JPH0926652A - Silver halide color photographic sensitive material and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain such a photosensitive material having a good gradation balance and reproducibility of tone and colors for both of a normal color developing process and a fast process by specifying conditions of gradations of yellow, magenta and cyan obtd. by plural developing processes and specifying the developing method. SOLUTION: This photosensitive material contains a coupler expressed by formula I in a red-sensitive silver halide emulsion layer, and when this material is developed in developing processes (1) and (2), the obtd. gradation satisfies the conditions of formula II. In formula I, R1 is -CONR4 R5 , R2 is a group which can be substituted for a naphthalene ring, k is an integer 0-3, R3 is a substitutent, X is a hydrogen atom, R and R5 are hydrogen atoms or the like. In formula II, γI(Y), γI(M), γI(C) are gradations of yellow, magnate and cyan when the developing process (I) is performed, and γII(Y), γII(M), γII(C) are gradations when the developing process (II) is performed. The developing process (I) is carried out with 3min to 3min and 15sec color developing time, while the developing process (II) is carried out with 50 to 70sec color developing time and other conditions. A specified developer is used for each process.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming an image on a silver halide color photographic light-sensitive material.
Improved photographic performance obtained when various types of processing are performed, in particular, the gradation of yellow, magenta and cyan color images are balanced to improve tone reproducibility and color reproducibility as well as excellent graininess and continuous processing. The present invention relates to an image forming method of a silver halide color photographic light-sensitive material, which sometimes has a small variation in cyan color density.

[0002]

2. Description of the Related Art With respect to basic metal compounds which are poorly soluble in water, for example, Japanese Patent Laid-Open No. 63-011940 (Reference 1) discloses a method in which the compound is contained in a light-sensitive material, and a complex-forming reaction occurs with the constituent metal ions of the compound. It is described to process with a developer containing a complex-forming compound that causes a reaction to release a base. As the cyan coupler according to the present invention, a so-called 2-equivalent coupler having a group capable of splitting off at the coupling position by a coupling reaction with an oxidized aromatic primary amine developer is a specific example or a different coupler. The combined use of a mother nucleus 4-equivalent coupler is disclosed. Although the use of these two-equivalent couplers certainly gives a high color density, particularly a high color density (Dmax), it is not always satisfactory in the graininess of the image quality. In particular, when rapid color development of a light-sensitive material in which these two-equivalent couplers and a poorly water-soluble basic metal compound are used in combination, there is a problem that the difference in graininess increases. Further, the use of the disclosed 4-equivalent coupler has another problem that the cyan color density varies greatly when a rapid continuous process is carried out.

On the other hand, regarding the development processing of the color negative,
Conventionally, the speeding up of processing has been mainly performed by shortening the processing time of the desilvering process. For example, in the quick processing CN-16FA of Fuji Photo Film Co., Ltd., which was introduced for the minilab market, the color development time of the processing is about 40% of the total processing time although it is shortened to 8 minutes and 15 seconds. Occupy
Therefore, reducing the color development time, which accounts for a large percentage of the total processing time of current color negatives, is a major challenge in the industry. Many proposals have been made to solve this problem. However, simply applying high temperature treatment of color development, high pH treatment of color developing solution, high concentration treatment of color developing agent, improvement of film quality of photosensitive material, thinning of photosensitive material constituting layer or combination thereof, Even if processing is performed with a shorter color development time than the current one, the color development of the red-sensitive layer coated on the side closer to the support is delayed, and the gradation balance of the three colors of yellow, magenta, and cyan, which are the most important color negatives, is balanced. Collapses greatly. Therefore, the color print from such a color negative image greatly deteriorates the tone reproducibility and the color reproducibility. In addition, the combination of the highly active 2-equivalent coupler and the poorly water-soluble basic metal compound causes a problem that the graininess is deteriorated when the rapid development of the color development is carried out, and a satisfactory shortening of the color development is achieved. The current situation is that it is not possible.

Therefore, the same light-sensitive material is processed by one of the color negative processing which is now widely distributed, and the other is subjected to a rapid processing in which the color development time is shortened. In order to obtain both excellent development finish quality, the gradation of the cyan image and the gradation balance of the three colors are controlled, and
The development of a technique for improving the image quality of graininess is very important, and technical development for this is strongly desired.

It should be noted that there is no description in Document 1 that the gradation degree satisfies the conditional expression according to the present invention even when a rapid process in which the development time is shortened is performed with respect to the described color development time. There is no speculative description. or,
Reference 1 shows that the pH of the color developing solution for the color negative photosensitive material is in the neutral range, so that the stability and safety of the developing solution over time can be improved, and sufficient image density (Dmax) can be obtained even if the processing time is short. The object of the present invention is to provide a possible image forming method, which is different from the object of the present invention. Further, in JP-A-3-017648, a light-sensitive material is similarly made to contain a poorly water-soluble basic metal compound, and a compound which releases a base when complexed with a metal ion constituting the compound is contained. Processing with a color developer is described. There is also a description of the cyan coupler according to the present invention. However, the composition of silver halide used in the light-sensitive material is the use of silver halide containing substantially no silver iodide and containing 80 mol% or more of silver chloride. Is a so-called 2-equivalent coupler, which is an image forming method in which the color developing solution containing the base-releasing compound is applied in a thin layer on the surface of a light-sensitive material, which is an image forming method different from the present invention. Further, similarly to the above, there is no description about satisfying the conditional expression of the gradation according to the present invention, and there is no speculative description.

[0006]

Therefore, the present invention has at least one blue-sensitive, green-sensitive, red-sensitive silver halide emulsion layer and at least one non-photosensitive layer, and contains a poorly water-soluble basic metal compound as described above. A color light-sensitive material containing at least one layer, and a color light-sensitive material containing a coupler represented by the general formula (II) or (III) in a red-sensitive silver halide emulsion layer is used. When the development processing I and the development processing II (the rapid processing with a shorter color development time than the development processing I) are performed, the gradation balance of the three colors is good, the tone reproducibility and the color reproducibility are good, and An object of the present invention is to provide a silver halide color photographic light-sensitive material excellent in graininess of image quality and having a small fluctuation in cyan color density even after rapid continuous processing, and an image forming method.

[0007]

Means for Solving the Problems The inventors of the present invention have balanced the gradations of the three colors of yellow, magenta, and cyan of the above problems, and provide good tone reproducibility, color reproducibility, and graininess of a cyan color image. An image forming method for a silver halide color photographic light-sensitive material has at least one blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layer and at least one non-photosensitive layer, and at least one of the above sparingly water-soluble basic metal compounds is used. Two types of color sensitizers containing a coupler represented by the general formula (II) or (III) in a red-sensitive silver halide emulsion layer, which are contained in one layer, and have different color development times. Can be achieved by a silver halide color photographic light-sensitive material which allows the resulting yellow, magenta and cyan color images to meet the conditional expression defining gradation.
The present invention has been completed. That is, the present invention

(1) A silver halide color photographic light-sensitive material having at least one blue-sensitive silver halide emulsion layer, green-sensitive silver halide emulsion layer, red-sensitive silver halide emulsion layer and non-photosensitive layer on a support. In the material, the red-sensitive silver halide emulsion layer of the photographic light-sensitive material has a 4-equivalent cyan coupler, and 90 mol% or more of the 4-equivalent cyan coupler is represented by the general formula (II) or the general formula (III). And a silver halide color photographic light-sensitive material containing at least one layer containing a poorly water-soluble basic metal compound, the following two types of development treatments (I) having different color development times:
And a gradation process of the yellow, magenta and cyan color images obtained by the two types of development processes when the development process (II) is carried out, which satisfies the following conditional expression. General formula (II)

[0009]

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In the formula, R ₁ is -CONR ₄ R ₅ , -SO _{2
NR 4 R 5, -NHCOR 4,} -NHCOOR 6, -N
HSO ₂ R ₆ , -NHCONR ₄ R ₅ or -NHSO
The ₂ NR ₄ R _5, the substituent groups R ₂ is a naphthalene ring, k is an integer of 0 to 3, R ₃ is a substituent, X represents a hydrogen atom. However, R ₄ and R ₅ may be the same or different and each independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R ₆ represents an alkyl group, an aryl group or a heterocyclic group. When k is plural, R _{2 s} may be the same or different, and may combine with each other to form a ring. R ₂ and R ₃ may combine with each other to form a ring. In addition, a dimer or a multimer of R ₁ , R ₂ or R _{3 which} is bonded to each other through a divalent or divalent or higher valent group may be formed. General formula (III)

[0011]

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In the formula, R ¹ represents an alkyl group, an aryl group or a heterocyclic group, R ² represents an aryl group, and Z represents a hydrogen atom. Conditional expression 0.8 ≦ γ _II (Y) / γ _I (Y) ≦ 1.2 0.8 ≦ γ _II (M) / γ _I (M) ≦ 1.2 0.8 ≦ γ _II (C) / γ _I (C) ≦ 1.2 (γ _I (Y), γ _I (M), and γ _I (C) represent gradation levels of yellow, magenta, and cyan when the development processing I is carried out, and γ _II (Y), γ _II (M), γ _II (C)
Represents the gradation levels of yellow, magenta, and cyan when the development processing II was carried out. (Development treatment I) Color development time is 3 minutes to 3 minutes 15 seconds, the temperature of the color developing solution is 37 to 39 ° C., and 2-methyl-4- [N-ethyl-N-as a color developing agent. (Β-
A development process characterized in that the color development process is performed using a color development solution containing 15 to 20 mmol / L of hydroxyethyl) amino] aniline. (Development Treatment II) Color development time is 50 to 70 seconds, the temperature of the color developing solution is 43 to 47 ° C., and 2-methyl-4- [N-ethyl-N- (β-hydroxy) is used as a color developing agent. 35-40 mmol of ethyl) amino] aniline /
A developing treatment, characterized in that the color developing treatment is carried out using a color developing solution containing a compound which promotes the release of a base from a basic metal compound having a solubility in water and a poorly water-soluble basic metal compound.

(2) The halogen according to (1), wherein the photographic light-sensitive material has a magnetic layer containing a ferromagnetic powder in a back layer on the side opposite to the side of the photosensitive emulsion layer with the support interposed therebetween. Silver halide color photographic light-sensitive material.

(3) A color image forming method characterized in that a color image is formed by carrying out the following development processing A using the silver halide color photographic light-sensitive material described in (1) or (2). . (Development treatment A) The color developing time is 150 to 200 seconds, the temperature of the color developing solution is 37 to 40 ° C., and a color developing solution containing 15 to 20 mmol / liter of a color developing agent is used. Development process.

(4) A color image forming method characterized in that a color image is formed by carrying out the following development processing B using the silver halide color photographic light-sensitive material described in (1) or (2). . (Development treatment B) Color development time is 25 to 90 seconds, temperature of color developing solution is 40 to 60 ° C., concentration of color developing agent is 25 to 80 mmol / liter, and basic metal compound hardly soluble in water is used. A development process comprising using a color developing solution containing a compound that accelerates the release of a base.

The embodiment (1) has at least one layer each of a blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layer and a non-photosensitive layer, and at least one layer of a poorly water-soluble basic metal compound. In the color light-sensitive material contained in (1), a color light-sensitive material containing a specific 4-equivalent cyan coupler represented by the general formula (II) or (III) in the red-sensitive silver halide emulsion layer is used. When two types of development processing, color negative processing time and shortened rapid processing, are carried out, the gradation balance of three colors is good when the gradations of the obtained yellow, magenta and cyan color images meet the specified conditional expressions. The object of the present invention is achieved by providing an image forming method of a color light-sensitive material which gives good tone reproducibility and color reproducibility and which is excellent in graininess of a cyan color image.

A preferred embodiment (2) is a method for forming an image of a color light-sensitive material having a magnetic layer containing a ferromagnetic powder in the back layer of the color light-sensitive material of the embodiment (1), which is a color light-sensitive material having a magnetic layer. Even if there is, the above-mentioned subject of the present invention is achieved.

In the preferred embodiments (3) and (4), two kinds of development processings having different color development times are defined separately, and these two separate development processings are carried out using the same light-sensitive material. Even if the obtained gradations of the three colors are in conformity with the defined conditional expressions (the graininess is good, and the cyan color density varies little even in the rapid continuous processing), it is an image forming method. Achieve the same.

The present invention will be described in detail below. First, the compound represented by formula (II) will be described in detail. R ₁ is -CONR ₄ R ₅ , -SO ₂ N
_{R 4 R 5, -NHCOR 4,} -NHCOOR 6, -NH
_{SO 2 R 6, -NHCONR 4 R} 5 or -NHSO ₂ N
R ₄ represents R ₅ , R ₄ , R ₅ and R ₆ are each independently an alkyl group having 1 to 30 total carbon atoms (hereinafter referred to as C number), an aryl group having 6 to 30 C atoms or 2 to 30 C numbers. Represents a heterocyclic group. R ₄ and R ₅ may also be hydrogen atoms.

R ₂ represents a group capable of substituting on a naphthalene ring (including an atom; the same applies hereinafter), and representative examples thereof include a halogen atom (F, Cl, Br, I), a hydroxyl group, a carbonyl group, an amino group and a sulfo group. , Cyano group, alkyl group, aryl group, heterocyclic group, carbonamido group, sulfonamide group, carbamoyl group, sulfamoyl group, ureido group, acyl group, acyloxy group, alkoxy group, aryloxy group, alkylthio group, arylthio group, Examples thereof include an alkylsulfonyl group, an arylsulfonyl group, a sulfamoylamino group, an alkoxycarbonylamino group, a nitro group and an imide group. Examples of the case where k = 2 include a dioxymethylene group and a trimethylene group.
The C number of (R ₂ ) _k is 0 to 30.

R ₃ represents a substituent and is preferably represented by the following formula (II-1). Formula (II-1) R ₇ (Y) _m − In formula (II-1), Y is>NH,> CO or> SO.
₂ , m is an integer of 0 or 1, R ₇ is a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms,
A heterocyclic group of the number 2 to 30, -COR ₈ ,

[0022]

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Or —SO ₂ R ₁₀ respectively. Here, R ₈ , R ₉ and R ₁₀ have the same meanings as R ₄ , R ₅ and R ₆ , respectively. In R ₁ or R ₇ , -N
R _{4 and} R ₅ of R ₄ R ₅ and R ₈ and R ₉ of —NR ₈ R ₉ may be bonded to each other to form a nitrogen-containing heterocycle (eg, pyrrolidine ring, piperidine ring, morpholine ring).

X represents a hydrogen atom. In the above, the alkyl group may be linear, branched or cyclic, and even if it contains an unsaturated bond, it is a substituent (for example, a halogen atom, a hydroxyl group, an aryl group, a heterocyclic group, an alkoxy group). , An aryloxy group, an alkylsulfonyl group, an arylsulfonyl group, an alkoxycarbonyl group, an acyloxy group, an acyl group),
Typical examples are methyl, isopropyl, isobutyl, t
-Butyl, 2-ethylhexyl, cyclohexyl, n-
There are dodecyl, n-hexadecyl, 2-methoxyethyl, benzyl, trifluoromethyl, 3-dodecyloxypropyl, 3- (2,4-di-t-pentylphenoxy) propyl.

Even if the aryl group is a condensed ring (for example, a naphthyl group), a substituent (for example, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group,
A cyano group, an acyl group, an alkoxycarbonyl group, a carbonamide group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group).
Tolyl, pentafluorophenyl, 2-chlorophenyl, 4-hydroxyphenyl, 4-cyanophenyl, 2
-Tetradecyloxyphenyl, 2-chloro-5-dodecyloxyphenyl, 4-t-butylphenyl.

Further, the heterocyclic group is O, N, S, P, Se, T
e is a 3- to 8-membered monocyclic or condensed-ring heterocyclic group containing at least one heteroatom in the ring, and has a substituent (for example, a halogen atom, a carboxyl group, a hydroxyl group,
Nitro group, alkyl group, aryl group, alkoxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, amino group, carbamoyl group, sulfamoyl group, alkylsulfonyl group, arylsulfonyl group), Representative examples include 2-pyridyl, 4-pyridyl, 2-furyl, 4-thienyl, benzotriazol-1-yl, 5-phenyltetrazole-
There are 1-yl, 5-methylthio-1,3,4-thiadiazol-2-yl and 5-methyl-1,3,4-oxadiazol-2-yl.

Examples of preferable substituents in the present invention will be described below. R ₁ is -CONR ₄ R ₅ or -SO
₂ NR ₄ R ₅ is preferable, and specific examples include carbamoyl,
N-n-butylcarbamoyl, N-n-dodecylcarbamoyl, N- (3-n-dodecyloxypropyl) carbamoyl, N-cyclohexylcarbamoyl, N- [3
-(2,4-di-t-pentylphenoxy) propyl]
Carbamoyl, N-hexadecylcarbamoyl, N-
[4- (2,4-di-t-pentylphenoxy) butyl] carbamoyl, N- (3-dodecyloxy-2-methylpropyl) carbamoyl, N- [3- (4-t-octylphenoxy) propyl] carbamoyl , N-hexadecyl-N-methylcarbamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N- [4- (2,
4-di-t-pentylphenoxy) butyl] sulfamoyl. R ₁ is particularly preferably —CONR ₄ R ₅ .

As R ₂ and k, k = 0, that is, unsubstituted one is most preferable, and then k = 1 is preferable. R ₂ is preferably a halogen atom, an alkyl group (eg, methyl,
Isopropyl, t-butyl, cyclopentyl), a carbonamide group (for example, acetamido, pivalinamide, trifluoroacetamide, benzamide), a sulfonamide (for example, methanesulfonamide, toluenesulfonamide) or a cyano group.

R ₃ is preferably m in formula (II-1).
= 0, more preferably R ₇ is —COR ₈ [eg formyl, acetyl, trifluoroacetyl, 2-
Ethylhexanoyl, pivaloyl, benzoyl, pentafluorobenzoyl, 4- (2,4-di-t-pentylphenoxy) butanoyl], -COOR ₁₀ [eg methoxycarbonyl, ethoxycarbonyl, isobutoxycarbonyl, 2-ethylhexyloxycarbonyl, n-
Dodecyloxycarbonyl, 2-methoxyethoxycarbonyl] or —SO ₂ R ₁₀ [eg methylsulfonyl, n-butylsulfonyl, n-hexadecylsulfonyl, phenylsulfonyl, p-tolylsulfonyl, p-
Chlorophenylsulfonyl, trifluoromethylsulfonyl], and particularly preferably R ₇ is —COOR ₁₀ .

The coupler represented by the general formula (II) may form a bis form in the substituents R ₁ , R ₂ or R ₃ , and the dimer which is bonded to each other via a divalent or divalent or more group. It may form a body or multimers. In this case, the number of carbon atoms may be out of the range specified for each substituent. When the coupler represented by the general formula (II) forms a multimer, a typical example is a homopolymer or copolymer of an addition-polymerizable ethylenically unsaturated compound (cyan color-forming monomer) having a cyan dye-forming coupler residue, It is preferably represented by formula (II-2). Formula (II-2) - (G i) gi - (H j) hj - group represented by the formula G _i is a repeating unit derived from the color forming monomer formula (II-2) (II- 3) And H _j is a repeating unit derived from a non-color-forming monomer, i is a positive integer, j is 0 or a positive integer, and gi and hi are the weight fractions of G _I or H _j , respectively. Represents Here, when i or j is plural, G _i or H _j means containing plural kinds of repeating units. Formula (II-3)

[0031]

[Chemical 6]

In the formula (II-3), R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a chlorine atom, and A
Represents -CONH-, -COO- or a substituted or unsubstituted phenylene group, and B represents a divalent group having carbon atoms below both such as a substituted or unsubstituted alkylene group, a phenylene group or an oxydialkylene group. And L is-
CONH-, -NHCONH-, -NHCOO-, -N
HCO-, -OCONH-, -NH-, -COO-,-
OCO -, - CO -, - O -, - SO 2 -, - NHSO
₂ -, or represents a -SO ₂ NH-. a, b, c are 0
Or an integer of 1. Q represents a cyan coupler residue obtained by removing one hydrogen atom from R ₁ , R ₂ or R _{3 of the} compound represented by the general formula (II).

Non-color-forming, ethylene-type monomers that do not couple with the oxidation product of the aromatic primary amine developing agent giving the repeating unit H _j include acrylic acid, α-chloroacrylic acid, and α-alkylacrylic acid. (Eg, methacrylic acid, etc.), amides or esters derived from these acrylic acids (eg, acrylamide, methacrylamide, n-butyl acrylamide, t-butyl acrylamide, diacetone acrylamide, methyl acrylate, ethyl acrylate, n-propyl acrylate). , N-butyl acrylate, t-butyl acrylate, iso-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl meta. Rilates and β-hydroxyethylmethacrylate), vinyl esters (eg vinyl acetate, vinyl propionate and vinyl laurate), acrylonitrile, methacrylonitrile, aromatic vinyl compounds (eg styrene and its derivatives, eg vinyltoluene, divinylbenzene, vinyl). Acetophenone and sulfostyrene), itaconic acid, citraconic acid,
There are crotonic acid, vinylidene chloride, vinyl alkyl ether (for example, vinyl ethyl ether), maleic ester, N-vinyl-2-pyrrolidone, N-vinyl pyridine and 2- and 4-vinyl pyridine.

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

As is well known in the field of polymer couplers, the ethylenically unsaturated monomer for copolymerization with the vinyl monomer corresponding to the above formula (II-3) is in the form of the copolymer to be formed, for example, solid. , Liquid, micelles and physical and / or chemical substances such as solubility (solubility in water or organic solvents), compatibility with photographic colloid composition binders such as gelatin, its flexibility , Thermal stability, coupling reactivity with an oxidized product of a developing agent, and diffusion resistance in a photographic colloid can be favorably influenced. These copolymers may be random copolymers or copolymers having a specific sequence (eg, block copolymer, alternating copolymer).

The number average molecular weight of the cyan polymer coupler used in the present invention is usually on the order of thousands to several millions, but oligomeric polymer couplers of 5000 or less can also be used. The cyan polymer coupler used in the present invention is an organic solvent (for example, ethyl acetate, butyl acetate, ethanol, methylene chloride, cyclohexanone,
Whether it is a lipophilic polymer soluble in dibutyl phthalate or tricresyl phosphate) or a hydrophilic polymer miscible with a hydrocolloid such as an aqueous gelatin solution, it has a structure and properties capable of forming micelles in the hydrocolloid. It may be a polymer having.

In order to obtain a lipophilic polymer coupler soluble in an organic solvent, a lipophilic non-color forming ethylene-like monomer (eg acrylic acid ester, methacrylic acid ester, maleic acid ester, vinylbenzenes, etc.) is mainly used as a copolymerization component. Is preferred. The general formula (II-
It may be prepared by dissolving a lipophilic polymer coupler obtained by polymerization of a vinyl-type monomer giving a coupler unit represented by 3) in an organic solvent and emulsifying and dispersing it in an aqueous gelatin solution in the form of latex. It may be prepared by an emulsion polymerization method.

A method of emulsion-dispersing a lipophilic polymer coupler in the form of a latex in an aqueous gelatin solution is described in US Pat. No. 3,451,820, and an emulsion polymerization is described in US Pat. Nos. 4,080,211 and 3,3. 370,952
The method described in the publication can be used. Alternatively, in order to obtain a neutral or alkaline water-soluble hydrophilic polymer coupler, N- (1,1-dimethyl-2-sulfonateethyl) acrylamide, 3-sulfonatepropylacrylate, sodium styrenesulfonate, Styrene potassium sulfinate, acrylamide,
It is preferable to use a hydrophilic non-color forming ethylene-like monomer such as methacrylamide, acrylic acid, methacrylic acid, N-vinylpyrrolidone, N-vinylpyridine, etc. as the copolymer component.

The hydrophilic polymer coupler can be added to the coating solution as an aqueous solution, and a water-miscible organic solvent such as lower alcohol, tetrahydrofuran, acetone, ethyl acetate, cyclohexanone, ethyl lactate, dimethylformamide and dimethylacetamide. It can also be dissolved in a mixed solvent of water and water and added. Further, it may be added by dissolving in an aqueous alkali solution or an organic solvent containing alkaline water. Further, a small amount of a surfactant may be added.

Specific examples of each substituent in the formula (II) and the cyan coupler represented by the formula (II) are shown below.

Example of R ₁

[0042]

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[0043]

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[0044]

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[0045]

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Example of R ₂

[0047]

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Examples of R ₃ NH-

[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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Specific examples of the cyan coupler represented by the general formula (II)

[0055]

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[0056]

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[0057]

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[0058]

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[0059]

[Chemical 21]

[0060]

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[0061]

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[0062]

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Specific examples of the cyan coupler represented by the formula (II) other than the above and / or a method for synthesizing these compounds are described in, for example, US Pat. No. 4,690,889, JP-A-60.
-237448, 61-153640, 61-
No. 145557, No. 63-208042, No. 64-3
1159 and West German Patent No. 3823049A. The cyan coupler represented by the formula (II) is
As described in JP-A-62-269958,
Using a small amount of a high-boiling organic solvent for dispersion, graininess,
It is preferable in improving sharpness.

Specifically, the high boiling point organic solvent is used in a weight ratio of 0.3 or less, more preferably 0.1 or less with respect to the cyan coupler represented by the formula (II). The cyan coupler represented by the formula (II) may be used alone,
Further, it is used in combination with a coupler of the general formula (III) described later. Further, two or more kinds can be used in combination. When the same color sensitivity is divided into two or more layers having different sensitivities, a coupler represented by the general formula (II) is used in at least one layer. Further, these couplers can be used properly according to the purpose. In the present invention, the general formula (I
The use of the coupler represented by the general formula (II) is preferable to the coupler represented by II). When used in combination with the coupler represented by the general formula (III), it is preferable to use 50 mol% or more of the coupler represented by the general formula (II). It is more preferably 70 mol% or more. The general formula (II) and
A coupler other than the coupler represented by (III) can be used according to the purpose. Further, the general formula (II) and (III)
The coupler represented by can be used in layers other than the red-sensitive layer.

Next, the phenolic cyan coupler represented by the general formula (III) will be described in detail below. In the general formula (III), R ¹ is an optionally substituted linear, branched or cyclic alkyl group having 1 to 36 (preferably 4 to 30) total carbon atoms (hereinafter referred to as C number),
An optionally substituted aryl group having a C number of 6 to 36 (preferably 12 to 30) or a C number of 2 to 36 (preferably 1)
2 to 30) is represented. Here, the heterocyclic group represents a 5 to 7-membered optionally condensed heterocyclic group having at least one hetero atom selected from N, O, S, P, Se and Te in the ring, and examples As 2-furyl, 2-thienyl, 2-pyridyl, 4-pyridyl, 4-pyrimidyl,
There are 2-imidazolyl, 4-quinolyl and the like. Examples of the substituent of R ¹ include a halogen atom, a cyano group, a nitro group,
Carboxyl group, sulfo group, alkyl group, aryl group,
Heterocyclic group, alkoxy group, aryloxy group, alkylthio group, arylthio group, alkylsulfonyl group, arylsulfonyl group, alkoxycarbonyl group, acyl group, carbonamide group, sulfonamide group, carbamoyl group, sulfamoyl group, imide group, amino Group, ureido group, alkoxylcarbonylamino group or sulfamoylamino group (hereinafter referred to as substituent group A),
Examples of preferable substituents are an aryl group, a heterocyclic group, an aryloxy group, an alkylsulfonyl group, an arylsulfonyl group or an imido group.

In the general formula (III), R ² has a C number of 6 to 36.
It represents an aryl group (preferably 6 to 15) and may be substituted with a substituent selected from the above-mentioned Substituent group A or may be a condensed ring. Here, as a preferable substituent, a halogen atom (F, Cl, Br, I), a cyano group, a nitro group, an acyl group (eg, acetyl, benzoyl), an alkyl group (eg, methyl, t-butyl, trifluoromethyl, trichloro). Methyl), alkoxy groups (eg methoxy, ethoxy, butoxy, trifluoromethoxy), alkylsulfonyl groups (eg methylsulfonyl, propylsulfonyl, butylsulfonyl, benzylsulfonyl), arylsulfonyl groups (eg phenylsulfonyl, p-tolylsulfonyl, p). -Chlorophenylsulfonyl), an alkoxycarbonyl group (eg methoxycarbonyl, butoxycarbonyl), a sulfonamide group (eg methanesulfonamide, trifluoromethanesulfonamide, toluenesulfonamide), Bamoiru group (e.g. N, N- dimethylcarbamoyl, N- phenylcarbamoyl), or a sulfamoyl group (e.g. N, N
-Diethylsulfamoyl, N-phenylsulfamoyl). R ² is preferably a phenyl group having at least one substituent selected from a halogen atom, a cyano group, a sulfonamide group, an alkylsulfonyl group, an arylsulfonyl group and a trifluoromethyl group, and more preferably 4-cyano. Phenyl, 4-cyano-3-halogenophenyl, 3-cyano-4-halogenophenyl, 4-alkylsulfonylphenyl, 4-alkylsulfonyl-3-halogenophenyl, 4-alkylsulfonyl-3-alkoxyphenyl, 3-alkoxy- 4-alkylsulfonylphenyl, 3,4-dihalogenophenyl, 4-halogenophenyl, 3,4,5-trihalogenophenyl, 3,4-dicyanophenyl, 3-cyano-4,5-dihalogenophenyl, 4- Trifluoromethylphenyl or 3-sulfon A Dofeniru, particularly preferably 4-cyanophenyl, 3-cyano -
4-halogenophenyl, 4-cyano-3-halogenophenyl, 3,4-dicyanophenyl or 4-alkylsulfonylphenyl.

In the general formula (III), Z represents a hydrogen atom. Specific examples of R ¹ and R ² in the general formula (III) are shown below.

Example of R ¹

[0069]

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[0070]

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[0071]

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[0072]

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[0073]

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[0074]

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[0075]

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Example of R ²

[0077]

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[0078]

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Specific examples of the cyan coupler represented by the general formula (III) are shown below. However, A to Z and a to f are chemical formula 2
5, chemical 26, chemical 27, chemical 28, chemical 29, chemical 30, chemical 31
It is a serial number of a specific example of R ¹ in.

[0080]

[Table 1]

[0081]

[Table 2]

[0082]

[Table 3]

[0083]

[Table 4]

[0084]

[Table 5]

Cyan couplers represented by the general formula (III) are disclosed in, for example, JP-A-56-65134 and JP-A-61-2757.
No. 63-159848, No. 63-161450.
No. 63-161451, JP-A No. 1-254956.
And US Pat. No. 4,923,791. In the present invention, the cyan coupler represented by the general formula (III) can be used alone. Preferably, the cyan couplers represented by the above general formulas (II) and (III) are used in combination.
In this case, the coupler of the general formula (II) and the coupler of the general formula (III) can be used in any ratio. That is, the general formula (I
I): The general formula (III) is 99.9: 0.1 to 0.1: 99.
The ratio can be 9 (molar ratio). Preferably the general formula (II)
Is 50 or more. More preferably, it is 70 (molar ratio) or more. Further, a cyan coupler other than the general formula (II) or (III) can be used in combination. At this time, the amount of the cyan couplers represented by the general formulas (II) and (III) used must be 90 mol% or more, more preferably 95 mol% or more, of all 4 equivalent cyan couplers in the red-sensitive layer. More preferably, it is 98 mol% or more. In the present invention, the total amount of the cyan couplers represented by the general formulas (II) and (III) is 1 × 10 ⁻³ to 2 mol per mol of silver halide when used in the photosensitive layer. It is a range. Preferably 1x
It is in the range of 10 ⁻² to 1 mol, and more preferably 2 × 10.
It is in the range of ^{-2 to} 0.5 mol. When used in the non-photosensitive layer, 1 is used per mol of silver halide in the adjacent photosensitive layer.
It is in the range of × 10 ^-3 to 1 mol. Preferably 2 × 10 ^-3
To 5 × 10 ^-1 mol, more preferably 5 × 10 ^-3
It is in the range of 2 × 10 ⁻¹ mol. In the present invention, when the same photosensitive layer is composed of a plurality of layers, the coupler represented by the general formula (II) and / or the general formula (III) of the present invention is used for at least one layer.

The cyan couplers represented by the general formulas (II) and (III) of the present invention can be introduced into the light-sensitive material by any known dispersion method, but preferably the oil-in-water described below is used. This is a method of adding a dispersion using a drop dispersion method.

The poorly water-soluble basic metal compound will be described below. Examples of the water-insoluble basic metal compound contained in the light-sensitive material in the present invention include solubility in water at 20 ° C. (grams of substance dissolved in 100 g of water).
There preferably those represented by the formula T _m X _n 0.5 or less. Where T is a transition metal such as Zn, Ni, Co, Fe, Mn, Cu, Al, S
n, Sb, Bi, etc., alkaline earth metals such as Ca, B
a, Sr, Mg, etc., wherein X is a counter ion of M that appears in the description of the complex-forming compound described below in water and exhibits alkalinity, for example, carbonate ion, phosphate ion , Silicate ion, borate ion, aluminate ion, hydroxy ion, and oxygen atom.
m and n each represent an integer such that the valences of T and X are balanced.

Preferred specific examples are listed below. Calcium carbonate, barium carbonate, magnesium carbonate, zinc carbonate, strontium carbonate, magnesium calcium carbonate (CaMg (CO ₃ ) ₂ ), magnesium oxide, zinc oxide,
Tin oxide, cobalt oxide, zinc hydroxide, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, antimony hydroxide, tin hydroxide, iron hydroxide, bismuth hydroxide,
Manganese hydroxide, calcium phosphate, magnesium phosphate, magnesium borate, calcium silicate, magnesium silicate, zinc aluminate, calcium aluminate,
Basic zinc carbonate _{(2ZnCO 3 · 3Zn (OH)} 2 · H 2
O), basic magnesium carbonate (3MgCO ₃ · Mg
_{(OH) 2 · 3H 2 O} ), basic nickel carbonate (NiCO
_{3 · 2Ni (OH) 2)} , basic bismuth carbonate (Bi ₂ (
CO ₃ ) O ₂ · H ₂ O), basic cobalt carbonate (2Co
CO ₃ .3Co (OH) ₂ ), aluminum magnesium oxide, copper hydroxide, basic copper carbonate and the like. Of these compounds, those that are not colored are particularly preferred.

The position at which the poorly water-soluble basic metal compound of the present invention is added to the light-sensitive material is an emulsion layer / non-light-sensitive layer (intermediate layer /
Any layer (protective layer, antihalation layer, white pigment layer, etc.) may be used, but a layer closer to the support is preferable. That is, it is preferably added to the non-photosensitive layer located between the emulsion layer closest to the support and the support or to the non-photosensitive intermediate layer adjacent to the emulsion layer in the emulsion layer closest to the support.
Of these, the most preferred addition position is in the non-photosensitive layer located between the emulsion layer closest to the support and the support. Further, it may be contained in only one layer, or may be contained in two or more layers.

The compound (trigger compound) for promoting the release of the base from the poorly water-soluble basic metal compound used in the color developer of the present invention will be described below. The trigger compound of the present invention is preferably a complex-forming compound that forms a complex salt having a stability constant of 1 or more at a log K with the metal ion constituting the basic metal compound.
For these complex-forming compounds, for example, AEMartell, RMSmith
Co-authored in "Critical Stability Constants, Volumes 1-5", Plenum Press. Specifically, aminocarboxylic acids, iminodiacetic acid and its derivatives, anilinecarboxylic acids, pyridinecarboxylic acids,
Aminophosphoric acids, carboxylic acids (mono-, di-, tri-, tetracarboxylic acids and further phosphono, hydroxy,
Oxo, ester, amide, alkoxy, mercapto,
Compounds having a substituent such as alkylthio and phosphino), alkali metals such as hydroxamic acids, polyacrylates and polyphosphoric acids, and salts such as guanidines, amidines and quaternary ammonium salts.

Preferred examples include picolinic acid and 5
-Ethylpicolinic acid, 2,3-pyridinedicarboxylic acid,
2,4-pyridinedicarboxylic acid, 5-ethoxycarbonylpicolinic acid, 2,6-pyridinedicarboxylic acid, 2,5
-Pyridinedicarboxylic acid, 4-dimethylaminopyridine-2,6-dicarboxylic acid, quinoline-2-carboxylic acid,
2-pyridylacetic acid, oxalic acid, citric acid, tartaric acid, isocitric acid, malic acid, gluconic acid, EDTA, NTA,
CDTA, hexametaphosphoric acid, tripolyphosphoric acid, tetraphosphoric acid, polyacrylic acid, 2,3-pyrazinedicarboxylic acid, 4,5-imidazoledicarboxylic acid, glycine, alanine, glutamic acid,

[0092]

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Alkali metal salts such as, salts of guanidines,
Examples thereof include salts of amidines and quaternary ammonium salts. Of these, an aromatic heterocyclic compound having at least one —CO ₂ M and one nitrogen atom in the ring is preferable. The ring may be a single ring or a condensed ring, and examples thereof include a pyridine ring and a quinoline ring. And -C
The position at which O ₂ M is bonded to the ring is particularly preferably the α position with respect to the N atom. M is any of alkali metal, guanidine, amidine and quaternary ammonium ions. More preferred compounds include those represented by the following formula.

[0094]

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In the above formula, R is any one of a hydrogen atom, an aryl group, a halogen atom, an alkoxy group, —CO ₂ M, a hydroxycarbonyl group, and an electron donating group such as an amino group, a substituted amino group and an alkyl group. Represents
Two Rs may be the same or different. Z ₁ and Z
₂ is the same as the definition in R, and Z ₁
And Z ₂ may combine to form a ring fused to a pyridine ring.

The most preferable examples of combinations of the sparingly water-soluble basic metal compound and the complex-forming compound are listed below (wherein M ⁺ is an alkali metal ion, a substituted or unsubstituted guanidinium ion or an amidinium ion). Or 4
Represents a secondary ammonium ion).

[0097]

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[0098]

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[0099]

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[0100]

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[0101]

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[0102]

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[0103]

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These combinations may be used alone or in combination of two or more. Here, the mechanism of generating a base in the film of the photosensitive material in the present invention will be described by taking a combination of potassium picolinate and zinc hydroxide as an example. The reaction of both is shown by the following formula, for example.

[0105]

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That is, when water in the treatment liquid is involved, the picolinate ion causes a complex formation reaction with the zinc ion and the reaction represented by the above formula proceeds, resulting in the generation of a base. The progress of this reaction is due to the stability of the complex formed, but the stability of the complex represented by ML, ML ₂ and ML ₃ formed from picolinate ion (L ⁻ ) and zinc ion (M ⁺ ) The constants are very large as shown below and well explain the progress of this reaction.

[0107]

[Table 6]

Basic metal compounds which are poorly soluble in water are disclosed in JP-A-59 / 1984.
It is desirable to contain the fine particle dispersion prepared by the method described in JP-A-174830, JP-A-53-102733, etc., and the average particle size thereof is preferably 50 μm or less, particularly preferably 5 μm or less. The addition amount varies depending on the type of treatment liquid, pH, complex formation compound species, compound species of basic metal compound, particle size, treatment temperature, etc., but cannot be specified unconditionally,
0.1 to 200 mmol / m ² , preferably 1 to 50 mmol / m ²
It is good to be about. The addition amount of the complex-forming compound contained in the treatment liquid varies depending on the kind of treatment liquid, pH, kind of complex-forming compound and the like, but is generally about 0.01 to 5 mol / liter. The complex-forming compound is contained in the treatment liquid before treatment, but may be contained in the replenisher.

The gradation degree in the present invention is obtained as follows. First, the test light-sensitive material is wedge-exposed with a light source having an energy distribution of black body radiation of 4800 K °,
After performing the designated development processing, the absorption densities of cyan, magenta, and yellow are measured under the status M condition, and the characteristic curve is obtained. From the obtained characteristic curve, the absorption densities of cyan, magenta, and yellow are fog +0.2, +0.5, +1.0, +1.5, + with respect to the logarithm of the exposure amount (horizontal axis).
After plotting the points of 2.0 respectively and linearly approximating these points by the method of least squares, tan with respect to the angle θ from the horizontal axis
θ is defined as the gradation degree γ of the photosensitive material, and γ of cyan, magenta, and yellow are γ (C), γ (M), and γ, respectively.
(Y).

The light-sensitive material of the present invention can be processed in the developing process I of the present invention
Gradients γ _I (C), γ _I (M), and γ _I (Y) of cyan, magenta, and yellow after carrying out, and the gradation γ _II (C) after carrying out the developing treatment II of the present invention. , Γ _II (M),
γ _II (Y) satisfies the following conditional expression. 0.8 ≦ γ _II (C) / γ _I (C) ≦ 1.2 0.8 ≦ γ _II (M) / γ _I (M) ≦ 1.2 0.8 ≦ γ _II (Y) / γ _I (Y) ≦ 1.2

More preferably 0.9 ≦ γ _II (C) / γ _I (C) ≦ 1.1 0.9 ≦ γ _II (M) / γ _I (M) ≦ 1.1 0.9 ≦ γ _II It satisfies the condition of (Y) / γ _I (Y) ≦ 1.1.

If this condition is not satisfied, the tint of the print obtained from the color negative developed in at least one of the developing processes A and B will be lost, and it will not be possible to obtain color reproduction that is enduring to the eye.

In the present invention, γ _I (C), γ
_I (M), γ _I (Y), γ _II (C), γ _II (M), γ _II
(Y) is preferably 0.50 to 0.90, more preferably 0.60 to 0.85,
It is particularly preferably 0.65 to 0.80.

The color developing solutions of the developing treatments I and II of the present invention will be described below. The development processing I of the present invention is a processing based on Kodak C-41 which is a processing for color negative which is widely used in the world at present.
It is designed so that a preferable gradation can be obtained in seconds. Further, the development processing II is a processing in which the development processing I is speeded up, and the development activity is increased by increasing the concentration of the main agent and the processing temperature.
It is designed so that a gradation close to that of the development processing I can be obtained in a color development processing time of a minute. However, when a light-sensitive material which is not included in the present invention is processed, development delay occurs in the red-sensitive layer, which is the lowermost layer, so that the gradation cannot be perfectly adjusted.

In the development processing I, the color development time is 3 minutes to 3 minutes 1
5 seconds, the temperature of the color developing solution is 37 to 39 ° C.,
2-Methyl-4- [N-ethyl-N as color developing agent
15- (β-hydroxyethyl) amino] aniline
This is a developing process characterized by carrying out a color developing process using a color developing solution containing 20 mmol / liter.

In the developing treatment II, the color developing time is 50 to 70 seconds, the temperature of the color developing solution is 43 to 47 ° C., and 2-methyl-4- [N-ethyl-N-as a color developing agent is used.
(Β-hydroxyethyl) amino] aniline 35-4
This is a developing treatment characterized by performing a color developing treatment using a color developing solution containing 0 mmol / liter of a compound (trigger compound) which accelerates release of a base from a poorly water-soluble basic metal compound.

The pH of the color developing solutions used in the developing treatments I and II is 1
It is 0.05. It is preferable to use a carbonate in order to keep the pH of the treatment liquid at 10.05. The addition amount is preferably 0.1 mol / liter or more, and particularly preferably in the range of 0.2 mol / liter to 0.3 mol / liter.
Further, as a preservative for the color developing agent, it is preferable to use hydroxylamine and sulfite. The addition amount of hydroxylamine is preferably in the range of 0.05 mol / liter to 0.2 mol / liter. The amount of sulfite added is 0.
The range of 02 mol / liter to 0.04 mol / liter is preferable. Bromide ions can be added to the color developing solution in order to control the developing rate. Further, various chelating agents can be added to the color developing solution.

The steps (desilvering step, washing step, stabilizing step) subsequent to color development in the development processings I and II are carried out by the methods described in the development processings A and B described later.

Specific examples of development processing I and development processing II are shown below. In the present invention, it is preferable to use the following specific examples. Specific Example of Development Treatment (I) The development treatment in which the color development has the following liquid composition, temperature, and processing time. (Color developer) Tank liquid (g) Diethylenetriaminepentaacetic acid 1.0 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide 1 0.5 mg hydroxylamine sulfate 2.4 4- [N-ethyl-N- (β-hydroxyethyl) amino] -2-methylaniline sulfate 4.5 Water was added to 1.0 liter pH (with potassium hydroxide Adjusted with sulfuric acid) 10.05 Temperature 38 ° C. Processing time 3 minutes 15 seconds Specific example of development processing (II) Color development is the following liquid composition, temperature and processing time. (Color developer) Tank liquid (g) Diethylenetriaminepentaacetic acid 2.0 1-Hydroxyethylidene-1,1-diphosphonic acid 3.3 Sodium sulfite 3.9 Potassium carbonate 37.5 Potassium bromide 2.0 Potassium iodide 1 .3 mg Hydroxylamine sulfate 4.5 2-Methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 11.0 Picolinic acid 12.0 Water was added to 1.0 liter pH (Adjust with potassium hydroxide and sulfuric acid) 10.05 Temperature 45 ° C Treatment time 60 seconds

To the color development processing solution of the present invention, a substance which promotes the release of a base from the poorly water-soluble basic metal compound of the present invention contained in a light-sensitive material can be added. These additives are the trigger compounds mentioned in the above description. Specifically, it is a complex-forming compound which forms a complex salt with a metal ion constituting these basic metal compounds, and particularly preferred are picolinic acid, pyridine-2,6-dicarboxylic acid, pyridine-2, Examples thereof include 5-dicarboxylic acid, 5-ethylpicolinic acid, 5-methylpicolinic acid and oxalic acid. However, these trigger compounds are not limited to the above specific examples, because the preferable combination changes depending on the kind of the hardly soluble basic metal salt contained in the photosensitive material.

Although picolinic acid was added to the color developing solution of the development processing II as a compound that promotes the release of a base from a poorly water-soluble basic metal compound, the compound that promotes it is not limited to picolinic acid. Instead, it can be selected according to the type of basic metal compound.

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

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

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

[0125] Bromide ion concentration, Br from a silver halide color photographic material ^- and elution, Br is replenished in the color developing solution ^- is determined by the amount, to keep the photographic properties during continuous processing stably The amount is 6 mmol or more and 14 mmol or less, preferably 9 mmol or more and 13 mmol or less, per liter of the treatment liquid.

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

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

Specifically, a color negative film processing agent, CN-16 or CN-1 manufactured by Fuji Photo Film Co., Ltd.
6X, CN-16Q, CN-16FA color developing solution and color developing replenishing solution, or color negative film processing agent C-41, C-41B manufactured by Eastman Kodak Company,
A color developing solution of C-41RA can be preferably used.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

The automatic developing machine used in the light-sensitive material of the present invention is disclosed in JP-A-60-191257 and 60-19125.
No. 8, No. 60-191259. JP-A-60-1
As described in JP-A-91257, such a transporting means can significantly reduce the carry-in of the processing liquid from the pre-bath to the post-bath, and is highly effective in preventing the performance of the processing liquid from deteriorating. Such an effect is particularly effective for reducing the processing time in each step and reducing the replenishing amount of the processing solution.

The amount of rinsing water in the rinsing step depends on the characteristics of the light-sensitive material (for example, depending on the material used such as the coupler), the application, the temperature of the rinsing water, the number of rinsing tanks (the number of stages), the replenishment method such as countercurrent and forward flow, and various other factors. It can be set in a wide range depending on the condition.
Of these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent system is described in the Journal of the Society of Motion Picturean.
d Television Engineers Volume 64, P. 248-253 (1955)
May issue). According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced.However, due to an increase in the residence time of water in the tank, bacteria are propagated, and the generated suspended matter adheres to the photosensitive material. Problem arises. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, the method of reducing calcium ions and magnesium ions described in JP-A-62-288838 can be used very effectively. Also, isothiazolone compounds and thiabendazoles described in JP-A-57-8,542, chlorine-based disinfectants such as chlorinated sodium isocyanurate, and other benzotriazoles, etc. (1986) Sankyo Publishing, Sanitary Technology Association, "Microbial Sterilization, Sterilization, and Antifungal Technology" (1982) Industrial Technology Association, Japan Society of Antimicrobial and Antifungal Activities, "Encyclopedia of Antimicrobial and Antifungal Agents" (1986) The bactericides described can also be used.

The pH of washing water in the processing of the light-sensitive material of the present invention is 3 to 9, preferably 4 to 8. Washing water temperature and washing time can also be variously set depending on the characteristics of the photosensitive material, application, and the like, but are generally in the range of 15 to 45 ° C for 20 seconds to 10 minutes, preferably in the range of 25 to 40 ° C for 30 seconds to 5 minutes. Selected. Further, the light-sensitive material of the present invention can be processed directly with a stabilizing solution instead of the above-mentioned washing. In such stabilization treatment, JP-A-57-8543, JP-A-58-14834 and JP-A-60-220345 are used.
All known methods described in (1) can be used.

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

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

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

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

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

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

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

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

The light-sensitive material of the present invention may have at least one light-sensitive layer provided on a support. A typical example is a silver halide photographic light-sensitive material having at least one light-sensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. It is. The photosensitive layer is a unit photosensitive layer having color sensitivity to any of blue light, green light, and red light, and in a multilayer silver halide color photographic material, the arrangement of the unit photosensitive layers is generally A red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are provided in this order from the support side. However, depending on the purpose, the order of installation may be reversed, or the order of installation may be such that different photosensitive layers are sandwiched between layers of the same color sensitivity. A non-light-sensitive layer may be provided between the silver halide light-sensitive layers and as the uppermost layer and the lowermost layer. These may contain a coupler, a DIR compound, a color mixing inhibitor, etc. described later. A plurality of silver halide emulsion layers constituting each unit light-sensitive layer are formed by sequentially exposing two layers, a high-speed emulsion layer and a low-speed emulsion layer, to a support as described in DE 1,121,470 or GB 923,045. It is preferable to arrange them so that the degree is low. In addition, JP-A-57-112751, 62-200350, 62-2
As described in 06541 and 62-206543, a low-sensitivity emulsion layer may be provided on the side farther from the support and a high-sensitivity emulsion layer may be provided on the side closer to the support. As specific examples, from the farthest side from the support, a low-sensitivity blue-sensitive layer (BL) / a high-sensitivity blue-sensitive layer (BH) / a high-sensitivity green-sensitive layer (GH) / a low-sensitivity green-sensitive layer (GL) / High-sensitivity red-sensitive layer (RH) / low-sensitivity red-sensitive layer (RL), or BH / BL / GL / GH / RH / RL, or BH / BL / GH / GL / RL / RH And so on. Also, as described in JP-B-55-34932, the blue-sensitive layer / GH / RH / GL starts from the side farthest from the support.
/ RL can be arranged in this order. JP-A-56-2573
8, as described in JP-A-62-63936, the layers may be arranged in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support. Further, as described in JP-B-49-15495, the upper layer is the silver halide emulsion layer having the highest sensitivity, the middle layer is the silver halide emulsion layer having a lower sensitivity, and the lower layer is a silver halide emulsion layer having a higher sensitivity than the middle layer. An example is an arrangement in which low silver halide emulsion layers are arranged and three layers having different sensitivities are sequentially lowered toward the support. Even when it is composed of such three layers having different sensitivities, as described in JP-A-59-202464, in the same color-sensitive layer, the medium-sensitivity emulsion layer / high-sensitivity layer is separated from the side distant from the support. You may arrange in order of a speed emulsion layer / a low speed emulsion layer. In addition, the layers may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer. Also, in case of 4 layers or more,
The arrangement may be changed as described above. In order to improve color reproducibility, BL, GL, described in US 4,663,271, 4,705,744, 4,707,436, JP-A-62-160448 and 63-89850, are described.
It is preferable that a donor layer (CL) having a multilayer effect having a spectral sensitivity distribution different from that of the main photosensitive layer such as RL is disposed adjacent to or close to the main photosensitive layer.

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

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

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

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

The photographic additives that can be used in the present invention are also described in RD, and the relevant portions are shown in the following table. Type of additive RD17643 RD18716 RD307105 Chemical sensitizer page 23, page 648, right column, page 866 2. Sensitivity enhancer, page 648, right column 3. Spectral sensitizer, pages 23 to 24, page 648, right column 866 to 868, supersensitizer, page 649, right column 4. Whitening agent, page 24, page 647, right column, page 868, 5 Light absorber, pages 25 to 26, page 649, right column, page 873, filter, page 650, left column, dye, ultraviolet absorber 6. Binder, page 26, page 651, left column 873 to 874, page 7. Plasticizer, page 27, page 650, right Column 876 Lubricants 8. Coating aids, 26-27 Pages 650 Right column 875-876 Pages Surfactant 9. Static 27 pages 650 Page right columns 876-877 Inhibitors 10. Matting agents 878-879

Various dye-forming couplers can be used in the light-sensitive material of the present invention, and the following couplers are particularly preferable. Yellow couplers: couplers represented by formulas (I) and (II) of EP 502,424A; couplers represented by formulas (1) and (2) of EP 513,496A (particularly Y-28 on page 18); EP 568,037A Claim 1
A coupler represented by formula (I) in US Pat. No. 5,066,576, column 1, lines 45 to 55; a coupler represented by formula (I) in paragraph 0008 of JP-A-4-274425; Couplers according to claim 1 of page 4 of EP 498,381A1 (especially D-35 on page 18); couplers of formula (Y) on page 4 of EP 447,969A1 (especially Y-1 (page 17), Y- 54 (p. 41)); US
Couplers represented by formulas (II) to (IV) at 4,476,219, column 7, lines 36 to 58 (especially II-17,19 (column 17), II-24 (column 19)). Magenta coupler; JP-A-3-39737 (L-57 (page 11, lower right), L-
68 (lower right of page 12), L-77 (lower right of page 13); EP 456,257 (A-4
-63 (p. 134), (A-4) -73, -75 (p. 139); EP 486,965
M-4, -6 (page 26), M-7 (page 27); EP 571,959A M-45 (19
(M-1) of JP-A-5-204106 (page 6); M-22 of paragraph 0237 of JP-A-4-32631. Cyan couplers preferably used including the couplers represented by the general formulas (II) and (III): CX of JP-A-4-204843
-1,3,4,5,11,12,14,15 (pages 14 to 16); JP-A-4-43345
C-7,10 (page 35), 34,35 (page 37), (I-1), (I-17) (pages 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, P-5 (p. 11) of JP-A-2-44345.

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

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

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

Next, the polyester support used in the present invention will be described. For details, including the light-sensitive material, processing, cartridge and examples described later, open technical report, Japanese Patent No. 94-6023 (Invention Society; 1994.3). .15.).
The polyester used in the present invention is formed by using a diol and an aromatic dicarboxylic acid as essential components, and 2,6-, 1,5-, 1,4-, and 2,7 as aromatic dicarboxylic acids.
-Naphthalenedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, diethylene glycol as diol,
Examples include triethylene glycol, cyclohexanedimethanol, bisphenol A, and bisphenol.
Examples of the polymerized polymer include homopolymers such as polyethylene terephthalate, polyethylene naphthalate, and polycyclohexanedimethanol terephthalate. Particularly preferred is a polyester containing 50 to 100 mol% of 2,6-naphthalenedicarboxylic acid. Among them, polyethylene 2,6-naphthalate is particularly preferred. Average molecular weight ranges from about 5,000 to
It is 200,000. The Tg of the polyester of the present invention is 50 ° C. or higher, preferably 90 ° C. or higher.

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

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

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

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

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

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

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

Hereinafter, the present invention will be described in more detail with reference to specific examples, but the present invention is not limited to the examples as long as the gist of the present invention is not exceeded.

[0185]

【Example】

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

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

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

Third Layer (Low Sensitivity Red Sensitive Emulsion Layer) Silver iodobromide Emulsion A Silver 0.50 Silver iodobromide Emulsion B Silver 0.50 ExS-1 6.9 × 10 ^-5 ExS-2 1.8 × 10 ^-5 ExS-3 3.1 × 10 ^-4 ExC-1 0.21 ExC-3 0.015 ExC-5 0.013 ExC-6 0.010 Cpd-2 0.025 HBS-1 0.10 Gelatin 0.87

Fourth Layer (Medium Sensitivity Red Sensitive Emulsion Layer) Silver Iodobromide Emulsion C Silver 1.05 ExS-1 3.5 × 10 ^-4 ExS-2 1.6 × 10 ^-5 ExS-3 5.1 × 10 ^-4 ExC-1 0.17 ExC-2 0.040 ExC-3 0.0035 ExC-5 0.010 ExC-6 0.0070 Cpd-2 0.023 HBS-1 0.10 Gelatin 0.75

Fifth layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion D Silver 1.68 ExS-1 2.4 × 10 ^-4 ExS-2 1.0 × 10 ^-4 ExS-3 3.4 × 10 ^-4 ExC-1 0.078 ExC-3 0.025 ExC-6 0.012 ExC-7 0.020 Cpd-2 0.050 HBS-1 0.22 HBS-2 0.050 Gelatin 1.10

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

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

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

9th layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion I Silver 1.25 ExS-4 3.7 × 10 ^-5 ExS-5 8.1 × 10 ^-5 ExS-6 3.2 × 10 ^-4 ExC-1 0.010 ExM-1 0.020 ExM-4 0.025 ExM-5 0.040 Cpd-3 0.040 HBS-1 0.25 Polyethyl acrylate latex 0.15 Gelatin 1.33

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

11th layer (low-sensitivity blue emulsion layer) Silver iodobromide emulsion J Silver 0.09 Silver iodobromide emulsion K Silver 0.09 ExS-7 8.6 × 10 ^-4 ExC-8 7.0 × 10 ^-3 ExY-1 0.050 ExY-2 0.22 ExY-3 0.50 ExY-4 0.020 Cpd-2 0.10 Cpd-3 4.0 × 10 ^-3 HBS-1 0.28 Gelatin 1.20

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

13th layer (first protective layer) UV-1 0.19 UV-2 0.075 UV-3 0.065 HBS-1 5.0 × 10 ^-2 HBS-4 5.0 × 10 ^-2 gelatin 1.8

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

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

[0201]

[Table 7]

In Table 7, (1) Emulsions J to L were prepared according to the examples of JP-A-2-91938.
Reduction sensitization was performed using thiourea dioxide and thiosulfonic acid during the preparation of the particles. (2) Emulsions A to I were prepared according to the examples of JP-A-3-237450.
Gold sensitization, sulfur sensitization and selenium sensitization were performed in the presence of the spectral sensitizing dye and sodium thiocyanate described in each photosensitive layer. (3) For preparing tabular grains, low molecular weight gelatin is used according to the examples of JP-A-1-158426. (4) Dislocation lines described in JP-A-3-237450 are observed in the tabular grains using a high-pressure electron microscope. (5) Emulsion L is a double-structured grain containing an internal high iodine core described in JP-A-60-143331.

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

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

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Next, sample 102 was prepared by adding zinc hydroxide as a poorly water-soluble basic metal compound according to the present invention to the second layer (intermediate layer) in an amount of 7.5 mmol / m ^2. did. The average particle size of the zinc hydroxide solid dispersion was 0.3μ. Hereinafter, the average particle size of the dispersion of the metal compound was set to 0.3 μm.

Subsequently, in Samples 103 and 104, the main cyan coupler ExC-1 used in the third to fifth layers was the coupler described in Example 7 of JP-A-63-011940 (Document 1). The weight of C-100 to 102 shown in Table 8 [g
/ M ² ], zinc hydroxide was not added to sample 103, and the same amount as sample 102 was added to sample 104 to prepare a sample. The coupler, C-10, quoted from document 1 here
0 is the coupler IIIC-1 of the present invention, C-101 is III
Corresponds to C-2. However, the use of the coupler of Document 1 is a combined use of the coupler represented by the general formula (III) of the present invention and the coupler other than the present invention, and the amount of the coupler of the present invention used is 80 mol%. It is different from the invention. Furthermore, the amounts of couplers used in Samples 103 and 104 were changed as shown in Table 8 to prepare Samples 105 to 110. The usage rate of the cyan coupler of the present invention in Samples 105 and 106 was 91%, that in Samples 107 and 108 was 96%, and that in Sample 10
9,110 is 100%. Samples 111 and 112
Was prepared in the same manner as in Samples 101 and 102, except that ExC-1 was replaced with the couplers described in Example 7 of Document 1 and the weights shown in Table 8 for C-14 and C-25. The coupler used in Samples 101 to 110 is a so-called 4
Equivalent couplers and the couplers used in Samples 111 and 112 correspond to 2-equivalent couplers. These couplers quoted are shown in Formula 60.

[0223]

Embedded image

Samples 113 and thereafter are replaced by an equimolar amount of the coupler represented by the general formula (II) and / or the general formula (III) of the present invention as shown in Tables 8 and 9, and a poorly water-soluble basic metal is used. Samples up to Sample 127 were prepared by changing the presence or absence of the compound or the type and amount of the compound.

These prepared samples were cut and processed to have a width of 35 mm and subjected to gradation exposure with white light and an R filter. The other set is a rapid development process (B-1) that shortens the color development time.
The treatment was carried out. The development processing steps and processing solution compositions are shown below. Note that the continuous treatment was performed on both samples 101
The samples taken by the camera were processed every day by 1 m ² until the replenisher of 3 times the tank capacity of the color developing solution was consumed, and then processed.

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

The composition of the processing liquid is shown below. (Color developer) Tank liquid (g) Replenisher (g) Diethylenetriaminepentaacetic acid 2.0 2.0 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 2.0 Sodium sulfite 3.9 5.1 Potassium carbonate 37.5 39.0 Potassium bromide 1.4 0.4 Potassium iodide 1.3 mg-Hydroxylamine sulfate 2.4 3.3 Disodium N, N-bis (sulfonate ethyl) hydroxylamine 1.5 2.0 2-Methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 4.8 6.5 Add water 1.0 liter 1.0 liter pH (prepared with potassium hydroxide and sulfuric acid) 10.05 10.15

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

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

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

(Washing water) Common to tank liquid and replenisher tap water is H type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH type strongly basic anion exchange resin (Amberlite IR). -40
Through a mixed-bed column packed with 0) to reduce the calcium and magnesium ion concentrations to 3 mg / l or less, followed by 20 mg / sodium diisocyanurate dichloride.
Liters and 150 mg / liter of sodium sulfate were added. The pH of this solution was in the range of 6.5 to 7.5.

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

(Development processing B-1) step and processing solution composition (processing step) step processing time processing temperature replenishment amount ^* tank capacity color development 1 minute 00 seconds 45.0 ° C 260 ml 2.5 liter bleach-fixing 1 minute 00 seconds 40.0 ° C 600 ml 2.5 liter Stability (1) 20 seconds 40.0 ℃ − 1.5 liter Stability (2) 20 seconds 40.0 ℃ − 1.5 liter Stability (3) 20 seconds 40.0 ℃ 400 ml 1.5 liter Dry 50 s 65 ℃ * Replenishment amount Is a countercurrent method from (3) to (1) for stabilizing bath per 1 m ² of light-sensitive material. The amount of developing solution brought into the bleach-fixing step, the amount of bleach-fixing solution brought into the washing step and the amount of washing solution brought into the stabilizing step were 40 ml, 38 ml, 45 ml and 65 ml per 1 m ² of the light-sensitive material, respectively. It was milliliters. The crossover time is 3 seconds in each case, and this time is included in the processing time of the previous step. As evaporation correction in each tank, JP-A-3-28
As described in No. 0042, the temperature and humidity of the outside air of the processor were detected by a thermo-hygrometer, and the evaporation amount was calculated and corrected. As the water for evaporation correction, the following ion-exchanged water for washing water was used.

The composition of the treatment liquid is shown below. (Color developer) Mother liquor (g) Replenisher (g) Diethylenetriaminepentaacetic acid 4.0 4.0 1-Hydroxyethylidene-1,1-diphosphonic acid 3.0 3.0 Sodium sulfite 4.0 6.7 Potassium carbonate 40.0 40.0 Potassium bromide 2.0-Potassium iodide 1.3 mg-picolinic acid 12.0 14.4 disodium N, N-bis (sulfonate ethyl) hydroxylamine 12.0 17.0 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 11.0 14.5 Water In addition 1.0 liter 1.0 liter pH (adjusted with potassium hydroxide and sulfuric acid) 10.05 10.30

(Bleach-fixing solution) Tank solution (g) Replenishing solution (g) Ethylenediaminetetraacetic acid ammonium ferric dihydrate 40.0 96.0 2-{[1- (carboxyethyl) -carboxymethylamino] ethyl} carboxymethylami Ammonium iron (III) benzoate monohydrate 0.10 mol 0.24 mol Ethylenediaminetetraacetic acid 6.0 14.4 Succinic acid 12.0 28.8 Ammonium sulfite 20 80 Ammonium thiosulfate aqueous solution (700 g / l) 290 700 Ammonium methanesulfinate 5.0 20 Ammonium iodide 2.0 1.7 Water 1.0 liter 1.0 liter pH [prepared with ammonia water and nitric acid] 6.0 5.8

(Stabilizing Solution) Common to Mother Liquor and Replenishing Solution (unit: g) Succinic acid 0.2 p-Toluenesulfinic acid sodium 0.03 Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.2 1 , 2-Benzisothiazolin-3-one 0.05 Chlorinated sodium isocyanurate 0.02 Add water 1.0 liter pH (adjusted with nitric acid and aqueous ammonia) 5.0

The density of each of the continuously processed samples was measured for cyan, magenta, and yellow, and the gradation was calculated from the obtained characteristic curve in accordance with the above-described method of calculating the gradation. Regarding the obtained gradation degrees, the gradation degree γ of the cyan, magenta, and yellow development processing (A-1) is γ _A, and the gradation degree γ of the development processing (B-1) is γ _B
As a result, the γ _B / γ _A ratio of the same sample was obtained.

On the other hand, a gradation exposure is performed by applying an R filter, and the above development processing (A-1) and development processing (B-1) are performed.
For the cyan color image obtained by carrying out the above, one was examined for graininess by giving a density of minimum density +0.5 by an ordinary method using an aperture having a diameter of 48 μm. . The other is to measure the density of a cyan color image immediately after the completion of both continuous treatments, and then to perform a 5 minute by weight addition of these samples with an aqueous solution of red blood salt (adjusted to pH = 9.0 with sodium carbonate) for 5 minutes. (38 ° C.) After the treatment, the sample was washed with running water for 10 minutes and the concentration was measured again. The change in the concentration of the same sample with and without the post-treatment was calculated by comparing the cyan concentration of the minimum concentration of the post-treated sample + 1.5 It was determined by the density ratio (%) in terms of the amount of exposure given. These results are summarized in Table 8 and Table 9.

[0239]

[Table 8]

[0240]

[Table 9]

From the table, the samples 106, 108, 1 of the present invention are shown.
10, 114 to 127 are the current continuous development processes (A-
Even if 1) is carried out or the rapid continuous processing (B-1) in which the color development time is shortened, good cyan color development is exhibited, and the gradation ratio (γ _B / γ _A ) is It is understood that the above conditional expression is satisfied, and the conditional expression is satisfied together with the gradation ratio of the magenta and yellow color images, and good tone reproducibility and color reproducibility are provided. Also, regarding both graininess, both treatments are good, but particularly in the rapid continuous treatment (B-1), excellent graininess is given. Further, in the present invention, a light-sensitive material containing a coupler represented by the general formula (II) and / or (III) of the present invention and a poorly water-soluble basic metal compound has a The smallness is also clear from the ratio of the concentration immediately after the continuous treatment and the concentration change when these samples were subjected to the oxidation bath treatment of the red blood salt aqueous solution. On the other hand, comparative samples 101 to 10
Nos. 5, 107, 109, and 111 to 113 do not satisfy all of the above-mentioned various performances, and even if the tone reproducibility and the color reproducibility are good, the graininess is poor or the density of cyan coloring changes. It has disadvantages such as From these results, even if the same photosensitive material is subjected to both the current development processing and the rapid development processing in which the color development time is shortened,
Provide an image forming method showing excellent cyan color development, excellent gradation balance of three colors of cyan, magenta, and yellow, giving good tone reproducibility, color reproducibility, and graininess, and having no change in color density of cyan color image. can do.

Example 2 Using the samples 101 to 127 prepared in Example 1, white light gradation exposure was applied to these samples, and one set was subjected to the development treatment (I-1) shown below and another The set is development processing (II-
1) was carried out. Then, the picolinic acid used in the color developer of the development treatment (II-1) was replaced with another trigger, and the same exposure was applied to perform the same treatment. (Development treatment II-2) Picolinic acid was replaced with pyridine-2,5-dicarboxylic acid in an equimolar amount. (Development processing II-3) Similarly, picolinic acid was replaced with 5-methylpicolinic acid in an equimolar amount. (Development processing II-4) Similarly, picolinic acid was changed to oxalic acid.
Replaced by 5 times the molar amount.

[0243]

Next, the composition of the processing liquid will be described. (Color developer) Tank liquid (g) Diethylenetriaminepentaacetic acid 1.0 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide 1.5 mg Hydroxylamine sulfate 2.4 4- [N -Ethyl-N- (β-hydroxyethyl) amino] -2-methylaniline sulfate 4.5 Water was added to 1.0 liter pH (adjusted with potassium hydroxide and sulfuric acid) 10.05

(Bleaching solution) Common to tank solution and replenishing solution (unit: g) Ethylenediaminetetraacetic acid ammonium ferric dihydrate 120.0 Ethylenediaminetetraacetic acid disodium salt 10.0 Ammonium bromide 100.0 Ammonium nitrate 10.0 Bleaching accelerator 0.005 mol (CH ₃ ) _{2 N-CH 2 -CH 2 -SS} -CH 2 -CH 2 -N (CH 3) 2 · 2HCl · ammonia water (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) Ethylenediaminetetraacetic acid ammonium ferric dihydrate 50.0 Ethylenediaminetetraacetic acid disodium salt 5.0 Sodium sulfite 12.0 Ammonium thiosulfate aqueous solution (700 g / l) 240.0 ml Ammonia water (27%) Add 6.0 ml water to 1.0 liter pH (adjust with ammonia water and acetic acid) 7.2

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

(Stabilizing Solution) (Unit: g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether (Average degree of polymerization: 10) 0.2 1,2-Benzisothiazolin-3-one sodium 0.10 Ethylenediamine tetra Acetic acid disodium salt 0.05 1,2,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 Water was added to 1.0 liter pH 8.5

Process of (Development treatment II-1) and composition of treatment liquid Treatment process Temperature time Color development 45 ° C. 60 seconds Bleach fixing 40 ° C. 60 seconds Rinsing with water (1) 40 ° C. 15 seconds with water (2) 40 ° C. 15 seconds with water ( 3) 40 ° C for 15 seconds Stability 40 ° C for 15 seconds Dry 80 ° C for 60 seconds (Washing was carried out in the three-tank countercurrent system from (3) to (1).)

Liquid composition (color developer) Tank liquid (g) Diethylenetriaminepentaacetic acid 2.0 1-Hydroxyethylidene-1,1diphosphonic acid 3.3 Sodium sulfite 3.9 Potassium carbonate 37.5 Potassium bromide 4.0 Potassium iodide 1.3 mg Picolinic acid 12 Hydroxylamine Sulfate 1.5 Disodium N, N-bis (sulfonate ethyl) hydroxylamine 10.0 2-Methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 18.0 Water was added to 1.0 liter pH (Prepared with potassium hydroxide and sulfuric acid) 10.05 (bleach-fixing solution) (unit mol) ethylenediamine- (2-carboxyphenyl) -N, N ', N'-triacetic acid 0.17 ferric nitrate nonahydrate 0.15 thio Ammonium sulfate 1.25 Ammonium sulfite 0.10 Metacarboxybenzenesulfinic acid 0.05 Add water 1.0 Liter pH (prepared with acetic acid and ammonia) 5.8 (wash water) Same composition as described in (I-1). (Stabilizer) The same composition as described in the treatment (I-1).

The developed sample was subjected to density measurement for each of cyan, magenta and yellow, and its gradation was calculated from the obtained characteristic curve in accordance with the above-mentioned method of calculating gradation. Regarding the obtained gradient, cyan,
Gradation γ of development processing (I-1) for magenta and yellow
Was defined as γ _I, and the gradation degree γ of the development process (B-No.) Was defined as γ _B-NO , and the γ _B-NO / γ _A ratio in the same sample was determined. Table 10 shows the results. Since magenta and yellow dye image of γ _B-NO / γ _A has the same results were obtained, representatively gamma _B-1
/ Γ _A value is shown.

[0252]

[Table 10]

From the table, the gradation of the cyan image obtained from the rapid processing (II-1) to (II-4) in which the color development time is shortened is almost the same as the current developing processing (I-
When the gradation degree with respect to the gradation of 1) was calculated, the result was the same as or almost the same as the result obtained in Example 1, and all of the samples 106, 108, 110, 114 to 127 of the present invention are shown above. It can be seen that the conditional expression of is satisfied. Further, even if the trigger used in the color developing solution for rapid processing is changed, the conditional expression is similarly satisfied, good cyan color development is provided, and the gradation balance of the three colors of cyan, magenta and yellow is excellent.
Therefore, it is possible to provide an image forming method that gives good tone reproducibility and color reproducibility even if these development processes are performed. Note that the sample subjected to gradation exposure with an R filter was subjected to the above development treatment, and the graininess was examined in the same manner as in Example 1. The development treatment (I-1) was the same as the development treatment of Example 1 ( The same results as in A-1) are obtained by the development processing (II-1) to (II-
In 4), the same results as in the development treatment (B-1) of Example 1 were obtained, and the samples 106, 108, 110, 114 to 1 of the present invention were obtained.
No. 27 was found to have good graininess even by the above treatment. In particular, the rapid processing (II-1) to (II-4) was also superior in the graininess as compared with the developing processing (I-1).

Example 3 1) Support The support used in this example was prepared by the following method. Polyethylene-2,6-naphthalate polymer 10
0 parts by weight and Tinuvin P.326 (Ciba
2 parts by weight of Ciba-Geigy)
After melting at 300 ℃, extrude from T-die, 140 ℃
, And then stretched 3.3 times at 130 ° C.
Double stretching was performed twice, and the film was heat-set at 250 ° C. for 6 seconds to obtain a PEN film having a thickness of 90 μm. This PEN
A blue dye, a magenta dye and a yellow dye can be used in the film (public technical report: I-described in Japanese Patent No. 94-6023)
1, I-4, I-6, I-24, I-26, I-27,
II-5) was added in an appropriate amount. Further, the support was wound around a stainless steel core having a diameter of 20 cm to give a heat history of 110 ° C. and 48 hours, thereby providing a support with which a winding habit was not easily formed.

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

3-1) Coating of antistatic layer A dispersion of fine particle powder having a specific resistance of 5 Ω · cm of a tin oxide-antimony oxide composite having an average particle diameter of 0.005 μm (secondary agglomerated particle diameter of about 0.08 μm). ) and 0.2 g / m ^2, gelatin _{^{0.05g / m 2, (CH 2}} = CHSO 2 CH 2 CH 2 NHCO) 2 CH 2 0.
02 g / m ² , poly (degree of polymerization 10) oxyethylene-p-
Coated with nonylphenol 0.005 g / m ² and resorcin. 3-2) Coating of Magnetic Recording Layer Cobalt-γ-iron oxide coated with 3-poly (degree of polymerization 15) oxyethylene-propyloxytrimethoxysilane (15% by weight) (specific surface area 43 m ² / g; Long axis 0.
14 μm, single axis 0.03 μm, saturation magnetization 89 emu / g,
Fe ^{+ 2} / Fe ⁺³ = 6/94, the surface of which is treated with silicon oxide aluminum oxide at 2% by weight of iron oxide) 0.06 g / m ² of diacetyl cellulose 1.2 g / m ² (of iron oxide Dispersion was carried out with an open kneader and sand mill), as a curing agent
C ₂ H ₅ C (CH ₂ OCONH-C ₆ H ₃ (CH ₃ ) NCO) ₃ 0.3 g / m ² was applied with a bar coater using acetone, methyl ethyl ketone, cyclohexanone, and dibutyl phthalate as a solvent to form a film thickness. A 1.2 μm magnetic recording layer was obtained. As a slip agent
C ₆ H ₁₃ CH (OH) C ₁₀ H ₂₀ COOC ₄₀ H ₈₁ 50 mg / m ² , silica particles (0.3 μm) as a matting agent and 3-poly (polymerization degree 1
5) 50 mg / amount of abrasive aluminum oxide (0.20 μm and 1.0 μm) treated and coated with oxyethylene-propyloxytrimethoxysilane (15% by weight), respectively.
It was added so as to be m ² and 10 mg / m ² . Drying is 11
It was carried out at 5 ° C for 6 minutes (115 ° C for all the rollers and conveying devices in the drying zone). X-light (blue filter)
The increase in D ^B color density of the magnetic recording layer is about 0.1, the saturation magnetization moment of the magnetic recording layer is 4.2 emu / g, the coercive force is 7.3 × 10 ⁴ A / m, and the squareness ratio is It was 65%.

3-3) Preparation of Sliding Layer A mixture of C ₆ H ₁₃ CH (OH) C ₁₀ H ₂₀ COOC ₄₀ H ₈₁ (6 mg / m ² ) was applied. This mixture was prepared by melting it in xylene / propylene monomethyl ether (1/1) at 105 ° C. and pouring and dispersing it in propylene monomethyl ether (10 times the volume) at room temperature. Average particle size 0.
01 μm) before adding. Drying was carried out at 115 ° C for 6 minutes (1 roller for the drying zone and 1 conveyor)
15 ° C). The sliding layer had a dynamic friction coefficient of 0.10 (5 mmφ stainless steel ball, load of 100 g, speed of 6 cm / min), static friction coefficient of 0.08 (clip method), and the dynamic friction coefficient of the emulsion surface and the sliding layer described later was 0.13. It had excellent characteristics.

4) Coating of Photosensitive Layer Next, on the opposite side of the back layer obtained as described above, each layer having the same composition as in Example 1 was multilayer coated to prepare a color negative film. These are designated as Samples 301 to 327.

The light-sensitive material prepared as described above is set to 24 mm
The photosensitive material is cut to a width of 160 cm, and two perforations of 2 mm square are provided at a distance of 5.8 mm 0.7 mm from one side in the length direction of the photosensitive material. We have made a set of these two sets at intervals of 32 mm, and we have US 5,296,8
It was housed in the plastic film cartridge described in FIG. 1 to FIG. For this sample, a head gap of 5 μm from the coated surface side of the magnetic recording layer and a head capable of inputting and outputting with a turn number of 2,000 was used, and during the above-mentioned perforation of the photosensitive material, an FM signal at a feed rate of 1,000 / s Was recorded.

For these light-sensitive materials, both continuous processing, development processing A-1 and development processing B-1 were carried out in the same manner as in Example 1 and the same performance evaluation was carried out. The results are the same as those obtained in Example 1,
The results are the same as those shown in Table 8 and Table 9, and the light-sensitive materials 306, 308, 310, 314 to 327 of the present invention exhibit good cyan color development, and the gradation ratio obtained from both the processes satisfies the conditional expression. In addition, the gradation balance of the three colors of cyan, magenta and yellow was excellent, and good graininess was exhibited. Also, a small change in color density was also obtained, and good results were obtained.

Further, with respect to the above-mentioned light-sensitive material, Zoom Cardia (manufactured by Fuji Photo Film Co., Ltd.) was modified so that the cartridge can be loaded, and an Abbeth chart was photographed using each light-sensitive material. After processing, Fuji Color Paper FA is used with these color negatives.
The image was visually evaluated by printing on (V). Further, the cyan image portion of the color negative was enlarged and printed 20 × 20 times, and the graininess thereof was also visually evaluated. As a result, the light-sensitive materials 306, 308, 310, 314 to 32 of the present invention.
The prints using the color negatives obtained from both processes of No. 7 were evaluated to be excellent in tone reproducibility, color reproducibility and graininess in the gray part. In contrast, comparative sample 301
˜305, 307, 309, 311 to 313, samples with poor tone balance and poor tone reproduction and color reproducibility, or poor graininess were observed.

The same result can be obtained by changing the amount of picolinic acid as the trigger of the development processing B-1 to the trigger used in Example 2 in the same amount.

[0263]

According to the present invention, a coupler represented by the general formula (II) or (III) is added to the red-sensitive silver halide emulsion layer of a light-sensitive material and at least one of the light-sensitive layer and the non-light-sensitive layer is added. Even if these sensitive materials using a poorly water-soluble basic metal compound in a layer are subjected to two kinds of color development treatments having different color development times, that is, a current development treatment and a rapid development treatment in which the color development time is shortened. Cyan color image development obtained by both processes is good, and even if a conditional expression defining the gradation degree obtained by both processes is set, the conditional expression is satisfied, and gradations of three colors of cyan, magenta, and yellow are satisfied. Good balance, excellent tone reproduction and color reproduction.
It is possible to provide an image forming method of a silver halide color photographic light-sensitive material which is excellent in graininess and has a small variation in cyan color density in rapid continuous processing.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] September 22, 1995

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0102

[Correction method] Change

[Correction contents]

[0102]

Embedded image

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display location G03C 7/00 530 G03C 7/00 530 550 550 7/20 7/20 7/26 7/26 7 / 392 7/392 Z 7/407 7/407

Claims (4)

[Claims] 1. A blue-sensitive silver halide emulsion layer on a support,
A silver halide color photographic light-sensitive material having at least one green-sensitive silver halide emulsion layer, at least one red-sensitive silver halide emulsion layer and at least one non-light-sensitive layer. A cyan coupler, and 90 mol% or more of the 4-equivalent cyan coupler is a coupler represented by the general formula (II) or the general formula (III),
Further, the silver halide color photographic light-sensitive material containing at least one layer containing a poorly water-soluble basic metal compound was subjected to the following two kinds of development processing (I) and development processing (II) having different color development times. At this time, the silver halide color photographic light-sensitive material is characterized in that the gradations of the yellow, magenta and cyan color images obtained by the two types of development processing satisfy the following conditional expressions. General formula (II) In the formula, R ₁ is —CONR ₄ R ₅ , —SO ₂ NR ₄ R ₅ ,
-NHCOR ₄ , -NHCOOR ₆ , -NHSO
₂ R _6, -NHCONR ₄ R ₅ or -NHSO ₂ NR
₄ R ₅ and R ₂ are groups capable of substituting on a naphthalene ring, k is an integer of 0 to 3, R ₃ is a substituent, and X is a hydrogen atom. However, R ₄ and R ₅ may be the same or different and each independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R ₆ represents an alkyl group, an aryl group or a heterocyclic group. When k is plural, R _{2 s} may be the same or different, and may combine with each other to form a ring. R ₂ and R ₃ may combine with each other to form a ring. In addition, a dimer or a multimer of R ₁ , R ₂ or R _{3 which} is bonded to each other through a divalent or divalent or higher valent group may be formed. General formula (III) In the formula, R ¹ represents an alkyl group, an aryl group, or a heterocyclic group, R ² represents an aryl group, and Z represents a hydrogen atom. Conditional expression 0.8 ≦ γ _II (Y) / γ _I (Y) ≦ 1.2 0.8 ≦ γ _II (M) / γ _I (M) ≦ 1.2 0.8 ≦ γ _II (C) / γ _I (C) ≦ 1.2 (γ _I (Y), γ _I (M), and γ _I (C) represent gradation levels of yellow, magenta, and cyan when the development processing I is carried out, and γ _II (Y), γ _II (M), γ _II (C)
Represents the gradation levels of yellow, magenta, and cyan when the development processing II was carried out. (Development treatment I) Color development time is 3 minutes to 3 minutes 15 seconds, the temperature of the color developing solution is 37 to 39 ° C., and 2-methyl-4- [N-ethyl-N-as a color developing agent. (Β-
A development process characterized in that the color development process is performed using a color development solution containing 15 to 20 mmol / L of hydroxyethyl) amino] aniline. (Development Treatment II) Color development time is 50 to 70 seconds, the temperature of the color developing solution is 43 to 47 ° C., and 2-methyl-4- [N-ethyl-N- (β-hydroxy) is used as a color developing agent. 35-40 mmol of ethyl) amino] aniline /
A developing treatment, characterized in that the color developing treatment is carried out using a color developing solution containing a compound which promotes the release of a base from a basic metal compound having a solubility in water and a poorly water-soluble basic metal compound. 2. The halogenated product according to claim 1, wherein the photographic light-sensitive material has a magnetic layer containing a ferromagnetic powder in a back layer on the side opposite to the side of the photosensitive emulsion layer with the support interposed therebetween. Silver color photographic light-sensitive material. 3. A color image forming method, which comprises forming a color image by carrying out the development processing A described below, using the silver halide color photographic light-sensitive material according to claim 1 or 2. (Development treatment A) The color developing time is 150 to 200 seconds, the temperature of the color developing solution is 37 to 40 ° C., and a color developing solution containing 15 to 20 mmol / liter of a color developing agent is used. Development process. 4. A color image forming method, wherein a color image is formed by carrying out the following development processing B using the silver halide color photographic light-sensitive material according to claim 1 or 2. (Development treatment B) Color development time is 25 to 90 seconds, temperature of color developing solution is 40 to 60 ° C., concentration of color developing agent is 25 to 80 mmol / liter, and basic metal compound hardly soluble in water is used. A development process comprising using a color developing solution containing a compound that accelerates the release of a base.