JP4081123B2 - Silver halide color photographic light-sensitive material - Google Patents

Description

  The present invention relates to a silver halide color photographic material having improved sensitivity.

  In the field of silver halide color photographic light-sensitive materials, it has been a long-standing problem to increase the sensitivity without impairing the graininess. In general, the photographic speed is determined by the size of the silver halide emulsion grains. The larger the emulsion grains, the more the photographic speed increases. However, since the graininess deteriorates with an increase in the size of silver halide grains, sensitivity and graininess are in a trade-off relationship. Increasing the sensitivity without deteriorating the graininess in the industry is the most fundamental and important issue in improving the image quality of a photographic photosensitive material.

Patent Document 1 discloses a technique for increasing sensitivity without deteriorating graininess by incorporating a compound having at least three heteroatoms that do not react with an oxidized developing agent into a silver halide photographic material. . However, although an increase in sensitivity is observed by the method described in the above publication, the effect is not sufficient, and there is a side effect due to the addition of the compound, and when the compound coexists with the silver halide emulsion, It was also found that an undesirable interaction occurs and an undesirable deterioration with time occurs when the coating solution is stored or when the photosensitive material is stored.
JP 2000-194085 A

  An object of the present invention is to provide a silver halide color photographic light-sensitive material containing a compound that increases sensitivity without deteriorating image quality such as graininess.

The above object of the present invention has been achieved by the following method.
[1] A silver halide color photographic light-sensitive material comprising a compound represented by the following general formula (1).

General formula (1)

In general formula (1), R ₁ represents an alkyl group. Z ₁ and Z ₂ represent a nitrogen atom or —C (R ₂ ) ═, and when Z ₁ represents a nitrogen atom, Z ₂ represents —C (R ₂ ) ═ and Z ₂ represents a nitrogen atom. , Z ₁ represents —C (R ₂ ) ═, R ₂ represents a group represented by the following general formula (2), and Y represents an arylthio group.

General formula (2)

In General Formula (2), R ₃ represents a substituent, j represents an integer of 0 to 4, and EWG represents an alkoxycarbonyl group, a carbamoyl group, a cyano group, a nitro group, an alkylsulfonyl group, and a sulfamoyl group.

  [2] The silver halide color photographic light-sensitive material as described in [1], wherein EWG in the group represented by the general formula (2) is a nitro group.

[3] The silver halide color photographic light-sensitive material according to [2], wherein at least one of R _{3 in} the group represented by the general formula (2) is an alkylthio group, an arylthio group, or a heterocyclic thio group. material.

  Although the detailed mechanism by which the compound of the general formula (1) increases the sensitivity is unknown, it is advantageous to have the property of adsorbing on the surface of the emulsion grains without changing the silver ion concentration in the film. It is presumed that the use of the compound of the general formula (1) of the present invention is more effective in this respect than the exemplified compounds described in 2000-194085. In addition, it is presumed that it is preferable to have an appropriate reactivity with an oxidized developing agent from the viewpoint of preventing undesirable latent image bleaching during development.

  The compound represented by the general formula (1) of the present invention has a specific selected substituent in a skeleton known as a pyrazolotriazole coupler in the field of silver halide color photographic light-sensitive materials, and a developing agent. It is a coupler having reactivity with an oxidant.

The compound represented by the general formula (1) will be described in detail.
In the general formula (1), R ₁ represents an alkyl group, and preferred carbon numbers and specific examples are the same as those mentioned in the description of the substituent represented by R ₃ in the description of the general formula (2) described later. is there.

Z ₁ and Z ₂ represent a nitrogen atom or —C (R ₂ ) ═, and when Z ₁ represents a nitrogen atom, Z ₂ represents —C (R ₂ ) ═, and Z ₂ represents a nitrogen atom. , Z ₁ represents —C (R ₂ ) ═, and R ₂ represents a group represented by the following general formula (2).

Y represents an arylthio group. The preferred carbon number and specific examples of the arylthio group represented by Y are the same as those described in the description of the substituent represented by R ₃ .

In General Formula (2), R ₃ represents a substituent, and j represents an integer of 0 to 4. Examples of the substituent represented by R ₃ include a halogen atom, an alkyl group (including a cycloalkyl group and a bicycloalkyl group), an alkenyl group (including a cycloalkenyl group and a bicycloalkenyl group), an alkynyl group, an aryl group, and a heterocyclic ring. Group, cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy, amino group (anilino) Group), acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, mercapto group, alkylthio group, arylthio group Heterocyclic thio group, sulfamoyl group, sulfo group, alkyl and arylsulfinyl group, alkyl and arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl and heterocyclic azo group, imide group, phosphino group , A phosphinyl group, a phosphinyloxy group, a phosphinylamino group, and a silyl group. More specifically, a halogen atom (for example, a chlorine atom, a bromine atom, an iodine atom), an alkyl group [a linear, branched, cyclic, substituted or unsubstituted alkyl group is represented. An alkyl group (preferably an alkyl group having 1 to 30 carbon atoms, for example, methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl), cycloalkyl A group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, such as cyclohexyl, cyclopentyl, 4-n-dodecylcyclohexyl), a bicycloalkyl group (preferably a substituted or unsubstituted group having 5 to 30 carbon atoms). A substituted bicycloalkyl group, that is, a monovalent group obtained by removing one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms, for example, bicyclo [1,2,2] heptan-2-yl, bicyclo [2, 2,2] octane-3-yl), and tricyclo structures with more ring structures. . An alkyl group (for example, an alkyl group of an alkylthio group) in the substituents described below also represents such an alkyl group. ], An alkenyl group [represents a linear, branched or cyclic substituted or unsubstituted alkenyl group. An alkenyl group (preferably a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, such as vinyl, allyl, prenyl, geranyl, oleyl), a cycloalkenyl group (preferably a substituted or unsubstituted group having 3 to 30 carbon atoms) A cycloalkenyl group, that is, a monovalent group obtained by removing one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms (for example, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl), a bicycloalkenyl group (Substituted or unsubstituted bicycloalkenyl group, preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom of a bicycloalkene having one double bond. For example, bicyclo [2,2,1] hept-2-en-1-yl, bicyclo [2,2,2 Octo-2-en-4-yl)], an alkynyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, such as ethynyl, propargyl, trimethylsilylethynyl group, aryl group (preferably having 6 carbon atoms) To 30 substituted or unsubstituted aryl groups such as phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl), heterocyclic groups (preferably 5 or 6 membered substituted or unsubstituted, A monovalent group obtained by removing one hydrogen atom from an aromatic or non-aromatic heterocyclic compound, which may be condensed with an aromatic ring such as a benzene ring, more preferably 3 to 30 carbon atoms. A 5- or 6-membered aromatic heterocyclic group such as 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothia Ryl), cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, such as methoxy, ethoxy, isopropoxy, t-butoxy, n- Octyloxy, 2-methoxyethoxy), aryloxy groups (preferably substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms, such as phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitro Phenoxy, 2-tetradecanoylaminophenoxy), a silyloxy group (preferably a silyloxy group having 3 to 20 carbon atoms, such as trimethylsilyloxy, t-butyldimethylsilyloxy), a heterocyclic oxy group (preferably having 2 carbon atoms) To 30 substituted or unsubstituted heterocyclic oxy Group, 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy), acyloxy group (preferably formyloxy group, substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, 7 to 30 carbon atoms) A substituted or unsubstituted arylcarbonyloxy group such as formyloxy, acetyloxy, pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy), a carbamoyloxy group (preferably a substituted or unsubstituted group having 1 to 30 carbon atoms) Substituted carbamoyloxy groups such as N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di-n-octylaminocarbonyloxy, Nn-octylcarbamoyl Xy), an alkoxycarbonyloxy group (preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, such as methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, n-octylcarbonyloxy), aryloxy A carbonyloxy group (preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, such as phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyloxy), amino A group (preferably an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted anilino group having 6 to 30 carbon atoms, such as amino, methylamino, dimethylamino; , Anilino, N-methyl-anilino, diphenylamino), acylamino group (preferably formylamino group, substituted or unsubstituted alkylcarbonylamino group having 2 to 30 carbon atoms, substituted or unsubstituted group having 7 to 30 carbon atoms) Arylcarbonylamino groups such as formylamino, acetylamino, pivaloylamino, lauroylamino, benzoylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino), aminocarbonylamino groups (preferably having 1 carbon atom) To 30 substituted or unsubstituted aminocarbonylamino, such as carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino), alkoxycarbonylamino group (preferably A substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, such as methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino), aryloxycarbonyl An amino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, such as phenoxycarbonylamino, p-chlorophenoxycarbonylamino, mn-octyloxyphenoxycarbonylamino), sulfamoyl An amino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms, such as sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octylamino; Sulfonylamino), alkyl and arylsulfonylamino groups (preferably substituted or unsubstituted alkylsulfonylamino having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonylamino having 6 to 30 carbon atoms, such as methylsulfonylamino, butylsulfonyl) Amino, phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino, p-methylphenylsulfonylamino), mercapto group, alkylthio group (preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms such as methylthio , Ethylthio, n-hexadecylthio), an arylthio group (preferably a substituted or unsubstituted arylthio having 6 to 30 carbon atoms, such as phenylthio, p-chlorophenylthio, m-methoxyphenylthio, -Butoxy-5-t-butylphenylthio, 4-hexanoylaminophenylthio, 2-benzamidophenylthio), a heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, for example, 2-benzothiazolylthio, 1-phenyltetrazol-5-ylthio, 1,3,4-thiadiazol-2-ylthio), a sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms, for example, N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N, N-dimethylsulfamoyl, N-acetylsulfamoyl, N-benzoylsulfamoyl, N- (N′-phenylcarbamoyl) ) Sulfamoyl), sulfo groups, alkyl and arylsulfinyl groups (preferably A substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms (eg, methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p-methylphenylsulfinyl), alkyl and aryl A sulfonyl group (preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms such as methylsulfonyl, ethylsulfonyl, phenylsulfonyl, p-methylphenylsulfonyl; ), An acyl group (preferably a formyl group, a substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, such as acetyl, pivaloyl, 2-chloroacetyl , Aroyl, benzoyl, pn-octyloxyphenylcarbonyl), aryloxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, such as phenoxycarbonyl, o-chlorophenoxycarbonyl, m -Nitrophenoxycarbonyl, pt-butylphenoxycarbonyl), alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n- Octadecyloxycarbonyl), a carbamoyl group (preferably a substituted or unsubstituted carbamoyl having 1 to 30 carbon atoms such as carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N N-di-n-octylcarbamoyl, N- (methylsulfonyl) carbamoyl), aryl and heterocyclic azo groups (preferably substituted or unsubstituted arylazo groups having 6 to 30 carbon atoms, substituted or unsubstituted carbon atoms having 3 to 30 carbon atoms) Substituted heterocyclic azo groups such as phenylazo, p-chlorophenylazo, 5-ethylthio-1,3,4-thiadiazol-2-ylazo), imide groups (preferably N-succinimide, N-phthalimide), phosphino groups (Preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, such as dimethylphosphino, diphenylphosphino, methylphenoxyphosphino), a phosphinyl group (preferably substituted or unsubstituted having 2 to 30 carbon atoms) Phosphinyl groups such as phosphinyl, dioctyloxy Phosphinyl, diethoxyphosphinyl), phosphinyloxy group (preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, such as diphenoxyphosphinyloxy, dioctyloxyphosphinyloxy ), A phosphinylamino group (preferably a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, such as dimethoxyphosphinylamino, dimethylaminophosphinylamino), a silyl group (preferably And a substituted or unsubstituted silyl group having 3 to 30 carbon atoms (for example, trimethylsilyl, t-butyldimethylsilyl, phenyldimethylsilyl). When j represents 2 or more, two or more R _{3 s} may be the same or different.

EWG is an alkoxycarbonyl group, a carbamoyl group, a cyano group, a nitro group, an alkylsulfonyl group, and a sulfamoyl group, and preferable number of carbon atoms and specific examples of these groups, in the description of the substituents represented by R ₃ Same as listed.

In the general formula (1), Y represents an arylthio group. The preferred carbon number and specific examples of the arylthio group represented by Y are the same as those described in the description of the substituent represented by R ₃ .

When the groups represented by R _{1 to} R ₃ and EWG are further substitutable groups, these groups may be further substituted, and the substituent in that case is the explanation of the substituent represented by R _3. The same as listed above.
The compound represented by the general formula (1) of the present invention may form a dimer or higher multimer via R ₁ or R ₂ of the substituent, and may be high via R ₁ or R _2. It may be bound to a molecular chain.

Next, the preferable range of the compound represented by the general formula (1) will be described.
R ₁ is most preferably a t-butyl group.

In the general formula (2), R ₃ represents a halogen atom, alkyl group, cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, amino group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group , Aryloxycarbonylamino group, alkyl and arylsulfonylamino group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, alkyl and arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, and Imido groups are preferred, halogen atoms, cyano groups, carboxyl groups, alkoxy groups, alkyl and arylsulfonylamino groups, alkylthio groups, arylthio groups, heterocyclic thio groups, alkoxycarbonyl groups, and A carbamoyl group is more preferred. j is preferably 0 or 1. R ₃ may be substituted at any position, but is most preferably in the ortho or para position relative to the position bonded to Z ₁ or Z ₂ . EWG is preferably a chlorine atom, an alkoxycarbonyl group, a carbamoyl group, a cyano group, a nitro group, an alkylsulfonyl group, and a sulfamoyl group, more preferably an alkoxycarbonyl group, a carbamoyl group, a cyano group, and a nitro group, and most preferably a nitro group. preferable. Although EWG may be substituted at any position, it is most preferably at the meta position relative to the position bonded to Z ₁ or Z ₂ .

In the general formula (1), Y is most preferably a phenylthio group having an acylamino group, an alkylsulfonamide group, an arylsulfonamide group, or an alkoxy group at the ortho or para position.
Although the preferable specific example of a compound represented by General formula (1) below is shown, this invention is not limited to these.

The compounds of the present invention are disclosed in U.S. Pat. Nos. 4,540,654, 4,705,863, JP-A-61-65245, 62-209457, 62-249155, and JP-B-47-27411. Can be synthesized by referring to the method described in US Pat. No. 3,725,067.
Hereinafter, it shows the synthesis example of reference compound (8).

Synthesis Example 1 [Synthesis of Reference Compound (8)]
Synthesized according to the following scheme.

Synthesis of Intermediate D Commercially available 4,4′-dithioaniline (176.8 g, 0.712 mol) was added to 1300 ml of N, N-dimethylacetamide (DMAC) (hereinafter also referred to as “mL”) and cooled with ice water. And stirred. To this, 197 mL (1.67 mol) of pivaloyl chloride was added dropwise over 40 minutes, and the mixture was further stirred for 1 hour. The reaction mixture was poured into 6500 mL of stirred ice water and stirred for 30 minutes. The precipitated crystals were collected by filtration, washed with water and dried to obtain 280 g of intermediate D (yield 94%).

Synthesis of intermediate C 157.1 g (0.615 mol) of intermediate A synthesized by the method described in Japanese Patent No. 2655249 was added to 1080 mL of DMAC, and the mixture was cooled in an ice water bath and stirred. To this, 164.9 g (0.644 mol) of 4-chloro-3-nitrobenzenesulfonyl chloride was added and stirred for 20 minutes. 100 mL (1.24 mol) of pyridine was added dropwise over 10 minutes, and the mixture was further stirred for 30 minutes. Commercially available methyl mercaptoacetate 57.4 mL (0.642 mol) was added, followed by sodium methoxide powder 99.1 g (1.83 mol) in 6 portions over 45 minutes, the ice water bath removed and stirred for 30 minutes. . 1226 mL of methanol was added to the reaction mixture, and then a solution of 112 mL of concentrated hydrochloric acid added to 1120 mL of water was added dropwise over 20 minutes. After stirring for 30 minutes, 616 mL of water was added dropwise over 20 minutes, and the mixture was further stirred for 1 hour. The precipitated crystals were collected by filtration and washed with a mixed solvent of methanol / water (2/3). Drying gave 309 g of intermediate C (yield 92%). Melting point 175 ° C
H ¹ -NMR (in DMSO-d ₆ ) 11.50 (s) 1H, 10.92 (s) 1H, 9.12 (s) 1H, 8.59 (d) 1H, 8.00 (dd) 1H, 7.89 (d) 2H, 7.72 (d ) 1H, 7.50 (d) 2H, 7.38 (d) 2H, 6.91 (d) 2H, 4.18 (s) 2H, 3.67 (s) 3H, 1.35 (s) 9H, 1.19 (s) 9H.

Synthesis of Reference Compound (8) 172.1 g (0.413 mol) of Intermediate D was added to 1280 mL of dichloromethane, cooled in a water bath at 15 ° C. and stirred. 50 mL (0.221 mol) of sulfuryl chloride was added dropwise over 10 minutes, and after stirring for 1 hour, the mixture was concentrated under reduced pressure, taking care not to increase the temperature, to obtain a sulfenyl chloride product.
300 g (0.551 mol) of intermediate C was added to 1500 mL of DMAC and dissolved by stirring at room temperature. The reaction vessel was cooled with ice water, and the sulphenyl chloride synthesized previously was diluted with 200 mL of acetonitrile and added over 20 minutes. After stirring at room temperature for 1.5 hours, 1500 mL of acetonitrile was added, followed by dropwise addition of 2000 mL of water over 40 minutes. The precipitated crystals were collected by filtration, washed with water, and dried to obtain crude crystals of Reference Compound (8). 600 mL of ethyl acetate was added to the crude crystals and dissolved by heating, followed by filtration. 3000 mL of acetonitrile was slowly added to the filtrate and stirred for 1 hour. The precipitated crystals were collected by filtration and washed with acetonitrile. By drying, 265 g of Reference Compound (8) (yield 64%) was obtained.

The compound of the general formula (1) of the present invention may be used for either a silver halide photosensitive layer or a non-photosensitive layer in a photosensitive material.
When used for a silver halide photosensitive layer, when the photosensitive layer is divided into a plurality of layers having different sensitivities, it may be used for any sensitive layer, but is preferably used for a highly sensitive layer.
When used for a non-photosensitive layer, it is preferably used for an intermediate layer located between a red-sensitive layer and a green-sensitive layer or between a green-sensitive layer and a blue-sensitive layer.

  The method for adding the compound of the general formula (1) to the light-sensitive material is not particularly specified, but it is a method of emulsifying and dispersing together with a high-boiling organic solvent, etc. There are a method, a method of adding at the time of preparing a silver halide emulsion, and the like.

The addition amount of the compound of the general formula (1) is preferably 0.1 to 1000 mg / m ^2, more preferably ^{1~500mg / m 2, 5~100mg / m} 2 is particularly preferred.
When used in a light-sensitive silver halide emulsion layer, 1 × 10 ⁻⁴ to 1 × 10 ⁻¹ mol is preferable, and 1 × 10 ^{−3 to} 5 × 10 ⁻² mol is more preferable per mol of silver in the same layer. .

When the compound of the general formula (1) is used after being emulsified and dispersed, it is preferably added after being co-emulsified with another coupler. The compound of the general formula (1) is preferably 0.01 mol to 5.0 mol, more preferably 0.1 mol to 1.0 mol, relative to 1 mol of another coupler added to the same layer as this compound.
The compound of the general formula (1) has an effect of improving the sensitivity / granularity ratio and reacts with an oxidized form of the developing agent to form a dye, so that it can also be used as a so-called main coupler.

  In the light-sensitive material of the present invention, it is sufficient that at least one blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layer is provided on the support. As a typical example, a blue-sensitive, green-sensitive, and red-sensitive layer composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivity are provided on a support. A silver halide photographic light-sensitive material having at least one. The photosensitive layer is a unit photosensitive layer having color sensitivity to any of blue light, green light, and red light.In a multilayer silver halide color photographic light-sensitive material, the arrangement of unit photosensitive layers is generally The red color-sensitive layer, the green color-sensitive layer, and the blue color-sensitive layer are installed in this order from the support side. However, depending on the purpose, the installation order may be reversed, or the installation order may be such that different photosensitive layers are sandwiched in the same color-sensitive layer. A non-photosensitive layer may be provided between the above-described silver halide photosensitive layers and as the uppermost layer and the lowermost layer. These may contain couplers, DIR compounds, color mixing inhibitors and the like described later. A plurality of silver halide emulsion layers constituting each unit photosensitive layer are sequentially exposed to a support, two layers of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer as described in DE 1,121,470 or GB 923,045. It is preferable to arrange so that the degree is low. In addition, as described in JP-A-57-112751, 62-200350, 62-206541, 62-206543, a low-sensitivity emulsion layer is provided on the side away from the support, and a high-sensitivity emulsion is provided on the side close to the support. Layers may be installed.

As a specific example, from the side farthest from the support, low sensitivity blue photosensitive layer (BL) / high sensitivity blue photosensitive layer (BH) / high sensitivity green photosensitive layer (GH) / low sensitivity green photosensitive layer (GL) / High-sensitivity red photosensitive layer (RH) / Low-sensitivity red photosensitive layer (RL) or BH / BL / GL / GH / RH / RL or BH / BL / GH / GL / RL / RH It can be installed in the order of.
Further, as described in Japanese Patent Publication No. 55-34932, it can be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the side farthest from the support. Further, as described in JP-A-56-25738 and JP-A-62-63936, they can be arranged in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support.

In addition, as described in JP-B-49-15495, the upper layer is a silver halide emulsion layer having the highest sensitivity, the middle layer is a silver halide emulsion layer having a lower sensitivity, and the lower layer is more sensitive than the middle layer. Examples include an arrangement composed of three layers having different sensitivities in which a low silver halide emulsion layer is arranged and the sensitivities are gradually lowered toward the support. Even in the case of being composed of three layers having different sensitivities, as described in JP-A-59-202464, the medium-sensitive emulsion layer / high They may be arranged in the order of sensitive emulsion layer / low sensitive emulsion layer.
In addition, they may be arranged in the order of high sensitivity emulsion layer / low sensitivity emulsion layer / medium sensitivity emulsion layer, or low sensitivity emulsion layer / medium sensitivity emulsion layer / high sensitivity emulsion layer.
Further, the arrangement may be changed as described above even when there are four or more layers.

  A 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% of silver iodide.

Silver halide grains in photographic emulsions have regular crystals such as cubes, octahedrons, tetradecahedrons, irregular crystal shapes such as spheres and plates, twin planes, etc. Those having crystal defects of the above or a composite form thereof may be used.
The grain size of the silver halide may be fine grains having a diameter of about 0.2 μm or less or large grains having a projected area diameter of about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion.

  Silver halide photographic emulsions that can be used in the present invention include, for example, Research Disclosure (hereinafter abbreviated as RD) No. 17643 (December 1978), pages 22-23, I. Emulsion preparation and types, and No. 18716 (November 1979), 648, No. 307105 (November 1989), 863-865, and Grafkide's "Physics and Chemistry of Photography", published by Paul Monter (P. Glafkides, Chimie et Phisique Photographiques, Paul Montel, 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (GF Duffin, Photographic Emulsion Chemistry, Focal Press, 1966), "Production and Coating of Photoemulsions", Focal It can be prepared using a method described in Press (VL Zelikman, et al., Making and Coating Photographic Emulsion, Focal Press, 164).

Also preferred are monodisperse emulsions described in US 3,574,628, 3,655,394 and GB 1,413,748.
Tabular grains having an aspect ratio of about 3 or more are particularly preferred and can be used in the present invention. Tabular grains are described by Gatoff, Photographic Science and Engineering, Vol. 14, 248-257 (1970); US 4,434,226, 4,414,310, 4,433,048, 4,439,520 and GB. It can be easily prepared by the method described in 2,112,157.
The crystal structure may be uniform, the inside and outside may be composed of different halogen compositions, or a layered structure may be formed. Silver halides having different compositions may be bonded by epitaxial bonding, and may be bonded to a compound other than silver halide, such as rhodium silver or lead oxide. A mixture of particles having various crystal forms may be used.

The above emulsion preferably has dislocations. In particular, tabular grains preferably have dislocations in the fringes. As a method for introducing the dislocation, there can be used a method in which an aqueous solution of alkali iodide or the like is added to form a high silver iodide layer, a method in which AgI fine particles are added, a method described in JP-A-5-323487, and the like. .
The above emulsion may be either a surface latent image type in which a latent image is mainly formed on the surface, an internal latent image type in which the latent image is formed inside the grain, or a type having a latent image on both the surface and the inside. It is necessary to be. Among the internal latent image types, a core / shell type internal latent image type emulsion described in JP-A-63-264740 may be used, and this preparation method is described in JP-A-59-133542. Although the thickness of the shell of this emulsion varies depending on the development processing or the like, it is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

As the silver halide emulsion, those subjected to physical ripening, chemical ripening and spectral sensitization are usually used. Additives used in such a process are described in RD No. 17643, No. 18716 and No. 307105, and the corresponding parts are summarized in the following table.
In the light-sensitive material of the present invention, two or more types of emulsions having at least one characteristic different in grain size, grain size distribution, halogen composition, grain shape, and sensitivity of a photosensitive silver halide emulsion are mixed in the same layer. Can be used.

  US Pat. No. 4,082,553 fogged silver halide grains, US Pat. No. 4,626,498, JP 59-214852, fogged silver halide grains, colloidal silver photosensitive silver halide emulsion layer and It is preferred to apply to / or a substantially light-insensitive hydrophilic colloid layer. The silver halide grains fogged inside or on the surface of the grains are silver halide grains that can be developed uniformly (non-imagewise) regardless of the unexposed and exposed areas of the photosensitive material. The preparation method thereof is described in US Pat. No. 4,626,498 and JP-A-59-214852. The silver halide forming the inner core of the core / shell type silver halide grain in which the inside of the grain is fogged may have a different halogen composition. Any silver chloride, silver bromide, silver iodobromide, or silver chloroiodobromide can be used as the silver halide fogged inside or on the surface of the grain. The average grain size of these fogged silver halide grains is preferably 0.01 to 0.75 μm, particularly preferably 0.05 to 0.6 μm. The grain shape may be a regular grain or a polydisperse emulsion, but it is monodisperse (at least 95% of the silver halide grain mass or number of grains has a grain size within ± 40% of the average grain size). Are preferred).

  In the present invention, it is preferable to use a non-photosensitive fine grain silver halide. The non-photosensitive fine grain silver halide is a silver halide fine grain which is not exposed during imagewise exposure for obtaining a dye image and is not substantially developed in the developing process, and is 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 as necessary. Preferably, it contains 0.5 to 10 mol% of silver iodide. The fine grain silver halide preferably has an average particle size (average value of equivalent circle diameter of projected area) of 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm.

The fine grain silver halide can be prepared 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 does not require spectral sensitization. However, prior to adding this to the coating solution, it is preferable to add a known stabilizer such as triazole, azaindene, benzothiazolium, mercapto compound or zinc compound in advance. This fine grain silver halide grain-containing layer can contain colloidal silver.
The silver coating amount of the light-sensitive material of the present invention is preferably 8.0 g / m ² or less.

Photographic additives that can be used in the present invention are also described in the RD, and the description locations related to the following table are shown.
Type of additive RD17643 RD18716 RD307105
1. Chemical sensitizer, page 23, page 648, right column, page 8662. Sensitivity increasing agent, right column, page 648 Spectral sensitizer, pages 23 to 24, page 648, right column, pages 866 to 868, supersensitizer to page 649, right column 4. Brightener 24 pages 647 pages right column 868 pages 5. 5. Light absorber, 25-26 pages, 649, right column, page 873 Filters, -page, left page, 650 Dyes, ultraviolet absorbers Binder page 26 page 651 left column page 873-874 Plasticizer, page 27, page 650, right column, page 876 Lubricant 8. Coating aid, page 26-27, page 650, right column, page 875-876, surface active agent 9. Static page 27 page 650 right column pages 876-877 inhibitor
Ten. Matting agents Pages 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 preferred.
Yellow couplers: couplers represented by formulas (I) and (II) of EP 502,424A; couplers represented by formulas (1) and (2) of EP 513,496A (especially Y-28 on page 18); EP 568,037A A coupler represented by formula (I) in claim 1; a coupler represented by general formula (I) on lines 45 to 55 in column 1 of US 5,066,576; represented by general formula (I) in paragraph 0008 of JP-A-4-74425 Couplers; couplers according to claim 1 on page 40 of EP 498,381A1 (especially D-35 on page 18); couplers represented by formula (Y) on page 4 of EP 447,969A1 (especially Y-1 (page 17)) Y-54 (page 41)); US Pat. No. 4,476,219, column 7, lines 36 to 58, couplers represented by formulas (II) to (IV) (particularly II-17, 19 (column 17), II-24 (column 19)).

  Magenta coupler; JP-A-3-9737 (L-57 (lower right of page 11), L-68 (lower right of page 12), L-77 (lower right of page 13); EP 456,257 (A-4) -63 ( 134), (A-4) -73, -75 (page 139); M-4, -6 (page 26), M-7 (page 27) of EP 486,965; M-45 (19 of EP 571,959A) (M-1) (page 6) of JP-A-5-204106; M-22 of paragraph 0237 of JP-A-4-362631.

Cyan coupler: CX-1,3,4,5,11,12,14,15 (pages 14-16) of JP-A-4-204843; C-7,10 (page 35) of JP-A-4-43345, 34 35 (page 37), (I-1), (I-17) (pages 42 to 43); a coupler represented by the general formula (Ia) or (Ib) of claim 1 of JP-A-6-67385.
Polymer coupler: P-1, P-5 (page 11) of JP-A-2-44345.

As couplers in which the coloring dye has an appropriate diffusibility, those described in US 4,366,237, GB 2,125,570, EP 96,873B, DE 3,234,533 are preferable.
A coupler for correcting unwanted absorption of the coloring dye is a yellow colored cyan coupler represented by the formula (CI), (CII), (CIII), (CIV) described on page 5 of EP 456,257A1 (especially on page 84). YC-86), yellow colored magenta coupler ExM-7 described in the EP, page 202, EX-1 (page 249), EX-7 (page 251), magenta colored cyan coupler CC-9 described in US 4,833,069 (Column 8), CC-13 (Column 10), US 4,837,136 (2) (Column 8), colorless masking coupler represented by the formula (A) of claim 1 of WO92 / 11575 (particularly examples on pages 36 to 45) Compound) is preferred.

  Examples of the compounds (including couplers) that release a photographically useful compound residue by reacting with oxidized developing agent include the following. Development inhibitor releasing compounds: compounds represented by formulas (I), (II), (III), (IV) described on page 11 of EP 378,236A1 (especially T-101 (page 30), T-104 (31) Page), T-113 (page 36), T-131 (page 45), T-144 (page 51), T-158 (page 58)), EP 436, 938A2 A compound represented by formula (1) of EP 568,037A (especially (23) (page 11)), a formula described on pages 5-6 of EP 440,195A2 ( Compounds represented by I), (II), (III) (especially I- (1) on page 29); Bleach accelerator releasing compounds: represented by formulas (I), (I ') on page 5 of EP 310,125A2 Compounds (especially (60), (61) on page 1) and compounds of formula (I) in claim 1 of JP-A-6-59411 (especially (7) (page 7); ligand releasing compounds: US 4,555,478) A compound represented by LIG-X according to claim 1 (particularly, a compound in columns 21 to 41 of column 12); a leuco dye-releasing compound: compounds 1 to 6 in columns 3 to 8 of US 4,749,641; a fluorescent dye-releasing compound: US 4,774,181 clay 1 compound represented by COUP-DYE (especially compounds 1 to 11 in columns 7 to 10); development accelerator or fogging agent releasing compound: in formula (1), (2) and (3) of column 3 of US 4,656,123 Compounds represented (especially (I-22) in column 25) and ExZK-2 at page 75, lines 36-38 of EP 450, 637A2; compounds which only release a group which becomes a dye after leaving: claim 1 of US 4,857,447 A compound represented by the formula (I): (especially Y-1 to Y-19 in columns 25 to 36).

As additives other than couplers, the following are preferable.
Oil-soluble organic compound dispersion medium: JP-A 62-215272, P-3, 5, 16, 19, 25, 30, 42, 49, 54, 55, 66, 81, 85, 86, 93 (140-144) Page); Latex for impregnation of oil-soluble organic compound: Latex described in US 4,199,363; Oxidant scavenger for developing agent: Compound (especially I-, ( 1), (2), (6), (12) (columns 4-5), US Pat. No. 4,923,787, column 2, line 5-10 (especially compound 1 (column 3); stain inhibitor: 4 of EP 298321A Pages 30-33, formulas (I)-(III), especially I-47,72, III-1,27 (pages 24-48); antifading agent: EP 298321A A-6, 7, 20, 21 , 23,24,25,26,30,37,40,42,48,63,90,92,94,164 (pages 69-118), US5,122,444, columns 25-38 II-1 to III-23, Especially III-10, EP 471347A, pages 8-12, I-1 to III-4, especially II-2, US 5,139,931, columns 32 to 40, A-1 to 48, especially A-39,42; Or a material that reduces the amount of color mixing inhibitor used: EP 411324A, pages 5 to 24, I-1 to II-15, especially I-46; Formalin Scavenger: EP 477932A, pages 24 to 29, SCV-1 to 28, especially SCV-8; Hardener: JP-A 1-214845, page 17, H-1,4,6,8,14, US 4,618,573 Compounds (H-1 to 54) represented by the formulas (VII) to (XII) in columns 13 to 23, compounds represented by the formula (6) on the lower right of page 8 of JP-A-2-214852 (H-1 to 76) ), In particular compounds described in claim 1 of H-14, US 3,325,287; development inhibitor precursors: P-24,37,39 (pages 6-7) of JP 62-168139; described in claim 1 of US 5,019,492 Compounds, especially columns 7, 28, 29; preservatives, fungicides: US 4,923,790, columns 3-15, I-1 to III-43, especially II-1,9,10,18, III-25; stable Agents, antifoggants: US Pat. No. 4,923,793, columns 6 to 16, I-1 to (14), especially I-1,60, (2), (13), US 4,952,483, columns 25 to 32, compounds 1 to 65, 36: chemical sensitizer: triphenylphosphine selenide, compound 50 of JP-A-5-40324; dye: a-1 to b-20 on pages 15-18 of JP-A-3-156450, in particular a-1,12, 18,27,35,36, b-5,27-29 V-1 to 23, especially V-1, EP 445627A, pages 33 to 55, FI-1 to F-II-43, especially FI-11, F-II-8, EP 457153A, pages 17 to 28, III- 1 to 36, especially III-1,3, WO 88/04794, 8 to 26, Dye-1 to 124 microcrystalline dispersion, EP 319999A, pages 6 to 11, compounds 1 to 22, especially compound 1, EP 519306A Compounds D-1 to 87 (pages 3 to 28) represented by formulas (1) to (3), compounds 1 to 22 (columns 3 to 10) represented by formula (I) of US 4,268,622, and formulas of US 4,923,788 Compounds (1) to (31) represented by (I) (columns 2 to 9); UV absorbers: compounds (18b) to (18r), 101 to 427 (pages 6 to 9), compounds (3) to (66) (pages 10 to 44) of EP 520938A and compounds HBT-1 to 10 (page 14) represented by formula (III) , EP 521823A, compounds (1) to (31) represented by formula (1) (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 television, color papers, color positive films and color reversal papers. Further, it is suitable for the lens-fitted film unit described in JP-B-2-32615 and JP-B-3-3794.
Suitable supports that can be used in the present invention are described in, for example, RD. No. 17643, page 28, RD. No. 18716, page 647, right column to page 648, left column, and RD. No. 307105, page 879. ing.

  The specific photographic sensitivity in the present invention is determined by the method described in JP-A-63-236035. This measuring method is in accordance with JIS K 7614-1981. The difference is that the development processing is completed within 30 minutes to 6 hours after exposure for sensitometry, and the development processing is based on Fuji Color Standard Processing Formula CN-16. In the point. Others are substantially the same as the measurement method described in JIS.

In the light-sensitive material of the present invention, the thickness from the light-sensitive silver halide layer closest to the support to the surface of the photographic light-sensitive material is preferably 24 μm or less, more preferably 22 μm or less. The membrane swelling speed T _1/2 is preferably 30 seconds or less, and more preferably 20 seconds or less. T _1/2 is the time until the film thickness reaches 1/2 when 90% of the maximum swollen film thickness reached when processed at 30 ° C for 3 minutes and 15 seconds with a color developer is the saturated film thickness. It is defined as The film thickness means the film thickness measured at 25 ° C and 55% relative humidity (2 days), and T _1/2 is photographic science and engineering by A.Green et al. (Photogr. Sci. Eng.), 19 卷, 2, 124-129. T _1/2 can be adjusted by adding a hardener to gelatin as a binder or changing the aging conditions after coating. The swelling rate is preferably 150 to 400%. The swelling ratio can be calculated from the maximum swollen film thickness under the conditions described above 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 to 20 μm is preferably provided on the side opposite to the side having the emulsion layer. This back layer preferably contains the aforementioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, and surfactant. The swelling rate of this back layer is preferably 150 to 500%.

  The light-sensitive material of the present invention is prepared by the usual methods described in the above-mentioned RD. No. 17643, pages 28 to 29, RD. No. 18716, 651, left column to right column, and RD. No. 307105, pages 880 to 881. It can be developed.

  Next, the color negative film processing solution used in the present invention will be described.

  As the color developer used in the present invention, compounds described in JP-A-4-21739, page 9, upper right column, line 1 to page 11, lower left column, line 4 can be used. In particular, as a color developing agent for rapid processing, 2-methyl-4- [N-ethyl-N- (2-hydroxyethyl) amino] aniline, 2-methyl-4- [N-ethyl-N- (3-Hydroxypropyl) amino] aniline and 2-methyl-4- [N-ethyl-N- (4-hydroxybutyl) amino] aniline are preferred.

  These color developing agents are preferably used in an amount of 0.01 to 0.08 mol, particularly 0.015 to 0.06 mol, more preferably 0.02 to 0.05, per liter of color developer (hereinafter, “L” is also expressed as “L”). It is preferable to use in the molar range. The color developer replenisher preferably contains 1.1 to 3 times the color developing agent of this concentration, and more preferably 1.3 to 2.5 times.

Hydroxylamine can be widely used as a color developer preservative, but if higher preservability is required, it has a substituent such as an alkyl group, a hydroxyalkyl group, a sulfoalkyl group, or a carboxyalkyl group. Hydroxylamine derivatives are preferred, specifically N, N-di (sulfoethyl) hydroxylamine, monomethylhydroxylamine, dimethylhydroxylamine, monoethylhydroxylamine, diethylhydroxylamine, N, N-di (carboxyethyl) hydroxylamine preferable. Among the above, N, N-di (sulfoethyl) hydroxylamine is particularly preferable. These may be used in combination with hydroxylamine, but it is preferable to use one or more in place 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, more preferably 0.04 to 0.1 mol. In the replenisher, it is preferable to contain a preservative at a concentration 1.1 to 3 times that of the mother liquor (processing tank solution), as in the case of the color developing agent.

In the color developer, sulfite is used as an anti-tarring agent for the oxide of the color developing agent. The sulfite is preferably used in the range of 0.01 to 0.05 mol per liter, particularly preferably in the range of 0.02 to 0.04 mol. In the replenisher, it is preferably used at a concentration of 1.1 to 3 times these.
The pH of the color developer is preferably in the range of 9.8 to 11.0, particularly preferably 10.0 to 10.5, and the replenisher should be set to a high value in the range of 0.1 to 1.0 from these values. preferable. In order to stably maintain such pH, known buffering agents such as carbonate, phosphate, sulfosalicylate, and borate are used.
The replenishment amount of the color developer is also expressed as 80 to 1300 mL per 1 m ² of the photosensitive material. ) Is preferable, but from the viewpoint of reducing the environmental pollution load, a smaller amount is preferable, specifically 80 to 600 mL, more preferably 80 to 400 mL.

The bromide ion concentration in the color developer is usually 0.01 to 0.06 mol per liter, but for the purpose of suppressing fog and improving discrimination while maintaining sensitivity, and improving graininess. It is preferable to set to 0.015 to 0.03 mol per liter. 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 preferable that the replenisher does not contain bromide ions.
C = A-W / V
C: Concentration of bromide ions in the color developer replenisher (mol / L)
A: Bromide ion concentration in target color developer (mol / L)
W: The amount (mole) of bromide ions eluted from the photosensitive material into the color developer when the photosensitive material of 1 m ² is color-developed.
V: Replenishment amount of color developer replenisher for 1m ² photosensitive material (L)
In addition, when the replenishment amount is reduced or when a high bromide ion concentration is set, as a method for increasing the sensitivity, 1-phenyl-3-pyrazolidone or 1-phenyl-2-methyl-2-hydroxymethyl-3-pyrazolidone is used. It is also preferable to use development accelerators such as thioether compounds typified by pyrazolidones represented by representatives and 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 are those described in JP-A-5-72694 and JP-A-5-17312, particularly 1,3-diaminopropanetetraacetic acid, JP-A-5 A ferric complex salt of the compound of Example 1 on page 7 of No. 173312 is preferred.

In order to improve the biodegradability of the bleaching agent, a compound ferric complex salt described in JP-A-4-25145, JP-A-4-268552, EP 588,289, 591,934, JP-A-6-208213 is used as a bleaching agent. It is preferable. The concentration of these bleaching agents is preferably 0.05 to 0.3 mol per liter of a solution having bleaching ability, and is preferably designed to be 0.1 to 0.15 mol for the purpose of reducing the discharge amount to the environment. Moreover, when the liquid which has bleaching ability is a bleaching liquid, it is preferable to contain 0.2-1 mol of bromide per liter, and it is preferable to contain 0.3-0.8 mol especially.
The replenisher of the solution having bleaching ability basically contains the concentration of each component calculated by the following formula. Thereby, 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 (processing tank solution) C _P : Concentration of component consumed during processing V ₁ : Replenishment having bleaching ability for 1 m ² photosensitive material Liquid replenishment volume (mL)
V ₂ : Amount brought in from the previous bath by 1m ² photosensitive material (mL)
In addition, it is preferable to contain a pH buffer in the bleaching solution, and it is particularly preferable to contain a dicarboxylic acid with little odor such as succinic acid, maleic acid, malonic acid, glutaric acid, and adipic acid. It is also preferable to use a known bleach accelerator described in JP-A-53-95630, RD No. 17129, US 3,893,858.
The bleaching solution is preferably replenished with 50 to 1000 mL of bleach replenisher per 1 m ² of the light-sensitive material, particularly preferably 80 to 500 mL, and more preferably 100 to 300 mL. Further, it is preferable to aerate the bleaching solution.

For the processing solution having fixing ability, the compounds and processing conditions described in JP-A-4-125558, page 7, lower left column, line 10 to page 8, lower right column, line 19 can be applied.
In particular, in order to improve the fixing speed and the preservability, the compounds represented by general formulas (I) and (II) of JP-A-6-301169 are incorporated into a processing solution having fixing ability alone or in combination. It is preferable. Use of sulfinic acid described in JP-A-1-224762 as well as p-toluenesulfinate is also preferable in terms of improving the preservability.

It is preferable to use ammonium as a cation from the viewpoint of improving the desilvering property in a solution having bleaching ability or a fixing ability, but it is preferable to reduce or eliminate ammonium for the purpose of reducing environmental pollution. .
In the bleaching, bleach-fixing, and fixing steps, it is particularly preferable to perform jet stirring described in JP-A-1-309059.
The replenishing amount of the replenisher in the bleach-fixing or fixing step is 100 to 1000 mL, preferably 150 to 700 mL, particularly preferably 200 to 600 mL per 1 m ² of the light-sensitive material.
In the bleach-fixing or fixing step, it is preferable to collect various silver recovery devices in-line or offline to recover silver. By installing in-line, the amount of replenishment can be reduced as a result of processing with reduced silver concentration in the liquid. It is also preferable to recover silver offline 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-pipe to be a multistage countercurrent system. From the balance with the size of the developing machine, a two-tank cascade configuration is generally efficient, and it is preferable that the ratio of the processing time in the front tank and the rear tank is in the range of 0.5: 1 to 1: 0.5. The range of 0.8: 1 to 1: 0.8 is particularly preferable.
In the bleach-fixing solution and the fixing solution, it is preferable that a free chelating agent that is not a metal complex is present from the viewpoint of improving the preservability, but as these chelating agents, the biodegradability described for the bleaching solution is used. It is preferred to use a chelating agent.

  Regarding the water washing and stabilization step, the contents described in JP-A-4-125558, page 12, lower right column, line 6 to page 13, lower right column, line 16 can be preferably applied. In particular, in place of formaldehyde, azolylmethylamines described in EP 504,609 and 519,190 and N-methylolazoles described in JP-A-4-362943 are used in place of formaldehyde, or a magenta coupler is bisected. It is preferable to use a surfactant solution that does not contain an image stabilizer such as formaldehyde from the viewpoint of maintaining the working environment.

  In order to reduce the adhesion of dust to the magnetic recording layer applied to the photosensitive material, a stabilizer 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 per 1 m ² of the photosensitive material, particularly 100 to 500 mL, and more preferably 150 to 300 mL, both for ensuring washing function and stabilizing waste and reducing waste solution for environmental conservation. To a preferable range. In such a replenishing amount, known methods such as thiabendazole, 1,2-benzisothiazolin-3-one, 5-chloro-2-methylisothiazolin-3-one are used to prevent the growth of bacteria and sputum. It is preferable to use water deionized with an antifungal agent, an antibiotic such as gentamicin, an ion exchange resin or the like. It is more effective to use deionized water together with antibacterial agents and antibiotics.
In addition, the amount of replenishment of the water in the water washing or stabilizing liquid tank is reduced by performing reverse osmosis membrane treatment described in JP-A-3-46652, 3-53246, 3-355542, 3-121448, and 3-12030. The reverse osmosis membrane in this case is preferably a low pressure reverse osmosis membrane.

In the processing in the present invention, it is particularly preferable to carry out the evaporation correction of the processing liquid disclosed in JIII Journal of Technical Disclosure No. 94-4992. In particular, a method of correcting using the temperature and humidity information of the developing machine installation environment based on (Formula-1) on the second page is preferable. The water used for evaporation correction is preferably collected from a replenishment tank for washing, in which case deionized water is preferably used as the washing replenishment water.
As the treating agent used in the present invention, those described in the third page, right column, line 15 to page 4, left column, line 32 of the above-mentioned published technical report are preferable. Moreover, as a developing machine used for this, the film processor described in the 22nd line to the 28th line of the right column of the 3rd page is preferable.
Specific examples of a processing agent, an automatic processor, and an evaporation correction method that are preferable for carrying out the present invention are described from the fifth page, right column, line 11 to the seventh page, right column, last line of the above published technical bulletin. .

  The treatment agent used in the present invention may be supplied in any form, such as a solution in the concentration or concentrated form of the working solution, or granules, powders, tablets, pastes, and emulsions. Examples of such treatment agents include a liquid agent contained in a container having low oxygen permeability in JP-A-63-17453, powders or granules in vacuum packaging in JP-A-4-19655 and 4-230748, 4- 221951 discloses granules containing a water-soluble polymer, JP-A-51-61837, JP-A-6-102628 discloses a tablet, and JP-A-57-500485 discloses a paste-like treatment agent, both of which are preferred. Although it can be used, it is preferable to use a liquid prepared in advance at a concentration in the state of use from the viewpoint of convenience during use.

In a container for storing these treatment agents, polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, nylon or the like is used alone or as a composite material. These are selected according to the required level of oxygen permeability. For an easily oxidized liquid such as a color developer, a low oxygen permeable material is preferable, and specifically, polyethylene terephthalate or a composite material of polyethylene and nylon is preferable. These materials have a thickness of 500 to 1500 μm, are used for containers, and preferably have an oxygen permeability of 20 mL / m ² · 24 hrs · atm or less.

Next, the color reversal film processing solution used in the present invention will be described.
Regarding processing for color reversal film, publicly known technology No. 6 (April 1, 1991) published by Aztec Co., Ltd., page 1, line 5 to page 10, line 5, and page 15, line 8 to page 24, page 2 The contents are described in detail in the lines, and any of the contents can be preferably applied.

In the processing of the color reversal film, the image stabilizer is contained in the adjustment bath or the final bath. Examples of such image stabilizers include formaldehyde sodium bisulfite and N-methylol azoles in addition to formalin. From the viewpoint of the working environment, sodium formaldehyde bisulfite or N-methylol azoles are preferred, and N-methylol is preferred. As the azole, N-methyloltriazole is particularly preferable. The contents relating to the color developer, bleaching solution, fixing solution, washing water and the like described in the processing of the color negative film can be preferably applied to the processing of the color reversal film.
Examples of preferable processing agents for color reversal films including the above contents include East-6 Kodak E-6 processing agent and Fuji Photo Film Co., Ltd. CR-56 processing agent.

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 liquid 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, etc. can be used. Co-coated ferromagnetic iron oxides such as Co-coated γFe ₂ O ₃ are preferred. The shape may be any of needle shape, rice grain shape, spherical shape, cubic shape, plate shape and the like. Preferably at least 20 m ² / g in S _BET is the specific surface area, and particularly preferably equal to or greater than 30 m ² / g.

The saturation magnetization (σs) of the ferromagnetic material is preferably 3.0 × 10 ^{4 to} 3.0 × 10 ⁵ A / m, and particularly preferably 4.0 × 10 ^{4 to} 2.5 × 10 ⁵ A / m. The ferromagnetic particles may be subjected to a surface treatment with silica and / or alumina or an organic material. Further, the magnetic particles may be treated with a silane coupling agent or a titanium coupling agent on the surface thereof as described in JP-A-6-61032. Also, magnetic particles having a surface coated with inorganic or organic substances as described in JP-A-4-59911 and 5-81652 can 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, a natural product polymer (cellulose) described in JP-A-4-19569. Derivatives, sugar derivatives, etc.) and mixtures thereof. The resin has a Tg of -40 ° C to 300 ° C and a mass average molecular weight of 20,000 to 1,000,000. Examples thereof include vinyl copolymers, cellulose diacetate, cellulose triacetate, cellulose acetate propionate, cellulose derivatives such as cellulose acetate butyrate, cellulose tripropionate, acrylic resins, and polyvinyl acetal resins, and gelatin is also preferable. Cellulose di (tri) acetate is particularly preferable. The binder can be cured by adding an epoxy-based, aziridine-based, or isocyanate-based crosslinking agent. Examples of isocyanate-based crosslinking agents include tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, and the like, and reaction products of these isocyanates with polyalcohol (for example, tolylene diene). Reaction products of 3 mol of isocyanate and 1 mol of trimethylolpropane), polyisocyanates formed by condensation of these isocyanates, and the like, for example, are described in JP-A-6-59357.

As a method for dispersing the above-mentioned magnetic substance in the binder, a kneader, a pin type mill, an annular type mill, etc. are 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, more preferably 0.3 μm to 3 μm. The mass ratio of the magnetic particles to the binder is preferably 0.5: 100 to 60: 100, more preferably 1: 100 to 30: 100. The coating amount of the magnetic particles is 0.005 to 3 g / m ² , preferably 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, more preferably 0.03 to 0.20, and particularly preferably 0.04 to 0.15. The magnetic recording layer can be provided on the entire surface or in a stripe shape on the back surface of the photographic support by coating or printing. As a method for applying the magnetic recording layer, an air doctor, blade, air knife, squeeze, impregnation, reverse roll, transfer roll, gravure, kiss, cast, spray, dip, bar, extraction, etc. can be used. The coating solution described in 341436 and the like is preferable.

  The magnetic recording layer may have functions such as lubricity improvement, curl adjustment, antistatic, adhesion prevention, head polishing, etc., or another functional layer may be provided to give these functions. An abrasive of non-spherical inorganic particles in which at least one kind of particles has a Mohs hardness of 5 or more is 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. The surface of these abrasives may be 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 that for the magnetic recording layer is preferable. Photosensitive materials having a magnetic recording layer are described in US 5,336,589, 5,250,404, 5,229,259, 5,215,874, and EP 466,130.

  Next, the polyester support preferably used in the present invention will be described. For details including the photosensitive material, treatment, cartridge, and examples described later, the published technical report, public technical number 94-6023 (Invention Association; 1994.3.15). .)It is described in. The polyester used in the present invention is formed with diol and aromatic dicarboxylic acid as essential components, and 2,6-, 1,5-, 1,4- and 2,7-naphthalenedicarboxylic acid, terephthalic as aromatic dicarboxylic acid Examples of the acid, isophthalic acid, phthalic acid, and diol include diethylene glycol, triethylene glycol, cyclohexanedimethanol, bisphenol A, and bisphenol. Examples of this polymer include homopolymers such as polyethylene terephthalate, polyethylene naphthalate, and polycyclohexanedimethanol terephthalate. Particularly preferred is a polyester containing 50 mol% to 100 mol% of 2,6-naphthalenedicarboxylic acid. Of these, polyethylene-2,6-naphthalate is particularly preferred. The average molecular weight range is about 5,000 to 200,000. The Tg of the polyester of the present invention is 50 ° C. or higher, more preferably 90 ° C. or higher.

Next, the polyester support is heat-treated 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 make it difficult to cause curl. The heat treatment may be performed at a constant temperature within this temperature range, or may be performed while cooling. This heat treatment time is 0.1 hours to 1500 hours, more preferably 0.5 hours to 200 hours. The heat treatment of the support may be performed in a roll shape or may be performed while being conveyed in a web shape. The surface may be improved by providing irregularities on the surface (for example, applying conductive inorganic fine particles such as SnO ₂ and Sb ₂ O ₅ ). It is also desirable to devise measures such as preventing knurling of the core part by imparting knurls to the end part and slightly raising only the end part. These heat treatments may be carried out at any stage after forming the support, after the surface treatment, after applying the back layer (antistatic agent, slip agent, etc.) and after applying the undercoat. Preferred is after application of the antistatic agent.
This polyester may be kneaded with an ultraviolet absorber. In order to prevent light piping, the purpose can be achieved by kneading commercially available dyes or pigments for polyester such as Mitsubishi Kasei's Diaresin and Nippon Kayaku's Kayaset.

  Next, in the present invention, it is preferable to perform a surface treatment in order to adhere the support and the light-sensitive material constituting layer. Examples of the surface activation treatment include chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, and ozone oxidation treatment. Among the surface treatments, ultraviolet irradiation treatment, flame treatment, corona treatment, and glow treatment are preferable.

Next, the primer method will be described. It may be a single layer or two or more layers. As a binder for the undercoat layer, starting from a copolymer starting from a monomer selected from vinyl chloride, vinylidene chloride, butadiene, methacrylic acid, acrylic acid, itaconic acid, maleic anhydride, etc. Examples include polyethyleneimine, epoxy resin, grafted gelatin, nitrocellulose, and gelatin. Examples of compounds that swell the support include resorcin and p-chlorophenol. For the undercoat layer, as a gelatin hardener, chromium salts (such as chromium alum), aldehydes (formaldehyde, glutaraldehyde, etc.), isocyanates, active halogen compounds (2,4-dichloro-6-hydroxy-S-triazine) Etc.), epichlorohydrin resins, active vinyl sulfone compounds and the like. SiO ₂ , TiO ₂ , inorganic fine particles or polymethyl methacrylate 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, carboxylates, polymers containing sulfonates, cationic polymers, and ionic surfactant compounds.
Most preferred as the antistatic agent is at least one selected from ZnO, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , SiO ₂ , MgO, BaO, MoO ₃ , V ₂ O _5. The volume resistivity of the seed is 10 ⁷ Ω · cm or less, more preferably 10 ⁵ Ω · cm or less. The particle size is 0.001 to 1.0 μm. Crystalline metal oxide or composite oxide thereof (Sb, P, B, In , S, Si, C, etc.), and also sol-like metal oxides or composite oxides thereof.

The addition amount to the photographic material, 5 to 500 mg / m ² is preferably 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 1/300 to 100/1, more preferably 1/100 to 100/5.

The light-sensitive material of the present invention preferably has slipperiness. The slip agent-containing layer is preferably used for both the photosensitive layer surface and the back surface. A preferable slip property is a dynamic friction coefficient of 0.25 or less and 0.01 or more. The measurement at this time represents the value when transported at 60 cm / min for a stainless steel ball having a diameter of 5 mm (25 ° C., 60% RH). In this evaluation, even if the counterpart material is replaced with the photosensitive layer surface, the value is almost the same.
Examples of slip agents that can be used in the present invention include polyorganosiloxanes, higher fatty acid amides, higher fatty acid metal salts, esters of higher fatty acids and higher alcohols, and examples of polyorganosiloxanes include polydimethylsiloxane, polydiethylsiloxane, Styrylmethylsiloxane, polymethylphenylsiloxane, and the like can be used. As the additive layer, the outermost layer of the emulsion layer or the back layer is preferable. In particular, polydimethylsiloxane and esters having a long chain alkyl group are preferred.

  The light-sensitive material of the present invention preferably contains a matting agent. The matting agent may be either the emulsion surface or the back surface, 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 is preferably a combination of both. For example, polymethyl methacrylate, poly (methyl methacrylate / 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, the particle size distribution is preferably narrow, and 90% or more of the total number of particles is preferably contained between 0.9 and 1.1 times the average particle size. It is also preferable to add fine particles of 0.8 μm or less at the same time in order to improve the matting property, for example, polymethyl methacrylate (0.2 μm), poly (methyl methacrylate / methacrylic acid = 9/1 (molar ratio), 0.3 μm)), Examples thereof include polystyrene particles (0.25 μm) and colloidal silica (0.03 μm).

Next, the film cartridge used in the present invention will be described. The main material of the cartridge used in the present invention may be metal or synthetic plastic.
Preferred plastic materials are polystyrene, polyethylene, polypropylene, polyphenyl ether and the like. Furthermore, the cartridge of the present invention may contain various antistatic agents, and carbon black, metal oxide particles, nonions, anions, cations and betaine surfactants or polymers can be preferably used. These antistatic cartridges are described in JP-A Nos. 1-312537 and 1-312538. In particular, the resistance at 25 ° C. and 25% RH is preferably 10 ¹² Ω or less. Usually, plastic patrone is manufactured using a plastic kneaded with carbon black or pigment to provide light shielding. The patrone size may be the same as the current 135 size. To reduce the size 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 cartridge case is 30 cm ³ or less, preferably 25 cm ³ or less. The mass of the plastic used for the cartridge and the cartridge case is preferably 5 to 15 g.

  Further, a cartridge that feeds a film by rotating a spool may be used in the present invention. Alternatively, the film leading end may be housed in the cartridge main body, and the film leading end may be sent out from the port portion of the cartridge by rotating the spool shaft in the film feeding direction. These are disclosed in US 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 that has been developed. Further, the raw film and the developed photographic film may be stored in the same new cartridge, or may be different cartridges.

The color photographic light-sensitive material of the present invention is also suitable as a negative film for an advanced photo system (hereinafter referred to as AP system), manufactured by Fuji Photo Film Co., Ltd. A film that has been processed into an AP system format like NEXIA H (in order ISO 200/100/400) and stored in a special cartridge can be listed. These AP system cartridge films are used by being loaded into an AP system camera such as FUJIFILM's EPION series (such as EPION 300Z). The color photographic light-sensitive material of the present invention is also suitable for a lens-equipped film such as a super slim, which is a Fuji color photorun made by Fuji Film.
The film photographed by these is printed through the following process in the minilab system.
(1) Reception (taking the exposed cartridge film from the customer)
(2) Detach process (transfer film from cartridge to intermediate cartridge for development process)
(3) Film development
(4) Rear touch process (return the developed negative film back to the original cartridge)
(5) Print (C / H / P 3 type print and index print are automatically printed on color paper [preferably Fujifilm SUPER FA8])
(6) Verification / shipping (Cartridge and index print are verified by ID number and shipped together with the print)
As these systems, FUJIFILM Minilab Champion Super FA-298 / FA-278 / FA-258 / FA-238 and FUJIFILM Digital Lab System Frontier are preferred. FP922AL / FP562B / FP562B, AL / FP362B / FP362B, AL are listed as minilab champion film processors. Fuji Color Just It CN-16L and CN-16Q are recommended chemicals. Examples of printer processors include PP3008AR / PP3008A / PP1828AR / PP1828A / PP1258AR / PP1258A / PP728AR / PP728A, and recommended processing chemicals are Fujicolor Justit CP-47L and CP-40FAII. In Frontier System, Scanner & Image Processor SP-1000 and Laser Printer & Paper Processor LP-1000P or Laser Printer LP-1000W are used. The detacher used in the detach process and the rear toucher used in the rear touch process are preferably DT200 / DT100 and AT200 / AT100 manufactured by Fuji Film, respectively.

  The AP system can also be enjoyed with a photo joy system centered on Fujifilm's digital image workstation Aladdin 1000. For example, you can load Aladdin 1000 directly with developed AP system cartridge film, or input image information of negative film, positive film, and print using 35mm film scanner FE-550 or flat head scanner PE-550. Digital image data can be easily processed and edited. The data can be output as a print by a digital color printer NC-550AL using a light-fixing type thermal color printing method, a pictography 3000 using a laser exposure heat development transfer method, or by an existing laboratory equipment through a film recorder. Aladdin 1000 can also output digital information directly to a floppy (registered trademark) disk or Zip disk, or to a CD-R via a CD writer.

On the other hand, at home, you can enjoy photos on a TV simply by loading the developed AP system cartridge film into the Fujifilm photo player AP-1, and if you load it into the Fujifilm photo scanner AS-1, Image information can also be captured continuously at high speed. In addition, Fujifilm's Photo Vision FV-10 / FV-5 can be used to input film, prints or three-dimensional objects into a personal computer. Furthermore, image information recorded on a floppy (registered trademark) disk, Zip disk, CD-R or hard disk can be processed and enjoyed in various ways on a personal computer using Fujifilm's application software photo factory. In order to output high-quality prints from a personal computer, Fujifilm's digital color printer NC-2 / NC-2D with a light fixing type thermal color printing method is suitable.
To store the developed AP system cartridge film, Fuji Color Pocket Album AP-5 Pop L, AP-1 Pop L, AP-1 Pop KG or Cartridge File 16 is preferred.

Examples of the present invention are shown below. However, the present invention is not limited to this example.
Example 1
The support used in this example was produced by the following method.
1) First layer and undercoat layer A polyethylene naphthalate support having a thickness of 90 μm has a treatment atmosphere pressure of 2.66 × 10 Pa, an H ₂ O partial pressure of 75% in an atmospheric gas, a discharge frequency of 30 kHz on each of both surfaces. Glow discharge treatment was performed at an output of 2500 W and a treatment strength of 0.5 kV · A · min / m ² . On this support, a coating solution having the following composition was applied as a first layer at a coating amount of 5 mL / m ² using the bar coating method described in JP-B-58-4589.

Conductive fine particle dispersion (SnO ₂ / Sb ₂ O ₅ particle concentration 50 parts by weight 10% aqueous dispersion. Secondary aggregate with primary particle size 0.005 μm and average particle size 0.05 μm)
Gelatin 0.5 part by mass Water 49 part by mass Polyglycerol polyglycidyl ether 0.16 part by mass Poly (polymerization degree 20) oxyethylene 0.1 part by mass
Sorbitan monolaurate.

Further, after coating the first layer, it is wound around a stainless steel core having a diameter of 20 cm, and heat-treated at 110 ° C. (Tg of PEN support: 119 ° C.) for 48 hours and subjected to an annealing treatment, and then supported. A coating solution having the following composition was applied as an undercoat layer for emulsion on the side opposite to the first layer side with a bar coating method at a coating amount of 10 mL / m ² .
Gelatin 1.01 parts by mass Salicylic acid 0.30 parts by mass Resorcin 0.40 parts by mass Poly (degree of polymerization 10) oxyethylene nonylphenyl ether
0.11 parts by mass Water 3.53 parts by mass Methanol 84.57 parts by mass n-Propanol 10.08 parts by mass Furthermore, the second and third layers described later are sequentially coated on the first layer, and finally, A transparent negative magnetic recording medium with a silver halide emulsion layer was prepared by coating a color negative photosensitive material having the composition described later on the opposite side of the support.

2) Second layer (transparent magnetic recording layer)
(i) Dispersion of magnetic substance Co-coated γ-Fe ₂ O ₃ magnetic substance (average major axis length: 0.25 μm, S _BET : 39 m ² / g, Hc: 6.56 × 10 ⁴ A / m, σ S: 77.1 Am ² / kg, σr: 37.4 Am ² / kg) 1100 parts by mass, 220 parts by mass of water and silane coupling agent [3- (poly (degree of polymerization 10) oxyethynyl) oxypropyl trimethoxysilane] 165 parts by mass Part was added and kneaded well with an open kneader for 3 hours. This coarsely dispersed viscous liquid was dried at 70 ° C. for one day and night to remove water, and then heat-treated at 110 ° C. for 1 hour to produce surface-treated magnetic particles.

Furthermore, it knead | mixed again with the following prescription for 4 hours with the open kneader.
Surface-treated magnetic particles 855 g
Diacetylcellulose 25.3 g
Methyl ethyl ketone 136.3 g
Cyclohexanone 136.3 g
Furthermore, the following formulation was finely dispersed in a sand mill (1 / 4G sand mill) at 2000 rpm for 4 hours. As media, 1 mmφ glass beads were used.

45 g of the above kneaded liquid
Diacetylcellulose 23.7 g
Methyl ethyl ketone 127.7 g
Cyclohexanone 127.7 g.

Furthermore, the magnetic substance containing intermediate solution was produced with the following prescription.
(ii) Production of magnetic substance-containing intermediate liquid 674 g of the above magnetic substance fine dispersion
Diacetylcellulose solution 24280 g
(Solid content: 4.34%, solvent: methyl ethyl ketone / cyclohexanone = 1/1)
Cyclohexanone 46 g
These were mixed and then stirred with a disper to produce a “magnetic substance-containing intermediate solution”.

An α-alumina abrasive dispersion of the present invention was prepared according to the following formulation.
(A) Sumicorundum AA-1.5 (average primary particle size 1.5 μm, specific surface area 1.3 m ² / g)
Preparation of particle dispersion Sumiko Random AA-1.5 152g
Silane coupling agent KBM903 (manufactured by Shin-Etsu Silicone) 0.48g
Diacetylcellulose solution 227.52 g
(Solid content 4.5%, solvent: methyl ethyl ketone / cyclohexanone = 1/1)
With the above formulation, fine dispersion was performed at 800 rpm for 4 hours using a ceramic-coated sand mill (1/4 G sand mill). As the media, 1 mmφ zirconia beads were used.
(B) Colloidal silica particle dispersion (fine particles)
“MEK-ST” manufactured by Nissan Chemical Co., Ltd. was used.
This is a dispersion of colloidal silica having an average primary particle diameter of 0.015 μm using methyl ethyl ketone as a dispersion medium, and the solid content is 30%.

(iii) Preparation of second layer coating solution 19053 g of the above magnetic substance-containing intermediate solution
Diacetylcellulose solution 264 g
(Solid content 4.5%, solvent: methyl ethyl ketone / cyclohexanone = 1/1)
Colloidal silica dispersion “MEK-ST” [dispersion b] 128 g
(Solid content 30%)
AA-1.5 dispersion [dispersion a] 12 g
Millionate MR-400 (manufactured by Nippon Polyurethane Co., Ltd.) Diluent 203 g
(Solid content 20%, diluent solvent: methyl ethyl ketone / cyclohexanone = 1/1)
Methyl ethyl ketone 170 g
Cyclohexanone 170 g
The coating solution obtained by mixing and stirring the above was coated with a wire bar so that the coating amount was 29.3 mL / m ² . Drying was performed at 110 ° C. The thickness of the magnetic layer after drying was 1.0 μm.

3) Third layer (layer containing higher fatty acid ester slip agent)
(i) Preparation of Sliding Agent Dispersion Solution The following solution A was heated and dissolved at 100 ° C., added to the solution A, and then dispersed with a high-pressure homogenizer to prepare a dispersing agent dispersion solution.

Liquid A The following compound 399 parts by mass C ₆ H ₁₃ CH (OH) (CH ₂ ) ₁₀ COOC ₅₀ H ₁₀₁
The following compound 171 parts by mass nC ₅₀ H ₁₀₁ O (CH ₂ CH ₂ O) ₁₆ H
Cyclohexanone 830 parts by mass Liquid I Cyclohexanone 8600 parts by mass
(ii) Preparation of spherical inorganic particle dispersion A spherical inorganic particle dispersion [c1] was prepared according to the following formulation.

Isopropyl alcohol 93.54 parts by mass Silane coupling agent KBM903 (manufactured by Shin-Etsu Silicone)
Compound _{1-1: (CH 3 O) 3} Si- (CH 2) 3 -NH 2)
5.53 parts by mass Compound 1 2.93 parts by mass

Seahosta KEP50 88.00 parts by mass (amorphous spherical silica, average particle size 0.5 μm, manufactured by Nippon Shokubai Co., Ltd.)
After stirring for 10 minutes with the above formulation, the following is added.
Diacetone alcohol 252.93 parts by mass The above liquid was dispersed for 3 hours using an ultrasonic homogenizer “SONIFIER450 (manufactured by BRANSON Co., Ltd.)” while cooling with ice and stirring to complete a spherical inorganic particle dispersion c1.

(iii) Preparation of spherical organic polymer particle dispersion A spherical organic polymer particle dispersion [c2] was prepared according to the following formulation.
XC99-A8808 (manufactured by Toshiba Silicone Co., Ltd., spherical crosslinked polysiloxane particles, average particle size 0.9 μm) 60 parts by mass Methyl ethyl ketone 120 parts by mass Cyclohexanone 120 parts by mass (solid content 20%, solvent: methyl ethyl ketone / cyclohexanone = 1/1 )
While cooling with ice and stirring, the mixture was dispersed for 2 hours using an ultrasonic homogenizer “SONIFIER450 (manufactured by BRANSON)” to complete a spherical organic polymer particle dispersion c2.

(iv) Production of third layer coating solution The above was added to 542 g of the above-mentioned slip agent dispersion stock solution to prepare a third layer coating solution.
Diacetone alcohol 5950 g
Cyclohexanone 176 g
Ethyl acetate 1700 g
Seahosta KEP50 dispersion [c1] 53.1 g
300 g of the above spherical organic polymer particle dispersion [c2]
FC431 2.65 g
(3M Co., Ltd., solid content 50%, solvent: ethyl acetate)
BYK310 5.3 g
(BYK Chemi Japan Co., Ltd., solid content 25%)
The third layer coating solution was applied onto the second layer at a coating amount of 10.35 mL / m ² , dried at 110 ° C., and further dried at 97 ° C. for 3 minutes.

4) Coating of photosensitive layer Next, on the opposite side to the support of the back layer obtained above, each layer having the following composition was applied in layers to prepare a color negative film sample 101.
(Composition of photosensitive layer)
The number corresponding to each component indicates the coating amount expressed in g / m ² unit, and for silver halide, the coating amount in terms of silver.

(Sample 101)
First layer (first antihalation layer)
Black colloidal silver Silver 0.114
0.07 μm silver iodobromide emulsion Silver 0.01
Gelatin 0.910
ExM-1 0.060
ExC-1 0.002
ExC-3 0.002
Cpd-2 0.001
F-8 0.001
HBS-1 0.050
HBS-2 0.002.

Second layer (second antihalation layer)
Black colloidal silver Silver 0.055
Gelatin 0.413
ExF-1 0.002
F-8 0.001
Solid disperse dye ExF-7 0.120
HBS-1 0.076.

Third layer (intermediate layer)
ExC-2 0.050
Cpd-1 0.090
Polyethyl acrylate latex 0.200
HBS-1 0.100
Gelatin 0.700.

4th layer (low sensitivity red sensitive emulsion layer)
Em-D Silver 0.510
Em-P Silver 0.322
ExC-1 0.193
ExC-2 0.010
ExC-3 0.073
ExC-4 0.124
ExC-5 0.010
ExC-6 0.007
ExC-8 0.053
ExC-9 0.020
Cpd-2 0.020
Cpd-4 0.025
Cpd-7 0.015
UV-2 0.047
UV-3 0.086
UV-4 0.018
HBS-1 0.240
HBS-5 0.038
Gelatin 0.994.

5th layer (medium sensitivity red emulsion layer)
Em-B Silver 0.485
Em-C Silver 0.460
ExC-1 0.151
ExC-2 0.076
ExC-3 0.023
ExC-4 0.100
ExC-5 0.023
ExC-6 0.010
ExC-8 0.016
ExC-9 0.005
Cpd-2 0.036
Cpd-4 0.028
Cpd-7 0.020
HBS-1 0.120
Gelatin 0.890.

6th layer (high-sensitivity red-sensitive emulsion layer)
Em-A Silver 1.115
ExC-1 0.240
ExC-3 0.038
ExC-6 0.025
ExC-8 0.110
ExC-9 0.022
ExY-3 0.010
Cpd-2 0.066
Cpd-4 0.079
Cpd-7 0.030
HBS-1 0.329
HBS-2 0.120
Gelatin 1.200.

7th layer (intermediate layer)
Cpd-1 0.094
Cpd-6 0.369
Solid disperse dye ExF-4 0.030
HBS-1 0.049
Polyethyl acrylate latex 0.088
Gelatin 0.886.

Eighth layer (a layer that gives a layered effect to the red-sensitive layer)
Em-J Silver 0.170
Em-K Silver 0.175
Cpd-4 0.030
ExM-2 0.149
ExM-3 0.013
ExY-1 0.012
ExY-4 0.036
ExC-7 0.026
HBS-1 0.218
HBS-3 0.003
HBS-5 0.030
Gelatin 0.614.

9th layer (low sensitivity green emulsion layer)
Em-H Silver 0.323
Em-G Silver 0.345
Em-I Silver 0.080
ExM-2 0.374
ExM-3 0.045
ExY-1 0.018
ExC-7 0.007
HBS-1 0.098
HBS-3 0.010
HBS-4 0.074
HBS-5 0.544
Cpd-5 0.010
Cpd-7 0.020
Gelatin 1.460.

10th layer (medium sensitive green sensitive emulsion layer)
Em-F Silver 0.452
ExM-2 0.066
ExM-3 0.026
ExY-3 0.005
ExC-6 0.013
ExC-7 0.011
ExC-8 0.010
HBS-1 0.064
HBS-3 0.002
HBS-4 0.020
HBS-5 0.020
Cpd-5 0.004
Cpd-7 0.010
Gelatin 0.438.

11th layer (high sensitivity green emulsion layer)
Em-E silver 0.790
ExC-6 0.003
ExC-8 0.010
ExM-1 0.018
ExM-2 0.030
ExM-3 0.033
ExY-3 0.007
Cpd-3 0.004
Cpd-4 0.007
Cpd-5 0.010
Cpd-7 0.020
HBS-1 0.144
HBS-3 0.003
HBS-4 0.020
HBS-5 0.037
Polyethyl acrylate latex 0.099
Gelatin 0.935.

12th layer (yellow filter layer)
Cpd-1 0.098
Solid disperse dye ExF-2 0.070
Solid disperse dye ExF-5 0.010
Oil-soluble dye ExF-6 0.010
HBS-1 0.049
Gelatin 0.626.

13th layer (low sensitivity blue-sensitive emulsion layer)
Em-O silver 0.120
Em-M Silver 0.310
Em-N Silver 0.240
ExC-1 0.020
ExC-7 0.015
ExY-1 0.002
ExY-2 0.889
ExY-4 0.056
Cpd-2 0.102
Cpd-3 0.004
HBS-1 0.225
HBS-5 0.070
Gelatin 1.540.

14th layer (high sensitivity blue-sensitive emulsion layer)
Em-L Silver 0.780
ExY-2 0.225
ExY-3 0.008
ExY-4 0.070
Cpd-2 0.074
Cpd-3 0.001
Cpd-7 0.030
HBS-1 0.120
Gelatin 0.660.

15th layer (first protective layer)
0.07 μm silver iodobromide emulsion Silver 0.305
UV-1 0.211
UV-2 0.132
UV-3 0.198
UV-4 0.026
UV-5 0.200
F-11 0.009
S-1 0.086
HBS-1 0.175
HBS-4 0.050
Gelatin 2.056.

16th layer (second protective layer)
H-1 0.400
B-1 (diameter 1.7 μm) 0.050
B-2 (diameter 1.7 μm) 0.150
B-3 0.050
S-1 0.200
Gelatin 0.750.

  Furthermore, in order to improve the preservability, processability, pressure resistance, antifungal / antibacterial properties, antistatic properties and coatability as appropriate for each layer, W-1 to W-11, B-4 to B-6, F-1 thru | or F-19 and lead salt, platinum salt, iridium salt, and rhodium salt are contained.

Preparation of Dispersion of Organic Solid Disperse Dye ExF-2 of the 12th layer was dispersed by the following method.
ExF-2 wet cake (including 17.6% by weight water) 2.800 kg
Sodium octylphenyldiethoxymethanesulfonate (31 mass% aqueous solution) 0.376 kg
F-15 (7% aqueous solution) 0.011 kg
W-11 (15% aqueous solution) 6.100 kg
1.020 kg of water
Total 10.310 kg.

(Adjusted to pH = 7.2 with NaOH)
After the slurry having the above composition is roughly dispersed by stirring with a dissolver, it is dispersed using an agitator mill LMK-4 at a peripheral speed of 10 m / s, a discharge rate of 0.6 kg / min, and a filling rate of zirconia beads having a diameter of 0.3 mm of 80%. Dispersion was performed until the absorbance ratio of the liquid reached 0.22, to obtain a solid fine particle dispersion. The average particle size of the fine dye particles was 0.10 μm.

Similarly, solid dispersions of ExF-4 and ExF-7 were obtained. The average particle diameters of the fine dye particles were 0.28 μm and 0.49 μm, respectively. ExF-5 was dispersed by the microprecipitation dispersion method described in Example 1 of European Patent No. 549,489A. The average particle size was 0.06 μm.

  In Table 1, emulsions A to C are added with an optimal amount of spectral sensitizing dyes 1 to 3, and are optimally gold sensitized, sulfur sensitized, and selenium sensitized. Emulsions E to G are added with an optimum amount of spectral sensitizing dyes 4 to 6, and are optimally gold sensitized, sulfur sensitized, and selenium sensitized. Emulsion J is added with an optimal amount of spectral sensitizing dyes 7 and 8, and is optimally gold sensitized, sulfur sensitized and selenium sensitized. Emulsion L is added with an optimal amount of spectral sensitizing dyes 9 to 11 and optimally gold sensitized, sulfur sensitized, and selenium sensitized. Emulsion O is added with an optimal amount of spectral sensitizing dyes 10 to 12, and is optimally gold sensitized and sulfur sensitized. Emulsions D, H, I, K, M, and N are added with an optimal amount of spectral sensitizing dyes listed in Table 2, and are optimally gold sensitized, sulfur sensitized, and selenium sensitized.

Emulsions A, B, C, E, and F are prepared by using silver iodobromide ultrafine particles using a stirring device described in JP-A-10-43570. Emulsions D, P, G, and H were prepared by changing the grain preparation conditions, dye type, amount, and the like from the preparation method of Example 1 emulsion b of Japanese Patent Application No. 2001-248120. In emulsions A to O, compound F-9 was appropriately added during chemical sensitization.

The sensitizing dyes listed in Table 2 are shown below.

For the preparation of tabular grains, low molecular weight gelatin is used according to the examples described in JP-A-1-158426.
Emulsions A to K contain optimum amounts of Ir and Fe.
Emulsions L to O are reduction sensitized during grain preparation.
When tabular grains are used with a high-voltage electron microscope, dislocation lines as described in JP-A-3-237450 are observed.
Emulsions A to C and J were introduced with dislocations using an iodide ion releasing agent according to the examples described in JP-A-6-117872.
In Emulsion E, dislocations were introduced using silver iodide fine grains prepared immediately before addition in another chamber having a magnetic coupling induction type stirrer described in JP-A-10-43570.

The compounds used for each layer are shown below.

The above silver halide color photographic light-sensitive material is referred to as Sample 101.
Sample 101 was exposed for 1/100 second through a gelatin filter SC-39 manufactured by FUJIFILM Corporation and a continuous wedge.

(Preparation of samples 102 to 113)
The sample 101 was prepared in the same manner as the sample 101 except that one compound of the present invention was added to the sixth layer, the eleventh layer, and the fourteenth layer of the sample 101 as shown in Table 3.

The exposed sample was processed by the method described below.
(Processing method)
Process Processing time Processing temperature Color development 3 minutes 15 seconds 38 ° C
White 3 minutes 00 seconds 38 ℃
Washing with water 30 seconds 24 ℃
3 minutes 00 seconds 38 ℃
Washing with water (1) 30 seconds 24 ℃
Washing with water (2) 30 seconds 24 ℃
Stable 30 seconds 38 ℃
Drying 4 minutes 20 seconds 55 ° C.

Next, the composition of the treatment liquid will be described.
(Color developer) (Unit: g)
Diethylenetriaminepentaacetic acid 1.0
1-hydroxyethylidene-1,1-diphosphonic acid 2.0
Sodium sulfite 4.0
Potassium carbonate 30.0
Potassium bromide 1.4
Potassium iodide 1.5mg
Hydroxylamine sulfate 2.4
4- [N-ethyl-N- (β-hydroxyethyl) amino]-
2-Methylaniline sulfate 4.5
Add water and add 1.0L
pH (adjusted with potassium hydroxide and sulfuric acid) 10.05.

(Bleaching solution) (Unit: g)
Ethylenediaminetetraacetic acid sodium ferric acid trihydrate 100.0
Ethylenediaminetetraacetic acid disodium salt 10.0
3-mercapto-1,2,4-triazole 0.03
Ammonium bromide 140.0
Ammonium nitrate 30.0
Aqueous ammonia (27%) 6.5 mL
Add water and add 1.0L
pH (adjusted with aqueous ammonia and nitric acid) 6.0.

(Fixing solution) (Unit: g)
Ethylenediaminetetraacetic acid disodium salt 0.5
Ammonium sulfite 20.0
Ammonium thiosulfate aqueous solution (700 g / L)
295.0 mL
Acetic acid (90%) 3.3
Add water and add 1.0L
pH (adjusted with aqueous ammonia and nitric acid) 6.7.

(Stabilizer) (Unit: g)
p-nonylphenoxypolyglycidol (average glycidol polymerization degree 10) 0.2
Ethylenediaminetetraacetic acid 0.05
1,2,4-triazole 1.3
1,4-bis (1,2,4-triazol-1-ylmethyl)
Piperazine 0.75
Hydroxyacetic acid 0.02
Hydroxyethyl cellulose 0.1
(Daicel Chemical HEC SP-2000)
1,2-benzisothiazolin-3-one 0.05
Add water and add 1.0L
pH 8.5.

The sensitivity of the red-sensitive layer, the green-sensitive layer, and the blue-sensitive layer is indicated by the logarithm of the reciprocal of the exposure amount that gives the minimum density +0.2 for the cyan, magenta, and yellow color image densities, respectively.
Graininess was evaluated by determining the RMS granularity of cyan, magenta, and yellow color images at a fog + 0.2 density. The relative value when the sample 101 is 100 is shown.
In order to evaluate a substantial increase in sensitivity, if the RMS granularity changes with an increase in sensitivity, the amount of ExY-3 in the sixth, eleventh, and fourteenth layers is adjusted so that the RMS granularity matches. And compared.

  As described above, it is clear that the method of the present invention is an excellent method for obtaining an image with high sensitivity without impairing the graininess.

Claims (1)

A silver halide color photographic light-sensitive material comprising a compound represented by the following general formula (1):
General formula (1)

In general formula (1), R ₁ represents an alkyl group. Z ₁ and Z ₂ represent a nitrogen atom or —C (R ₂ ) ═, and when Z ₁ represents a nitrogen atom, Z ₂ represents —C (R ₂ ) ═, and Z ₂ represents a nitrogen atom. , Z ₁ represents —C (R ₂ ) ═, R ₂ represents a group represented by the following general formula (2), and Y represents an arylthio group.
General formula (2)

In General Formula (2), R ₃ represents a substituent, j represents an integer of 0 to 4, and EWG represents an alkoxycarbonyl group, a carbamoyl group, a cyano group, a nitro group, an alkylsulfonyl group, and a sulfamoyl group.