS-7 2.8 × 10 ⁻⁴ ExY-2 0.20 HBS-1 0.070 Gelatin 0.69 14th layer (first protective layer) Emulsion G Silver 0.20 UV-4 0.11 UV-5 0.1 7 HBS-1 5.0 × 10 ^-2 gelatin 1.00 Fifteenth layer (second protective layer) H-1 0.40 B-1 (diameter 1.7 μm) 5.0 × 10 ^-2 B-2 ( Diameter 1.7 μm) 0.10 B-3 0.10 S-1 0.20 Gelatin 1.20 Furthermore, all layers have storability, processability, pressure resistance, mildew / bacterial resistance, antistatic property and coating. In order to improve the sex, W-1,
W-2, W-3, 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, F-1
3, F-14, F-15, F-16, F-17, and iron salt, lead salt, gold salt, platinum salt, iridium salt, and rhodium salt are contained.

Emulsions A to G used to prepare Sample 101
Is shown in Table 1 below.

[0215]

[Table 1] In Table 1, (1) Emulsions A to G were reduction-sensitized at the time of grain preparation using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-191938. (2) Emulsions A to G were subjected to gold sensitization, sulfur sensitization and selenium sensitization in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate according to the examples of Japanese Patent Application No. 2-34090. It has been subjected. (3) For the preparation of tabular grains, low molecular weight gelatin is used according to the examples of JP-A-1-158426. (4) Dislocation lines as described in Japanese Patent Application No. 2-34090 are observed in tabular grains and normal crystal grains having a grain structure by using a high voltage electron microscope.

The structural formulas of the compounds used in the preparation of Sample 101 are shown in Chemical Formulas 62 to 74 below.

[0217]

[Chemical formula 62]

[0218]

[Chemical 63]

[0219]

[Chemical 64]

[0220]

[Chemical 65]

[0221]

[Chemical 66]

[0222]

[Chemical 67]

[0223]

[Chemical 68]

[0224]

[Chemical 69]

[0225]

[Chemical 70]

[0226]

[Chemical 71]

[0227]

[Chemical 72]

[0228]

[Chemical 73]

[0229]

[Chemical 74] (Samples 102 to 112) Third and Fourth Samples 101
The colored cyan couplers of the present invention were added to the layer as shown in Table 2 below to prepare samples 102 to 112.

[0230]

[Table 2] These samples were subjected to red imagewise exposure and subjected to the color development processing described below. The value obtained by subtracting the yellow fog density from the yellow density at a constant cyan density (fog + 2.0) is shown in Table 3 below as the color turbidity.

[0231]

[Table 3] Processing method Processing time Processing temperature Replenishment amount Tank capacity Color development 3 minutes 15 seconds 37.8 ℃ 20ml 10 liters Bleach 45 seconds 38 ℃ 5ml 4liters Bleach fixing 45 seconds 38 ℃ -4liters Bleach fixing (2) 45 seconds 38 ℃ 30ml 4 liters Washed with water (1) 20 seconds 38 ℃ -2 liters Washed with water (2) 20 seconds 38 ℃ 30ml 2 liters Stabilized 20 seconds 38 ℃ 20ml 2 liters Dry 1 minute 55 ℃ Replenishment amount per 35mm width 1m length The steps of bleach-fixing and washing are (2) to (1) respectively.
And the overflow of the bleaching solution was all introduced into the bleach-fixing (2).

In the above processing, the amount of the bleach-fixing solution brought into the washing step was 2 ml per 1 m length of the light-sensitive material having a width of 35 mm. (Color developer) Mother liquor (g) Replenisher (g) Diethylenetriaminepentaacetic acid 5.0 6.0 Sodium sulfite 4.0 5.0 Potassium carbonate 30.0 37.0 Potassium bromide 1.3 0.5 Iodide Potassium 1.2 mg-hydroxylamine sulfate 2.0 3.6 4- [N-ethyl-N-β-hydroxyethylamino] 2-methylaniline sulfate 4.7 6.2 Water was added to 1.0 liter 1 0.0 liter pH 10.00 10.15 (bleaching solution) Mother liquor (g) Replenishing solution (g) 1,3-Diaminopropane tetraacetic acid Ferric ammonium monohydrate 144.0 206.0 1,3-Diaminopropane Tetraacetic acid 2.8 4.0 Ammonium bromide 84.0 120.0 Ammonium nitrate 17.5 25.0 Ammonia water (27%) 10.0 1.8 Acetic acid (98%) 51.1 7 0.0 Water 1.0 liter 1.0 liter pH 4.3 3.4 (bleach-fixer) mother liquor (g) replenisher (g) ethylenediaminetetraacetic acid ammonium ferric dihydrate 50.0-ethylenediamine Tetraacetic acid disodium salt 5.0 25.0 Sodium sulfite 12.0 20.0 Ammonium thiosulfate aqueous solution (700 g / l) 290.0 ml 320.0 ml Ammonia water (27%) 6.0 ml 15.0 ml Add water 1 0.0 liter 1.0 liter pH 6.8 8.0 (wash water) mother liquor and replenisher common tap water is H type strong acid cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH type strong Basic anion exchange resin (the same Amberlite IRA-4
00) packed in a mixed bed column to treat calcium and magnesium ions at a concentration of 3 mg / liter or less, and then 20 mg of sodium isocyanurate dichloride /
L and 150 mg / L of sodium sulfate were added. The pH of this liquid was in the range of 6.5 to 7.5. (Stabilizing Solution) mother liquor replenisher common (units g) Formalin (37%) 1.2 ml Surfactant _{(C 10 H 21 -O- (CH} 2 CH 2 O) 10 -H) 0.4 Ethylene glycol 1. 0 Water was added to obtain 1.0 liter pH 5.0 to 7.0. Then, 101 to 112 of these samples were processed into a Leica size for camera photography, and then a color rendition chart manufactured by Macbeth was used for the same light source. And photographed and developed, printed on Fujicolor HG paper so that a gray plate with an optical density of 0.7 reproduces both lightness and hue, and measured the yellow density and magenta density of the skin color part of the Macbeth chart and the yellowness of the skin color, It was used as a redness scale. This is shown in Table 3. In addition, the results of visually evaluating the flesh tones are also shown in Table 3 above.

[0233]

As described above, according to the present invention, it is possible to improve the saturation of red color without impairing the color reproducibility of a color such as a mixture of red and other colors such as skin color. A silver halide color photographic light-sensitive material having improved color reproducibility can be provided.

Claims (1)

[Claims] 1. A silver halide color photographic light-sensitive material having at least one layer of a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer on a support. At least one of the silver halide emulsion layers contains both a yellow colored cyan coupler and a magenta colored cyan coupler, and the content of the yellow colored cyan coupler in the layer is the content of the magenta colored cyan coupler in the layer. A silver halide color photographic light-sensitive material having a molar ratio of 0.3 to 2.5.