JP2001125231A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material improved in fastness and stain of a colored image, fogging and low contrast owing to an aged emulsion, preservable property of a latent image, aged color developing property, etc. SOLUTION: This silver halide photographic sensitive material contains a compound shown by general formula 1. In the general formula 1, R1, R2 and R3 are each a halogen atom or an alkyl, aryl, heterocyclic, cyano, hydroxy, nitro, carboxyl, sulfo, amino, alkoxy, aryloxy, acylamino, alkylamino, anilino, ureido, alkylthio, arylthio, alkoxycarbonylamino, sulfonamido, carbamoyl, sulfamoyl, sulfonyl, alkoxycarbonyl, oxyheterocyclic, azo, acyloxy, carbamoyloxy, silyloxy, aryloxycarbonylamino, imido, sulfinyl, aryloxycarbonyl, or acyl group; k and n are each an integer of 0-5; m is an integer of 0-4.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a silver halide photographic material. More specifically, it relates to a silver halide photographic material using a high-boiling organic solvent having excellent solubility, dispersibility, dispersion stability, etc., which has improved poor coloring properties over time and deterioration of storage stability of emulsions and latent images. .

[0002]

2. Description of the Related Art Photographically useful compounds which are conventionally hardly soluble in water are dissolved in a suitable oil-forming agent, that is, a high-boiling organic solvent, and dispersed in a hydrophilic organic colloid solution represented by gelatin in the presence of a surfactant. And used in a hydrophilic organic colloid layer. At this time, phthalic acid ester compounds and phosphoric acid ester compounds are generally used as the high boiling point organic solvent.

[0003] High-boiling organic solvents are required to have the following broad performances. Excellent solubility of photographically useful compounds, affinity for gelatin, dispersibility, dispersion stability, etc. Do not reduce the reactivity of the photographically useful compound (such as the color forming properties of couplers and the redox reactivity of redox compounds such as color mixing inhibitors). The ability to optimally adjust the hue of the dye formed by the color reaction. Excellent chemical stability of the high boiling organic solvent itself. Do not accelerate the decomposition of the dispersed photographically useful compound. Do not promote the fading of the formed dye to light, humidity and heat. A phenomenon in which a photographically useful compound contained in a photosensitive material or a compound present in a processing solution and remaining in the photosensitive material after processing is decomposed and colored by light, humidity, and heat (stain).
Do not promote. Do not degrade the storage stability of emulsions and latent images. Inexpensive. It is easy to obtain.

[0004] Phosphoric acid ester-based high-boiling organic solvents satisfy these properties, but the conventional phosphoric acid ester-based high-boiling organic solvents have various unsatisfactory points. In particular, there has been a problem that the color developing property of the coupler is reduced, the softening is caused, and the storage stability of the emulsion under wet heat conditions is deteriorated due to the movement of the high boiling point organic solvent in the light-sensitive material over time. Movement over time can be suppressed by using a high-boiling organic solvent having a large molecular weight and high hydrophobicity.However, a high-boiling organic solvent having a large molecular weight has a problem in that the reactivity of a photographically useful compound such as coupler coloring is reduced. However, it was difficult to achieve both diffusivity and reactivity.

As a result of diligent studies of phosphate compounds having a large molecular weight, the present inventors have found that bis-type aryl phosphate ester-based high-boiling organic solvents having a specific structure can achieve both diffusion resistance and reactivity. The present inventors have found that all the properties required as a high-boiling organic solvent for materials are satisfied, and have completed the present invention.

Here, the prior art will be described. JP-A-2-125254, 2-282250, 5-
313327, JP-A-61-200538, 62
-9348, 63-314543, U.S. Pat.
No. 288,715 describes bis-type phosphoric esters, but the compounds described therein have different structures from those of the compound of the present invention, and also have color development properties, storage stability of emulsions, dispersibility, etc. Performance was insufficient.

US Pat. Nos. 5,219,510 and 5,1
No. 04,450 describes a compound having a structure similar to the high boiling point organic solvent of the present invention. However, these patents only describe a support and a mixture with a cellulose ester, and have nothing to do with the silver halide photographic light-sensitive material of the present invention.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is, first, to provide a light-sensitive material using a high-boiling organic solvent having high solubility and excellent dispersibility and dispersion stability. Second, it is an object of the present invention to provide a light-sensitive material having improved color image fastness and stain generation. Third, it is an object of the present invention to provide a light-sensitive material in which the fogging and softening of the emulsion over time are improved. Fourth, to improve the storage stability of the latent image. Fifth, it is an object of the present invention to provide a light-sensitive material in which a decrease in color development over time is improved. Sixth, it is to suppress various adverse effects caused by the movement of the dispersion medium over time. Seventh, it is an object of the present invention to solve the problems caused by the conventional high-boiling organic solvent by using an inexpensive and easily available high-boiling organic solvent.

[0009]

SUMMARY OF THE INVENTION The object of the present invention is to provide a silver halide photographic material having at least one silver halide emulsion layer on a support, and a non-color-forming material represented by the following general formula (1): It has been found that this is achieved by a silver halide photographic material characterized by containing at least one compound.

[0010]

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In the formula, R ₁ , R ₂ and R ₃ each independently represent an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, a halogen atom, a heterocyclic group, a cyano group, Hydroxy group, nitro group,
Carboxyl group, sulfo group, amino group, alkoxy group,
Aryloxy group, acylamino group, alkylamino group, anilino group, ureido group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, It represents an azo group, an acyloxy group, a carbamoyloxy group, a silyloxy group, an aryloxycarbonylamino group, an imide group, a sulfinyl group, an aryloxycarbonyl group, or an acyl group.

K and n each independently represent an integer of 0 to 5. m represents an integer of 0 to 4.

[0013]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.

In the general formula (1), R ₁ , R ₂ and R ₃ each independently represent an alkyl group, an aryl group, a halogen atom, a heterocyclic group, a cyano group, a hydroxy group, a nitro group, a carboxyl group, a sulfo group. Group, amino group, alkoxy group, aryloxy group, acylamino group, alkylamino group, anilino group, ureido group, alkylthio group, arylthio group,
Alkoxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group,
Represents an aryloxycarbonylamino group, an imide group, a sulfinyl group, an aryloxycarbonyl group, or an acyl group. When R ₁ is two or more, two R ₁ may form a carbocyclic or heterocyclic 5- or 6-membered. Similarly,
When there are two or more R ₂ , two R ₂ may form a 5- or 6-membered carbocyclic or heterocyclic ring.

More specifically, R ₁ , R ₂ and R _{3 each} represent a substituted or unsubstituted alkyl group (a substituted or unsubstituted linear or branched alkyl group having 1 to 32 carbon atoms, for example,
Methyl, ethyl, n-propyl, isopropyl, t-butyl, n-tridecyl), alkenyl group (substituted or unsubstituted linear or branched alkenyl group having 2 to 30 carbon atoms, for example, allyl, prenyl, geranyl, oleyl) ), An alkynyl group (a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, for example, 1-propyn-1-yl), a cycloalkyl group (a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, for example, , Cyclohexyl, cyclopentyl), cycloalkenyl group (having 3 carbon atoms)
To 30 substituted or unsubstituted cycloalkenyl groups,
For example, 1-cyclohexen-1-yl), an aryl group (a substituted or unsubstituted aryl group having 6 to 30 carbon atoms,
For example, phenyl, naphthyl, p-chlorophenyl),
A halogen atom (eg, a chlorine atom, a bromine atom, an iodine atom), a heterocyclic group (preferably a substituted or unsubstituted heterocyclic group having at least one nitrogen atom, oxygen atom or sulfur atom, having 3 to 20 carbon atoms); Ring, for example, imidazolyl, pyrazolyl, triazolyl), cyano group,
Hydroxy, nitro, carboxyl, sulfo,
Amino group, alkoxy group (substituted or unsubstituted
To 20 alkoxy groups such as methoxy, ethoxy,
Methoxyethoxy, 2-dodecylethoxy), aryloxy group (substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms, for example, phenoxy, p-methoxyphenoxy), acylamino group (substituted or unsubstituted carbon atom having 1 to 20 carbon atoms) 20 acylamino groups, for example, acetylamino, pivaloylamino, benzoylamino), alkylamino groups (substituted or unsubstituted alkylamino groups having 1 to 30 carbon atoms, for example, methylamino, diethylamino, hexadecylamino), anilino group ( A substituted or unsubstituted anilino group having 6 to 30 carbon atoms, for example, N-methylanilino, N-hexadecylanilino), a ureido group (a substituted or unsubstituted ureido group having 1 to 20 carbon atoms, for example, methylaminocarbonyl Amino group), alkylthio group (substituted or Substituted alkylthio groups having 1 to 20 carbon atoms, such as methylthio, ethylthio, tetradecylthio), arylthio groups (substituted or unsubstituted arylthio groups having 6 to 20 carbon atoms, such as phenylthio, naphthylthio), alkoxycarbonylamino groups ( Substituted or unsubstituted alkoxycarbonylamino group having 2 to 20 carbon atoms, for example, methoxycarbonylamino, ethoxycarbonylamino, octyloxycarbonylamino), sulfonamide group (substituted or unsubstituted sulfonamide group having 1 to 20 carbon atoms) For example, methanesulfonylamino, benzenesulfonylamino, toluenesulfonylamino), carbamoyl group (substituted or unsubstituted carbamoyl group having 1 to 20 carbon atoms, for example, aminocarbonyl group, methylaminocarbonyl group , A sulfamoyl group (a substituted or unsubstituted sulfamoyl group having from 1 to 20 carbon atoms, for example, methylaminosulfonyl,
Octylaminosulfonyl), sulfonyl group (substituted or unsubstituted sulfonyl group having 1 to 20 carbon atoms, for example,
Methanesulfonyl, dodecanesulfonyl, toluenesulfonyl), alkoxycarbonyl group (substituted or unsubstituted alkoxycarbonyl group having 2 to 20 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl), heterocyclic oxy group (preferably, A substituted or unsubstituted carbon atom having at least one nitrogen atom, oxygen atom, or sulfur atom
0 heterocyclic oxy group, for example, 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy), azo group (substituted or unsubstituted azo group having 3 to 20 carbon atoms, for example, phenylazo), acyloxy group (Substituted or unsubstituted acyloxy group having 1 to 20 carbon atoms,
For example, acetyloxy, pivaloyloxy), carbamoyloxy group (substituted or unsubstituted having 1 to 20 carbon atoms)
A carbamoyloxy group such as dimethylaminocarbonyloxy), a silyloxy group (substituted or unsubstituted silyloxy group having 1 to 20 carbon atoms such as trimethylsilyloxy), an aryloxycarbonylamino group (substituted or unsubstituted carbon atom 6) To 20 aryloxycarbonylamino groups such as phenoxycarbonylamino), imide groups (substituted or unsubstituted C1 to C20 imide groups such as phthalimide), sulfinyl groups (substituted or unsubstituted C1 to C20) 20 sulfinyl groups such as methanesulfinyl and dodecanesulfinyl), aryloxycarbonyl groups (substituted or unsubstituted aryloxycarbonyl groups having 7 to 20 carbon atoms such as phenoxycarbonyl), acyl groups (substituted or unsubstituted carbon atoms); 1 to 20 acyl group, for example, represents acetyl, pivaloyl, benzoyl).

In the present specification, when each substituent is an unsubstituted group, the “carbon number” refers to the number of all carbon atoms of the group. On the other hand, when each substituent is a substituted group, the “carbon number” refers to the number of carbon atoms in the skeleton portion, excluding the number of carbon atoms of the substituted group.

In the present specification, when each substituent is a substituted group, examples of the substituted group include an alkyl group, an aryl group, a halogen atom, a heterocyclic group, a cyano group, a hydroxy group, Nitro group, carboxyl group, sulfo group, amino group, alkoxy group, aryloxy group, acylamino group, alkylamino group, anilino group, ureido group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamide group, carbamoyl group, Sulfamoyl, sulfonyl, alkoxycarbonyl, heterocyclic oxy, azo, acyloxy, carbamoyloxy, silyloxy, aryloxycarbonylamino, imide, sulfinyl, aryloxycarbonyl, acyl groups Can be. Specific examples thereof include methyl, ethyl, isopropyl, phenyl, chlorine atom, bromine atom, pyrazolyl, cyano, hydroxy, nitro, carboxy, sulfo, amino, methoxy, ethoxy, phenoxy, acetylamino, pivaloylamino, methylamino, diethylamino, Anilino, methylaminocarbonylamino, methylthio, phenylthio, methoxycarbonylamino,
Methanesulfonylamino, methylaminocarbonyl, methylaminosulfonyl, methanesulfonyl, methoxycarbonyl, 1-phenyltetrazol-5-oxy, phenylazo, acetyloxy, dimethylaminocarbonyloxy, trimethylsilyloxy, phenoxycarbonyloxy, phthalimide, methanesulfinylphenoxycarbonyl And acetyl.

Preferably, R ₁ and R ₃ are the same.

R ₁ , R ₂ and R _{3 each} represent an alkyl group (having 1 carbon atom).
To 5 unsubstituted alkyl groups, for example, methyl, ethyl, isopropyl, t-butyl), aryl groups (aryl groups having 6 to 10 carbon atoms, for example, phenyl), alkoxy groups (alkoxy groups having 1 to 5 carbon atoms, For example, methoxy, ethoxy), halogen atom (chlorine atom, bromine atom)
Is preferred.

Among them, methyl, ethyl, phenyl,
Methoxy and chlorine are preferred.

R ₁ , R ₂ and R ₃ may be substituted at any position of o, m and p- with respect to the oxygen atom directly bonded to the phosphorus atom. The substitution positions of R ₁ and R ₃ are preferably the same as each other. Also, a mixture of these positional isomers may be used. In terms of solubility, mixtures are preferred.

K and n each independently represent an integer of 0 to 5. m represents an integer of 0 to 4.

K and n are preferably 0 or 1. m is 0
Or 1 is preferred. The phenylene group bonded to two oxygen atoms bonded to the phosphorus atom may be any one of o, m, and p-phenylene groups. Among them, an m-phenylene group is preferable. For this preferred m-phenylene group,
The substitution position of R ₂ is the following group:

[0024]

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From the viewpoint, the o-position is preferred.

Further preferred compounds of the general formula (1) are those wherein R ₁ and R ₃ are phenyl, methoxy and chlorine atoms;
R ₂ is a methyl, methoxy, chlorine atom, k and n are the same and are 0 or 1, and m is 0 or 1.

Among them, Compound 2 is more preferable.

The following are examples of compounds of the high boiling point organic solvent used in the present invention.

[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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Hereinafter, a method for synthesizing the compound represented by the general formula (1) will be described.

The compound of the present invention can be easily synthesized according to a known method for synthesizing a phosphate ester. Hereinafter, the synthesis method will be described in detail.

[0039]

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The compound of the present invention can be synthesized by reacting a phenol derivative with phosphorus oxychloride to produce an intermediate A, and then reacting the intermediate A with a dihydroxybenzene derivative.

(Step 1) The phenol derivative is preferably used in an amount of 1.5 to 3 equivalents to phosphorus oxychloride, and more preferably 1.8 to 2.2 equivalents. The solvent is
No solvent or aromatic solvent (toluene, xylene, etc.), nitrile solvent (acetonitrile, propionitrile, etc.), sulfolane, hydrocarbon solvent (octane, etc.)
Can be used. The reaction temperature is preferably from 0 ° C to 200 ° C, more preferably from 20 ° C to 80 ° C. Lewis acids (such as aluminum chloride) can be used to accelerate the reaction.

(Step 2) It is preferable to use 0.2 to 1.5 equivalents of dihydroxybenzene with respect to the intermediate A. Furthermore, it is 0.3 to 0.8 equivalent. As the reaction solvent, the solvent described in Step 1 can be used. A base can be used to accelerate the reaction. Organic bases (triethylamine, pyridine, etc.)
Is preferred. The reaction temperature is preferably from 30 to 200 ° C,
Further, the temperature is preferably from 80 to 150 ° C.

One of the compounds represented by the general formula (1) of the present invention is Rhophos RDP (manufactured by Ajinomoto Co., Inc.).
CAS. No. 57583-54-7; corresponds to compound 2 of the invention. ) And can be purchased at low cost.

The compound represented by the general formula (1) of the present invention is a non-color-forming compound which does not form a dye by a coupling reaction with an oxidized form of a developing agent, and therefore has a molecular structure It has no coupler residue.

The amount of the compound represented by the general formula (1) can be changed according to the purpose. The amount used is preferably from 0.2 mg to ²⁰ g per 1 m ² of the photosensitive material,
The amount is more preferably 1 mg to 5 g, and usually, the weight ratio is generally 0.1 to 4 and preferably 0.1 to 2 with respect to a photographically useful reagent such as a coupler. The amount of the dispersion of the compound represented by the general formula (1) of the present invention and the photographically useful compound such as a coupler to be used in the dispersion medium is 2 to 0.1, preferably 1 to 1 in terms of weight ratio. .0
０．２0.2. Examples of photographically useful compounds other than couplers include photo-fading inhibitors, dark-fading inhibitors, stain inhibitors, color-mixing inhibitors, UV absorbers, dyes (anti-irradiation and anti-halation), and photographic useful compounds during processing. (E.g., block compounds and DIRs)
Hydroquinone, dye-releasing redox compounds, etc.). Here, a typical dispersion medium is, for example, gelatin, and a hydrophilic polymer such as polyvinyl alcohol. The dispersion in the present invention can contain various compounds depending on the purpose, in addition to the above-mentioned photographically useful drugs.

The compounds represented by the general formula (1) of the present invention can be used alone or in combination of two or more. When two or more kinds are used in combination, as described above, it is preferable to use a mixture of positional isomers for R ₁ , R ₂ and R _{3 from} the viewpoint of solubility.

The compound represented by the general formula (1) of the present invention can be added in the same manner as the method of adding a conventionally known high boiling solvent to a light-sensitive material.

The compound represented by the general formula (1) of the present invention is added to any hydrophilic colloid layer to which a photographic compound using the compound represented by the general formula (1) of the present invention as a solvent is to be added. can do. Specifically, it can be added to at least one of a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer.

The compound represented by the general formula (1) of the present invention can be used in combination with a conventionally known high-boiling organic solvent outside the scope of the general formula (1) of the present invention. When these conventionally known high-boiling organic solvents are used in combination, with respect to the total amount of the high-boiling organic solvents,
The compound represented by the general formula (1) is preferably used in a weight ratio of at least 10%, more preferably at least 30%.

Examples of the high boiling point solvent which can be used in combination with the compound represented by formula (1) of the present invention are shown below.

[0051]

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[0052]

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[0053]

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[0054]

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[0055]

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[0056]

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[0057]

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[0058]

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[0059]

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[0060]

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[0061]

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[0062]

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[0063]

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[0064]

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[0065]

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[0066]

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[0067]

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[0068]

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When the silver halide photographic light-sensitive material of the present invention (hereinafter also referred to as "light-sensitive material" or "light-sensitive material") is applied to a color light-sensitive material, at least one light-sensitive layer is provided on a support. What is necessary is just to be provided. A typical example is
This is a silver halide photographic material having at least one photosensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. The light-sensitive layer is a unit light-sensitive 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 the unit light-sensitive layers is generally A red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are provided in this order from the support side. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between layers of the same color sensitivity. A non-light-sensitive layer may be provided between the silver halide light-sensitive layers and as the uppermost layer and the lowermost layer. These include couplers described later, DI
An R compound, a color mixing inhibitor, and the like may be included. The plurality of silver halide emulsion layers constituting each unit photosensitive layer are DE1,
As described in 121,470 or GB923,045, it is preferable to arrange two layers of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer so that the sensitivity gradually decreases toward the support. Also,
JP-A-57-112751, 62-200350, 62-206541, 62-2065
As described in 43, a low-speed emulsion layer may be provided on the side farther from the support, and a high-speed emulsion layer may be provided on the side closer to the support.

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

Further, as described in JP-B-55-34932, the blue-sensitive layer / GH / RH
They can also be arranged in the order of / GL / RL. JP-A-56-2
As described in 5738 and 62-63936, the layers may be arranged in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support.

Further, as described in JP-B-49-15495, the upper layer is 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 a layer having a higher sensitivity than the middle layer. An example is an arrangement in which a silver halide emulsion layer having a low sensitivity is arranged and three layers having different sensitivities are sequentially reduced in sensitivity toward a support. Even when such a three-layer structure having different photosensitivity is used,
As described in JP-A-59-202464, in the same color-sensitive layer, the layers may be arranged in the order of medium-speed emulsion layer / high-speed emulsion layer / low-speed emulsion layer from the side away from the support.

In addition, a high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or a low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer may be arranged in this order. The arrangement may be changed as described above even in the case of four or more layers.

To improve color reproducibility, US Pat. No. 4,663,27
1, 4,705,744, 4,707,436, JP-A-62-160448, 63
It is preferred to arrange a donor layer (CL) having a multilayer effect having a spectral sensitivity distribution different from that of the main photosensitive layer such as BL, GL, RL described in the specification of -89850 adjacent to or close to the main photosensitive layer.

Preferred silver halides for use in the present invention are silver iodobromide, silver iodochloride, or silver iodochlorobromide containing up to about 30 mole percent silver iodide. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 10 mol% silver iodide.

The silver halide grains in the photographic emulsion include those having regular crystals such as cubic, octahedral and tetradecahedral, those having irregular crystal forms such as spherical and plate-like,
It may have a crystal defect such as a twin plane or a composite form thereof.

The silver halide may be fine grains having a grain size 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.

The silver halide photographic emulsion usable in the present invention is, for example, Research Disclosure (hereinafter referred to as RD).
No. 17643 (December 1978), pp. 22-23, "I. Emulsion preparation and types", and N.
o.18716 (November 1979), p.648, No.307105 (November 1989)
Pp. 863-865, and Grafkid, "Physics and Chemistry of Photography", published by Paul Montell (P. Glafkides, Chimie et P.)
hisique Photographiques, Paul Montel, 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (GF
Duffin, Photographic Emulsion Chemistry, Focal Pr
ess, 1966), "Manufacture and coating of photographic emulsions" by Zelikman et al., Focal Press (VL Zelikman, et a
l., Making and Coating Photographic Emulsion, Foca
l Press, 1964).

US Pat. Nos. 3,574,628 and 3,655,394 and GB 1,413,
The monodisperse emulsion described in 748 is also preferred.

Further, tabular grains having an aspect ratio of about 3 or more can be used in the present invention. Tabular grains are described in Gutoff, Photographic Science and Engineering (Gutoff, Photographic Science and E).
ngineering), Vol. 14, pp. 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 the outside may be composed of different halogen compositions, or may have a layered structure. Silver halides having different compositions may be bonded by epitaxial bonding, or may be bonded to a compound other than silver halide such as, for example, silver rhodan or lead oxide. Also, a mixture of particles of various crystal forms may be used.

The above emulsion may be a surface latent image type in which a latent image is mainly formed on the surface, an internal latent image type in which a latent image is formed inside the grains, or a type having a latent image on both the surface and the inside. Type emulsion. Among the internal latent image types, core / shell type internal latent image type emulsions described in JP-A-63-264740 may be used.
-133542. The thickness of the shell of this emulsion varies depending on the development process and the like, but is preferably 3 to 40 nm, and 5 to 40 nm.
20 nm is particularly preferred.

As the silver halide emulsion, usually, those subjected to physical ripening, chemical ripening and spectral sensitization are used. Additives used in such a process are RD No. 17643 and RD No. 187.
16 and No. 307105, and the relevant portions are summarized in the table below.

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

US Pat. No. 4,082,553 describes a silver halide grain with a fogged surface, US Pat. No. 4,626,498, a silver halide grain with a fogged inside described in JP-A-59-214852, and colloidal silver as a photosensitive halide. It is preferably applied to a silver halide emulsion layer and / or a substantially light-insensitive hydrophilic colloid layer. The term "silver halide particles having a fogged interior or surface" refers to silver halide grains that can be uniformly (non-imagewise) developed regardless of unexposed portions and exposed portions of the photosensitive material. The preparation method thereof is disclosed in US Pat. No. 4,626,498, JP-A-59-2148.
52. The silver halide forming the internal nucleus of the core / shell type silver halide grain having the inside of the grain fogged may have a different halogen composition. The silver halide having the inside or surface of the grain covered is silver chloride,
Any of silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. The average grain size of these fogged silver halide grains is 0.01 to 0.75 μm, particularly 0.05 to 0.6 μm.
μm is preferred. The grains may be regular grains or polydisperse emulsions, but may be monodisperse (at least 95% of the weight or the number of silver halide grains has a grain size within ± 40% of the average grain size). Is preferable.

In the present invention, it is preferable to use non-photosensitive fine grain silver halide. Non-photosensitive fine grain silver halide is silver halide fine grains that are not exposed during imagewise exposure to obtain a dye image and are not substantially developed in the developing process, and are preferably not fogged in advance. . The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may contain silver chloride and / or silver iodide as needed. Preferably, it contains 0.5 to 10 mol% of silver iodide. The fine grain silver halide has an average grain size (average value of the circle equivalent diameter of the projected area).
It is preferably from 0.01 to 0.5 μm, more preferably from 0.02 to 0.2 μm.

The fine grain silver halide can be prepared in the same manner as in the case of ordinary light-sensitive silver halide. The surface of the silver halide grains does not need to be optically sensitized, and no spectral sensitization is required. However, before adding this to the coating solution, a triazole-based, azaindene-based,
It is preferable to add a known stabilizer such as a benzothiazolium-based or mercapto-based compound or a zinc compound. Colloidal silver can be contained in the layer containing fine silver halide grains.

The coated silver amount of the light-sensitive material of the present invention was 6.0 g / m ^2.
Or less, and most preferably 4.5 g / m ² or less.

The photographic additives which can be used in the present invention are also described in the RD, and the relevant portions are shown in the following table.

Types of Additives RD17643 RD18716 RD307105 Chemical sensitizer page 23, page 648, right column, page 866 2. Sensitivity enhancer page 648, right column 3. Spectral sensitizer, pages 23 to 24, page 648, right column 866 to 868, supersensitizer-page 649, right column 4. Brightener 24 page 647, right column, page 868 5 Light absorbers, pages 25 to 26, page 649, right column, page 873 Filters, page 650, left column Dyes, ultraviolet absorbers 6. Binders, page 26, page 651, left column 873 to 874 7. Plasticizers, page 27, page 650, right Column page 876 Lubricant 8. Coating aid, page 26-27 page 650 right column page 875-876 Surfactant 9. Static page 27 page 650 right column 876-877 Inhibitor 10. Matting agent 878-879.

Although various dye-forming couplers can be used in the light-sensitive material of the present invention, the following couplers are particularly preferred.

Yellow coupler: Formula (I) of EP 502,424A
Coupler represented by (II); Formulas (1) and (2) of EP 513,496A
(Especially Y-28 on page 18); EP 568,037A
A coupler of the formula (I) of claim 1 of US Pat.
6,576 column 1, lines 45 to 55, couplers represented by general formula (I); JP-A-4-74425, paragraph 0008, couplers represented by general formula (I); EP 498,381 A1, page 40, claim 1 Couplers (especially D-35 on page 18); EP 447,969A1-4
Couplers represented by the formula (Y) on the page (especially Y-1 (page 17), Y-54
(Page 41)); US Pat. No. 4,476,219, column 7, lines 36 to 58, formula (II)
~ (IV) (especially II-17,19 (column 1
7), II-24 (column 19)).

Magenta coupler; JP-A-3-39737 (L-57 (1
L-68 (lower right of page 12), L-77 (lower right of page 13); EP 456,
257 (A-4) -63 (p. 134), (A-4) -73, -75 (p. 139);
EP486,965 M-4, -6 (page 26), M-7 (page 27); EP 571,959A
M-45 (page 19); JP-A-5-204106 (M-1) (page 6); JP-A-4-204106
M-22 of paragraph 0237 of 362631.

Cyan coupler: CX-1, described in JP-A-4-04843
3,4,5,11,12,14,15 (pages 14 to 16); JP-A 4-43345 C-
7,10 (p. 35), 34, 35 (p. 37), (I-1), (I-17) (pp. 42-43);
A coupler represented by the general formula (Ia) or (Ib) according to claim 1 of JP-A-6-67385.

Polymer coupler: P-1, described in JP-A-2-44345
P-5 (page 11).

Examples of couplers in which the coloring dyes have an appropriate diffusibility include US Pat. No. 4,366,237, GB 2,125,570, EP 96,873B,
Those described in DE 3,234,533 are preferred.

Couplers for correcting unnecessary absorption of a coloring dye are described in formulas (CI), (CII) and (CI) described on page 5 of EP 456,257A1.
II), yellow colored cyan couplers represented by (CIV) (especially YC-86 on page 84), yellow colored magenta couplers ExM-7 (page 202), EX-1 (page 249), EX
-7 (p. 251), Magenta colored cyan coupler CC-9 (column 8), CC-13 (column 10) described in US 4,833,069, US
4,837,136 (2) (column 8), a colorless masking coupler of the formula (A) in claim 1 of WO 92/11575 (especially 36
-Exemplified compounds on page 45).

The compounds (including couplers) which react with oxidized developing agents to release photographically useful compound residues include the following. Development inhibitor releasing compound:
Compounds of the formulas (I), (II), (III) and (IV) described on page 11 of EP 378,236A1 (especially T-101 (page 30), T-104 (page 31), T-11
3 (page 36), T-131 (page 45), T-144 (page 51), T-158 (page 58)), EP43
Compounds represented by the formula (I) described on page 7 of 6,938A2 (particularly D-49 (page 51)), compounds represented by the formula (1) of EP 568,037A (particularly (23) (page 11)), Compounds of the formulas (I), (II) and (III) described on pages 5 to 6 of EP 440,195 A2 (especially on page 29)
I- (1)); Bleaching accelerator releasing compounds: compounds represented by the formulas (I) and (I ′) on page 5 of EP 310,125A2 (particularly, (60),
(61)) and the compound represented by the formula (I) of claim 1 of JP-A-6-59411 (particularly (7) (page 7));
A compound represented by LIG-X described in claim 1 of 4,555,478 (especially a compound on line 21 to 41 of column 12); a leuco dye-releasing compound: compound 1 of column 3 to 8 of US 4,749,641
~ 6; fluorescent dye releasing compound: of claim 1 of US 4,774,181
Compound represented by COUP-DYE (especially compounds 1 to 11 in columns 7 to 10); Development accelerator or fogging agent releasing compound: US
Compounds represented by the formulas (1), (2) and (3) in column 3 of 4,656,123 (especially (I-22) in column 25) and EP 450,637A2
ExZK-2, p. 75, lines 36-38; Compound which releases a group which becomes a dye only after leaving: Formula (I) of claim 1 of US 4,857,447
(Especially Y-1 to Y-19 in columns 25 to 36)
.

As the additives other than the coupler, the following are preferable.

Dispersion medium for oil-soluble organic compound: JP-A-62-215
272 P-3,5,16,19,25,30,42,49,54,55,66,81,85,86,93
Latex for impregnating oil-soluble organic compound: Latex described in US Pat. No. 4,199,363; Oxidized developing agent scavenger: Compound represented by formula (I) in column 2, lines 54 to 62 of US 4,978,606 Especially I-, (1), (2), (6), (12)
(Columns 4-5), US Pat. No. 4,923,787, column 5, lines 5-10 (especially compound 1 (column 3); stain inhibitor: EP
Formulas (I) to (III) on page 4, lines 30 to 33 of 298321A, especially I-47, 72,
III-1, 27 (pages 24 to 48); Anti-fading agent: A-6 of EP 298321A,
7,20,21,23,24,25,26,30,37,40,42,48,63,90,92,94,164
(Pp. 69-118), II-5-II of columns 25-38 of US 5,122,444
I-23, especially III-10, I-1 to III- on pages 8 to 12 of EP 471347A
4, especially II-2, US 5,139,931 columns 32 to 40, A-1 to 48,
In particular, A-39, 42; a material that reduces the amount of a color-enhancing agent or color-mixing inhibitor used: EP 411324A, pages 5 to 24, I-1 to II-15,
Especially I-46; Formalin Scavenger: 24 of EP 477932A
SCV-1 to 28 on page 29, especially SCV-8; hardener: JP-A 1-21
4845, page 17, H-1,4,6,8,14, US 4,618,573, columns 13-
Compounds (H-1 to 54) represented by formulas (VII) to (XII) of 23, compounds represented by formula (6) at the lower right of page 8 of JP-A-2-214852 (H
-1 to 76), especially compounds described in claim 1 of H-14, US Pat. No. 3,325,287; development inhibitor precursors: disclosed in JP-A-62-168139.
P-24, 37, 39 (pages 6 to 7); compounds described in claim 1 of US Pat. No. 5,019,492, especially 28, 29 of column 7; preservatives, fungicides:
US 4,923,790, columns 3-15, I-1 to III-43, especially II-
1,9,10,18, III-25; stabilizer, antifoggant: US 4,923,
793 columns 6 to 16 I-1 to (14), especially I-1,60, (2), (13),
Compounds 1-65, especially 3 in columns 25-32 of US 4,952,483
6: Chemical sensitizer: triphenylphosphine selenide, compound 50 of JP-A-5-40324; dye: 15-1 of JP-A-3-156450
A-1 to b-20 on page 8, especially a-1,12,18,27,35,36, b-5,27 to 2
V-1 to 23 on page 9, especially FI on page 33 to 55 of V-1, EP 445627A
-1 to F-II-43, especially FI-11, F-II-8, 17 to 2 of EP 457153A
III-1 to 36 on page 8, especially III-1,3, 8 to 26 in WO 88/04794
A microcrystalline dispersion of Dye-1 to 124, compounds 1 to 22 on pages 6 to 11 of EP 319999A, in particular compounds D-1 to 87 (compounds 1 and 519306A represented by formulas (1) to (3)). (Pages 3 to 28), US 4,2
Compounds 1 to 22 represented by the formula (I) of 68,622 (columns 3 to
10), compounds (1) to (4) of the formula (I) of US Pat.
(31) (Columns 2 to 9); UV absorber: Formula of JP-A-46-3335
Compounds (18b) to (18r), 101 to 427 (6 to
9), and the compounds (3) to (6) represented by the formula (I) in EP 520938A.
6) (Pages 10 to 44) and compound HBT-1 represented by formula (III)
~ 10 (page 14), a compound represented by formula (1) in EP 521823A
(1) to (31) (columns 2 to 9).

The present invention can be applied to various color light-sensitive materials such as color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers. In addition, Tokuhei 2-32615, actual fairness
It is suitable for a film unit with a lens described in 3-39784.

Suitable supports which can be used in the present invention include, for example, the aforementioned RD. No. 17643, page 28, RD. No. 18716, page 647 right column to page 648 left column, and RD. It is described in.

In the light-sensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or less, more preferably 23 μm or less, further preferably 18 μm or less, and more preferably 16 μm or less. Particularly preferred. Further, the film swelling speed T _1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. T _1/2 is defined as 90% of the maximum swollen film thickness reached when the color developing solution is processed at 30 ° C. for 3 minutes and 15 seconds as a saturated film thickness.
It is defined as the time until the film thickness reaches 1/2. The film thickness refers to a film thickness measured at 25 ° C. and a relative humidity of 55% under humidity control (2 days), and T _1/2 is a _{value obtained} by A. Green et al. In Photographic Science and Engineering. (Photogr. Sci. Eng.), Vol. 19, pp. 2,124-129, which can be used for measurement. T _1/2 can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating. The swelling ratio is
150-400% is preferred. The swelling ratio is calculated from the maximum swelling film thickness under the conditions described above by the formula: (maximum swelling film thickness-film thickness).
/ Thickness can be calculated.

The light-sensitive material of the present invention is preferably provided with a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm on the side opposite to the side having the emulsion layer. In this back layer, the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder,
It is preferable to include a plasticizer, a lubricant, a coating aid, and a surfactant. The swelling ratio of the back layer is preferably from 150 to 500%.

The light-sensitive material of the present invention is prepared according to the above-mentioned RD.
No. 18716, No. 18716, 651 left column to right column, and N
o. 307105, pages 880 to 881.

Next, a processing solution for a color negative film to which the present invention can be applied will be described. The 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 the color developing solution. As a color developing agent for particularly rapid processing, 2-methyl-4-
[N-ethyl-N- (2-hydroxyethyl) amino]
Aniline, 2-methyl-4- [N-ethyl-N- (3-
Hydroxypropyl) amino] aniline, 2-methyl-
4- [N-ethyl-N- (4-hydroxybutyl) amino] aniline is preferred.

These color developing agents are used in an amount of 0.1 per liter of a color developing solution (hereinafter, liter is referred to as “L”).
It is preferably used in the range of 01 to 0.08 mol, particularly
It is preferably used in the range of 0.015 to 0.06 mol, more preferably 0.02 to 0.05 mol. The replenisher of the color developing solution preferably contains 1.1 to 3 times the concentration of the color developing agent, particularly preferably 1.3 to 2.5 times the concentration.

As a preservative of the color developing solution, hydroxylamine can be used widely. However, when higher preservation is required, substitution with an alkyl group, a hydroxyalkyl group, a sulfoalkyl group, a carboxyalkyl group, or the like is required. A hydroxylamine derivative having a group is preferable, and specifically, N, N-di (sulfoethyl) hydroxylamine, monomethylhydroxylamine, dimethylhydroxylamine, monoethylhydroxylamine, diethylhydroxylamine, N, N-di (carboxyethyl) Hydroxylamines are preferred. Among the above, N, N-di (sulfoethyl) hydroxylamine is particularly preferred. These may be used in combination with hydroxylamine, but it is preferable to use one or more of them instead of hydroxylamine.

The preservative is preferably used in the range of 0.02 to 0.2 mol per liter, particularly preferably 0.03 to 0.15 mol, more preferably 0.04 to 0.1 mol. As in the case of the color developing agent, the replenisher preferably contains a preservative at a concentration of 1.1 to 3 times the concentration of the mother liquor (processing tank solution).

In the color developing solution, a 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 (hereinafter, liter is also referred to as “L”), and particularly preferably in the range of 0.02 to 0.04 mol. In the replenisher, it is preferable to use the replenisher at a concentration 1.1 to 3 times the above.

The pH of the color developing solution is preferably in the range of 9.8 to 11.0, particularly preferably 10.0 to 10.5, and the replenisher is set to a higher value in the range of 0.1 to 1.0 from these values. Preferably. In order to stably maintain such a pH, a known buffer such as carbonate, phosphate, sulfosalicylate, and borate is used.

The replenishment amount of the color developing solution is 80 to 1300 ml per m ² of the light-sensitive material (the milliliter is hereinafter referred to as “mL”).
Also described as. ) Is preferred, but from the viewpoint of reducing the environmental pollution load, a smaller amount is more preferred, and specifically 80 to 60
0 mL, more preferably 80-400 mL.

The bromide ion concentration in the color developing solution is usually from 0.01 to 0.06 mol per liter. However, while maintaining sensitivity, fog is suppressed, discrimination is improved, and graininess is improved. From the purpose, per 1L
It is preferably set to 0.015 to 0.03 mol. When the bromide ion concentration is set in such a range, the replenisher may contain bromide ions calculated by the following formula. However, when C becomes negative, it is preferred that the replenisher does not contain bromide ions.

C = A−W / V C: bromide ion concentration in the color developing replenisher (mol / L) A: target bromide ion concentration in the color developing solution (mol / L) W: 1 m ² exposure Amount (mol) of bromide ions eluted from the light-sensitive material into the color developer when the material is color-developed. V: Replenishment amount (L) of the color-developing replenisher for 1 m ² of the light-sensitive material.

When the replenishment rate is reduced or when the bromide ion concentration is set to a high value, 1-phenyl-3-pyrazolidone or 1-phenyl-
Pyrazolidones represented by 2-methyl-2-hydroxymethyl-3-pyrazolidone and 3,6-dithia-1,8
It is also preferable to use a development accelerator such as a thioether compound represented by octanediol.

The compounds and processing conditions described in JP-A-4-125558, page 4, lower left column, line 16 to page 7, lower left column, line 6 can be applied to the processing solution having bleaching ability in the present invention. .

The bleaching agent preferably has an oxidation-reduction potential of 150 mV or more, and specific examples thereof include JP-A-5-72694 and JP-A-5-72694.
Preferred are 1,3-diaminopropanetetraacetic acid and Specific Example 1 on page 7 of JP-A-5-73312.
Are preferred.

In order to improve the biodegradability of the bleaching agent, JP-A-4-251845, JP-A-4-268552, EP588,289, and 591,9
34, It is preferable to use a compound ferric complex salt described in JP-A-6-208213 as a bleaching agent. The concentration of these bleaching agents is preferably 0.05 to 0.3 mol per liter of a liquid having bleaching ability, and particularly preferably 0.1 mol to 0.15 mol for the purpose of reducing the amount discharged to the environment. When the solution having bleaching ability is a bleaching solution, it preferably contains 0.2 mol to 1 mol of bromide, and more preferably 0.3 to 0.8 mol per liter.

The replenisher of the solution having the 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.

CR = CT × (V1 + V2) / V1 + CP CR: Concentration of component in replenisher CT: Concentration of component in mother liquor (treatment tank solution) CP: Concentration of component consumed during treatment V1: 1m Replenishment amount (mL) of replenisher having bleaching ability for photosensitive material ² (mL) V2: Amount (mL) brought in from the previous bath by 1 m ² of photosensitive material.

In addition, the bleaching solution preferably contains a pH buffer, particularly preferably a dicarboxylic acid having a low odor, such as succinic acid, maleic acid, malonic acid, glutaric acid and adipic acid. Also, JP-A-53-9
It is also preferable to use known bleaching accelerators described in US Pat. No. 5,630, RD No. 17129, US Pat.

The bleaching solution contains 50 to 1000 per m ² of the light-sensitive material.
It is preferable to replenish the bleaching replenisher of mL, especially 80 to
It is preferred to replenish 500 mL, more preferably 100-300 mL. Further, it is preferable to perform aeration on the bleaching solution.

The processing solution having a fixing ability is disclosed in
The compounds and processing conditions described on page 7, lower left column, line 10 to page 8, lower right column, line 19 of 4-125558 can be applied.

Particularly, in order to improve the fixing speed and the preservability, the processing solution having the fixing ability by using the compounds represented by the general formulas (I) and (II) of JP-A-6-301169, alone or in combination. Is preferably contained. In addition to the use of p-toluenesulfinic acid salts, the use of sulfinic acids described in JP-A-1-224762 is also preferable from the viewpoint of improving the preservation. It is preferable to use ammonium as a cation in the solution having the bleaching ability or the solution having the fixing ability from the viewpoint of improving the desilvering property, but it is more 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-1-309590. The replenishment rate of the replenisher in the bleach-fixing or fixing step is from 100 to 1000 mL, preferably from 150 to 700 mL, particularly preferably from 200 to 600 mL, per m ² of the light-sensitive material.

In the bleach-fixing and fixing steps, it is preferable to install various silver recovery devices in-line or off-line to recover silver. By installing in-line, the processing can be carried out with a reduced silver concentration in the solution, so that the replenishment amount can be reduced. It is also preferable to recover silver off-line and reuse the remaining liquid as a replenisher.

The bleach-fixing step and the fixing step can be constituted by a plurality of processing tanks, and it is preferable that each tank is cascaded to form a multistage countercurrent system. From the balance with the size of the developing machine, a two-tank cascade configuration is generally efficient, and the ratio of the processing time in the former tank and the latter tank is preferably in the range of 0.5: 1 to 1: 0.5. In particular, the range of 0.8: 1 to 1: 0.8 is preferable.

It is preferable that a free chelating agent not forming a metal complex is present in the bleach-fixing solution or the fixing solution from the viewpoint of improvement in preservation. These chelating agents are described in connection with the bleaching solution. Preferably, a biodegradable chelating agent is used.

Regarding the washing and stabilizing steps, see JP-A-4-125558, page 12, lower right column, line 6 to page 13, lower right column, no.
The contents described in the line can be preferably applied. In particular, EP504,60 instead of formaldehyde is used in the stabilizing solution.
Azolylmethylamines described in 9, 519, 190 and
Use of the N-methylolazoles described in 4-362943 or dimerization of the magenta coupler to form a surfactant-free liquid containing no image stabilizer such as formaldehyde can improve the working environment. Is preferred. Also,
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 can be adjusted according to the photosensitive material 1
80 to 1000 mL per m ² is preferable, and particularly 100 to 500 mL, and more preferably 150 to 300 mL, is a preferable range in terms of both securing a washing or stabilizing function and reducing waste liquid for environmental protection. In the treatment performed with such a replenishing amount, thiabendazole, 1, 1
2-benzoisothiazoline-3-one, 5-chloro-2-
It is preferable to use a known fungicide such as methylisothiazolin-3-one, an antibiotic such as gentamicin, or water deionized with an ion exchange resin.
It is more effective to use a combination of deionized water and a bactericide or antibiotic.

Further, the liquid in the washing or stabilizing liquid tank is
JP-A-3-46652, 3-53246, -355542, 3-121448,
It is also preferable to reduce the replenishment amount by performing the reverse osmosis membrane treatment described in the above-mentioned 3-126030, and in this case, the reverse osmosis membrane is preferably a low pressure reverse osmosis membrane.

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

As the treating agent used in the present invention, those described in the above-mentioned published technical report from page 3, right column, line 15 to page 4, left column, line 32 are preferable. In addition, as a developing machine used for this,
The film processor described on page 3, right column, lines 22 to 28 is preferred.

Specific examples of preferred processing agents, automatic developing machines, and evaporation correction methods for carrying out the present invention are described in the above-mentioned published technical report from page 5, right column, line 11 to page 7, right column, last line. Have been.

The supply form of the treating agent used in the present invention is as follows.
It may be in any form, such as a liquid preparation in the form of a liquid used or a concentrated form, or granules, powders, tablets, pastes, and emulsions. As an example of such a treating agent, JP-A-63-1
7453 discloses a liquid agent contained in a container having low oxygen permeability,
19655, 4-230748, vacuum-packed powder or granules, 4-221951, granules containing a water-soluble polymer,
JP-A-51-61837 and JP-A-6-102628 describe tablets and JP-A-57-5
JP-A-48585 discloses a paste-like treatment agent, and any of them can be preferably used, but from the viewpoint of simplicity in use,
It is preferable to use a liquid that has been prepared in advance in a concentration for use.

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

Next, a processing solution for a color reversal film that can use the present invention will be described. For the processing for the color reversal film, see page 6, line 5 to page 10, line 5 and page 15, line 8 to page 24, 2 of the publicly known technique No. 6 (April 1, 1991) issued by Aztec Co., Ltd. Each row is described in detail, and any of the contents can be preferably applied. In processing color reversal films, the image stabilizer is contained in a conditioning or final bath. Examples of such image stabilizers include, in addition to formalin, sodium formaldehyde sodium sulfite and N-methylolazoles.
From the viewpoint of working environment, sodium formaldehyde sodium bisulfite or N-methylolazole is preferable, and N-methyloltriazole is particularly preferable as N-methylolazole. Further, the contents relating to the color developing solution, the bleaching solution, the fixing solution, the 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.

As a preferred color reversal film treating agent containing the above contents, Eastman Kodak E-6
Examples of the treating agent include CR-56 treating agent manufactured by Fuji Photo Film Co., Ltd.

The color photographic light-sensitive material using the present invention is also suitable as a negative film for an advanced photo system (hereinafter, referred to as an AP system), and NEXIA manufactured by Fuji Photo Film Co., Ltd. (hereinafter, referred to as Fuji Film). A, N
Films processed into the AP system format such as EXIA F and NEXIA H (in order, ISO 200/100/400) and stored in a special cartridge can be mentioned. These APs
The cartridge film for a system is used by being loaded into a camera for an AP system such as an EPION series (EPION 300Z, etc.) manufactured by FUJIFILM Corporation. Further, the photographic light-sensitive material of the present invention is also suitable for a film with a lens such as Fujifilm's Fujicolor Photorun Super Slim.

The film photographed by the above is printed in the mini lab system through the following steps.

(1) Acceptance (exposed cartridge film received from customer) (2) Detach step (transfer film from cartridge to intermediate cartridge for development step) (3) Film development (4) Rear touch step (development (5) Print (continuous automatic printing of C / H / P 3 type prints and index prints on color paper (preferably SUPER FA8 made by FUJIFILM)) (6) Verification and shipping (collating cartridges and index prints with ID numbers and shipping with prints).

These systems include Fujifilm Minilab Champion Super FA-298 / FA-278 / FA-258 / F
A-238 and Fujifilm Digital Lab System Frontier are preferred. FP922AL / FP562B / FP562B, AL / FP362B / FP as minilab champion film processors
362B, AL, and the recommended treatment chemicals are Fujicolor Justit CN-16L and CN-16Q. As a printer processor, PP3008AR / PP3008A / PP1828AR / PP1828A / PP12
58AR / PP1258A / PP728AR / PP728A, and the recommended treatment 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 L
P-1000W is used. The detacher used in the detaching step and the rear toucher used in the rear attaching step are preferably DT200 / DT100 and AT200 / AT100 of Fujifilm, respectively.

The AP system can also be enjoyed by a photo joy system centered on the Fuji Film Aladdin 1000 digital image workstation. For example, you can load the developed AP system cartridge film directly into the Aladdin 1000, or transfer image information of negative film, positive film, and print to a 35mm film scanner FE.
The digital image data obtained by inputting using the -550 or PE-550 flat head scanner can be easily processed and edited. The data are stored in a digital color printer NC-550AL using a light fixing type thermal color printing system and a pictograph 3000 using a laser exposure thermal development transfer system.
Or as prints by existing laboratory equipment through a film recorder. The Aladdin 1000 can also transfer digital information directly to a floppy disk, Zip disk, or via a CD writer.
You can also output to CD-R.

On the other hand, at home, a developed AP system cartridge film is transferred to a photo player AP manufactured by FUJIFILM.
You can enjoy photos on TV just by loading it in -1,
By loading it onto a Fujifilm AS-1 photo scanner, image information can be continuously and rapidly captured on a personal computer. To input a film, print or three-dimensional object to a personal computer, use Fujifilm PhotoVision FV-10 / FV
-5 is available. Furthermore, image information recorded on a floppy disk, Zip disk, CD-R, or hard disk can be variously processed and enjoyed on a personal computer using Fujifilm's application software Photo Factory. In order to output high-quality prints from a personal computer, a digital color printer NC-2 / NC-2D manufactured by Fujifilm of a light fixing type thermal color print system is suitable.

In order to store the developed AP system cartridge film, the Fuji Color Pocket Album AP-5 POP L, AP-1 POP L, AP-1 POP KG or the cartridge file 16 is preferable.

Next, the magnetic recording layer that can be used in the present invention will be described.

The magnetic recording layer is obtained by coating an aqueous or organic solvent-based coating solution in which magnetic particles are dispersed in a binder on a support.

[0148] Magnetic particles used include ferromagnetic iron oxide such as γFe ₂ O _3, Co deposited γFe ₂ O _3, Co-coated magnetite, C
O-containing magnetite, ferromagnetic chromium dioxide, ferromagnetic metal, ferromagnetic alloy, hexagonal Ba ferrite, Sr ferrite, Pb ferrite, Ca ferrite, etc. can be used. Co
Co-coated ferromagnetic iron oxide, such as γ-Fe ₂ O _3, is 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,
Particularly preferably, it is 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 surface of the magnetic particles may be treated with a silane coupling agent or a titanium coupling agent as described in JP-A-6-161032. Also, magnetic particles having a surface coated with an inorganic or organic substance described in JP-A-4-259911 and JP-A-5-81652 can be used.

The binder used for the magnetic particles may be a thermoplastic resin, a thermosetting resin, a radiation-curable resin, a reactive resin, an acid, an alkali or a biodegradable polymer, or a natural material described in JP-A-4-219569. Combinations (cellulose derivatives, sugar derivatives, etc.) and mixtures thereof can be used. The above resin has a Tg of -40 ° C to 300 ° C and a weight average molecular weight of
It is between 2,000 and 1,000,000. Examples thereof include vinyl copolymers, cellulose derivatives such as cellulose diacetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, and cellulose tripropionate, acrylic resins, and polyvinyl acetal resins, and gelatin is also preferable. Particularly, cellulose di (tri) acetate is preferable. The binder can be cured by adding an epoxy-based, aziridine-based, or isocyanate-based crosslinking agent. As the isocyanate-based crosslinking agent, tolylene diisocyanate,
Isocyanates such as 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, and the reaction products of these isocyanates with polyalcohols (for example, the reaction product of 3 mol of tolylene diisocyanate and 1 mol of trimethylolpropane) ), And polyisocyanates formed by condensation of these isocyanates, and the like, which are described in, for example, JP-A-6-59357.

As a method for dispersing the above-mentioned magnetic material in the binder, a kneader, a pin type mill, an annular type mill and the like are preferably used, 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, it is 0.3 μm to 3 μm. The weight ratio between the magnetic particles and the binder is preferably 0.5: 100 to 60: 100, and more preferably 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 , and 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, and 0.03 to 0.20.
Is more preferable, and 0.04 to 0.15 is particularly preferable. The magnetic recording layer may be provided on the entire back surface of the photographic support by coating or printing, or in a stripe shape. Methods for applying the magnetic recording layer include air doctor, blade, air knife, squeeze, impregnation, reverse roll, transfer roll, gravure, kiss, cast, spray,
Dip, bar, extrusion, etc. are available,
The coating liquid described in JP-A-5-341436 is preferred.

The magnetic recording layer has lubricating properties, curl control,
It may have functions such as antistatic, antiadhesion, and head polishing, or may provide another functional layer to provide these functions. At least one of the particles has a Mohs hardness of 5 or more. Abrasives of the above non-spherical inorganic particles are preferred. As the composition of the non-spherical inorganic particles, oxides such as aluminum oxide, chromium oxide, silicon dioxide, titanium dioxide and silicon carbide, carbides such as silicon carbide and titanium carbide, and fine powders such as diamond are preferable. These abrasives may have their surfaces treated with a silane coupling agent or a titanium coupling agent. These particles may be added to the magnetic recording layer, or may be overcoated (for example, a protective layer, a lubricant layer, etc.) on the magnetic recording layer. As the binder used at this time, the above-mentioned binders can be used, and the same binder as the binder for the magnetic recording layer is preferable. US 5,336,589, US 5,250,404, US 5,336,589
229,259, 5,215,874 and EP466,130.

Next, the polyester support used in the present invention will be described. For details including photosensitive materials, treatments, cartridges and examples to be described later, refer to Published Technical Report, Official Technique No. 94-6023 (Invention Association; .15.).
The polyester used in the present invention is formed by using a diol and an aromatic dicarboxylic acid as essential components, and 2,6-, 1,5-, 1,4-, and 2,7 as aromatic dicarboxylic acids.
-Naphthalenedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, diethylene glycol as diol,
Examples include triethylene glycol, cyclohexanedimethanol, bisphenol A, and bisphenol.
Examples of the polymer include homopolymers such as polyethylene terephthalate, polyethylene naphthalate, and polycyclohexanedimethanol terephthalate. Particularly preferred is a polyester containing 50 to 100 mol% of 2,6-naphthalenedicarboxylic acid. Among them, polyethylene 2,6-naphthalate is particularly preferred. Average molecular weight ranges from about 5,000 to 20
It is 0,000. The Tg of the polyester of the present invention is 50 ° C. or higher, preferably 90 ° C. or higher.

Next, the polyester support is heat-treated at a heat treatment temperature of 40 ° C. or more and less than Tg, more preferably Tg−20 ° C. or more and less than Tg, in order to make it difficult to form a curl. The heat treatment may be performed at a constant temperature within this temperature range, or may be performed while cooling. The heat treatment time is 0.1 to 1500 hours, more preferably 0.5 to 200 hours. The heat treatment of the support may be performed in the form of a roll, or may be performed while being transported in the form of a web. Irregularities may be imparted to the surface (for example, conductive inorganic fine particles such as SnO ₂ or Sb ₂ O ₅ may be applied) to improve the surface state. It is also desirable to take measures such as applying knurls to the ends and making the ends slightly higher so as to prevent the cut end of the core from appearing. These heat treatments may be performed at any stage after the formation of the support, after the surface treatment, after the application of the back layer (antistatic agent, slip agent, etc.), and after the application of the undercoat. Preferably after application of the antistatic agent.

An ultraviolet absorber may be incorporated in this polyester. In order to prevent light piping, the purpose can be achieved by kneading a commercially available dye or pigment for polyester, such as Diaresin manufactured by Mitsubishi Kasei or Kayaset manufactured by Nippon Kayaku.

Next, in the present invention, it is preferable to perform a surface treatment in order to bond the support and the light-sensitive material constituting layer. Chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment,
Surface activation treatments such as laser treatment, mixed acid treatment, ozone oxidation treatment and the like can be mentioned. Among the surface treatments, ultraviolet irradiation treatment, flame treatment, corona treatment, and glow treatment are preferable.

Next, the undercoating method will be described. The coating may be a single layer or two or more layers. As the binder for the undercoat layer, vinyl chloride, vinylidene chloride, butadiene, methacrylic acid, acrylic acid, itaconic acid, including copolymers starting from monomers selected from maleic anhydride, as a starting material, Examples include polyethyleneimine, epoxy resin, grafted gelatin, nitrocellulose, and gelatin.
Compounds that swell the support include resorcinol and p-chlorophenol. In the undercoat layer, as a gelatin hardener, chromium salt (chromium alum, etc.), aldehydes (formaldehyde, glutaraldehyde, etc.), isocyanates, active halogen compounds (2,4-dichloro-6) are used.
-Hydroxy-S-triazine), epichlorohydrin resin, active vinyl sulfone compound 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 such antistatic agents include polymers containing carboxylic acid and carboxylate and sulfonate, cationic polymers, and ionic surfactant compounds.

The most preferred antistatic agent is Zn.
O, TiO_Two, SnO_Two, Al_TwoO_Three, In_TwoO_Three, SiO _Two, MgO, BaO, Mo
O_Three, V_TwoO_FiveAt least one type of volume resistivity selected from
Ten⁷Ωcm or less, more preferably 10^FiveGrains that are Ω · cm or less
0.001 to 1.0 μm crystalline metal oxide or
Fine particles of these composite oxides (Sb, P, B, In, S, Si, C, etc.),
Furthermore, sol-like metal oxides or composite oxides thereof
Particles. The content in the photosensitive material is 5 ~ 500mg / m
^TwoIs preferably 10 to 350 mg / m^TwoIt is. Conductive
Of crystalline oxide or its composite oxide and binder
Is preferably 1/300 to 100/1, more preferably 1/100.
~ 100/5.

The light-sensitive material of the present invention preferably has a slip property. The slip agent-containing layer is preferably used on both the photosensitive layer surface and the back surface. A preferable slip property is a dynamic friction coefficient of 0.
It is 25 or less and 0.01 or more. The measurement at this time represents the value when the stainless steel ball having a diameter of 5 mm was conveyed at 60 cm / min (25
° C, 60% RH). In this evaluation, even if the surface of the photosensitive layer is replaced as the partner material, the values are almost the same level.

Examples of the slipping agent usable in the present invention include polyorganosiloxanes, higher fatty acid amides, higher fatty acid metal salts, esters of higher fatty acids and higher alcohols, and polyorganosiloxanes such as polydimethylsiloxane and polydiethyl Siloxane, polystyrylmethylsiloxane, polymethylphenylsiloxane, or the like can be used. The additional layer is preferably the outermost layer of the emulsion layer or the back layer. Particularly, polydimethylsiloxane or an ester having a long-chain alkyl group is preferable.

The light-sensitive material of the present invention preferably contains a matting agent. The matting agent may be on either the emulsion side or the back side, but is particularly preferably added to the outermost layer on the emulsion side.
The matting agent may be soluble in the processing solution or insoluble in the processing solution, and preferably both are used in combination. For example, 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, and the particle size distribution is preferably narrower, and the average particle size is 0.9 to 1.1 μm.
It is preferable that 90% or more of the total number of particles be contained during the doubling. It is also preferable to simultaneously add fine particles having a size of 0.8 μm or less in order to enhance the matting property. For example, polymethyl methacrylate (0.2 μm), poly (methyl methacrylate / methacrylic acid = 9/1 (molar ratio), 0.3 μm)), 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 patrone used in the present invention may be metal or synthetic plastic.

Preferred plastic materials are polystyrene, polyethylene, polypropylene, polyphenyl ether and the like. Further, the patrone of the present invention may contain various antistatic agents, and carbon black, metal oxide particles, nonionic, anionic, cationic and betaine surfactants or polymers can be preferably used. These antistatic patrones are disclosed in
37, 1-312538. Particularly, the resistance at 25 ° C. and 25% RH is preferably 10 ¹² Ω or less. Usually, a plastic patrone is manufactured using a plastic into which carbon black, a pigment, or the like is kneaded to impart light-shielding properties. The size of the patrone may be the same as the current 135 size, and in order to reduce the size of the camera, it is effective to reduce the diameter of the current 135 size 25 mm cartridge to 22 mm or less.
The volume of the patrone case is 30 cm ³ or less, preferably 25 c
It is preferably at most m ³ . The weight of plastic used for patrone and patrone case is 5g ~ 15g
Is preferred.

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

There are no particular restrictions on the various additives and development methods used when the present invention is applied to black-and-white photographic materials. For example, JP-A-2-68539 and JP-A-5-11389.
And Japanese Patent Application Laid-Open No. 2-58041 can be preferably used. Examples of black-and-white photosensitive materials include black-and-white negative films, black-and-white photographic paper, plate making films (lith films), and X-ray films. Further, a monochrome photosensitive material using a coupler can also be mentioned as an example.

1. Silver halide emulsion and its manufacturing method:
No. 68539, page 8, lower right column, line 6 to lower right, page 10 upper right column, line 12, Chemical sensitization method: page 10, line 13 in the upper right column to column 16 in the lower left column
2. line, selenium sensitization method described in JP-A-5-11389; Antifoggant / stabilizer: JP-A-2-68539, page 10, lower left column, line 17 to page 11, upper left column, line 7 and page 3, lower left column, line 2 to page 4, lower left column, 4. 4. Spectral sensitizing dyes: page 4, lower right column, line 4 to page 8, lower right column and JP-A-2-58041, page 12, lower left column, line 8 to lower right column, line 19; Surfactant / antistatic agent: Japanese Patent Application Laid-Open No. 2-68539 No. 11
Line 14 in the upper left column of the page to line 9 in the upper left column of the page 12 and JP-A-2-58
No. 041, page 2, lower left column, line 14 to page 5, line 12, Matting agent, plasticizer, slip agent: page 12, upper left column, line 10 to upper right column, line 10 and JP-A-2-58041, page 5, lower left column, line 13 to page 10, lower left column, line 3 Eyes, 7. Hydrophilic colloid: JP-A-2-68539, page 12, upper right column
7. Line 11 to line 16 in the lower left column. Hardener: page 12, lower left column, line 17 to page 13, upper right column 6,
Line 9, Developing method: same as page 15, upper left column, line 14 to lower left column 13,
Line.

The silver halide light-sensitive material of the present invention is a US
4,500,626, JP-A-60-133449, JP-A-59-218443, JP-A-61-1
Also applicable to the photothermographic materials described in JP238056, EP210,660A2 and the like.

[0168]

EXAMPLES Examples are shown below, but the present invention is not limited to these examples.

Example 1 Each layer having the following composition was superposed on the support in Example 3.
Apply to make a monochrome photosensitive material sample 101
did. Here, the number corresponding to each component is g / m ^TwoIn units
The coating amount shown is shown.
It was shown as a converted amount of coating. However, for sensitizing dyes,
In moles per mole of silver halide per layer
expressed.

The materials and emulsions used for each layer are described in Example 3.

(Sample 101) First layer (green-sensitive silver halide emulsion layer) Silver iodobromide emulsion E silver 0.16 silver iodobromide emulsion F silver 0.19 silver iodobromide emulsion G silver 0.20 ExS-4 2.3 × 10 ^{− 5} ExS-5 8.0 × 10 ^-5 ExS-6 3.7 × 10 ^-4 ExS-7 7.4 × 10 ^-5 ExS-8 3.3 × 10 ^-4 ExM-3 0.385 HBS-1 0.393 HBS-3 0.016 Gelatin 1.039.

Second Layer (Intermediate Layer) Gelatin 2.000.

Third layer (yellow coloring layer) ExY-2 1.000 HBS-1 0.333 gelatin 2.409.

Fourth layer (protective layer) H-1 0.18 B-1 (diameter 1.7 μm) 0.05 B-2 (diameter 1.7 μm) 0.12 B-3 0.15 ES-1 0.25 gelatin 2.14.

(Preparation of Samples 102 to 115) The high-boiling organic solvent HBS-1 in the first layer of the sample 101 was prepared by using the compound represented by the general formula (1) of the present invention (hereinafter referred to as “the high-boiling organic solvent of the present invention”). Sample 10 except that 1,2,3,6,12,19 or the following high-boiling organic solvents a to h for comparison were replaced with the same weight.
Samples 102 to 115 were produced in the same manner as in No. 1.

In recent years, a film with a lens represented by “sharp run” has exploded, and the photographing area has greatly expanded. Since these are smaller and less expensive than ordinary cameras, they are often treated rough. One of the unforeseen troubles associated with this is the disruption of gradation balance caused by exposure to ultra-high humidity conditions. This leads to a shift in the color of the print and a remarkable decrease in the finished quality, so that measures are strongly desired.

[0177] This trouble is caused when the lens-equipped film is placed in the inner pocket where the temperature and humidity easily rise, is put in a bag with wet clothing, or when the lens-equipped film itself is directly wetted. It is thought to occur in.

When searching for an ultra-high humidity condition for reproducing an actual failure, it was found that the conditions of a temperature of 40 ° C. and a relative humidity of 100% were met.

(Test of change in photographic performance under ultra-high humidity conditions) Two samples 101 to 115 were prepared, one of which was stored at 40 ° C and a relative humidity of 65% for 16 hours (storage condition A: comparison. (Standard humidity conditions), the other was stored at 40 ° C and 100% relative humidity for 16 hours
(Storage condition B).

Next, each sample was subjected to wedge exposure using white light, and subjected to the development processing described in Example 3. However, the processing time of the color development was 2 minutes and 45 seconds. The sample after the treatment was subjected to sensitometry to obtain the maximum color density (Dmax) and the density ratio (storage condition B vs. storage condition A).

The results are shown in the table below.

Table High boiling organic solvent Dmax (A) Dmax (B) Dmax (B) / Dmax (A) Sample 101 (comparative) HBS-1 1.90 1.36 0.72 Sample 102 (invention) 1 1.89 1.86 0.98 Sample 103 (book) (Invention) 2 1.90 1.91 1.01 Sample 104 (Invention) 3 1.88 1.87 0.99 Sample 105 (Invention) 6 1.88 1.87 0.99 Sample 106 (Invention) 12 1.93 1.90 0.99 Sample 107 (Invention) 19 1.86 1.87 1.01 Sample 108 (Comparison) ) a 1.22 0.97 0.80 Sample 109 (comparison) b 1.62 1.61 0.99 Sample 110 (comparison) c 1.35 1.27 0.94 Sample 111 (comparison) d 1.98 1.19 0.60 Sample 112 (comparison) e 1.51 1.53 1.01 Sample 113 (comparison) f 1.81 1.54 0.85 Sample 114 (comparison) g 0.72 0.70 0.97 Sample 115 (comparison) h 0.66 0.67 1.02.

From the table, it was found that the sample using the high boiling point organic solvent of the present invention had a high color density under storage condition A and storage condition B
However, it can be seen that there is almost no decrease in density. The decrease in color density due to storage under ultra-high humidity conditions is caused by the diffusion of the green-sensitive silver halide emulsion layer to another layer of a high boiling point organic solvent, here the blue-sensitive silver halide emulsion layer. It is considered that the decrease in the amount of the high boiling point organic solvent in the emulsion layer resulted in a decrease in the color developing reactivity of the magenta coupler. The decrease in color density due to storage under ultra-high humidity conditions
Although it is improved by changing from HBS-1 (tricresyl phosphate) to a more hydrophobic high-boiling organic solvent e, g, h, on the other hand, a marked decrease in color density under standard conditions (storage condition A) Invite. Therefore, the use of the bis-arylphosphate-type high-boiling organic solvent of the present invention makes it possible to achieve both the color-forming performance under standard conditions and the color-forming performance after storage under ultra-high humidity conditions.

Example 2 Each layer having the following composition was superposed on the support of Example 3.
Apply to make sample 201 which is a monochrome photosensitive material
did. Here, the number corresponding to each component is g / m ^TwoIn units
The coating amount shown is shown.
It was shown as a converted amount of coating. However, for sensitizing dyes,
In moles per mole of silver halide per layer
expressed.

The materials and emulsions used for each layer are described in Example 3.

(Sample 201) First layer (magenta coloring layer) ExM-3 0.385 HBS-1 0.393 HBS-3 0.016 Gelatin 1.039.

Second layer (middle layer) Gelatin 2.000.

Third layer (blue-sensitive silver halide emulsion layer) Silver iodobromide emulsion J silver 0.18 silver iodobromide emulsion K silver 0.08 silver iodobromide emulsion L silver 0.36 ExS-9 8.4 × 10 ^-4 ExY-2 1.000 HBS-1 0.333 gelatin 2.409.

Fourth layer (protective layer) H-1 0.18 B-1 (1.7 μm in diameter) 0.05 B-2 (1.7 μm in diameter) 0.12 B-3 0.15 ES-1 0.25 Gelatin 2.14.

(Preparation of Samples 202 to 216) The high-boiling organic solvent HBS-1 in the first layer of the sample 201 was replaced with the high-boiling organic solvent 1, 2, 3, 6, 12, 19 of the invention of the present invention or the following. Sample 20 except that the comparative high-boiling organic solvents a to h were each replaced with an equal weight.
Samples 202 to 215 were produced in the same manner as in 1. Further, a sample 216 was prepared in the same manner as in the sample 201 except that the magenta coupler ExM-3 and the high boiling point organic solvent HBS-1 and HBS-3 in the first layer of the sample 201 were removed.

(Test of changes in photographic performance under ultra-high humidity conditions) Two samples 201 to 216 were prepared, and one of them was stored at 40 ° C and a relative humidity of 65% for 16 hours (storage condition A: comparison. (Standard humidity conditions), the other was stored at 40 ° C and 100% relative humidity for 16 hours
(Storage condition B).

Next, each sample was subjected to wedge exposure with white light, and the development processing described in Example 3 was performed. However, the processing time of the color development was 2 minutes and 45 seconds. Sensitometry was performed on the sample after the processing, and the gradient of the gradation, that is, the gamma at the exposure amount giving a color density of 1/2 of the maximum color density was obtained for each of the storage conditions A and B. The results are shown in the table below.

Table High-boiling organic solvents gamma (A) gamma (B) Sample 201 (comparison) HBS-1 0.78 0.84 Sample 202 (invention) 1 0.77 0.77 Sample 203 (invention) 2 0.77 0.78 Sample 204 (invention) 3 0.77 0.77 Sample 205 (invention) 6 0.78 0.79 Sample 206 (invention) 12 0.76 0.77 Sample 207 (invention) 19 0.77 0.77 Sample 208 (comparison) a 0.79 0.84 Sample 209 (comparison) b 0.78 0.78 Sample 210 (comparison) ) c 0.80 0.85 Sample 211 (comparison) d 0.79 0.85 Sample 212 (comparison) e 0.77 0.78 Sample 213 (comparison) f 0.78 0.82 Sample 214 (comparison) g 0.76 0.77 Sample 215 (comparison) h 0.77 0.77 Sample 216 (comparison) None 0.77 0.77.

As can be seen from the table, the sample of the present invention hardly changed in gamma even when stored under ultra-high humidity conditions (storage condition B). When stored in ultra-high humidity conditions with a high boiling organic solvent HBS-1, a, c, or d, the gamma of the blue-sensitive silver halide emulsion layer increases. Considering the results of Sample 216, this indicates that the high-boiling organic solvent in the green-sensitive silver halide emulsion layer diffuses into the blue-sensitive silver halide emulsion layer and promotes the coloring reaction of the yellow coupler ExY-2. You can think.

In addition to the results of Example 1, the photographic material using the high-boiling organic solvent of the present invention can suppress the change in photographic performance of not only its own layer but also other layers even when exposed to ultra-high humidity conditions. It can be said that there is.

Example 3 1) Support The support used in this example was prepared by the following method. Polyethylene-2,6-naphthalate polymer 100
After drying 2 parts by weight and 2 parts by weight of Tinuvin P.326 (manufactured by Ciba-Geigy Co.) as an ultraviolet absorber, 300 ° C.
After being melted at, extruded from a T-die, and stretched 3.3 times at 140 ° C, then stretched 3.3 times at 130 ° C, and heat-fixed at 250 ° C for 6 seconds to make a 90 μm thick PEN. I got a film. The PEN film has a blue dye, a magenta dye and a yellow dye (public technical report: official technical report No. 94-6023).
I-1, I-4, I-6, I-24, I-26, I-27, II-5) described in the above items were added in appropriate amounts. Furthermore, the support was wound around a stainless steel core having a diameter of 20 cm to give a heat history of 110 ° C. and 48 hours, thereby providing a support that was not easily curled.

2) Coating of Undercoat Layer The support was subjected to a corona discharge treatment, a UV irradiation treatment and a glow discharge treatment on both surfaces thereof, and then one surface of the support was coated with 0.1 g / m ² of gelatin and sodium α-sulfodium. -2-ethylhexyl succinate 0.01 g / m ² , salicylic acid 0.04 g / m ² , p-chlorophenol 0.2 g / m ² , (CH ₂ = CHSO ₂ CH ₂ CH ₂ NHCO) ₂ CH ₂
0.012 g / m ² , polyamide-epichlorohydrin polycondensate
An undercoat solution of 0.02 g / m ² was applied (10 mL / m ² , using a bar coater) to provide an undercoat layer on the high-temperature side during stretching. 115 dry
6 ° C. for 6 minutes (all rollers and conveyors in the drying zone are at 115 ° C.).

3) Coating of Back Layer On the other side of the support after the undercoating, an antistatic layer, a magnetic recording layer and a sliding layer having the following composition were coated as a back layer.

3-1) Coating of antistatic layer Tin oxide-antimony oxide composite having an average particle diameter of 0.005 μm has a specific resistance of 5 Ω · cm, a dispersion of fine particle powder (secondary aggregated particle diameter of about 0.08 μm). 0.2 g / m ^2, gelatin 0.05g / m _^2, (CH ²
_{= CHSO 2 CH 2 CH 2 NHCO} ) 2 CH 2 0.02g / m 2, was coated with polyoxyethylene -p- nonylphenol (polymerization degree 10) 0.005g / m ² and resorcin 0.22 g / m ^2.

3-2) Coating of Magnetic Recording Layer Cobalt-γ-iron oxide coated with 3-polyoxyethylene-propyloxytrimethoxysilane (degree of polymerization: 15; 15% by weight) (specific surface area: 43 m ² / g, long axis 0.14μm, single axis
0.03 μm, saturation magnetization 89 emu / g, Fe ^{+ 2} / Fe ⁺³ = 6/94, the surface is treated with aluminum oxide silicon oxide with 2% by weight of iron oxide) 0.06 g / m ² diacetyl cellulose 1.2 g / m ² (dispersion of iron oxide was carried out with an open kneader and a sand mill), C ₂ H ₅ C (CH ₂ OCONH-C ₆ H ₃ (CH ₃ ) NCO) ₃ 0.3 g / m as a curing agent
² was applied with a bar coater using acetone, methyl ethyl ketone, and cyclohexanone as a solvent, and a film thickness of 1.2
A μm magnetic recording layer was obtained. Silica particles as matting agent
(0.3 μm) and aluminum oxide (0.15 μm) as an abrasive coated with 3-polyoxyethylene-propyloxytrimethoxysilane (degree of polymerization: 15; 15% by weight) were added so as to be 10 mg / m ² . . Drying was performed at 115 ° C. for 6 minutes (all rollers and transport devices in the drying zone were 115 ° C.). X- write saturation magnetization moment of the magnetic recording layer of the D color density increment of about 0.1 of ^B, also the magnetic recording layer is 4.2 emu / g, coercive force 7.3 × 10 ⁴ A / m, the squareness ratio in (blue filter) Was 65%.

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

4) Coating of Photosensitive Layer Next, on the side opposite to the support of the back layer obtained above, layers having the following compositions were applied in a multi-layered manner to prepare a color negative film. This is referred to as a sample 301.

(Composition of photosensitive layer) The main materials used in each layer are classified as follows: ExC: cyan coupler UV: ultraviolet absorber ExM: magenta coupler HBS: high boiling point organic solvent ExY: yellow coupler H: Gelatin hardener ExS: Sensitizing dye The number corresponding to each component indicates the coating amount in g / m ² , and the silver halide indicates the coating amount in terms of silver.
However, with respect to the sensitizing dye, the coating amount is shown in mol units per mol of silver halide in the same layer.

(Sample 301) First Layer (First Antihalation Layer) Black Colloidal Silver Silver 0.14 Gelatin 0.50.

Second Layer (Second Antihalation Layer) Black Colloidal Silver Silver 0.12 Gelatin 0.57 ExM-1 0.12 ExF-1 2.0 × 10 ^-3 Solid Disperse Dye ExF-2 0.030 Solid Disperse Dye ExF-3 0.040 HBS-1 0.15 HBS-2 0.02.

Third layer (intermediate layer) Silver iodobromide emulsion N silver 0.06 ExC-2 0.05 polyethyl acrylate latex 0.20 gelatin 0.70

Fourth layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion A silver 0.27 silver iodobromide emulsion B silver 0.12 ExS-1 5.8 × 10 ^-4 ExS-2 0.8 × 10 ^-5 ExS-3 2.5 × 10 ^-4 ExC-1 0.28 ExC-3 0.058 ExC-4 0.19 ExC-5 0.03 ExC-6 0.02 Cpd-2 0.025 HBS-1 0.28 Gelatin 2.00.

Fifth layer (medium-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion B Silver 0.77 ExS-1 6.5 × 10 ^-4 ExS-2 0.9 × 10 ^-5 ExS-3 2.8 × 10 ^-4 ExC-1 0.12 ExC-2 0.04 ExC-3 0.055 ExC-4 0.08 ExC-5 0.02 ExC-6 0.015 Cpd-4 0.024 Cpd-2 0.025 HBS-1 0.10 Gelatin 0.92.

Sixth layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion Silver 0.93 ExS-1 5.8 × 10 ^-4 ExS-2 0.8 × 10 ^-5 ExS-3 2.8 × 10 ^-4 ExC-1 0.044 ExC-3 0.022 ExC-6 0.012 ExC-7 0.010 Cpd-2 0.065 Cpd-4 0.065 HBS-1 0.16 HBS-2 0.080 Gelatin 1.10.

Seventh layer (intermediate layer) Cpd-1 0.060 Solid disperse dye ExF-4 0.030 HBS-1 0.043 Polyethyl acrylate latex 0.19 Gelatin 1.05.

Eighth layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion E silver 0.18 silver iodobromide emulsion F silver 0.21 silver iodobromide emulsion G silver 0.22 ExS-7 8.1 × 10 ^-5 ExS-8 3.6 × 10 ^-4 ExS-4 2.5 × 10 ^-5 ExS-5 8.8 × 10 ^-5 ExS-6 4.1 × 10 ^-4 ExM-3 0.20 ExM-4 0.06 ExY-1 0.01 ExY-5 0.0020 HBS-1 0.18 HBS- 3 0.008 Cpd-4 0.010 Gelatin 0.73.

Ninth layer (medium-speed green-sensitive emulsion layer) Silver iodobromide emulsion G silver 0.47 silver iodobromide emulsion H silver 0.35 ExS-4 3.9 × 10 ^-5 ExS-7 2.0 × 10 ^-4 ExS-8 8.9 × 10 ^-4 ExC-8 0.0020 ExM-3 0.18 ExM-4 0.055 ExC-6 0.016 ExY-4 0.001 ExY-5 0.001 Cpd-4 0.015 HBS-1 0.18 HBS-3 0.009 Gelatin 1.00.

Tenth Layer (High Sensitive Green Sensitive Emulsion Layer) Silver Iodobromide Emulsion I Silver 0.95 ExS-4 6.2 × 10 ^-5 ExS-7 1.6 × 10 ^-4 ExS-8 7.7 × 10 ^-4 ExC-6 0.03 ExM-4 0.020 ExM-2 0.010 ExM-5 0.001 ExM-6 0.001 ExM-3 0.034 Cpd-4 0.030 HBS-1 0.27 Polyethyl acrylate latex 0.15 Gelatin 1.20.

Layer D (donor layer of multilayer effect) Silver iodobromide emulsion D (0.58 μm) Silver 0.45 ExS-6 6.5 × 10 ^-4 ExS-10 2.3 × 10 ^-4 ExM-3 0.10 ExM-4 0.031 ExY -1 0.034 HBS-1 0.30 Cpd-4 0.004 Gelatin 0.51.

Eleventh layer (yellow filter layer) Yellow colloidal silver silver 0.001 Cpd-1 0.11 ExF-5 0.15 HBS-1 0.05 gelatin 0.70.

Twelfth layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion J silver 0.18 silver iodobromide emulsion K silver 0.08 silver iodobromide emulsion L silver 0.36 ExS-9 8.4 × 10 ^-4 ExC-1 0.023 ExC-8 7.0 × 10 ^-3 ExY-1 0.033 ExY-2 0.91 ExY-3 0.01 ExY-4 0.01 Cpd-2 0.005 Cpd-4 0.001 HBS-1 0.28 Gelatin 2.20.

13th layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion M silver 0.42 ExS-9 6.0 × 10 ^-4 ExY-2 0.16 ExY-3 0.001 ExY-4 0.002 Cpd-2 0.10 Cpd-3 1.0 × 10 ^-3 Cpd-4 5.0 × 10 ^-3 HBS-1 0.075 Gelatin 0.70.

Fourteenth layer (first protective layer) Silver iodobromide emulsion N silver 0.10 UV-1 0.13 UV-2 0.10 UV-3 0.16 UV-4 0.025 ExF-8 0.03 ExF-9 0.005 ExF-10 0.005 ExF- 11 0.02 HBS-1 5.0 × 10 ^-2 HBS-4 5.0 × 10 ^-2 Gelatin 1.8.

Fifteenth layer (second protective layer) H-1 0.40 B-1 (1.7 μm in diameter) 0.04 B-2 (1.7 μm in diameter) 0.09 B-3 0.13 ES-1 0.20 Gelatin 0.70.

Further, in order to improve the storability, processing property, pressure resistance, fungicidal / antibacterial properties, antistatic property and coatability of each layer, W-1 to W-3, B-4 to B- 6, F-
1 to F-18 and iron salts, lead salts, gold salts, platinum salts, palladium salts, iridium salts, and rhodium salts.

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[Table 1]

In Table 1, (1) Emulsions J to M were reduction-sensitized during the preparation of grains using thiourea dioxide and thiosulfonic acid according to the examples of US Pat. No. 5,061,614.

(2) Emulsions B to D and M are described in EP 443,45.
According to the example of No. 3A, gold sensitization, sulfur sensitization and selenium sensitization were performed in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate.

(3) Preparation of tabular grains is described in
According to the example of No. 26, low molecular weight gelatin is used.

(4) Ten or more dislocation lines as described in European Patent No. 443,453A are observed in tabular grains using a high voltage electron microscope.

(5) Emulsions A to E, G, H, and J to M
h, Ir, and Fe are contained in optimal amounts. The flatness is
When the average equivalent circle diameter in the projected area of the tabular grains is Dc and the average thickness of the tabular grains is t, it is defined as Dc / t ² .

Preparation of Dispersion of Organic Solid Disperse Dye ExF-2 shown below was dispersed by the following method. That is, water 21.7
5 mL and 5 mL of a 10% aqueous solution of sodium salt of dioctyl sulfosuccinate are placed in a 700 mL pot mill, and the dye ExF
-2 5.0 g and zirconium oxide beads (diameter 1 mm) 500
mL was added and the contents were dispersed for 2 hours. For this dispersion, a BO type vibration ball mill manufactured by Chuo Koki was used. After dispersion, take out the contents, add to 8 g of 12.5% gelatin aqueous solution,
The beads were removed by filtration to obtain a gelatin dispersion of the dye.
The average particle size of the fine dye particles was 0.44 μm.

In the same manner, solid dispersions of ExF-3, ExF-4 and ExF-5 were obtained. The average particle diameters of the fine dye particles were 0.25 μm, 0.44 μm, and 0.46 μm, respectively.

The sample manufactured as described above is designated as 301.

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(Preparation of Samples 302 to 306) Except that HBS-1 in the eighth layer of Sample 301 was replaced by the high boiling organic solvents 1, 2, and 3 of the present invention or the comparative high boiling organic solvents d and f described above. sample
Samples 302 to 306 were produced in the same manner as 301. Here, the amount of the high boiling point organic solvent used was determined so that the gradation of the green-sensitive silver halide emulsion layer of Sample 301 was matched. However,
When the high boiling point organic solvents a, b, c, e, g, and h for comparison are replaced with HBS-1, the gradation becomes soft, and the gradation is adjusted even if the usage amount is increased in a realistic range. As a result, the preparation of the sample was abandoned.

(Test of change in photographic performance under ultra-high humidity conditions) Two samples 301 to 306 were prepared, and one of them was stored at 40 ° C and a relative humidity of 65% for 16 hours (storage condition A: comparison. (Standard humidity conditions), the other was stored at 40 ° C and 100% relative humidity for 16 hours
(Storage condition B).

Next, each sample was subjected to wedge exposure with white light, and subjected to the following development processing. Sensitometry is performed on the processed sample, and a predetermined exposure amount (sample 3
In the storage condition A of No. 01, the magenta density at the shoulder of the magenta gradation and the exposure amount that gives a density of about 2.5 in terms of color density was determined. The value of magenta concentration (storage condition B) -magenta concentration (storage condition A) was determined for each of the samples 301 to 306, and the value was defined as a value of a decrease in magenta concentration due to storage under ultra-high humidity conditions.

The results are shown in the table below.

Table High-boiling organic solvent Magenta concentration decrease Sample 301 (Comparative Example) HBS-1 -0.30 Sample 302 (Invention) 1 +0.03 Sample 303 (Invention) 2 +0.02 Sample 304 (Invention) 3 +0.02 Sample 305 (comparative example) d -0.46 Sample 306 (comparative example) f -0.25.

From the table, it can be seen that the sample using the high-boiling organic solvent of the present invention has a small decrease in magenta concentration and a small softening of gradation due to storage under ultra-high humidity conditions.

Hereinafter, the developing method will be described. After exposing the above color photographic light-sensitive material, using a negative processor FP-350 manufactured by Fuji Photo Film Co., Ltd., by the method described below (until the cumulative replenishment amount of the liquid becomes three times the mother liquor tank capacity). Processed.

(Processing method) Step Processing time Processing temperature Replenishment amount Color development 3 min. 15 sec. 38 ° C. 45 mL Bleaching 1 min. 00 sec. 38 ° C. 20 mL Bleach overflows completely into bleach-fix bath Bleach-fix 3 min. 15 sec. 38 ℃ 30mL Rinse 1 40 seconds 35 ° C Countercurrent piping system from (2) to (1) Rinse 2 1 minute 00 seconds 35 ° C 30mL Stable 40 seconds 38 ° C 20mL Dry 1 minute 15 seconds 55 ° C * Replenishment amount Is 35 mm width per 1.1 m length (corresponding to one 24Ex.) Next, the composition of the processing solution is described.

(Color developing solution) Tank solution (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1.0 1.1 1-hydroxyethylidene-1,1-diphosphonic acid 2.0 2.0 Sodium sulfite 4.0 4.4 Potassium carbonate 30.0 37.0 Potassium bromide 1.4 0.7 Iodine Potassium iodide 1.5 mg-hydroxylamine sulfate 2.4 2.8 4- [N-ethyl-N- (β-hydroxyethyl) amino] -2-methylaniline sulfate 4.5 5.5 Add water and add 1.0 L 1.0 L pH (potassium hydroxide And adjusted with sulfuric acid) 10.05 10.10.

(Bleaching solution) Common to tank solution and replenishing solution (unit: g) Ethylenediaminetetraacetate ammonium dihydrate 120.0 Ethylenediaminetetraacetic acid disodium salt 10.0 Ammonium bromide 100.0 Ammonium nitrate 10.0 Bleaching accelerator 0.005 mol (CH ₃ ) _{2 N-CH 2 -CH 2 -SS} -CH 2 -CH 2 -N (CH 3) 2 · 2HCl aqueous ammonia (27%) was added 15.0 mL water 1.0 L pH (adjusted with aqueous ammonia and nitric acid) 6.3 .

(Bleach-fixing solution) Tank solution (g) Replenisher (g) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 50.0-Ethylenediaminetetraacetic acid disodium salt 5.0 2.0 Sodium sulfite 12.0 20.0 Aqueous ammonium thiosulfate (700 g / L) 240.0 mL 400.0 mL Aqueous ammonia (27%) 6.0 mL-Add water 1.0 L 1.0 L pH (adjusted with aqueous ammonia and acetic acid) 7.2 7.3.

(Washing solution) Common tank water and replenisher tap water is H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH type anion exchange resin (Amberlite IR-400). The mixture was passed through a mixed-bed column packed with to treat the calcium and magnesium ion concentrations at 3 mg / L or less, and then 20 mg / L of sodium isocyanurate dichloride and 0.15 g / L of sodium sulfate were added. The pH of this solution is 6.5-
It was in the range of 7.5.

(Stabilizing solution) Common to tank solution and replenisher (unit: g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization: 10) 0.2 Disodium ethylenediaminetetraacetate 0.05 1, 2,4-Triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 1,2-Benzoisothiazolin-3-one 0.10 Add water 1.0 L pH 8.5.

Example 4 After a corona discharge treatment was applied to the surface of a support having both sides of paper coated with polyethylene resin, a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided. A seventh layer of a photographic component layer was sequentially coated to prepare a sample (400) of a silver halide color photographic light-sensitive material having the following layer configuration. The coating solution for each photographic constituent layer was prepared as follows.

Preparation of Coating Solution for Fifth Layer 300 g of cyan coupler (ExC-1), 250 g of color image stabilizer (Cpd-1), 1 color image stabilizer (Cpd-9)
0 g, color image stabilizer (Cpd-10) 10 g, color image stabilizer (Cpd-12) 20 g, ultraviolet absorber (UV-1) 1
4 g, UV absorber (UV-2) 50 g, UV absorber (UV-3) 40 g and UV absorber (UV-4) 6
0 g was dissolved in 230 g of a solvent (Solv-6) and 350 mL of ethyl acetate, and this solution was emulsified and dispersed in 6500 g of a 10% aqueous gelatin solution containing 200 mL of 10% sodium dodecylbenzenesulfonate to prepare an emulsified dispersion C.

On the other hand, silver chlorobromide emulsion C (cubic, 1: 4 mixture of large-size emulsion C having an average grain size of 0.50 μm and small-size emulsion C having a size of 0.41 μm (silver molar ratio). The coefficients of variation are 0.09 and 0.11, respectively.
In each size emulsion, 0.5 mol% of silver bromide was locally contained on a part of the surface of the silver chloride-based grain).

This emulsion has a red-sensitive sensitizing dye G shown below.
And H were added in an amount of 6.0 × 10 ⁻⁵ mol for the large-sized emulsion C and 9.0 × 10 ⁻⁵ mol for the small-sized emulsion C, respectively, per mol of silver. The chemical ripening of this emulsion was optimally performed by adding a sulfur sensitizer and a gold sensitizer.

The emulsified dispersion C and this silver chlorobromide emulsion C were mixed and dissolved to prepare a fifth layer coating solution having the following composition. The emulsion coating amount indicates a coating amount in terms of silver amount.

The coating solutions for the first to fourth layers and the sixth to seventh layers were prepared in the same manner as the coating solution for the fifth layer. As a gelatin hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used.

In each layer, Ab-1, Ab-2, Ab-
3 and Ab-4 in a total amount of 15.0 mg /
^{m 2, 60.0mg / m 2,} 5.0mg / m 2 and 1
It was added to a concentration of 0.0 mg / m ² .

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The following spectral sensitizing dyes were used for the silver chlorobromide emulsion in each photosensitive emulsion layer.

Blue-sensitive emulsion layer

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(Sensitizing dyes A, B and C were used in an amount of 1.4 ×
^10-4 moles, ^1.7x each for small size emulsions
10 ^-4 mol was added. ).

Green-sensitive emulsion layer

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(Sensitizing dye D was added per mole of silver halide,
3.0 × 10 for large emulsions ^-FourMol, small size
3.6 × 10 for emulsion^-FourMol and sensitizing dye E
Per mole of silver halide and for large emulsions
4.0 × 10^-Five7.0 × for mole, small size emulsions
10^-FiveMole of sensitizing dye F per mole of silver halide.
2.0 × 10 for large emulsions^-FourMole, small
2.8 × 10 for size emulsion^-FourMole added
Was. ).

Red-sensitive emulsion layer

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(Sensitizing dyes G and H were converted to silver halide 1
6.0 × 1 per mole for large size emulsions
0 ^-5 mol, respectively 9.0 × 1 to the small size emulsion
0 ^-5 mol was added. ).

Further, the following compound I was added to the red-sensitive emulsion layer in an amount of 2.6 × 10 ^-3 mol per mol of silver halide. ).

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Also, 1- (3-methylureidophenyl) -5-mercaptotetrazole was added to the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer in an amount of 3.3 × 10 5 per mol of silver halide. ^-4 mol, 1.0 × 10 ^-3
Mol and 5.9 × 10 ^-4 mol.

Further, the second layer, the fourth layer, the sixth layer, and the
0.2mg / m each for 7 layers ^Two0.2 mg /
m^Two, 0.6 mg / m^Two0.1 mg / m^TwoSo that
Was added.

Further, 4-hydroxy-6-methyl-1,3,3a, 7 was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer.
Tetrazindene was added in an amount of 1 × 10 ⁻⁴ mol and 2 × 10 ⁻⁴ mol per mol of silver halide.

In the red-sensitive emulsion layer, a copolymer of methacrylic acid and butyl acrylate (weight ratio 1: 1, average molecular weight 2
(0000 to 400,000) was added at 0.05 g / m ² .

[0285] Also, the second layer was added the fourth layer and the sixth layer in disodium catechol-3,5-disulfonate as respectively a ^{6mg / m 2, 6mg / m} 2, 18mg / m 2.

To prevent irradiation, the following dyes were added to the emulsion layer (the amount in parentheses indicates the coating amount).

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(Layer Structure) The structure of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion is
It represents the silver equivalent coating amount.

Support Polyethylene resin laminated paper (A white pigment (TiO ₂ ;
Content 16% by weight, ZnO; content 4% by weight) and optical brighteners (4,4'-bis (benzoxazolyl) stilbene and 4,4'-bis (5-methylbenzoxazolyl)
8/2 mixture of stilbene: content 0.05% by weight),
Blue dye (including ultramarine blue)).

First Layer (Blue-Sensitive Emulsion Layer) Silver chlorobromide emulsion (cubic, 3: 7 mixture of large-size emulsion A having an average grain size of 0.72 μm and small-size emulsion A having a 0.60 μm size (silver molar ratio) The coefficient of variation of the grain size distribution was 0.08 and 0.10, respectively. In each size emulsion, 0.3 mol% of silver bromide was contained locally on a part of the grain surface based on silver chloride.) 0.26 Gelatin 1.35 Yellow coupler (ExY) 0.62 Color image stabilizer (Cpd-1) 0.08 Color image stabilizer (Cpd-2) 0.04 Color image stabilizer (Cpd-3) 08 Solvent (Solv-1) 0.23.

Second layer (color mixture prevention layer) Gelatin 0.99 Color mixture prevention agent (Cpd-4) 0.09 Color image stabilizer (Cpd-5) 0.018 Color image stabilizer (Cpd-6) 0.13 Color image stabilizer (Cpd-7) 0.01 Solvent (Solv-2) 0.28.

Third Layer (Green-Sensitive Emulsion Layer) Silver chlorobromide emulsion B (cubic, 1: 3 mixture of large-size emulsion B having an average grain size of 0.45 μm and small-size emulsion B having an average grain size of 0.35 μm (silver mole The coefficient of variation of the grain size distribution was 0.10 and 0.08, respectively. In each size emulsion, 0.4 mol% of silver bromide was locally contained on a part of the grain surface based on silver chloride.) 0.14 Gelatin 1.36 Magenta coupler (ExM) 0.15 UV absorber (UV-1) 0.05 UV absorber (UV-2) 0.03 UV absorber (UV-3) 0.02 UV absorption Agent (UV-4) 0.04 Color image stabilizer (Cpd-2) 0.02 Color image stabilizer (Cpd-4) 0.002 Color image stabilizer (Cpd-6) 0.09 Color image stabilizer ( Cpd-8) 0.02 Color image stabilizer (Cpd-9) 0.03 Image stabilizer (Cpd-10) 0.01 Color image stabilizer (Cpd-11) 0.0001 Solvent (Solv-3) 0.11 Solvent (Solv-4) 0.22 Solvent (Solv-5) 0.20 .

Fourth layer (color mixture prevention layer) Gelatin 0.71 Color mixture prevention agent (Cpd-4) 0.06 Color image stabilizer (Cpd-5) 0.013 Color image stabilizer (Cpd-6) 0.10 Color image stabilizer (Cpd-7) 0.007 Solvent (Solv-2) 0.20.

Fifth Layer (Red-Sensitive Emulsion Layer) Silver chlorobromide emulsion C (cubic, 1: 4 mixture of large-size emulsion C having an average grain size of 0.50 μm and small-size emulsion C having an average grain size of 0.41 μm (silver mole The coefficient of variation of the grain size distribution was 0.09 and 0.11, respectively. In each size emulsion, 0.5 mol% of silver bromide was locally contained on a part of the grain surface based on silver chloride.) 0.20 Gelatin 1.11 Cyan coupler (ExC-1) 0.30 Ultraviolet absorber (UV-1) 0.14 Ultraviolet absorber (UV-2) 0.05 Ultraviolet absorber (UV-3) 0.04 UV absorber (UV-4) 0.06 Color image stabilizer (Cpd-1) 0.25 Color image stabilizer (Cpd-9) 0.01 Color image stabilizer (Cpd-10) 0.01 Color image stabilizer Agent (Cpd-12) 0.02 Solvent (Solv-6) 0.23

Sixth layer (ultraviolet absorbing layer) Gelatin 0.66 Ultraviolet absorbing agent (UV-1) 0.19 Ultraviolet absorbing agent (UV-2) 0.06 Ultraviolet absorbing agent (UV-3) 0.06 Ultraviolet absorbing Agent (UV-4) 0.05 Ultraviolet absorber (UV-5) 0.09 Solvent (Solv-7) 0.25.

Seventh layer (protective layer) Gelatin 1.00 Acrylic modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.04 Liquid paraffin 0.02 Surfactant (Cpd-13) 0.01.

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Further, a sample 401 was prepared in which the composition of the fifth layer was changed as follows from the silver halide color photographic light-sensitive material 400 prepared as described above.

Fifth Layer (Red-Sensitive Emulsion Layer) Silver chlorobromide emulsion C (cubic, 1: 4 mixture of large-size emulsion C with an average grain size of 0.50 μm and small-size emulsion C with an average grain size of 0.41 μm (silver mole The coefficient of variation of the grain size distribution was 0.09 and 0.11, respectively. In each size emulsion, 0.8 mol% of silver bromide was contained locally on a part of the grain surface based on silver chloride.) 0.12 Gelatin 1.11 Cyan coupler (ExC-2) 0.13 Cyan coupler (ExC-3) 0.03 Color image stabilizer (Cpd-1) 0.05 Color image stabilizer (Cpd-6) 05 Color image stabilizer (Cpd-7) 0.02 Color image stabilizer (Cpd-9) 0.04 Color image stabilizer (Cpd-10) 0.01 Color image stabilizer (Cpd-14) 0.01 color Image stabilizer (Cpd-15) 0.06 Color image stabilizer (Cpd-16) 0.09 Color image stabilizer (Cpd-17) 0.09 Color image stabilizer (Cpd-18) 0.01 Solvent (Solv-5) 0.15 Solvent (Solv-8) 0.05 Solvent (Solv- 9) 0.10.

The high-boiling organic solvent Solv-2 (same as the above f) in the fourth layer of the sample 401 was mixed with the high-boiling organic solvent HBS-1,
Sample 40 except that 1, 2, 3, or d was replaced by an equal weight
Samples 402 to 406 were produced in the same manner as in No. 1.

Next, the samples 402 to 406 were subjected to wedge exposure with red light, subjected to the following development processing, and measured for density. The magenta color density in the exposure region where the maximum cyan color density was obtained was determined, and the reactivity of the color mixture preventing agent in the fourth layer was examined. Here, the lower the magenta density, the higher the reactivity of the color mixture inhibitor and the direction in which the color turbidity is reduced, which is desirable.

Further, these samples were irradiated with xenon light for 3 hours.
Exposure to 10,000 lux was performed for 3 weeks, and the concentration was measured again.
The residual ratio of cyan density after light exposure at a cyan density of 2.0 before light exposure was determined and used as a measure of cyan image light fastness. The following table summarizes the test results.

Table High-boiling point organic solvent Magenta concentration (mixed color) Cyan concentration residual ratio (light fastness) Sample 401 (Comparative Example) Solv-2 (f) 0.24 76% Sample 402 (Comparative Example) HBS-1 0.25 69% Sample 403 (Invention) 1 0.22 81% Sample 404 (Invention) 2 0.21 83% Sample 405 (Invention) 3 0.23 79% Sample 406 (Comparative Example) d 0.24 61%.

From the table, it can be seen that in the sample using the high boiling point organic solvent of the present invention, the mixing of the magenta density with the cyan density was well suppressed and the light fastness of the cyan image was improved.

The high-boiling organic solvent of the present invention enhances the reactivity of the color-mixing inhibitor, and presumably hardly causes diffusion of the high-boiling organic solvent into the fifth red-sensitive silver halide emulsion layer. It is presumed that adverse effects on sex have been eliminated.

The following is a description of a developing method.

The above photosensitive material was processed into a roll having a width of 127 mm, and was processed by a printer processor manufactured by Fuji Photo Film Co., Ltd.
Continuous processing (running test) was performed using PP1820V until imagewise exposure and replenishment of twice the tank capacity of color development in the following processing steps.

Processing Step Temperature Time Replenishment amount * Color development 38.5 ° C 45 seconds 45mL Bleaching and fixing 38 ° C 45 seconds 35mL Rinse (1) 38 ° C 22 seconds-Rinse (2) 38 ° C 22 seconds-Rinse (3) 38 ° C 22 seconds 175mL rinse (4) 38 ° C. 22 seconds - drying 80 ° C. 60 seconds * replenishment rate per photosensitive material 1 m ² (rinse was a four-tank counter-current system to (1) to (4)).

The composition of each treatment liquid is as follows.

[Color developer] [Tank solution] [Replenisher] Water 800 mL 800 mL Ethylenediaminetetraacetic acid 4.0 g 4.0 g 4,5-Dihydroxybenzene-1,3-disulfonic acid disodium salt 0.5 g 0.5 g Triethanol Amine 12.0 g 12.0 g Potassium chloride 10.0 g-Potassium bromide 0.04 g-Potassium carbonate 27.0 g 27.0 g Triazinyl diaminostilbene-based fluorescent brightener (Hakkoru FWA-SF, manufactured by Showa Chemical Industry Co., Ltd.) 2.0 g 5.0 g Sulfurous acid Sodium 0.1 g 0.1 g Disodium-N, N-bis (sulfonatoethyl) hydroxylamine 5.0 g 11.5 g Dimethylpolysiloxane-based surfactant (Silicone KF351A / Shin-Etsu Chemical Co., Ltd.) 0.1 g 0.1 g N-ethyl-N- (Β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline / 3/2 sulfuric acid / 1 Salt 5.0 g 16.0 g Water to make 1000 mL 1000 mL pH (adjusted with 25 ° C. / potassium hydroxide and sulfuric acid) 10.00 12.50.

[Bleach-fixing solution] [Tank solution] [Replenisher] Water 600 mL 150 mL Ammonium thiosulfate (750 g / L) 110 mL 220 mL Ammonium sulfite 45 g 90 g Ammonium iron (III) ethylenediaminetetraacetate 45 g 90 g Ethylenediaminetetraacetic acid 115 g 3.0 g Imidazole 15 g 30 g Nitric acid (67%) 15 g 30 g Add water 1000 mL 1000 mL pH (adjusted at 25 ° C / acetic acid and aqueous ammonia) 7.0 6.0.

[Rinse solution] (The tank solution and the replenisher are the same.) Chlorinated sodium isocyanurate O.02 g Deionized water (conductivity 5 μs / cm or less) 1000 mL pH 6.5.

Example 5 Preparation of Sample 501 A multilayer color light-sensitive material comprising the following layers was prepared on an undercoated cellulose triacetate film support having a thickness of 127 μm to prepare Sample 501. The numbers represent the amount added per m ² . The effect of the added compound is not limited to the use described.

First layer: Antihalation layer Black colloidal silver 0.10 g Gelatin 1.90 g Ultraviolet absorber U-1 0.10 g Ultraviolet absorber U-3 0.040 g Ultraviolet absorber U-4 0.10 g High boiling organic solvent Oil-1 0.10 g 0.10 g of a microcrystalline solid dispersion of Dye E-1.

Second layer: Intermediate layer Gelatin 0.40 g Compound Cpd-C 5.0 mg Compound Cpd-J 5.0 mg Compound Cpd-K 3.0 mg High boiling organic solvent Oil-3 0.10 g Dye D-4 0.80 mg.

Third layer: Intermediate layer A fine-grain silver iodobromide emulsion whose surface and inside are fogged (average particle size 0.06 μm, coefficient of variation 18%, AgI content 1 mol%) Silver amount 0.050 g Yellow colloidal silver Silver amount 0.030 g 0.40 g of gelatin.

Fourth layer: low-sensitivity red-sensitive emulsion layer Emulsion A silver amount 0.30 g Emulsion B silver amount 0.20 g gelatin 0.80 g coupler C-1 0.15 g coupler C-2 0.050 g coupler C-3 0.050 g coupler C-9 0.050 g Compound Cpd-C 5.0 mg Compound Cpd-J 5.0 mg High boiling organic solvent Oil-2 0.10 g Additive P-1 0.10 g.

Fifth layer: Medium-speed red-sensitive emulsion layer Emulsion B Silver amount 0.20 g Emulsion C silver amount 0.30 g Gelatin 0.80 g Coupler C-1 0.20 g Coupler C-2 0.050 g Coupler C-3 0.20 g High boiling organic solvent Oil-2 0.10 g Additive P-1 0.10 g.

Sixth layer: High-sensitivity red-sensitive emulsion layer Emulsion D Silver amount 0.40 g Gelatin 1.10 g Coupler C-1 0.30 g Coupler C-2 0.10 g Coupler C-3 0.70 g Additive P-1 0.10 g.

Seventh layer: Intermediate layer Gelatin 0.60 g Additive M-1 0.30 g Color mixing inhibitor Cpd-I 2.6 mg Dye D-5 0.020 g Dye D-6 0.010 g Compound Cpd-J 5.0 mg High boiling organic solvent Oil -2 0.020 g.

Eighth layer: Intermediate layer A silver iodobromide emulsion whose surface and inside are fogged (average grain size: 0.06 μm, coefficient of variation: 16%, AgI content: 0.3 mol%) Silver content 0.020 g Yellow colloidal silver Silver content 0.020 g Gelatin 1.00 g Additive P-1 0.20 g Color mixing inhibitor Cpd-A 0.10 g Compound Cpd-C 0.10 g.

Ninth layer: low-sensitivity green-sensitive emulsion layer Emulsion E silver amount 0.10 g Emulsion F silver amount 0.20 g Emulsion G silver amount 0.20 g gelatin 0.50 g Coupler C-4 0.10 g Coupler C-7 0.050 g Coupler C-8 0.10 g Compound Cpd-B 0.030 g Compound Cpd-D 0.020 g Compound Cpd-E 0.020 g Compound Cpd-F 0.040 g Compound Cpd-J 10 mg Compound Cpd-L 0.020 g High boiling organic solvent Oil-2 0.20 g.

Tenth layer: medium-sensitive green-sensitive emulsion layer Emulsion G silver amount 0.30 g Emulsion H silver amount 0.10 g gelatin 0.60 g coupler C-4 0.070 g coupler C-7 0.050 g coupler C-8 0.050 g compound Cpd-B 0.030 g Compound Cpd-D 0.020 g Compound Cpd-E 0.020 g Compound Cpd-F 0.050 g Compound Cpd-L 0.050 g High boiling organic solvent Oil-2 0.010 g.

Eleventh layer: High-sensitivity green-sensitive emulsion layer Emulsion I Silver amount 0.50 g Gelatin 1.00 g Coupler C-4 0.20 g Coupler C-7 0.10 g Coupler C-8 0.050 g Compound Cpd-B 0.080 g Compound Cpd-E 0.020 g Compound Cpd-F 0.040 g Compound Cpd-K 5.0 mg Compound Cpd-L 0.020 g High boiling organic solvent Oil-2 0.040 g.

Twelfth layer: Intermediate layer Gelatin 0.60 g Compound Cpd-L 0.050 g High boiling organic solvent Oil-2 0.050 g.

13th layer: Yellow filter layer Yellow colloidal silver Silver amount 0.020 g Gelatin 1.10 g Color mixture inhibitor Cpd-A 0.010 g Compound Cpd-L 0.010 g High boiling organic solvent Oil-2 0.010 g Fine crystals of dye E-2 0.030 g of solid dispersion 0.020 g of microcrystalline solid dispersion of dye E-3.

14th layer: Intermediate layer 0.60 g of gelatin.

Fifteenth layer: low-sensitivity blue-sensitive emulsion layer Emulsion J Silver amount 0.20 g Emulsion K Silver amount 0.30 g Gelatin 0.80 g Coupler C-5 0.20 g Coupler C-6 0.10 g Coupler C-10 0.40 g.

Sixteenth layer: Medium-sensitivity blue-sensitive emulsion layer Emulsion L silver amount 0.30 g Emulsion M silver amount 0.30 g gelatin 0.90 g Coupler C-5 0.10 g Coupler C-6 0.10 g Coupler C-10 0.60 g.

17th layer: High-sensitivity blue-sensitive emulsion layer Emulsion N silver amount 0.20 g Emulsion O silver amount 0.20 g gelatin 1.20 g Coupler C-5 0.10 g Coupler C-6 0.10 g Coupler C-10 0.60 g High boiling organic solvent Oil-2 0.10 g.

[0339]

Nineteenth layer: Second protective layer Yellow colloidal silver Silver content 0.10 mg Fine grain silver iodobromide emulsion (average particle size 0.06 μm, AgI content 1 mol%) Silver content 0.10 g Gelatin 0.40 g.

Twentieth layer: Third protective layer Gelatin 0.40 g Polymethyl methacrylate (average particle size 1.5 μ) 0.10 g Copolymer of methyl methacrylate and methacrylic acid (average particle size 1.5 μ) 0.10 g Silicone oil SO-1 0.030 g Surfactant W-1 3.0 mg Surfactant W-2 0.030 g.

Further, additives F-1 to F-8 were added to all the emulsion layers in addition to the above composition. Further, in addition to the above composition, gelatin hardener H-1 and surfactants W-3, W-4, W-5 and W-6 for coating and emulsification were added to each layer.

Further, phenol and 1,1 are used as preservatives and fungicides.
2-Benzisothiazolin-3-one, 2-phenoxyethanol, phenethyl alcohol, p-hydroxybenzoic acid butyl ester were added.

Preparation of Dispersion of Organic Solid Disperse Dye Dye E-1 was dispersed by the following method. That is, water and 200 g of Pluronic F88 (ethylene oxide-propylene oxide block copolymer) manufactured by BASF were added to 1430 g of a wet cake of a dye containing 30% of methanol.
And stirred to obtain a slurry having a dye concentration of 6%. Next, Ultra Viscomil manufactured by Imex Co., Ltd. (UVM
2) Fill 1700 mL of zirconia beads with an average particle size of 0.5 mm, pass through the slurry at a peripheral speed of about 10 m / sec, and discharge 0.5 L.
/ Min for 8 hours. The beads were removed by filtration, diluted with water to a dye concentration of 3% by adding water, and then 90 ° C for stabilization.
For 10 hours. The average particle size of the obtained fine dye particles is 0.
60μm, and the size distribution of the particle size (particle size standard deviation x 100
/ Average particle size) was 18%.

Similarly, solid dispersions of dyes E-2 and E-3 were obtained. The average particle sizes were 0.54 μm and 0.56 μm.

[0346]

[Table 2]

[0347]

[Table 3]

[0348]

[Table 4]

[0349]

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[0350]

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[0351]

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[0352]

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[0353]

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[0354]

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[0355]

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[0356]

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[0357]

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[0358]

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[0359]

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[0360]

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[0361]

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[0362]

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[0363]

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The high-boiling organic solvent Oil-2 in the seventh, twelfth, and seventeenth layers of the sample 501 was replaced with the high-boiling organic solvent of the present invention,
Samples 502 to 508 were prepared in the same manner as Sample 501 except that 2, 3, 4, 6, 12, or 20 was replaced with an equal weight.

The samples 501 to 508 were subjected to wedge exposure with white light and subjected to the following development processing. The density of the sample after the treatment was measured, and then the yellow image was subjected to a light fastness test.

As a result of the test, in the sample of the present invention, color mixing was suppressed and the light fastness of the yellow image was improved.

[0367] The method of development processing is described below.

Processing Step Time Temperature Tank capacity Replenishment amount First development 6 minutes 38 ° C 12L 2200mL / m ² First water washing 2 minutes 38 ° C 4L 7500mL / m ² Inversion 2 minutes 38 ° C 4L 1100mL / m ² Color development 6 minutes 38 ℃ 12L 2200mL / m ² before Bleaching 2 min 38 ℃ 4L 1100mL / m ² Bleaching 6 min 38 ℃ 12L 220mL / m ² Fixing 4 min 38 ℃ 8L 1100mL / m ² second water washing 4 minutes 38 ° C. 8L 7500 ml / m ² Final rinse 1 minute 25 ° C 2L 1100mL / m ² .

The composition of each processing solution was as follows. [First developer] [Tank solution] [Replenisher] Nitrilo-N, N, N-trimethylenephosphonic acid / 5 sodium salt 1.5 g 1.5 g Diethylenetriaminepentaacetic acid / 5 sodium salt 6.0 g 6.0 g Sodium sulfite 30 g 30 g Potassium hydroquinone monosulfonate 23 g 23 g Potassium carbonate 15 g 20 g Sodium bicarbonate 12 g 15 g 1-Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 1.5 g 2.0 g Potassium bromide 2.5 g 1.4 g Potassium thiocyanate 1.2 g 1.2 g Potassium iodide 2.0 mg-Diethylene glycol 13 g 15 g Water was added to 1000 mL 1000 mL pH 9.60 9.60 The pH was adjusted with sulfuric acid or potassium hydroxide.

[Reversal solution] [Tank solution] [Replenishment solution] Nitrilo-N, N, N-trimethylenephosphonic acid pentasodium salt 3.0 g Same as tank solution Stannous chloride dihydrate 1.9 g p-amino acid Phenol 1 mg Sodium hydroxide 8 g Glacial acetic acid 15 mL Add water 1000 mL pH 6.00 pH was adjusted with acetic acid or sodium hydroxide.

[Color developing solution] [Tank solution] [Replenisher] Nitrilo-N, N, N-trimethylenephosphonic acid · pentasodium salt 7.0 g 7.0 g Sodium sulfite 7.0 g 7.0 g Trisodium phosphate / 12 dehydrate 36 g 36 g Potassium bromide 0.7 g-Potassium iodide 40 mg-Sodium hydroxide 3.0 g 3.0 g Citradic acid 0.6 g 0.6 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4- Aminoaniline / 3/2 sulfuric acid monohydrate 11 g 11 g 3,6-dithiaoctane-1,8-diol 1.0 g 1.0 g Add water 1000 mL 1000 mL pH 11.80 12.00 Adjust pH with sulfuric acid or potassium hydroxide did.

[Pre-bleaching] [Tank solution] [Replenisher] Ethylenediaminetetraacetic acid disodium salt dihydrate 8.0 g 8.0 g Sodium sulfite 6.0 g 8.0 g 1-thioglycerol 0.4 g 0.4 g Sodium formaldehyde sodium bisulfite adduct 30 g 35 g Water was added and 1000 mL 1000 mL pH 6.30 6.10 pH was adjusted with acetic acid or sodium hydroxide.

[Bleaching solution] [Tank solution] [Replenisher] Ethylenediaminetetraacetic acid / disodium salt / dihydrate 2.0 g 4.0 g Ethylenediaminetetraacetic acid / Fe (III) / ammonium / dihydrate 120 g 240 g Bromide Potassium 100 g 200 g Ammonium nitrate 10 g 20 g Water was added to 1000 mL 1000 mL pH 5.70 5.50 The pH was adjusted with nitric acid or sodium hydroxide.

[Fixing solution] [Tank solution] [Replenisher] Ammonium thiosulfate 80 g Same sodium sulfite 5.0 g ナ ト リ ウ ム Sodium bisulfite 5.0 g タ ン ク Water was added to 1000 mL ｐＨ pH 6.60 pH was adjusted with acetic acid or aqueous ammonia. It was adjusted.

[Stabilizing solution] [Tank solution] [Replenisher] 1,2-Benzoisothiazolin-3-one 0.02 g 0.03 g Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization: 10) 0.3 g 0.3 g Polymalein Acid (average molecular weight 2,000) 0.1 g 0.15 g Add water 1000 mL 1000 mL pH 7.0 7.0.

Claims (1)

[Claims] 1. A silver halide photographic material having at least one photosensitive silver halide emulsion layer on a support, characterized by containing a non-color-forming compound represented by the following general formula (1). Silver halide photographic material. Embedded image In the formula, R ₁ , R ₂ and R ₃ each independently represent an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, a halogen atom, a heterocyclic group, a cyano group, a hydroxy group, Nitro group, carboxyl group, sulfo group, amino group, alkoxy group, aryloxy group, acylamino group, alkylamino group, anilino group, ureido group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamide group, carbamoyl group, Represents a sulfamoyl group, a sulfonyl group, an alkoxycarbonyl group, a heterocyclic oxy group, an azo group, an acyloxy group, a carbamoyloxy group, a silyloxy group, an aryloxycarbonylamino group, an imide group, a sulfinyl group, an aryloxycarbonyl group, and an acyl group. k and n each independently represent an integer of 0 to 5. m
Represents an integer of 0 to 4.