JPH09319043A - Silver halide color photographic sensitive material and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a color photosensitive material small in disturbance of gradation balance. SOLUTION: This photosensitive material contains a polyester type compound having a viscosity of 300mPa.s in a red sensitive layer and satisfies the following expressions at the time of executing development processings I and II: 0.8<=γII(C)/γI(C)<=1.2, 0.8<=γII(M)/γI(M)<=1.2, 0.8<=γII(Y)/γI(Y)<=1.2 where each of γI(Y), γI(M), γI(C) is each of yellow, magenta, and cyan gradations, when development processing 1 is executed and each of γII(Y), γII(M), γII(C) is each of yellow, magenta, and cyan gradations, when development processing II is executed, and development processing I is a color development processing in a developing time of 3min 15sec and using a developing solution at a temperature of 38 deg.C and containing a developing agent of 2-methyl-4-[N-ethyl-N-(β- hydroxyethyl)amino]anilin in 15mmol/l, and development processing II is a color development processing in a developing time of 55sec and using a developing solution at a temperature of 45 deg.C and containing the same developing agent in 38mmol/l.

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 suitable for rapid processing and a color image forming method. More specifically, it improves the deterioration of gradation balance due to shortening of color development time, The present invention relates to a silver halide color photographic light-sensitive material and a color image forming method capable of obtaining an image having the same gradation in both the processing and the rapid processing which are currently widely used.

[0002]

2. Description of the Related Art The development processing time of a color negative photosensitive material is
It was significantly accelerated by the Kodak C-41 treatment introduced in 1972, and the wet treatment time without a drying step was 17 minutes and 20 seconds. In addition, the wet processing time of the CN-16FA processing of Fuji Photo Film Co., Ltd., which has been recently introduced into the minilab market, is 8 minutes and 15 seconds due to further speeding up.

Even with the rapid progress of processing, when a user requests printing of a negative photosensitive material (color negative) taken by a user, it takes about 30 minutes to finish even the fastest in-store processing (so-called minilab). The current situation is that most users are forced to visit a photo shop twice. In the current system of color negative and color paper, further shortening of the development processing time is desired in order to meet the demand of the user who wants to visit the photo shop only once.

Conventional development processing time has been shortened mainly in the desilvering step after the color development processing step. Taking the above-mentioned C-41 processing and CN-16FA processing as examples,
The color development time of the former is 3 minutes 15 seconds and that of the latter is 3 minutes 5
Seconds, there is almost no change in color development time. In the CN-16FA processing, the color development time accounts for about 40% of the total development processing time.
In order to significantly shorten the development processing time, it is extremely difficult to reduce the color development time.

On the other hand, C-41 processing and development processing compatible with it (for example, CN-16FA processing) are now widespread all over the world. In order to be introduced to the market, this rapid process is required to be compatible with the C-41 process. Normally, a color negative light-sensitive material is composed of several color-sensitive silver halide emulsion layers and is designed so that the gradation balance of each emulsion layer is optimal when developed.
When rapid processing was performed with a shortened color development time, the gradation balance was lost and the color reproducibility was significantly deteriorated.

A processing method for obtaining similar gradations even if development processing is carried out at different color development times is disclosed in, for example, Japanese Patent Application Laid-Open No. HEI-2.
No. 2553. According to the processing method,
Equivalent gradation can be obtained by changing the processing temperature, the concentration of the color developing agent in the color developing solution and the color developing time.
Specifically, in Example 1 of the patent, the treatment temperature was 38 ° C.,
Color developing agent concentration: 15 mmol / l, color developing time: 3 minutes 15 seconds (conceivable to be equivalent to C-41 processing)
The gradation equivalent to the gradation (gamma value) obtained in the above is the processing temperature of 38 ° C., the concentration of the color developing agent is 150 mmol / liter,
It is shown that a color development time of 1 minute and 30 seconds is obtained.

However, the shortening of the color developing time by the processing method is because the concentration of the color developing agent exceeds 100 mmol / liter, so that the self-coupling reaction of the color developing agent in the liquid is remarkably promoted and after storage. The change in photographic property due to the decrease in the concentration of the color developing agent
Coloring of the light-sensitive material due to the product of the self-coupling reaction is increased. Further, the amount of the color developing agent remaining in the light-sensitive material after the development processing increases, and when the light-sensitive material is stored indoors, the density (stain) of the unexposed areas remarkably increases.

In order to avoid the above problems, the concentration of the color developing agent is set to 80 mmol / l or less and the processing temperature is set to 40 ° C. or more, so that the color developing processing time is 1 minute 3 minutes.
When the time is shortened to 0 seconds or less, the diffusion of the color developing agent becomes rate-determining, and the development of the lower layer (emulsion layer on the side closer to the support) is lower than the development of the upper layer (emulsion layer on the side far from the support) of the light-sensitive material. Due to the delay, the gradation balance between the upper layer and the lower layer was lost, and the color reproducibility was significantly deteriorated.

[0009]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to improve the deterioration of gradation balance due to the shortening of the color development time, and to achieve the ultra-rapid development which is widely used at present and shortens the color development time. It is intended to provide a silver halide color photographic light-sensitive material and a color image forming method capable of obtaining an image having an equivalent gradation in any of the treatments.
Further, the present invention provides a silver halide color light-sensitive material which can be favorably processed under any of two development processing conditions.

[0010]

The above objects of the present invention have been achieved by the following method. (1) In a silver halide color photographic light-sensitive material having at least one red-sensitive silver halide emulsion layer, green-sensitive silver halide emulsion layer and blue-sensitive silver halide emulsion layer on a support, the red-sensitive halogen The silver halide emulsion layer contains at least one selected from polyester compounds having a repeating unit represented by the following general formula [I] and having a viscosity at 25 ° C. of 300 mPa · s or more, and the following two types having different color development times. When development processing I and development processing II are performed, yellow obtained by the two types of development processing,
A silver halide color photographic light-sensitive material for development processing A and development processing B, characterized in that gradations of magenta and cyan satisfy the following conditional expressions.

0.8 ≦ γII (C) / γI (C) ≦ 1.2 0.8 ≦ γII (M) / γI (M) ≦ 1.2 0.8 ≦ γII (Y) / γI (Y) ≤1.2

(ΓI (Y), γI (M), γI (C) represent the gradations of yellow, magenta, and cyan when the development processing I is carried out, and γII (Y) and γII.
(M) and γII (C) represent gradation levels of yellow, magenta, and cyan, respectively, when development processing II is performed. ) General formula [I]

[0013]

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In a polyester compound having the formula [I] as a repeating unit and having a viscosity at 25 ° C. of 300 mPa · s or more, n represents an integer of 1 to 30, and R ₁ and R ₂ in the repeating unit are alkylene groups. Represents an alkenylene group or an arylene group. (Development Processing I) Color development time is 3 minutes and 15 seconds, the temperature of the color developing solution is 38 ° C., and the color developing agent is 2-
Color development processing is carried out using a color developer containing 15 mmol / liter of methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline.

(Development processing II) The color development time is 55 seconds, the temperature of the color developing solution is 45 ° C., and 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) is used as a color developing agent. ) Amino] aniline is color-developed using a color developer containing 38 mmol / l.

(Development processing A) Color development time is 150 to 2
It is 00 seconds, the temperature of the color developing solution is 37 to 40 ° C., and a color developing solution containing a color developing agent in an amount of 15 to 20 mmol / liter is used for color development processing.

(Development processing B) Color development time is 25 to 90
Seconds, the temperature of the color developing solution is 40 to 60 ° C., and the color developing treatment is performed using the color developing solution containing the concentration of the color developing agent of 25 to 80 mmol / liter.

(2) A color image forming method characterized in that the silver halide color photographic light-sensitive material described in (1) is subjected to the following developing treatment A. (Development Treatment A) Color development time is 150 to 200 seconds, temperature of color developer is 37 to 40 ° C., and color development treatment is performed using a color developer containing 15 to 20 mmol / l of a color developing agent. To do.

(3) A color image forming method characterized in that the silver halide color photographic light-sensitive material described in (1) is subjected to the following development processing B. (Development processing B) Color development time is 25 to 90 seconds, color developing solution temperature is 40 to 60 ° C., and color development is performed using a color developing solution containing a color developing agent concentration of 25 to 80 mmol / liter. To develop.

The present invention utilizes the large temperature dependence of the viscosity of oil droplets using the polyester compound having the repeating unit represented by the above-mentioned general formula [I].
Even if the color development time is changed, the improvement of the balance of gradation can be effectively achieved.

The polyester compound having a repeating unit represented by the general formula [I] will be described in detail below. The polyester compound used in the present invention is 25 ° C.
Has a viscosity of 300 mPa · s or more, preferably 300 to 5000 mPa · s, more preferably 300 to 3
000 mPa · s, particularly preferably 1000 to 30
It is 00 mPa · s. The viscosity handled here is in accordance with JIS K7117 at 25 ° C.

In the repeating unit represented by the general formula [I], R ₁ has 1 to 30 carbon atoms (hereinafter referred to as C number), preferably 1 to 20, more preferably 1 to 15, and R ₂ has 2 to 2 carbon atoms. Three
0, preferably 2 to 20, more preferably 2 to 15 is an alkylene group, an alkenylene group or an arylene group, and among these, an alkylene group is particularly preferred as R ₁ .
An arylene group, an ethylene Specific examples of preferred R _1, trimethylene, tetramethylene, hexamethylene, octamethylene, para, and the like, Also particularly preferred as R ₂ is an alkylene group, preferred R ₂ Specific examples include ethylene, methylethylene, 1-methyltrimethylene (1,3-butane-di-yl), hexamethylene, 2-ethylhexamethylene (2
-Ethyl-1,6-hexane-di-yl) and the like.

In the repeating unit represented by the general formula [I], n represents an integer of 1 to 30, preferably 1 to 20, and more preferably 2 to 10.

Examples of the terminal group of the polyester compound include an alkoxycarbonyl group, an acyloxy group, a phosphonyloxy group and a sulfonyloxy group depending on the type of the blocking agent used, and preferably an alkoxycarbonyl group, an acyloxy group and a phosphonyl group. An oxy group, more preferably an alkoxycarbonyl group and an acyloxy group, and particularly preferable alkoxycarbonyl groups and acyloxy groups include the following. R ₃ OCO- R ₄ COO- wherein R ₃ and R ₄ each C number from 1 to 25 (preferably 1 to 15) of optionally substituted linear, branched,
Alternatively, a cyclic alkyl group, an optionally substituted aryl group having a C number of 6 to 25 (preferably 6 to 20), or an optionally substituted heterocyclic ring having a C number of 2 to 25 (preferably 2 to 15) Represents a group. Specific examples of R ₃ and R ₄ include methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, cyclohexyl, phenyl, 2-ethylhexyl, 2-pyridyl, 4-pyridyl, 4-pyrimidyl, 2-imidazolyl, 4- Examples include quinolyl.

The polyester compound may have a molecular weight distribution depending on the distribution of the number of repeating units n described above. This molecular weight distribution may be one obtained during the synthesis, a degree of polymerization, a terminal group, a repeating structure, etc. It may be a mixture obtained by mixing different compounds. The weight average molecular weight of these mixtures is 1000 to 1500.
0, preferably 1000 to 8000, more preferably 1
000 to 5000, particularly preferably 1000 to 3
000.

More preferred polyester compounds having a repeating unit represented by the general formula [I] are shown below. In the formula, R ₁ , R ₂ , R ₃ and R ₄ are the above R ₁ ,
It represents the same group as R ₂ , R ₃ and R ₄ .

[0027]

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[0028]

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Specific examples of the polyester compound having a repeating unit represented by the general formula [I] are shown below together with comparative examples, but the present invention is not limited to these specific examples.

[0030]

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[0031]

[Table 1]

[0032]

[Table 2]

Next, the synthesis of the polyester compound will be described. Polyester is synthesized by dehydration condensation of diol and dibasic acid (catalyst: sulfuric acid, methanesulfonic acid, toluenesulfonic acid, trifluoromethanesulfonic acid, solid acid catalyst, etc.) and dealcoholization condensation of diol and dibasic acid lower alcohol ester. (Catalyst: the acid catalyst or tetraalkoxide of titanium (IV)), etc., and various alcohols and acids (carboxylic acid, phosphoric acid, sulfonic acid, etc.) are used as the termination method. Hereinafter, a synthesis example of the polyester compound (synthesis of Concrete Example I-1) will be described. 18 mol of adipic acid is added to 35 mol of 1,6-n-hexanediol, and the system is heated to a carbon dioxide gas atmosphere and then heated. When the solid acid raw material is dissolved, stirring is started. When the temperature of the reaction system reaches 90 to 110 ° C, once the temperature rise is suppressed,
After that, the temperature is gradually raised and kept at 195 ° C. During this time, water is removed from the system by a flocculator. When the acid number reaches 55, the temperature is lowered to 160 ° C. and 10 ml of 2-ethylhexanol are added. When the acid value became 6, 2-ethylhexanol was distilled off, cooled, washed and vacuum dried to obtain a liquid polyester compound.

The polyester compound having a repeating unit represented by the general formula [I] includes polysizer, monosizer, (manufactured by Dainippon Ink and Chemicals, Inc.) Sansocizer P (manufactured by Shin Nippon Rika Co., Ltd.) and the like. It can also be obtained as a commercially available product.

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

Color development processing A of the present invention will be described below. The color development time of the color development processing A of the present invention is 15
It is 0 second or more and 200 seconds or less, preferably 165 seconds or more and 195 seconds or less. The color development time depends on the type and concentration of the developing agent in the processing solution, halogen ion (especially Br-).
It can be changed depending on the concentration, the temperature of the processing solution, the pH, and the like.

The developing agent for color development processing A of the present invention is preferably 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline, 2-methyl-4-.
[N-ethyl-N- (3-hydroxypropyl) amino] aniline, 2-methyl-4- [N-ethyl-N-
(4-hydroxybutyl) amino] aniline, more preferably 2-methyl-4- [N-ethyl-N
-(Β-hydroxyethyl) amino] aniline,
The concentration of the developing agent is 15 mmol or more and 20 mmol or less, preferably 15 mmol or more and 18 mmol or less, per liter of the processing liquid.

The bromide ion concentration is determined by the amount of Br-eluted from the silver halide color photographic light-sensitive material and the amount of Br-supplemented to the color developing solution. It is preferably 9 mmol or more and 14 mmol or less, and more preferably 10 mmol or more and 13 mmol or less per liter of the treatment liquid.

The replenisher for the color developing solution preferably has a bromide ion concentration reduced to 0.004 mol / liter or less from the viewpoint of reducing the replenishment amount, and particularly has a bromide ion concentration of 0.002 mol / liter or less. Is preferred. The replenishing amount is preferably 700 ml or less, and more preferably 200 ml or more and 600 ml or less per 1 m ² of the light-sensitive material.

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

The pH of the treatment liquid is preferably 9.9 or more and 1
0.3 or less, more preferably 10.0 or more and 10.
2 or less.

Further, a hydroxylamine having a substituent described in JP-A-3-158849 and JP-A-3-174152 may be contained as a preservative, and in particular, a hydroxylamine having a sulfoalkyl group as a substituent. The one containing Further, as a chelating agent, diethylenetriaminepentaacetic acid, 1-hydroxyethylidene-
Those containing 1,1-diphosphonic acid and 4,5-dihydroxybenzene-1,3-disulfonic acid are preferable.

The development processing A is specifically a color negative film processing agent, CN-, manufactured by Fuji Photo Film Co., Ltd.
16, CN-16X, CN-16Q, CN-16FA color developer and color developer replenisher, or Eastman Kodak color negative film processing agent, C-4.
1, C-41B and C-41RA color developers can be preferably used.

Color development processing B of the present invention will be described below. The color development time of the color development processing B of the present invention is preferably 25 seconds or more and 90 seconds or less, more preferably 35 seconds or more and 75 seconds or less, and most preferably 45 seconds or more and 65 seconds or less.

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

The developing agent in color development processing B of the present invention is p
-Phenylenediamine derivatives, preferable representative examples of which are shown below. (D-1) 2-methyl-4- [N-ethyl-N- (β
-Hydroxyethyl) amino] aniline (D-2) 2-methyl-4- [N-ethyl-N- (3
-Hydroxypropyl) amino] aniline (D-3) 2-methyl-4- [N-ethyl-N- (4
-Hydroxybutyl) amino] aniline (D-4) 2-methyl-N, N-diethyl-p-phenylenediamine (D-5) 2-methyl-4- [N-ethyl-N- (β
-Methanesulfonamidoethyl) amino] aniline (D-6) 2-methoxy-4- [N-ethyl-N-
(Β-Hydroxyethyl) amino] aniline (D-7) 4-amino-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, D-11 are particularly preferable, and D-1, D-2, D-3
Is more preferable, and D-1 is the most preferable.

The concentration of the developing agent is preferably 25 mmol or more and 80 mmol or less, more preferably 25 mmol or more and 60 mmol or less, still more preferably 27 mmol or more and 50 mmol or less, and particularly preferably 30 per liter of the processing liquid. It is not less than 45 mmol and not more than 45 mmol.

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

In the color development processing B of the present invention, bromide ion (Br ⁻ ) is particularly important as an antifoggant,
The Br ⁻ concentration is preferably 1 per liter of processing liquid.
5 millimole or more and 60 millimole or less, more preferably 16
The amount is in the range of millimole to 42 millimole and particularly preferably in the range of 16 millimole to 35 millimole.

If necessary, I ⁻ or Cl ⁻ may be contained as a halogen ion other than Br ⁻ . From the viewpoint of reducing the replenishment amount, the replenisher for the color developing solution preferably has a bromide ion concentration reduced to 0.004 mol / liter or less, and particularly preferably a bromide ion concentration of 0.002 mol / liter or less. The replenishing amount is preferably 600 ml or less, more preferably 100 ml or more and 500 ml or less, and particularly preferably 130 ml or more and 400 ml or less per 1 m ² of the light-sensitive material.

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

The pH of the treatment liquid is preferably 9.9 or higher and 1
1.0 or less, more preferably 10.0 or more and 10.
5 or less.

A silver halide solvent may be added as a development accelerator, and thiosulfates, methanesulfonates,
Imidazoles described in JP-A-3-203735, mesoionic compounds described in JP-A-4-130431, and thioethers described in JP-A-4-317055 are preferable.

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

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

In the development processing I, the color development time is from 3 minutes to 3 minutes 1
5 seconds, the temperature of the color developing solution is 37 to 39 ° C.,
2-Methyl-4- [N-ethyl-N as color developing agent
15- (β-hydroxyethyl) amino] aniline
This is a developing process characterized by carrying out a color developing process using a color developing solution containing 20 mmol / liter. In the development processing II, the color developing time is 50 to 70 seconds, the temperature of the color developing solution is 43 to 47 ° C., and the color developing agent is 2
The development processing is characterized in that the color development processing is performed using a color developing solution containing 35-40 mmol / l of methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline.

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

Regarding the steps after the color development of the development processings I and II (for example, the desilvering step, the washing step, the stabilizing step), the conventional method, for example, the description of the development processing A or B described later is given. You can do it by the method.

Specific examples of the development processing I and the development processing II are shown below. In the present invention, it is preferable to use the following specific examples.

Development Treatment (I) A development treatment in which color development has the following liquid composition, temperature and processing time. (Color developer I) 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 2-Methyl -4- [N-Ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 4.5 Water was added to 1.0 liter pH (adjusted with potassium hydroxide and sulfuric acid) 10.05 Temperature 38 ° C Treatment time 3 minutes 15 seconds

Development Treatment (II) A development treatment in which the color development has the following liquid composition, temperature and processing time. (Color developer II) Tank liquid (g) Diethylenetriaminepentaacetic acid 2.0 1-Hydroxyethylidene-1,1-diphosphonic acid 3.3 Sodium sulfite 3.9 Potassium carbonate 37.5 Potassium bromide 2.0 Potassium iodide 1.3 mg Hydroxylamine sulfate 4.5 2-Methyl -4- [N-Ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 11.0 Water was added to 1.0 liter pH (adjusted with potassium hydroxide and sulfuric acid) 10.05 Temperature 45 ° C Treatment time 55 seconds The dual-use silver halide color photographic light-sensitive material according to the invention more preferably satisfies the following conditions. 0.9 ≦ γII (C) / γI (C) ≦ 1.1 0.9 ≦ γII (M) / γI (M) ≦ 1.1 0.9 ≦ γII (Y) / γI (Y) ≦ 1. 1

Next, the parts common to the developing processes A and B will be described. In the color developer of the present invention, compounds which directly preserve the aromatic primary amine color developing agent are described in JP-A-63-5341, JP-A-63-106655 and JP-A-4-144446. Various hydroxylamines, hydroxamic acids described in JP-A-63-43138, hydrazines and hydrazides described in 63-143,043, phenols described in 63-46457 and 63-58443, 63 -4
Α-Hydroxy ketones and α-amino ketones described in No. 4656, various sugars described in 63-36244 and the like can be contained. Further, in combination with the above compounds, JP-A-63-4235, JP-A-63-24254,
No. 63-21647, No. 63-146040, No. 6
Monoamines described in JP-A-3-27841 and JP-A-63-25654, JP-A-63-30845, JP-A-63-14
No. 640, No. 63-43139, diamines described in JP-A Nos. 63-21647, 63-26655 and 63-44655, polyamines described in No. 63-44655, and No. 63
Nitroxyl radicals described in JP-A-53551, 63
Alcohols described in JP-A-43140 and JP-A-63-53549, oximes described in JP-A-63-56654, and tertiary amines described in JP-A-63-239947 can be used. Other preservatives are disclosed in
Various metals described in Nos. 44148 and 57-53749, salicylic acids described in 59-180588, alkanolamines described in 54-3582, and polyethyleneimines described in 56-94349. And an aromatic polyhydroxy compound described in U.S. Pat. No. 3,746,544, if necessary.
Particularly preferred preservatives are described in JP-A-3-144446.
And hydroxylamines represented by the general formula (I), and among them, compounds having a sulfo group or a carboxy group are preferable.

Others In the color developing solution of the present invention, various additives described in JP-A-3-144446 can be used. For example, examples of the buffer for maintaining the pH include carbonic acid, phosphoric acid, boric acid, hydroxybenzoic acid, etc., from line 6 in the upper right column to line 1 in the lower left column on page (9) of the publication. As the chelating agent, the lower left column, line 2 to the lower right column 18 of the same page
Various aminopolycarboxylic acids, phosphonic acids, and sulfonic acids in the row are preferably ethylenediaminetetraacetic acid, triethylenetetraminehexaacetic acid, 1,3-diaminopropanoltetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediamine-N, N, N ', N '-Tetrakis (methylene phosphonic acid) and catechol-3,5-disulfonic acid are preferred. Examples of the development accelerator include various additives described on page 9, lower left column, line 19 to page 10, upper right column, line 7 of the same publication. Examples of the antifoggant include halide ions described in the same publication (10), page 8, upper right column, line 8 to lower left column, line 5;
Organic antifoggants; If necessary, various surfactants such as alkyl sulfonic acid, aryl sulfonic acid, aliphatic carboxylic acid, aromatic carboxylic acid may be added.

When the color developing solution of the present invention is processed by an automatic developing machine, it is preferable that the area (opening area) in which the color developing solution comes into contact with air is as small as possible. For example, when the aperture ratio is a value obtained by dividing the opening area (cm ² ) by the volume of the developer (cm ³ ), the aperture ratio is preferably 0.01 cm ^-1 or less, and
It is more preferably 005 cm ^-1 or less. The color developing solution can be regenerated and used. Regeneration of the color developing solution means that the used developing solution is subjected to anion exchange resin or electrodialysis, or a processing chemical called a regenerant is added to increase the activity of the color developing solution and to use it again as a color developing solution. That is. In this case, the regeneration rate (ratio of the overflow solution in the replenisher) is preferably 50% or more,
It is particularly preferably 70% or more. In the process using the color developer regeneration, the overflow solution of the color developer is regenerated and then used as a replenisher. As a method of regenerating the color developer, it is preferable to use an anion exchange resin. Particularly preferred anion exchange resin compositions and resin regeneration methods include those described in DIAION Manual (I) (14th edition, 1986) issued by Mitsubishi Kasei Co., Ltd. Among the anion exchange resins, resins having the composition described in JP-A-2-952 and JP-A-1-281152 are preferable.

In the present invention, the light-sensitive material treated with the processing solution having a bleaching ability is fixed or bleach-fixed. Such a fixing solution or a bleach-fixing solution is also disclosed in JP-A-3-33847, page 6, lower right column, lines 16 to 8.
The one described in line 15 on the upper left column of the page is preferable. Specific examples of the desilvering process including bleaching, bleach-fixing and fixing include the following. Bleaching-fixing Bleaching-washing-fixing Bleaching-bleaching fixing Bleaching-washing-bleaching fixing Bleaching-bleaching fixing-fixing Bleaching fixing The fixing agents contained in the fixing and bleaching-fixing solution include sodium thiosulfate, ammonium thiosulfate and sodium ammonium thiosulfate, Thiosulfate such as potassium thiosulfate, sodium thiocyanate, ammonium thiocyanate, thiocyanate (rhodan salt) thiourea such as potassium thiocyanate, thioether and the like can be used.

When thiosulfate is used alone as the fixing agent, the amount of the thiosulfate is from 0.3 to 1 per liter of the fixing solution and the bleach-fixing solution.
It is about 3 mol, preferably about 0.5 to 2 mol, and when thiocyanate is used alone, it is about 1 to 4 mol. The amount of the fixing agent may be 0.3 to 5 mol, and preferably 0.5 to 3.5 mol, per liter of the fixing solution or the bleach-fixing solution, including the case where the fixing agent is generally used in combination. However, when used in combination, the total amount may be within the above range. In addition, as compounds other than thiocyanate that can be used in combination with thiosulfate, thiourea, thioether (for example, 3,6-dithia-1,8-octanediol) and the like can be mentioned. In the case of ammonium thiosulfate, which is commonly used as a fixing agent in bleach-fixing solutions,
Although similar, other known fixing agents such as mesoionic compounds, thioether compounds, thioureas, large amounts of iodides, hypo may be substituted.

The fixing solution or the bleach-fixing solution contains a sulfite as a preservative (for example, sodium sulfite, potassium sulfite, ammonium sulfite) and hydroxylamine,
Hydrazine, a bisulfite adduct of an acetaldehyde compound (for example, acetaldehyde sodium bisulfite) and the like can be contained. In addition, various optical brighteners, defoamers or surfactants, polyvinylpyrrolidone,
Although it is possible to include an organic solvent such as methanol,
In particular, as the preservative, it is desirable to use the sulfinic acid compounds described in JP-A-60-283881.

Further, the fixing solution and / or the bleach-fixing solution may contain various aminopolycarboxylic acids for the purpose of stabilizing the processing solution,
A chelating agent such as an organic phosphonic acid is preferably added. Preferred chelating agents include 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediamine-N, N,
Examples thereof include N ′, N′-tetrakis (methylenephosphonic acid), nitrilotrimethylenephosphonic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, and 1,2-propylenediaminetetraacetic acid. Among these, 1-hydroxyethylidene-1,1-diphosphonic acid and ethylenediaminetetraacetic acid are particularly preferable.

The pH of the fixer or bleach-fixer is
5-9 are preferable and 5.5-8 are more preferable. The fixer and / or the bleach-fixer preferably contains a compound having a pKa in the range of 6.0 to 9.0 for pH adjustment or as a buffer. As these compounds, imidazole compounds are preferred. The imidazole compound represents imidazole and its derivatives, and preferable substituents of imidazole include an alkyl group, an alkenyl group, an alkynyl group, an amino group, a nitro group, a halogen atom, and the like. Further, the alkyl group, alkenyl group, and alkynyl group may be further substituted with an amino group, a nitro group, a halogen atom, or the like. The preferred total carbon number of the substituents of imidazole is 1 to 6, and the most preferred substituent is a methyl group.

Specific examples of the imidazole compound include imidazole, 1-methylimidazole, 2-methylimidazole, 4-methylimidazole and 4- (2).
-Hydroxyethyl) -imidazole, 2-ethylimidazole, 2-vinylimidazole, 4-propylimidazole, 4- (2-aminoethyl) imidazole,
2,4-dimethylimidazole and 2-chloroimidazole are mentioned. Among these, preferred compounds are imidazole, 2-methyl-imidazole and 4-methyl-imidazole, and most preferred compound is imidazole. The content of these imidazole compounds is preferably 0.01 mol / liter or more, more preferably 0.1 to 10 mol / liter, particularly preferably 0.2 to 3 mol / liter.

When the replenishing system is adopted in the processing of the present invention, the replenishing amount of the fixing solution or the bleach-fixing solution is preferably 30 to 3000 ml, and more preferably 40 to 1800 ml, per 1 m ² of the light-sensitive material. The replenishment of the bleach-fixing solution may be carried out as a bleach-fixing replenisher.
Alternatively, an overflow solution of a bleaching solution and a fixing solution may be used as described in JP-A-143755 and JP-A-3-213853. In the present invention, it is preferable that the processing solution having the bleaching ability is subjected to aeration upon processing.
Means known in the art can be used for aeration, and blowing of air into the bleaching solution or absorption of air using an ejector can be performed. When blowing air,
Air is preferably released into the liquid through an air diffusing tube having fine pores. Such an air diffuser is widely used as an aeration tank in activated sludge treatment. For aeration, Z issued by Eastman Kodak Company
-121, Eusing Process C-41 3rd Edition (1
982), and the items described on pages BL-1 to BL-2 can be used.

In the fixing step, stirring is preferably strengthened at the same time as bleaching and bleach-fixing. Specifically, the jet stirring method is most preferable. In the present invention, the fixing solution and / or the bleach-fixing solution can be subjected to silver recovery by a known method, and a regenerating solution subjected to such silver recovery can be used. The silver recovery method includes an electrolysis method (described in French Patent No. 2299667) and a precipitation method (JP-A-52).
-73037, German Patent No. 2331220),
Ion exchange method (Japanese Patent Laid-Open No. 51-17114, German Patent No. 2548237) and metal substitution method (UK Patent No. 1)
No. 353805) is effective. These silver recovery methods are preferably performed in-line from the tank liquid, because the rapid processing suitability is further improved. In the processing with the bleaching solution and / or the bleach-fixing solution of the present invention, it is preferred that the stirring is intensified, and the practice thereof is JP-A-3-33847.
The contents described on page 8, upper right column, line 6 to lower left column, line 2 of the publication can be used as they are. Among them, the jet stirring method in which the bleaching solution is sprayed on the emulsion surface of the light-sensitive material is particularly preferable. In the present invention, the total processing time of the desilvering process consisting of a combination of bleaching, bleach-fixing and fixing is preferably
20 seconds to 3 minutes, more preferably 30 seconds to 2 minutes. The processing temperature is 30 to 60 ° C, preferably 35 to 55 ° C.
It is.

After the treatment step with the fixer and / or the bleach-fixer, a washing treatment step is usually performed. It is also possible to use a simple processing method in which after the treatment with the treatment liquid having the fixing ability, the stabilizing treatment using the stabilizing liquid is carried out without substantially washing with water. The washing water used in the washing step and the stabilizing solution used in the stabilizing step may contain various surfactants in order to prevent water droplet unevenness during drying of the processed light-sensitive material. Among these, it is preferable to use a nonionic surfactant, and an alkylphenol ethylene oxide adduct is particularly preferable. Octyl, nonyl, dodecyl and dinonylphenol are particularly preferable as the alkylphenol, and 8 to 14 are particularly preferable as the number of moles of ethylene oxide added. It is also preferable to use a silicon surfactant having a high defoaming effect.

The washing water and the stabilizing solution may contain various antibacterial agents and antifungal agents in order to prevent water stains and fungi on the processed light-sensitive material. In addition, it is preferable to include various chelating agents in the washing water and the stabilizing solution. Preferred chelating agents include aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetraacetic acid, diethylenetriamine-N, N, N ', N'-tetramethylene. Examples thereof include organic phosphonic acids such as phosphonic acid, and a hydrolyzate of a maleic anhydride polymer described in European Patent No. 345172A1. It is also preferable to include a preservative which can be contained in the above-mentioned fixing solution or bleach-fixing solution in the washing water and the stabilizing solution.

The stabilizing solution used in the stabilizing step is a processing solution for stabilizing the dye image, such as an organic acid or a pH of 3 to 10.
6, a solution containing an aldehyde (for example, formalin or glutaraldehyde), or the like. The stabilizing solution may contain all compounds that can be added to the washing water, and if necessary, ammonium compounds such as ammonium chloride and ammonium sulfite, metal compounds such as Bi and Al, optical brighteners, and hardeners. Agents such as alkanolamines described in U.S. Pat. No. 4,786,583 can be used.

In the present invention, it is preferable that the stabilizing solution does not substantially contain formaldehyde as a stabilizer for the dye image. The term "substantially free of formaldehyde" means that the total amount of free formaldehyde and its hydrate is 0.003 mol or less per liter of the stabilizing solution. By using such a stabilizing solution, it is possible to suppress the scattering of formaldehyde vapor during processing. In this case, for the purpose of stabilizing the magenta dye, it is preferable that the formaldehyde substitute compound is present in the stabilizing solution, the bleaching solution or its prebath (for example, a preparation bath).

Preferred compounds as the formaldehyde substitute compound are hexamethylenetetramine and its derivatives, formaldehyde bisulfite adducts, N-methylol compounds and azolylmethylamine compounds. In addition to stabilizing the magenta dye, these preferable compounds suppress the generation of yellow stain over time.

Hexamethylenetetramine and its derivatives include "Beilsteins Handbook Der.
Organischen Hemy "(Beilsteins Handbuch der
Organishen Chemie), Vol. 26, pp. 200-P.
212 can be used.
Hexamethylenetetramine is preferred. Further, as the formaldehyde bisulfite addition product, sodium formaldehyde bisulfite is preferable.

As the N-methylol compound, an N-methylol compound of pyrazole and its derivative, an N-methylol compound of triazole and its derivative, and an N-methylol compound of urazole and its derivative are particularly preferable. Specific examples of these N-methylol compounds include 1-hydroxymethylpyrazole, 1-hydroxymethyl-2-methylpyrazole, 1-hydroxymethyl-2, 4-dimethylpyrazole, 1-hydroxymethyl-1,2,4 -Triazole, 1-hydroxymethylurazole and the like. Of these, particularly preferred are 1-hydroxymethylpyrazole and 1-hydroxymethyl-1,2,4-triazole.

As the azolylmethylamine compound,
Examples thereof include 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine and 1,4-bis (pyrazol-1-ylmethyl) piperazine, and a compound having an azole such as 1,2,4-triazole or pyrazole. Combined (Japanese Patent Application No. 3
-159918) is particularly preferable because of high image stability and low formaldehyde vapor pressure. The preferable addition amount of the formaldehyde substitute compound is 0.003 to 0.2 mol, preferably 0.005 to 0.05 mol, per liter of the treatment liquid. Two or more of these formaldehyde substitute compounds may be used in combination in the bath.

The pH of the stabilizing solution is preferably 3-9, more preferably 4-7. The washing process and stabilization process are
A multi-stage countercurrent system is preferable, and the number of stages is preferably 2 to 4. The replenishing amount is 1 to 50 times, preferably 1 to 30 times, more preferably 1 to 50 times the amount brought in from the previous bath per unit area.
10 times. Regarding the washing and stabilizing steps carried out in the present invention, the contents described in JP-A-3-33847, page 11, lower right column, line 9 to page 12, upper right column, line 19 can be preferably carried out. .

As the water used in the washing step and the stabilizing step, tap water can be used. Water and halogen deionized to have Ca and Mg ion concentrations of 5 mg / liter or less by an ion exchange resin or the like. It is preferable to use water that has been sterilized by an ultraviolet sterilization lamp or the like. Further, by using a method in which the overflow solution in the washing step or the stabilization step is caused to flow into a bath having a fixing ability, which is a pre-bath,
This is preferable because the amount of waste liquid can be reduced.

In the treatment of the present invention, in order to correct the concentration due to evaporation, it is preferable to replenish an appropriate amount of water or a correction solution or a processing replenishing solution. Although there is no particular limitation on the specific method for replenishing water,
The monitor water tank different from the bleaching tank described in No. 54959 and No. 1-254960 is installed, the evaporation amount of water in the monitor water tank is obtained, and the evaporation amount of water in the bleaching tank is calculated from the evaporation amount of this water. However, a method for replenishing the bleaching tank with water in proportion to this evaporation amount and Japanese Patent Application Nos. 2-46743 and 2-477.
No. 77, No. 2-47778, No. 2-47779, and No. 2-117977, the evaporation correction method using a liquid level sensor or an overflow sensor is preferable. In addition, tap water may be used as water for correcting the amount of 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 transparent magnetic recording layer used in the present invention will be described. The magnetic particles used in the present invention are γFe ₂
Ferromagnetic iron oxide such as O _3, Co deposited γFe ₂ O _3, Co
Adhered magnetite, Co-containing magnetite, ferromagnetic chromium dioxide, ferromagnetic metal, ferromagnetic alloy, hexagonal Ba ferrite, Sr ferrite, Pb ferrite, Ca ferrite and the like can be used. Co-coated ferromagnetic iron oxide, such as Co-coated γFe ₂ O _3, is preferred. The shape is needle-shaped,
It may be any of rice grains, spheres, cubes, plates and the like. Preferably at least 20 m ² / g in SBET is the specific surface area, 30 m ² /
g or more is particularly preferred. Saturation magnetization (σs) of ferromagnet
Is preferably 400 to 3000 Oe, and particularly preferably 600 to 3000 Oe. Ferromagnetic particles,
Surface treatment with silica and / or alumina or an organic material may be applied. Further, magnetic particles are disclosed in JP-A-6-
The surface may be treated with a silane coupling agent or a titanium coupling agent as described in 161032. Further, magnetic materials described in JP-A-4-259911 and 5-81652, the surface of which is coated with an inorganic or organic substance, can also be used.

Next, the binder used for the magnetic particles is
Thermoplastic resins, thermosetting resins, radiation curable resins, reactive resins, acids, alkalis or biodegradable polymers, natural polymers (cellulose derivatives, sugar derivatives, etc.) and mixtures described in JP-A-4-219569. Can be used. The Tg of the above resin is -40 ° C to 300 ° C, and the weight average molecular weight is 20,000 to 1,000,000. Examples thereof include vinyl copolymers, cellulose diacetate, cellulose triacetate, cellulose derivatives such as cellulose acetate propionate, cellulose acetate butyrate, and cellulose tripropionate, acrylic resins and polyvinyl acetal resins, and gelatin is also preferable. Particularly, cellulose di (tri) acetate is preferable. The binder can be cured by adding an epoxy-based, aziridine-based, or isocyanate-based crosslinking agent. Examples of the isocyanate-based cross-linking agent include isocyanates such as tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, and xylylene diisocyanate, and reaction products of these isocyanates and polyalcohols (for example, tolylene diisocyanate). Examples thereof include a reaction product of 3 mol of isocyanate and 1 mol of trimethylolpropane), and polyisocyanate produced by condensation of these isocyanates, and they are described in, for example, JP-A-6-59357.

As a method for dispersing the above-mentioned magnetic material in the above-mentioned binder, a kneader, a pin type mill, an annular type mill, etc. are preferable and a combination thereof is also preferable, as in the method described in JP-A-6-35092. JP-A-5-08828
The dispersant described in 3 or other known dispersants can be used. The thickness of the magnetic recording layer is 0.1 μ to 10 μ, preferably 0.2 μ to 5 μ, and more preferably 0.3 μ to 3 μ. The weight ratio of magnetic particles to binder is preferably less than 0.1.
It is composed of 5: 100 to 60: 100, more preferably 1: 100 to 30: 100. The coating amount as a magnetic substance is 0.005 to 3 g / m ² , preferably 0.01 to ² g
/ M ² , more preferably 0.02 to 0.5 g / m ² . The magnetic recording layer used in the present invention can be provided on the back surface of the photographic support by coating or printing and provided in the entire surface or in a stripe shape. As a method for applying the magnetic recording layer, an air doctor, a blade, an air knife, a squeeze,
Impregnation, reverse roll, transfer roll, gravure, kiss, cast, spray, dip, bar, extrusion and the like can be used.
The coating liquid described in No. 6 is preferable.

The magnetic recording layer has improved lubricity, curl adjustment,
It may have functions such as antistatic, anti-adhesion and head polishing, or may be provided with another functional layer to impart these functions, and at least one kind of particles has a Mohs hardness of 5 or more. The above-mentioned non-spherical inorganic particle abrasives are preferable. As the composition of the non-spherical inorganic particles, oxides such as aluminum oxide, chromium oxide, silicon dioxide, titanium dioxide and silicon carbide, carbides such as silicon carbide and titanium carbide, and fine powders such as diamond are preferable. These abrasives may have their surfaces treated with a silane coupling agent or a titanium coupling agent. These particles may be added to the magnetic recording layer, or may be overcoated (for example, a protective layer, a lubricant layer, etc.) on the magnetic recording layer. The binder used at this time may be the same as the binder described above for the magnet layer, and preferably the same binder as the binder for the magnet layer. For the light-sensitive material having a magnetic recording layer, see US Pat. Nos. 5,336,589 and 5,250,404.
No. 5,229,259, No. 5,215,874
, EP 466130.

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

The light-sensitive material of the present invention is processed by the developing treatment A of the present invention.
Gradients γ _A (C), γ _A (M), and γ _A (Y) of cyan, magenta, and yellow after carrying out, and the gradient γ _B (C) after carrying out the development processing B of the present invention. , Γ _B (M),
γ _B (Y) satisfies the following conditional expression.

0.8 ≦ γ _B (C) / γ _A (C) ≦ 1.2 0.8 ≦ γ _B (M) / γ _A (M) ≦ 1.2 0.8 ≦ γ _B (Y) / Γ _A (Y) ≦ 1.2

More preferably 0.9 ≦ γ _B (C) / γ _A (C) ≦ 1.1 0.9 ≦ γ _B (M) / γ _A (M) ≦ 1.1 0.9 ≦ γ _B The conditional expression of (Y) / γ _A (Y) ≦ 1.1 is satisfied.

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

In the present invention, γ _A (C), γ
_A (M), γ _A (Y), γ _B (C), γ _B (M), γ _B
(Y) is preferably 0.50 to 1.00, more preferably 0.60 to 0.90,
It is particularly preferably 0.65 to 0.80.

In the present invention, any commercially available color paper may be used for printing. The preferred gradation of color paper is about 2.7 ± 0.1 in colorimetric density. (For the colorimetric density, see page 387, "Basics of Photographic Engineering" edited by The Photographic Society of Japan, "Gin-Salt Photograph").

The silver halide color photographic light-sensitive material of the present invention is preferably applied to a photographic light-sensitive material. The specific photographic sensitivity of this light-sensitive material is preferably 160 or more. The specific photographic sensitivity referred to here is I which is an international standard.
It is a sensitivity according to the SO sensitivity, and is disclosed in JP-A-63-22665.
It is described in detail from the lower right column on page (3) to the upper left column on page (6) of Japanese Patent Publication No. However, the evaluation method of the specific photographic sensitivity in the present invention is different in the following points. After exposure 0.
The evaluation is carried out in a relatively short time of 5 to 6 hours and by a specific development process.
Alternatively, development processing B and II are adopted.

The light-sensitive material of the present invention may have at least one light-sensitive layer provided on a support. A typical example is a silver halide photographic light-sensitive material having at least one light-sensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. It is. The photosensitive layer is a unit photosensitive layer having color sensitivity to any of blue light, green light, and red light, and in a multilayer silver halide color photographic material, the arrangement of the unit photosensitive layers is generally A red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are provided in this order from the support side. However, 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 the same color-sensitive layers. A non-light-sensitive layer may be provided between the silver halide light-sensitive layers and as the uppermost layer and the lowermost layer. These may contain a coupler, a DIR compound, a color mixing inhibitor, etc. described later. A plurality of silver halide emulsion layers constituting each unit light-sensitive layer are formed by sequentially exposing two layers, a high-speed emulsion layer and a low-speed emulsion layer, to a support as described in DE 1,121,470 or GB 923,045. It is preferable to arrange them so that the degree is low. In addition, JP-A-57-112751, JP-A-62-200350, and JP-A-57-112751
As described in JP-A Nos. 62-206541 and 62-206543, a low-sensitivity emulsion layer may be provided on the side farther from the support and a high-sensitivity emulsion layer may be provided on the side closer to the support. As a specific example, from the side farthest from the support, low-sensitivity blue photosensitive layer (BL) / high-sensitivity blue photosensitive layer (BH) / high-sensitivity green photosensitive layer (GH) / low-sensitivity green photosensitive layer (GL) / High-sensitivity red photosensitive layer (RH) / Low-sensitivity red photosensitive layer (RL), or BH / BL / GL / GH / RH / RL,
Or they can be installed in the order of BH / BL / GH / GL / RL / RH. Further, as described in JP-B-55-34932, from the side farthest from the support, the blue photosensitive layer / GH / RH /
It can also be arranged in the order of GL / RL. Also, JP-A-56-257
As described in No. 38 and No. 62-63936, blue-sensitive layer / GL / RL / GH / RH may be arranged in this order from the side farthest from the support. Further, as described in JP-B-49-15495, the upper layer is the silver halide emulsion layer having the highest sensitivity, the middle layer is a silver halide emulsion layer having a lower sensitivity, and the lower layer is more light sensitive than the middle layer. A silver halide emulsion layer having a low photosensitivity is arranged, and the photosensitivity is gradually decreased toward the support. Even in the case of such three layers having different sensitivities, as described in JP-A-59-202464, the medium-sensitivity emulsion layer / layer in the same color-sensitive layer from the side away from the support. They may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer. In addition, the layers may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer. The arrangement may be changed as described above even in the case of four or more layers. In order to improve color reproducibility, US 4,663,271, US 4,705,744 and US 4,7
No. 07,436, JP-A Nos. 62-160448 and 63-89850, the main photosensitive layer such as BL, GL, and RL has a multi-layer effect donor layer (CL) having a spectral sensitivity distribution different from that of the main photosensitive layer. It is preferably located adjacent to or in close proximity to the layers.

The preferred silver halide for use in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide containing less than about 30 mol% 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 have regular crystals such as cubes, octahedra and tetradecahedrons, grains having irregular crystal forms such as spheres and plates, twin planes, etc. It may have a crystal defect of, or a composite form thereof. The grain size of silver halide is about 0.2 μm or less, and the projected area diameter is about
Large-sized grains up to 10 μm may be used, and polydisperse emulsion or monodisperse emulsion may be used. The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (hereinafter abbreviated as RD) No. 17643 (December 1978), 22-23.
Page, "I. Emulsion preparation and type
s) ”and ibid. No. 18716 (November 1979), p. 648, ibid.
307105 (Nov. 1989), pages 863-865, and Graphide, Physics and Chemistry of Photography, published by Paul Montel (P.Glaf).
kides, Chemie et Phisique Photographique, Paul Mon
(Tel, 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (GF Duffin, Photographic Emulsion Chem.
istry Focal Press, 1966), "Manufacturing and coating of photographic emulsions" by Zelikmann et al., published by Focal Press (VL Zelikm
anet al., Making and Coating Photographic Emulsion,
Focal Press, 1964) and the like.

US 3,574,628, US 3,655,394 and GB
The monodisperse emulsions described in 1,413,748 are also preferred. Further, tabular grains having an aspect ratio of about 3 or more can be used in the present invention. Tabular grains are described in Gutoff, Photographic Science and Engineering,
Volume 14, Pages 248-257 (1970); US 4,434,226, ibid.
4,414,310, 4,433,048, 4,439,520 and G
It can be easily prepared by the method described in B 2,112,157. The crystal structure may be uniform, or the inside and outside may have different halogen compositions, may have a layered structure, and silver halides having different compositions may be joined by epitaxial joining, For example, it may be bonded to a compound other than silver halide such as silver rhodanide and lead oxide. Also, a mixture of particles of various crystal forms may be used. The above emulsion may be either a surface latent image type which forms a latent image mainly on the surface, an internal latent image type which is formed inside the grain or a type which has a latent image both on the surface and inside, but a negative type emulsion. It is necessary to be. Among the internal latent image type emulsions, core / shell type internal latent image type emulsions described in JP-A-63-264740 may be used, and the preparation method thereof is described in JP-A-59-133542. The thickness of the shell of this emulsion varies depending on development processing 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. US Pat. No. 4,082,553, the surface of which is covered with a silver halide grain; US Pat. No. 4,626,498;
No. 9-214852, silver halide grains having the inside of the grains fogged, colloidal silver is added to a photosensitive silver halide emulsion layer and / or
Alternatively, it is preferably applied to a substantially non-photosensitive hydrophilic colloid layer. The fogged silver halide grain inside or on the surface is a silver halide grain that enables uniform (non-imagewise) development regardless of the unexposed area and exposed area of the light-sensitive material. , Its preparation method is US 4,626,498
And JP-A-59-214852. The silver halide forming the internal nucleus of the core / shell type silver halide grain having the inside of the grain fogged may have a different halogen composition. As the silver halide having the inside or surface of the grain fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. The average grain size of these fogged silver halide grains is 0.01 to 0.
75 μm, particularly 0.05 to 0.6 μm is preferable. The grain shape may be regular grain or polydisperse emulsion, but monodispersity (at least 95% of the weight or number of silver halide grains has a grain size within ± 40% of the average grain size). It is preferable that

In the present invention, it is preferable to use a non-photosensitive fine grain silver halide. Non-photosensitive fine grain silver halide is silver halide fine grains that are not exposed during imagewise exposure to obtain a dye image and are not substantially developed in the developing process, and are preferably not fogged in advance. . The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may optionally contain silver chloride and / or silver iodide. Preferably, it contains 0.5 to 10 mol% of silver iodide. Fine grain silver halide has an average grain size (average value of circle equivalent diameter of projected area)
Is preferably 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm. Fine grain silver halide can be prepared by the same method as that for ordinary photosensitive silver halide. The surface of the silver halide grain need not be chemically sensitized nor spectrally sensitized. However, prior to adding this to the coating solution, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, or mercapto-based compound or a zinc compound in advance. Colloidal silver can be contained in the layer containing fine silver halide grains. Coated silver amount of the light-sensitive material of the present invention is preferably 6.0 g / m ² or less, 4.5 g / m ² or less is most preferred.

The photographic additives that can be used in the present invention are also described in RD, and the relevant portions are shown in the table below. Types of additives RD17643 RD18716 RD307105 1. 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 pages Strong Color sensitizer: page 649, right column 4. Whitening agent: page 24, page 647, right column 868, page 5. Light absorber, page 25-26, page 649, right column, page 873, filter: page 650, left column Dye, UV absorber 6. Binder, page 26, page 651, left column 873 to 874 page, 7. Plasticizer, page 27, page 650, right column, page 876, lubricant 8. Coating aid, page 26-27, page 650, right column, page 875-876, surfactant 9 . Static, page 27, page 650, right column, page 876 to page 877, inhibitor 10. matt agent, page 878 to page 879

Various dye-forming couplers can be used in the light-sensitive material of the present invention, and the following couplers are particularly preferable. Yellow couplers: couplers represented by formulas (I) and (II) of EP 502,424A; couplers represented by formulas (1) and (2) of EP 513,496A (particularly Y-28 on page 18); EP 568,037A Claim 1
A coupler represented by the general formula (I) in US Pat. No. 5,066,576, column 1, lines 45 to 55; a coupler represented by the general formula (I) in paragraph 0008 of JP-A-4-274425; A coupler according to claim 1 of EP 498,381A1 on page 40 (particularly D-35 on page 18); a coupler of formula (Y) on page 4 of EP 447,969A1 (in particular Y-1 (page 17), Y- 54 (p. 41)); US
Couplers represented by formulas (II) to (IV) at 4,476,219, column 7, lines 36 to 58 (especially II-17,19 (column 17), II-24 (column 19)). Magenta coupler; JP-A-3-39737 (L-57 (page 11, lower right), L-
68 (lower right of page 12), L-77 (lower right of page 13); EP 456,257 (A-4
-63 (p. 134), (A-4) -73, -75 (p. 139); EP 486,965
M-4, -6 (page 26), M-7 (page 27); EP 571,959A M-45 (19
(M-1) of JP-A-5-204106 (page 6); M-22 of paragraph 0237 of JP-A-4-32631. Cyan coupler: CX-1,3,4,5,11,12,1 of JP-A-4-204843
4,15 (pages 14 to 16); C-7,10 (page 35) of JP-A-4-43345, 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.
The cyan coupler of the present invention is particularly preferable.

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

The coupler used in the present invention can be introduced into the photographic material by various known dispersion methods. Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,222.
No. 027 and the like. Specific examples of the high boiling point organic solvent having a boiling point of 175 ° C. or higher at atmospheric pressure used in the oil-in-water dispersion method include phthalic acid esters (for example, dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, Bis (2,4-di-t-amylphenyl) phthalate, bis (2,4-di-t-amylphenyl) isophthalate,
Bis (1,1-di-ethylpropyl) phthalate), phosphoric acid or phosphonic acid esters (eg, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, Tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2
-Ethylhexylphenylphosphonate), benzoates (eg, 2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate), amides (eg, N, N-diethyldodecaneamide, N, N-diethyllauramide),
N-tetradecylpyrrolidone), alcohols or phenols (eg, isostearyl alcohol, 2,4
-Di-tert-amylphenol), aliphatic carboxylic acid esters (bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate),
Aniline derivative (N, N-dibutyl-2-butoxy-5
-Tert-octylaniline), hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene) and the like. The auxiliary solvent has a boiling point of about 30.
Organic solvents having a temperature of not less than 50 ° C., preferably not less than 50 ° C. and not more than about 160 ° C. can be used, and typical examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide and the like. . The steps and effects of the latex dispersion method and specific examples of latex for impregnation are described in US Pat. No. 4,199,363, West German Patent Application (OLS).
No. 2,541,274 and No. 2,541,230
No. etc.

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

The present invention can be applied to various color light-sensitive materials such as color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers. In addition, Japanese Patent Publication No.
Suitable for the lens-fitted film unit described in 3-39784. Suitable supports that can be used in the present invention are
For example, the RD. Page 28 of No.17643, 6 of No.18716
From page 47, right column to page 648, left column, and No. 307105, page 879. In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is preferably 28 μm or less, more preferably 23 μm or less, and 18 μm or less.
m or less, more 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 the time required for the film thickness to reach 1/2 when the saturated film thickness is 90% of the maximum swollen film thickness reached when the color developing solution is processed at 30 ° C. for 3 minutes and 15 seconds. Is defined. The film thickness means the film thickness measured at 25 ° C. and 55% relative humidity (2 days), and T _1/2 is A Green (A.Gr
een) et al., Photographic Science and Engineering (Photogr.Sci.Eng.), 19 volumes, 2,124 ~
It can be measured by using a swellometer (swelling meter) of the type described on page 129. T _1/2 can be adjusted by adding a hardening agent to gelatin as a binder or changing the aging condition after coating. The swelling rate is preferably 150 to 400%. The swelling ratio can be calculated from the maximum swelling film thickness under the conditions described above by the formula: (maximum swelling film thickness-film thickness) / film thickness. In the light-sensitive material of the present invention, a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm is preferably provided on the side opposite to the side having the emulsion layer. The back layer preferably contains the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, and surfactant. The swelling ratio of the back layer is preferably from 150 to 500%.

The light-sensitive material of the present invention has the RD. No.176
No. 18716, No. 18716, left column to right column, and No. 18716
No. 307105, pages 880 to 881 can be used for development. The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution mainly containing an aromatic primary amine color developing agent. Aminophenol compounds are also useful as the color developing agent, but p-phenylenediamine compounds are preferably used.Typical examples and preferred examples thereof are compounds described in EP 556700A, page 28, lines 43 to 52. Is mentioned. Two or more of these compounds can be used in combination depending on the purpose. The color developer is an alkali metal carbonate,
It contains a pH buffer such as borate or phosphate, a chloride salt, a bromide salt, an iodide salt, a development inhibitor such as a benzimidazole, a benzothiazole or a mercapto compound, or an antifoggant. It is common. If necessary, hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine, various preservatives such as catecholsulfonic acids, ethylene glycol, Organic solvent such as diethylene glycol, benzyl alcohol,
Development accelerators such as polyethylene glycol, quaternary ammonium salts, amines, dye-forming couplers, competing couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, tackifiers, aminopolycarboxylic acids, aminopolyphosphones. Acid, alkylphosphonic acid, various chelating agents represented by phosphonocarboxylic acid, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic 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 their salts are added.

When the reversal process is carried out, black and white development is usually carried out and then color development is carried out. In this black-and-white developer, known black-and-white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol are used alone. Alternatively, they can be used in combination. The pH of these color developing solutions and black-and-white developing solutions is generally 9 to 12. The replenishing amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per square meter of the photographic material, and is reduced to 500 ml or less by reducing the bromide ion concentration in the replenishing solution. You can also. When the replenishment rate is reduced, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the processing tank with the air. The processing effect due to the contact between the photographic processing solution and the air in the processing tank is determined by the aperture ratio (= [the contact area between the processing solution and the air c
m ² ] ÷ [volume of treatment liquid cm ³ ]). This aperture ratio is preferably 0.1 or less, more preferably 0.001 to 0.05. As a method for reducing the aperture ratio, in addition to providing a cover such as a floating lid on the photographic processing liquid surface of the processing tank, a method using a movable lid described in JP-A-1-82033 and JP-A-63-216050 are disclosed. The slit development processing method described can be mentioned. The aperture ratio is preferably reduced not only in both the color development and black-and-white development steps but also in the following various steps, for example, in all the steps such as bleaching, bleach-fixing, fixing, washing and stabilization. The amount of replenishment can also be reduced by using means for suppressing the accumulation of bromide ions in the developer. The color development processing time is usually set between 45 seconds and 5 minutes, but high temperature and high pH
Further, the processing time can be further shortened by using the color developing agent in a high concentration.

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

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

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

In the present invention, an antistatic agent is preferably used. Examples of these antistatic agents include carboxylic acids and carboxylates, polymers containing sulfonates, cationic polymers, and ionic surfactant compounds. The most preferred antistatic agent is Zn
O ₂ , TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , SiO ₂ , MgO, BaO,
At least one selected from MoO ₃ and V ₂ O ₅ has a volume resistivity of 10 ⁷ Ω · cm or less, more preferably 10 ⁵ Ω · cm or less, a particle size of 0.001 to 1.0 μm crystalline metal The particles are fine particles of oxides or complex oxides thereof (Sb, P, B, In, S, Si, C, etc.), and further are sol-like metal oxides or fine particles of these complex oxides. The content in the sensitive material is 5 ~
Preferably 500 mg / m ^2, particularly preferably 10 to 350 mg / m ^2. The ratio of the conductive crystalline oxide or its composite oxide to the binder is preferably 1/300 to 100/1, more preferably 1/100 to 100/5.

The light-sensitive material of the present invention preferably has a slip property. The slip agent-containing layer is preferably used on both the photosensitive layer surface and the back surface. A preferable slip property is a dynamic friction coefficient of 0.
It is 25 or less and 0.01 or more. The measurement at this time represents the value when the stainless steel ball having a diameter of 5 mm is transported at 60 cm / min (25
℃, 60% RH). In this evaluation, even when 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 photosensitive material of the present invention preferably contains a matting agent. The matting agent may be on either the emulsion side or the back side, but is particularly preferably added to the outermost layer on the emulsion side.
The matting agent may be soluble in the processing solution or insoluble in the processing solution, and preferably both are used in combination. For example, polymethylmethacrylate, poly (methylmethacrylate / methacrylic acid = 9/1 or 5/5 (molar ratio), polystyrene particles, etc. are preferred.The particle size is preferably 0.8 to 10 μm, and the particle size distribution is preferably narrow. Average particle size 0.9-1.
It is preferable that 90% or more of the total number of particles be contained in one time. It is also preferable to add fine particles of 0.8 μm or less at the same time in order to enhance the matting property. For example, polymethylmethacrylate (0.2 μm), poly (methylmethacrylate / methacrylic acid = 9/1 (molar ratio), 0.3 μm)) , Polystyrene particles (0.25 μm), colloidal silica (0.03 μm
m).

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 1-312538. Particularly, the resistance at 25 ° C. and 25% RH is preferably 10 ¹² Ω or less. Usually, a plastic patrone is manufactured using a plastic into which carbon black, a pigment, or the like is kneaded in order to impart light shielding properties. The size of the patrone may be the same size as the current 135 size, or the size of the current 135 size 25 mm cartridge can be reduced to 22 mm for miniaturization of the camera.
The following is also effective. The volume of the case of the cartridge is 30 cm ³ or less, preferably 25 cm ³ or less. The weight of the plastic used in the cartridge and cartridge case is preferably 5 to 15 g.

Further, a patrone used in the present invention may be one that rotates the spool to feed the film. Further, a structure may be employed in which the leading end of the film is housed in the patrone main body, and the leading end of the film is sent out from the port portion of the patrone 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 developed photographic film. Further, the raw film and the developed photographic film may be housed in the same new cartridge, or may be different cartridges.

[0118]

EXAMPLES The present invention will be described in more detail with reference to specific examples, but the present invention is not limited to the examples unless it exceeds the gist of the present invention. Example 1 1) Support The support used in this example was prepared by the following method. 100 parts by weight of a commercially available polyethylene-2,6-naphthalate polymer and Tinuvin P.326 as an ultraviolet absorber
2 parts by weight (manufactured by Ciba-Geigy) were dried by a conventional method, melted at 300 ° C., extruded from a T-die, stretched at 140 ° C. by 3.0 times, and then stretched for 1 time.
The film was stretched 3.0 times at 30 ° C. and further stretched at 250 ° C. for 6 times.
The film was heat-set for 2 seconds to obtain a 90 μm thick PEN film.
Further, a part thereof was wound around a stainless steel core having a diameter of 20 cm to give a heat history at 110 ° C. for 48 hours. 2) Coating of undercoat layer The support is subjected to a corona discharge treatment, a UV discharge treatment, a glow discharge treatment, and a flame treatment on both surfaces thereof.
An undercoat solution having the following composition was applied to each surface, and an undercoat layer was provided on the high-temperature side during stretching. Pillar for corona discharge treatment
A 30 cm wide support is processed at 20 m / min using a solid state corona processor 6KVA model manufactured by lar. At this time, the object to be processed is 0.3
Treatment of 75 KV · A · min / m ² was performed. The discharge frequency during the treatment was 9.6 KHz, and the gap clearance between the electrode and the dielectric roll was 1.6 mm. The UV discharge treatment was performed while heating at 75 ° C. Further, in the glow discharge treatment, irradiation was performed with a cylindrical electrode at 3000 W for 30 seconds. Gelatin 3g Distilled water 25ml Zodium α-sulfodi-2-ethylhexyl succinate 0.05g formaldehyde 0.02g salicylic acid 0.1g diacetylcellulose 0.5g p-chlorophenol 0.5g resorcin 0.5g cresol 0.5g (CH ₂ = CHSO ₂ CH ₂ CH ₂ NHCO) ₂ CH ₂ 0.2 g Trimethylolpropane aziridine 3-fold molar adduct 0.2 g Trimethylolpropane-toluene diisocyanate 3-fold molar adduct 0.2 g Methanol 15 ml Acetone 85 ml Formaldehyde 0.01 g Acetic acid 0.01 g Concentrated hydrochloric acid 0.01 g

3) Coating of Back Layer On one surface of the above-mentioned support after undercoating, an antistatic layer, a magnetic recording layer and a slipping layer having the following compositions were coated as back layers. 3-1) Coating of antistatic layer 3-1-1) Preparation of conductive fine particle dispersion (tin oxide-antimony oxide composite dispersion) 230 parts by weight of stannic chloride hydrate and antimony trichloride 2
3 parts by weight were dissolved in 3000 parts by weight of ethanol to obtain a homogeneous solution. To this solution, a 1N aqueous solution of sodium hydroxide was added dropwise until the pH of the solution reached 3, to obtain a coprecipitate of colloidal stannic oxide and antimony oxide. The obtained coprecipitate was left at 50 ° C. for 24 hours to obtain a red-brown colloidal precipitate.

The reddish brown colloidal precipitate was separated by centrifugation. To remove excess ions, the precipitate was added with water and washed by centrifugation. This operation was repeated three times to remove excess ions. 200 parts by weight of the colloidal precipitate from which excess ions were removed were redispersed in 1500 parts by weight of water,
The mixture was sprayed into a baking furnace heated to ℃ to obtain fine tinned oxide-antimony oxide fine particle powder having an average particle size of 0.005 μm. The specific resistance of the fine particle powder was 5Ω · cm. A mixture of 40 parts by weight of the fine particle powder and 60 parts by weight of water was adjusted to pH 7.0, and after coarse dispersion with a stirrer, a horizontal sand mill (trade name: Dynomill; WILLYA.BA)
(CHOFENAG) until the residence time became 30 minutes. The average particle size of the secondary aggregate at this time was about 0.04 μm.

3-1-2) Coating of Conductive Layer A conductive layer having the following formulation was coated so that the dry film thickness would be 0.2 μm, and dried at 115 ° C. for 60 seconds. Conductive fine particle dispersion prepared in 3-1-1) 20 parts by weight Gelatin 2 parts by weight Water 27 parts by weight Methanol 60 parts by weight P-chlorophenol 0.5 parts by weight Resorcinol 2 parts by weight Polyoxyethylene nonylphenyl ether 0. 01 parts by weight The resistance of the obtained conductive film was 10 ^8.0 (100 V), and it had excellent antistatic performance. 3-2) Coating of magnetic recording layer Magnetic substance Co-coated γ-Fe ₂ O ₃ (major axis 0.14 μm, single axis 0.1 μm)
Acicular shape of 03 μm, specific surface area 41 m ² / g, saturation magnetization 89 e
mu / g, the surface is aluminum oxide and silicon oxide, Fe ₂ O ₃ respectively
A coercive force of 930 Oe, which has been surface treated with 2% by weight of
1100 g of Fe ^{+ 2} / Fe ⁺³ ratio is 6/94), 220 g of water and 150 g of a silane coupling agent of poly (degree of polymerization 16) oxyethylenepropyltrimethoxysilane are added,
Kneaded well in an open kneader for 3 hours. The coarsely dispersed viscous liquid was dried at 70 ° C. for 24 hours to remove water, and heated at 110 ° C. for 1 hour to prepare magnetic particles whose surface was treated. Further, the mixture was kneaded again with an open kneader according to the following formulation.

The above-mentioned surface-treated magnetic particles 1000 g Diacetyl cellulose 17 g Methyl ethyl ketone 100 g Cyclohexanone 100 g Furthermore, 200 with a sand mill (1/4 G) with the following formulation.
rpm, and finely dispersed for 4 hours. The above kneaded product 100 g Diacetyl cellulose 60 g Methyl ethyl ketone 300 g Cyclohexanone 300 g Further, diacetyl cellulose and a 3-fold molar addition product of trimethylolpropane-toluene diisocyanate as a curing agent were added to the binder at 20 wt%. The obtained liquid was diluted with equal amounts of methyl ethyl ketone and cyclohexanone so that the viscosity of the liquid was about 80 cp. The coating was carried out on the conductive layer with a bar coater to a thickness of 1.2.
It performed so that it might be set to micrometer. The amount of the magnetic material is 0.6 g / m ²
It applied so that it might become. As a matting agent, silica particles (0.3 μm) and an abrasive aluminum oxide (0.5 μm) were added so as to be 10 mg / m ² . Drying is 11
The test was performed at 5 ° C. for 6 minutes (the temperature of the rollers and the transporting device in the drying zone was 115 ° C.). The increase in the color density of D ⁸ of the magnetic recording layer when the blue filter was used in the status M of X-light was about 0.1. The saturation magnetization moment of the magnetic recording layer was 4.2 emu / m ² , the coercive force was 923 Oe, and the squareness ratio was 65%.

3-3) Preparation of Sliding Layer The following formulation liquid was applied so that the solid coating amount of the compound was as follows, and dried at 110 ° C. for 5 minutes to obtain a sliding layer. Diacetyl cellulose 25 mg / m ² C ₆ H ₁₃ CH (OH) C ₁₀ H ₂₀ COOC ₄₀ H ₈₁ (compound a) 6 mg / m ² C ₅₀ H ₁₀₁ O (CH ₂ CH ₂ O) ₁₆ H (compound b) 9 mg / m ^{2 The} compound a / compound b (6: 9) was composed of xylene and propylene glycol monomethyl ether (volume ratio 1:
1) Heat and dissolve in a solvent at 105 ° C., and dissolve this solution in a 10-fold amount of propylene glycol monomethyl ether (25
C.) to give a fine dispersion. After further diluting in 5 times the volume of acetone, the mixture was redispersed with a high-pressure homogenizer (200 atm) to obtain a dispersion (average particle size: 0.01 μm) and then used. The performance of the obtained sliding layer was as follows: a dynamic friction coefficient of 0.06 (a stainless steel hard ball of 5 mmφ, a load of 100
g, speed 6 cm / minute), static friction coefficient 0.07 (clip method), and excellent characteristics. The sliding property with respect to the emulsion surface, which will be described later, also had a dynamic friction coefficient of 0.12.

4) Coating of light-sensitive material layer Next, on the opposite side of the back layer obtained above, each layer having the following composition was multi-layer coated to prepare a color negative film.
This is designated as Sample 101.

(Photosensitive layer composition) The main materials used for each layer are classified as follows: ExC: Cyan coupler UV: UV absorber ExM: Magenta coupler HBS: High boiling organic solvent ExY: Yellow coupler H: Gelatin hardening agent ExS: Sensitizing dye The number corresponding to each component indicates the coating amount expressed in units of g / m ² , and for silver halide, the coating amount in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown in mol unit per mol of silver halide in the same layer.

(Sample 101) First layer (first antihalation layer) Black colloidal silver 0.08 gelatin 58 Second layer (second antihalation layer) Black colloidal silver 0.09 gelatin 0.64 ExM-1 0.12 ExF-1 2.0 × 10 ^-3 Solid disperse dye ExF-2 0.030 Solid disperse dye ExF-3 0.040 HBS-1 0.15 HBS-2 0.02

Third layer (intermediate layer) ExC-2 0.05 Polyethyl acrylate latex 0.20 Gelatin 0.47

Fourth Layer (Low Sensitivity Red Sensitive Emulsion Layer) Silver iodobromide Emulsion A Silver 0.26 Silver iodobromide Emulsion B Silver 0.23 Silver iodobromide Emulsion C Silver 0.10 ExS-1 4.3 × 10 ^-4 ExS-2 1.8 × 10 ^-5 ExS-3 5.9 × 10 ^-4 ExC-1 0.33 ExC-2 0.02 ExC-3 0.06 ExC-4 0.014 ExC-5 0.021 ExC-6 0.002 Cpd-2 0.033 HBS-1 0.13 Gelatin 1.37

Fifth Layer (Medium Sensitivity Red Sensitive Emulsion Layer) Emulsion C Silver 0.15 Emulsion D Silver 0.46 ExS-1 4.0 × 10 ^-4 ExS-2 2.1 × 10 ^-5 ExS-3 5.7 × 10 ^-4 ExC-1 0.23 ExC-2 0.02 ExC-3 0.03 ExC-4 0.017 ExC-5 0.02 ExC-6 0.001 Cpd-4 0.030 Cpd-2 0.05 HBS-1 0.10 Gelatin 0.93

Sixth Layer (High Sensitivity Red Sensitive Emulsion Layer) Silver Iodobromide Emulsion 1.30 ExS-1 2.8 × 10 ^-4 ExS-2 1.2 × 10 ^-5 ExS-3 4.1 × 10 ^-4 ExC-1 0.12 ExC-3 0.10 ExC-4 0.037 ExC-6 0.003 ExC-7 0.010 Cpd-2 0.059 Cpd-4 0.020 HBS-1 0.22 HBS-2 0.050 Gelatin 1.40

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

Eighth Layer (Low Sensitivity Green Sensitive Emulsion Layer) Silver iodobromide Emulsion F Silver 0.22 Silver iodobromide Emulsion G Silver 0.35 ExS-7 6.2 × 10 ⁻⁴ ExS-8 1.4 × 10 ⁻⁴ ExS-4 2.7 × 10 ^-5 ExS-5 7.0 × 10 ^-5 ExS-6 2.7 × 10 ^-4 ExM-3 0.38 ExM-4 0.084 ExC-4 0.002 ExY-1 0.040 ExY-5 0.003 HBS-1 0.30 HBS-3 0.015 Cpd- 4 0.010 Gelatin 1.07

Ninth Layer (Medium-Sensitivity Green Sensitive Emulsion Layer) Silver Iodobromide Emulsion G Silver 0.60 Silver Iodobromide Emulsion H Silver 0.52 ExS-4 5.6 × 10 ^-5 ExS-7 1.09 × 10 ^-3 ExS-8 2.5 × 10 ^-4 ExS-4 0.004 ExS-8 0.002 ExM-3 0.126 ExM-4 0.035 ExY-1 0.008 ExY-4 0.010 ExY-5 0.0050 Cpd-4 0.011 HBS-1 0.13 HBS-3 4.4 × 10 ^-3 Gelatin 1.02

10th layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion I Silver 1.34 ExS-4 4.6 × 10 ⁻⁵ ExS-7 5.5 × 10 ⁻⁴ ExS-8 1.2 × 10 ⁻⁴ ExC-9 0.019 ExM-1 0.010 ExM-2 0.030 ExM-5 0.0070 ExM-6 0.0050 Cpd-3 0.015 Cpd-4 0.031 HBS-1 0.25 Polyethyl acrylate latex 0.15 Gelatin 1.29

Eleventh layer (yellow filter layer) Yellow colloidal silver Silver 0.030 Cpd-1 0.10 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 0.69

12th Layer (Low Sensitivity Blue Sensitive Emulsion Layer) Silver iodobromide Emulsion J Silver 0.05 Silver iodobromide Emulsion K Silver 0.10 Silver iodobromide Emulsion L Silver 0.25 ExS-9 8.4 × 10 ^-4 ExC-9 0.01 ExC-8 7.0 × 10 ^-3 ExC-6 0.024 ExY-1 0.050 ExY-2 0.55 ExY-3 0.60 ExY-4 0.040 Cpd-2 0.10 Cpd-4 0.01 Cpd-3 4.0 × 10 ^-3 HBS-1 0.28 Gelatin 2.45

Thirteenth Layer (High Sensitivity Blue Sensitive Emulsion Layer) Silver Iodobromide Emulsion M Silver 0.51 ExS-9 3.1 × 10 ^-4 ExY-2 0.070 ExY-3 0.070 ExY-4 0.0050 Cpd-2 0.019 Cpd-3 1.0 × 10 ^-3 Cpd-4 0.02 HBS-1 0.070 Gelatin 0.50

Fourteenth Layer (First Protective Layer) Silver Iodobromide Emulsion N Silver 0.10 UV-1 0.13 UV-2 0.10 UV-3 0.16 UV-4 0.025 ExF-8 0.001 ExF-9 0.002 HBS-1 5.0 × 10 ^-2 HBS-4 5.0 × 10 ^-2 Gelatin 1.99

Fifteenth layer (second protective layer) H-1 0.40 B-1 (diameter 1.7 μm) 0.06 B-2 (diameter 1.7 μm) 0.09 B-3 0.13 ES-1 0.20 gelatin 0.74

Further, W-1 to W-3, B-4 to B- are added to each layer in order to improve the storability, processability, pressure resistance, mold resistance, antibacterial property, antistatic property and coating property. 6, F-
1 to F-18, and iron salts, lead salts, gold salts, platinum salts, palladium salts, iridium salts, and rhodium salts.

[0141]

[Table 3]

In Table 3, (1) Emulsions J to L were reduction-sensitized at the time of grain preparation using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-191938. (2) Emulsions CE, GI and M are described in JP-A-3-23745.
According to the Example of No. 0, gold sensitization, sulfur sensitization and selenium sensitization were performed in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate. (3) 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) Emulsions A to E, G, H and J to L are Rh, Ir and F
e in an optimal amount. Also, represented by tabularity = D _C / t ² when the average circle equivalent diameter D _C of the projected area of the tabular grains a tabularity, and the average thickness of the tabular grains was t.

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

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

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As shown in Table 4 from the reference sample 101 prepared as described above, the high boiling organic solvents of the low-sensitivity red-sensitive emulsion layer, the medium-sensitivity red-sensitive emulsion layer and the high-sensitivity red-sensitive emulsion layer are shown in Table 1 and Table 2.
Sample 102 in which an equivalent weight of the polyester compound in the sample was replaced
~ 114 were produced. The samples 101 to 114 were subjected to wedge exposure with a standard white light source and a light source having an energy distribution of black body radiation of 4800 ° K to perform development processes I-1 and II-1. The developing treatments I-1 and II-1 are specific examples of the developing treatments I and II shown in claim 1, but the developing treatments I and II are not limited to the specific examples. After treatment,
The cyan, magenta, and yellow absorption densities of the respective samples were measured to obtain characteristic curves. From the obtained characteristic curve,
Gradients γ _I (C), γ _I (M), and γ _I (Y) of cyan, magenta, and yellow after development processing I-1 and cyan, magenta after development processing II-1, Yellow gradations γ _II (C), γ _II (M), and γ _II (Y) are obtained, and γ _II (C) / γ _I (C), γ _II (M) / γ
The values of _I (M) and γ _II (Y) / γ _I (Y) were calculated.

[0166]

[Table 4]

(Development processing I-1) Step Processing time Processing temperature Color development 3 minutes 15 seconds 38 ° C Bleaching 1 minute 00 seconds 38 ° C Bleaching fixing 3 minutes 15 seconds 38 ° C Washing (1) 1 minute 00 seconds 38 ° C Washing (2) 1 minute 00 seconds 38 ℃ Dry 2 minutes 00 seconds 60 ℃

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

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

(Bleach-fixing solution) Tank solution (g) Ethylenediaminetetraacetic acid ammonium ferric dihydrate 50.0 Ethylenediaminetetraacetic acid disodium salt 5.0 Sodium sulfite 12.0 Ammonium thiosulfate aqueous solution (700 g / l) 240.0 ml Ammonia water (27%) ) 6.0 milliliters Add water 1.0 liter pH (adjust with ammonia water and acetic acid) 7.2

(Washing Solution) Common to Tank Solution and Replenishing Solution Tap water is used as H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH type anion exchange resin (Amberlite IR-400). Water was passed through a mixed bed column filled with to adjust the concentration of calcium and magnesium ions to 3 mg / liter or less, and then 20 mg / liter of sodium diisocyanurate dichloride and 0.15 g / liter of sodium sulfate were added. The pH of this solution was in the range of 6.5 to 7.5.

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

Development Processing II-1 Process and Processing Solution Composition Processing Process Temperature Time Color development 45 ° C 55 seconds Bleaching fixing 40 ° C 60 seconds Washing with water (1) 40 ° C 15 seconds Washing with water (2) 40 ° C 15 seconds Washing with water (3) 40 ℃ for 15 seconds Stability 40 ℃ for 15 seconds Dry 80 ℃ for 60 seconds (Washing was done with 3 tanks countercurrent from (3) to (1).)

Liquid composition (color developer) Tank liquid (g) Diethylenetriaminepentaacetic acid 2.0 1-Hydroxyethylidene-1,1diphosphonic acid 3.3 Sodium sulfite 3.9 Potassium carbonate 37.5 Potassium bromide 4.0 Potassium iodide 1.3 mg Hydroxylamine sulfate 4.5 2-Methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 11.0 Water was added to 1.0 liter pH (prepared with potassium hydroxide and sulfuric acid) 10.05 (bleach-fixing solution) (unit Mol) Same composition as described in Treatment I-1 (Wash water) Same composition as described in Treatment I-1 (Stabilizer) Same composition as described in Treatment I-1

From the results in Table 4, in Experiments A01 to A04, the value of (γ _II (C) / γ _I (C)) was less than 0.8,
The γ _II (C) after the development treatment II-1 was significantly smaller than the γ _I (C) after the development treatment I-1,
It can be seen that the same color tone is not obtained and the color reproducibility is deteriorated. On the other hand, in experiments A05 to A14, (γ _II (C) / γ _I
The value of (C) is 0.8 to 1.2, and the same color tone is obtained by the development processings I-1 and II-1 having different color development times according to the present invention, and good color reproducibility is obtained even by rapid processing. An image was obtained.

Example 2 Using the samples 101 to 114 prepared in Example 1, the same wedge exposure as in Example 1 was performed, and then the developing treatments A-1 and B- were used.
1. Further, development processing C-1 in which only the color development processing temperature and the developing agent concentration were changed to B-1 was performed. Development processing A-
1 and B-1 are specific examples of the development processes A and B described in claims 2 and 3, respectively, but the development processes A and B are not limited to these specific examples.

After the treatment, the absorption densities of cyan, magenta and yellow of each sample were measured to obtain a characteristic curve. From the obtained characteristic curve, the gradation degrees γ A (C) of cyan, magenta, and yellow after performing the development processing A-1,
Gradients γB (C), γ of cyan, magenta, and yellow after performing γA (M), γA (Y) and development processing B-1
B (M), γB (Y), and cyan, magenta, and yellow gradations γC (C), γC after development processing C-1 is performed.
(M), γC (Y), γB (C) / γA (C),
γB (M) / γA (M), γB (Y) / γA (Y) and γC (C) / γA (C), γC (M) / γA (M), γ
The value of C (Y) / γA (Y) was calculated. The obtained results are shown in Tables 5 and 6.

[0178]

[Table 5]

[0179]

[Table 6]

The processing steps and processing liquid compositions of development processing A-1 are shown below. (Processing step) Processing time Processing temperature Replenishment amount ^* Tank capacity Color development 3 minutes 5 seconds 38.0 ℃ 20 ml 17 liter Bleach 50 seconds 38.0 ℃ 5 ml 5 liter Fixing (1) 50 seconds 38.0 ℃ −5 liter Fixing (2 ) 50 seconds 38.0 ° C 8 ml 5 liters Water wash 30 seconds 38.0 ° C 17 ml 3.5 liters Stable (1) 20 seconds 38.0 ° C −3 liters Stable (2) 20 seconds 38.0 ° C 15 ml 3 liters Dry 1 minute 30 seconds 60 ° C * Replenishment amount per 35m width of photosensitive material 1.1m (equivalent to 24Ex. 1) Stabilizer is countercurrent method from (2) to (1), and overflow liquid of washing water is all introduced to fixing (2). did. The fixer is also connected from (2) to (1) by a countercurrent pipe. The amount of the developer brought into the bleaching step, the amount of the bleaching liquid brought into the fixing step, and the amount of the fixing liquid brought into the washing step were 2.5 ml and 2.0 ml, respectively, per 1.1 mm of 35 mm width photosensitive material. , 2.0 ml. The crossover time is 6 seconds in all cases, and this time is included in the processing time of the previous step. The opening area of the above processor is 100 cm ^{2 for the} color developing solution and 1 for the bleaching solution.
20 cm ^2, other processing solutions was about 100 cm ^2.

The composition of the processing liquid is shown below. (Color developer) Tank liquid (g) Replenisher (g) Diethylenetriaminepentaacetic acid 2.0 2.0 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 2.0 Sodium sulfite 3.9 5.3 Carbonic acid Potassium 37.5 39.0 Potassium bromide 1.4 0.4 Potassium iodide 1.3 mg-Disodium N, N-bis (sulfonate ethyl) hydroxylamine 8.0 11.0 2-Methyl-4- [N -Ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 4.5 6.4 Water was added to 1.0 liter 1.0 liter pH (adjusted with potassium hydroxide and sulfuric acid) 10.05 10. 18

(Bleaching Solution) Tank Solution (g) Replenishing Solution (g) 1,3-Diaminopropaneferric Acid Ferric Acid Ammonium Monohydrate 118 180 Ammonium Bromide 80 115 Ammonium Nitrate 14 21 Succinic Acid 40 60 Maleic Acid 33 50 Water was added to 1.0 liter 1.0 liter pH [prepared with aqueous ammonia] 4.4 4.0

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

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

(Stabilizing Solution) Tank Solution and Replenishing Solution Common (Unit g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether (Average degree of polymerization: 10) 0.2 Disodium ethylenediaminetetraacetic acid Salt 0.05 1,2,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 1,2-benzisothiazolin-3-one 0.10 water Add 1.0 liter pH 8.5

The processing steps and processing liquid compositions of development processing B-1 are shown below. (Processing process) Processing time Temperature Time Replenishment amount * Color development 45 ℃ 55 seconds 10mL Bleaching fixing 45 ℃ 65 seconds 10mL Stable (1) 45 ℃ 13 seconds --Stable (2) 45 ℃ 13 seconds --Stable (3 ) 45 ℃ 13 seconds 10 ml Dry 75 ℃ 30 seconds-(Stabilization was a 3 tank countercurrent system from (3) to (1).) * 24mm × 160cm per bottle

The composition of each processing liquid is as follows. (Color developer) (Unit: g) Tank solution Replenisher Diethylenetriaminepentaacetic acid 4.0 4.0 4,5-Dihydroxybenzene-1,3-disulfonic acid disodium salt 0.5 0.5 Sodium sulfite 4.08 0.0 potassium carbonate 38.0 38.0 potassium bromide 2.0 --potassium iodide 1.3 mg --disodium N, N-bis (sulfonate ethyl) hydroxylamine 15.0 20.0 2-methyl-4 -[N-Ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 11.0 (0.038M) 14.5 Water was added to 1.0 liter 1.0 liter pH (adjusted with potassium hydroxide and sulfuric acid) 10. 05 10.40

(Bleaching Fixing Solution) (Unit: g) Tank Solution Replenishing Solution 2-{[1- (carboxyethyl) -carboxymethylamino] ethyl} -carboxymethylaminoaminoiron (III) benzoate ammonium monohydrate 0.1. 08 mol 0.10 mol Ethylenediaminetetraacetic acid iron (III) ammonium dihydrate 0.10 mol 0.12 mol Ammonium thiosulfate aqueous solution (700 g / l) 300 ml 350 ml Ammonium iodide 1.0 --Ammonium sulfite 20.0 50.0 Ammonium methanethiosulfinate 5.0 5.0 Succinic acid 12.0 12.0 Water is added to 1.0 liter 1.0 liter pH (adjusted with nitric acid and aqueous ammonia) 6.0 5.5

(Stabilizing Solution) The tank solution and the replenishing solution have the same formulation (unit: g) sodium p-toluenesulfinate 0.03 1,2-benzisothiazolin-3-one 0.05 polyoxyethylene-p-monononylphenyl Ether (average degree of polymerization: 10) 0.2 Sodium chlorinated isocyanurate 0.02 Add water 1000 ml pH 8.5

The processing steps and processing liquid compositions of development processing C-1 are shown below. (Processing process) Processing time Temperature Time Replenishment amount * Color development 38 ℃ 55 seconds 10ml Bleaching fixing 45 ℃ 65sec 10ml Stable (1) 45 ℃ 13sec --Stable (2) 45 ℃ 13sec --Stable (3 ) 45 ℃ 13 seconds 10 ml Dry 75 ℃ 30 seconds-(Stability was set to 3 tank counter current method from (3) to (1).) * 24mm × 160cm per bottle

The composition of each processing liquid is as follows. (Color developer) Same as color developer B-1 except that the concentration of the color developing agent was changed as follows. (Unit: g) Tank solution Replenisher solution 2-Methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 18.5 (0.064M) 25.4

(Bleach-fixing solution) Same as Bleach-fixing solution B-1. (Stabilizing liquid) Same as stabilizing liquid B-1.

From Tables 5 and 6, it is clear that according to the present invention, images having good color reproducibility can be obtained by the development treatments A-1 and B-1 having different color development times. On the other hand, B-1
From the results, it was found that the color reproduction was deteriorated in the processing C-1 in which the color development time and the developing agent concentration were changed.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location G03C 7/407 G03C 7/407

Claims (3)

[Claims] 1. At least one layer each on a support,
In a silver halide color photographic light-sensitive material having a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a blue-sensitive silver halide emulsion layer, the red-sensitive silver halide emulsion layer is represented by the following general formula [I]. The following two types of development processing I and development processing which contain at least one selected from polyester compounds having a repeating unit shown and a viscosity at 25 ° C. of 300 mPa · s or more and different in color development time.
A silver halide color photograph for development processing A and development processing B, characterized in that the gradations of yellow, magenta, and cyan obtained by the two types of development processing when II is carried out satisfy the following conditional expressions: Photosensitive material. 0.8 ≦ γII (C) / γI (C) ≦ 1.2 0.8 ≦ γII (M) / γI (M) ≦ 1.2 0.8 ≦ γII (Y) / γI (Y) ≦ 1. 2 (γI (Y), γI (M), γI (C) represent the gradations of yellow, magenta, and cyan, respectively, when the development processing I is carried out, and γII (Y), γII (M), γII (C) )
Represents the gradation levels of yellow, magenta, and cyan when the development processing II was carried out. ) General formula [I] (In the polyester compound having a viscosity of 300 mPa · s or more at 25 ° C. having the general formula [I] as a repeating unit, n represents an integer of 1 to 30, and R ₁ and R ₂ in the repeating unit are an alkylene group and alkenylene. Represents a group or an arylene group.) (Development Treatment I) Color development time is 3 minutes and 15 seconds, the temperature of the color developing solution is 38 ° C., and the color developing agent is 2-
Color development processing is carried out using a color developer containing 15 mmol / liter of methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline. (Development processing II) Color development time is 55 seconds, the temperature of the color developer is 45 ° C., and 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) is used as a color developing agent.
Color development processing is performed using a color developing solution containing 38 mmol / liter of amino] aniline. (Development Treatment A) Color development time is 150 to 200 seconds, color developer temperature is 37 to 40 ° C., and color development treatment is performed using a color developer containing 15 to 20 mmol / l of a color developing agent. To do. (Development processing B) Color development time is 25 to 90 seconds, color developing solution temperature is 40 to 60 ° C., and color development is performed using a color developing solution containing a color developing agent concentration of 25 to 80 mmol / liter. Develop. 2. A color image forming method, which comprises subjecting the silver halide color photographic light-sensitive material according to claim 1 to the following development processing A. (Development Treatment A) Color development time is 150 to 200 seconds, temperature of color developer is 37 to 40 ° C., and color development treatment is performed using a color developer containing 15 to 20 mmol / l of a color developing agent. To do. 3. A color image forming method, which comprises subjecting the silver halide color photographic light-sensitive material according to claim 1 to the following development processing B. (Development processing B) Color development time is 25 to 90 seconds, color developing solution temperature is 40 to 60 ° C., and color development is performed using a color developing solution containing a color developing agent concentration of 25 to 80 mmol / liter. To develop.