JPH0954406A - Photographic coupler, silver halide color photographic sensitive material and color image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photographic coupler useful for a silver halide photographic sensitive material, etc., having satisfactory coloring performance in rapid processing and ensuring superior gradation of cyan density and superior gradation balance of three colors by using a specified naphthol deriv. SOLUTION: This photographic coupler is represented by the formula, wherein R1 is alkyl, aryl or a heterocyclic group, each of R2 and R3 is H, alkyl or aryl, (n) is an integer of 1-10, L is -CO-, -C(O)O-, -C(O)N(R6 )-, -SO2 N(R6 )-, -N(R6 )C(O)-, -N(R6 )C(O)O-, etc., R4 is -C(O)R8 , -C(O)OR8 , -C(O)N(R6 )(R8 ), etc., R6 is H, alkyl or aryl, R8 is alkyl or aryl, R5 is a substituent, (m) is an integer of 0-3 and X is H or a substituent which is released in coupling with the oxidized body of a developing agent.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a coupler useful for a silver halide photographic light-sensitive material, a silver halide photographic light-sensitive material containing the coupler and an image forming method thereof. Improves the photographic performance obtained when the same color development and rapid color development are performed, in particular, the tone gradations of the three colors of yellow, magenta, and cyan are improved, and tone reproduction and color reproducibility are improved. Silver halide color photographic light-sensitive material, and
The present invention relates to an image forming method.

[0002]

2. Description of the Related Art In recent years, a great deal of research and development has been conducted on the color development processing of color photographic light-sensitive materials in order to shorten the processing time. With regard to color negative development processing, the conventional processing has been speeded up mainly by shortening the processing time of the desilvering process. For example, Fuji Photo Film Co., Ltd. introduced for the minilab market. In the rapid processing CN-16FA, the time is shortened to 8 minutes and 15 seconds. However, in this processing, the color development time accounts for about 40% of the total color negative development processing time. Therefore, reducing the color development time, which accounts for a large proportion of the total processing time of the current color negative development processing step, is a major problem in the art. In addition, many proposals have been made to solve this problem.

However, high temperature processing for color development is
Applying high pH treatment of developer, high concentration treatment of color developing agent, improvement of film quality of light-sensitive material, thinning of photosensitive material constituent layers or combination of these, processing is performed with shorter color development time than current However, the gradation balance of the three colors of yellow, magenta, and cyan, which are the most important as a color negative, is greatly disturbed, and the color development of cyan in the red-sensitive layer coated on the side closer to the support is delayed. Therefore, the color print from such a color negative is seriously impairing the tone reproducibility and the color reproducibility, and at present, it is not possible to achieve a satisfactory reduction of the color development time. Therefore, now
In order to obtain excellent development finish quality, one of the same sensitized materials is developed by a widely-distributed color negative processing, and the other is processed by rapid processing with different color development times. The development of a technique for controlling the density gradation and the gradation balance of the three colors is very important, and technical development for this purpose is strongly desired. Under such circumstances, control of the color forming property of the cyan coupler is one of the important techniques.
The use of the 5-amidonaphthol-based cyan couplers described in JP-A-14891, JP-A-2-2302239 and JP-A-4-73750 was insufficient to obtain excellent development finish quality.

[0004]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to firstly provide a coupler useful for a silver halide photographic light-sensitive material and the like. Secondly, a cyan which has a sufficient color forming performance in rapid processing. A silver halide color photographic light-sensitive material containing a coupler and an image forming method are provided. Thirdly, to provide a silver halide color photographic light-sensitive material and an image forming method which are excellent in gradation of cyan density and gradation balance of three colors in ordinary color negative processing and rapid processing.

[0005]

The objects of the present invention have been achieved by the following. (1) A photographic coupler represented by the following general formula [I]. General formula [I]

[0006]

Embedded image

In the formula, R ₁ represents an alkyl group, an aryl group or a heterocyclic group, and R ₂ and R ₃ represent a hydrogen atom, an alkyl group or an aryl group. n represents an integer of 1 to 10. L is -CO-, -C (O) O-, -C (O) N
_{(R 6) -, - SO} 2 N (R 6) -, - N (R 6) C
(O) -, - N ( R 6) C (O) O -, - N (R 6) C
_{(O) N (R 7)} -, - N (R 6) SO 2 - or -N
_{(R 6) SO 2 N (} R 7) - represents, R ₄ is -C (O)
_{R 8, -C (O) OR} 8, -C (O) N (R 6)
_{(R 8), - SO 2} R 8 or _{-SO 2 N (R 6) (} R
₈ ). R ₆ represents a hydrogen atom, an alkyl group or an aryl group, and R ₇ represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. R ₈ represents an alkyl group or an aryl group. R ₅ represents a substituent, and m represents 0, 1, 2 or 3. X represents a hydrogen atom or a substituent which is released upon coupling with an oxidized product of a developing agent. (2) A photographic coupler represented by the following general formula [II]. General formula (II)

[0008]

Embedded image

Where R ₁ , R ₂ , R ₃ , n, R ₄ ,
R < ₅ >, R < ₆ >, R <_7> , R < ₈ > and m have the same meanings as those in the general formula [I], and Y represents a substituent which leaves upon coupling with the oxidized product of the developing agent. (3) A photographic coupler represented by the following general formula [III]. General formula [III]

[0010]

[Chemical 6]

Where R ₁ , R ₂ , R ₃ , n, R ₄ ,
R ₅ , R ₆ , R ₇ , R ₈ and m have the same meanings as those in the formula [I], and Z represents a halogen atom.

(4) A silver halide color photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, which is represented by the general formula [I] described in (1) above. A coupler, a coupler represented by the general formula [II] described in the above (2), or the above (3)
A silver halide color photographic light-sensitive material containing a coupler represented by the general formula [III] described in 1.

(5) A color image forming method characterized in that a color image is formed by processing the silver halide color photographic light-sensitive material described in (4) above with a developing solution A described below. . (Development treatment A) A development treatment using a color developing solution having a color developing time of 150 to 200 seconds, a color developing solution temperature of 37 to 40 ° C., and a color developing agent concentration of 15 to 20 mmol / liter.

(6) A color image forming method characterized in that a color image is formed by processing the silver halide color photographic light-sensitive material described in (4) above with a developing processing solution B described below. . (Development processing B) Color development time is 25 to 90 seconds, temperature of color developing solution is 40 to 60 ° C., and development processing using color developing solution containing 25 to 80 mmol / l of concentration of color developing agent .

(7) The silver halide according to the above (4), which has a magnetic recording layer containing magnetic grains on the side opposite to the photosensitive silver halide emulsion layer with the support interposed therebetween. Color photographic light-sensitive material.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below.
In the couplers represented by the general formula [I], the general formula [II] and the general formula [III], R ₁ represents an alkyl group, an aryl group or a heterocyclic group, and the alkyl group has 1 to 1 carbon atoms.
32, preferably 1 to 22 saturated or unsaturated, chain or cyclic, linear or branched, substituted or unsubstituted alkyl group. As the substituent of the substituted alkyl group, a halogen atom (for example, fluorine, chlorine, bromine), a hydroxy group, a cyano group, a nitro group, a carboxyl group, an aryl group (having 6 to 20 carbon atoms. For example, phenyl, naphthyl, 4-methoxyphenyl) , 2-dodecyloxyphenyl, 2-ethoxycarbonylphenyl), alkoxy groups (having 1 carbon atom)
~ 20. For example, methoxy, ethoxy, isopropoxy, butoxy, 2-ethylhexyloxy, methoxyethoxy, 2-phenoxyethoxy) aryloxy group (having 6 to 24 carbon atoms, phenoxy, 2-methoxyphenoxy, 2-ethoxycarbonylphenoxy, 4-chloro). Phenoxy, 4-methylphenoxy, 4-phenylphenoxy, 2,4-di-t-amylphenoxy, 3-pentadecylphenoxy), heterocyclic oxy group (having 3 to 1 carbon atoms)
0. For example, 3-pyrazolylroxy, 2-pyridyloxy, 4-pyridyloxy), an alkoxycarbonyl group (having 2 to 24 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl, isoamylcarbonyl, dodecyloxycarbonyl), an aryloxycarbonyl group (carbon Number 7 to 24. For example, phenoxycarbonyl, 2-methoxyphenoxycarbonyl, naphthyloxycarbonyl), acylamino group (having 2 to 24 carbon atoms, for example, acetamide, butanoic acid amide, hexanoic acid amide, pivalic acid amide, dodecanoic acid amide, Benzamide, 4-t
-Butylbenzamide), a carbamoyl group (having 1 to 1 carbon atoms
24. For example, N-butylcarbamoyl, N, N-diethylcarbamoyl, N-phenylcarbamoyl, N-cyclohexylcarbamoyl), a sulfonamide group (having 1 to 24 carbon atoms, for example, methanesulfonamide, butanesulfonamide, octanesulfonamide, hexadecane). Sulfonamide, benzenesulfonamide, 4-dodecyloxybenzenesulfonamide,

2-octyloxy-5-t-octylbenzenesulfonamide), sulfamoyl group (having 1 carbon atom)
~ 24. For example, N-ethylsulfamoyl, N-cyclehexylsulfamoyl, N, N-diethylsulfamoyl, N-phenylsulfamoyl), alkoxycarbonylamino group (having 2 to 24 carbon atoms, for example, ethoxycarbonylamino). , Butoxycarbonylamino, benzyloxycarbonylamino), an alkylthio group (having 1 to 24 carbon atoms, for example, methylthio, ethylthio, butylthio, hexylthio, benzylthio), an arylthio group (having 6 to 24 carbon atoms, for example, phenylthio, naphthylthio, 4-). Octyloxyphenylthio, 2-ethoxycarbonylphenylthio, 2-butoxy-5-t-octylphenylthio), alkylsulfonyl group (having 1 carbon atom)
~ 24. For example, methylsulfonyl, butylsulfonyl, octylsulfonyl, dodecylsulfonyl), an arylsulfonyl group (having 6 to 24 carbon atoms, for example, benzenesulfonyl, 2-butoxy-5-t-octylphenylsulfonyl, 4-dodecyloxyphenylsulfonyl), Ureido group (having 1 to 24 carbon atoms, for example, N-phenylureido, N, N-diethylureido), heterocyclic group (having 1 to 12 carbon atoms, at least one or more nitrogen atom, oxygen atom or sulfur atom as a hetero atom) Having 3 to 12, preferably a 5- or 6-membered monocyclic or condensed ring, for example, 2-pyridyl, 1-pyrrolyl, morpholino, indolyl), an acyl group (having 2 to 20 carbon atoms, for example, acetyl, benzoyl, Pivaloyl), an imide group (having 4 to 24 carbon atoms. For example, succinic acid Bromide, phthalic acid imide) and the like. The above substituents may further have a substituent. Examples of the substituent include the substituents mentioned here.

The aryl group represented by R ₁ represents a substituted or unsubstituted aryl group, and the substituent of the substituted aryl group includes the substituents and alkyl groups described above for the substituted alkyl group. The heterocyclic group for R ₁ has 1 to 1 carbon atoms.
2. As a hetero atom, for example, at least one nitrogen atom, oxygen atom or sulfur atom is a 3 to 12, preferably 5 or 6 membered monocyclic or condensed ring (for example, imidazolyl, pyrazolyl, tetrazolyl, furyl, pyrrolyl, benzimidazolyl). , Zenzotriazolyl). R ₁ is preferably an alkyl group or an aryl group, more preferably an alkyl group. Most preferably, it is an unsubstituted alkyl group.

In the couplers represented by the general formula [I], the general formula [II] and the general formula [III], R ₂ and R ₃
Each represents a hydrogen atom, an alkyl group or an aryl group, and the alkyl group and the aryl group have the same meanings as the alkyl group and the aryl group described for R ₁ . R ₂ and R ₃ may be the same or different. R ₂ and R ₃ are preferably a hydrogen atom, an alkyl group or an aryl group, more preferably R ₂ is a hydrogen atom, and R 2
₃ is an alkyl group. Most preferably R ₂ and R ₃
Are both hydrogen atoms. n represents an integer of 1 to 10,
It is preferably an integer of 1 to 4, more preferably 1
Or 2, and most preferably 1.

In the coupler represented by the general formula [I], L is --CO--, --C (O) O--, --C (O) N (R
_{6) -, - SO 2 -} , - SO 2 N (R 6) -, - N (R
_{6) C (O) -,} - N (R 6) C (O) O -, - N (R
_{6) C (O) N (} R 7) -, - N (R 6) SO 2 - or _{-N (R 6) SO 2 N} (R 7) - represents a. R ₆ represents a hydrogen atom, an alkyl group or an aryl group, and R ₇ represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. The alkyl group and aryl group of R ₆ are the same as the above R ₁
Synonymous with the alkyl group and the aryl group described in,
The alkyl group, aryl group and heterocyclic group for R _{7 have} the same meaning as the alkyl group, aryl group and heterocyclic group described for R ₁ . L is -C (O) O-, -C (O) N
_{(R 6) -, - SO} 2 N (R 6) -, - N (R 6) C
(O) -, - N ( R 6) C (O) O -, - N (R 6) C
_{(O) N (R 7)} - or -N (R ₆₎ SO ₂ - are preferred, -C (O) O -, - C (O) N (R 6) -, - N
_{(R 6) C (O)} -, - N (R 6) C (O) O-, or _{-N (R 6) C (O} ) N (R 7) - is more preferred. Most preferably -C (O) O- or -C (O)
N (R ₆₎ - is. R ₆ is preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom or an alkyl group. Most preferably, it is a hydrogen atom. R ₇ is preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom or an alkyl group. Most preferably, it is a hydrogen atom.

In the couplers represented by the general formulas [I], [II] and [III], R ₄ is --C (O).
_{R 8, -C (O) OR} 8, -C (O) N (R 6)
_{(R 8), - SO 2} R 8 or _{-SO 2 N (R 6) (} R
₈ ). R ₆ has the same meaning as described above. R
₈ represents an alkyl group or an aryl group, and the alkyl group and the aryl group have the same meanings as the alkyl group and the aryl group described for R ₁ . R ₄ is -C (O) R _8, -
C (O) OR ₈ or —SO ₂ R ₈ is preferable, and —C
(O) R ₈ or —C (O) OR ₈ is more preferable.
Most preferably -C (O) OR _8. R ₈ is preferably an alkyl group, more preferably an unsubstituted alkyl group.

In the couplers represented by the general formula [I], the general formula [II] and the general formula [III], R ₅ represents a substituent, and the substituent is an alkyl group or the above R ₁ . Represents a substituent of the substituted alkyl group. R ₅ is preferably a halogen atom, an acylamino group, an alkoxy group,
Sulfonamide groups are preferred. m is 0, 1, 2 or 3
When m is 2 or 3, the substituents of R ₅ may be the same or different. m is preferably 0 or 1, and most preferably 0. In the coupler represented by the general formula [I], X represents a hydrogen atom or a substituent capable of splitting off upon coupling with an oxidized product of a developing agent. Specific examples of X include a hydrogen atom, a halogen atom (eg, chlorine atom, bromine atom), an alkoxy group (eg, methoxy, ethoxy, methylsulfonylmethoxy, 2-carboxyethoxy, methoxymethoxy, methanesulfonamidomethoxy, 2-carboxy). Methylthioethoxy), aryloxy group (eg, phenoxy, 4-carboxyphenoxy, 4-t-octylphenoxy, 4′-hydroxybenzenesulfonylphenoxy, 2-acetylaminophenoxy), acyloxy group (eg, acetoxy, benzoyloxy group) A sulfonyloxy group (eg, methanesulfonyloxy, benzenesulfonyloxy),
Carbonamido group (eg, pentafluorobutyroylamino, trifluoroacetylamino), sulfonamide group (eg, methanesulfonylamino, p-chlorobenzenesulfonylamino), alkoxycarbonyloxy group (eg, ethoxycarbonyloxy, isobutoxycarbonyloxy) ), An arylcarbonyloxy group (eg, phenoxycarbonyloxy, 1-naphthyloxycarbonyloxy), a heterocyclic group (eg, 1-
Pyrazolyl, 1-imidazolyl), imide group (for example,
Succinimide, methylhydantoin-1-yl, 5,
5-dimethylhydantoin-1-yl, 5,5-dimethyloxazolidin-2,5-dione-3-yl, pyrazolyl), an alkylthio group (for example, dodecylthio, 2-
Ethoxycarbonyltetradecylthio), an arylthio group (for example, phenylthio, 2-butoxy-5-t-octylphenylthio, 2-pivaloylphenylthio, 2
-Benzyloxycarbonylaminophenylthio), a heterocyclic thio group (eg, tetrazolylthio, oxadiazolethio, thiadiazolethio), a sulfoxide group (eg, methylsulfoxide, ethylsulfoxide,
Phenyl sulfoxide), a carbamoyloxy group (for example, N, N-dimethylcarbamoyloxy, N-ethoxycarbonylmethylcarbamoyloxy, N-phenylcarbamoyloxy, N-methyl-N-phenylcarbamoyloxy), an azo group (for example, phenylazo, 2-
(Methoxycarbonylphenylazo) and the like.

Preferred X is a hydrogen atom, a halogen atom, an aryloxy group or an alkoxy group, more preferably a hydrogen atom, a halogen atom or an alkoxy group. Most preferably, it is a chlorine atom.

Y of the coupler represented by the general formula [II] represents a substituent which is released upon coupling with the oxidized product of the developing agent and has the same meaning as the substituent described in the above X. Y is preferably a halogen atom, an aryloxy group or an alkoxy group, more preferably a halogen atom or an alkoxy group. Most preferably, it is a chlorine atom. General formula (II
Z of the coupler represented by I] represents a halogen atom, preferably a chlorine atom.

The couplers represented by the general formulas [I], [II] and [III] do not form a so-called bis body having two or more coupler skeletons or a so-called polymer having a repeating unit. The couplers represented by the general formula [I] and the general formula [II] are preferable, and the couplers represented by the general formula [I]
The coupler represented by is most preferable. In the coupler represented by the general formula [I], preferably R ₁ is an alkyl group or an aryl group, R ₂ and R ₃ are hydrogen atoms,
It is an alkyl group or an aryl group, and L is -C (O) O.
-, - C (O) N (R 6) -, - SO 2 N (R 6) -,
_{-N (R 6) C (O} ) -, - N (R 6) C (O) O-,
_{-N (R 6) C (O} ) N (R 7) - or -N (R ₆₎
SO ₂ −, n is an integer of 1 to 4, and R ₄ is −.
_{C (O) R 8, -C} (O) OR 8 or -SO ₂ R _8,
, M is 0, X is a hydrogen atom, a halogen atom,
It is a coupler represented by an aryloxy group and an alkoxy group.

More preferred couplers are those in which R ₁ is an alkyl group, R ₂ is a hydrogen atom, R ₃ is an alkyl group, n is 1 or 2, L is --C (O) O--,-. C
_{(O) N (R 6)} -, - N (R 6) C (O) -, - N
_{(R 6) C (O)} O-, or _{-N (R 6) C (O} ) N
(R ₇₎ - a and, R ₄ is -C (O) R ₈ or -C
(O) OR ₈ , R ₆ and R ₇ are hydrogen atoms or alkyl groups, R ₈ is an alkyl group, m is 0, and X is a hydrogen atom, a halogen atom or an alkoxy group. It is a coupler.

Most preferred couplers are those in which R ₁ is an unsubstituted alkyl group, R ₂ and R ₃ are both hydrogen atoms,
n is 1 and L is -C (O) O- or -C (O) N
(R ₆₎ - a and, R ₄ is -C (O) OR _8, R
₆ is a hydrogen atom, R ₈ is an unsubstituted alkyl group, m is 0, and X is a coupler represented by a chlorine atom.

Specific representative examples of the couplers used in the present invention are shown below, but the couplers are not limited to these.

[0029]

[Chemical 7]

[0030]

Embedded image

[0031]

Embedded image

[0032]

Embedded image

[0033]

Embedded image

Next, a general method for synthesizing the coupler of the present invention will be described. The general synthesis method of the present invention is Japanese Patent Publication No.
It can be synthesized by the method described in JP-A-14891, JP-A-63-93754 and JP-B-6-43380.

Next, a concrete synthesis example will be described. Synthesis Example-1 (Exemplary Coupler C-1) Synthesis Scheme (A)

[0036]

[Chemical 12]

(Synthesis of Compound (1)) 100 g of glycine
Then, 500 ml of acetic acid was added to 207 g of phthalic anhydride, and the mixture was heated under reflux for 6 hours. The reaction solution was poured into 2000 ml of water, and the precipitated crystals were filtered, washed with water and dried. 264 g (96.9%) of compound (1) was obtained.

(Synthesis of compound (3)) Toluene (5) was added to 264 g (1.29 mol) of compound (1) obtained by the above-mentioned synthesis method.
00 ml was added and the mixture was heated and stirred. To this solution, 141 ml of thionyl chloride was added dropwise, and the mixture was heated and stirred for 8 hours. After completion of the reaction, toluene and excess thionyl chloride were distilled off under reduced pressure to synthesize acid chloride (compound (2)). 118 g of this acid chloride (compound (2)) was added to 200 ml of ethyl acetate.
It was dissolved in ml. This solution was added to dodecanol 93.2.
Ethyl acetate 400 ml and dimethylacetamide 10 g
The solution added with 0 ml was added dropwise with stirring. After dropping,
The mixture was stirred for 4 hours at room temperature. After the reaction was completed, water was added to the reaction solution and the mixture was extracted with ethyl acetate. Wash the ethyl acetate layer with water,
After drying over anhydrous magnesium sulfate, ethyl acetate was distilled off under reduced pressure. Hexane was added to the residue to precipitate crystals. The crystals were filtered and dried. Compound (3) 17
7.8 g (95.2%) was obtained.

(Synthesis of Compound (4)) To 162 g (0.434 mol) of the compound (3) synthesized by the above method, 650 ml of ethanol was added and stirred at room temperature. 23.9 g (0.477 mol) of hydrazine monohydrate was added dropwise to this solution. After stirring at room temperature for 1 hour, heating and stirring were performed for 4 hours. After completion of the reaction, the mixture was cooled to room temperature and 43 ml of hydrochloric acid was added dropwise. Precipitated crystals (phthalhydrazide) were removed by filtration, and the filtrate was neutralized by adding an aqueous sodium hydroxide solution (sodium hydroxide 20 g, water 100 ml). 800 ml of ethyl acetate was added to this solution for extraction. The ethyl acetate solution was washed with saturated saline and dried over anhydrous sodium sulfate, and then ethyl acetate was distilled off under reduced pressure. 98.0 g (92.8%) of compound (4) was obtained.

(Synthesis of Compound (6)) 24.3 g (0.1 mol) of Compound (4) obtained by the above method, Compound (5)
Dimethylacetamide 3 was added to 41.7 g (0.11 mol).
00 ml was added, and the mixture was heated and stirred at 100 ° C. under a nitrogen gas stream. After heating and stirring for 5 hours, the mixture was cooled to room temperature.
After completion of the reaction, methanol (750 ml) and water (200 ml) were added to the reaction solution.
Crystals were precipitated by adding ml. The crystals were filtered, washed with methanol, and then dried. This crystal was subjected to silica gel column chromatography (eluent: n-hexane /
After purification with chloroform), it was recrystallized with methanol. 37.2 g (70.4%) of compound (6) was obtained.

Synthesis of (Exemplified Coupler C-1) To 26.4 g (0.05 mol) of the compound (6) obtained by the above method, 200 ml of ethyl acetate was added and stirred at room temperature. 6.75 g (0.05 mol) of sulfuryl chloride was added dropwise to this solution. After stirring at room temperature for 2 hours, the reaction solution was washed with water.
The ethyl acetate solution was dried over anhydrous magnesium sulfate,
Ethyl acetate was distilled off under reduced pressure. Methanol 3 in the residue
50 ml was added to precipitate crystals. The crystals were filtered and dried, and then recrystallized with a mixed solvent of n-hexane / ethanol for purification. 26.3 g of exemplified coupler C-1
(93.4%) was obtained. Proton NMR (ppm) (multiplicity, integration _{value) (CDCl 3) 13.4 (s} , 1H), 8.40~8.
28 (br, 1H), 8.25 (d, 1H), 8.06
(D, 1H), 7.53 (t, 1H), 7.42 (s,
1H), 7.09 (t, 1H), 4.30 to 4.15
(M, 4H), 4.01 (d, 2H), 2.12 to 1.
90 (m, 1H), 1.80 to 1.65 (m, 2H),
1.47 to 1.15 (br, 18H), 1.00 (d,
6H), 0.90 (t, 3H)

The proton N of some exemplary couplers of this invention
The results of MR are shown in Table 1.

[0043]

[Table 1]

The cyan couplers represented by the general formulas [I], [II] and [III] have the same coupler when the red-sensitive emulsion layer is divided into two or more layers having different sensitivities. They may be used, or different couplers may be used properly. Further, a plurality of couplers can be mixed and used in the same layer.

The couplers represented by the general formula [I], the general formula [II] and the general formula [III] are 1 × 10 ^-3 to 2 mol, preferably 1 per mol of silver halide in the layer which is usually used.
X10 ^-2 to 1 mol, more preferably 5 x 10 ^{-2 to} 5 x 1
It can be used in the range of 0 ^-1 mol.

The couplers represented by the general formula [I], the general formula [II] and the general formula [III] are usually used in the red-sensitive silver halide emulsion layer, but the other light-sensitive layer is a green-sensitive halogen. It can also be used in a silver halide emulsion layer, a blue-sensitive silver halide emulsion layer and the like according to the purpose. Further, it can be used for a non-photosensitive layer such as an antihalation layer, an intermediate layer and the like. In this case, the amount used is in the range of 1 × 10 ⁻⁶ to 1 × 10 ⁻³ mol per 1 m ^{2 of} the layer used. A preferable range is 5 × 10 ^{−6 to} 5 × 10 ⁻⁴ mol.

The use of the couplers represented by the general formula [I], the general formula [II] and the general formula [III] is similar even when two kinds of color development processing steps having different color development times are carried out. Cyan color density is obtained, the gradation is not changed, the gradation balance of three colors of yellow, magenta and cyan is good, and excellent tone reproduction and color reproduction are provided.

Next, the development processing A and the development processing B of the present invention.
Will be described in detail. The development processing A and the development processing B of the present invention each include a color development step, a desilvering step, and a drying step. Specific preferred examples are shown below, but the invention is not limited thereto. Color development-bleach-fix-wash-stable-dry Color development-bleach-bleach-fix-fix-wash-stable-dry Color development-bleach-fix-wash-stable-dry Color-bleach-bleach-fix-wash-stable- Drying Color development-bleach-fixing-fixing-washing-stabilization-drying Color development-bleaching-washing-fixing-washing-stability-drying In the above processing step, washing in the step before stabilization can be omitted. The final stability can also be omitted. In the development processing A and the development processing B of the present invention, the desilvering step of the color development processing may be the same or different.

The color development processing A in the development processing A of the present invention will be described in detail below. The color development time of the color development processing A of the present invention is 150 seconds or more and 200 seconds or less, preferably 165 seconds or more and 195 seconds or less. The color development time can be changed depending on the type and concentration of the developing agent in the processing liquid, the halogen ion (particularly Br ⁻ ) concentration, the temperature of the processing liquid, the pH and the like.

The developing agent in color development processing A of the present invention is 2
-Methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] alinine, 2-methyl-4- [N-ethyl-N- (3-hydroxypropyl) amino] aniline, 2-methyl- 4- [N-ethyl-N- (4-hydroxybutyl) amino] aniline is preferred, and 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline is particularly preferred. The concentration of the developing agent is 15 mmol or more and 20 mmol or less, preferably 15 mol mil or more and 18 mmol or less, per liter of the processing liquid. These developing agents are preferably hydrochloride, p-toluenesulfonate or sulfate.

The bromide ion concentration, Br from a silver halide color photographic material ^- and elution, Br is replenished in the color developing solution ^- is determined by the amount, to keep the photographic properties during continuous processing stably The amount is 6 mmol or more and 14 mmol or less, preferably 9 mmol or more and 13 mmol or less, per liter of the treatment liquid.

The temperature of the treatment liquid is 37 ° C. or higher and 40 ° C. or lower, preferably 37 ° C. or higher and 39 ° C. or lower.

The pH of the treatment liquid is 9.9 or more and 10.3 or less, preferably 10.0 or more and 10.2 or less.

Concretely, a processing agent for color negative films, CN-16 or CN-1 manufactured by Fuji Photo Film Co., Ltd.
6X, CN-16Q, CN-16FA, CN-16L color developer and color developer replenisher, or Eastman
Kodak Color Negative Film Treatment Agent, C-4
1, C-41B and C-41RA color developers can be preferably used.

The color development processing B in the development processing B of the present invention will be described below. The color development time of the color development treatment B of the present invention is 25 seconds or more and 90 seconds or less, preferably 35 seconds or more and 75 seconds or less, and most preferably 45 seconds or more 6
5 seconds or less.

The color development time of the present invention is a time including the crossover time (the time from the exit of the color development solution to the processing solution of the next step), and the shorter the crossover time is, the more preferable. From the viewpoint of the performance of the processing equipment, 2 seconds or more and 10 seconds or less are preferable, and 3 seconds or more and 7 seconds or less are more preferable.

The color developing time can be changed in the same manner as in the color developing treatment A depending on the kind and concentration of the developing agent in the processing solution, the halogen ion (particularly Br ⁻ ) concentration, the temperature of the processing solution, the pH and the like.

The developing agent in color development processing B of the present invention is p
-Phenylenediamine derivatives, preferable representative examples of which are shown below. (D-1) 2-methyl-4- [N-ethyl-N- (β
-Hydroxyethyl) amino] aniline (D-2) 2-methyl-4- [N-ethyl-N- (3
-Hydroxypropyl) amino] aniline (D-3) 2-methyl-4- [N-ethyl-N- (4
-Hydroxybutyl) amino] aniline (D-4) 2-methyl-N, N-diethyl-p-phenylenediamine (D-5) 2-methyl-4- [N-ethyl-N- (β
-Methanesulfonamidoethyl) amino] aniline (D-6) 2-methoxy-4- [N-ethyl-N-
(Β-Hydroxyethyl) amino] aniline (D-7) 4-methyl-3-methoxy-N, N-bis (3-hydroxypropyl) aniline (D-8) 4-amino-3-isopropoxy-N,
N-bis (β-hydroxyethyl) aniline (D-9) 1- (β-hydroxyethyl) -5-amino-6-methyl-indoline (D-10) 1,2,3,4-tetrahydro-1-
(3,4-dihydroxybutyl) -2,2,4,7-tetramethyl-6-amino-quinoline (D-11) 1,2,3,4-tetrahydro-1- (β
-Hydroxyethyl) -4-hydroxymethyl-6-amino-7-methyl-quinoline

In the color development processing B of the present invention, D-
1, D-2, D-3, D-6, D-7, D-8, D-1
0 and D-11 are particularly preferable, D-1, D-2 and D-3 are more preferable, and D-1 is the most preferable.

The concentration of the developing agent is 25 to 80 mmol, preferably 25 to 60 mmol, more preferably 27 to 50 mmol, and most preferably 30 to 45 per liter of the processing solution. It is below millimolar.

Within the concentration range of the developing agent, two or more kinds of the developing agents may be used in combination.

In the color development processing B of the present invention, the bromide ion is particularly important as an antifoggant, and the Br ^- concentration is 15 mmol or more and 60 mmol or less, preferably 16 mmol or more and 42 mmol or less per liter of the processing liquid. And particularly preferably 16 mmol or more and 35 mmol or less.

Note that picolinic acid is added to the color developer of the development processing B as a compound that accelerates the release of the base from the poorly water-soluble basic metal compound, but the promoting compound is not limited to picolinic acid. Instead, it can be selected according to the type of basic metal compound.

The temperature of the treatment liquid is 40 ° C. or higher and 60 ° C. or lower, preferably 42 ° C. or higher and 55 ° C. or lower, and particularly preferably 43 ° C. or higher and 50 ° C. or lower.

The pH of the treatment liquid is 9.9 or more and 11.0 or less, preferably 10.0 or more and 10.5 or less.

Further, a silver halide solvent may be contained as a development accelerator, and thiosulfates, methanethiosulfonates, imidazoles described in JP-A-3-203735, and JP-A-4-130431 can be used. And the thioethers described in JP-A-4-317055 are preferred.

Color development processing A and / or B of the present invention
Can contain the following compounds. For example, other than hydroxylamine, diethylhydroxylamine,
Various hydroxylamines represented by the general formula (I) of JP-A-3-144446, sulfites, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine and catecholsulfonic acids. Preservatives, organic solvents such as ethylene glycol, diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, 1-phenyl-3-pyrazolidone, etc. Auxiliary developing agents, viscosity imparting agents, various chelating agents represented by aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid, phosphonocarboxylic acid, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid. , Shi B hexane diaminetetraacetic 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 their salts can be mentioned as representative examples.

Among the above, substituted hydroxylamine is most preferable as the preservative, and among them, diethylhydroxylamine, monomethylhydroxylamine or an alkyl group substituted with a water-soluble group such as a sulfo group, a carboxy group or a hydroxyl group is used as a substituent. Those having are preferred. The most preferable example is N, M-bis (2-sulfoethyl).
Hydroxylamine, monomethylhydroxylamine,
Diethyl hydroxylamine and the like can be mentioned.

Further, any antifoggant can be added.
As the antifoggant, alkali metal halides such as sodium chloride, potassium bromide and potassium iodide and organic antifoggants can be used. Examples of the organic antifoggant include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole,
Representative examples include nitrogen-containing heterocyclic compounds such as 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine and adenine.

In order to maintain the pH of the color developing solution, it is preferable to use various buffers. As the buffer, carbonate, phosphate, borate, tetraborate, hydroxybenzoate, glycyl salt, N, N-dimethylglycine salt, leucine salt, norleucine salt, guanine salt, 3,4- Dihydroxyphenylalanine salt, alanine salt, aminobutyric acid salt, 2-amino-2-methyl-1,3-propanediol salt, valine salt, proline salt, trishydroxyaminomethane salt, lysine salt and the like can be used. Particularly, use of a carbonate is preferred. The amount of the buffer added to the developer is preferably 0.1 mol / liter or more,
Particularly preferably, it is 0.1 mol / liter to 0.4 mol / liter. Further, a compound having biodegradability is preferable as the chelating agent. Examples of this are JP-A-63-146998 and JP-A-63-199295.
JP-A-63-267750, JP-A-63-267
751, JP-A-2-229146, and JP-A-3-18.
6841, German Patent 3,739,610, European Patent 468,325 and the like can be cited as chelating agents. It is preferable that the processing solution in the color developing solution replenishing tank or the processing tank is shielded with a liquid agent such as a high-boiling point organic solvent to reduce the contact area with air. Liquid paraffin is most preferred as the liquid shielding agent. It is particularly preferable to use it as a replenisher. In addition, the replenishment amount is 1
30 to 800 ml, preferably 50 per square meter
It is about 500 ml. Any development accelerator can be added to the color developing solution of the present invention, if necessary. As a development accelerator, Japanese Examined Patent Publication Nos. 37-16088, 37-5987 and 38-7826
No. 44-12380, No. 45-9019 and U.S. Pat.
Thioether compounds represented by JP-A No. 247, etc.
-49829 and 50-15554, p-phenylenediamine compounds, JP-A-50-137726, JP-B-44-300
74, quaternary ammonium salts represented by JP-A-56-156826 and JP-A-52-43429, US Pat. No. 2,494,903,
No. 3,128,182, No. 4,230,796, No. 3,253,919, Japanese Patent Publication No. 41-11431, U.S. Patent No. 2,482,546, No. 2,596,92
6 and 3,582,346, etc., amine compounds, JP-B-37-16088, JP-B-42-25201, U.S. Pat.
No. 4, Japanese Patent Publication Nos. 41-11431 and 42-23883, and U.S. Pat.
Polyalkylene oxides represented by 532,501 and the like,
In addition, 1-phenyl-3-pyrazolidones, imidazoles, and the like can be added as needed.

Next, the desilvering process of the present invention will be described in detail. As the bleaching agent used in the processing solution having a bleaching ability, aminopolycarboxylic acid iron (III) complex, persulfate,
Bromate, hydrogen peroxide, and red blood salt are used,
The aminopolycarboxylic acid (III) complex can be most preferably used. The ferric iron complex salt used in the present invention may be added and dissolved as a complexed iron complex salt in advance, and the complex forming compound and the ferric iron salt (for example, ferric sulfate, ferric chloride) may be added. Iron, ferric bromide, iron (III) nitrate, iron (III) sulfate ammonium, etc.) may coexist to form a complex salt in a liquid having a bleaching ability. The complex-forming compound may be slightly in excess of the amount required for complex formation with ferric ion, and when it is added in excess, it is usually preferably in the range of 0.01 to 10%.

In the present invention, the compounds forming a ferric complex salt in a liquid having a bleaching ability include ethylenediaminetetraacetic acid (EDTA), 1,3-propanediaminetetraacetic acid (1,3-PDTA), Diethylenetriaminepentaacetic acid, 1,2-cyclohexanediaminetetraacetic acid, iminodiacetic acid, methyliminodiacetic acid, N- (2-acetamido) iminodiacetic acid, nitrilotriacetic acid, N- (2-carboxyethyl) iminodiacetic acid, N- (2-Carboxymethyl) iminodipropionic acid, β-alanine diacetic acid, 1,
4-diaminobutane tetraacetic acid, glycol ether diamine tetraacetic acid, N- (2-carboxyphenyl) iminodiacetic acid, ethylenediamine-N- (2-carboxyphenyl) -N, N ', N'-triacetic acid, ethylenediamine-
N, N'-disuccinic acid, 1,3-diaminopropane-
N, N'-disuccinic acid, ethylenediamine-N, N'-
Examples thereof include dimaleonic acid and 1,3-diaminopropane-N, N′-dimalonic acid, but are not particularly limited thereto.

The concentration of the ferric complex salt in the bleaching treatment solution of the present invention is appropriately in the range of 0.005 to 1.0 mol / liter, and 0.01 to 0.50 mol / liter.
The range of liter is preferable, and more preferably 0.02 to
It is in the range of 0.30 mol / liter. The concentration of the ferric complex salt in the replenisher for the processing solution having bleaching ability is preferably 0.005 to 2 mol / liter, more preferably 0.01 to 1.0 mol / liter.

Various compounds can be used as a bleaching accelerator in a bath having a bleaching ability or a prebath thereof. For example, US Pat. No. 3,893,858,
German Patent No. 1,290,812, JP-A-53
-95630 and Research Disclosure No. 17129 (July 1978), compounds having a mercapto group or a disulfide bond, and JP-B-4.
5-8506, JP-A-52-20832, and 53-
Thiourea compounds described in US Pat. No. 32735, U.S. Pat. No. 3,706,561 and the like, or halides such as iodine and bromide ions are preferable because of their excellent bleaching power.

Other bleaching baths applicable to the present invention include bromide (eg, potassium bromide, sodium bromide, ammonium bromide) or chloride (eg, potassium chloride, sodium chloride, ammonium chloride). Alternatively, a rehalogenating agent such as iodide (eg, ammonium iodide) can be included. PH buffering capacity of borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, malonic acid, succinic acid, glutaric acid as required And at least one of inorganic acids, organic acids and alkali metal or ammonium salts thereof, or a corrosion inhibitor such as ammonium nitrate and guanidine. Further, the bath having a bleaching ability may contain various other fluorescent whitening agents, antifoaming agents or surfactants, polyvinylpyrrolidone, organic solvents such as methanol.

The fixing agent component in the bleach-fixing solution or the fixing solution is
Known fixing agents, ie, thiosulfates such as sodium thiosulfate and ammonium thiosulfate; sodium thiocyanate,
Thiocyanates such as ammonium thiocyanate; ethylenebisthioglycolic acid, 3,6-dithia-1,8-
It is a water-soluble silver halide dissolving agent such as a thioether compound such as octanediol, a mesoionic compound and thioureas, and these can be used alone or as a mixture of two or more. Also, Japanese Patent Application Laid-Open No. 55-15535
A special bleach-fixing solution comprising a combination of the fixing agent described in No. 4 with a large amount of a halide such as potassium iodide or the like can also be used. In the present invention, the use of thiosulfates, particularly ammonium thiosulfate and sodium thiosulfate, is preferred. The amount of the fixing agent per liter is preferably 0.3 to 2 mol, more preferably 0.5 to 2 mol.
１．０1.0 mol. The bleach-fixing solution and the fixing solution of the present invention preferably contain sulfite (or bisulfite or metabisulfite) as a preservative, but especially 0.08 to 0.4 mol / liter, Preferably 0.
It is preferable to contain 1 to 0.3 mol / liter. By using this concentration range and further using the final bath of the present invention,
Not only the magnetic recording performance was remarkably improved, but also desirable results were obtained in terms of image storability. The bleach-fixing solution and the fixing solution of the present invention include sulfites (eg, sodium sulfite, potassium sulfite, ammonium sulfite) and bisulfites (eg, ammonium bisulfite, sodium bisulfite, potassium bisulfite) described above as preservatives. , Metabisulfite (eg, potassium metabisulfite, sodium metabisulfite,
In addition to containing sulfite ion-releasing compounds such as ammonium metabisulfite), aldehydes (benzaldexide, acetaldehyde, etc.), ketones (acetone, etc.),
Ascorbic acids, hydroxylamines and the like can be added as necessary.

Further, a bleaching solution, a bleach-fixing solution and a fixing solution may be added with a buffering agent, a fluorescent whitening agent, a chelating agent, a defoaming agent, an antifungal agent and the like, if necessary. In the bleaching solution and the bleach-fixing solution used in the present invention, the preferred pH range is 4.5.
It is -6.2 and more preferably 5-6. Even if the pH is higher or lower than the present pH, the magnetic recording performance may not be sufficiently exhibited. In the case of a fixer, pH 5
About 8 is desirable.

Bleaching solution, bleach-fixing solution used in the present invention,
The replenishing amount of the fixing solution is 50 to 200 per 1 m ² of the light-sensitive material.
It is 0 ml, particularly preferably 100 to 1000 ml. Further, washing water as a post-bath or overflow solution of a stabilizing bath may be replenished as necessary. The processing temperature of the bleaching solution, the bleach-fixing solution and the fixing solution is 20 to 50 ° C, preferably 30 to 45 ° C. The processing time is 10 seconds to 3 minutes, preferably 20 seconds to 2 minutes.

The processing solution having a bleaching ability of the present invention is particularly preferably subjected to aeration during processing because the photographic performance is kept extremely stable. Means known in the art can be used for aeration, and blowing of air into a processing solution having a bleaching ability or absorption of air using an ejector can be performed. When blowing air, it is preferable to release air into the liquid through a diffuser having fine pores. Such an air diffuser is widely used as an aeration tank in activated sludge treatment. Regarding aeration, Eastman Kodak's Z-121, Using Process C-41 No. 3
The matters described in the edition (1982), pages BL-1 to BL-2 can be used. In the processing using the processing solution having the bleaching ability of the present invention, it is preferable that the stirring is strengthened.
Page, upper right column, line 6-lower left column, line 2
Can be used as is.

In the desilvering process, it is preferable that the stirring is strengthened as much as possible. As a specific method of strengthening the stirring, a method described in JP-A-62-183460, in which a jet of a processing solution is made to impinge on the emulsion surface of a photosensitive material, or a method using a rotating means described in JP-A-62-183461, is used. A method of increasing the effect, a method of moving the photosensitive material while bringing the wiper blade provided in the solution into contact with the emulsion surface, and increasing the stirring effect by turbulently flowing the emulsion surface, and circulating the entire processing solution. There is a method of increasing the flow rate. Such stirring improving means include 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 consequently increases the desilvering speed. Further, the above-mentioned means for improving the stirring is more effective when a bleaching accelerator is used, and can significantly increase the accelerating effect or eliminate the fixing inhibiting effect of the bleaching accelerator.

The automatic developing machine used for 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 an effect is particularly effective for reducing the processing time in each step and reducing the replenishing amount of the processing solution.

The amount of rinsing water in the rinsing step depends on the characteristics of the light-sensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the rinsing water, the number of rinsing tanks (the number of stages), the replenishment system such as countercurrent and forward flow, and various other factors. It can be set in a wide range depending on the condition.
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 Picturean.
d Television Engineers Volume 64, P. 248-253 (1955)
May May issue). According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly 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. Problem arises. In the processing of the color light-sensitive material of the present invention, the method of reducing calcium ion and magnesium ion described in JP-A-62-288838 can be used very effectively as a solution to such a problem. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8,542, chlorinated germicides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., Hiroshi Horiguchi "Chemistry of antibacterial and fungicide" (1986) Sankyo Publishing, Sanitary Technology Association, "Microbial Sterilization, Sterilization, and Antifungal Technology" (1982) Industrial Technology Association, Japan Antibacterial and Antifungal Society, "Encyclopedia of Antibacterial and Antifungal Agents" (1986) The disinfectants described can also be used.

The pH of washing water in the processing of the light-sensitive material of the present invention is 3 to 9, preferably 4 to 8. The washing water temperature and washing time can be variously set depending on the characteristics and use of the light-sensitive material, but in general, the range is 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 stabilization treatment, JP-A-57-8543, JP-A-58-14834 and JP-A-60-220345 are used.
Any of the known methods described in No. 1 can be used.

In the stabilizing solution, compounds that stabilize the dye image, such as formalin, benzaldehydes such as m-hydroxybenzaldehyde, formaldehyde bisulfite adduct, hexamethylenetetramine and its derivatives, hexahydrotriazine and its derivatives, Examples include N-methylol compounds such as dimethylol urea and N-methylol pyrazole, organic acids and pH buffering agents. The preferable addition amount of these compounds is from 0.001 to 0.02 mol per liter of the stabilizing solution. However, the lower the concentration of free formaldehyde in the stabilizing solution, the less the formaldehyde gas is scattered. From these viewpoints, examples of the dye image stabilizer include N-methylolazoles such as m-hydroxybenzaldehyde, hexamethylenetetramine and N-methylolpyrazole described in JP-A-4-270344, and N, N'-bis (1 4,3,4-triazol-1-ylmethyl) piperazine and the like.
Azolylmethylamines described in 13753 are preferred. In particular, azoles such as 1,2,4-triazole and 1,4-bis (1,2,4) described in JP-A-4-359249 (corresponding to EP-A-519190A2).
A combination of azolylmethylamine and its derivative such as (-triazol-1-ylmethyl) piperazine is preferable because of high image stability and low formaldehyde vapor pressure. Further, if necessary, ammonium compounds such as ammonium chloride and ammonium sulfite, metal compounds such as Bi and Al, a fluorescent brightener, a hardener, and US Pat.
No. 86,583, and a preservative which can be contained in the above-mentioned fixing solution or bleach-fixing solution, for example, a sulfinic acid compound described in JP-A-1-231105 is also preferable. .

The washing water and / or the stabilizing solution may contain various surfactants in order to prevent unevenness of water droplets during drying of the processed light-sensitive material. Among these, it is preferable to use a nonionic surfactant, and an alkylphenol ethylene oxide adduct is particularly preferable. Octyl, nonyl, dodecyl and dinonylphenol are particularly preferable as the alkylphenol, and 8 to 14 are particularly preferable as the number of moles of ethylene oxide added. Further, it is also preferable to use a silicon-based surfactant having a high defoaming effect.

Various chelating agents are preferably contained in the wash water and / or the stabilizing solution. Preferred chelating agents include aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N, N '.
-Trimethylene phosphonic acid, diethylene triamine-
Organic phosphonic acids such as N, N, N ', N'-tetramethylenephosphonic acid or EP 345,172A
The hydrolyzate of the maleic anhydride polymer described in No. 1 can be used.

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 developing machine or the like, when each of the above processing solutions is concentrated by evaporation,
In order to correct the concentration by evaporation, it is preferable to replenish an appropriate amount of water or a correction solution or a processing replenisher. There is no particular limitation on a specific method for performing water replenishment. Among them, a monitor water tank separate from the bleaching tank described in JP-A Nos. 1-254959 and 1-254960 is installed, and water in the monitor water tank is provided. The amount of evaporation of water is calculated, the amount of evaporation of water in the bleaching tank is calculated from the amount of evaporation of water, and water is supplied to the bleaching tank in proportion to the amount of evaporation.
Nos. 3,249,644, 3,249,645, and 3,249,646, the evaporation correction method using a liquid level sensor and an overflow sensor are preferable.
Tap water may be used as water for correcting the evaporation of each processing solution, but it is preferable to use deionized water or sterilized water which is preferably used in the above-mentioned washing step.

Next, the magnetic recording layer used in the present invention will be described. The magnetic recording layer used in the present invention is obtained by coating a support with an aqueous or organic solvent-based coating solution in which magnetic particles are dispersed in a binder. Magnetic particles used in the present invention include ferromagnetic iron oxide such as γFe ₂ O _3, Co deposited γFe ₂ O _3, Co coated magnetite, Co containing magnetite, ferromagnetic dioxide Guromu, ferromagnetic metal, ferromagnetic alloy Hexagonal Ba ferrite, Sr ferrite, Pb ferrite, Ca ferrite, etc. can be used. Co deposited γFe ₂ O ₃
Co-coated ferromagnetic iron oxides such as The shape may be needle-like, rice grain-like, spherical, cubic, plate-like or the like.
Preferably 20 m ² / g or more S _BET is the specific surface area, 30 m ² /
g or more is particularly preferred. The saturation magnetization (σs) of a ferromagnet is
It is preferably 3.0 × 10 ⁴ to 3.0 × 10 ⁵ A / m, and particularly preferably 4.0 × 10 ⁴ to 2.5 × 10 ⁵ A / m. The ferromagnetic particles may be subjected to a surface treatment with silica and / or alumina or an organic material. Further, magnetic particles are disclosed in
The surface may be treated with a silane coupling agent or a titanium coupling agent as described in 161032. Further, the inorganic surface described in JP-A-4-259911 and 5-81652,
Magnetic particles coated with an organic substance can also be used.

Next, the binder used for the magnetic particles is
Thermoplastic resin, thermosetting resin, radiation-curable resin, reactive resin, acid, alkali or biodegradable polymer, natural product polymerizable (cellulose derivative,
Sugar derivatives, etc.) and mixtures thereof can be used. The Tg of the above resin is -40 ° C to 300 ° C, and the weight average molecular weight is 20,000 to 1,000,000. For example, vinyl-based copolymer,
Cellulose diacetate, cellulose triacetate,
Examples thereof include cellulose derivatives such as cellulose acetate propionate, cellulose acetate butyrate, and cellulose tripropionate, acrylic resins, polyvinyl acetal resins, and gelatin is also preferable. Particularly, cellulose di (tri) acetate is preferable. The binder can be cured by adding an epoxy-based, aziridine-based, or isocyanate-based crosslinking agent. Examples of the isocyanate-based cross-linking agent include isocyanates such as tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, and xylylene diisocyanate, and reaction products of these isocyanates and polyalcohols (for example, tolylene diisocyanate). Reaction products of 3 mol of isocyanate and 1 mol of trimethylolpropane), and polyisocyanates formed by condensation of these isocyanates are mentioned, for example, as described in JP-A-6-59357.

As a method for dispersing the above-mentioned magnetic material in the binder, a kneader, a pin type mill, an annular type mill or the like is preferable as in the method described in JP-A-6-35092, and the combined use is also preferable. The dispersant described in JP-A-5-088283 and other known dispersants can be used. The thickness of the magnetic recording layer is 0.1 μm to 10 μm, preferably 0.2 μm to 5
μm, more preferably 0.3 μm to 3 μm. The weight ratio of the magnetic particles to the binder is preferably 0.5: 100 to 60: 1.
It consists of 00, more preferably 1: 100 to 30: 100. The coating amount of magnetic particles is 0.005 to 3 g / m ² , preferably 0.01.
˜2 g / m ² , more preferably 0.02 to 0.5 g / m ² . The magnetic recording layer used in the present invention can be provided on the back surface of the photographic support by coating or printing and provided in the entire surface or in a stripe shape. As a method for applying the magnetic recording layer, an air doctor, a blade, an air knife, a squeeze,
Impregnation, reverse roll, transfer roll, gravure, kiss, cast, spray, dip, bar, extrusion and the like can be used, and the coating liquid described in JP-A-5-341436 is preferable.

The magnetic recording layer has improved lubricity, curl adjustment,
It may have functions such as antistatic, anti-adhesion and head polishing, or may be provided with another functional layer to impart these functions, and at least one kind of particles has a Mohs hardness of 5 or more. The above-mentioned non-spherical inorganic particle abrasives are preferable. As the composition of the non-spherical inorganic particles, oxides such as aluminum oxide, chromium oxide, silicon dioxide, titanium dioxide and silicon carbide, carbides such as silicon carbide and titanium carbide, and fine powders such as diamond are preferable. These abrasives may have their surfaces treated with a silane coupling agent or a titanium coupling agent. These particles may be added to the magnetic recording layer, or may be overcoated (for example, a protective layer, a lubricant layer, etc.) on the magnetic recording layer. As the binder used at this time, the above-mentioned binders can be used, and the same binder as the binder for the magnetic recording layer is preferable. US Pat. Nos. 5,336,589 and 5,250,404 for photosensitive materials having a magnetic recording layer.
No. 5,229,259, No. 5,215,874, and EP 466,130.

The light-sensitive material of the present invention may be provided with at least one light-sensitive layer on a support. A typical example is a silver halide photographic light-sensitive material having at least one light-sensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. It is. The photosensitive layer is a unit photosensitive layer having color sensitivity to any of blue light, green light, and red light, and in a multilayer silver halide color photographic material, the arrangement of the unit photosensitive layers is generally A red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are provided in this order from the support side. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layers. A non-light-sensitive layer may be provided between the silver halide light-sensitive layers and as the uppermost layer and the lowermost layer. These may contain a coupler, a DIR compound, a color mixing inhibitor, etc. described later. A plurality of silver halide emulsion layers constituting each unit light-sensitive layer are formed by sequentially exposing two layers, a high-speed emulsion layer and a low-speed emulsion layer, to a support as described in DE 1,121,470 or GB 923,045. It is preferable to arrange them so that the degree is low. In addition, JP-A-57-112751, 62-200350, 62-2
As described in 06541 and 62-206543, 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 specific examples, from the farthest side from the support, a low-sensitivity blue-sensitive layer (BL) / a high-sensitivity blue-sensitive layer (BH) / a high-sensitivity green-sensitive layer (GH) / a low-sensitivity green-sensitive layer (GL) / High-sensitivity red-sensitive layer (RH) / low-sensitivity red-sensitive layer (RL), or BH / BL / GL / GH / RH / RL, or BH / BL / GH / GL / RL / RH And so on. Also, as described in JP-B-55-34932, the blue-sensitive layer / GH / RH / GL starts from the side farthest from the support.
/ RL can be arranged in this order. JP-A-56-2573
8, as described in JP-A-62-63936, the layers may be arranged in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support. Further, 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 a silver halide emulsion layer having a higher sensitivity than the middle layer. An example is an arrangement in which low silver halide emulsion layers are arranged and three layers having different sensitivities are sequentially lowered toward the support. Even when it is composed of such three layers having different sensitivities, as described in JP-A-59-202464, in the same color-sensitive layer, the medium-sensitivity emulsion layer / high-sensitivity layer is separated from the side distant from the support. You may arrange in order of a speed emulsion layer / a 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, in case of 4 layers or more,
The arrangement may be changed as described above. In order to improve color reproducibility, BL, GL, described in US 4,663,271, 4,705,744, 4,707,436, JP-A-62-160448 and 63-89850, are described.
It is preferable that a donor layer (CL) having a multilayer effect having a spectral sensitivity distribution different from that of the main photosensitive layer such as RL is disposed adjacent to or close to the main photosensitive layer.

The preferred silver halide used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide, containing up to about 30 mol% silver iodide. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 10 mol% silver iodide. Silver halide grains in photographic emulsions have regular crystals such as cubes, octahedra and tetradecahedrons, grains having irregular crystal forms such as spheres and plates, twin planes, etc. It may have a crystal defect of, or a composite form thereof. The grain size of silver halide is about 0.2 μm or less
It may be large-sized grains up to 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 (hereinafter abbreviated as RD) No. 17643 (December 1978), 22-23.
Page, "I. Emulsion preparation and type
s) ”and ibid. No. 18716 (November 1979), p. 648, ibid N.
o.307105 (November 1989), pages 863-865, and Graphide, Physics and Chemistry of Photography, published by Paul Montel (P.Gl).
afkides, Chemie et Phisique Photographique, Paul M
ontel, 1967), Duffin, Photographic Emulsion Chemistry, Focal Press (GF Duffin, Photographic Emulsion C)
hemistry, Focal Press, 1966), "Manufacturing and coating of photographic emulsions" by Zelikmann et al., published by Focal Press (VL Ze
likman, et al., Making and Coating Photographic Em
ulsion, Focal Press, 1964).

US 3,574,628, US 3,655,394 and GB 1,4
Monodisperse emulsions described in 13,748 are also preferred. Further, tabular grains having an aspect ratio of about 3 or more can be used in the present invention. Tabular grains are described in Gutof, Photographic Science and Engineering (Gutof
f, Photographic Science and Engineering), Volume 14
248-257 (1970); US 4,434,226, US 4,414,310,
It can be easily prepared by the methods described in 4,433,048, 4,439,520 and GB 2,112,157. The crystal structure may be uniform, the inside and the outside may be composed of different halogen compositions, or may have a layered structure. Silver halides having different compositions may be joined by epitaxial joining, or may be joined to a compound other than silver halide, such as, for example, silver rhodanate or lead oxide. Also, a mixture of particles of various crystal forms may be used. The above emulsion is a surface latent image type that forms a latent image mainly on the surface,
Either an internal latent image type formed inside the grain or a type having a latent image both on the surface and inside may be used, but it is necessary that the emulsion is a negative type. Of the internal latent image types, JP-A-6
The core / shell type internal latent image type emulsion described in 3-264740 may be used, and its preparation method is described in JP-A-59-133542. The thickness of the shell of this emulsion varies depending on the development process, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

The silver halide emulsion is usually one which has been physically ripened, chemically ripened and spectrally sensitized. Additives used in such a process are RD No. 17643 and RD No. 187.
16 and No. 307105, and the relevant portions are summarized in the table below. In the light-sensitive material of the present invention, two or more types of emulsions having at least one characteristic different from each other in the grain size, grain size distribution, halogen composition, grain shape and sensitivity of the photosensitive silver halide emulsion are mixed in the same layer. Can be used. US Pat. No. 4,082,553, the surface of which is covered with silver halide grains, US Pat. No. 4,626,498, and JP-A-59-21.
4852, a silver halide grain in which the inside of the grain is fogged,
It is preferred to apply colloidal silver to the light-sensitive silver halide emulsion layer and / or the substantially light-insensitive hydrophilic colloid layer. The fogged silver halide grain inside or on the surface means a silver halide grain which enables uniform (non-imagewise) development regardless of the unexposed area and exposed area of the light-sensitive material. , Its preparation method is described in US 4,626,498 and JP-A-59-214852. The silver halide forming the internal nucleus of the core / shell type silver halide grain having the inside of the grain fogged may have a different halogen composition.
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 average grain size of these fogged silver halide grains is 0.01 to 0.75 μm,
Particularly, the thickness is preferably 0.05 to 0.6 μm. The grains may be regular grains or polydispersed emulsions, but may be monodisperse (at least 95% of the weight or the number of silver halide grains).
% Having a particle diameter within ± 40% of the average particle diameter).

In the present invention, it is preferable to use a non-photosensitive fine grain silver halide. Non-photosensitive fine grain silver halide is silver halide fine grains that are not exposed during imagewise exposure to obtain a dye image and are not substantially developed in the developing process, and are preferably not fogged in advance. . The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may contain silver chloride and / or silver iodide, if necessary. Preferably, it contains 0.5 to 10 mol% of silver iodide. Fine grain silver halide has an average grain size (average value of circle equivalent diameter of projected area)
Is preferably 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm. Fine grain silver halide can be prepared by the same method as that for ordinary photosensitive silver halide. The surface of the silver halide grains does not need to be optically sensitized, and no spectral sensitization is required. However, prior to adding this to the coating solution, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, or mercapto-based compound or a zinc compound in advance. Colloidal silver can be contained in the layer containing fine silver halide grains. Coated silver amount of the light-sensitive material of the present invention is preferably 6.0 g / m ² or less, 4.5 g / m ² or less is most preferred.

The photographic additives which can be used in the present invention are also described in RD, and the relevant portions are shown in the following table. Type of additive RD17643 RD18716 RD307105 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 866 to 868, supersensitizer, page 649, right column 4. Whitening agent, page 24, page 647, right column, page 868, 5 Light absorber, pages 25 to 26, page 649, right column, page 873, filter, page 650, left column, dye, ultraviolet absorber 6. Binder, page 26, page 651, left column 873 to 874, page 7. Plasticizer, page 27, page 650, right Column 876 Lubricants 8. Coating aids, 26-27 Pages 650 Right column 875-876 Pages Surfactant 9. Static 27 pages 650 Page right columns 876-877 Inhibitors 10. Matting agents 878-879

Various dye-forming couplers can be used in the light-sensitive material of the present invention, and the following couplers are particularly preferable. Yellow couplers: couplers represented by formulas (I) and (II) of EP 502,424A; couplers represented by formulas (1) and (2) of EP 513,496A (particularly Y-28 on page 18); EP 568,037A Claim 1
A coupler represented by formula (I) in US Pat. No. 5,066,576, column 1, lines 45 to 55; a coupler represented by formula (I) in paragraph 0008 of JP-A-4-274425; Couplers according to claim 1 of page 4 of EP 498,381A1 (especially D-35 on page 18); couplers of formula (Y) on page 4 of EP 447,969A1 (especially Y-1 (page 17), Y- 54 (p. 41)); US
Couplers represented by formulas (II) to (IV) at 4,476,219, column 7, lines 36 to 58 (especially II-17,19 (column 17), II-24 (column 19)). Magenta coupler; JP-A-3-39737 (L-57 (page 11, lower right), L-
68 (lower right of page 12), L-77 (lower right of page 13); EP 456,257 (A-4
-63 (p. 134), (A-4) -73, -75 (p. 139); EP 486,965
M-4, -6 (page 26), M-7 (page 27); EP 571,959A M-45 (19
(M-1) of JP-A-5-204106 (page 6); M-22 of paragraph 0237 of JP-A-4-32631. Polymer coupler: P-1, P-5 (p. 11) of JP-A-2-44345.

Examples of couplers in which the color forming dye has an appropriate diffusibility include US 4,366,237, GB 2,125,570, EP 96,873B,
Those described in DE 3,234,533 are preferred. Couplers for correcting unnecessary absorption of color-forming dyes are yellow colored cyan couplers represented by the formulas (CI), (CII), (CIII), and (CIV) described on page 5 of EP 456,257A1 (especially on page 84). YC-86), the EP
Yellow colored magenta coupler ExM-7 (202
), EX-1 (page 249), EX-7 (page 251), US 4,833,069
Magenta colored cyan coupler CC-9 (column
8), CC-13 (column 10), (2) of US 4,837,136 (column 8),
Colorless masking couplers of formula (A) in claim 1 of WO 92/11575 (especially the exemplified compounds on pages 36 to 45) are preferred. Examples of the compound (including a coupler) which releases a photographically useful compound residue by reacting with an oxidized developing agent include the following. Development inhibitor releasing compound: EP 37
Compounds represented by the formulas (I), (II), (III) and (IV) described on page 11 of 8,236A1 (especially T-101 (page 30), T-104 (page 31), T-113 ( 36
T-131 (p. 45), T-144 (p. 51), T-158 (p. 58)), EP436, 93
Compounds of formula (I) described on page 7 of 8A2 (particularly D-4
9 (page 51)), the compound of formula (1) of EP 568,037A (especially (23) (page 11)), and the compounds of formulas (I), (II), Compounds represented by (III) (especially I-
(1)); Bleaching accelerator releasing compounds: compounds represented by formulas (I) and (I ′) on page 5 of EP 310,125A2 (especially (60) and (6) on page 61)
1)) and the compound represented by formula (I) of claim 1 of JP-A-6-59411 (particularly (7) (page 7)); Ligand releasing compound: US
Compound represented by LIG-X described in claim 1 of 4,555,478 (especially compound on lines 21 to 41 of column 12); Leuco dye-releasing compound: compound 1 of columns 3 to 8 of US 4,749,641
~ 6; Fluorescent dye-releasing compound: C in claim 1 of US 4,774,181
Compounds represented by OUP-DYE (particularly compounds 1 to 11 in columns 7 to 10); development accelerator or fogging agent releasing compound: US
4,656,123, the compounds of formulas (1), (2) and (3) in column 3 (especially (I-22) in column 25) and EP 450,637A2
ExZK-2, p. 75, lines 36-38; Compound which releases a group which becomes a dye only when it is cleaved: Formula (I) of claim 1 of US 4,857,447
(Especially Y-1 to Y-19 in columns 25 to 36)
.

The following additives are preferable as additives other than the coupler. Dispersion medium of oil-soluble organic compound: P-3,5, JP-A-62-215272
16,19,25,30,42,49,54,55,66,81,85,86,93 (140-144
Page); Latex for impregnation of oil-soluble organic compounds: US 4,199,
Latex described in 363; Oxidized developer scavenger: a compound represented by the formula (I) in column 2, lines 54 to 62 of US Pat. ) (Column 4-
5), US Pat. No. 4,923,787, columns 5 to 10 of formula (particularly compound 1 (column 3); stain inhibitor: EP 298321A 4
Formulas (I) to (III) on page 30-33, especially I-47, 72, III-1, 27 (24
-48 pages); Anti-fading agent: A-6, 7, 20, 21, 23, 2 of EP 298321A
4,25,26,30,37,40,42,48,63,90,92,94,164 (69-118
P.), US 5,122,444, columns 25-38 II-1 to III-23, especially
III-10, EP 471347A I-1 to III-4 on pages 8 to 12, especially II-
2, US 5,139,931 columns 32-40 A-1 to 48, especially A-39,
42; Material that reduces the amount of color enhancer or color mixture inhibitor used: I-1 to II-15 on pages 5 to 24 of EP 411324A, especially I-4
6; Formalin scavenger: EP 477932A, pages 24 to 29 SCV-1 to 28, especially SCV-8; Hardener: JP-A 1-214845
Formulas in columns 13-23 of H-1,4,6,8,14, US 4,618,573 on page 17
Compounds (H-1 to 54) represented by (VII) to (XII),
214852, page 8, lower right, compound represented by formula (6) (H-1 to 7
6), especially the compound described in claim 1 of H-14, US 3,325,287; Development inhibitor precursor: P-2 of JP-A-62-168139
4,37,39 (pages 6-7); compounds as claimed in claim 1 of US 5,019,492, in particular column 7, 28,29; preservatives, fungicides: US
4,923,790 columns 3 to 15 I-1 to III-43, especially II-1,
9,10,18, III-25; Stabilizer, antifoggant: US 4,923,79
I-1 to (14) in columns 6 to 16 of 3, especially I-1,60, (2), (13), U
S 4,952,483 columns 25-32 compounds 1-65, especially 36:
Chemical sensitizer: triphenylphosphine selenide, compound 50 of JP-A-5-40324; dye: 15-18 of JP-A-3-156450
A-1 to b-20, especially a-1,12,18,27,35,36, b-5,27 to 29
Pages V-1 to 23, especially V-1, EP 445627A pages 33 to 55 FI-
1 to F-II-43, especially FI-11, F-II-8, EP 457153A 17 to 28
Pages III-1 to 36, especially III-1,3, WO 88/04794 8-26
Microcrystalline dispersion of Dye-1 to 124, compounds 1 to 22 of EP 319999A, pages 6 to 11, especially compound 1, compounds D-1 to 87 (3) represented by formulas (1) to (3) of EP 519306A. ~ Page 28), US 4,26
8,622 compounds represented by the formula (I) (columns 3 to 1)
0), compounds (1) to (4) of US Pat.
(31) (Columns 2 to 9); UV absorber: Formula of JP-A-46-3335
Compounds (18b) to (18r), 101 to 427 (6 to
9), and the compounds (3) to (6) represented by the formula (I) in EP 520938A.
6) (Pages 10 to 44) and compound HBT-1 represented by formula (III)
~ 10 (page 14), a compound represented by formula (1) in EP 521823A
(1) to (31) (columns 2 to 9).

The present invention can be applied to various color light-sensitive materials such as color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers. In addition, Japanese Patent Publication No.
Suitable for the lens-fitted film unit described in 3-39784. Suitable supports that can be used in the present invention are
For example, page 28 of RD. No. 17643 mentioned above, 6 of the same RD.
From page 47, right column to page 648, left column, and No. 307105, page 879. Preferred are polyester-based supports. In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is preferably 28 μm or less, more preferably 23 μm or less, further preferably 18 μm or less, and particularly preferably 16 μm or less. Further, the film swelling speed T _1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. T _1/2 is defined as 90% of the maximum swollen film thickness reached when the color developing solution is processed at 30 ° C. for 3 minutes and 15 seconds, and the saturated film thickness is defined as:
It is defined as the time until the film thickness reaches 1/2. The film thickness means the film thickness measured under a humidity condition of 25 ° C. and a relative humidity of 55% (2 days), and T _1/2 is a photograph science and engineering of A. Green et al. (Photogr.Sci.Eng.), 19 square, 2, 124 to 129 can be measured by using a swellometer (swelling meter) of the type. T _1/2 can be adjusted by adding a hardening agent to gelatin as a binder or changing the aging condition after coating. The swelling rate is preferably 150 to 400%. The swelling ratio can be calculated from the maximum swelling film thickness under the conditions described above by the following formula: (maximum swelling film thickness-film thickness) / film thickness. The light-sensitive material of the present invention is
On the side opposite to the side with the emulsion layer, the total dry film thickness is 2 μm
It is preferable to provide a hydrophilic colloid layer (referred to as a back layer) having a thickness of 20 μm. This back layer includes the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid,
It is preferable to include a surfactant. The swelling ratio of the back layer is preferably from 150 to 500%.

Next, the polyester support used in the present invention will be described. For details, including the light-sensitive material, processing, cartridges and examples described later, open technical report, official technique number 94-6023 (Invention Society; 1994.3). .15.).
The polyester used in the present invention is formed by using a diol and an aromatic dicarboxylic acid as essential components, and 2,6-, 1,5-, 1,4-, and 2,7 as aromatic dicarboxylic acids.
-Naphthalenedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, diethylene glycol as diol,
Examples include triethylene glycol, cyclohexanedimethanol, bisphenol A, and bisphenol.
Examples of the polymerized polymer include homopolymers such as polyethylene terephthalate, polyethylene naphthalate, and polycyclohexanedimethanol terephthalate. Particularly preferred is a polyester containing 50 to 100 mol% of 2,6-naphthalenedicarboxylic acid. Among them, polyethylene 2,6-naphthalate is particularly preferred. Average molecular weight ranges from about 5,000 to
It is 200,000. The Tg of the polyester of the present invention is 50 ° C. or higher, preferably 90 ° C. or higher.

Next, the polyester support is subjected to a heat treatment at a heat treatment temperature of 40 ° C. or higher and lower than Tg, more preferably Tg−20 ° C. or higher and lower than Tg in order to prevent the curling tendency. The heat treatment may be performed at a constant temperature within this temperature range, or may be performed while cooling. The heat treatment time is 0.1 to 1500 hours, more preferably 0.5 to 200 hours. The heat treatment of the support may be performed in the form of a roll, or may be performed while transporting the support in the form of a web.
Surface irregularities may be imparted (for example, conductive inorganic fine particles such as SnO ₂ or Sb ₂ O ₅ may be applied) to improve the surface state. It is also desirable to take measures such as applying knurls to the ends and raising the ends only slightly to prevent cut-out of the core. These heat treatments are performed after forming the support, after surface treatment,
It may be carried out at any stage after application of the back layer (antistatic agent, slip agent, etc.) and after application of the undercoat. Preferably after application of the antistatic agent. An ultraviolet absorber may be incorporated into this polyester. Also, to prevent light piping,
The purpose can be achieved by kneading dyes or pigments commercially available for polyesters such as Diaresin manufactured by Mitsubishi Kasei and Kayaset manufactured by Nippon Kayaku.

Next, in the present invention, it is preferable to carry out a surface treatment in order to bond the support and the light-sensitive material constituting layer. Chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment,
Surface activation treatments such as laser treatment, mixed acid treatment, ozone oxidation treatment and the like can be mentioned. Among the surface treatments, ultraviolet irradiation treatment, flame treatment, corona treatment, and glow treatment are preferable. Next, the undercoating method will be described. It may be a single layer or two or more layers. As the binder for the undercoat layer, vinyl chloride, vinylidene chloride, butadiene, methacrylic acid,
Examples include a copolymer using a monomer selected from acrylic acid, itaconic acid, maleic anhydride and the like as a starting material, polyethylene imine, epoxy resin, grafted gelatin, nitrocellulose, and gelatin. Compounds that swell the support include resorcin and p-chlorophenol. As a gelatin hardening agent for the undercoat layer, chromium salts (chrome alum, etc.), aldehydes (formaldehyde, glutaraldehyde, etc.), isocyanates, active halogen compounds (2,4-dichloro-6-) are used.
Hydroxy-S-triazine, etc.), epichlorohydrin resin, active vinyl sulfone compound and the like. SiO ₂ , TiO ₂ , inorganic fine particles or polymethylmethacrylate copolymer fine particles (0.01 to 10 μm) may be contained as a matting agent.

Further, in the present invention, an antistatic agent is preferably used. Examples of these antistatic agents include carboxylic acids and carboxylates, polymers containing sulfonates, cationic polymers, and ionic surfactant compounds. The most preferred antistatic agent is Z
_{nO, TiO 2, SnO 2,} Al 2 O 3, In 2 O 3, SiO 2, MgO, BaO,
MoO ₃ , at least one selected from V ₂ O ₅ has a volume resistivity of 10 ⁷ Ω · cm or less, more preferably 10 ⁵ Ω · cm or less. Fine particles of oxides or composite oxides thereof (Sb, P, B, In, S, Si, C, etc.), and sol-like metal oxides or fine particles of these composite oxides. The content in the photosensitive material should be between 5 and
500 mg / m ² are preferred and particularly preferably 10 to 350 mg / m ^2. The ratio of the amount of the conductive crystalline oxide or its composite oxide to the binder is preferably from 1/300 to 100/1, more preferably from 1/100 to 100/5.

The light-sensitive material of the present invention preferably has a slip property. The slip agent-containing layer is preferably used on both the photosensitive layer surface and the back surface. A preferable slip property is a dynamic friction coefficient of 0.
It is 25 or less and 0.01 or more. The measurement at this time represents the value when the stainless steel ball with a diameter of 5 mm is transported at 60 cm / min (25
℃, 60% RH). In this evaluation, even if the surface of the photosensitive layer is replaced as the partner material, the values are almost the same level. Examples of the slip agent usable in the present invention include polyorganosiloxanes, higher fatty acid amides, higher fatty acid metal salts, esters of higher fatty acids and higher alcohols, and polyorganosiloxanes such as polydimethyl siloxane, polydiethyl siloxane, poly Styrylmethylsiloxane, polymethylphenylsiloxane, or the like can be used. The additional layer is preferably the outermost layer of the emulsion layer or the back layer. Particularly, polydimethylsiloxane or an ester having a long-chain alkyl group is preferable.

The light-sensitive material of the present invention preferably contains a matting agent. The matting agent may be on either the emulsion side or the back side, but is particularly preferably added to the outermost layer on the emulsion side.
The matting agent may be soluble in the processing solution or insoluble in the processing solution, and preferably both are used in combination. For example, polymethylmethacrylate, poly (methylmethacrylate / methacrylic acid = 9/1 or 5/5 (molar ratio)), polystyrene particles and the like are preferable. The particle size is preferably 0.8 to 10 μm, and the particle size distribution is preferably narrow, and the average particle size is 0.9 to 1.
It is preferable that 90% or more of the total number of particles be contained in one time. It is also preferable to simultaneously add fine particles of 0.8 μm or less in order to enhance the matting property. Particles (0.25μm), colloidal silica (0.03μm)
Is mentioned.

Next, the film cartridge used in the present invention will be described. The main material of the patrone used in the present invention may be metal or synthetic plastic. Preferred plastic materials are polystyrene, polyethylene, polypropylene, polyphenyl ether and the like. Further, the patrone of the present invention may contain various antistatic agents, and carbon black, metal oxide particles, nonionic, anionic, cationic and betaine surfactants or polymers can be preferably used. These antistatic patrones are described in JP-A 1-312537 and JP-A 1-312538. Particularly, the resistance at 25 ° C. and 25% RH is preferably 10 ¹² Ω or less. Usually, a plastic patrone is manufactured using a plastic into which carbon black, a pigment, or the like is kneaded in order to impart light shielding properties. The size of the patrone may be 135 size at present, and for miniaturization of the camera,
It is also effective to reduce the diameter of the current 135 size 25 mm cartridge to 22 mm or less. The volume of the patrone case is preferably 30 cm ³ or less, more preferably 25 cm ³ or less. The weight of the plastic used for the patrone and the patrone case is preferably 5 g to 15 g.

Further, a patrone used in the present invention may be one that rotates the spool to feed the film. Further, a structure may be employed in which the leading end of the film is housed in the cartridge body, and the leading end of the film is sent out from the port of the cartridge by rotating the spool shaft in the film sending direction. These are disclosed in US Pat. Nos. 4,834,306 and 5,226,613. The photographic film used in the present invention may be a so-called raw film before development, or may be a photographic film subjected to development processing. Also, raw film and developed photographic film may be stored in the same new patrone,
Different patrones may be used.

Hereinafter, the present invention will be described in more detail with reference to specific examples, but the present invention is not limited to the examples without departing from the gist of the present invention.

[0111]

【Example】

Example 1 On a subbed cellulose triacetate film support,
Each layer having the composition shown below was applied in multiple layers to prepare Sample 101, which is a multilayer color light-sensitive material. (Composition of photosensitive layer) The main materials used for each layer are classified as follows: ExC: cyan coupler UV: ultraviolet absorber ExM: magenta coupler HBS: high boiling point organic solvent ExY: yellow coupler H: gelatin Curing agent ExS: Sensitizing dye The number corresponding to each component indicates the coating amount in g / m ² , and for silver halide, it indicates the coating amount in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown in mol unit per mol of silver halide in the same layer.

(Sample 101) First layer (antihalation layer) Black colloidal silver Silver 0.09 Gelatin 1.60 ExM-1 0.12 ExF-1 2.0 × 10 ^-3 Solid disperse dye ExF-2 0.030 Solid disperse dye ExF-3 0.040 HBS- 1 0.15 HBS-2 0.02

Second layer (intermediate layer) Silver iodobromide emulsion M Silver 0.065 ExC-2 0.04 Polyethyl acrylate latex 0.20 Gelatin 1.04

Third Layer (Low Sensitivity Red Sensitive Emulsion Layer) Silver iodobromide emulsion A Silver 0.25 Silver iodobromide 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 0.025 ExC-4 0.10 ExC-5 0.020 ExC-6 0.010 Cpd-2 0.025 HBS-1 0.10 Gelatin 0.87

Fourth Layer (Medium Sensitivity Red Sensitive Emulsion Layer) Silver Iodobromide Emulsion C Silver 0.70 ExS-1 3.5 × 10 ^-4 ExS-2 1.6 × 10 ^-5 ExS-3 5.1 × 10 ^-4 ExC-1 0.13 ExC-2 0.060 ExC-3 0.006 ExC-4 0.090 ExC-5 0.015 ExC-6 0.0070 Cpd-2 0.023 HBS-1 0.10 Gelatin 0.75

Fifth layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion D Silver 1.40 ExS-1 2.4 × 10 ^-4 ExS-2 1.0 × 10 ^-4 ExS-3 3.4 × 10 ^-4 ExC-1 0.10 ExC-3 0.037 ExC-6 0.020 ExC-7 0.010 Cpd-2 0.050 HBS-1 0.22 HBS-2 0.050 Gelatin 1.10

Sixth layer (intermediate layer) Cpd-1 0.090 Solid disperse dye ExF-4 0.030 HBS-1 0.050 Polyethyl acrylate latex 0.15 Gelatin 1.10

Seventh Layer (Low Sensitivity Green Sensitive Emulsion Layer) Silver iodobromide Emulsion E 0.15 Silver iodobromide Emulsion F Silver 0.10 Silver iodobromide Emulsion G Silver 0.10 ExS-4 3.0 × 10 ^-5 ExS-5 2.1 × 10 ^-4 ExS-6 8.0 × 10 ^-4 ExM-2 0.33 ExM-3 0.086 ExY-1 0.015 HBS-1 0.30 HBS-3 0.010 Gelatin 0.73

Eighth Layer (Medium-Sensitivity Green Sensitive Emulsion Layer) Silver Iodobromide Emulsion H Silver 0.80 ExS-4 3.2 × 10 ^-5 ExS-5 2.2 × 10 ^-4 ExS-6 8.4 × 10 ^-4 ExC-8 0.010 ExM-2 0.10 ExM-3 0.025 ExY-1 0.018 ExY-4 0.010 ExY-5 0.040 HBS-1 0.13 HBS-3 4.0 × 10 ^-3 Gelatin 0.80

Ninth layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion I Silver 1.25 ExS-4 3.7 × 10 ^-5 ExS-5 8.1 × 10 ^-5 ExS-6 3.2 × 10 ^-4 ExC-1 0.010 ExM-1 0.020 ExM-4 0.025 ExM-5 0.040 Cpd-3 0.040 HBS-1 0.25 Polyethyl acrylate latex 0.15 Gelatin 1.33

10th layer (yellow filter layer) Yellow colloidal silver Silver 0.015 Cpd-1 0.16 Solid disperse dye ExF-5 0.060 Solid disperse dye ExF-6 0.060 Oil-soluble dye ExF-7 0.010 HBS-1 0.60 Gelatin 0.60

Eleventh layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion J Silver 0.09 Silver iodobromide emulsion K Silver 0.09 ExS-7 8.6 × 10 ^-4 ExC-8 7.0 × 10 ^-3 ExY-1 0.050 ExY-2 0.22 ExY-3 0.50 ExY-4 0.020 Cpd-2 0.10 Cpd-3 4.0 × 10 ^-3 HBS-1 0.28 Gelatin 1.20

12th layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion L Silver 1.00 ExS-7 4.0 × 10 ^-4 ExY-2 0.10 ExY-3 0.10 ExY-4 0.010 Cpd-2 0.10 Cpd-3 1.0 × 10 ^-3 HBS-1 0.070 Gelatin 0.70

Thirteenth layer (first protective layer) UV-1 0.19 UV-2 0.075 UV-3 0.065 HBS-1 5.0 × 10 ^-2 HBS-4 5.0 × 10 ^-2 gelatin 1.8

14th layer (second protective layer) Silver iodobromide emulsion M Silver 0.10 H-1 0.40 B-1 (diameter 1.7 μm) 5.0 × 10 ^-2 B-2 (diameter 1.7 μm) 0.15 B-3 0.13 S-1 0.20 Gelatin 0.70

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

[0127]

[Table 2]

In Table 2, (1) Emulsions J to L were prepared according to the examples of JP-A-2-91938.
It is reduction-sensitized during grain preparation using thiourea dioxide and thiosulfonic acid. (2) Emulsions A to I were prepared according to the examples of JP-A-3-237450.
Gold sensitization, sulfur sensitization and selenium sensitization were performed in the presence of the spectral sensitizing dye and sodium thiocyanate described in each photosensitive layer. (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 described in JP-A-3-237450 are observed in the tabular grains using a high-pressure electron microscope. (5) Emulsion L is a double-structured grain containing an internal high iodine core described in JP-A-60-143331.

Preparation of Dispersion of Organic Solid Disperse Dye ExF-2 shown below was dispersed by the following method. That is, water 21.7
3 ml of 5% sodium p-octylphenoxyethoxyethoxyethane sulfonate and 5% aqueous solution
0.5 g of an aqueous solution of p-octylphenoxypolyoxyethylene ether (degree of polymerization: 10) was put in a 700 ml pot mill, and 5.0 g of dye ExF-2 and 500 ml of zirconium oxide beads (diameter 1 mm) were added. The contents were dispersed for 2 hours. For this dispersion, a BO type vibration ball mill manufactured by Chuo Koki was used. After dispersion, the contents were taken out, added to 8 g of a 12.5% gelatin aqueous solution, and the beads were removed by filtration to obtain a gelatin dispersion of the dye. The average particle size of the dye particles is 0.44
μm.

Similarly, solid dispersions of ExF-3, ExF-4 and ExF-6 were obtained. The average particle diameters of the fine dye particles were 0.24 μm, 0.45 μm, and 0.52 μm, respectively.
ExF-5 is a microprecipitation described in Example 1 of European Patent Application Publication (EP) 549,489A.
Dispersed by a dispersion method. The average particle size was 0.06 μm.

[0131]

Embedded image

[0132]

Embedded image

[0133]

Embedded image

[0134]

Embedded image

[0135]

Embedded image

[0136]

Embedded image

[0137]

Embedded image

[0138]

Embedded image

[0139]

[Chemical 21]

[0140]

Embedded image

[0141]

Embedded image

[0142]

Embedded image

[0143]

Embedded image

[0144]

[Chemical formula 26]

[0145]

Embedded image

[0146]

Embedded image

[0147]

[Chemical 29]

[0148]

Embedded image

Hereinafter, the cyan coupler E of the third to fifth layers will be described.
Samples 102 to 115 were prepared by replacing xC-1, 3 and 4 with cyan couplers shown in Table 3 in equimolar amounts.

These samples 101 to 115 were cut and processed to have a width of 35 mm, subjected to gradation exposure of white light, and then subjected to the following development processing A.

Process of (Development treatment A) and composition of treatment liquid. Process Processing time Processing temperature Color development 3 minutes 15 seconds 38 ℃ Bleaching 1 minute 00 seconds 38 ℃ Bleaching fixing 3 minutes 15 seconds 38 ℃ Water washing (1) 1 minute 00 seconds 38 ℃ Water washing (2) 1 minute 00 seconds 38 ℃ Dry 2 minutes 00 seconds 60 ℃

Next, the composition of the treatment liquid will be described.

(Color developer) Tank liquid (g) Diethylenetriaminepentaacetic acid 1.0 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Iodine Potassium iodide 1.5 mg Hydroxylamine sulfate 2.4 4- [N-ethyl-N- (β-hydroxyethyl) amino] -2-methylaniline sulfate 4.5 Water was added to 1.0 liter pH (water Adjusted with potassium oxide and sulfuric acid) 10.05

(Bleaching Solution) Common to Tank Solution and Replenisher (Unit: g) Ethylenediaminetetraacetic acid ammonium ferric dihydrate 120.0 Ethylenediaminetetraacetic acid disodium salt 10.0 Ammonium bromide 100.0 Ammonium nitrate 10.0 Bleaching accelerator 0.005 mole _{(CH 2) 2 N-CH} 2 -CH 2 -SS-CH 2 -CH 2 -N (CH 2) 2 · 2HCl aqueous ammonia (27%) 1 was added to 15.0 ml water 0.0 liter pH (adjusted with ammonia water and nitric acid) 6.3

(Bleach-fixing solution) Tank solution (g) Ethylenediaminetetraacetic acid ammonium ferric dihydrate 50.0 Ethylenediaminetetraacetic acid disodium salt 5.0 Sodium sulfite 12.0 Ammonium thiosulfate aqueous solution (700 g / l) 240. 0 ml ammonia water (27%) 6.0 ml Water was added to 1.0 liter pH (adjusted with ammonia water and acetic acid) 7.2

(Washing Water) Tap water was used as an H-type strongly acidic cation exchange resin (Amberlite IR manufactured by Rohm and Haas Co.).
-120B) and an OH-type strongly basic anion exchange resin (Amberlite IR-400) and passed through a mixed bed column to treat calcium and magnesium at a concentration of 3 mg / liter or less, and then dichloride. 20 mg / l of sodium isocyanurate and 150 mg / l of sodium sulfate were added. The pH of this solution was in the range of 6.5 to 7.5.

The developed sample was measured for each density of yellow, magenta and cyan under the condition of status M,
Their characteristic curves were obtained. The density of each sample at the exposure amount at which the cyan density of Sample 101 shows 1.00 was read, and the color forming property of the cyan coupler was evaluated. Table 3 shows the results.

[0158]

[Table 3]

As is clear from the results in Table 3, the samples according to the present invention had a large cyan density and an excellent color density. This indicates that the coupler of the present invention has high reaction activity.

Example 2 Using the samples 101 to 115 prepared in Example 1, the development processing B (rapid processing) shown below was performed, and the exposure amount at which the density of Sample 101 was 1.0 as in Example 1. The density of each sample was read and the color development was evaluated. The results obtained are shown in Table 4.

[0161]

[Table 4]

As is clear from the results of Table 4, Example 1
Similarly to Samples 107 to 115 of the present invention, the color density of the red-sensitive layer was high and the color development was excellent even in the rapid processing.
This indicates that the coupler of the present invention has high reaction activity even in rapid processing.

Process of (Development treatment B) and composition of treatment liquid Treatment process Temperature Time Color development 45 ° C. 60 seconds Bleach fixing 40 ° C. 60 seconds Water washing (1) 40 ° C. 15 seconds Water washing (2) 40 ° C. 15 seconds Water washing ( 3) 40 ° C for 15 seconds Stability 40 ° C for 15 seconds Drying 80 ° C for 60 seconds (Washing was performed with 3 tanks countercurrent from (3) to (1).)

Composition of processing liquid (color developer) Tank liquid (g) Diethylenetriaminepentaacetic acid 2.0 1-Hydroxyethylidene-1,1-disulfonic acid 3.3 Sodium sulfite 3.9 Potassium carbonate 37.5 Potassium bromide 2 0.0 potassium iodide 1.3 mg Hydroxylamine sulfate 4.5 2-Methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 11.0 Water was added to 1.0 liter. pH (adjusted with potassium hydroxide and sulfuric acid) 10.05

(Bleach-fixing solution) (Unit mol) ethylenediamine- (2-carboxyphenyl) -N, N ', N'-triacetic acid 0.17 ferric nitrate nonahydrate 0.15 ammonium thiosulfate 1.25 Ammonium sulfite 0.10 Metacarboxybenzenesulfinic acid 0.05 Water was added to 1.0 liter pH (adjusted with acetic acid and ammonia) 5.8

(Washing water) Same composition as described in Treatment A

(Stabilizing Solution) (Unit g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether (Average degree of polymerization: 10) 0.2 1,2-Benzisothiazolin-3-one. Sodium 0.10 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. 1.0 liter pH 8.5

Example 3 1) Support The support used in this example was prepared by the following method. Polyethylene-2,6-naphthalate polymer 10
After drying 0 part by weight and 2 parts by weight of Tinuvin P.326 (manufactured by Ciba-Geigy) as an ultraviolet absorber, 3
After melting at 00 ° C, it was extruded from a T-die, longitudinally stretched 3.3 times at 140 ° C, then transversely stretched 3.3 times at 130 ° C, and heat set at 250 ° C for 6 seconds. To obtain a PEN film having a thickness of 90 μm. The PEN film contains a blue dye, a magenta dye and a yellow dye (I-1 and I-described in Public Technical Report No. 94-6023).
4, I-6, I-24, I-26, I-27, II-5)
Was added in an appropriate amount. Furthermore, by winding it around a stainless steel core with a diameter of 20 cm, and giving it a thermal history of 110 ° C. for 48 hours,
The support is one that does not tend to curl.

2) Coating of undercoat layer The above-mentioned support was subjected to corona discharge treatment, UV discharge treatment and glow discharge treatment on both sides thereof, and then gelatin 0.1 g / m ² and sodium-α on each side. -Sulfodi-2-ethylhexyl succinate 0.01 g / m ² , salicylic acid 0.04 g / m ² , p-chlorophenol 0.2 g / m ² ,
_{(CH 2 = CHSO 2 CH 2} CH 2 NHCO) 2 CH 2 0.012g / m 2, polyamide - epichlorohydrin polycondensate was coated an undercoat solution ^{0.02g / m 2 (10cc / m} 2, using a bar coater ), An undercoat layer was provided on the high-temperature side during stretching. Drying was carried out at 115 ° C. for 6 minutes (all rollers and transport devices in the drying zone were 1
15 ° C). 3) Coating of Back Layer An antistatic layer, a magnetic recording layer and a sliding layer having the following composition were coated as a back layer on one surface of the support after the undercoat.

3-1) Coating of antistatic layer A dispersion of fine particle powder having a specific resistance of 5 Ω · cm of a tin oxide-antimony oxide composite having an average particle diameter of 0.005 μm (secondary agglomerated particle diameter of about 0.08 μm). ) and 0.2 g / m ^2, gelatin _{^{0.05g / m 2, (CH 2}} = CHSO 2 CH 2 CH 2 NHCO) 2 CH 2 0.02
It was coated with g / m ² , poly (degree of polymerization 10) oxyethylene-p-nonylphenol 0.005 g / m ² and resorcin.

3-2) Coating of magnetic recording layer Cobalt-γ-iron oxide coated with 3-poly (degree of polymerization 15) oxyethylene-propyloxytrimethoxysilane (15% by weight) (non-surface area 43 m ² / G, long axis 0.
14 μm, uniaxial 0.03 μm, saturation magnetization 89 emu / g, Fe
^{+ 2} / Fe ⁺³ = 6/94, the surface is treated with aluminum oxide and silicon oxide with 2% by weight of iron oxide) 0.06 g / m ² of diacetyl cellulose 1.2 g / m ² (of iron oxide Dispersion was carried out in an oven kneader and sand mill), C ₂ H as a curing agent
₅ C (CH ₂ OCONH-C ₆ H ₃ (CH ₃ ) NCO) ₃ 0.3 g / m ² as a solvent, acetone, methyl ethyl ketone, cyclohexanone,
It was coated with a bar coater using dibutyl phthalate to obtain a magnetic recording layer having a thickness of 1.2 μm. Lubricant C ₆ H ₁₃ CH (OH)
C ₁₀ H ₂₀ COOC ₄₀ H ₈₁ 50 mg / m ² , treated with silica particles (0.3 μm) and 3-poly (polymerization degree 15) oxyethylene-propyloxytrimethoxysilane (15 wt%) as a matting agent Aluminum oxide abrasive (0.20μ
m) and a (1.0 .mu.m) were respectively added in an amount of 50 mg / m ² and 10 mg / m ^2. Drying is 115 ° C, 6
(All rollers and conveying devices in the drying zone are at 115 ° C.). The increase in the color density of D ³ of the magnetic recording layer by the X-light (blue filter) is about 0.1, the saturation magnetization moment of the magnetic recording layer is 4.2 emu / g, and the coercive force is 7.3.
× 10 ⁴ A / m, and the squareness ratio was 65%.

3-3) Preparation of sliding layer C ₆ H ₁₃ CH (OH) C ₁₀ H ₂₀ COOC ₄₀ H ₈₁ 6 mg / m ² was applied. This product was prepared by melting it in xylene / propylene monomethyl ether (1/1) at 105 ° C and pouring and dispersing it in propylene monomethyl ether (10 times the volume) at room temperature. The diameter was adjusted to 0.01 μm) before adding. Drying was carried out at 115 ° C. for 6 minutes (115 ° C. for all rollers and conveying devices in the drying zone). The sliding layer has a dynamic friction coefficient of 0.10 (stainless steel balls with a diameter of 5 mm and a load of 100).
g, speed 6 cm / min), coefficient of static friction 0.08 (clip method), and coefficient of dynamic friction between the emulsion surface and the sliding layer, which will be described later, was 0.13, which were excellent characteristics.

4) Coating of Photosensitive Layer Next, each layer having the composition described in Example 1 was multilayer coated on the side opposite to the back layer obtained above to prepare a color negative film sample 201. Further, the cyan couplers ExC-1, 3 and 4 of the third layer to the fifth layer of the sample 201 are replaced with the cyan couplers shown in Table 5 to substantially match the color density and gradation of each color-sensitive layer of the sample 201. Corresponding to the sample 202 by appropriately adjusting the coupler amount, silver amount, etc. of other samples
~ 215 were prepared.

Samples 201 to 215 prepared as described above
The photosensitive material of No. 2 is cut into a width of 24 mm and 160 cm, and two perforations of 2 mm square are provided at a distance of 5.8 mm at a position 0.7 mm from one side width direction of the photosensitive material.
Create a set of these two sets at 32mm intervals,
It was housed in the plastic film cartridge described in FIGS. 1 to 7 of US Pat. No. 5,296,887. For this sample, a head gap of 5 μm from the coated surface side of the magnetic recording layer and a head capable of inputting and outputting with a turn number of 2,000 was used.
The FM signal was recorded at a feed rate of 000 / s.

These samples 201 to 215 were cut and processed to have a width of 35 mm, subjected to gradation exposure of white light, and then subjected to the following continuous (running) processings A-1 and B-1. . Furthermore, in the process B-1, the pH of the color developing solution was adjusted to pH 10.05 to 10.
Processing changed to 00 (processing A-2), and 10.12.
The process changed to (Process A-3) was performed. With respect to the developed sample, the respective densities of yellow, magenta and cyan were measured under the condition of status M, and their characteristic curves were obtained. The cyan density of the sample 201 subjected to the process A-1 is 1.
On the basis of the exposure amount of 00, the densities of the respective samples subjected to the processing A-1 and the processing B-1 were read, and the coloring property of the cyan coupler and the time dependence of the coloring property were evaluated. In addition, Zoom Cardia (Fuji Film Co., Ltd.)
Manufactured by Fujifilm Co., Ltd., so that the cartridge can be loaded, and a Macbeth chart is photographed under the same conditions for each light-sensitive material, subjected to the same development processing, and printed on Fuji Color Paper FA-V using these color negatives. Then, the image quality was visually evaluated. Table 5 shows the results.

[0176]

[Table 5]

As is apparent from Table 5, the samples 207 to 215 according to the present invention are the continuous and rapid treatments, that is, in the treatment B-1 and the treatment A-1. The concentration is high, and the difference in concentration between treatment times is very small. Further, p of the color developing solution of processing B-1
Even if H is changed to 10.00, 10.05, and 10.10, the increment of the color density is small, and the stability of the color density against the fluctuation of the pH during color development is very excellent. all right. On the other hand, when the sample printed on the color paper was visually evaluated, the print from the negative of the comparative sample 201 which was subjected to the rapid processing (process B-1) had a low negative cyan density and had a low gradation, so the gray portion was cyan. It was clear that the color tone was excellent and the color reproducibility was significantly deteriorated. In contrast, samples 207 to 215 of the present invention
Showed good gray reproducibility.

(Development processing A-1) processing step and liquid composition (processing step) step processing time processing temperature replenishment amount ^* tank capacity color development 3 minutes 5 seconds 38.0 ° C. 23 ml 17 liters bleaching 50 seconds 38.0 ° C. 5 ml 5 liter bleach-fixing 50 seconds 38.0 ℃ -5 liter fixing 50 seconds 38.0 ℃ 16 ml 5 liter water washing 30 seconds 38.0 ℃ 34 ml 3.5 liter stability (1) 20 seconds 38.0 ℃ -3 liter stability (2) 20 seconds 38.0 ℃ 20 ml 3 liter Dry 1 min 30 sec 60 ℃ * Replenishment amount per 35 m width of photosensitive material 1.1 m (equivalent to 24Ex. 1) Stabilizer is countercurrent method from (2) to (1) The overflow of washing water was introduced into the fixing bath. When replenishing the bleach-fixing bath, a cutout is provided on the bleaching tank of the automatic processor and on the top of the fixing tank. I was allowed to flow in. The amount of developing solution brought into the bleaching step, the amount of bleaching solution brought into the bleach-fixing step, the amount of bleach-fixing solution brought into the fixing step, and the amount of fixing solution brought into the water washing step were 1. 2.5 ml, 2.0 ml, 2.0 ml, 2.0 per meter
It was milliliters. The crossover time is 6 seconds in all cases, and this time is included in the processing time of the previous step.

The composition of the treatment liquid is shown below. (Color developer) Tank solution (g) Replenisher (g) Diethylenetriaminepentaacetic acid 2.0 2.0 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 2.0 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 Disodium N, N-bis (sulfonate ethyl) hydroxylamine 1.5 2.0 2-Methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 4.8 6.5 Add water 1.0 liter 1.0 liter pH (prepared with potassium hydroxide and sulfuric acid) 10.05 10.15

(Bleaching solution) Tank solution (g) Replenishing solution (g) 1,3-Diaminopropane tetraacetic acid Ammonium monohydrate 130 195 Ammonium bromide 70 105 Ammonium nitrate 14 21 Hydroxyacetic acid 50 75 Acetic acid 40 60 1.0 liter by adding water 1.0 liter pH [Prepared with ammonia water] 4.4 4.4

(Bleaching Fixing Tank Liquid) A 15:85 (volume ratio) mixture of the above bleaching tank liquid and the following fixing tank liquid. (P
H7.0)

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

(Washing water) Common to tank liquid and replenisher tap water was prepared by using H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas Co.) and OH-type strongly basic anion exchange resin (Amberlite IR). -40
0) 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 diisocyanurate dichloride /
L and 150 mg / L of sodium sulfate were added. The pH of this solution was in the range of 6.5 to 7.5.

(Stabilizing Solution) Tank Solution and Replenishing Solution Common (Unit g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether (Average degree of polymerization: 10) 0.2 1,2-benzo Isothiazolin-3-one sodium 0.10 Ethylenediaminetetraacetic acid disodium salt 0.05 1,2,4-Triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0 Add 0.75 water 1.0 liter pH 8.5

(Processing Step and Liquid Composition of Development Processing B-1) (Processing Step) Step Processing Time Processing Temperature Replenishment Amount ^* Tank Capacity Color Development 60 seconds 45.0 ° C 260 ml 1 liter Bleach 20 seconds 45.0 ° C 130 ml 1 liter Settling 40 seconds 45.0 ℃ 100 ml 1 liter Water wash (1) 15 seconds 45.0 ℃ -1 liter Water wash (2) 15 seconds 45.0 ℃ -1 liter Water wash (3) 15 seconds 45.0 ℃ 400 ml 1 liter Dry 45 80 ° C / s * Replenishment amount per 1 m ² of light-sensitive material (4 tank counter-current multi-stage cascade from (3) to fixing in washing)

The composition of the processing liquid is shown below. (Color developer) Tank liquid (g) Replenisher (g) Diethylenetriaminepentaacetic acid 2.0 4.0 1-Hydroxyethylidene-1,1-diphosphonic acid 3.3 3.3 Sodium sulfite 3.9 6.5 Potassium carbonate 37.5 39.0 Potassium bromide 2.0-Potassium iodide 1.3 mg-Disodium N, N-bis (sulfonate ethyl) hydroxylamine 12.0 17.0 2-Methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 11.5 15.0 Water was added 1.0 Liter 1.0 liter pH (prepared with potassium hydroxide and sulfuric acid) 10.05 10.25

(Bleaching solution) Tank solution (mol) Replenishing solution (mol) 1,3-diaminopropanetetraacetic acid ferric acid ammonium monohydrate 0.33 0.50 ferric nitrate nonahydrate 0.30 4.5 ammonium bromide 0.80 1.20 Ammonium nitrate 0.20 0.30 Acetic acid 0.67 1.0 Add water 1.0 liter 1.0 liter pH [Prepared with ammonia water] 4.5 4.0

(Fixer) Common to tank and replenisher (g) Ammonium sulfite 28 Ammonium thiosulfate aqueous solution (700 g / liter) 280 ml imidazole 15 Ethylenediaminetetraacetic acid 15 Water-added 1.0 liter pH [Prepared with ammonia water and acetic acid] 5.8

(Washing Water) The same composition as the washing water of the developing treatment A-1 was used.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location G03C 7/413 G03C 7/413 G11B 5/633 G11B 5/633

Claims (7)

[Claims] 1. A photographic coupler represented by the following general formula [I]. General formula [I] In the formula, R ₁ represents an alkyl group, an aryl group or a heterocyclic group, and R ₂ and R ₃ represent a hydrogen atom, an alkyl group or an aryl group. n represents an integer of 1 to 10. L is-
CO -, - C (O) O -, - C (O) N (R 6) -, -
_{SO 2 N (R 6) -} , - N (R 6) C (O) -, - N
_{(R 6) C (O)} O -, - N (R 6) C (O) N
_{(R 7) -, - N} (R 6) SO 2 - or -N (R ₆₎
SO ₂ N (R ₇₎ - represents, R ₄ is -C (O) R _8, -
C (O) OR ₈ , -C (O) N (R ₆ ) (R ₈ ), -S
O ₂ R ₈ or -SO ₂ N (R ₆₎ represents a (R _8). R
₆ represents a hydrogen atom, an alkyl group or an aryl group, and R
₇ represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. R ₈ represents an alkyl group or an aryl group. R
₅ represents a substituent, and m represents 0, 1, 2 or 3. X
Represents a hydrogen atom or a substituent which is released upon coupling with an oxidized product of a developing agent. 2. A photographic coupler represented by the following general formula [II]. General formula [II] In the formula, R ₁ , R ₂ , R ₃ , n, R ₄ , R ₅ , R ₆ ,
R ₇ , R ₈ and m have the same meanings as in the general formula [I], and Y represents a substituent which is released upon coupling with the oxidized product of the developing agent. 3. A photographic coupler represented by the following general formula [III]. General formula [III] In the formula, R ₁ , R ₂ , R ₃ , n, R ₄ , R ₅ , R ₆ ,
R ₇ , R ₈ and m have the same meaning as in formula [I], and Z represents a halogen atom. 4. A silver halide color photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, a coupler represented by the general formula [I] described in claim 1. The general formula [I
A silver halide color photographic light-sensitive material comprising a coupler represented by I] or a coupler represented by the general formula [III] described in claim 3. 5. A color image forming method comprising forming a color image by processing the silver halide color photographic light-sensitive material according to claim 4 with a developing processing solution A described below. (Development treatment A) A development treatment using a color developing solution having a color developing time of 150 to 200 seconds, a color developing solution temperature of 37 to 40 ° C., and a color developing agent concentration of 15 to 20 mmol / liter. 6. A color image forming method comprising forming a color image by processing the silver halide color photographic light-sensitive material according to claim 4 with a development processing solution B described below. (Development processing B) Color development time is 25 to 90 seconds, temperature of color developing solution is 40 to 60 ° C., and development processing using color developing solution containing 25 to 80 mmol / l of concentration of color developing agent . 7. A silver halide color photograph according to claim 4, further comprising a magnetic recording layer containing magnetic grains on the side opposite to the photosensitive silver halide emulsion layer with the support interposed therebetween. Photosensitive material.