JP3359469B2 - Silver halide color photographic light-sensitive material and image forming method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material and an image forming method thereof. Yellow, magenta, cyan 3
The present invention relates to a silver halide color photographic light-sensitive material improved so that the color gradation is balanced and an image forming method thereof.

[0002]

2. Description of the Related Art In recent years, efforts have been made to shorten the processing time of color development processing of color photographic light-sensitive materials. Taking color negative development as an example, the conventional processing has been speeded up mainly by shortening the processing time of the desilvering process. Fuji Photo Film Co., Ltd.'s rapid processing CN- In 16FA, it is reduced to 8 minutes and 15 seconds. However, the color development time accounts for about 40% of the total color negative development processing time.
Therefore, reducing the color development time, which accounts for a large proportion of the total processing time of the current color negative development processing step, is a major challenge in the art. Many proposals have been made for solving this problem. However, simply applying high temperature processing of color development, high pH processing of developer, high concentration processing of color developing agent, improvement of film quality, thinning of photosensitive material constituent layer, or a combination of these, shortened compared to the present. Even if processing is performed during the color development time, the tone balance of the red-sensitive layer, green-sensitive layer, and blue-sensitive layer, which are the most important color negatives, will be greatly disrupted, and the tone reproducibility and color reproducibility of color prints will be greatly impaired. As a result, a satisfactory reduction in color development time has not yet been achieved. Therefore, in order to obtain excellent finish quality even when developing with color negative processing which is currently widely distributed and when performing rapid processing different from color developing processing, a technique for controlling gradation and gradation balance is required. Development is very important and technical development for this is strongly desired.

On the other hand, with respect to a base precursor capable of releasing a base during development processing, for example, Japanese Patent Application Laid-Open No. 63-011940
Patent Document 1 (Document 1) contains a basic metal compound which is hardly soluble in water in a photosensitive material, and contains a complex forming compound which causes a complex forming reaction to metal ions constituting the basic metal compound and releases a base. It is described that development processing is performed using a processing solution. However, in Reference 1, there is no description that the gradation degree satisfies the conditional expression according to the present invention even when a rapid processing in which the development time is shortened with respect to the described color development time is performed. There is no description that can be made. Furthermore, Document 1 aims to provide an image forming method which improves the stability and safety of a developer over time and can provide a sufficient image density (maximum density (Dmax)) even if the processing time is short. Is what you do. Also, JP-A-3-017
No. 648 (Literature 2) also discloses that a light-sensitive material contains a basic metal compound which is hardly soluble in water and releases a base when complexing with a metal ion constituting the basic metal compound. Processing with a color developer containing a compound is described. However, in the above reference 2, the composition of the silver halide used in the light-sensitive material is a silver halide containing 80 mol% or more of silver chloride without substantially containing silver iodide. The color developer containing a compound is a color image forming method applied in a thin layer on the surface of a photosensitive material, and is an image forming method different from the present invention as described later. Further, as described above, there is no description relating to satisfying the conditional expression of the gradient according to the present invention, and there is no description that can be inferred.

[0004]

Accordingly, the present invention has at least one blue-sensitive silver halide emulsion layer, 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 color photographic material containing a base precursor capable of releasing a base at the time of development processing in at least one of the above-mentioned layers, and two types of development processing I and development processing II having different color development times (the processing time is shorter than the development time I). (A short rapid processing), a color photographic material that satisfies a conditional expression in which the gradation of yellow, magenta and cyan obtained by the two types of development processing satisfies a prescribed conditional expression. Providing a silver halide color photographic light-sensitive material with a good balance of color gradation of three colors, which matches color tone reproducibility and color reproducibility well in color printing even after performing various types of color development processing. An object of the present invention is to. Another object of the present invention is to provide a color image forming method suitable for achieving the above object.

[0005]

Means for Solving the Problems The present inventors have developed a silver halide color photographic light-sensitive material having the above-mentioned gradation balance, which comprises a blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layer and a non-light-sensitive layer. And at least one layer, each of which contains a base precursor capable of releasing a base during development in the above-mentioned at least one layer, and is obtained by yellow and magenta obtained by specific two types of development having different color development times. It has been found that by adjusting to a conditional expression that defines the cyan gradation, it is possible to obtain a light-sensitive material in which the color gradations of three colors are well balanced, and have completed the present invention. That is, the present invention

(1) It has at least one each of a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, a red-sensitive silver halide emulsion layer and a non-light-sensitive layer, and can release a base during development processing. In the above silver halide color photographic light-sensitive material containing a base precursor in at least one layer, the following two types of development processing I and development processing differing in color development time
A silver halide color photographic light-sensitive material characterized in that the gradation of yellow, magenta and cyan obtained by the two types of development processing when performing II satisfies the following conditional expression. 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), γ I (C) represents yellow when carrying out the development processing I, magenta, the gradient of cyan, gamma _II (Y), γ _II (M), γ _II (C)
Represents the gradient of yellow, magenta, and cyan when the development process II is performed, respectively. (Development Processing I) The color development time is 3 minutes to 3 minutes 15 seconds, the temperature of the color developer is 37 to 39 ° C., and 2-methyl-4- [N-ethyl-N- (Β-
A development process characterized by performing color development using a color developer containing 15 to 20 mmol / l of [hydroxyethyl) amino] aniline. (Development treatment II) The color development time is 50 to 70 seconds, the temperature of the color developer is 43 to 47 ° C, and 2-methyl-4- [N-ethyl-N- (β-hydroxy Ethyl) amino] aniline at 35-40 mmol /
A color developing process using a color developing solution containing a liter and a compound that promotes the release of a base from the base precursor.

(2) The silver halide color photographic material as described in (1), wherein the base precursor is a poorly water-soluble basic metal compound. (3) A color image forming method, wherein a color image is formed by performing the following development processing A using the silver halide color photographic light-sensitive material described in (1). (Development process 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 / l of a color developing agent is used. Development process. (4) A color image forming method, wherein a color image is formed by performing the following development processing B using the silver halide color photographic light-sensitive material according to (1). (Development process B) The color development time is 25 to 90 seconds, the temperature of the color developer is 40 to 60 ° C., the concentration of the color developing agent is 25 to 80 mmol / L, and the base from the base precursor is A development process characterized by using a color developer containing a compound that promotes release.

In the above embodiment (1), a base precursor which has at least one blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layer and at least one non-light-sensitive layer and can release a base during development processing is used. When the silver halide color photographic light-sensitive material contained in at least one layer is subjected to two specific development processes having different color development times, the gradations of the three colors yellow, magenta, and cyan satisfy the specific conditional expression. It is a silver halide color photographic light-sensitive material. Such a technique is a technique which has not been disclosed so far for a color photographic light-sensitive material, and defines two specific types of developing processes, and obtains yellow and magenta obtained by performing the two types of developing processes. When the gradation of three colors of cyan and cyan satisfies a specific conditional expression, the tone reproducibility and the color reproducibility in the color print are 3
The object of the present invention is achieved by providing a color negative with a good balance of color gradation.

The preferred embodiment (2) is a preferred embodiment for achieving the above object of the present invention by making the base precursor capable of releasing a base during development processing a poorly water-soluble basic metal compound.

In the embodiments (3) and (4), the two types of development processing having different color development times of the embodiment (1) are separately defined, thereby satisfying the conditional expression defining the gradient of three colors. This is an image forming method that can achieve the object of the present invention by performing any of these methods.

Hereinafter, the present invention will be described in detail. First, the base precursor will be described in detail. The base precursor contained in the light-sensitive material of the present invention may be any compound as long as it can release a base during color development processing or preprocessing. However, since the base precursor is incorporated in the light-sensitive material, it is desired that the base precursor be a compound that does not exhibit basicity when the light-sensitive material is stored. A method for generating a base from a base precursor at the time of development processing or pretreatment thereof may be a chemical reaction or a physical method (for example, heating). When a chemical reaction is used, a method of generating a base by adding a compound that promotes release of a base from the base precursor (hereinafter referred to as a trigger compound) to a color developing solution or a prebath thereof may be used. it can. Since the trigger compound is used after being added to the treatment solution, it is desired that the trigger compound has sufficiently high water solubility. Examples of preferred combinations of the base precursor and the trigger compound include the combination of a poorly soluble basic metal salt and a water-soluble salt described in JP-A-62-174745, U.S. Pat. No. 3,260,598, and JP-A-62-129848. Combination of a sparingly soluble basic metal salt and a water-soluble chelating agent described in JP-B-5-75108, JP-A-63-24242.
And the combination of a sulfinic acid salt and an electrophile described in Japanese Patent Application Nos. 6-61093 and 277236.

Among these combinations, a combination of a hardly soluble basic metal salt and a water-soluble salt or a water-soluble chelate is particularly preferable. The method using these hardly soluble basic metal salts will be described in detail below.

In the present invention, examples of the poorly water-soluble basic metal compound to be contained in the light-sensitive material include solubility in water at 20 ° C. (grams of a substance dissolved in 100 g of water).
There preferably those represented by the formula T _m X _n 0.5 or less. Here, T is a transition metal, for example, Zn, Ni, Co, Fe, Mn, Cu, Al, S
alkaline earth metals such as n, Sb, Bi, etc., eg, Ca, B
a, Sr, Mg, etc., wherein X can be a counter ion of M in the description of a complex-forming compound described later in water and shows 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 valence of each of T and X can be 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.

In the present combination, the trigger compound to be contained in the treatment solution may be a complex-forming compound which forms a complex salt having a stability constant of 1 or more in log K with a metal ion constituting the basic metal compound. preferable. These complex-forming compounds are described in, for example, "Critical Stability Konstanz (CrM)", co-authored by AE Martell and RMSmith.
Ital Stability Constants, Vols. 1-5 ", Plenum Press. Specifically, aminocarboxylic acids, iminodiacetic acid and its derivatives, aniline carboxylic acids, pyridine carboxylic acids, amino phosphoric acids, Carboxylic acids (mono, di, tri, tetracarboxylic acids and further compounds having substituents such as phosphono, hydroxy, oxo, ester, amide, alkoxy, mercapto, alkylthio, phosphino), hydroxamic acids, polyacrylates, polyphosphoric acids, etc. And salts of alkali metals, guanidines, amidines or quaternary ammonium salts.

Preferred specific examples include picolinic 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, isocrine Acid, malic acid, gluconic acid, EDTA, NTA, CDTA, hexametaphosphoric acid, tripolyphosphoric acid, tetraphosphoric acid, polyacrylic acid,

[0017]

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Alkali metal salts, salts of guanidines, etc.
Amidine salts, quaternary ammonium salts and the like. Among them, an aromatic heterocyclic compound having at least one —CO ₂ M and having 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 α-position 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.

[0019]

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In the above formula, R represents 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 or an alkyl group. Or
Two Rs may be the same or different. Z ₁ and Z
₂ is the same as defined for R, and Z ₁
And Z ₂ may combine to form a ring fused to a pyridine ring.

Next, examples of the most preferable combination of a basic metal compound which is hardly soluble in water and a complex-forming compound are listed (where M ⁺ is an alkali metal ion, a substituted or unsubstituted guanidinium ion, an amidinium ion Or 4
Represents a secondary ammonium ion).

[0022]

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[0023]

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[0024]

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[0025]

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[0026]

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[0027]

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

[0029]

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That is, when water in the treatment liquid is involved, picolinic acid ions cause a complex formation reaction with zinc ions, and the reaction represented by the above formula proceeds, thereby generating a base. The progress of the reaction, but due to the stability of the resulting complex, picolinic acid ion (L ^-) and generates from the zinc ion (M ⁺⁾ ML, stability of the complex represented by ML _2, ML ₃ The constants are very large, as described below, and well explain the progress of this reaction.

[0031]

[Table 1]

Basic metal compounds which are hardly soluble in water are disclosed in
It is desirable to contain it as a fine particle dispersion prepared by the methods described in JP-A-174830, JP-A-53-102733 and the like, and the average particle size is preferably 50 µ or less, particularly preferably 5 µ or less. The amount of addition depends on the type of processing solution, pH, type of complex forming compound, type of basic metal compound, particle size, processing temperature, etc., and cannot be specified unconditionally.
0.1~200mmol / m ^2, preferably 1~50mmol / m ²
It is good to be about. The amount of the complex-forming compound to be contained in the processing solution varies depending on the type of the processing solution, pH, the type of the complex-forming compound and the like, but is generally preferably about 0.01 to 5 mol / l. The complex-forming compound is contained in the treatment liquid before the treatment in advance, but may also be contained in the replenisher.

Specific examples of the combination of silver acetylide and halide ion are shown below. The present invention is not limited to these combinations.

[0034]

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Specific examples of the combination of the sulfinate and the electrophile are shown below. The present invention is not limited to these combinations.

[0036]

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[0037]

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The amounts of silver acetylide and sulfinate added to the light-sensitive material and the amounts of halide ions and electrophiles added to the processing solution depend on the amount of the basic metal salt added to the light-sensitive material and the amount of complexation. It is preferable to use the same amount of the compound to be added to the treatment liquid.

Next, a base generation method utilizing physical stimulation will be described. The physical stimuli that can be used include heat, pressure, electricity, magnetism and ultrasound, but the use of heat is the simplest and preferred.

In order to generate a base by heat, a pyrolytic base precursor as described below may be used as the base precursor incorporated in the light-sensitive material. In this case, the light-sensitive material must be heated so that the base precursor contained therein is sufficiently decomposed at the time of development processing or preprocessing to generate a base.

Examples of the pyrolytic base precursor that can be used in the present invention include JP-A-59-180537 and JP-A-61-18037.
-51139, 61-51140, 61-52
No. 638, No. 64-68746 and the like.
Organic compounds described in 166943 and 63-96159. Of these, particularly preferred are
It is a hardly soluble decarboxylate carboxylate described in JP-A-64-68746. In this case, the base precursor is incorporated in the light-sensitive material as a solid dispersion.

Preferred specific examples of the pyrolytic base precursor used in the present invention are shown below, but the present invention is not limited to these.

[0043]

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[0044]

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[0045]

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The amount of the base precursor that releases the base by these physical methods is preferably the same as the amount of the basic metal salt described above.

The base precursor of the present invention may be added to the light-sensitive material in any of an emulsion layer and a non-photosensitive layer (intermediate layer, protective layer, antihalation layer, white pigment layer, etc.).
A layer closer to the support is preferred. That is, it is preferably added to the non-photosensitive intermediate layer adjacent to the emulsion layer in the non-photosensitive layer located between the emulsion layer closest to the support and the support or 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 gradient in the present invention is obtained as follows. First, the test photosensitive material was wedge-exposed with a light source having an energy distribution of 4800 K ° of blackbody radiation,
After performing the specified development processing, the absorption densities of cyan, magenta, and yellow are measured under the status M condition, and a characteristic curve is obtained. From the obtained characteristic curves, the absorption densities of cyan, magenta, and yellow are expressed as fog +0.2, +0.5, +1.0, +1.5, and + with respect to the logarithm of the exposure amount (horizontal axis).
2.0 points were plotted, and these points were linearly approximated by the least squares method.
θ is defined as the gradient γ of the photosensitive material, and γ of cyan, magenta, and yellow are respectively γ (C), γ (M), γ
(Y).

The light-sensitive material of the present invention can be prepared by using the developing process I of the present invention.
Γ _I (C), γ _I (M), and γ _I (Y) of cyan, magenta, and yellow after the development, and the gradation γ _II (C) after the development II of the present invention is performed. , 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 color of a print obtained from a color negative developed in at least one of the developing processes A and B will be distorted, and color reproduction that can withstand viewing cannot be obtained.

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

The color developing solutions of the developing processes I and II of the present invention will be described below. The developing process I of the present invention is a process according to Kodak C-41, which is a color negative process widely used in the world at present, and is usually 3 minutes 15 minutes.
It is designed so that a preferable gradation can be obtained in seconds. Developing process II is a process in which developing process I is accelerated.
It is designed so that a gradation close to the development processing I can be obtained in a color development processing time of minutes. However, when a light-sensitive material not included in the present invention is processed, the development of the red-sensitive layer, which is the lowermost layer, is delayed, so that the gradation cannot be completely adjusted.

In the development processing I, the color development time was 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 a color developing agent
-(Β-hydroxyethyl) amino] aniline from 15 to
The color developing process is performed 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-
(Β-hydroxyethyl) amino] aniline in 35-4
A development process characterized by performing color development using a color developer containing 0 mmol / liter and a compound (trigger compound) that promotes the release of a base from a base precursor. The trigger compound to be added to the color developer of Processing II can be selected according to the type of the base releasing agent to be added to the light-sensitive material, and the amount thereof is preferably in the range of 0.02 to 0.5 mol / L. Preferably 0.05-0.
It is in the range of 3 mol / l.

The pH of the color developing solutions of the developing processes I and II is 1
0.05. In order to maintain the pH of the treatment liquid at 10.05, it is preferable to use a carbonate. The amount of addition is preferably 0.1 mol / L or more, and particularly preferably in the range of 0.2 mol / L to 0.3 mol / L.
It is preferable to use hydroxylamine and sulfite as preservatives of the color developing agent. The amount of hydroxylamine added is preferably in the range of 0.05 mol / l to 0.2 mol / l. The amount of sulfite added is 0.
The range is preferably from 02 mol / l to 0.04 mol / l. Bromide ions can be added to the color developing solution to adjust the developing speed. Various chelating agents can be added to the color developing solution.

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

Specific Examples of Development Process (I) Color development is a development process in which the following liquid composition, temperature, and processing time are used. (Color developing solution) Tank solution (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 2.5 mg hydroxylamine sulfate 2.4 4- [N-ethyl-N- (β-hydroxyethyl) amino] -2-methylaniline sulfate 4.5 Add water and add 1.0 liter pH (with potassium hydroxide 10.05 Temperature 38 ° C Processing time 3 minutes 15 seconds Specific examples of development processing (II) Color development is development processing in which the following liquid composition, temperature, and processing time are used. (Color developing solution) Tank solution (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 0.3 mg Hydroxylamine sulfate 4.5 2-Methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 11.0 Picolinic acid 12.0 Add water 1.0 L pH (Adjusted with potassium hydroxide and sulfuric acid) 10.05 Temperature 45 ° C Processing time 60 seconds In addition, picolinic acid was added to the color developing solution of the development processing II as a compound that promotes release of a base from a base precursor. However, the accelerating compound is not limited to picolinic acid, and can be selected according to the type of base precursor.

Next, development processing A and 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 comprise a color development step, a desilvering step, and a drying step. Preferred specific examples are shown below, but are not limited thereto. Color development-bleach-fixing-wash-stable-dry Color development-bleach-bleach-fix-fix-wash-stable-dry Color development-bleach-fix-wash-stable-dry Color development-bleach-bleach-fix-wash-stable- Drying Color development-bleach-fixing-fixing-washing-stable-drying Color-developing-bleaching-washing-fixing-washing-stable-drying In the above processing steps, washing with water before stabilization can be omitted. Also, the final stability can 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.

Hereinafter, the color developing process A in the developing process A of the present invention will be described in detail. The color development time of the color development processing A of the present invention is from 150 seconds to 200 seconds, preferably from 165 seconds to 195 seconds. Emitting color development time, the type and concentration of the developing agent in the processing liquid, a halogen ion (particularly Br ^-) concentration, temperature of the processing liquid can be changed by the pH or the like.

The developing agent of the color development processing A of the present invention comprises 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 from 15 to 20 mmol, preferably from 15 to 18 mmol per liter of the processing solution. These developing agents are preferably hydrochloride, p-toluenesulfonate or sulfate.

[0062] 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 from 6 to 14 mmol, preferably from 9 to 13 mmol, per liter of the treatment liquid.

The temperature of the treatment liquid is from 37 ° C. to 40 ° C., preferably from 37 ° C. to 39 ° C.

The pH of the treatment liquid is 9.9 to 10.3, preferably 10.0 to 10.2.

Specifically, a processing agent for a color negative film manufactured by Fuji Photo Film Co., Ltd., such as CN-16 or CN-1
6X, CN-16Q, CN-16FA color developing solutions and color developing replenishers, or color negative film processing agents manufactured by Eastman Kodak Co., C-41, C-41B,
A C-41RA color developer can be preferably used.

Hereinafter, the color developing process B in the developing process B of the present invention will be described. The color development time of the color development processing B of the present invention is from 25 seconds to 90 seconds, preferably from 35 seconds to 75 seconds, and most preferably from 45 seconds to 6 seconds.
5 seconds or less.

The color development time of the present invention is a time including a crossover time (time from exiting the color developing solution to entering the processing solution in the next step), and the shorter the crossover time is, the more preferable. From the viewpoint of the performance of the processing equipment, it is preferably from 2 seconds to 10 seconds, more preferably from 3 seconds to 7 seconds.

[0068] Also emitting color developing time, the type and concentration of the developing agent in the color development processing A as well as the treatment liquid, a halogen ion (particularly Br ^-) concentration, temperature of the processing liquid can be changed by the pH or the like.

The developing agent of the color development processing B of the present invention is p
A phenylenediamine derivative, and preferred representative examples 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 preferred, D-1, D-2 and D-3 are more preferred, and D-1 is most preferred.

The concentration of the developing agent is from 25 mmol to 80 mmol, preferably from 25 mmol to 60 mmol, more preferably from 27 mmol to 50 mmol, particularly preferably from 30 mmol to 45 mmol, per liter of processing solution. Mmol or less.

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

In the color development processing B of the present invention, bromide ions are particularly important as an antifoggant, and the Br ^- concentration is 15 to 60 mmol, preferably 16 to 42 mmol per liter of the processing solution. And it is particularly preferably at least 16 mmol and at most 35 mmol.

A compound (trigger compound) for accelerating the release of a base from a base precursor is added to the color developing solution of the developing treatment B. The trigger compound to be used can be selected according to the type of the base releasing agent added to the light-sensitive material.
For example, when a solid dispersion of zinc hydroxide is added to the light-sensitive material and used, a chelating agent such as picolinic acid or pyridine-2,6-dicarboxylic acid can be used as the trigger compound. The amount of the trigger compound added to the treatment solution is preferably in the range of 0.01 to 0.5 mol / l, and more preferably in the range of 0.05 to 0.3 mol / l.

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

The pH of the processing solution 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 are described. And thioethers described in JP-A-4-317055 are preferred.

Color development processing A and / or B of the present invention
May contain the following compounds. For example, hydroxylamine, diethylhydroxylamine,
Various types such as hydroxylamines, sulfites, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine and catecholsulfonic acids represented by the general formula (I) in JP-A-3-144446. Preservatives, organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, such as 1-phenyl-3-pyrazolidone Auxiliary developing agents, viscosity-imparting agents, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, various chelating agents represented by phosphonocarboxylic acids, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid , 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, a substituted hydroxylamine is most preferred as a preservative. Among them, diethylhydroxylamine, monomethylhydroxylamine, or an alkyl group substituted by a water-soluble group such as a sulfo group, a carboxy group, or a hydroxyl group is used as a substituent. Are preferred. The most preferred example is N, M-bis (2-sulfoethyl)
Hydroxylamine, monomethylhydroxylamine,
And diethylhydroxylamine.

Further, an optional 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. Examples of the buffer include carbonate, phosphate, borate, tetraborate, hydroxybenzoate, glycyl salt, N, N-dimethylglycine salt, leucine salt, norleucine salt, guanine salt, 3,4- Dihydroxyphenylalanine salt, alanine salt, aminobutyrate, 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 / L or more,
In particular, it is particularly preferably from 0.1 mol / liter to 0.4 mol / liter. As the chelating agent, a compound having biodegradability is preferable. Examples of this are disclosed in JP-A-63-146998 and JP-A-63-199295.
JP-A-63-267750, JP-A-63-267
No. 751, JP-A-2-229146, JP-A-3-18
And the chelating agents described in German Patent No. 6841, German Patent No. 3,739,610 and European Patent No. 468,325. It is preferable that the processing solution in the replenishing tank or processing tank of the color developing solution be 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
30 to 800 ml per square meter, preferably 50
It is about 500 ml. An optional development accelerator can be added to the color developing solution of the present invention, if necessary. As development accelerators, JP-B-37-16088, JP-B-37-5987 and JP-B-38-7826
Nos. 44-12380, 45-9019 and U.S. Pat.
No. 247, etc .;
-49829 and 50-15554, p-phenylenediamine compounds, JP-A-50-137726, JP-B-44-300
No. 74, quaternary ammonium salts represented in JP-A-56-156826 and JP-A-52-43429, U.S. Pat.No. 2,494,903,
3,128,182, 4,230,796, 3,253,919, JP 41-11431, U.S. Pat.Nos. 2,482,546, 2,596,92
No. 6, No. 3,582,346, etc., amine compounds described in JP-B-37-16088, JP-B-42-25201, U.S. Pat.
No., JP-B-41-11431, JP-B-42-23883 and U.S. Pat.
Polyalkylene oxide represented by 532,501, etc.,
In addition, 1-phenyl-3-pyrazolidones, imidazoles, and the like can be added as needed.

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

In the present invention, compounds forming a ferric complex salt in a solution 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 diacetate, 1,
4-diaminobutanetetraacetic acid, glycol ether diaminetetraacetic 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'-
Dimalonic acid, 1,3-diaminopropane-N, N'-dimalonic acid, and the like are included, but not particularly limited thereto.

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

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

Other baths having bleaching ability 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. The bath having the bleaching ability may contain other various types of fluorescent whitening agents, antifoaming agents, surfactants, and organic solvents such as polyvinylpyrrolidone and methanol.

The fixing agent component in the bleach-fixing solution or the fixing solution is
Known fixing agents, that is, 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 or fixing solution of the present invention desirably contains a sulfite (or bisulfite or metabisulfite) as a preservative, particularly preferably 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 may contain the above-mentioned sulfite (for example, sodium sulfite, potassium sulfite, ammonium sulfite) or bisulfite (for example, ammonium bisulfite, sodium bisulfite, potassium bisulfite) as a preservative. , Metabisulfites (eg, potassium metabisulfite, sodium metabisulfite,
In addition to containing sulfite ion releasing compounds such as ammonium metabisulfite), aldehydes (benzaldehyde, acetaldehyde, etc.), ketones (acetone, etc.),
Ascorbic acids, hydroxylamines and the like can be added as needed.

Further, the bleaching solution, the bleach-fixing solution and the fixing solution may optionally contain a buffer, a fluorescent brightener, a chelating agent, an antifoaming agent, a fungicide, and the like. In the bleaching solution and the bleach-fixing solution used in the present invention, the preferable pH range is 4.5.
To 6.2, more preferably 5 to 6. Even if the pH is higher or lower than the present pH, magnetic recording performance may not be sufficiently exhibited. In the case of a fixing solution, the pH is 5
About 8 is desirable.

The bleaching solution, the bleach-fixing solution used in the present invention,
The replenishing amount to the fixing solution is 50 to 200 per m ² of the photosensitive material.
0 ml, particularly preferably 100-1000 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, bleach-fixing solution and fixing solution is from 20 to 50C, preferably from 30 to 45C. The processing time is 10 seconds to 3 minutes, preferably 20 seconds to 2 minutes.

The processing solution having the bleaching ability of the present invention is particularly preferably subjected to aeration during processing, since photographic performance is extremely stably maintained. Any means known in the art can be used for aeration, and air can be blown into a processing solution having bleaching ability, or air can be absorbed using an ejector. When blowing air, it is preferable to release air into the liquid through a diffuser having fine pores. Such a diffuser is widely used for 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 to lower left column, line 2
Can be used as is.

In the desilvering step, it is preferable that 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 light-sensitive material, or a method using a rotating means described in JP-A-62-183461, is used. A method for improving the effect, a method for moving the photosensitive material while bringing the wiper blade provided in the solution into contact with the emulsion surface, and making the emulsion surface turbulent to improve the stirring effect, and a circulation of 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 improving the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film, and as a result, increases the desilvering speed. Further, the above-described means for improving the stirring is more effective when a bleaching accelerator is used, and can significantly increase the accelerating effect or eliminate the fixing inhibiting effect of the bleaching accelerator.

The automatic developing machine used for the light-sensitive material of the present invention is described in JP-A-60-191257 and JP-A-60-19125.
No. 8, No. 60-191259. JP-A-60-1
As described in Japanese Patent No. 91257, such a conveying 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 washing water in the washing step is determined by the characteristics of the photosensitive material (for example, depending on the material used such as a coupler), the application, the washing water temperature, the number of washing tanks (the number of stages), the replenishment method such as countercurrent and forward flow, and various others. Can be set in a wide range depending on the conditions.
Of these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is described in the Journal of the Society of Motion Picture
d Television Engineers Vol. 64, pp. 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 significantly reduced, but bacteria increase due to an increase in the residence time of water in the tank, and the generated floating substances adhere 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., written by Hiroshi Horiguchi, "Bactericidal and Fungicide Chemistry" (1986) Sankyo Publishing, Sanitary Technology Association, "Microbial Sterilization, Sterilization, and Antifungal Technology" (1982) Industrial Technology Association, Japan Society of Antimicrobial and Fungicide, "Encyclopedia of Antifungal Agents" (1986) The bactericides described can also be used.

The pH of the washing water in the processing of the light-sensitive material of the present invention is from 3 to 9, preferably from 4 to 8. Washing water temperature and washing time can also be variously set depending on the characteristics of the photosensitive material, application, etc., but generally ranges from 15 to 45 ° C for 20 seconds to 10 minutes, preferably from 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 water washing. In such a stabilization treatment, JP-A-57-8543, JP-A-58-14834, JP-A-60-220345
All known methods described in (1) can be used.

The stabilizing solution contains a compound for stabilizing a dye image, for example, benzaldehydes such as formalin and m-hydroxybenzaldehyde, formaldehyde bisulfite adduct, hexamethylenetetramine and derivatives thereof, hexahydrotriazine and derivatives thereof, N-methylol compounds such as dimethylol urea and N-methylol pyrazole, organic acids and pH buffers are included. The preferable addition amount of these compounds is from 0.001 to 0.02 mol per liter of the stabilizing solution. 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 Japanese Patent No. 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 photosensitive material. Among them, it is preferable to use a nonionic surfactant, and particularly preferable is an alkylphenol ethylene oxide adduct. Octyl, nonyl, dodecyl, and dinonylphenol are particularly preferred as the alkylphenol, and the number of moles of ethylene oxide added is particularly preferably 8 to 14. It is also preferable to use a silicon surfactant having a high defoaming effect.

It is preferable that the washing water and / or the stabilizing solution contain various chelating agents. 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'-tetramethylene phosphonic 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 washing and / or replenishment of the stabilizing solution can be reused in other steps such as a 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 in the bleaching tank is calculated from the amount of evaporation of water, and the amount of water in the bleaching tank is replenished in proportion to the amount of evaporation.
The evaporation correction method using a liquid level sensor or an overflow sensor described in JP-A Nos. 3-249644, 3-249645 and 3-249646 is preferable.
Tap water may be used as the 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.

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 light-sensitive layer is a unit light-sensitive layer having color sensitivity to any of blue light, green light, and red light.In a multilayer silver halide color photographic light-sensitive material, the arrangement of the unit light-sensitive layers is generally A red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are provided in this order from the support side. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between layers of the same color sensitivity. A non-light-sensitive layer may be provided between the silver halide light-sensitive layers and as the uppermost layer and the lowermost layer. These may contain a coupler, a DIR compound, a color mixing inhibitor and the like described below. As described in DE 1,121,470 or GB 923,045, a plurality of silver halide emulsion layers constituting each unit light-sensitive layer are formed by sequentially exposing two layers of a high-speed emulsion layer and a low-speed emulsion layer toward a support. It is preferable to arrange them so that the degree is low. Also, JP-A-57-112751, 62-200350, 62-2
As described in JP-A Nos. 06541 and 62-206543, a low-sensitivity emulsion layer may be provided on the side remote from the support, and a high-sensitivity emulsion layer may be provided on the side close 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. Further, as described in JP-B-55-34932, the blue-sensitive layer / GH / RH / GL is arranged 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 can be arranged in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support. Also, as described in JP-B-49-15495, the upper layer is the most sensitive silver halide emulsion layer, the middle layer is the silver halide emulsion layer of lower sensitivity, and the lower layer is more sensitive than the middle layer. An example is an arrangement in which a low silver halide emulsion layer is disposed and three layers having different sensitivities are sequentially reduced in sensitivity toward a support. Even when such three layers having different sensitivities are used, as described in JP-A-59-202464, the medium-sensitive emulsion layer / high The layers may be arranged in the order of a light-sensitive emulsion layer / a light-sensitive emulsion layer. In addition, high-speed emulsion layers / low-speed emulsion layers / medium-speed emulsion layers, or low-speed emulsion layers / medium-speed emulsion layers / high-speed emulsion layers may be arranged in this order. Also, when there are four or more layers,
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 preferred 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.

Preferred silver halides for use in the present invention are silver iodobromide, silver iodochloride, or silver iodochlorobromide containing up to about 30 mole percent silver iodide. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 10 mol% silver iodide. 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. Even if the grain size of silver halide is about 0.2 μm or less, the projected area diameter is about
Large-sized grains up to 10 μm may be used, and polydisperse emulsions or monodisperse emulsions may be used. Silver halide photographic emulsions that can be used in the present invention include, for example, Research Disclosure (hereinafter abbreviated as RD) No. 17643 (December 1978), 22 to 23.
Page, “I. Emulsion preparation and type
s) "and No. 18716 (November 1979), p. 648,
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), "Manufacture and coating of photographic emulsions" by Zerikman 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
The monodisperse emulsion described in 13,748 is 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 Photographic Science and Engineering (Gutof)
f, Photographic Science and Engineering), Volume 14
248-257 (1970); US 4,434,226; 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 outside may have different halogen compositions, or may have a layered structure. Silver halides having different compositions may be bonded by epitaxial bonding, or may be bonded to a compound other than silver halide such as, for example, silver rhodan or lead oxide. Also, a mixture of particles of various crystal forms may be used. The above emulsion is a surface latent image type in which a latent image is mainly formed on the surface,
Either an internal latent image type formed inside the grains or a type having a latent image on both the surface and the inside may be used, but a negative emulsion is required. Of the internal latent image type,
The emulsion may be a core / shell type internal latent image type emulsion described in 3-264740, 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 and the like, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

As the silver halide emulsion, usually, those subjected to physical ripening, chemical ripening and spectral sensitization are used. Additives used in such a process are RD No. 17643 and RD No. 187.
16 and No. 307105, and the relevant portions are summarized in the table below. 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. U.S. Pat.No.4,082,553.
The silver halide grains covered with the grains according to 4852,
It is preferred to apply colloidal silver to the light-sensitive silver halide emulsion layer and / or to the substantially light-insensitive hydrophilic colloid layer. The term "silver halide particles having a fogged interior or surface" refers to silver halide grains that can be uniformly (non-imagewise) developed regardless of unexposed portions and exposed portions of the photosensitive material. Its preparation is described in US Pat. No. 4,626,498, 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.
Any of silver chloride, silver chlorobromide, silver bromoiodide and silver chloroiodobromide can be used as the silver halide having the inside or the surface of the grain fogged. 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 non-photosensitive fine grain silver halide. Non-photosensitive fine grain silver halide is silver halide fine grains that are not exposed during imagewise exposure to obtain a dye image and are not substantially developed in the developing process, and are preferably not fogged in advance. . The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may contain silver chloride and / or silver iodide as needed. Preferably, it contains 0.5 to 10 mol% of silver iodide. Fine grain silver halide has an average grain size (average value of projected area equivalent circle diameter)
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, page 23-24 page 648, right column 866-868 superstrong sensitizer ~ page 649, right column 4. Brightener 24 page 647, right column page 868 5 Light absorbers, pages 25 to 26, page 649, right column, page 873 Filters, page 650, left column Dyes, ultraviolet absorbers 6. Binders, page 26, page 651, left column 873 to 874 7. Plasticizers, page 27, page 650, right Column 876 Lubricant 8. Coating aid, pages 26 to 27 Page 650 Right column 875 to 876 Surfactant 9. Static 27 page 650 650 Right column 876 to 877 Inhibitor 10. Mast agent 878 to 879

Various dye-forming couplers can be used in the light-sensitive material of the present invention, and the following couplers are particularly preferable. Yellow couplers: couplers represented by formulas (I) and (II) in EP 502,424A; couplers represented by formulas (1) and (2) in EP 513,496A (especially Y-28 on page 18); EP 568,037A Claim 1
A coupler represented by the general formula (I) in column 1, line 45 to 55 of US 5,066,576; a coupler represented by the general formula (I) in paragraph 0008 of JP-A-4-274425; Couplers described in claim 1 on page 40 of EP 498,381 A1 (especially D-35 on page 18); Couplers of the formula (Y) on page 4 of EP 447,969A1 (especially Y-1 (page 17), Y- 54 (p. 41)); US
4,476,219 couplers represented by formulas (II) to (IV) in columns 7 to 36 to 58 (particularly 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 page) of JP-A-5-204106 (page 6); M-22 of paragraph 0237 of JP-A-4-36631. Cyan coupler: CX-1,3,4,5,11,12,1 of JP-A-4-204843
4,15 (pages 14 to 16); JP-A-4-43345, C-7,10 (page 35), 3
4, 35 (page 37), (I-1), (I-17) (pages 42 to 43); JP-A-6-67385
A coupler represented by the general formula (Ia) or (Ib) according to claim 1. Polymer coupler: P-1, P-5 (p. 11) of JP-A-2-44345.

Examples of couplers in which the color forming dye has an appropriate diffusibility include US Pat. No. 4,366,237, GB 2,125,570, EP 96,873B,
Those described in DE 3,234,533 are preferred. Couplers for correcting unnecessary absorption of 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),
Preference is given to colorless masking couplers of formula (A) of claim 1 of WO 92/11575 (especially the exemplary compounds on pages 36 to 45). Examples of compounds (including couplers) that release 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
A compound represented by LIG-X described in claim 1 of 4,555,478 (especially, a compound on lines 21 to 41 of column 12); a leuco dye releasing compound: compound 1 of columns 3 to 8 of US 4,749,641
~ 6; Fluorescent dye releasing compound: Claim 1, C of US 4,774,181
Compound represented by OUP-DYE (especially 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 according to No. 363; oxidized developing agent scavenger: a compound represented by the formula (I) in columns 54 to 62 of column 2, 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: SCV-1 to 28 on pages 24 to 29 of EP 477932A, especially SCV-8; hardener: JP-A 1-214845
Formula of 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),
Compound represented by the formula (6) at the lower right of page 8 of 214852 (H-1 to 7
6), especially compounds described in claim 1 of H-14, US Pat. No. 3,325,287; development inhibitor precursor: P-2 of JP-A-62-168139
No. 4,37,39 (pages 6 to 7); compounds described in claim 1 of US Pat. No. 5,019,492, especially 28, 29 of column 7; preservatives, fungicides: US
4,923,790 columns 3 to 15 I-1 to III-43, especially II-1,
9,10,18, III-25; Stabilizer, antifoggant: US 4,923,79
3 columns 6 to 16 I-1 to (14), especially I-1,60, (2), (13), U
Compounds 1-65 of columns 25-32 of S 4,952,483, especially 36:
Chemical sensitizer: triphenylphosphine selenide, compound 50 of JP-A-5-40324; dye: 15-18 of JP-A-3-156450
Page a-1 to b-20, especially a-1,12,18,27,35,36, b-5,27 to 29
Page V-1 to 23, especially V-1, EP 445627A, page 33 to 55 FI-
1 to F-II-43, especially FI-11, F-II-8, 17 to 28 of EP 457153A
Pages III-1 to 36, especially III-1,3, WO 88/04794
Microcrystal dispersion of Dye-1 to 124, Compounds 1 to 22 on pages 6 to 11 of EP 319999A, in particular Compounds D-1 to 87 (3 ~ 28 pages), US 4,26
8,622 compounds represented by the formula (I) 1 to 22 (columns 3 to 1)
0), compounds (1) to (4) of the formula (I) of US Pat.
(31) (Columns 2 to 9); UV absorber: Formula of JP-A-46-3335
Compounds (18b) to (18r), 101 to 427 (6 to
9), and the compounds (3) to (6) represented by the formula (I) in EP 520938A.
6) (Pages 10 to 44) and compound HBT-1 represented by formula (III)
~ 10 (page 14), a compound represented by formula (1) in EP 521823A
(1) to (31) (columns 2 to 9).

The present invention can be applied to various color light-sensitive materials such as color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers. In addition, Tokuhei 2-32615, actual fairness
It is suitable for the film unit with lens described in 3-39784. Suitable supports that can be used in the present invention are
For example, RD. No. 17643, page 28, and RD.
No. 307105, page 879, from page 47 right column to page 648 left column. 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 refers to a film thickness measured at 25 ° C. and a relative humidity of 55% under humidity control (2 days), and T _1/2 is a value obtained by A. Green et al. In Photographic Science and Engineering. (Photogr. Sci. Eng.), Vol. 19, pp. 2,124-129, which can be used for measurement. T _1/2 can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating. The swelling ratio is preferably from 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) of about 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%.

The photographic light-sensitive material of the present invention preferably has a specific photographic sensitivity of 160 or more. The specific photographic sensitivity in the present invention is determined by the method described in JP-A-63-236035. This measuring method is based on JIS
It is based on K7614-1981. However, the difference is that the development processing is completed within 30 minutes or more and 6 hours after the exposure for sensitometry, and the development processing is performed using the Fujicolor standard processing recipe CN-16. The specific photographic sensitivity is more preferably 200 or more. The upper limit is up to 3200.

Next, the magnetic recording layer used in the present invention will be described. The magnetic recording layer used in the present invention is obtained by coating a support with an aqueous or organic solvent-based coating solution in which magnetic particles are dispersed in a binder. Magnetic particles used in the present invention include ferromagnetic iron oxide such as γFe ₂ O _3, Co deposited γFe ₂ O _3, Co coated magnetite ,, Co-containing magnetite, ferromagnetic chromium dioxide, ferromagnetic metal, ferromagnetic Alloy, hexagonal Ba ferrite, Sr ferrite, Pb ferrite, Ca ferrite can be used. Co deposited γFe ₂ O
Co-coated ferromagnetic iron oxides such as ₃ are preferred. The shape may be any of needle shape, rice grain shape, spherical shape, cubic shape, plate shape and 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 ferromagnetic material is
It is preferably from 3.0 × 10 ⁴ to 3.0 × 10 ⁵ A / m, and particularly preferably from 4.0 × 10 ^{4 to} 2.5 × 10 ⁵ A / m. The ferromagnetic particles may be subjected to a surface treatment with silica and / or alumina or an organic material. Further, magnetic particles are disclosed in
The surface may be treated with a silane coupling agent or a titanium coupling agent as described in 161032. Also, magnetic particles having a surface coated with an inorganic or organic substance described in JP-A-4-259911 and JP-A-5-81652 can be used.

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

As a method for dispersing the above-mentioned magnetic material in the binder, a kneader, a pin type mill, an annular type mill and the like are preferably used, as in the method described in JP-A-6-35092. Dispersants described in JP-A-5-088283 and other known dispersants can be used. The thickness of the magnetic recording layer is 0.1 μm to 10 μm, preferably 0.2 μm to 5 μm.
m, more preferably 0.3 μm to 3 μm. The weight ratio between the magnetic particles and the binder is preferably 0.5: 100 to 60: 100.
And more preferably from 1: 100 to 30: 100. The coating amount of the magnetic particles 0.005~ 3g / m ^2, preferably from 0.01 to 2
g / m ² , more preferably 0.02 to 0.5 g / m ² . The transmission yellow density of the magnetic recording layer is preferably 0.01 to 0.50,
03 to 0.20 is more preferable, and 0.04 to 0.15 is particularly preferable.
The magnetic recording layer may be provided on the entire back surface of the photographic support by coating or printing, or in a stripe shape. Methods for applying the magnetic recording layer include air doctor, blade, air knife, squeeze, impregnation, reverse roll,
Transfer rolls, gravure, kisses, casts, sprays, dips, bars, extrusions and the like can be used, and the coating solutions described in JP-A-5-341436 are preferred.

In the magnetic recording layer, lubricity improvement, curl control,
It may have functions such as antistatic, antiadhesion, and head polishing, or may provide another functional layer to provide these functions. At least one of the particles has a Mohs hardness of 5 or more. Abrasives of the above non-spherical inorganic particles are preferred. As the composition of the non-spherical inorganic particles, oxides such as aluminum oxide, chromium oxide, silicon dioxide, titanium dioxide and silicon carbide, carbides such as silicon carbide and titanium carbide, and fine powders such as diamond are preferable. These abrasives may have their surfaces treated with a silane coupling agent or a titanium coupling agent. These particles may be added to the magnetic recording layer, or may be overcoated (for example, a protective layer, a lubricant layer, etc.) on the magnetic recording layer. As the binder used at this time, the above-mentioned binders can be used, and the same binder as the binder for the magnetic recording layer is preferable. For photosensitive materials having a magnetic recording layer, see US Pat.
5,229,259, 5,215,874 and EP 466,130.

Next, the polyester support used in the present invention will be described. For details including sensitizing materials, treatments, cartridges and examples described later, see Japanese Patent Publication No. 94-6023 (Invention Association; .15.).
The polyester used in the present invention is formed by using a diol and an aromatic dicarboxylic acid as essential components, and 2,6-, 1,5-, 1,4-, and 2,7 as aromatic dicarboxylic acids.
-Naphthalenedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, diethylene glycol as diol,
Examples include triethylene glycol, cyclohexanedimethanol, bisphenol A, and bisphenol.
Examples of the polymer include homopolymers such as polyethylene terephthalate, polyethylene naphthalate, and polycyclohexanedimethanol terephthalate. Particularly preferred is a polyester containing 50 to 100 mol% of 2,6-naphthalenedicarboxylic acid. Among them, polyethylene 2,6-naphthalate is particularly preferred. Average molecular weight ranges from about 5,000 to
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 heat-treated at a heat treatment temperature of 40 ° C. or more and less than Tg, more preferably Tg−20 ° C. or more and less than Tg, in order to make it difficult to form a curl. The heat treatment may be performed at a constant temperature within this temperature range, or may be performed while cooling. The heat treatment time is 0.1 to 1500 hours, more preferably 0.5 to 200 hours. The heat treatment of the support may be performed in the form of a roll, or may be performed while transporting the support in the form of a web.
Irregularities may be imparted to the surface (for example, conductive inorganic fine particles such as SnO ₂ or Sb ₂ O ₅ may be applied) to improve the surface state. It is also desirable to take measures such as applying knurls to the ends and raising the ends only slightly so as to prevent the cut end of the core from appearing. 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 a commercially available dye or pigment such as Diaresin manufactured by Mitsubishi Kasei or Kayaset manufactured by Nippon Kayaku for polyester.

Next, in the present invention, it is preferable to perform a surface treatment in order to bond the support and the light-sensitive material constituting layer. Chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment,
Surface activation treatments such as laser treatment, mixed acid treatment, ozone oxidation treatment and the like can be mentioned. Among the surface treatments, ultraviolet irradiation treatment, flame treatment, corona treatment, and glow treatment are preferable. Next, the undercoating method will be described. It may be a single layer or two or more layers. Undercoat layer binders include 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 resorcinol and p-chlorophenol. In the undercoat layer, as a gelatin hardener, chromium salts (chromium alum, etc.), aldehydes (formaldehyde, glutaraldehyde, etc.), isocyanates, active halogen compounds (2,4-dichloro-6-
Hydroxy-S-triazine, etc.), epichlorohydrin resin, active vinyl sulfone compound and the like. SiO ₂ , TiO ₂ , inorganic fine particles or polymethyl methacrylate copolymer fine particles (0.01 to 10 μm) may be contained as a matting agent.

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

The light-sensitive material of the present invention preferably contains a matting agent. The matting agent may be on either the emulsion side or the back side, but is particularly preferably added to the outermost layer on the emulsion side.
The matting agent may be soluble in the processing solution or insoluble in the processing solution, and preferably both are used in combination. For example, polymethyl methacrylate, poly (methyl methacrylate / methacrylic acid = 9/1 or 5/5 (molar ratio)), polystyrene particles and the like are preferable. The particle size is preferably 0.8 to 10 μm, and the particle size distribution is preferably 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. For example, polymethyl methacrylate (0.2 μm), poly (methyl methacrylate / methacrylic acid = 9/1 (molar ratio), 0.3 μm)), polystyrene 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 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 for feeding a film by rotating a spool may be used. Further, a structure may be employed in which the film tip is housed in the cartridge body, and the film tip is sent out from the port portion of the cartridge by rotating the spool shaft in the film sending direction. These are disclosed in US Pat. Nos. 4,834,306 and 5,226,613. The photographic film used in the present invention may be a so-called raw film before development or a photographic film that has been subjected to development processing. Also, raw film and developed photographic film may be stored in the same new patrone,
A different patrone may be used.

Hereinafter, the present invention will be described in more detail by way of specific examples.

[0123]

【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, with respect to the sensitizing dye, the coating amount is shown in mol units per mol of silver halide in the same layer.

(Sample 101) First Layer (Antihalation Layer) Black Colloidal Silver Silver 0.09 Gelatin 1.60 ExM-1 0.12 ExF-1 2.0 × 10 ^-3 Solid Disperse Dye ExF-2 0.030 Solid Disperse Dye ExF-3 0.040 HBS- 1 0.15 HBS-2 0.02

Second layer (intermediate layer) Silver iodobromide emulsion M silver 0.065 ExC-2 0.04 polyethyl acrylate latex 0.20 gelatin 1.04

Third layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion A silver 0.25 silver iodobromide emulsion B silver 0.25 ExS-1 6.9 × 10 ^-5 ExS-2 1.8 × 10 ^-5 ExS-3 3.1 × 10 ^-4 ExC-1 0.17 ExC-3 0.030 ExC-4 0.10 ExC-5 0.020 ExC-6 0.010 Cpd-2 0.025 HBS-1 0.10 Gelatin 0.87

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

Fifth layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion D Silver 1.40 ExS-1 2.4 × 10 ^-4 ExS-2 1.0 × 10 ^-4 ExS-3 3.4 × 10 ^-4 ExC-1 0.10 ExC-3 0.045 ExC-6 0.020 ExC-7 0.010 Cpd-2 0.050 HBS-1 0.22 HBS-2 0.050 Gelatin 1.10

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

Seventh layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion E silver 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 Speed Green Sensitive Emulsion Layer) Silver Iodobromide Emulsion H Silver 0.80 ExS-4 3.2 × 10 ^-5 ExS-5 2.2 × 10 ^-4 ExS-6 8.4 × 10 ^-4 ExC-8 0.010 ExM-2 0.10 ExM-3 0.025 ExY-1 0.018 ExY-4 0.010 ExY-5 0.040 HBS-1 0.13 HBS-3 4.0 × 10 ^-3 Gelatin 0.80

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

Tenth Layer (Yellow Filter Layer) Yellow Colloidal Silver Silver 0.015 Cpd-1 0.16 Solid Disperse Dye ExF-5 0.060 Solid Disperse Dye ExF-6 0.060 Oil-soluble Dye ExF-7 0.010 HBS-1 0.60 Gelatin 0.60

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

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

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

Fourteenth 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

In order to improve the storability, processability, pressure resistance, fungicidal / antibacterial properties, antistatic properties and coatability of each layer, W-1 to W-3, B-4 to B- 6, F
-1 to F-17, and iron salts, lead salts, gold salts, platinum salts,
Contains palladium, iridium and rhodium salts.

[0139]

[Table 2]

In Table 2, (1) Emulsions J to L were prepared according to the examples in 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% aqueous solution of sodium p-octylphenoxyethoxyethoxyethoxyethanesulfonate and 5% of 5% aqueous solution
0.5 g of an aqueous solution of p-octylphenoxypolyoxyethylene ether (degree of polymerization 10) was placed 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. To disperse the contents for 2 hours. For this dispersion, a BO type vibration ball mill manufactured by Chuo Koki was used. After the 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 dye dispersion of gelatin. The average particle size of the fine dye particles is 0.44
μm.

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

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Next, samples 102 to 11 were modified from sample 101 as shown in Table 3 and to which the base precursor of the present invention was added.
0 was produced. The average particle size of the base precursor dispersion used was 0.3 μm. Sample 101 fabricated
Samples 110 to 110 were cut and processed into a width of 35 mm, and subjected to white light gradation exposure, and then subjected to the following processing.

Step of (Development Processing I) and Composition of Processing Solution Step Processing time Processing temperature Color development 3 minutes 15 seconds 38 ° C. Bleaching 1 minute 00 seconds 38 ° C. Bleaching fix 3 minutes 15 seconds 38 ° C. Rinse with water (1) 1 minute Second 38 ° C Rinse (2) 1 minute 00 seconds 38 ° C Drying 2 minutes 00 seconds

Next, the composition of the processing solution will be described. (Color developing solution) Tank solution (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 Add water and add 1.0 liter pH (adjusted with potassium hydroxide and sulfuric acid) 10.05

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

(Washing water) Tap water was replaced with H-type strongly acidic cation exchange resin (Amberlite IR- manufactured by Rohm and Haas Co.)
120B) and a mixed bed column packed with an OH type strongly basic anion exchange resin (Amberlite IR-400) to reduce the calcium and magnesium ion concentration 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-Benzoisothiazolin-3-one sodium 0.10 Ethylenediamine4 Disodium acetate 0.05 1,2,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 Add water and add 1.0 liter pH 8.5

(Development Processing II) Step and Composition of Processing Solution Processing Step Temperature Time Color development 45 ° C. 60 seconds Bleaching and fixing 40 ° C. 60 seconds Rinse with water (1) 40 ° C. 15 seconds Rinse with water (2) 40 ° C. 15 seconds Rinse with water (3) 40 ° C 15 seconds Stable 40 ° C 15 seconds Drying 80 ° C 60 seconds (Washing was performed in a three-tank countercurrent method from (3) to (1).)

Processing solution composition (color developing solution) Tank solution (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 Add water and add 1.0 liter pH (prepared with potassium hydroxide and sulfuric acid) 10.05 (Bleaching and fixing) Liquid) (unit mol) ethylenediamine- (2-carboxyphenyl) -N, N ', N'-triacetic acid 0.17 ferric nitrate nonahydrate 0.15 ammonium thiosulfate 1.25 ammonium sulfite 0.10 metacarboxybenzenesulfinic acid 0.05 Add water 1.0 liter pH (prepared with acetic acid and ammonia) 5.8 (washing water) Same composition as the (stabilizing solution) The same composition as described in the process I.

The samples obtained by the above development were measured for yellow, magenta and cyan densities, and their characteristic curves were obtained. From these characteristic curves, as described above, with respect to the logarithm of the exposure amount (horizontal axis), the absorption densities of yellow, magenta, and cyan are the minimum densities +0.2, +0.5, +1.0,
The points +1.5 and +2.0 are plotted, and these points are linearly approximated by the least squares method.
Is defined as the gradient γ of the photosensitive material, γ
(Y), γ (M), and γ (C). The gradient γ obtained in the processing (I) is expressed as γ _I (Y), γ _I (M), γ _I
(C), γ of the treatment (II) was obtained by changing the subscript I to II, and the ratio of the treatment (II) / the treatment (I) was calculated for Y, M, and C. Table 3 shows the results.

[0169]

[Table 3]

From Table 3, it can be seen that a base precursor capable of releasing a base during development processing was added as a fine particle dispersion to at least one of the silver halide emulsion layer and the non-photosensitive layer constituting the light-sensitive layer of the light-sensitive material. When used, the ratio of the gradient obtained from the processing (I), which is almost equivalent to the current color negative processing, and the processing (II), in which rapid processing is performed using a developer containing a trigger, is the same as that of the present invention described above. 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 is satisfied, and it can be seen that a good result with a good balance can be obtained with values in which the gradients of Y, M, and C are almost the same.

Example 2 Using the samples 101 to 110 prepared in Example 1 and changing the picolinic acid used in the color developing solution of the development processing (II) to another trigger, the same evaluation as in Example 1 was performed. Carried out. (Development treatment II-1) A developer in which picolinic acid used in the color developer is replaced with an equimolar amount of 2,6-pyridinedicarboxylic acid. (Development treatment II-2) A developer in which picolinic acid used in the color developer is replaced with an equimolar oxalic acid. (Development treatment II-3) A developer in which picolinic acid was replaced with an equimolar amount of ethylenediaminetetraacetic acid.

The ratios of the gradients were determined for the development processing (I). Table 4 shows the results. Developing treatment II-1 in the table
Indicates that the γ _II-1 / γ _I.

[0173]

[Table 4]

From Table 4, as in Table 3 of Example 1, processing II-1 in which rapid processing is performed using a developer containing a trigger
-II-3 are within the range of the conditional expression of the present invention, and give values in which the gradients of Y, M, and C are substantially the same, and a photosensitive material having a good balance of three colors is used. It can be seen that the present invention provides an image forming method.

Example 3 Samples 301 to 304 were prepared by replacing the base precursor, zinc hydroxide, used in the second layer of sample 102 prepared in Example 1 with an equimolar amount as shown in Table 5. The samples 301 and 302 were subjected to the following development II-4 together with the sample 101, and the samples 303 and 304 were subjected to the development II-5 together with the sample 101 in the same manner as in Example 1. Carried out. (Development treatment II-4) A developer in which picolinic acid used in the developer of development treatment II is replaced with an equimolar amount of potassium benzenesulfinate. (Development process II-5) The picolinic acid used in the developer of the development process II is removed, and the photosensitive material is removed by 120 before the color development process.
After heating at 5 ° C for 5 seconds, development processing is performed. Table 5 shows the results.

[0176]

[Table 5]

From Table 5, it can be seen that the ratio of the gradients satisfies the conditional expression of the present invention, and that the balance of the three colors of Y, M and C is good. Even if the base precursor is of a thermal decomposition type, by performing a heat treatment immediately before the development processing, it is possible to provide a photosensitive material that gives similarly good results, and to provide an image forming method.

Example 4 Using the samples 101 to 110 prepared in Example 1, the developing treatments (I) and (II) similarly performed in Example 1 were subjected to the following continuous processing A-1 and B-1 (rapid processing). Processing) and the same evaluation was performed. In the continuous processing, the sample 101 was used and photographed with a camera at a rate of 1 m ² per day for 15 days.

The obtained result satisfies the conditional expression of the gradation of the present invention, as in the case of the first embodiment, and the gradation balance of the three colors of Y, M and C gives almost the same value, and a good image is formed. I found out.

Processing Step and Solution Composition of (Development Processing A-1) (Processing Step) Step Processing Time Processing Temperature Replenishment Quantity ^* Tank Capacity Color Development 3 minutes 5 seconds 38.0 ° C. 23 ml 17 liter Bleaching 50 seconds 38.0 ° C. 5 ml 5 liters Bleach-fix 50 seconds 38.0 ℃-5 liters Fixed 50 seconds 38.0 ℃ 16 ml 5 liters Washing 30 seconds 38.0 ℃ 34 ml 3.5 liters stable (1) 20 seconds 38.0 ℃-3 liters stable (2) 20 seconds 38.0 ℃ 20 ml 3 liter Drying 1 minute 30 seconds 60 ℃ * Replenishment amount per 35 mm of photosensitive material 1.1 m width (24Ex. 1 bottle) Stabilizing solution is a countercurrent method from (2) to (1) The overflow of the washing water was all introduced into the fixing bath. For replenishment to the bleach-fixing bath, a cut is provided at the top of the bleaching tank and the fixing tank of the automatic processor, and all the overflow liquid generated by supplying the replenisher to the bleaching tank and the fixing tank is transferred to the bleach-fixing bath. It was made to flow in. The amount of the developer brought into the bleaching step, the amount of the bleaching liquid brought into the bleach-fixing step, the amount of the bleach-fixing liquid brought into the fixing step, and the amount of the fixing liquid brought into the washing step were 35 mm width of the photosensitive material. 2.5 ml, 2.0 ml, 2.0 ml, 2.0 ml
Milliliters. The crossover time is 6 seconds in each case, and this time is included in the processing time of the previous step.

The composition of the processing liquid is shown below. (Color developing solution) Tank solution (g) Replenisher (g) Diethylenetriaminepentaacetic acid 2.0 2.0 1-hydroxyethylidene-1,1-diphosphonic acid 2.0 2.0 Sodium sulfite 3.9 5.1 Potassium carbonate 37.5 39.0 Potassium bromide 1.4 0.4 Potassium iodide 1.3 mg-hydroxylamine sulfate 2.4 3.3 disodium N, N-bis (sulfonateethyl) 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) Replenisher (g) 1,3-diaminopropanetetraacetic acid ferric ammonium monohydrate 130 195 Ammonium bromide 70 105 Ammonium nitrate 14 21 Hydroxyacetic acid 50 75 Acetic acid 40 60 Add water 1.0 liter 1.0 liter pH (prepared with aqueous ammonia) 4.4 4.4

(Bleach-fixing tank solution) A mixture of the above bleaching tank solution and the following fixing tank solution in a ratio of 15 to 85 (volume ratio). (P
H7.0)

(Fixing solution) Tank solution (g) Replenisher (g) Ammonium sulfite 1957 Ammonium thiosulfate aqueous solution 280 mL 840 mL (700 g / L) Imidazole 15 45 Ethylenediaminetetraacetic acid 15 45 Add water 1.0 L 1.0 L pH [Prepared with ammonia water and acetic acid] 7.4 7.45

(Washing water) Tank water and replenisher common tap water was 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 replenisher (unit: g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization: 10) 0.2 1,2-benzoyl 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 .75 1.0 liter with water pH 8.5

(Development Processing B-1) Process and Composition of Processing Solution (Processing Process) Process Processing Time Processing Temperature Replenishment Volume ^* Tank Capacity Color Development 60 seconds 45.0 ° C. 260 ml 1 liter Bleaching 20 seconds 45.0 ° C. 130 ml 1 liter Fixing 40 seconds 45.0 ℃ 100 ml 1 liter Rinse (1) 15 seconds 45.0 ℃-1 liter Rinse (2) 15 seconds 45.0 ℃-1 liter Rinse (3) 15 seconds 45.0 ℃ 400 ml 1 liter Dry 45 sec 80 ° C. * the replenishing amount is the light-sensitive material 1 m ² per (water wash (3) 4 tank countercurrent multistage cascade to the fixing from)

The composition of the processing liquid is shown below. (Color developing solution) Tank solution (g) Replenisher (g) Diethylenetriaminepentaacetic acid 2.0 4.0 1-hydroxyethylidene-1,1-diphosphonic acid 3.3 3.3 Sodium sulfite 3.9 6.5 Potassium carbonate 37.5 39.0 Potassium bromide 2.0-Potassium iodide 1.3 mg-picolinic acid 12 14.4 disodium N, N-bis (sulfonatoethyl) hydroxylamine 12.0 17.0 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 11.5 15.0 water 1.0 liter 1.0 liter pH (prepared with potassium hydroxide and sulfuric acid) 10.05 10.25

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

(Fixing solution) Common to tank solution and replenisher (g) Ammonium sulfite 28 Ammonium thiosulfate aqueous solution (700 g / L) 280 mL Imidazole 15 Ethylenediaminetetraacetic acid 15 Add water and 1.0 L pH [prepared with aqueous ammonia and acetic acid] 5.8

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

(Stabilizing solution) A solution having the same composition as the stabilizing solution of the developing treatment A-1 was used.

Example 5 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 as UV absorber
After drying 2 parts by weight of Geigy 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
The film has a blue dye, a magenta dye and a yellow dye (disclosed in I-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 support was subjected to a corona discharge treatment, a UV discharge treatment, and a Glouc discharge treatment on both surfaces, and then gelatin 0.1 g / m ² and sodium α- Suruhoji-2-ethylhexyl succinate 0.01 g / m ^2, salicylic acid 0.04g / 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 tin oxide-antimony oxide composite having an average particle size of 0.005 μm has a specific resistance of 5 Ω · cm, a dispersion of fine particle powder (secondary aggregated particle size 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 0.005 g / m ^{2 of} nonylphenol and resorcinol. 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
0.3 g / m ² of C ₂ H ₅ C (CH ₂ OCONH-C ₆ H ₃ (CH ₃ ) NCO) ₃ was applied with a bar coater using acetone, methyl ethyl ketone, cyclohexanone, and dibutyl phthalate as a solvent. A magnetic recording layer of 1.2 μm 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 matting agent and 3-poly (degree of polymerization 1
5) Abrasive aluminum oxide (0.20 μm and 1.0 μm) coated with oxyethylene-propyloxytrimethoxysilane (15% by weight) was coated at 50 mg / each.
was added such that the m ² and 10 mg / m ^2. 11 for drying
The test was performed at 5 ° C. for 6 minutes (115 ° C. for all rollers and transport devices in the drying zone). X-light (blue filter)
Magnetic saturation magnetization moment of the increase of the color density of D ^B of the recording layer is about 0.1, also the magnetic recording layer is 4.2 emu / g, coercive force 7.3 × 10 ⁴ A / m in, squareness ratio 65%.

3-3) Preparation of sliding layer C ₆ H ₁₃ CH (OH) C ₁₀ H ₂₀ COOC ₄₀ H ₈₁ (6 mg / m ² ) was applied.
This is prepared by melting at 105 ° C. in xylene / propylene monomethyl ether (1/1), pouring and dispersing the mixture in propylene monomethyl ether (10-fold amount) at room temperature, and then dispersing the dispersion (average) in acetone. (Particle size: 0.01 μm). Drying was performed at 115 ° C. for 6 minutes (all rollers and conveying devices in the drying zone were 115 ° C.). The sliding layer has a kinetic friction coefficient of 0.10 (stainless hard ball of 5 mmφ, load of 100 g, speed of 6 cm / min), a static friction coefficient of 0.08 (clip method), and a kinetic friction coefficient of 0.13 between the emulsion surface and the sliding layer described later. Excellent characteristics.

4) Coating of Photosensitive Layer Next, on the side opposite to the back layer obtained above, each layer having the composition described in Example 1 was applied in a multi-layered manner to prepare a color negative film. These are referred to as samples 501 to 510.

Samples 501 to 510 prepared as described above
Is cut into a width of 24 mm and a size of 160 cm, and two perforations of 2 mm square are provided at a distance of 5.8 mm at 0.7 mm from one width direction of the length of the photosensitive material.
Create these two sets at 32mm intervals,
It was housed in a plastic film cartridge described in FIGS. 1 to 7 of US Pat. No. 5,296,887. A head gap of 5 μm and a number of turns of 2,000 for input and output were used on both sides of the magnetic recording layer on the sample.
FM signals were recorded at a feed rate of 1,000 / s.

These photosensitive materials were evaluated by performing the continuous (running) processing, processing A-1 and processing B-1 used in Example 3 in the same manner as in Example 1. Furthermore, Zoom Cardia (Fuji Photo Film Co., Ltd.)
Was modified so that the cartridges could be loaded, and a Macbeth chart was photographed for each photosensitive material, developed and printed on Fuji Color Paper FAV using these color negatives, and the image quality was visually evaluated.

The evaluation of the gradient of the continuously processed sample was the same as the result obtained in Example 3, and the sample 502 of the present invention was evaluated.
510 satisfy the conditional expression for the gradient of the present invention, and the balance of the Y, M, and C gradations is also good. On the other hand, when the sample printed on the color paper was visually evaluated, the comparative sample 501 had a low cyan density of the negative gradation and a low density. Of the samples 502 to 51 of the present invention.
0 indicated good gray reproducibility.

[0201]

According to the present invention, any one of the silver halide emulsion layer and the non-light-sensitive layer constituting the light-sensitive layer of the light-sensitive material is used.
A layer containing a base precursor capable of releasing a base at the time of development processing is used for two types of processing with different color development times, the current processing and the rapid processing. This makes it possible to provide a silver halide color photographic light-sensitive material having a good balance of color gradation of three colors, yellow, magenta and cyan, which have good matching of tone reproducibility and color reproducibility. Can be provided.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ identification code FI G03C 7/392 G03C 7/392 Z 7/407 7/407 (58) Fields investigated (Int.Cl. ⁷ , DB name) G03C 1/42 G03C 7/392 G03C 7/407 G03C 7/00 510 G03C 7/00 520 G03C 7/00 530 G03C 7/26

Claims (4)

(57) [Claims] 1. A base having at least one blue-sensitive silver halide emulsion layer, one green-sensitive silver halide emulsion layer, one red-sensitive silver halide emulsion layer and one non-light-sensitive layer, and capable of releasing a base during development processing. In the silver halide color photographic light-sensitive material containing a precursor in at least one of the above layers, the following two types of development processing I and development processing II differing in color development time.
Wherein the gradation of yellow, magenta and cyan obtained by the two types of development processing satisfies the following conditional expression. 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), γ I (C) represents yellow when carrying out the development processing I, magenta, the gradient of cyan, gamma _II (Y), γ _II (M), γ _II (C)
Represents the gradient of yellow, magenta, and cyan when the development process II is performed, respectively. (Development Processing I) The color development time is 3 minutes to 3 minutes 15 seconds, the temperature of the color developer is 37 to 39 ° C., and 2-methyl-4- [N-ethyl-N- (Β-
A development process characterized by performing color development using a color developer containing 15 to 20 mmol / l of [hydroxyethyl) amino] aniline. (Development treatment II) The color development time is 50 to 70 seconds, the temperature of the color developer is 43 to 47 ° C, and 2-methyl-4- [N-ethyl-N- (β-hydroxy Ethyl) amino] aniline at 35-40 mmol /
A color developing process using a color developing solution containing a liter and a compound that promotes the release of a base from the base precursor. 2. The silver halide color photographic light-sensitive material according to claim 1, wherein the base precursor is a poorly water-soluble basic metal compound. 3. A color image forming method, wherein a color image is formed by performing the following development processing A using the silver halide color photographic light-sensitive material according to claim 1. (Development process 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 / l of a color developing agent is used. Development process. 4. A color image forming method, wherein a color image is formed by performing the following development processing B using the silver halide color photographic light-sensitive material according to claim 1. (Development process B) The color development time is 25 to 90 seconds, the temperature of the color developer is 40 to 60 ° C., the concentration of the color developing agent is 25 to 80 mmol / L, and the base from the base precursor is A development process characterized by using a color developer containing a compound that promotes release.