JPH09138488A - Silver halide color photographic sensitive material and its packing body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To impact high sensitivity and gradation, to exhibit satisfactory coloring property and to prevent the variation of sensitivity and the increase of fog when a sensitive material is preserved by incorporating a specified coupler and a specified hydroxylamine compd. SOLUTION: This sensitive material with at least one photosensitive silver halide emulsion layer and at least one nonphotosensitive layer on the substrate contains a coupler represented by formula I and a hydroxylamine compd. represented by formula II. In the formula I, R1 is tert. alkyl, R2 is halogen, alkoxy, aryloxy, etc., R3 is alkoxycarbonyl or alkylsulfonyloxy, R4 is halogen, alkyl, alkoxy, etc., (m) is an integer of 0-2, each of R5 and R6 is H or alkyl and X is O or S. In the formula II, Ra1 is alkyl, alkenyl, etc., and Ra2 is H or a group represented by Ra1 .

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide color photographic light-sensitive material and a light-sensitive material package. More specifically, the present invention relates to a silver halide color photographic light-sensitive material and a package of the light-sensitive material, in which the color development is improved, and the storability of the light-sensitive material and the time-dependent sensitization that occurs when the light-sensitive material is stored after photographing are suppressed. .

[0002]

2. Description of the Related Art A silver halide color photographic light-sensitive material, particularly a color sensitive material for photographing, has high sensitivity and little fog, and its photographic property does not change even after the color sensitive material is photographed. A color image obtained by color development is required to have excellent image quality and color image storability.
The above-mentioned various performances are required even in the yellow coupler used for the current color photographic material for photographing based on the subtractive color method, but these requirements are not satisfied. At present, for photography, especially in color negative light-sensitive materials, 2-equivalent benzoylacetanilide type couplers (hereinafter abbreviated as BA type couplers) are mainly used as yellow couplers. This B
The A-type coupler has a higher coupling activity than other yellow couplers, for example, a 2-equivalent pivaloylacetanilide-type coupler (hereinafter abbreviated as PA-type coupler), and has a high molecular extinction coefficient of the dye formed. It has excellent characteristics. However, in the spectral absorption characteristics of the obtained dye, the absorption in the green light region on the long wavelength side is large, and the fastness of the color image is also inferior to the PA type coupler, and a coupler that compensates for these drawbacks is currently available. However, it has not appeared yet. The yellow coupler according to the present invention is the above-mentioned PA type coupler and is described in, for example, US Pat. No. 5,451,492. This type of coupler is characterized by a so-called ballast group, and is characterized by a leaving group portion which is substituted at the coupling active position.
The coupling activity is higher than that of the A-type coupler, and it is preferable in that the drawback of the PA-type coupler is compensated. But,
Although the coupling activity is high and it is advantageous for high sensitivity, the increase of fog accompanying this is large, and it becomes clear that the increase of fog is further increased when the photosensitive material is aged,
In addition, it was clarified that the amount of sensitized material increases and decreases with time after storage. The coupler according to the present invention, which can improve the sensitivity by taking advantage of the excellent characteristics of the PA-type coupler such as image quality and color image fastness, is therefore the BA-type if the storage stability after storage and the storage stability after photographing can be improved. It is strongly expected to replace the coupler and its improvement is strongly desired.
Also, the combined use with a BA type coupler becomes easy with the increase in sensitivity.

On the other hand, the use of the hydroxylamine derivative according to the present invention in a photographic photosensitive layer is described, for example, in US Pat. Nos. 4,339,515 and 4,330,606. However, all of these publications are intended to improve the storability of a color image produced by a coupling reaction between a coupler and an oxidized product of a color developing agent, and there is no description about improvement of storability of a light-sensitive material over time. There is no description that can be guessed. In order to improve the storage stability of the above light-sensitive material, a compound having an s-triazine (1,3,5-triazine) ring is disclosed, for example, in JP-A-59-162546, which has an active vinyl group. JP-A-7-97134 discloses that the storage stability of a latent image is improved by the combined use with a compound, and the fog is reduced by the combined use with an emulsion comprising tabular silver halide grains in JP-A-59-97134. No. 239540 describes that a tabular silver halide grain having a dislocation line and a compound according to the present invention are used to prevent pressure resistance and increase in fog due to storage over time. Above is a description of similar couplers according to the invention. However, regarding the coupler itself according to the present invention, there is no description that can be expected to prevent sensitization with time when the light-sensitive material is stored after being photographed.
It was found that when a compound having a triazine (1,3,5-triazine) ring was used, the effect of improvement was not found at a satisfactory level but further improvement was necessary. In particular, it was necessary to improve the storability of small format high density light sensitive materials.

[0004]

Therefore, the present invention provides high sensitivity and gradation and shows good color development, prevents the sensitivity change and the rise of fog when the photographic material is stored with the passage of time, and prevents the occurrence of fog after photographing. It is an object of the present invention to provide a silver halide color photographic light-sensitive material and a package in which the color light-sensitive material is stored, in which increase or decrease in the light-sensitive material during storage is suppressed.

[0005]

Means for Solving the Problems The inventors of the present invention have found that at least one layer of the photographic property variation of the photographic material during storage with time and the photographic property variation occurring when the photographic material is stored with time after photographing have been described. Of a color light-sensitive material having a photosensitive silver halide emulsion layer and a non-light-sensitive layer, containing at least one layer of the acetanilide type 2-equivalent yellow coupler substituted with an acyl group of a specific tertiary alkyl group. It has been found that the present invention can be improved by using a silver halide color photographic light-sensitive material containing a specific hydroxylamine compound, and that it can be improved even with a package containing the color sensitive material in a specific cartridge. It came to completion. That is, the present invention provides (1) a silver halide color photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer and a non-light-sensitive layer provided on a support, represented by the general formula [I]. Silver halide color photographic light-sensitive material containing a coupler selected from the formulas (A-I), (A-II) or (A-III). .

[0006]

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In the general formula [I], R ₁ is a tertiary alkyl group, R ₂ is a halogen atom, an alkoxy group, an aryloxy group, an alkyl group, an alkylsulfonyloxy group,
Or a cycloalkyl group, R ₃ is an alkoxycarbonyl group, or an alkylsulfonyloxy group, R ₄ is a halogen atom, an alkyl group, an alkoxy group, a carbonamido group, or a sulfonamide group, and m is an integer of 0 to 2. , R ₅ and R ₆ each independently represent a hydrogen atom or an alkyl group, and X represents an oxygen atom or a sulfur atom.

[0008]

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In the general formula (AI), R _a1 is an alkyl group, an alkenyl group, an aryl group, an acyl group, an alkyl or aryl sulfonyl group, an alkyl or aryl sulfinyl group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group or aryl. It represents an oxycarbonyl group, and R _a2 represents a hydrogen atom or a group represented by R _a1 . However, when R _a1 is an alkyl group, an alkenyl group or an aryl group, R _a2 is an acyl group, an alkyl or arylsulfonyl group, an alkyl or arylsulfinyl group,
A carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group. R _a1
And R _a2 may combine with each other to form a 5- to 7-membered ring, provided that they do not form an S-triazine ring. In formula (A-II), X represents a heterocyclic group excluding the S-triazine ring, and R _b1 represents an alkyl group, an alkenyl group or an aryl group. X and R _b1 may combine with each other to form a 5- to 7-membered ring, provided that they do not form an S-triazine ring. In the general formula (A-III), Y represents a nonmetallic atom group necessary for forming a 5-membered ring together with -N = C-. Y further represents a group of non-metal atoms necessary for forming a 6-membered ring together with the -N = C- group, and the terminal of Y bonded to the carbon atom of the -N = C- group
-N (R _C1 )-, -C (R _C2 ) (R _C3 )-, -C (R _C4 ) =, -O-, -S-
Represents a group selected from among the groups (bonded to the carbon atom of -N = C- on the left side of each group). However, it does not form an S-triazine ring. R _{C1 to} R _C4 each represent a hydrogen atom or a substituent.

(2) A silver halide color photographic light-sensitive material as described in (1), which contains a coupler represented by the following general formula [Y].

[0011]

[Chemical 6]

In the general formula [Y], R ₁ is an aryl group, R ₂ is a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an alkyl group or a dialkylamino group, and R ₃ is a benzene ring. , X ₀ represents a hydrogen atom or a group capable of splitting off by a coupling reaction with an oxidation product of an aromatic primary amine developing agent, and p represents an integer of 0 to 4. However, when p is plural, plural R
₃ may be the same or different.

(3) The silver halide color as described in (1) or (2), which has a magnetic recording layer containing magnetic grains on the side opposite to the side having the emulsion layer and the support. Photographic material.

(4) Inside the cartridge body 101,
A spool 103 around which a photographic light-sensitive material 102 having an emulsion layer on a support is wound is rotatably accommodated, and the tip of the photographic light-sensitive material can be freely sent out of the cartridge by the rotation of the spool. In order to feed the photographic light-sensitive material, it has a photographic light-sensitive material feed-out passage having a light-shielding mechanism, and inside the spool shaft 112 of the spool, inside the both ends of the spool shaft 112, a pair of flanges 113 with lips, respectively.
In the photographic light-sensitive material package 100 in which 114 is attached for holding the photographic light-sensitive material, the photographic light-sensitive material is the silver halide color photographic light-sensitive material described in any one of (1) to (3). A photosensitive material packaging body characterized by:

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION In the above aspect (1), at least one photosensitive silver halide emulsion layer and a non-photosensitive layer are each provided on a support, and at least one of the layers contains a specific tertiary alkyl group. A silver halide color photographic light-sensitive material containing an acetanilide type 2-equivalent yellow coupler substituted with an acyl group having a group and containing a specific hydroxylamine compound. Such a 2-equivalent yellow coupler represented by the general formula [I] is a conventional acetanilide type 2-equivalent capula substituted with an acyl group having a tertiary alkyl group, for example, US Pat. No. 3,933,501. In comparison with a so-called O-elimination type 2-equivalent coupler in which the leaving group at the coupling active position is bound via an oxygen atom, the coupling activity is high, and high sensitivity and gradation are imparted, and good color development is achieved. However, when the photosensitive material is preserved with time, the fog is further increased, and when the photosensitive material is also aged after photographing, the temporal sensitization is increased. It has been found that the object of the present invention can be satisfactorily achieved by using a specific hydroxylamine compound represented by the general formulas (AI) to (A-III) in combination with a light-sensitive material to solve this problem. Is.

In the embodiment (2), the 2-equivalent yellow coupler represented by the general formula [I] is used in combination with the benzoylacetanilide type 2-equivalent yellow coupler represented by the general formula [Y]. Even in such a method of use, the increase in fog during storage of the light-sensitive material without any problem and the sensitization over time even after the light-sensitive material is photographed can be solved by using the specific hydroxylamine compound. The object of the invention can be achieved brilliantly as well.

Aspect (3) is a color light-sensitive material having a magnetic recording layer containing magnetic particles on the back surface opposite to the side having the photosensitive layer of the light-sensitive material with the support interposed therebetween. When the photosensitive material provided with a recording layer is rolled up and stored for a long time, the above-mentioned problems of fog and sensitization with time become more serious, but the present invention suppresses the increase of fog with time of the light-sensitive material and the sensitization after shooting. Therefore, the object of the present invention can be effectively achieved.

Aspect (4) is a package in which a color sensitive material is housed in a specific cartridge. In this aspect, a package in which the sensitive material is long and tightly wound and enclosed easily causes the above-mentioned feeling over time. It also solves the problems of material fogging and sensitization with time after photographing, and achieves the object of the present invention brilliantly.

First, the yellow coupler of the present invention will be described in detail below. In the general formula [I], R ₁
Is preferably a tertiary alkyl group having 4 to 16 carbon atoms and has a substituent (for example, a halogen atom, an aryl group, an alkoxy group, an aryloxy group) even if it has a monocyclic or polycyclic structure. You may have. Specific examples of R ₁ include t-butyl group, 1-methylcyclopropan-1-yl group, 1-ethylcyclopropan-1-yl group, 1-benzylcyclopropan-1-yl group, 1-methylcyclobutane-1. -Yl group, 1-methylcyclopentan-1-yl group, 1-methylcyclohexane-1-yl group, 2,
2,5-trimethyl-1,3-dioxan-5-yl group, bisiloku [2,1,0] pentan-1-yl group, bicyclo [2,2,0] hexan-1-yl group, bicyclo [3 , 1,0] Hexan-1-yl group, bicyclo [4,4]
1,0] heptan-1-yl group, bicyclo [1,1,
1] Pentan-1-yl group, bicyclo [2,1,1] hexan-1-yl group, bicyclo [2,2,1] heptan-1-yl group, bicyclo [2,2,2] octane-1 −
And an adamantane-1-yl group.

In the general formula [I], R ₂ is preferably a halogen atom (F, Cl, Br, I), having 1 to 1 carbon atoms.
24 alkoxy groups (eg, methoxy group, butoxy group,
Tetradecyloxy group), an aryloxy group having 6 to 24 carbon atoms (for example, phenoxy group, p-methoxyphenoxy group, p-t-octylphenoxy group), an alkyl group having 1 to 8 carbon atoms (for example, methyl group, Ethyl group, isopropyl group, t-butyl group, benzyl group, trifluoromethyl group), or cycloalkyl group having 3 to 8 carbon atoms (for example, cyclopropyl group, cyclopentyl group, cyclohexyl group), 1 to 24 carbon atoms Is an alkylsulfonyloxy group (eg, methylsulfonyloxy group, hexadecylsulfonyloxy group).

In the general formula [I], R ₃ is preferably an ether oxygen atom having 6 to 30 carbon atoms or an optionally esterified alkoxycarbonyl group or alkylsulfonyloxy group. R ₃ may have a substituent (for example, a halogen atom, an aryl group, an aryloxy group). R ₃ is preferably a group having a size and shape sufficient to impart resistance to diffusion in a hydrophilic colloid to the yellow coupler represented by the general formula [I]. R ₃
The substitution position of is preferably the 3-position, 4-position, or 5-position on the benzene ring, and particularly preferably the 5-position.

In the general formula [I], R ₄ is preferably a halogen atom (F, Cl, Br, I), having 1 to 10 carbon atoms.
8 alkyl groups (eg methyl, isopropyl, t
-Butyl group), an alkoxy group having 1 to 8 carbon atoms (eg, methoxy group, butoxy group, benzyloxy group), a carbonamido group having 1 to 8 carbon atoms (eg, acetamido group, benzamido group), or the number of carbon atoms 1 to 8 sulfonamide groups (eg, methanesulfonamide group, p-toluenesulfonamide group).

In the general formula [I], m is an integer of 0-2. When m is an integer of 1 or 2, the substitution position of R ₄ is preferably the 3-, 4-, or 5-position on the benzene ring.

In the general formula [I], R ₅ and R ₆ are preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms (eg, methyl group, ethyl group, butyl group, hexyl group).
It is.

In the general formula [I], X is preferably an oxygen atom.

Particularly preferred embodiments of the coupler of the present invention are as follows. That is, in the general formula [I],
R ₁ is a t-butyl group, 1-alkylcyclopropane-1
-Yl group, or 5-alkyl-1,3-dioxane-
5-yl group, more preferably t-butyl group or 1-alkylcyclopropan-1-yl group, and particularly preferably t-butyl group. R ₂ is a halogen atom or an alkoxy group. R ₃ has 8 to 24 carbon atoms
Is a linear or branched alkyl group which may be separated by an ether oxygen atom or ester. R ₄
Is a halogen atom or an alkoxy group. m is an integer of 0 or 1. When m is 1, the substitution position of R ₄ is 3
Position or fourth position is preferred. R ₅ and R ₆ are a hydrogen atom or an alkyl group having 1 to 4 hydrogen atoms. General formula [I]
Of the couplers represented by, particularly preferred couplers are represented by the following general formula [II].

[0027]

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In the general formula [II], R ₁ , R ₂ and R
₃ , R ₄ , R ₅ , R ₆ and X are respectively the same as R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and X in the general formula [I], and n is 0 or Represents an integer of 1.

Specific examples of the yellow coupler of the present invention are shown below, but the present invention is not limited thereto.
In the following table, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ ,
R ₆ , X, and m are according to general formula [I].

[0030]

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[0031]

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[0032]

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[0033]

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The yellow coupler of the present invention is disclosed in JP-A-55 / 1988.
-598, 56-87041, JP-A-4-218.
042, 4-344640, 5-53269.
, No. 5-80469, Research Disclosure No. 18053 (1979), EP
It can be synthesized by the method described in No. 672,946A or the like.

The yellow coupler of the present invention can be added to any layer of the light-sensitive material, but in a multilayer color light-sensitive material, it is particularly preferably added to the blue-sensitive silver halide emulsion layer or its adjacent non-light-sensitive layer. . The amount of coupler added is 0.01 mmol to 10 mmol, preferably 0.1 mmol to 5 mmol, and more preferably 0.2 to 2 mmol per m ² of the light-sensitive material.

The yellow coupler of the present invention can be used together with other known yellow couplers such as benzoylacetanilide type couplers, malondianilide type couplers, dialkylcarbamoylacetanilide type couplers and 1-indolinylcarbonylacetanilide type couplers. it can. The yellow coupler of the present invention can be added to a light-sensitive material by, for example, a method of preparing a coupler dispersion by an oil-in-water dispersion method described in US Pat. No. 2,322,027 and adding the dispersion to a coating solution. Done. The amount of the high boiling organic solvent used in the oil-in-water dispersion method in the coupler is 3 g or less per 1 g of the coupler.
It is preferably 2 g or less, more preferably 1 g or less. It is particularly preferably 0.5 g or less. The lower limit value is 0.01 g, but a dispersion of the coupler alone without any high boiling organic solvent may be used. Alternatively, a latex dispersion method in which the high boiling point organic solvent is used may be applied.

The compounds represented by formulas (AI) to (A-III) will be described in more detail. The alkyl group referred to in the present invention is a linear, branched, or cyclic alkyl group, and may have a substituent. In the general formula (AI), R
_a1 is an alkyl group (preferably an alkyl group having 1 to 36 carbon atoms such as methyl, ethyl, i-propyl, cyclopropyl, butyl, isobutyl, cyclohexyl, t-octyl, decyl, dodecyl, hexadecyl, benzyl),
Alkenyl group (preferably an alkenyl group having 2 to 36 carbon atoms such as allyl, 2-butenyl, isopropenyl,
Oleyl, vinyl), aryl groups (preferably having 6 carbon atoms)
To 40 aryl groups such as phenyl and naphthyl, acyl groups (preferably C2 to C36 acyl groups such as acetyl, benzoyl, pivaloyl, α- (2,4-di-tert-amylphenoxy) butyryl, ( 3-cyclohexen-1-yl) -carbonyl, myristoyl, stearoyl, naphthoyl, m-pentadecylbenzoyl,
(5-norbornen-2-yl) carbonyl, isonicotinoyl), an alkyl or arylsulfonyl group (preferably an alkyl or arylsulfonyl group having 1 to 36 carbon atoms, such as methanesulfonyl, octanesulfonyl,
Benzenesulfonyl, toluenesulfonyl), alkyl or arylsulfinyl group (preferably having 1 to 4 carbon atoms).
An alkyl or arylsulfinyl group of 0 such as methanesulfinyl and benzenesulfinyl), a carbamoyl group (including an N-substituted carbamoyl group, preferably a carbamoyl group having 1 to 40 carbon atoms such as N-ethylcarbamoyl, N-phenylcarbamoyl, N, N-dimethylcarbamoyl, N-butyl-N-phenylcarbamoyl), a sulfamoyl group (including an N-substituted sulfamoyl group, preferably a sulfamoyl group having 1 to 40 carbon atoms such as N-methylsulfamoyl, N, N-diethylsulfamoyl, N-phenylsulfamoyl, N-cyclohexyl-N-phenylsulfamoyl, N-ethyl-N-dodecylsulfamoyl), alkoxycarbonyl group (preferably alkoxy having 2 to 36 carbon atoms) For example, a carbonyl group Alkoxycarbonyl, cyclohexyloxycarbonyl, benzyloxycarbonyl, isoamyl oxycarbonyl, hexadecyl oxycarbonyl)
Alternatively, it represents an aryloxycarbonyl group (preferably an aryloxycarbonyl group having 7 to 40 carbon atoms, such as phenoxycarbonyl or naphthoxycarbonyl).
R _a2 represents a hydrogen atom or the group represented by R _a1 above.

In the general formula (A-II), the heterocyclic group of X is a 5- to 7-membered S-triazine ring (1 having a nitrogen atom, a sulfur atom, an oxygen atom or a phosphorus atom as a ring-constituting atom). , 3,5-triazine ring), which is a group forming a hetero ring, and the bonding position of the hetero ring (1
The position of the valence group) is preferably a carbon atom, for example 1,
2,4-triazin-3-yl, pyridin-2-yl,
Pyrazinyl, pyrimidinyl, purinyl, quinolyl, imidazolyl, 1,2,4-triazol-3-yl, benzimidazol-2-yl, thienyl, furyl, imidazolidinyl, pyrrolinyl, tetrahydrofuryl, morpholinyl, phosphinolin-2-yl. Represent. R _b1 has the same meaning as the alkyl group, alkenyl group or aryl group in R _a1 of the above general formula (AI).

In the general formula (A-III), Y is -N = C.
-A non-metallic atom group necessary to form a 5-membered ring together with (for example, the ring group formed is imidazolyl, benzimidazolyl, 1,3-thiazol-2-yl, 2-imidazolin-2-yl, purinyl, 3H -Indol-2-yl). Y is a group of nonmetallic atoms necessary for forming a 6-membered ring together with the -N = C- group, and -N
The end of Y bonded to the carbon atom of the ═C-group is -N (R _C1 )-, -C
(R _C2 ) (R _C3 )-, —C (R _C4 ) =, —O—, a group selected from —S— (bonded to the carbon atom of —N═C— on the left side of each group) Represents However, it does not form an S-triazine (1,3,5-triazine) ring. R _{c1 to} R _c4 may be the same or different and each represents a hydrogen atom or a substituent (for example, an alkyl group, an alkenyl group, an aryl group, an alkoxy group,
Aryloxy group, alkylthio group, arylthio group,
Alkylamino group, arylamino group, halogen atom)
Represents Here, the alkyl group, the alkenyl group, and the aryl group have the same meanings as the alkyl group, the alkenyl group, and the aryl group in R _a1 of the general formula (A-1), and the alkoxy group, the alkylthio group, the alkyl group of the alkylamino group, The aryl group of aryloxy group, arylthio group and arylamino group also has the same meaning as described for R _a1 in formula (A-1). The halogen atom represents, for example, chlorine, bromine or fluorine atom. Examples of the 6-membered ring group formed by Y include quinolyl, isoquinolyl, phthalazinyl, quinoxalinyl, 6H-1,2,
5-thiadiazin-6-yl is mentioned.

In the general formula (AI) or (A-II), R _a1 and R _a2 , and X and R _b1 may combine with each other to form a 5- to 7-membered ring, for example, a succinimide ring or a phthalimide ring. , Triazole ring, urazole ring, hydantoin ring, and 2-oxo-4-oxazolidinone ring. However, the S-triazine ring is excluded. General formula (AI)
Each group of the compounds represented by to (A-III) may be further substituted with a substituent. Examples of these substituents include an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a hydroxy group, an alkoxy group, an aryloxy group,
Alkylthio group, arylthio group, amino group, acylamino group, sulfonamide group, alkylamino group, arylamino group, carbamoyl group, sulfamoyl group, sulfo group, carboxyl group, halogen atom, cyano group, nitro group, sulfonyl group, acyl group , An alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, a hydroxyamino group and the like.

In the general formula (AI), R _a2 is a hydrogen atom, an alkyl group, an alkenyl group or an aryl group, and R _a1 is an acyl group, an alkyl or aryl sulfonyl group, an alkyl or aryl sulfinyl group or a carbamoyl group. , Sulfamoyl group, alkoxycarbonyl group,
It is preferably an aryloxycarbonyl group, more preferably R _a2 is an alkyl group or an alkenyl group, and R _a1 is an acyl group, an alkyl or arylsulfonyl group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, or aryloxy. A compound that is a carbonyl group. Most preferably, R _a2 is an alkyl group and R _a1 is an acyl group.

In the general formula (A-II), R _b1 is preferably an alkyl group or an alkenyl group, more preferably an alkyl group. On the other hand, the general formula (A-II) is preferably represented by the following general formula (A-II-1).

[0043]

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[0044] In formula (A-II-1), R b1 represents R _b1 in formula (A-II), X ₁ is -C = N-with necessary to form a 5- or 6-membered ring Represents a non-metallic atomic group. Among the compounds represented by formula (A-II-1), it is more preferable that X ₁ forms a 5- or 6-membered heteroaromatic ring. However, it does not form an S-triazine ring.

Of the compounds represented by the general formula (A-III), it is preferable that Y is a group of non-metal atoms necessary for forming a 5-membered ring, and it is bonded to the carbon atom of the -N = C- group. It is more preferable that the terminal atom of Y is a nitrogen atom. However, it does not form an S-triazine ring. Most preferably, Y forms an imidazoline ring. This imidazoline ring may be condensed with a benzene ring.

Among the compounds represented by the general formulas (AI) to (A-III), compounds having a total carbon number of 15 or less are preferable in that they act on layers other than the additive layer, and vice versa. A compound having a total carbon number of 16 or more is preferable for the purpose of acting only on the additive layer. General formula (AI)-(A-
Among the compounds represented by III), the general formula (AI),
Those represented by (A-II) are preferable, and those represented by general formula (AI) are more preferable. Specific examples of the compounds represented by formulas (AI) to (A-III) of the present invention are shown below, but the present invention is not limited thereto.

[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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These compounds and the above-mentioned general formula (AI)
The correspondence with (A-III) is as follows. General formula (AI): A-1 to A-9, A-11 to A-1
8, A-33 to A-55. General formula (A-II): A-10, A-20, A-30. General formula (A-III): A-19, A-21 to A-29, A
-31, A-32. These compounds of the present invention are described in J. Org. Chem., 27, 405.
4 ('62), J. Amer. Chem. Soc., 73,2981 ('51), Japanese Patent Publication No. 4
It can be easily synthesized by the method described in 9-10692 or the like or a method similar thereto. In the present invention, the compounds represented by the general formulas (A-I) to (A-III) are water-soluble solvents such as water, methanol, ethanol, dimethylformamide, and dimethyl sulfoxide, or
It may be added by dissolving in these mixed solvents or by emulsifying and dispersing. Further, they may be added in advance during the preparation of the emulsion. In the present invention, general formulas (AI) to (A
Two or more of the compounds represented by formula (III) may be used in combination. The coating amount of the compounds (A-I) to (A-III) is preferably 0.01 to 200 mg / m ² per layer. 0.1-10
0 mg / m ² is more preferable, and 1 to 50 mg / m ² is even more preferable. In the present invention, the use of these compounds is at least one layer of the silver halide photosensitive layer or the non-photosensitive layer, but the same compound may be used in a plurality of layers, or different compounds may be used in the respective photosensitive layers. You may use it for a photosensitive layer or a non-photosensitive layer. The non-photosensitive layer in the present invention is, for example,
Intermediate layer, yellow filter layer containing colloidal silver, AH
A layer, a protective layer, etc.

In the present invention, general formulas (AI) to
The compound represented by (A-III) is preferably an oil-soluble compound. It is preferable to use the oil-soluble compound in the layer containing the coupler represented by the general formula [I] or in the layer adjacent thereto. It is particularly preferable to use the same layer containing the coupler represented by the general formula [I]. Further, depending on the purpose, water-soluble compounds represented by the general formulas (AI) to (A-III) can be used. As described above, the yellow coupler represented by the general formula [I] has a higher coupling activity and a higher coupling activity than conventionally used acetanilide type 2-equivalent couplers substituted with an acyl group of a tertiary alkyl group. It provides sensitivity and gradation, and exhibits excellent color development, but the fog also increases with it, and in particular, the fog increases significantly when the photosensitive material is aged, and the latent image increases when the photosensitive material is photographed. There is a problem that the feeling is great. To solve this problem, the present invention provides the above general formulas (AI) to (A-II).
The compound represented by I) is used, and the problem is solved by applying the compound particularly preferably to the same layer containing the coupler represented by the formula [I]. By being able to solve this problem, acetanilide type couplers substituted with an acyl group having a tertiary alkyl group have excellent properties, that is, small absorption in the green light region on the long wavelength side, good color reproducibility, and excellent color image fastness. It is possible to effectively utilize the coupler provided with.

Further, in the present invention, the coupler represented by the general formula [I] is preferably used in the same light-sensitive material as the benzoylacetanilide type coupler represented by the general formula [Y] described later. Even in the combined use, the above-mentioned object of the present invention can be achieved successfully.

Next, in the present invention, the above-mentioned general formula [I]
The yellow dye-forming coupler represented by the general formula [Y] (also referred to as yellow coupler) which is preferably used together with the coupler represented by In the formula [Y], R ₁ is an aryl group, R ₂ is a hydrogen atom, a halogen atom (F, Cl, Br, I and below, the same in the description of the formula [Y]), an alkoxy group, an aryloxy group, an alkyl group. Or a dialkylamino group, R ₃ is a group capable of substituting on the benzene ring, X ₀ is a group capable of splitting off by a coupling reaction with a hydrogen atom or an oxidized product of an aromatic primary amine developer (referred to as a splitting group). ), And p represents an integer of 0 to 4, respectively. However, when p is plural, plural R ₃ may be the same or different.

Here, as examples of R _3, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbonamide group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, There are alkylsulfonyl groups, arylsulfonyl groups, ureido groups, sulfamoylamino groups, alkoxycarbonylamino groups, nitro groups, heterocyclic groups, cyano groups, acyl groups, acyloxy groups, alkylsulfonyloxy groups, arylsulfonyloxy groups, Examples of the leaving group for X ₀ include a heterocyclic group, an aryloxy group, an arylthio group, an acyloxy group, an alkylsulfonyloxy group, a heterocyclic oxy group, and a halogen atom which are bonded to the coupling active position by a nitrogen atom.

When the substituent in the formula [Y] is an alkyl group or contains an alkyl group and is not particularly specified, the alkyl group is unsaturated even if it is linear, branched or cyclic. An alkyl group which may contain a bond (for example, methyl, isopropyl, t-butyl, cyclopentyl, t-pentyl, cyclohexyl, 2-ethylhexyl, 1,1,3,3-tetramethylbutyl, dodecyl,
Hexadecyl, allyl, 3-cyclohexenyl, oleyl, benzyl, trifluoromethyl, hydroxymethyl, methoxyethoxy, ethoxycarbonylmethyl, phenoxyethyl).

When the substituent in the formula [Y] is an aryl group or contains an aryl group and there is no particular limitation, the aryl group may be an optionally substituted monocyclic or condensed ring aryl group (eg, phenyl, 1 -Naphthyl, p-tolyl, o-tolyl, p-chlorophenyl, 4-methoxyphenyl, 8-quinolyl, 4-hexadecyloxyphenyl, pentafluorophenyl, p-hydroxyphenyl, p-cyanophenyl, 3-pentadecylphenyl ,
2,4-di-t-pentylphenyl, p-methanesulfonamidophenyl, and 3,4-dichlorophenyl).

When the substituent in the formula [Y] is a heterocyclic group or contains a heterocyclic group and is not particularly specified, the heterocyclic group is at least one of O, N, S, P, Se and Te. An optionally substituted 3- to 8-membered monocyclic or condensed-ring heterocyclic group containing a heteroatom in the ring (for example, 2-furyl, 2
-Pyridyl, 4-pyridyl, 1-pyrazolyl, 1-imidazolyl, 1-benzotriazolyl, 2-benzotriazolyl, succinimide, phthalimide, 1-benzyl-2,4-imidazolidinedione-3-yl) means. Hereinafter, the substituents preferably used in the formula [Y] will be described.

In the formula [Y], R ₁ is preferably the total number of carbon atoms which may be substituted (hereinafter abbreviated as C number) 6 to 3
0 represents an aryl group, and examples of the substituent thereof include a halogen atom, an alkyl group, an alkoxy group, a nitro group, an amino group, a carbonamido group, and a sulfonamide group.

In the formula [Y], R ₂ is preferably a halogen atom, which may have a C number of 1 to 30 which may be substituted.
Alkoxy group, aryloxy group having 6 to 30 C, C
It represents an alkyl group having 1 to 30 or a dialkylamino group having 2 to 30 carbon atoms, and examples of the substituent thereof include a halogen atom, an alkyl group, an alkoxy group, and an aryloxy group.

In the formula [Y], R ₃ is preferably a halogen atom, an optionally substituted alkyl group having 1 to 30 C atoms, an aryl group having 6 to 30 C atoms, or an alkoxy group having 1 to 30 C atoms. , C2-30 alkoxycarbonyl group, C7-30 aryloxycarbonyl group, C1-30 carbonamido group, C1-30 sulfonamide group, C1-30 carbamoyl group , C number 0-3
0 sulfamoyl group, C 1-30 alkylsulfonyl group, C 6-30 arylsulfonyl group, C 1
To 30 ureido group, C number 0 to 30 sulfamoylamino group, C number 2 to 30 alkoxycarbonylamino group, C number 1 to 30 heterocyclic group, C number 1 to 30 acyl group, C number It represents an alkylsulfonyloxy group having 1 to 30 or an arylsulfonyloxy group having 6 to 30 carbon atoms, and the substituent thereof is, for example, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group,
Heterocyclic oxy group, alkylthio group, arylthio group, heterocyclic thio group, alkylsulfonyl group, arylsulfonyl group, acyl group, carbonamide group, sulfonamide group, carbamoyl group, sulfamoyl group, alkoxycarbonylamino group, sulfamoylamino Group, ureido group, cyano group, nitro group, acyloxy group, alkoxycarbonyl group, aryloxycarbonyl group, alkylsulfonyloxy group, and arylsulfonyloxy group.

In the formula [Y], p preferably represents an integer of 1 or 2, and the substitution position of R ₃ is

[0064]

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On the other hand, the meta position or the para position is preferred.

In the formula [Y], X ₀ preferably represents a heterocyclic group or an aryloxy group bonded to the coupling active position by a nitrogen atom.

[0067] When X ₀ represents a heterocyclic group, X ₀ is preferably a heterocyclic monocyclic or condensed or 5- to 7-membered ring which may be substituted, succinimide as an example, maleinimide, phthalimide, Diglycolimide, pyrrole, pyrazole, imidazole, 1,2,4-triazole, tetrazole, indole, indazole, benzimidazole, benzotriazole, imidazolidine-2,4-dione, oxazolidine-2,4-dione, thiazolidine-2 , 4-dione, imidazolidine-
2-one, oxazolin-2-one, thiazoline-2-
On, benzimidazolin-2-one, benzoxazolin-2-one, benzothiazolin-2-one, 2-pyrrolin-5-one, 2-imidazolin-5-one, indoline-2,3-dione, 2,6 -Dioxypurine, parabanic acid, 1,2,4-triazolidine-3,5-dione, 2-pyridone, 4-pyridone, 2-pyrimidone, 6
-Pyridazone, 2-pyrazone, 2-amino-1,3,4
-Thiazolidine, 2-imino-1,3,4-thiazolidine-4-one and the like, and these heterocycles may be substituted. Examples of substituents of these heterocyclic groups include halogen atom, hydroxyl group, nitro group, cyano group, carboxyl group, sulfo group, alkyl group, aryl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, alkyl group. Sulfonyl group, arylsulfonyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, acyloxy group, amino group, carbonamido group, sulfonamide group, carbamoyl group, sulfamoyl group, ureido group, alkoxycarbonylamino group, sulfamoyl group There is an amino group.

When X ₀ represents an aryloxy group, X
₀ preferably represents an aryloxy group having a C number of 6 to 30, and may be substituted with a group selected from the substituent group mentioned when X ₀ is a heterocyclic group. Substituents for the aryloxy group include halogen atom, cyano group, nitro group, carboxyl group, trifluoromethyl group, alkoxycarbonyl group, carbonamido group, sulfonamide group, carbamoyl group, sulfamoyl group, alkylsulfonyl group, arylsulfonyl group. Groups or acyl groups are preferred.

Substituents particularly preferably used in formula [Y] will be described below.

R ₁ is particularly preferably a phenyl group or a phenyl group substituted with a chlorine atom, a methyl group, a methoxy group, an ethoxy group or a butoxy group.

R ₂ is particularly preferably a chlorine atom, a fluorine atom, an alkyl group having a C number of 1 to 6 (eg methyl, trifluoromethyl, ethyl, isopropyl, t-butyl), C
Alkoxy groups of the formulas 1 to 8 (for example, methoxy, ethoxy,
Methoxyethoxy, butoxy) or an aryloxy group having 6 to 24 carbon atoms (for example, phenoxy, p-tolyloxy, p-methoxyphenoxy), most preferably a chlorine atom or a methoxy group.

R ₃ is particularly preferably a halogen atom, an alkoxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbonamido group, a sulfonamide group, a carbamoyl group or a sulfamoyl group, and most preferably an alkoxy group, an alkoxycarbonyl group, A carbonamide group or a sulfonamide group.

X ₀ is particularly preferably a group represented by the following formula [Y-1] or [Y-2].

[0074]

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In the formula [Y-1], Z is

[0076]

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Or

[0078]

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Represents Here, R ₄ , R ₅ , R ₈ and R ₉ are each independently a hydrogen atom, an alkyl group, an aryl group,
An alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group or an amino group, wherein R ₆ and R ₇ are a hydrogen atom, an alkyl group, an aryl group, an alkylsulfonyl group,
It represents an arylsulfonyl group or an alkoxycarbonyl group, and R ₁₀ and R ₁₁ represent a hydrogen atom, an alkyl group or an aryl group. R ₁₀ and R ₁₁ may combine with each other to form a benzene ring. R ₄ and R ₅ , R ₅ and R ₆ , R
₆ and R ₇ or R ₄ and R ₈ may combine with each other to form a ring (for example, cyclobutane, cyclohexane, cycloheptane, cyclohexene, pyrrolidine, piperidine).

Among the heterocyclic groups represented by the formula [Y-1], a particularly preferred one is Z in the general formula [Y-1].

[0081]

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Is a heterocyclic group

The C number of the heterocyclic group represented by the formula [Y-1] is 2 to 30, preferably 4 to 20, and more preferably 5.
~ 16.

[0084]

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In the formula [Y-2], at least one of R ₁₂ and R ₁₃ is a halogen atom, a cyano group, a nitro group, a trifluoromethyl group, a carboxyl group, an alkoxycarbonyl group, a carbonamido group, a sulfonamide group or carbamoyl. A group selected from a group, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group or an acyl group, and the other may be a hydrogen atom, an alkyl group or an alkoxy group. R ₁₄ represents a group having the same meaning as R ₁₂ or R _13, and m represents an integer of 0 to 2. Formula [Y
-2], the C number of the aryloxy group is 6 to 3
0, preferably 6 to 24, and more preferably 6 to 15.

The coupler represented by the formula [Y] has substituents R ₁ , X ₀ or

[0087]

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In the above, a dimer or a multimer having a valence of 2 or more may be bonded to each other to form a multimer. In this case, the number of carbon atoms may be out of the specified range for each substituent.

When the coupler represented by the formula [Y] forms a multimer, a typical example is a homopolymer or copolymer of an addition polymer ethylenically unsaturated compound (yellow color-forming monomer) having a yellow dye-forming coupler residue. And is preferably represented by the formula [Y-3].

[0090]

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In the formula [Y-3], G _i is a repeating unit derived from a color forming monomer, and is represented by the following formula [Y-
4], H _j is a group which is a repeating unit derived from a non-color-forming monomer, i represents a positive integer, j represents 0 or a positive integer, and g
i and hj represent the weight fraction of G _i or H _j , respectively. Here, when i or j is plural, G _i or H _j
Represents containing a plurality of types of repeating units. gi
Is not 0, and the ratio of gi to hj can be arbitrarily set. As the ratio of gi to hj, gi is 20 to
80 and hj are preferably in the range of 80 to 20.

[0092]

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In the formula [Y-4], R is a hydrogen atom and has 1 to 10 carbon atoms.
4 alkyl groups or chlorine atoms, A is -CON
H-, -COO- or a substituted or unsubstituted phenylene group, B represents a substituted or unsubstituted alkylene group, phenylene group or aralkylene group, and L represents-.
CONH-, -NHCONH-, -NHCOO-, -N
HCO-, -OCONH-, -NH-, -COO-,-
OCO -, - CO -, - O -, - S -, - SO 2 -, -
Represents NHSO ₂ — or —SO ₂ NH—. a,
b and c represent 0 or 1. Q is R ₁ , X _{0 of the} compound represented by the general formula [Y], or

[0094]

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A yellow coupler residue in which one hydrogen atom has been removed is shown below. Examples of the non-color forming ethylene type monomer that does not couple with the oxidation product of the aromatic primary amine developing agent that gives the repeating unit H _j include acrylic acid, α-chloroacrylic acid, α-alkylacrylic acid (for example, methacrylic acid, etc.). ) Amides or esters derived from these acrylic acids (eg, acrylamide, methacrylamide, n-butyl acrylamide, t-butyl acrylamide, diacetone acrylamide, methyl acrylate, ethyl acrylate, n-propyl acrylate)
, N-butyl acrylate, t-butyl acrylate
, Iso-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and β-hydroxymethacrylate. G)), vinyl esters (eg vinyl acetate, vinyl propionate and vinyl laurate), acrylonitrile, methacrylonitrile, aromatic vinyl compounds (eg styrene and its derivatives such as vinyltoluene, divinylbenzene, vinylacetophenone and sulfostyrene). , Itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ethers (eg vinyl ethyl ether), maleic acid esters, N-vinyl-2-pyrrolidone, N-vinyl pyridine and 2 And 4 there is vinylpyridine.

Acrylic acid esters, methacrylic acid esters and maleic acid esters are particularly preferred. The non-color-forming ethylene type monomer used here can be used in combination of two or more kinds. For example, methyl acrylate and butyl acrylate, butyl acrylate and styrene, butyl methacrylate and methacrylic acid, methyl acrylate and diacetone acrylamide, etc. can be used.

As well known in the field of polymer couplers, the ethylenically unsaturated monomer for copolymerization with the vinyl monomer corresponding to the above formula [Y-4] is in the form of the copolymer formed, For example, solid, liquid, micellar or physical and / or chemical properties such as solubility (solubility in water or organic solvent), compatibility with photographic colloid composition binders such as gelatin, The flexibility, the thermal stability, the coupling reactivity with the oxidized form of the developing agent, the diffusion resistance in the photographic colloid, etc. can be selected so as to be favorably influenced.
These copolymers may be random copolymers or copolymers having a specific sequence (eg, block copolymer, alternating copolymer).

The number average molecular weight of the yellow polymer coupler used in the present invention is usually on the order of thousands to hundreds of thousands, but oligomeric polymer couplers of 5000 or less can also be used.

The yellow coupler used in the present invention is a lipophilic polymer soluble in an organic solvent (eg, ethyl acetate, butyl acetate, ethanol, methylene chloride, cyclohexanone, dibutyl phthalate, tricresyl phosphate) or an aqueous gelatin solution. It may be a hydrophilic polymer that is miscible with the hydrocolloid, or may be a polymer having a structure and properties capable of forming micelles in the hydrocolloid.

The yellow polymer coupler used in the present invention is a gelatin prepared by dissolving a lipophilic polymer coupler obtained by polymerization of a vinyl-type monomer giving a coupler unit represented by the above formula [Y-4] in an organic solvent. It may be prepared by emulsion-dispersing it in the form of a latex in an aqueous solution, or may be prepared by a direct emulsion polymerization method.

US Pat. No. 3,451,820 for a method of emulsion-dispersing a lipophilic polymer coupler in the form of a latex in an aqueous gelatin solution, and US Pat. No. 4,084 for emulsion polymerization.
The methods described in Nos. 0,211 and 3,370,952 can be used. Specific examples of the yellow coupler represented by the formula [Y] are shown below.

[0102]

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[0103]

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[0104]

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[0105]

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[0106]

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[0107]

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[0108]

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[0109]

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Examples of compounds other than the yellow couplers used in the present invention and / or methods for synthesizing these yellow couplers are described in, for example, US Pat. Nos. 3,227,554, 3,408,194, 3,644,498 and 3,770,445.
, No. 3,894,875, No. 3,933,501, No. 3,973,
No. 968, No. 4,022,620, No. 4,032,347, No. 4,
No. 046,575, No. 4,049,458, No. 4,057,432, No. 4,115,121, No. 4,133,958, No. 4,157,919
No. 4,201,584, No. 4,203,768, No. 4,248,
961, No. 4,266,019, No. 4,314,023, No. 4,
326,024, 4,327,175, 4,401,752, 4,420,556, 4,511,649, 4,617,256
No. 4, No. 4,711,837, No. 4,729,944, No. 4,758,
501, European Patent Nos. 30,747A, 272,041A, and
280,330A, 284,081A, 296,793A, 31
3,308A, British patent 1,040,710, West German patent 3,107,
173C, JP-A-58-42044, 59-174839, 60-696.
53, 62-200349, 62-276547, 63-23153
No. 63-43144, No. 63-123047, etc.

The yellow coupler represented by the formula [Y] is contained in at least one layer of the light-sensitive material. At least one layer may be a photosensitive silver halide emulsion layer or a non-photosensitive layer (for example, an antihalation layer, an intermediate layer, a yellow filter layer, a protective layer). It is preferably a blue-sensitive emulsion layer and / or a non-light-sensitive layer adjacent thereto. More preferably, it is used in at least one of the blue-sensitive emulsion layers. The amount of the photosensitive material of the yellow couplers represented by formula (Y), the photosensitive material 1 m ² per 1.0 × 10 ^-3 ~3.
The range is 0 g. Preferably 5.0 × 10 ^{−3 to} 2.0
g, and more preferably in the range of 1.0 × 10 ^{-2 to} 1.5 g. The yellow coupler represented by the formula [Y] may be introduced into the light-sensitive material by any known dispersion method. Preferred is a method in which a high-boiling-point organic solvent described later is used and an oil-in-water dispersion method is applied to introduce the emulsion-dispersed dispersion into a photosensitive material. The coupler represented by the formula [Y] is preferably used in the blue-sensitive emulsion layer and / or the adjacent non-photosensitive layer together with the coupler represented by the formula [I]. When the blue-sensitive emulsion layer has a constitution of two or more layers, both couplers represented by the formula [I] and the formula [Y] may be used in combination in the same layer, and the different layers may be represented by the formula [I]. ] The coupler represented by the formula] and the coupler represented by the formula [Y] can be selectively used according to the purpose required for the light-sensitive material.

The coupler represented by the above formula [Y] is preferably used in the same layer and / or the layer adjacent to the compounds represented by the above general formulas (AI) to (A-III).
It is particularly preferred to use both in the same layer. Such use can be achieved by using the coupler represented by the above formula [I] and the formula (AI).
To (A to III), similarly to the case of using the compound represented by (A to III), the problems of increase in fog with time of the light-sensitive material and sensitization with time when the light-sensitive material after photography is aged are solved. The object of the present invention can be achieved brilliantly. Therefore, the coupler represented by the formula [I] and the coupler represented by the formula [Y] can be optionally used in the light-sensitive material depending on the purpose of the light-sensitive material.

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 chromium dioxide, ferromagnetic metal, ferromagnetic Alloy, hexagonal Ba ferrite, Sr ferrite, Pb ferrite, Ca ferrite can be used. Co deposited γFe ₂ O
Co-coated ferromagnetic iron oxides such as ₃ are preferred. 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 from 3.0 × 10 ⁴ to 3.0 × 10 ⁵ A / m, and particularly preferably from 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, magnetic particles having a surface coated with an inorganic or organic material described in JP-A-4-259911 and 5-81652 can also be used.

The binder used for the magnetic particles is a thermoplastic resin, a thermosetting resin, a radiation curable resin, a reactive resin, an acid, an alkali or a biodegradable polymer described in JP-A-4-219569, and a natural product Coalescence (cellulose derivatives, sugar derivatives, etc.) and mixtures thereof can be used. The above resin has a Tg of -40 ° C to 300 ° C and a weight average molecular weight of 2,000 to 1,000,000. Examples thereof include vinyl copolymers, cellulose diacetate, cellulose triacetate, cellulose derivatives such as cellulose acetate propionate, cellulose acetate butyrate, and cellulose tripropionate, acrylic resins and 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 crosslinking agent include isocyanates such as tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, and xylylene diisocyanate, and reaction products of these isocyanates with polyalcohol (for example, 3mol of isocyanate and 1m of trimethylolpropane
ol reaction product), and polyisocyanates formed by condensation of these isocyanates.
For example, it is 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, etc. are preferable and a combination thereof is also preferable, as in the method described in JP-A-6-35092. Dispersants 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.
m, more preferably 0.3 μm to 3 μm. The weight ratio between the magnetic particles and the binder is preferably 0.5: 100 to 60: 100.
And more preferably from 1: 100 to 30: 100. The coating amount of the magnetic particles 0.005~ 3g / m ^2, preferably from 0.01 to 2
g / m ² , more preferably 0.02 to 0.5 g / m ² . The transmission yellow density of the magnetic recording layer is preferably 0.01 to 0.50,
03 to 0.20 is more preferable, and 0.04 to 0.15 is particularly preferable.
The magnetic recording layer can be provided on the entire back surface of the photographic support by coating or printing, or in a stripe shape. As a method of applying the magnetic recording layer, an air doctor, a blade, an air knife, a squeeze, an impregnation, a reverse roll,
Transfer rolls, gravure, kisses, casts, sprays, dips, bars, extrusions and the like can be used, and the coating solutions described in JP-A-5-341436 are preferred.

In the magnetic recording layer, improvement of 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. For photosensitive materials having a magnetic recording layer, see US Pat.
5,229,259, 5,215,874 and EP 466,130.

Usually, a light-sensitive material having a magnetic recording layer on the back surface affects the photographic properties of the light-sensitive material when the light-sensitive material is rolled up and brought into contact with the surface having the photosensitive emulsion layer for a long period of time. Degrade the performance of. When the coupler represented by the general formula [I] of the present invention is used, the problems of the above-mentioned increase in fog and latent image sensitization become serious.
This problem can be solved by applying the compounds represented by -I) to (A-III), and the object of the present invention can be achieved successfully.

The structure of the photographic light-sensitive material package (hereinafter, also referred to as "photographic film cartridge") 100 of the present invention will be described below with reference to the drawings. 1 is an exploded perspective view of the photographic film cartridge, FIG. 2 is a view of the photographic film cartridge viewed from the radial direction, and FIG. 3 is a view of the photographic film cartridge viewed from the radial direction at a position different from FIG. The photographic film cartridge 100 includes a cartridge body 101 in which a spool 103 around which a photographic photosensitive material (photo film) 102 is wound is rotatably housed.
A cartridge label 104 is adhered to the outer periphery of 1.
The cartridge body (patrone body) 101 is composed of upper and lower cases 105 and 106 which are two molded parts.

An upper case 105 having a gate 150,
Photo film 1 on the front side joint with the lower case 106
A film delivery port 107 (passage) for delivering 02 is formed. A lid member 108 for preventing light from entering there is behind the film delivery port 107.
And a separation claw 109 which is arranged at the back of the separation film and separates the tip of the photographic film 102. The lid member 108 has key grooves 110,
111 is formed, and the keyway 11 is formed when loaded in the camera.
The opening / closing drive shaft on the camera side that engages with 0 and 111 is rotated between a closed position that closes the film feed opening 107 and an open position that allows entry and exit of the photographic film. FIG. 5 shows a state in which the lock pawl 144 and the lid member 108 are engaged with each other and the lid member is locked at the closed position.

The spool 103 has a pair of lip flanges 113, 1 on the inner sides of the spool shaft 112, respectively.
14 is attached, and a data disk is provided on the outside of one flange 113. The other flange 1
A use display member 123 is attached to the outer side of 14. A data label is attached to the data disk 115. A pair of flange engaging portions 1 with which the spool shaft 112, the data disk 115, and the respective flanges 113 and 114 are engaged.
17, 118, slit 11 for locking the rear end of the photographic film
9 and the use display member supporting portion 120 are formed integrally with each other, and when the spool 10 is mounted on the camera,
The drive shaft on the camera side is engaged with the key grooves 121 and 122 on the key holes provided at both ends of the drive shaft 3, and is rotated by the rotation of the drive shaft.

The use display member 123 includes a bearing portion 12
The four ratchet pawls 125, the gear 126, and the use display plate 127 are integrally formed, and these rotate integrally with the spool shaft 112.

The inside of the photographic film cartridge 100 is
A spool lock 128 is housed so as to mesh with the gear 126. This spool lock 128 is a lid member 1.
When 08 is in the closed position, the gear 126 is engaged to lock the rotation of the spool shaft 112, prevent careless feeding of the photographic film 102, and cover member 108.
When is in the open position, it disengages from the gear 126.

The pair of flanges 113 and 114 are formed of a plastic material and have a thin cup-shaped cross section. The cup-shaped bottom has a flange engaging portion 117,
Round holes 129 and 130 are rotatably engaged with 118, respectively. Also, the cup-shaped opening edge 13
1, 132 are arranged to face each other when attached to the spool shaft 112, and wrap around the outermost ends of the photographic film 102 wound between them (see FIG. 6). The opening edge portions 131 and 132 allow the rotation of the spool 103 to be transmitted to the outermost periphery of the photographic film 102 and prevent the film roll 142 from being loosened.

Four holes 133 are formed in the flange 114 at a predetermined pitch so as to surround the round holes 130. These holes 133 are provided with a display member 123 for use when the spool shaft 112 rotates in the photo film feeding direction.
Ratchet claw 125 of is engaged. Ratchet claw 125
Transmits the rotation of the spool shaft 112 to the flange 114 when engaged with the hole 133, and when the spool shaft 112 rotates in the photo film winding direction, the ratchet claw 125 of the use indicating member 123 causes the hole 133 to rotate. Therefore, the rotation of the spool shaft 112 is not transmitted to the flange 114.

When the photographic film 102 is fed, the spool 103 is rotated in the film feeding direction. When the spool 103 is rotated in the film feeding direction, the tip of the photographic film 102 is separated by the separation claw 10.
9 and is separated from the part wound inside the leading edge of the photographic film. When the spool 103 is subsequently rotated, since the pair of thin flanges 113 and 114 has elasticity, the pair of flanges 113 and 114 are pushed outward by the separated film tips. The leading edge of the photographic film (143 in FIG. 3) released from the wrapping is delivered to the outside of the photographic film cartridge 100 through the film delivery port. Further, when the spool shaft 112 rotates in the photo film winding direction (the direction opposite to the photo film feeding direction), the flanges 113 and 114 do not rotate integrally with the spool shaft 112. Therefore, the photographic film 102
Since the flanges 113 and 114 do not rotate when the film is wound, a slip occurs between the opening edge portions 131 and 132 and the photographic film 102, and the photographic film 102.
Slides under the opening edges 131, 132 of the flanges to wrap the photographic film.

The data disk 115 has a large-diameter fan-shaped portion 1
34 and a notch portion 135. The barcode label 116 has a shape similar to that of the data disc 115 and is attached to the data disc.

A bar code is printed on the bar code label 116 and represents various information such as the type of the photo film 102 to be stored. This information is obtained when the spool 103 is rotated in the film feeding direction.
As shown in FIG. 5, it is read by a reading sensor provided on the camera side through an opening 136 formed on one side surface of the upper case 105 to calculate an exposure value and count the number of exposures of stored photo films. Used.

In this photographic film cartridge 100,
Since even the leading edge of the photographic film 102 is stored, it is indistinguishable from the external appearance whether the unexposed photographic film or the exposed photographic film is stored. Therefore, in order to prevent the photographic film cartridge 100 containing the exposed photographic film from being reloaded into the camera and taking pictures, a post-loading prevention opening 137 is formed on one side surface of the lower case 106. There is. This one side surface is a side that is inserted toward the cartridge chamber of the camera, and a lever that enters the opening 137 is provided in the cartridge chamber.

The photographic film cartridge 100 stores the unexposed photographic film so that the large-diameter fan-shaped portion 134 is exposed in the opening 137 when the exposed photographic film is stored. If so, the stop position of the spool 103 is controlled by the drive shaft on the camera side so that the large-diameter fan-shaped portion 134 is not exposed in the opening 137. Therefore, by detecting the amount of movement of the lever, the camera side can discriminate between the exposed and unexposed photographic film.

Further, in order to allow the user to grasp from the appearance, the photo film patrone 100 is
As shown in FIG. 4, on the other side surface (the side surface opposite to the side surface on which the openings 136 and 137 are provided), an opening 138 for displaying the usage state when the unexposed photo film is stored, a part thereof is photographed. When the photographic film is stored, the usage status display opening 139, when the exposed photo film that has been photographed on all is stored, the usage status display opening 140, and when the developed photographic film is stored Of the four use status display openings 138 to 141 are formed by exposing the use display plate 127 located in the back by controlling the stop position of the spool 103. The usage status of the film is displayed.

Further, the present cartridge 100 is provided with a sensitivity detecting notch 145 used for detecting the sensitivity of the stored photographic film 102. This is a notch for detecting sensitivity with an inexpensive camera that does not have a bar code reader that reads the bar code written on the bar code label. When the sensitivity detecting notch 145 is provided as shown in FIG. 5, the stored photographic film 102 is IS.
The O sensitivity is 400 or more, and the ISO sensitivity is 400 or less when there is no notch.

Further, the present cartridge 100 is provided with a developed display tab showing whether or not the stored photographic film 102 has been developed. As shown in FIG.
The tab 147 is provided in an opening 146 provided on one side surface of the cartridge 100, and when the tab 147 is broken off, it means that the stored photographic film 102 has been developed.

Next, a typical example of the manufacturing method of the cartridge 100 of the present invention will be specifically described. Upper case / lower case 1
05, 106, the spool 103, and the lid member 108,
High-impact polystyrene resin (Denkastyrol HI-R-Q manufactured by Denki Kagaku Kogyo) is added with 1.0% by weight of carbon black (Mitsubishi Carbon Black # 950 manufactured by Mitsubishi Chemical) for imparting light-shielding properties, and lubricity. Silicone oil for use (Shin-Etsu Chemical Co., Ltd. Shin-Etsu Silicone KF96H-viscosity 30,000 cs) is molded by injection molding using a resin kneaded with 1.5% by weight. The use indication member 123 is made by injection molding using a resin obtained by kneading the above-mentioned high impact polystyrene resin with 0.01% by weight of the above carbon black and 3.5% by weight of titanium oxide (CR60-2 manufactured by Ishihara Sangyo). Mold.

The flanges 113 and 114 are formed by a vacuum / pneumatic method using a film having a thickness of 150 μm made of a polymer alloy of polystyrene resin and polyphenylene ether resin (Zylon X9101, manufactured by Asahi Kasei).

The Patrone label 104 has a thickness of 50.
A coating for imparting printability is provided on one side of a polystyrene film containing a white pigment having a thickness of μm, an adhesive is attached to the back side thereof, and a release paper is attached to the release label to prepare an adhesive label stock. As shown in FIG. 7, on the surface of the original fabric,
Patrone ID number printing space written in numbers 15
1. A manufacturer name, a product name, a film type / sensitivity / the number of exposures, a cautionary note, and a print space 152 for a product type for printing a memo field to be filled by the user, and a bar code print space 153. First, a printing space such as a product type is printed, then half-cut processing is performed, and thereafter, a barcode and a Patrone ID number are printed to create. The bar code contains the manufacturer's name, production lot, production date, type of photo film stored, sensitivity, number of exposures,
Also, the Patrone ID number and the like are encoded and printed. The cartridge ID number is a unique number attached to each cartridge.

The bar code label 116 has a thickness of 50 μm.
A transparent vapor deposition polystyrene film with a thickness of about 400 Å is provided on one side of the transparent vapor deposition film, and an adhesive label is attached on top of it to create an adhesive label with release paper, and a bar on the opposite side of the aluminum vapor deposition layer. After printing the code, half cut the outer peripheral part, and then punch out the center to create.

The present invention stores the light-sensitive material of the present invention in the above-mentioned specific cartridge. The sensitive material stored in the cartridge is not always put under the optimum storage condition under control. Especially, when it is passed to the user, it is exposed to severe temperature and humidity, for example, midsummer. Often left in a car under the sun for a long time. When the photosensitive material is aged under such high temperature and high humidity, its performance is generally deteriorated. Also in the present invention, when the color sensitive material using the coupler represented by the general formula [I] is stored in the specific cartridge of the present invention as compared with the case of being stored in the existing 135 type cartridge, the fog is increased. The problem of latent image sensitization becomes more serious. Therefore, the present invention relates to a coupler represented by the general formula [I] and general formulas (AI) to
It has been found that these problems can be prevented even when a color sensitive material containing a compound represented by (A-III) is used in combination and stored in the above-mentioned cartridge. You can

The light-sensitive material of the present invention may have at least one light-sensitive layer provided 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, depending on the purpose, the order of installation may be reversed, or the order of installation may be such that different photosensitive layers are sandwiched between layers of the same color sensitivity. 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 about 30 mol% or less of 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 include those having regular crystals such as cubic, octahedral and tetradecahedral, those having irregular crystal forms such as spheres and plates, twin planes, etc. 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.
o.307105 (November 1989), pp.863-865, and Grafkid, "Physics and Chemistry of Photography", published by Paul Montell (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), "Production and coating of photographic emulsions" by Zelikmann et al., published by Focal Press (VLZel).
ikman, et al., Making and Coating Photographic Emu
lsion, Focal Press, 1964) and the like.

US 3,574,628, US 3,655,394 and GB 1,4
Monodisperse emulsions described in 13,748 are also preferred. Tabular grains having an aspect ratio of about 3 or more can also 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. 17643.
18716 and No. 307105, and the relevant locations are summarized in the table below. The light-sensitive material of the present invention includes a light-sensitive silver halide emulsion having a grain size, a grain size distribution,
Two or more kinds of emulsions having different characteristics of at least one of halogen composition, grain shape, and sensitivity can be mixed and used in the same layer. U.S. Pat.No.4,082,553.
It is preferable to apply the silver halide grains and the colloidal silver covered with the inside of the grains described in 9-214852 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 preferably 0.05 to 0.6 μm. The grains may be regular grains or polydisperse emulsions, but may be monodisperse (at least the weight or the number of silver halide grains).
95% have a particle size within ± 40% of the average particle size)
It is preferred that

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 that can be used in the present invention are also described in RD, and the relevant portions are shown in the table below. 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 Super sensitizer, page 649, right column 4. Brightener 24 page 647, right column page 868 5 Light absorbers, pages 25 to 26, page 649, right column, page 873 Filters, page 650, left column Dyes, ultraviolet absorbers 6. Binders, page 26, page 651, left column 873 to 874 7. Plasticizers, page 27, page 650, right Column 876 Lubricant 8. Coating aid, pages 26 to 27 Page 650 Right column 875 to 876 Surfactant 9. Static 27 page 650 650 Right column 876 to 877 Inhibitor 10. Mast agent 878 to 879

Various dye-forming couplers can be used in the light-sensitive material of the present invention, and the following couplers are particularly preferable. 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); A-4 -6 of EP 456,257
3 (p. 134), A-4 -73, -75 (p. 139); M-4, -6 in EP 486,965
(Page 26), M-7 (page 27); EP-571,959A M-45 (page 19);
5-204106 (M-1) (page 6); JP-A-4-362631, paragraph 0237 M-
twenty two. Cyan coupler: CX-1,3,4,5,11,12,1 of JP-A-4-204843
4,15 (pages 14 to 16); C-7,10 (page 35), 34,3 of JP-A-4-43345.
5 (page 37), (I-1), (I-17) (pages 42 to 43); A coupler represented by formula (Ia) or (Ib) of claim 1 of JP-A-6-67385. Polymer coupler: P-1, P-5 (p. 11) of JP-A-2-44345.

As couplers in which the color forming dye has an appropriate diffusibility, 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)
.

As the additives other than the coupler, the following are preferable. Dispersion medium for oil-soluble organic compound: JP-A-62-2
15272 P-3,5,16,19,25,30,42,49,54,55,66,81,85,86,
93 (pages 140-144); Latex for impregnation of oil-soluble organic compounds: Latex described in US Pat. (Especially I-, (1), (2), (6), (12)
(Columns 4-5), formulas in rows 5-10 of column 2 of US 4,923,787 (especially compound 1 (column 3); stain inhibitor: EP
Formulas (I) to (III) on page 4, lines 30 to 33 of 298321A, especially I-47, 72,
III-1,27 (pages 24-48); Anti-fading agent: A-6 of EP 298321A,
7,20,21,23,24,25,26,30,37,40,42,48,63,90,92,94,164
(Pp. 69-118), II-5-II of columns 25-38 of US 5,122,444
I-23, especially III-10, I-1 to III- on pages 8 to 12 of EP 471347A
4, especially II-2, US 5,139,931 columns 32 to 40, A-1 to 48,
In particular, A-39, 42; a material that reduces the amount of a color-enhancing agent or color-mixing inhibitor used: EP 411324A, pages 5 to 24, I-1 to II-15,
Especially I-46; Formalin Scavenger: 24 of EP 477932A
SCV-1 to 28 on page 29, especially SCV-8; Hardener: JP-A 1-21
4845, page 17, H-1,4,6,8,14, US 4,618,573, columns 13-
Compounds (H-1 to 54) represented by formulas (VII) to (XII) of 23, compounds represented by the formula (6) at the lower right of page 8 of JP-A-2-214852 (H
-1 to 76), especially the compound described in claim 1 of H-14, US 3,325,287; Development inhibitor precursor: JP-A-62-168139
P-24, 37, 39 (pages 6 to 7); compounds described in claim 1 of US Pat. No. 5,019,492, in particular, 28, 29 of column 7;
US 4,923,790, columns 3-15, I-1 to III-43, especially II-
1,9,10,18, III-25; stabilizer, antifoggant: US 4,923,
793 columns 6-16 I-1 ~ (14), especially I-1,60, (2), (13),
Compounds 1-65, especially 3 in columns 25-32 of US 4,952,483
6: Chemical sensitizer: triphenylphosphine selenide, compound 50 of JP-A-5-40324; dye: 15-1 of JP-A-3-156450
A-1 to b-20 on page 8, especially a-1,12,18,27,35,36, b-5,27 to 2
V-1 to 23 on page 9, especially V-1, EP 445627A FI on pages 33 to 55
-1 to F-II-43, especially FI-11, F-II-8, 17 to 2 of EP 457153A
Page 8 III-1 to 36, especially III-1,3, WO 88/04794 8-26
A microcrystalline dispersion of Dye-1 to 124, compounds 1 to 22 on pages 6 to 11 of EP 319999A, in particular compounds D-1 to 87 (compounds 1 and 519306A represented by formulas (1) to (3)). (Pages 3 to 28), US 4,2
Compounds 1 to 22 represented by the formula (I) of 68,622 (columns 3 to
10), compounds (1) to (4) of the formula (I) 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, the RD. No. 17643, page 28, same No. 18716
Page 647, right column to page 648, left column, and No. 307105, 8
It is described on page 79. In the light-sensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or less, more preferably 23 μm or less,
It is more preferably at most 18 μm, particularly preferably at most 16 μm. Further, the film swelling speed T _1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. T _1/2 is 30 ° C., 3
When 90% of the maximum swelling film thickness reached when the treatment is performed for 15 minutes is defined as the saturated film thickness, it is defined as the time until the film thickness reaches half. The film thickness is controlled at 25 ° C and 55% relative humidity (2
T1 _{/ 2} is the thickness measured in A. Green et al. (Photogr. Sci. Eng.), 19 vol.
It can be measured by using a serometer (swelling meter) of the type described on pages 2,124-129. 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%. From the maximum swelling film thickness under the conditions described above,
It can be calculated by the formula: (maximum swollen film thickness-film thickness) / film thickness. In the light-sensitive material of the present invention, a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm is preferably provided on the side opposite to the side having the emulsion layer. The back layer preferably contains the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, and surfactant. The swelling ratio of the back layer is preferably from 150 to 500%.

The light-sensitive material of the present invention is the same as RD. No. 17
The development can be carried out by a usual method described on pages 28 to 29 of 643, 651 left column to right column of No. 18716, and pages 880 to 881 of No. 307105. Next, the processing solution for the color negative film used in the present invention will be described. The color developing solution used in the present invention is described in JP-A-4-2171.
The compounds described on page 9, upper right column, line 1 to page 11 lower left column, line 4 can be used. As a color developing agent for particularly rapid processing, 2-methyl-4- [N-ethyl-N- (2-hydroxyethyl) amino] aniline,
2-Methyl-4- [N-ethyl-N- (3-hydroxypropyl) amino] aniline, 2-methyl-4- [N-
Ethyl-N- (4-hydroxybutyl) amino] aniline is preferred. These color developing agents are preferably used in the range of 0.01 to 0.08 mol per liter of the color developing solution, particularly preferably in the range of 0.015 to 0.06 mol, more preferably 0.02 to 0.05 mol. The replenisher for the color developing solution preferably contains 1.1 to 3 times the concentration of the color developing agent, and particularly preferably 1.3 to 2.5 times the concentration.

Hydroxylamine can be widely used as a preservative in the color developing solution. However, when higher preservability is required, substitution of an alkyl group, a hydroxyalkyl group, a sulfoalkyl group, a carboxyalkyl group or the like is required. A hydroxylamine derivative having a group is preferable, and specifically, N, N-di (sulfoethyl) hydroxylamine, monomethylhydroxylamine, dimethylhydroxylamine, monoethylhydroxylamine, diethylhydroxylamine, N, N-di (carboxyethyl). Hydroxylamine is preferred. Among the above, N, N-di (sulfoethyl) hydroxylamine is particularly preferred. These may be used in combination with hydroxylamine, but it is preferable to use one or more of them instead of hydroxylamine. The preservative is preferably used in the range of 0.02 to 0.2 mol per liter, particularly preferably 0.03 to 0.15 mol, and further preferably 0.04 to 0.1 mol. As in the case of the color developing agent, the replenisher preferably contains a preservative at a concentration of 1.1 to 3 times the concentration of the mother liquor (processing tank solution). The color developer contains
Sulfite is used as an anti-talling agent for oxides of color developing agents. The sulfite is preferably used in an amount of 0.01 to 0.05 mol, and particularly preferably 0.02 to 0.04 mol, per liter. In the replenisher, these 1.1 ~
It is preferable to use it at a concentration of 3 times. Further, the pH of the color developing solution is preferably in the range of 9.8 to 11.0, but particularly 10.0
˜10.5 is preferable, and in the replenisher, it is preferable to set a high value in the range of 0.1 to 1.0 from these values. In order to stably maintain such a pH, a known buffer such as carbonate, phosphate, sulfosalicylate, and borate is used.

The replenishing amount of the color developing solution is preferably 80 to 1300 ml per 1 m ² of the light-sensitive material, but it is preferably smaller from the viewpoint of reducing the environmental pollution load, specifically 80 to 6
It is preferably 00 ml, more preferably 80 to 400 ml. The bromide ion concentration in the color developing solution is usually 0.01 to 1 liter / liter.
Although it is 0.06 mol, it is preferably set to 0.015 to 0.03 mol per liter for the purpose of suppressing the fog while maintaining the sensitivity, improving the discrimination, and improving the graininess. When the bromide ion concentration is set in such a range, the replenisher may contain bromide ions calculated by the following formula. However, when C becomes negative, it is preferred that the replenisher does not contain bromide ions. C = A-W / V C: Bromide ion concentration in the color developing replenisher (mol / liter) A: Target bromide ion concentration in the color developing solution (mol / liter) W: 1m ² of light-sensitive material is colored Amount of bromide ion eluted from the light-sensitive material to the color-developing solution when developed (mol) V: Replenishment amount of color-development replenisher for a light-sensitive material of 1 m ² (liter). When the bromide ion concentration is set, 1-phenyl-3-pyrazolidone or 1-phenyl-2-methyl-2 can be used as a method for increasing the sensitivity.
It is also preferable to use a development accelerator such as pyrazolidones represented by -hydroxymethyl-3-pyrazolidone and thioether compounds represented by 3,6-dithia-1,8-octanediol.

The compounds and processing conditions described in JP-A-4-125558, page 4, lower left column, line 16 to page 7, lower left column, line 6 can be applied to the processing solution having bleaching ability in the present invention. . The bleaching agent preferably has an oxidation-reduction potential of 150 mV or more, and specific examples thereof include JP-A-5-72694 and JP-A-5-7333.
The compounds described in No. 12 are preferred, and 1,3-diaminopropanetetraacetic acid, particularly, a ferric complex salt of the compound of Specific Example 1 on page 7 of JP-A-5-73312 is preferred. In addition, in order to improve the biodegradability of the bleaching agent, JP-A-4-218845, 4-268552, EP588,
289, 591,934, and the compound ferric complex salts described in JP-A-6-208213 are preferably used as a bleaching agent. The concentration of these bleaching agents is 0.05 per liter of bleaching solution.
The amount is preferably from 0.3 to 0.3 mol, and particularly from the viewpoint of reducing the amount discharged to the environment, it is preferably designed from 0.1 to 0.15 mol. Further, when the bleaching solution is a bleaching solution, it is preferable to contain 0.2 mol to 1 mol of bromide per liter, particularly 0.3 to 0.8 mol. The replenisher for the bleaching solution basically contains the concentrations of the respective components calculated by the following formula. This allows
The concentration in the mother liquor can be kept constant. C _R = C _T × (V ₁ + V ₂ ) / V ₁ + C _P C _R : Concentration of component in replenisher C _T : Concentration of component in mother liquor (treatment tank liquid) C _P : Consumed during treatment Concentration of components V ₁ : Replenishing amount of replenisher having bleaching ability for 1 m ² of light-sensitive material (mL) V ₂ : Bring-in amount of 1 m ² of light-sensitive material from the previous bath (mL) It is preferable to contain an agent, and it is particularly preferable to contain a dicarboxylic acid having a low odor such as succinic acid, maleic acid, malonic acid, glutaric acid, and adipic acid. Also, JP-A-53-95630, RDN
It is also preferable to use known bleaching accelerators described in O. 17129, US 3,893,858. The bleaching solution is preferably replenished with 50 to 1000 ml of the bleach replenishing solution per 1 m ² of the light-sensitive material, particularly 80 to 500 ml, more preferably 100 to 300 ml. Further, it is preferable to perform aeration on the bleaching solution.

The processing solution having a fixing ability is disclosed in
The compounds and processing conditions described on page 7, lower left column, line 10 to page 8, lower right column, line 19 of 4-125558 can be applied. In particular, in order to improve the fixing speed and the homeostasis, the compounds represented by the general formulas (I) and (II) of JP-A-6-301169 are contained alone or in combination in a processing solution having fixing ability. It is preferable. In addition to the p-toluenesulfinic acid salt, the sulfinic acid described in JP-A 1-224762 can also be used.
It is preferable from the viewpoint of improving the homeostasis. It is preferable to use ammonium as a cation in a solution having a bleaching ability and a solution having a fixing ability from the viewpoint of improving desilvering ability, but from the viewpoint of reducing environmental pollution, it is preferable to reduce or eliminate ammonium. . In the bleaching, bleach-fixing and fixing steps, jet stirring described in JP-A-1-309059 is particularly preferable. The replenishing amount of the replenisher in the bleach-fixing or fixing step is 100 to 1000 ml, preferably 150 to 700 ml, and particularly preferably 200, per 1 m ² of the light-sensitive material.
~ 600 ml. In the bleach-fixing and fixing steps, it is preferable to install various silver recovery devices in-line or off-line to recover silver. By installing in-line, the processing can be carried out with a reduced silver concentration in the solution, so that the replenishment amount can be reduced. It is also preferable to recover silver off-line and reuse the remaining liquid as a replenisher. The bleach-fixing step and the fixing step can be composed of a plurality of processing tanks, and it is preferable that each tank is cascade-piped to form a multistage countercurrent system. Generally, the two-tank cascade configuration is efficient because of the balance with the size of the developing machine.
The ratio of the processing time in the front tank and the rear tank is
The range of 0.5: 1 to 1: 0.5 is preferable, and the range of 0.8: 1 to 1: 0.8 is particularly preferable. In the bleach-fixing solution or the fixing solution, it is preferable to allow a free chelating agent which is not a metal complex to be present from the viewpoint of improving the preservative property. It is preferred to use chelating agents.

Regarding the washing and stabilizing steps, the above-mentioned JP-A-4-125558, page 12, lower right column, line 6 to page 13, lower right column, line 16
The contents described in the line can be preferably applied. In particular, EP 504,60 replaces formaldehyde in stabilizers.
9. Use of the azolylmethylamines described in 519,190 and N-methylolazoles described in JP-A-4-362943, and the use of an interface free of image stabilizers such as formaldehyde by dimerizing a magenta coupler. It is preferable to use a liquid of the activator from the viewpoint of preserving the working environment. Further, in order to reduce the adhesion of dust to the magnetic recording layer coated on the light-sensitive material, the stabilizing solution described in JP-A-6-289559 can be preferably used. The amount of washing and replenishment of the stabilizing solution is preferably 80 to 1000 ml / m ² of the light-sensitive material, and particularly 100 to 5 ml.
00 ml, and more preferably 150 to 300 ml, are preferable ranges from the viewpoint of ensuring the washing or stabilizing function and reducing waste liquid for environmental protection. In the treatment performed with such a supplement amount, thiabendazole, 1,2-benzisothiazolin-3one,
Known antifungal agents such as 5-chloro-2-methylisothiazolin-3-one and antibiotics such as gentamicin,
It is preferable to use water deionized with an ion exchange resin or the like. It is more effective to use deionized water in combination with antibacterial agents and antibiotics. Also, the liquid in the washing or stabilizing liquid tank is disclosed in JP-A-3-46652, JP-A-3-53246 and JP-A-3-53246.
It is also preferable to reduce the replenishment amount by performing the reverse osmosis membrane treatment described in 55542, 3-121448, and 3-26030. In this case, the reverse osmosis membrane is preferably a low-pressure reverse osmosis membrane.

In the processing of the present invention, it is particularly preferable to carry out the evaporation correction of the processing liquid disclosed in JIII Journal of Technical Disclosure, Japanese Patent No. 94-4992. In particular, a method of making a correction using the temperature and humidity information of the environment where the developing machine is installed is preferable based on (Equation-1) on page 2. The water used for evaporation correction is preferably collected from a replenishment tank for washing,
In that case, it is preferable to use deionized water as the replenishing water for washing.

As the treating agent used in the present invention, those described on page 3, right column, line 15 to page 4, left column, line 32 of the above-mentioned Kokai Giho are preferable. In addition, as a developing machine used for this,
The film processor described on page 3, right column, lines 22 to 28 is preferred. Specific examples of preferred processing agents, automatic processors, and evaporation correction methods for carrying out the present invention are described on page 5, right column, line 11 to page 7, right column, last line. .

The supply form of the treating agent used in the present invention is as follows:
It may be in any form, such as a liquid preparation in the form of a liquid used or a concentrated form, or granules, powders, tablets, pastes, and emulsions. As an example of such a treating agent, JP-A-63-1
7453 discloses a liquid agent contained in a container having low oxygen permeability,
19655, 4-230748, vacuum-packed powders or granules, 4-221951, granules containing a water-soluble polymer,
JP-A-51-61837 and JP-A-6-102628 have tablets and special tables
Discloses a paste-like treating agent, which can be preferably used, but from the viewpoint of simplicity at the time of use,
It is preferable to use a liquid which has been prepared in advance in a concentration at the state of use. Polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, nylon and the like are used alone or as a composite material in a container for containing these treatment agents. These are selected according to the required level of oxygen permeability. For an easily oxidizable liquid such as a color developing solution, a material having low oxygen permeability is preferable, and specifically, a polyethylene terephthalate or a composite material of polyethylene and nylon is preferable. These materials are used in containers having a thickness of 500 to 1500 μm, and preferably have an oxygen permeability of 20 ml / m ² · 24 hrs · atm or less.

Next, the processing solution for the color reversal film used in the present invention will be described. Regarding the processing for the color reversal film, known technology No. 6 (April 1, 1991), page 1, line 5 to page 10, line 5, and page 15, line 8 to page 24, 2 of Aztec Co., Ltd. It is described in detail in the line, and any of its contents can be preferably applied. In color reversal film processing, image stabilizers are included in either the conditioning bath or the final bath. Examples of such an image stabilizer include formalin, formaldehyde sodium bisulfite, and N-methylolazoles.
From the viewpoint of the working environment, sodium formaldehyde bisulfite or N-methylolazoles are preferable, and as N-methylolazoles, N-methyloltriazole is particularly preferable. The contents relating to the color developing solution, the bleaching solution, the fixing solution, the washing water, etc. described in the processing of the color negative film can be preferably applied to the processing of the color reversal film. A preferred color reversal film treating agent containing the above is E-manufactured by Eastman Kodak Company.
6 processing agents and CR-56 processing agents of Fuji Photo Film Co., Ltd. can be mentioned.

Next, the polyester support used in the present invention will be described. For details including the light-sensitive material other than the above, processing, cartridge and examples, open technical report, official technique number 94-6023 (Invention Society; 1994.3.15.). The polyester used in the present invention is formed by using diol and aromatic dicarboxylic acid as essential components. As aromatic dicarboxylic acids, 2,6-, 1,5-, 1,4- and 2,7-naphthalenedicarboxylic acid, terephthalic acid Examples of the acid, isophthalic acid, phthalic acid, and diol include diethylene glycol, 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 is particularly preferable.
-Naphthalate. The average molecular weight ranges from about 5,000 to 200,000. Tg of the polyester of the present invention is 50 ° C.
And more 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.

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, the cartridge used in the present invention may be a cartridge 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.

[0166]

EXAMPLES The present invention will be described in more detail with reference to specific examples, but the present invention is not limited to the examples unless it exceeds the gist of the present invention. Example 1 1) Support The support used in this example was prepared by the following method. Polyethylene-2,6-naphthalate polymer 100
After drying 2 parts by weight and 2 parts by weight of Tinuvin P.326 (manufactured by Ciba-Geigy Co.) as an ultraviolet absorber, 300 ° C.
After being melted at, it was extruded from a T-die, stretched 3.3 times at 140 ° C, then stretched 3.3 times at 130 ° C, and heat-fixed at 250 ° C for 6 seconds to form a 90 μm thick PEN.
I got a film. The PEN film has a blue dye, a magenta dye, and a yellow dye (public technical report: I-1, I-4, I-6, I-24, I-26, I-26 described in the official gazette number 94-6023). 27, II-5)
Was added in an appropriate amount. Further, the support was wound around a stainless steel core having a diameter of 20 cm to give a heat history of 110 ° C. and 48 hours, thereby providing a support that was not easily curled.

2) Coating of undercoat layer The above-mentioned support was subjected to corona discharge treatment, UV irradiation treatment and glow discharge treatment on both surfaces thereof, and then gelatin 0.1 g / m ² and sodium α-sulfodione were applied to each surface. -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, a bar coater used), provided with a subbing layer hotter side at the time of stretching. Dry 1
The test was carried out at 15 ° C for 6 minutes (all rollers and transport devices in the drying zone were at 115 ° 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 tin oxide-antimony oxide composite having an average particle size of 0.005 μm has a specific resistance of 5 Ω · cm and is a dispersion of fine particle powder (secondary agglomerated particle size of about 0.08 μm). 0.2 g / m ^2, gelatin 0.05g / m ^2, (C
H ₂ = CHSO ₂ CH ₂ CH ₂ NHCO) ₂ CH ₂ 0.02 g / m ² , poly (degree of polymerization 10)
Coated with 0.005 g / m ^{2 of} oxyethylene-p-nonylphenol and resorcin. 3-2) Coating of magnetic recording layer 3-poly (degree of polymerization: 15) Cobalt-γ-iron oxide coated with oxyethylene-propyloxytrimethoxysilane (15% by weight) (specific surface area: 43 m ² / g; Long axis 0.14μm, single axis 0.03μm, saturation magnetization 89emu / g, Fe ^{+ 2} / Fe ⁺³ = 6/94, the surface is treated with silicon oxide aluminum oxide with 2% by weight of iron oxide) 0.06g / m ² diacetyl cellulose 1.2 g / m ² (dispersion of the iron oxide was carried out using an open kneader and a sand _{mill), C 2 H 5 C (} CH 2 OCONH-C 6 H 3 (CH 3) NCO) as a curing agent ₃
0.3 g / m ² was applied with a bar coater using acetone, methyl ethyl ketone, cyclohexanone as a solvent,
A magnetic recording layer having a thickness of 1.2 μm was obtained. Abrasive aluminum oxide (0.15 μm) coated with silica particles (0.3 μm) and 3-poly (degree of polymerization 15) oxyethylene-propyloxytrimethoxysilane (15% by weight) as matting agents, respectively
It was added to 10 mg / m ² . Drying was carried out at 115 ° C for 6 minutes.
° C). X- write saturation magnetization moment of the magnetic recording layer of the D color density increment of about 0.1 of ^B, also the magnetic recording layer is 4.2 emu / g, coercive force 7.3 × 10 ⁴ A / m, the squareness ratio in (blue filter) Was 65%.

3-3) Preparation of sliding layer Diacetyl cellulose (25 mg / m ² ), C ₆ H ₁₃ CH (OH) C ₁₀ H ₂₀ C
OOC ₄₀ H ₈₁ (compound a, 6 mg / m ² ) / C ₅₀ H ₁₀₁ O (CH ₂ CH ₂ O) ₁₆ H
(Compound b, 9 mg / m ² ) mixture was applied. This mixture was melted at 105 ° C in xylene / propylene glycol monomethyl ether (1/1), poured and dispersed in propylene glycol monomethyl ether (10 times the volume) at room temperature, and then dispersed in acetone. (Average particle size: 0.01 μm). As a matting agent, silica particles (0.3 μm) and abrasive 3-poly (degree of polymerization 15) oxyethylene-propyloxytrimethoxysilane (aluminum oxide (0.15 μm) coated with 15% by weight) were each added at 15 mg / m ² . Drying was carried out at 115 ° C for 6 minutes (all rollers and conveyors in the drying zone were at 115 ° C.) The sliding layer had a dynamic friction coefficient of 0.06 (5mmφ stainless steel hard spheres, load of 100g, speed)
6 cm / min), the coefficient of static friction was 0.07 (clip method), and the coefficient of kinetic friction between the emulsion surface and the sliding layer described later was 0.12, which were excellent characteristics.

4) Coating of Sensitive Material Layer Next, each layer having the following composition was coated on the side opposite to the back layer obtained above to prepare a color sensitive material. This is sample 1
01. The number corresponding to each component indicates the coating amount expressed in g / m ² . For silver halide, the coating amount is expressed in terms of silver.

First layer (gelatin layer) Polyethyl acrylate latex 0.10 Gelatin 1.00

Second Layer (Emulsion Layer) Silver iodobromide emulsion (octahedral, core high iodine double structure, average iodine content 5 mol%, average equivalent spherical diameter 0.45 μm, coefficient of variation 10%) 1.60 coupler (Comparative coupler (1)) 1.23 Tris (2-ethylhexyl) phosphate 0.31 Gelatin 3.00

Third Layer (Protective Layer) Gelatin 2.00 Hardener 0.20 Comparative coupler (1) and hardener are shown in Chemical formula 36.

[0174]

Embedded image

The following samples were prepared below. Sample 102 The comparative coupler (1) of Sample 101 was replaced with the exemplary coupler Y-1 of the present invention in an equimolar amount, and tris (2-ethylhexyl) phosphate (TE) was used as the coupler solvent.
HP) was added in the same manner as in Sample 101 so that the weight ratio was 0.25 times per unit weight of the coupler. Samples 103 and 104 Samples 101 and 102 were prepared by adding Comparative Compound (1) to the second emulsion layer so that the coating amount was 0.020 g / m ² . Samples 105 and 106 Samples 103 and 104 were prepared by replacing comparative compound (1) with comparative compound (2) in an equimolar amount. Samples 107 and 108 The comparative compound (1) used in Samples 103 and 104 was prepared by substituting the compound A-50 represented by the general formula (AI) of the present invention in an equimolar amount. The addition was made to coexist with the coupler, and TEHP was additionally added so as to be equal in weight to the weight of the compound. Comparative compounds (1) and (2) are also shown in Chemical formula 36.

Samples 109 to 118 The yellow coupler Y-1 of Sample 108 was replaced with another exemplary coupler represented by the general formula [I] of the present invention in an equimolar amount as shown in Table 1, and TEHP as a high boiling point organic solvent was used. A sample was prepared by adjusting the amount of the compound used to be 0.25 times the weight of the coupler. Samples 119 to 126 The compound A-50 represented by the general formula (A-I) used for the sample 110 is as shown in Table 1 as shown in the general formula (A-) of the present invention.
I) to (A-III) were replaced by other exemplary compounds in equimolar amounts, and TEHP was used in the same manner as in Sample 110, using the same amount of TEHP as the weight of the compound. Sample 127 In the first gelatin layer of Sample 110, the general formula (A-
A dispersion was prepared by emulsifying and dispersing A-50 of the above compound represented by I) using the same weight of TEHP, and adding the compound A-50 to a coating amount of 0.010 g / m ² . Sample 128 Sample 103 had the same general formula (A-
Compound A-50 represented by I) was added as an emulsified dispersion in the same manner as in Sample 127 described above so that a coating amount of 0.033 g / m ² was obtained.

[0177]

[Table 1]

The sample manufactured as described above was used in a width of 24 mm, 1
Cut into 60 cm, and further perforate 2 mm square at 0.7 mm from one side width direction of the sample in the length direction.
Two are provided at intervals of 8 mm. A set in which these two sets were provided at intervals of 32 mm was prepared and housed in the plastic film cartridge described in FIGS. 1 to 7.
A head gap 5
Using a head capable of input / output of μm and number of turns of 2,000, 1,000 /
The FM signal was recorded at a feed rate of s.

These samples were stored at 30 ° C. and 60% relative humidity for 3 days and then examined for the following properties. (1) Storage property over time One set was stored at 25 ° C and 55% relative humidity, and the other set was stored for 7 days in a car under the hot sun in summer. There was a heat-humidity history in a car in the hot summer in the temperature range of 25 ° C to a maximum of 75 ° C and relative humidity of 50% to 75%. After the above storage period was completed, the samples were taken out from the cartridges, and all the samples were exposed to white light for 1/100 seconds using a sensitometric wedge using a portion close to the core, and then subjected to the color development processing described below. I went. The density of the obtained yellow color image was measured, and from the characteristic curve, the minimum density (fog) value and the minimum density +0.
The logarithm of the reciprocal of the exposure dose giving a density of 2 was determined. These characteristic values are the fog increase (△ fog) between the same samples, based on the samples stored at 25 ℃.
Regarding the sensitivity, the difference in sensitivity (ΔS ₁ ) was similarly determined using the sample stored at 25 ° C. as a reference. (2) Latent image storability After exposure to white light for 1/100 seconds using a sensitometric wedge, one set was 5 ° C and 35% relative humidity
In the other set, each set was stored for 7 days in the same car in the hot summer weather as above, and then continuously developed at the same time. The temperature-humidity range in the car under the hot sun in the summer was the same as that of the sample of (1), and thus the same storage conditions were used. The density of the developed sample was measured in the same manner as described above, and the logarithmic value of the reciprocal of the exposure dose giving the density of the minimum density + 0.2 was obtained from the characteristic curve. The difference (ΔS ₂ ) between the obtained sensitivity values was calculated using the samples stored at 5 ° C. as a reference between the same samples. The larger the difference, the larger the latent image sensitization, and the larger the change in photographic property over time after photographing, which is not preferable. (3) Photographic properties of fresh light-sensitive material Using a wedge for sensitometry, the same exposure as above was applied, the following development processing was performed, and the sensitivity was obtained in the same manner as in (1). The difference in sensitivity (ΔS ₃ ) was calculated. The larger the value, the higher the sensitivity. The color development processing carried out in the above (1) to (3) is shown below.

[0180] Fuji Photo Film Co., Ltd. automatic processor FP-360B
The color development processing was carried out by using Fuji Color Negative Super Ace 400 (manufactured by Fuji Photo Film Co., Ltd.) with a camera, and the following processing was carried out for 15 days at a rate of 1 m ² per day (running processing). The above sample was processed. The remodeling was performed so that the overflow solution of the bleaching bath was not discharged to the post-bath but was entirely discharged to the waste liquid tank.
This FP-360B is equipped with the evaporation correction means described in JIII Journal of Technical Disclosure No. 94-4992. The treatment process and the treatment liquid composition are shown below.

(Processing step) Processing time Processing temperature Replenishment amount * Tank capacity Color development 2 minutes 45 seconds 38.0 ° C 20 ml 17 liter Bleach 50 seconds 38.0 ° C 5 ml 5 liter Fixing (1) 50 seconds 38.0 ° C -5 liter Fixing (2) 50 seconds 38.0 ℃ 8 ml 5 liters Water wash 30 seconds 38.0 ℃ 17 ml 3.5 liters Stable (1) 20 seconds 38.0 ℃ −3 liters Stable (2) 20 seconds 38.0 ℃ 15 ml 3 liters Dry 1 minute 30 60 ° C / sec * Replenishment amount per 35m width of photosensitive material 1.1m (equivalent to 24Ex. 1) Stabilizer is countercurrent method from (2) to (1), and overflow liquid of washing water is fixed (2) ) Was introduced. The fixing solution is also connected from (2) to (1) by a countercurrent pipe. The amount of developing solution brought into the bleaching process, the amount of bleaching solution brought into the fixing process, and the amount of fixing solution brought into the washing process were 2.
It was 5 ml, 2.0 ml, and 2.0 ml. The crossover time is 6 seconds in all cases, and this time is included in the processing time of the previous step. The opening area of the above processor is 100 cm ^{2 with the} color developer,
The bleaching solution had a volume of 120 cm ² , and the other processing solutions had a volume of approximately 100 cm ² .

The composition of the processing liquid is shown below. (Color developer) Tank liquid (g) Replenisher (g) Diethylenetriaminepentaacetic acid 2.0 2.0 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 2.0 Sodium sulfite 3.9 5.3 Potassium carbonate 37.5 39.0 Potassium bromide 1.4 0.4 Potassium iodide 1.3 mg-Disodium-N, N-bis (sulfonate ethyl) hydroxylamine 2.0 2.0 Hydroxylamine sulfate 2.4 3.3 2-Methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 4.5 6.4 Add water 1.0 liter 1.0 liter pH (adjusted with potassium hydroxide and sulfuric acid) 10.05 10.18

(Bleaching Solution) Tank Solution (g) Replenishing Solution (g) 1,3-Diaminopropaneferric Acid Ammonium Ferric Acid Monohydrate 118 180 Ammonium Bromide 80 115 Ammonium Nitrate 14 21 Succinic Acid 40 60 Maleic Acid 33 50 1.0 liter by adding water 1.0 liter pH [Prepared with ammonia water] 4.4 4.0

(Fixing liquid) Tank liquid (g) Replenishing liquid (g) Ammonium methanesulfinate 10 30 Ammonium methanethiosulfonate 4 12 Ammonium thiosulfate aqueous solution (700 g / l) 280 ml 840 ml Imidazole 7 20 Ethylenediaminetetraacetic acid 15 45 1.0 liter by adding water 1.0 liter pH [Prepared with ammonia water and acetic acid] 7.4 7.45

(Washing Water) Tap water was used as an H-type strongly acidic cation exchange resin (Amberlite IR-produced by Rohm and Haas).
120B) and OH-type strongly basic anion exchange resin (Amberlite IR-400) were passed through a mixed bed column to adjust the concentration of calcium and magnesium ions to 3 mg.
Per liter or less, followed by 20 mg / liter of sodium diisocyanurate and 150 mg of sodium sulfate.
mg / l was added. The pH of this solution is 6.5 to 7.
5 range.

(Stabilizing Solution) Common to Tank Solution and Replenishing Solution (Unit g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether 0.2 (Average degree of polymerization 10) Disodium ethylenediaminetetraacetate Salt 0.05 1,2,4-triazol 1.3 1,4-bis (1,2,4-triazol-1-yl methylpiperazine 0.75 1,2-benzisothiazolin-3-one 0.10 water 1.0 liter pH 8.5 The results of (1) to (3) above are summarized in Table 1.

From the table, the couplers represented by the general formula [I] satisfying the constitution of the present invention and the general formulas (AI) to (A-
Sample 108 using a combination of the compounds represented by III)
No. 128 has a small fluctuation in photographic properties such as fog and sensitivity during storage with time, suppresses latent image sensitization even after aging the sample after photographing, improves storage stability with time and latent image, and further improves freshness. It is clear from the comparison with Comparative Samples 101 to 107 that the sensitive material of (1) has a high sensitivity and gives a good color developability, and the object of the present invention has been excellently achieved. In addition,
It can be seen from the characteristic curve that the gradation becomes harder as high sensitivity is given to the fresh sensitive material. Such an improvement in color development is due to the coupler ligation activity of the coupler, even if the weight ratio of the high boiling point organic solvent to the weight of the coupler is small (0.25).
It is considered that the compound exhibits high activity in combination with the use of the compounds represented by I) to (A-III). In addition, since high gradation can be provided, the coating amount can be reduced in order to obtain a photosensitive material having the same gradation. Another advantage is that the amount of coated silver can be reduced and the product cost can be reduced. Also has. Further, in the present invention, the same layer containing the coupler represented by the general formula [I] has the same general formula (A-I) to
It can be seen from the comparison between Sample 108 and Sample 128 that it is preferable to use the compound represented by (A-III) together. Furthermore, it can be seen that it is more preferable to use both in the same layer and to use the compound in an adjacent layer.

Example 2 A sample 201, which is a multilayer color light-sensitive material, was obtained by applying a multilayer coating of a nuclear phase having the following composition to the side opposite to the back surface of the support provided with the back surface prepared in Example 1. Was produced.
The multilayer coating was carried out in a single coating step in which all 15 layers were simultaneously coated. (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, as for the sensitizing dye, the coating amount is shown in mol unit with respect to 1 mol of silver halide in the same layer.

(Sample 101) First layer (first antihalation layer) Black colloidal silver 0.08 Gelatin 0.70 Second layer (second antihalation layer) Black colloidal silver 0.09 Gelatin 1.00 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

Third layer (intermediate layer) ExC-2 0.05 Polyethyl acrylate latex 0.20 Gelatin 0.70

Fourth Layer (Low Sensitivity Red Sensitive Emulsion Layer) Silver iodobromide Emulsion A Silver 0.20 Silver iodobromide Emulsion B Silver 0.23 Silver iodobromide Emulsion C Silver 0.10 ExS-1 3.8 × 10 ^-4 ExS-2 1.6 × 10 ^-5 ExS-3 5.2 × 10 ^-4 ExC-1 0.17 ExC-2 0.02 ExC-3 0.030 ExC-4 0.10 ExC-5 0.020 ExC-6 0.010 Cpd-2 0.025 HBS-1 0.10 Gelatin 1.10

Fifth Layer (Medium-Sensitivity Red Sensitive Emulsion Layer) Silver iodobromide emulsion C Silver 0.15 Silver iodobromide emulsion D Silver 0.46 ExS-1 4.0 × 10 ^-4 ExS-2 2.1 × 10 ^-5 ExS-3 5.7 × 10 ^-4 ExC-1 0.14 ExC-2 0.02 ExC-3 0.03 ExC-4 0.090 ExC-5 0.02 ExC-6 0.01 Cpd-2 0.05 HBS-1 0.10 Gelatin 0.75

Sixth Layer (High Sensitivity Red Sensitive Emulsion Layer) Silver Iodobromide Emulsion 1.30 ExS-1 2.5 × 10 ^-4 ExS-2 1.1 × 10 ^-5 ExS-3 3.6 × 10 ^-4 ExC-1 0.12 ExC-3 0.11 ExC-6 0.020 ExC-7 0.010 Cpd-2 0.050 HBS-1 0.22 HBS-2 0.050 Gelatin 1.40

Seventh layer (intermediate layer) Cpd-1 0.060 Solid disperse dye ExF-4 0.030 HBS-1 0.040 Polyethyl acrylate latex 0.15 Gelatin 1.10

Eighth layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion F Silver 0.22 Silver iodobromide emulsion G Silver 0.35 ExS-7 6.2 × 10 ^-4 ExS-8 1.4 × 10 ^-4 ExS-4 2.7 × 10 ^-5 ExS-5 7.0 × 10 ^-5 ExS-6 2.7 × 10 ^-4 ExM-3 0.410 ExM-4 0.086 ExY-1 0.070 ExY-5 0.0070 HBS-1 0.30 HBS-3 0.015 Gelatin 0.95

Ninth layer (medium-speed green emulsion layer) Silver iodobromide emulsion G Silver 0.48 Silver iodobromide emulsion H Silver 0.48 ExS-4 4.8 × 10 ^-5 ExS-7 9.3 × 10 ^-4 ExS-8 2.1 × 10 ^-4 ExC-8 0.0020 ExM-3 0.115 ExM-4 0.035 ExY-1 0.010 ExY-4 0.010 ExY-5 0.0050 HBS-1 0.13 HBS-3 4.4 × 10 ^-3 Gelatin 0.80

The tenth layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion I Silver 1.30 ExS-4 4.5 × 10 ^-5 ExS-7 5.3 × 10 ^-4 ExS-8 1.2 × 10 ^-4 ExC-1 0.021 ExM-1 0.010 ExM-2 0.030 ExM-5 0.0070 ExM-6 0.0050 Cpd-3 0.017 HBS-1 0.25 Polyethyl acrylate latex 0.15 Gelatin 1.33

Eleventh 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

Twelfth layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion J Silver 0.10 Silver iodobromide emulsion K Silver 0.11 Silver iodobromide emulsion L Silver 0.28 ExS-9 8.4 × 10 ^-4 ExC-1 0.03 ExC-8 7.0 × 10 ^-3 ExY-1 0.050 ExY-2 0.66 ExY-3 0.40 ExY-4 0.040 Cpd-2 0.10 Cpd-3 4.0 × 10 ^-3 HBS-1 0.265 Gelatin 2.10

13th layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion M Silver 0.70 ExS-9 3.5 × 10 ^-4 ExY-2 0.100 ExY-3 0.035 ExY-4 0.0050 Cpd-2 0.10 Cpd-3 1.0 × 10 ^-3 HBS-1 0.068 Gelatin 0.70

Fourteenth layer (first protective layer) Silver iodobromide emulsion N silver 0.10 UV-1 0.13 UV-2 0.10 UV-3 0.16 UV-4 0.025 ExF-8 0.001 ExF-9 0.002 HBS-1 5.0 × 10 ^-2 HBS-4 5.0 x 10 ^-2 Gelatin 1.8

Fifteenth layer (second protective layer) H-1 0.40 B-1 (diameter 1.7 μm) 0.06 B-2 (diameter 1.7 μm) 0.09 B-3 0.13 ES-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-4, 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.

[0204]

[Table 2]

In Table 1, (1) Emulsions J to M were prepared according to the examples of JP-A-2-91938.
Reduction sensitization was performed using thiourea dioxide and thiosulfonic acid during the preparation of the particles. (2) Emulsions CE, GI, and M were subjected to gold sensitization and sulfur sensitization in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate according to the examples of JP-A-3-237450. And selenium sensitization. (3) For preparing tabular grains, low molecular weight gelatin is used according to the examples of JP-A-1-158426. (4) When a high-pressure electron microscope is used for the tabular grains, dislocation lines as described in JP-A-3-237450 are observed. (5) Emulsions A to E, G, H and J to M are Rh, Ir, F
e in an optimal amount. The tabularity is defined as Dc / t ² , where Dc is the average equivalent circle diameter in the projected area of the tabular grains and t is the average thickness of the tabular grains.

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.

In the same manner, 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.

[0208]

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[0209]

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[0210]

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[0211]

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[0212]

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[0213]

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[0214]

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[0215]

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[0216]

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[0219]

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[0218]

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[0219]

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[0220]

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[0221]

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[0222]

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[0223]

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[0224]

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Subsequently, the following samples were prepared. Sample 202 In the twelfth and thirteenth layers of the blue-sensitive emulsion layer of Sample 201,
The comparative compound used in Example 1 was 0.03 in the 12th layer.
The coating amount was 3 g / m ² and the 13th layer was formed by adding 0.004 g / m ^{2 to} the coating amount. Samples 203 and 204 ExY-2 and E of yellow couplers used for the blue-sensitive emulsion layers of the 12th and 13th layers of Samples 201 and 202
xY-3 was produced by substituting Y-2 and Y-22, which are exemplary couplers represented by the general formula [I] of the present invention, in equimolar amounts. Sample 205 The comparative compound (1) used for the twelfth layer and the thirteenth layer of the sample 204 was prepared by substituting the exemplary compound A-50 represented by the general formula (AI) of the present invention in an equimolar amount. A
-50 is added as an emulsified dispersion by coexisting with the coupler. Samples 206 to 210 Yellow couplers Y-2 and Y-22 used in the twelfth layer and the thirteenth layer of Sample 205 are represented by the general formula [I] of the present invention.
Was produced by substituting an equimolar amount for the other coupler shown in Table 3 represented by. Samples 211 to 215 The compound A-50 represented by the general formula (AI) of the present invention used for the twelfth layer and the thirteenth layer of the sample 207 is represented by the general formula (AI) of the present invention shown in Table 3. ) To (A-III) were replaced with other compounds in an equimolar amount. Sample 216 In the eleventh layer of the yellow filter of Sample 206, Y-34, which is also an exemplary compound of the present invention, was added at 0.003 g / m ² , A
It was prepared by adding -50 to a coating amount of 0.010 g / m ² . Y-34 and A-50 are HB used in the same layer
It was added as a dispersion coexisting with S-1.

Samples 217 to 224 Couplers Y-2 and Y-2 represented by the general formula [I] of the present invention used in the twelfth and thirteenth layers of Sample 205.
2 to the coupler represented by the formula [I] and the formula [Y],
As shown in Table 4, the equimolar amounts were replaced, and the formula (A-
A sample was prepared in the same manner as in Sample 205, except that Compound A-50 represented by I) was replaced with another compound of the present invention in an equimolar amount. Sample 225 The compound A-50 was added to the 11th layer of Sample 217 at 0.12 g /
It was prepared by adding so that the coating amount was m ² . In addition, A-5
The weight ratio of HBS-1 used in the same layer to the weight of 0 was 1.
It was carried out additionally to be 0.

These prepared samples were cut and processed as described in Example 1, FM signals were recorded on the magnetic recording layer, and then the samples were similarly stored. These samples were stored at 30 ° C. and a relative humidity of 60% for 3 days in the same manner as in Example 1, and the storability of the light-sensitive material according to the method described in Example 1 was evaluated. The photographic properties of the material were examined. However, the color development time in the color development processing was set to 3 minutes and 5 seconds, and the color image obtained by exposure for 1/100 second was performed for the yellow color image. The results are shown in Tables 3 and 4.

[0228]

[Table 3]

[0229]

[Table 4]

From the table, the couplers represented by the general formula [I] of the present invention and the couplers represented by the general formula [Y] are used, and the general formulas (AI) to (A-III) are used. Samples 205 to 225 satisfying the constitution of the present invention, in which the compound represented by
It is clear that the storage stability of the photosensitive material with time, the storage stability of the photosensitive material after being photographed are improved, and high sensitivity is imparted and excellent color development is exhibited as compared with Nos. 01 to 204. Further, the coupler represented by the formula [I] and the coupler represented by the formula [Y] of the present invention may be used together in a two-layer blue-sensitive emulsion layer, or may be used separately. ,
It can be known from Samples 217 to 225 that the above performances are both superior to those of the Comparative Samples. Further, even in a sample containing [I] satisfying the constitution of the present invention and a compound selected from the formulas (A-I) to (A-III) in the same layer, a non-photosensitive layer adjacent to the sample of the present invention By using the compound, the storage stability of the photosensitive material with time and the storage stability of the photosensitive material after photographing can be further improved.
16 and samples 217 and 225.

Example 3 Substrates were replaced with undercoated cellulose triacetate supports to prepare Samples 301 to 325 having the same layer constitution as Samples 201 to 225 prepared in Example 2. Samples having the same last two digits have the same composition of the constituent layers, indicating that only the support is changed. The prepared sample has a width of 35 mm,
It was cut to a length of 160 cm, provided with the same perforations as the current 135 type, wound on the existing spool and stored in the cartridge. These sensitive materials were stored at 30 ° C. and 60% relative humidity for 3 days in the same manner as in Example 2, and
As with the above, the yellow color image was examined for storability of the sensitive material with time, increase / decrease with time of the sensitive material after photography, and photographic properties of the fresh sensitive material after preparation of the sensitive material. Tables 5 and 6 show these results.

[0232]

[Table 5]

[0233]

[Table 6]

From the table, similar to the results of Example 2, the couplers of the formula [I] and / or the formula [Y] of the present invention and the formulas (AI) to (A-III) are used. Samples 305 to 325 satisfying the constitution of the present invention, in which the compound was used in the same layer
Clearly improves the storage stability of the light-sensitive material with time, the storage stability of the light-sensitive material after storage and the photographic property of the fresh light-sensitive material as compared with Comparative Samples 301 to 304, and achieves the object of the present invention brilliantly. I understand that Further, it can be seen that the same result as in Example 2 can be obtained by further improving the non-photosensitivity of the adjacent layer by using the compound of the present invention.
Further, when comparing the results of this embodiment with the results of the above-mentioned second embodiment, the photosensitive material in which the magnetic recording layer is provided on the back surface and the photosensitive material is stored in the specific cartridge according to the present invention described above is Compared with the stored sensitive material, it is deteriorated in the storage stability of the above-mentioned sensitive material, the storage stability of the sensitive material after shooting, etc. compared with the stored sensitive material As can be seen from the sample, it is clear that the sample satisfying the constitution of the present invention improves the storage stability after storage, storage stability after photographing, etc., and achieves the object of the present invention. is there.

[0235]

According to the present invention, each of at least 1
At least one of the constituent layers of the color light-sensitive material consisting of a photosensitive silver halide emulsion layer and a non-photosensitive layer comprises a coupler represented by the general formula (I), and The silver halide color photographic light-sensitive material containing a compound selected from the group consisting of -I) to (A-III) suppresses fluctuations in photographic properties such as fog and sensitivity when the color light-sensitive material is stored over time, It is possible to provide a silver halide color photographic light-sensitive material capable of reducing the increase / decrease in aging that occurs when the color photographic material is stored for a long time after photography and imparting high sensitivity and excellent color forming property. Further, a package containing the color sensitive material can be provided together.

[Brief description of the drawings]

FIG. 1 is an exploded perspective view of a photographic light-sensitive material package (photographic film cartridge) according to one embodiment of the present invention.

FIG. 2 is a diagram of the photographic light-sensitive material package as viewed from a radial direction.

FIG. 3 is a view of the photographic light-sensitive material package viewed from a radial direction at a position different from that in FIG.

FIG. 4 is a view of the photographic light-sensitive material package as viewed from one side in the axial direction thereof.

FIG. 5 is a view of the photographic light-sensitive material package as seen from the other axial direction.

FIG. 6 is a sectional view of the photographic light-sensitive material package cut along the axial direction.

FIG. 7 is a diagram showing an adhesive label stock sheet with release paper.

[Explanation of symbols]

 100 Photo Film Patrone 101 Patrone Main Body 102 Photo Film 103 Spool 104 Patrone Label 105 Upper Case 106 Lower Case 107 Film Feed Out Port 108 Lid Member 109 Separation Claw 110 Key Groove 111 Key Groove 112 Spool Shaft 113 Flange 114 Flange 115 Data Disc 116 Bar Code Label 117 Flange engaging portion 118 Flange engaging portion 119 Slit 120 Use display member support portion 121 Key groove 122 Key groove 123 Use display member 124 Bearing portion 125 Ratchet pawl 126 Gear 127 Display plate 128 Spool lock 129 Round hole 130 Round hole 131 Opening edge 132 Opening edge 133 Hole 134 Large-diameter fan-shaped portion 135 Notch 136 Opening 137 Opening 138 Displaying opening 139 Table Display opening 140 Display opening 141 Display opening 142 Film roll 143 Film tip 144 Rock paw 145 Sensitivity detection notch 146 Opening 147 Developed display tab 150 Gate 151 ID number printing space 152 Variety printing space 153 Bar code printing space

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location G03C 3/00 599 G03C 3/00 599A 7/00 510 7/00 510 530 530 7/392 7 / 392 A

Claims (4)

[Claims] 1. A silver halide color photographic light-sensitive material in which at least one light-sensitive silver halide emulsion layer and a non-light-sensitive layer are provided on a support, each containing a coupler represented by the general formula [I]. And the general formula (AI),
A silver halide color photographic light-sensitive material comprising a compound selected from formula (A-II) or formula (A-III). Embedded image In the general formula [I], R ₁ is a tertiary alkyl group, R ₂
Is a halogen atom, an alkoxy group, an aryloxy group, an alkyl group, an alkylsulfonyloxy group, or a cycloalkyl group, R ₃ is an alkoxycarbonyl group, or an alkylsulfonyloxy group, R ₄ is a halogen atom,
An alkyl group, an alkoxy group, a carbonamido group, or a sulfonamide group, m is an integer of 0 to 2, R ₅ and R ₆ are each independently a hydrogen atom or an alkyl group, and X is an oxygen atom or a sulfur atom. Represent. Embedded image In the general formula (AI), _Ra1 represents an alkyl group, an alkenyl group, an aryl group, an acyl group, an alkyl or arylsulfonyl group, an alkyl or arylsulfinyl group,
A carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group;
_a2 represents a hydrogen atom or a group represented by R _a1 . However,
When R _a1 is an alkyl group, an alkenyl group or an aryl group, R _a2 is an acyl group, an alkyl or arylsulfonyl group, an alkyl or arylsulfinyl group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group. R _a1 and R _a2 may combine with each other to form a 5- to 7-membered ring, provided that S
-Does not form a triazine ring. General formula (A-I
In I), X represents a heterocyclic group excluding the S-triazine ring, and R _b1 represents an alkyl group, an alkenyl group or an aryl group. X and R _b1 may combine with each other to form a 5- to 7-membered ring, provided that they do not form an S-triazine ring. In the general formula (A-III), Y is -N =
Represents a group of nonmetallic atoms necessary for forming a 5-membered ring together with C-. Y further represents a nonmetallic atom group necessary for forming a 6-membered ring together with the -N = C- group, and -N = C
The terminal of Y bonded to the carbon atom of the -group is -N (R _C1 )-, -C
(R _C2 ) (R _C3 )-, -C (R _C4 ) =, -O-, a group selected from -S- (bonded to the carbon atom of -N = C- on the left side of each group) Represents However, it does not form an S-triazine ring. R _{C1 to} R _C4 each represent a hydrogen atom or a substituent. 2. The silver halide color photographic light-sensitive material according to claim 1, which contains a coupler represented by the following general formula [Y]. Embedded image In the general formula [Y], R ₁ is an aryl group, R ₂ is a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an alkyl group or a dialkylamino group, and R ₃ is a group which can be substituted on the benzene ring. , X ₀ represents a hydrogen atom or a group capable of splitting off by a coupling reaction with an oxidation product of an aromatic primary amine developing agent, and p represents an integer of 0 to 4, respectively. However, when p is plural, plural R ₃ may be the same or different. 3. A silver halide color photographic light-sensitive material according to claim 1, which has a magnetic recording layer containing magnetic grains on the side opposite to the side having the emulsion layer and the support. . 4. A cartridge 103 is rotatably housed inside a cartridge body 101, around which a photographic light-sensitive material 102 having an emulsion layer provided on a support is wound, and the free end of the photographic light-sensitive material is rotated by the rotation of the spool. The cartridge main body has a photographic light-sensitive material feed-out passage having a light-shielding mechanism for feeding out the photographic light-sensitive material, and a pair of flanges 113 with lips are respectively provided inside both ends of the spool shaft 112 of the spool. , 11
4. A photographic light-sensitive material package 100 in which 4 is attached for holding a photographic light-sensitive material, wherein the photographic light-sensitive material is the silver halide color photographic light-sensitive material according to any one of claims 1 to 3. And a photosensitive material package.