JPH0296148A - Image forming of silver halide color photography - Google Patents

Abstract

PURPOSE:To prevent the fluctuation of the photographic characteristic of a photosensitive material caused by processing it with an automatic developing device at the time of continuously processing the material without deteriorating the max. optical density of the material by developing a specified photosensitive material with a color developer contg. prescribed amounts of a chlorine ion and a bromine ion respectively. CONSTITUTION:The photosensitive material comprises a silver halide emulsion with a high silver chloride content which has a silver bromide content of 0.5 - 6mol% in a red sensitive silver halide emulsion layer, and is developed with the color developer contg. the chlorine ion of 3.5X10<-2> - 1.5X10<-1>mol/l and the bromine ion of 3.0X10<-5> - 1.0X10<-3>mol/l respectively. Thus, the excellent photographic performances of the photosensitive material such as the high sensitivity, the high max. optical density and the low min. optical density at the time of rapidly processing the material, is obtd. And the fluctuation of the photographic performance at the time of continuously processing is prevented.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to an image forming method for silver halide color photography, and more specifically, it relates to an image forming method for silver halide color photography. The present invention relates to an image forming method that has a small amount of oxidation and has excellent developability.

(Prior Art) In recent years, in the photographic processing of color photographic materials, it has been desired to shorten the processing time due to the shortening of the finishing delivery time and the reduction of laboratory work.

Increasing the temperature and increasing the amount of replenishment are common methods to shorten the time of each processing step, but many other methods have been proposed, such as increasing stirring or adding various accelerators. .

In particular, for the purpose of speeding up color development and/or reducing the amount of replenishment, color photographic materials containing silver chloride emulsions instead of conventionally widely used silver bromide emulsions or silver iodide emulsions are processed. There are known ways to do this. for example,
International Publication WO 3704534 describes a method for rapidly processing a silver halide color photographic light-sensitive material with a high silver chloride content using a color developer substantially free of sulfite ions and benzyl alcohol. is listed.

However, it has been found that when development is carried out using an automatic paper processing machine based on the above method, variations in photographic properties (particularly minimum density) may occur and the white background may be significantly contaminated.

As described above, rapid development using high-silver chloride color photographic materials has a serious problem of fluctuations in photographic properties, and a solution to these problems has been strongly desired.

In rapid processing methods using high-silver chloride color photographic light-sensitive materials, organic It is known to use antifoggants.

However, it has been found that its antifogging effect is insufficient to prevent an increase in the minimum density due to continuous processing, and that when used in a large amount, the maximum density decreases.

be.

(Means for Solving the Problems) An object of the present invention is to provide at least one blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer on a support. In an image forming method in which a coated silver halide color photographic light-sensitive material is processed with a color developer containing at least one aromatic primary amine color developing agent, the red-sensitive silver halide emulsion layer is , a silver halide color photosensitive material containing a high silver chloride silver halide emulsion with a silver bromide content of 0.5 mol % or more and 6 mol % or less was treated with 3.5 x 10 -2 chloride ions.
], 5×10 −′ mol/l, and processed with a color developer containing 3.0×10 −5 to 1.0×10″3 mol/l of bromide ions. This was achieved by the image forming method.

Chlorine ions are well known as one of the antifogging agents, but their effect is small, and even when used in large amounts, they completely prevent the increase in fog that accompanies continuous processing.
No. 552 describes a method for reducing developer replenishment by using a high chloride silver halide color photographic light-sensitive material and adding a replenishing amount to the developing bath during development in an amount that does not cause overflow. Publication No. 63-106651 discloses that, for the purpose of stabilizing processing, a silver halide color photographic light-sensitive material in which the silver halide emulsion layer has a high silver chloride content is colored with a hydroxyamine compound and chloride at a predetermined concentration or higher. A method of developing with a developer is disclosed.

However, with these methods, fluctuations in photographic properties during continuous processing, which occur during processing using the automatic processor described above, are observed.
This did not solve the above problems.

(Problem to be Solved by the Invention) An object of the present invention is to use a high-silver chloride color photographic light-sensitive material O'4 to have excellent photographic properties with high sensitivity, high maximum density, and low minimum density in rapid processing. However, it has not been possible to provide an image forming method in which fluctuations in photographic properties (especially minimum density) due to continuous processing are significantly suppressed, and on the contrary, it has had the negative effect of delaying development and lowering maximum density. Ta.

Bromine ions are also well known as one of the antifoggants, but depending on the amount added, they can prevent fog caused by continuous processing to some extent, but it is not sufficient, and furthermore, it may suppress development and The concentration and sensitivity were lowered, and the result was not practical.

However, as a result of various studies, the present inventors discovered that using a high silver chloride photosensitive material containing a compound represented by the general formula (S) with a silver chloride content of 80 mol% or more, chloride ions and bromide ions 3.5×10-2 to 1.5×10 respectively
-'mol/IV, 3.0X10-5 to 1.0X10-
By processing with a color developer containing 'mol/l, the maximum density does not decrease, and the fluctuations in photographic properties (especially minimum density) that occur with continuous processing that occur in automatic processor processing.
We found that it is possible to prevent

Chloride ions and bromine ions alone do not have such an effect, and furthermore, by combining them within the concentration range of the present invention,
The fact that such an effect was obtained for the first time was completely unexpected and truly surprising.

The present invention will be explained in detail below.

In the present invention, 3.5 chloride ions are added to the color developer.
X10-2 ~], it is necessary to contain 5X10-' mol/l. Preferably, it is 4×10 −” to 1×10 −1 mol/l. If the chloride ion concentration is more than 1.5×10 −1 mol/ρ, it has the disadvantage that development is delayed and maximum density and sensitivity are lowered. , does not achieve the purpose of the present invention, which is rapid and low maximum concentration.Also, 3.5X
10-2 mol/! If it is less than 100%, the photographic properties (especially minimum density) will vary greatly due to continuous processing, and the amount of residual silver will be large, so that the object of the present invention cannot be achieved.

In the present invention, 3.0% bromine ion is added to the color developer.
It is necessary to contain OX 10-5 mol/l-1,0X10-'' mol/l.
~5X10-'mol/! It is. Bromine ion concentration is 1×
10-3 mol/p, sodium bromide, which retards development if more than 10-3 mol/p.

When eluting from the light-sensitive material in the developer, both chlorine and bromine ions may be supplied from the emulsion, or may be supplied from a source other than the emulsion.

JP-A-63-106655 describes a method of processing a photosensitive material containing 70 mol % or more of silver chloride using a developer containing 2×10 −2 mol or more of chloride. However, the concentration of bromide in the developer is a treatment outside the scope of the present invention, and furthermore, the specific effects of the combination of appropriate amounts of bromide ions and chloride ions of the present invention are not described at all, and this problem cannot be solved by the present invention. There is also no mention of the problems associated with this, and the present invention is not inferred.

Combination of appropriate amounts of chlorine ions and bromide ions of the present invention・U
The effect of suppressing fluctuations in photographic properties due to continuous processing is a balance between high development activity due to the use of a high silver chloride emulsion and decreased activity due to the presence of appropriate amounts of bromide and chloride ions, that is, high activity and high suppression. This cannot be explained solely by the fact that mold development is caused by suppression of photographic variation. Bromine ion and chlorine irradiation, maximum concentration and sensitivity decrease, 3.0X1
If it is less than 0-''mol/1, it will not be possible to prevent fluctuations in photographic properties (especially minimum density) due to continuous processing, and the object of the present invention will not be achieved.

Here, chlorine ions and bromine ions may be directly added to the developer, or may be eluted from the photosensitive material in the developer.

When added directly to a color developer, chloride ion supplying substances include thorium chloride, potassium chloride, ammonium chloride, nickel chloride, magnesium chloride, manganese chloride, calcium chloride, and cadmium chloride.
Among them, preferred are sodium chloride and potassium chloride.

It may also be supplied in the form of a salt-resistant fluorescent brightener added to the developer. As a supply material for bromide ions, sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, magnesium bromide, manganese bromide, manganese bromide, cadmium bromide, cerium bromide,
Examples include thallium bromide, of which thallium bromide is preferred.The meaning of the combination in the concentration range of the present invention will be elucidated through future research.

In the present invention, from the viewpoint of processing stability during continuous processing and prevention of streaky pressure fog, it is preferable that the color developer contains substantially no sulfite ions, but in order to suppress deterioration of the developer, In this case, physical measures such as not using the developer for a long time, using a floating pig to suppress the effects of air oxidation, or reducing the opening degree of the developer tank, reducing the developer temperature, and using organic preservatives are recommended. Chemical means such as adding agents can be used. Among these, the method using an organic preservative is advantageous in terms of simplicity.

The organic preservative according to the present invention refers to any organic compound that reduces the deterioration rate of an aromatic primary amine color developing agent when added to a processing solution for a color photographic light-sensitive material. In other words, organic metal compounds that have the function of preventing color developing agents from being oxidized by air, etc., include hydroxylamine derivatives (excluding hydroxylamine; the same applies hereinafter), hydroxamic acids, hydrazines, hydrazides, and phenols. , α-hydroxyketones, α-aminoketones, sugars, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals,
Particularly effective organic preservatives include alcohols, oximes, diamide compounds, and fused ring amines. These are Japanese Patent Application No. 61-147823 and Japanese Patent Application No. 61-1735.
No. 95, No. 61165621, No. 61-188619
No. 61-197760, No. 611865611, No. 61-198987, No. 61-201861,
No. 61-186559, No. 61-170756, No. 61-188742, No. 61188741, U.S. Patent No. 3,615,503, No. 2,494,903,
JP-A No. 52-143020, JP-A No. 48-30496
It is disclosed in the issue.

The ring structure is a 5- to 6-membered ring composed of carbon atoms, hydrogen atoms, halogen atoms, oxygen atoms, nitrogen atoms, sulfur atoms, etc., and may be saturated or unsaturated.

It is preferable that R11 and RI2 are an alkyl group or an alkenyl group, and the number of carbon atoms is preferably 1 to 10, particularly 1 to
5 is preferred. Examples of the nitrogen-containing heterocycle formed by linking RI1 and RI2 include a piperidyl group, a pyrrolysilyl group, an N-alkylpiperazyl group, a morpholyl group, an indolinyl group, and a benztriazole group.

Preferred substituents for R and R12 are a hydroxy group, an alkoxy group, an alkyl or arylsulfonyl group, an amide group, a carboxy group, a cyano group, a sulfo group, a nitro group and an amino group.

Compound 1 1 C2H5N C2) I5H I 2 CH+0CJ4N C2114
0 GHzH Regarding the above-mentioned preferred organic preservative, its general formula and specific compounds are listed below, but the present invention is not limited thereto.

In addition, the amount of the following compounds added to the color developing solution is 0.00
5 mol/l to 0.5 mol/l, preferably 0.03 mol/l to 0.1 mol/l! It is desirable to add it to a concentration of .

Particularly preferred is the addition of hydroxylamine derivatives and/or hydrazine derivatives.

The hydroxylamine derivative is preferably one represented by the following general formula (1).

General formula (1) In the formula, RI I and RI2 represent a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted aryl group, or a heteroaromatic group. RII and R'2 do not become hydrogen atoms at the same time, and may be linked to each other to form a heterocycle together with a nitrogen atom. Heterocycle C2H50C2H4N CH
2CH-CHzH H -5 As the hydrazines and hydrazides, the following are preferred.

General formula (II) In the formula, R31, R32, and R33 represent a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, or a heterocyclic group, and R34 represents a hydroxy group, a hydroxyamino group, a substituted or unsubstituted alkyl group, or a heterocyclic group. , represents an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a carbamoyl group, and an amiki group. The heterocyclic group is a 5- to 5-membered ring composed of C, Hlo, N, S, and halogen atoms, and may be either saturated or unsaturated. X31 is -C
Represents a divalent group selected from OH 502-1 or -〇-, n
is O or 1. In particular, when n=0, R34 represents a group selected from an alkyl group, an aryl group, and a heterocyclic group,
R33 and Rsa may jointly form a heterocycle.

In general formula (II), R31, R32, and R33 are preferably a hydrogen atom or an alkyl group of 01 to C0°,
In particular, it is most preferable that R31 and R32 are hydrogen atoms.

In general formula (n), R34 is an alkyl group, aryl (compound example) NHzNH+ Ctl. NarsOffl+NH2NH+
CL +Toff NII2NHCOCH.

Preferably, it is a Nil□NlIC0OC2H5 group, an alkoxy group, a carbamoyl group, or an amino group. Particularly preferred are alkyl groups and substituted alkyl groups. Preferred substituents for the alkyl group here include a carboxyl group, a sulfo group, a nitro group, an amino group, a phosphono group, and the like. X31 is preferably CO- or -3Ch-, most preferably CO-.

t-8 ■ NH2NICONH2 ■ ■ NlhNIISO3■ ■ H NHJIICNII□ ■ NHJt(COCOofJHNH2 ■ NH2NHCIIzCLCLSOJ ■ Nl(JHCtlCOOH C4119(n) ■ N82NHCII2CH2COO H A compound represented by the above general formula (1) or (II) and the following general formula (1) It is more preferable to use the amines represented by (IV) in combination, from the viewpoint of improving the stability of the color developer and further improving the development stability of continuous processing.

In the formula, R71, R72, R? 3 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a heterocyclic group. Here, R71 and R7gR71 and R7
3 or R? 2 and R? 3 may be connected to form a nitrogen-containing heterocycle.

Here, R7+, R72 and R11 may have a substituent. R71, R72, and R73 are particularly preferably a hydrogen atom or an alkyl group. Substituents include hydroxyl group, sulfo group, carboxyl group, halogen atom,
Examples include a nitro group, an amino group, and the like.

■-21 ■-22 (Compound example) To÷CI(2CH2011)3 H2NCH2CH20H 40H H2NCH2CH20H)2 Cdl, 5N (C112CIICI+2011)2II
I-10(HOCH2C112TENC)IzC)Iz
SOzCt(3Ill-111[[-12 NH+ CH2COO'H) 2 HOOCCH2
CH2CHCOOHNll□ ■ LNCHzCLSO□NH2 ■ ■ HEN C+CH20H) 2 HOCH2C)IcOOI+ NH.

■ In the formula, X+ represents -N or 7CH.

R1 and R2 are defined simultaneously in general formula (IV), and R3 represents the same group as R1 and R2, or CH2C-.

In general formula (IV-a), ν is preferably]N. The number of carbon atoms in R1, R2, and R3 is preferably 6 or less, more preferably 3 or less, and most preferably 2.

R1, R2, and R3 are preferably an alkylene group or an arylene group, and most preferably an alkylene group.

(2) General formula (IV) In the formula, X represents a trivalent atomic group necessary to complete the condensed ring, and R' and R'' represent an alkylene group, an arylene group, an alkenylene group, or an aralkylene group.

Here, R1 and R2 may be the same or different.

Among general formulas (IV), particularly preferred are general formulas (I
These are compounds represented by Va) and (IV-b).

In the formula, R1 and R2 are defined as in general formula (IV).

In general formula (IV-b), the number of carbon atoms in R' and R'' is preferably 6 or less. R', , R2 is an alkylene group,
An arylene group is preferred, and an alkylene group is most preferred.

Among the compounds of general formulas (IV-a) and (IV-b), the compound represented by general formula (IV-a) is particularly preferred■■■V-9 ■-10■■■■■■■-14 ■-15 ■-17 ■ The color developer used in the present invention will be explained below.

The color developer used in the present invention contains a known aromatic primary amine color developing agent. A preferred example is p-phenylenediamine, and representative examples are shown below, but the invention is not limited thereto.

D-IN, N-diethyl-p-phenylenediamine D-24-(N-ethyl-N-(β-hydroxyethyl) aminocoaniline D-32-methyl-4-[N-ethyl-N(β-hydroxyethyl) ethyl)amino]aniline D-44-amino-3-methyl-N-ethyl N-(β-
Methanesulfonamidoethyl)aniline These p-phenylenediamine derivatives may also be salts such as sulfate, hydrochloride, p-toluenesulfonate, and the like. The above-mentioned organic preservative for aromatic-grade amine development can be obtained as a commercially available product.
It can also be synthesized by the method described in No. 124038 and No. 62-24374.

=32 The amount of herbal medicine used is preferably about 0.1 g per developing solution IP.
~20g, more preferably from about 0.5 to about 10g.

The color developer used in the present invention preferably has a pH of
9 to 12, more preferably 9 to 11.0, and the color developer may contain other known developer component compounds.

In order to maintain the above pH, it is preferable to use various buffers. Buffers include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate. ,
Sodium tetraborate (borax), potassium tetraborate, 0
-Sodium hydroxybenzoate (sodium salicylate), potassium 0-hydroxybenzoate, 5-sulfo-
2-hydro; sodium tocybenzoate (sodium 5-sulfosalicylate), potassium 5-sulpo-2hydroxybenzoate (potassium 5-sulfosalicylate), and the like.

The amount of the buffer added to the color developer is 0.1 mol/I.
It is preferably 2 or more, especially 0.1 mol/l-0
, 4 mol/l is particularly preferred.

In addition, various chelating agents can be used in the color developer as an agent for preventing precipitation of calcium or magnesium, or to improve the stability of the color developer.

Specific examples are shown below, but the invention is not limited to these. Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, triethylenetetraminehexaacetic acid,
N,N,N-)rimethylenephosphonic acid, ethylenediamine-N,N,N'N'-tetramethylenephosphonic acid, 1
．． 3-Diamino-2-propatoltetraacetic acid, transcyclohexanediaminetetraacetic acid, nitrilotripropionic acid, 1,2-diaminopropanetetraacetic acid, hydroxyethyliminodiacetic acid, glycol etherdiaminetetraacetic acid, hydroxyethylenediaminetriacetic acid, ethylenediamine orthoacetic acid Hydroxyphenylacetic acid, 2-phosphonobutane-1
, 2,4-1-Recarbon No. 7726, Special Publication No. 1973-3
No. 0074, JP-A-56-156826 and JP-A-56-156826
-43429 etc. quaternary ammonium salts,
U.S. Patent Nos. 2,610,122 and 4.1194
p-aminophenols described in US Pat. No. 62, U.S. Pat.
494,903, 3.128182, i, 2
No. 30,796, No. 3,253゜919, Special Public Showa 4m
-11431, amine compounds described in U.S. Patent No. 2,482.546, U.S. Pat.
No. 42-25201, U.S. Patent No. 3 128 183
1-Phenyl-3-
Pyrazolidones, hydrazines, mesoionic compounds,
Ionic compounds, imidazoles, etc. can be added as necessary.

The color developer is made by converting Hensyl alcohol into an acid, 1-
Hydroxyethylidene-11-diphosphone M, N, N'
-Bis(2-hydroxyhensyl)ethylenediamine~
N,N'-diacetic acid, catechol-3,4,6-1-disulfonic acid, catechol-3,5-disulfonic acid, 5-sulfosalicylic acid, 4-sulfosalicylic acid. More than one species may be used in combination.

These chelating agents may be added in an amount sufficient to sequester metal ions in the color developer. For example 11
It is about 0.1g to 10g per serving.

Any development accelerator can be added to the color developer if necessary.

As a development accelerator, Japanese Patent Publication No. 37-16088 and No. 3
No. 7-5987, No. 38-7826, No. 44-123
No. 80, No. 45-9019 and U.S. Patent No. 3,813
．． 247, etc.; p-phenylenediamine compounds shown in JP-A-52-49829 and JP-A-50-15554;
It is preferable not to contain -13. Substantially means 2.0 ml or less per color developer, more preferably not at all. When it is not substantially contained, fluctuations in photographic properties during continuous processing are smaller, and more preferable results can be obtained.

In the present invention, in addition to chlorine ions and bromide ions, any antifoggant can be added as necessary. As antifoggants, alkali metal halides such as potassium iodide and organic antifoggants can be used. Examples of organic antifoggants include benzotriazole, 6-
Nidropenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-diazolyruhenzimidazole, 2-thiazolylmethyl-henzimidazole, indazuru, hydroxy Representative examples include nitrogen-containing heterocyclic compounds such as azaindolizine and adenine.

The color developer used in the present invention preferably contains a fluorescent whitening side. As the fluorescent whitening agent, 44'-diamino-2,2'-disulfostylhene compounds are preferred. The amount added is 0 to 10g/1. ．． Preferably 0.1~
6g/! It is.

Furthermore, various surfactants such as alkylsulfonic acid, allylphosphonic acid, aliphatic carboxylic acid, and aromatic carboxylic acid may be added as necessary.

The processing temperature of the color developer of the present invention is 20 to 50°C, preferably 30 to 40°C. Processing time is 20 seconds ~ 5
minutes, preferably 30 seconds to 2 minutes.

Usually, in color development, the developer is replenished.

The amount of replenishment depends on the photosensitive material to be processed, but is generally about 180 to 10,100 O per square meter of the photosensitive material. Replenishment is a means to keep the components of the color developing solution constant in order to avoid changes in development finish characteristics due to changes in component concentration in a development processing method in which a large amount of photosensitive material is continuously processed using an automatic developer. Refilling inevitably generates a large amount of overflow liquid, which is economically and pollution-prone.
Preferably, the amount of replenishment is small. This preferred replenishment amount may include the addition of alkali metal or ammonium salts, or corrosion inhibitors such as ammonium nitrate, guanidine, and the like.

The fixing agent used in the bleach-fixing solution or fixing solution according to the present invention is a known fixing agent, namely sodium thiosulfate,
Thiosulfates such as ammonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate; water-soluble such as thioether compounds and thioureas such as ethylene bisdioglycolic acid and 3,6-cythia-1.8 octanediol These silver halide solubilizers can be used alone or in combination of two or more. It is also possible to use a special bleach-fix solution made of a combination of a fixing agent and a large amount of a halide such as potassium iodide as described in JP-A-55-155354. In the present invention, preference is given to using thiosulfates, especially ammonium thiosulfates. The amount of fixing agent per 11 is preferably in the range of 0.3 to 2 moles, more preferably in the range of 0.5 to 1.0 moles.

The amount is 20 to 150 mfl per bottle of optical material. Although it varies somewhat depending on the photosensitive material, the photosensitive material In? The per-replenishment amount 20 is an amount such that the amount of processing liquid taken out by the photosensitive material and the amount of replenishment are approximately equal, and overflow is substantially eliminated. The present invention is effective even in such low replenishment processing.

In the present invention, desilvering treatment is performed after color development. The desilvering step generally consists of a bleaching step and a fixing step, but it is particularly preferable that they are carried out simultaneously.

The bleach or bleach-fix solution used in the present invention may contain bromides (e.g., potassium bromide, thorium bromide, ammonium bromide), or chlorides (e.g., potassium chloride, thorium chloride, ammonium chloride), or iodine. Rehalogenating agents such as oxides (eg, ammonium iodide) can be included.

If necessary, one or more types with PH buffering ability such as boric acid, borax, sodium metaborate, acetic acid, sodium acetate, thorium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, thorium citrate, tartaric acid, etc. The pH range of the inorganic acid, organic acid, and the bleach-fix solution or fix solution used in the present invention is preferably 3 to 10, and particularly preferably 5 to 9. If the pH is lower than this, the desilvering performance will be improved, but the deterioration of the solution and the leucoization of the cyan dye will be promoted. On the other hand, if the pH is higher than this, desilvering is delayed and staining is more likely to occur.

In order to adjust the pH, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, bicarbonate, ammonia, caustic potash, caustic soda, sodium carbonate, potassium carbonate, etc. can be added as necessary.

The bleach-fix solution may also contain various other fluorescent brighteners, antifoaming agents, surfactants, and organic solvents such as polyvinylpyrrolidone and methanol.

The bleach-fix solution and fixer solution used in the present invention contain sulfites (e.g., sodium sulfite, potassium sulfite,
ammonium sulfite, etc.), bisulfites (e.g. ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.), metabisulfites (e.g. potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.) ) and other sulfite ion-releasing compounds. These compounds are approximately 0.0 in terms of sulfite ion.
2-0.50 mol/! It is preferable to contain gold, more preferably 0.04 to 0.40 mol/l.

Sulfites are commonly added as preservatives, but other preservatives include ascorbic acid, carbonyl bisulfite adducts,
Sulfinic acids, carbonyl compounds, sulfinic acids, etc. may be added.

Furthermore, a buffering agent, a fluorescent whitening agent, a cleaning agent, a fungicide, etc. may be added as necessary.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to a water washing and/or stabilization process after fixing or desilvering treatment such as bleach-fixing.

The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (the number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set over a wide range. this house,
Regarding the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method, journal and fixed baths are preferably used.

Further, following the water washing treatment, a further stabilization treatment may be carried out; an example of this is a stabilizing bath containing formalin and a surfactant, which is used as a final bath for color photosensitive materials for photography. Can be done.

The processing time of the present invention is defined as the time from when the photosensitive material comes into contact with the color developer until it exits the final bath (generally water washing or stabilization bath).
The effects of the present invention can be significantly exhibited in a rapid treatment process in which the processing time is 30 minutes or less, preferably 4 minutes or less.

The color photographic light-sensitive material of the present invention can be constructed by coating at least one blue-sensitive silver halide emulsion layer, one green-sensitive silver halide emulsion layer, and one red-sensitive silver halide emulsion layer on a support. In general color photographic paper, the layers are usually coated on the support in the above order, but they may be applied in a different order. These photosensitive holes Wl1
The layers contain silver halide emulsions sensitive to each wavelength range produced by Eti On Motion Picture and Television Engineers (Jo
Urnal of the 5ociety of M
Picture and Terevisi
on Engineers) Volume 64, p. 248-2
53 (May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria will breed, and the generated suspended matter will adhere to the photosensitive material. The problem arises. In the processing of the color photosensitive material of the present invention, as a solution to such problems,
Patent Application No. 61-1343, No. 60-220345, No. 6o-238832-, No. 60-239784, No. 60239749, No. 61-4054, No. 6111
All known methods described in No. 87/19 etc. can be used. Especially 1-hydroxyethylidene-1,1-
Ammonium containing diphosphonic acid, 5-chloro-2methyl-4-isodeapurin-3-one, bismuth compounds, ammonium compounds, etc., and pigments that are complementary colors to the light they are exposed to - yellow for blue, magenta for green, etc. By containing a so-called color coupler that forms cyan for red, subtractive color reproduction can be performed. However, the coloring hues of the photosensitive layer and the coupler may not correspond as described above.

In the present invention, the red-sensitive silver halide emulsion layer must contain a high silver chloride emulsion having a silver bromide content of 0.5 mol % or more and 6 mol % or less. The high silver chloride mentioned here is
2. From the viewpoint of rapidity, preferably 94 mol% or more, more preferably 98 mol% or more.
Refers to silver chlorobromide or silver chloride that does not substantially contain silver iodide. If the silver bromide content is less than 0.5 mol%, a decrease in sensitivity and fluctuations in photographic properties due to continuous processing are likely to occur.
- If the old silver bromide content exceeds 6 mol%, it may not be possible to obtain a high maximum density, or the sensitivity may decrease and fluctuations in photographic properties due to continuous processing may worsen. The silver bromide content of blue-sensitive and green-sensitive silver halide emulsions is
In either case, it is preferable that the silver bromide content is lower than that of the silver halide emulsion in the red-sensitive silver halide emulsion layer from the viewpoint of continuous processing stability and processing dependence. The halogen composition preferably has a silver chloride content of 94 mol% or more, more preferably 98 mol% or more of silver chlorobromide or pure silver chloride.

As the silver halide emulsion of the red-sensitive silver halide emulsion layer used in the present invention, one consisting of high silver chloride containing substantially no silver iodide can be preferably used. Here, "substantially free of silver iodide" means that the silver iodide content is 1 mol%.
Hereinafter, it is preferably 0°2 mol% or less. The halogen composition of the emulsion may be different or the same among the grains, but if an emulsion having the same halogen composition among the grains is used, it is easy to make the properties of each grain uniform.

Furthermore, regarding the halogen composition distribution inside the silver halide emulsion grains, it is preferable to determine which part of the silver halide grains the halogen composition is distributed within. The halogen composition of the localized layer preferably has a silver bromide content of at least 10 mol%, more preferably more than 20 mol%. These localized layers can then be inside the particles, on the edges, corners or faces of the particle surfaces. As one preferable example,
Examples include those in which part of the corner of the particle is epitaxially grown.

On the other hand, in order to minimize the decrease in sensitivity when the photosensitive material is subjected to pressure, even in high silver chloride emulsions with a silver bromide content of 6 mol% or less, grains with a uniform structure with a small distribution of halogen composition within the grains are used. It is also preferable to use

The average grain size of the silver halide grains contained in the silver halide emulsion used in the present invention (the grain size is defined as the diameter of a circle equivalent to the projected area of the grain, and the number average thereof is taken) is 0.1μ. ~2μ is preferred.

In addition, these grain size distributions are determined by the coefficient of variation (the standard deviation of grain size divided by the average grain size). Particles with a so-called layered structure in which the halogen composition differs between the shell (-layer or multiple layers), or structures with a non-layered portion with a different halogen composition inside or on the surface of the particle (if it is on the surface of the particle, Particles with edges, corners, or surfaces (structures in which portions of different compositions are bonded to each other) can be appropriately selected and used.To obtain high sensitivity, it is recommended to use one of the latter two types rather than particles with a uniform structure. It is advantageous and preferable from the viewpoint of pressure resistance.When the silver halide grains have the above-mentioned structure, the boundaries between portions that differ in halogen composition may be clear boundaries. , a mixed crystal may be formed due to a compositional difference and the boundaries may be unclear, or a continuous structural change may be actively provided.

In such high silver chloride emulsions, the so-called so-called so-called silver bromide localized layer of 20% or less, preferably 15% or less of the above-mentioned structure having a layered or non-layered silver bromide localized layer inside and/or on the surface of the silver halide grains. Monodisperse ones are preferred. At this time, in order to obtain a wide latitude, it is preferable to blend the above-mentioned monodispersed emulsions in the same layer or to apply multilayer coating.

The silver halide grains contained in photographic emulsions are formed in regular shapes such as cubes, tetradecahedrons, or octahedrons.
lar) those with crystal shapes, those with irregular crystal shapes such as spherical, plate-like, etc.
Alternatively, a composite form of these can be used. Moreover, it may be made of a mixture of crystals having various crystal forms. In the present invention, among these particles, it is preferable to contain 50% or more, preferably 70% or more, and more preferably 90% or more of particles having a regular crystal form.

In addition to these, the average aspect ratio (yen equivalent diameter/
Emulsions in which the projected area of tabular grains having a thickness of 5 or more, preferably 8 or more, exceeds 50% of the total grains can also be preferably used.

The total coating amount of silver in the silver halide color photographic light-sensitive material of the present invention is preferably 0.80 g/ffl or less. When the total amount of coated silver is more than 0.80g10f, rapidity and fluctuations in photographic properties due to continuous processing are large. Preferably it is 0.75 g/+d or less.

The silver chlorobromide emulsion used in the present invention is P, Glafkid
Chemie et Ph1sique Pho by es
tographique (Pau1Mante1, 1967), Pho by G. F. Duufin
tographic Emulsion Chemises
try (Focal Press, 1966)
, V. L., Zelikman et al.
Kingand Coating Photograp
hic Emulsion (Focal Press TI, 1964). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble root salt with the soluble halogen salt may be any method such as one-sided mixing method, simultaneous mixing method, or a combination thereof. May be used. A method in which particles are formed in an atmosphere with an excess of negative ions (so-called back mixing method) can also be used. As one type of simultaneous mixing method, pAg in the liquid phase in which silver halide is produced can be kept constant. Regarding the compounds used for chemical sensitization, please refer to the lower right column of the 18th paragraph of the specification of JP-A No. 62-215272.
Those described in the upper right column of page 22 are preferably used.

Spectral sensitization is carried out for the purpose of imparting spectral sensitivity in a desired light wavelength range to the emulsion of each layer in the light-sensitive material of the present invention. In the present invention, it is preferable to add a spectral sensitizing dye that absorbs light in a wavelength range corresponding to the desired spectral sensitivity. Spectral sensitizing dyes used at this time include, for example, F, H, Ilarmer) 1 et
erocyclic compoundsCyanin
e dies and related compou
nds (John Wiley & 5ons [Na
Examples include those described in ``W York, London J., 1964''. As specific examples of the compounds, those described in the above-mentioned JP-A-62-215272 specification, page 22, upper right column to page 38, are preferably used.

For the silver halide emulsion used in the present invention, the so-called Chondrold double jet method, which is an important method for preventing fogging or stabilizing photographic performance during the manufacturing process, storage, or photographic processing of light-sensitive materials, may be used. You can also do it. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

Various polyvalent metal ion impurities can be introduced into the silver halide emulsion used in the present invention during the process of emulsion grain formation or physical ripening.

Examples of compounds used include cadmium, zinc, lead,
Salts such as copper and thallium, or iron, which is a group II element,
Examples include salts or complex salts of ruthenium, rhodium, palladium, osmium, iridium, platinum, and the like. In particular, the above-mentioned Group Ⅰ elements can be preferably used. The amount of these compounds added varies over a wide range depending on the purpose, but is preferably from 10@-9 to 10@-2 mol relative to silver halide.

The silver halide emulsion used in the present invention is usually subjected to chemical sensitization and spectral sensitization.

Chemical sensitization methods include sulfur sensitization represented by the addition of unstable sulfur compounds, noble metal sensitization represented by gold sensitization, and reduction sensitization, either alone or in combination with various compounds or their precursors. body can be added. These are commonly called photographic stabilizers. As specific examples of these compounds, those described on pages 39 to 72 of the specification of JP-A-61-215272 mentioned above are preferably used.

The emulsion used in the present invention may be either a so-called surface latent image type emulsion in which a latent image is mainly formed on the grain surface or a so-called internal latent image type emulsion in which a latent image is mainly formed inside the grain. Also good.

In color light-sensitive materials, yellow couplers, magenta couplers, and cyan couplers, which develop yellow magenta and cyan colors, respectively, by coupling with oxidized products of aromatic amine color developers are commonly used.

Among the yellow couplers that can be used in the present invention, acylacetamide derivatives such as henzoylacetanilide and pivaloylacetanilide are preferred.

Among them, the following general formula CY- is used as a yellow coupler.
1] and CY-2') are preferred.

For details of X (Y l] [Y 2] pivaloylacetanilide-type yellow couplers, see U.S. Pat. No. 4,622,2872), (Y
-7), (1-8), (Y-12) (Y-20
), (Y-21), (Y-23) (Y-29)
etc. are preferable.

Other preferred examples include U.S. Patent No. 34081
Typical specific example (34) described in column 6 of specification No. 94,
Compound examples (16) and (19) described in column 8 of specification No. 3,933.501, compound examples (9) described in columns 7 to 8 of specification no. 4,046,575, 4,133,
Compound example (1) described in columns 5 and 6 of specification No. 958,
Compound Example 1 described in column 5 of the specification of 401 752 and the following compounds a) to h) can be mentioned.

Column 3, line 15 to column 8, line 39 of the specification and 4623.
It is described in column 14, line 50 to column 19, line 41 of the specification of No. 616.

For more information on benzoylacetanilide type yellow couplers, see U.S. Pat. /108,194, 3,9
No. 33,501, No. 4,046,575, No. 4,13
It is described in No. 3,958, No. 4.401752, etc.

Specific examples of pivaloylacetanilide type yellow couplers include compound examples (Y-1) to (Y-
39), among which (Y-1), (
Y-4), (Y-6) (Y-7), (Y-15),
(Y-21), (Y22), (Y-23), (Y-26
), (Y35), (Y-36), (Y-37), (
Y-38), (Y-39), etc. are preferred.

Also, No. 1 of the above-mentioned U.S. Pat. No. 4,623,616
Compound examples (Y-1) to (Y-33) in columns 9 to 24 can be mentioned, and among them, (Y=58-). - Pyrazolone couplers provide high color density.

As pyrazoloazole couplers, U.S. Patent Box 2,
369,879, preferably the pyrazoloC5,1-C)(1,2,4)) liazoles described in U.S. Pat. No. 3,725.067, Research Disclosure 24220 ( 1
Pyrazolotetrazoles and Research Disclosure 24230 (June 1984) and Research Disclosure 24230 (June 1984)
Examples include pyrazolopyrazoles described in June 2013).

Any of the couplers mentioned above may be polymeric couplers.

Specifically, these compounds have the following general formula CM-1)
, (M-2) or (M-3).

Among the above-mentioned couplers, those having a nitrogen atom as a leaving atom are particularly preferred.

Examples of the Mazenk coupler used in the present invention include oil-protected couplers of indacylon type or cyanoacetyl type, preferably pyrazoloazole type couplers such as 5-pyrozolone type and pyrazolotriazoles. The 5-pyrazolone coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamino group from the viewpoint of the hue and color density of the coloring dye. Same 2nd.
No. 343,703, No. 2.600,788, No. 2
, No. 908,573, No. 3.062653, No. 3
, No. 152,896 and No. 3,936,015.

Equivalent leaving groups for 5-pyrazolone couplers include the nitrogen atom leaving groups described in U.S. Pat. No. 4,310,619 and U.S. Pat.
Among the pyrazoloazole couplers, the arylthio group described in (PCT) 8810/I 795η is preferred, as it is preferred in U.S. Pat.
The imidazo(1,2-b)pyrazoles described in US Pat. No. 500,630 are preferred, and the pyrazolo(1,5-b)(1,2,4) triazoles described in U.S. Pat. preferable.

In addition, pyrazolotriazole couplers in which a branched alkyl group is directly connected to the 2, 3 or 6 position of the pyrazolotriazole ring as described in JP-A-61-65245, and as described in JP-A-61-65246 Pyrazoloazole couplers containing a sulfonamide group in the molecule, pyrazoloazole couplers having an alkoxyphenylsulfonamide ballast group as described in JP-A-61147254, and those described in European Patent Publication No. 226-849. It is preferable to use a pyrazolotriazole coupler having an alkoxy group or an aryloxy group at the 6-position as shown in FIG.

Specific examples of these couplers are listed below.

(M (M (M (M (M) 6 days (M (M (M

As a phenolic cyan coupler, US patents 2 and 3
No. 69,929, No. 4,518,687, No. 4,51
As described in No. 1,647 and No. 3,772,002, etc.
There are compounds (including polymer couplers) that have an acylamino group at the 2-position of the phenol nucleus and an alkyl group at the 5-position; typical examples include Canadian Patent No. 625,
Coupler of Example 2 as described in '822, U.S. Pat. No. 3,7
Compound (1) described in No. 72.002, compound (I-4) and (1-5) described in No. 4,564°590, compound (1) described in JP-A-61-39045, (2),
Examples include (3), (24), and the compound (C-2) described in No. 62-70846.

As a phenolic cyan coupler, U.S. Patent 2
, No. 772,162, No. 2,895,826, No. 4,
No. 334,011, No. 4.500653 and JP-A-59
There is a 2,5-diacylaminophenol coupler described in No.-164555, and typical examples thereof include:
Compound (■) described in U.S. Patent No. 2895.826, compound θ′I) described in U.S. Patent No. 4゜557.999, No. 4,
Compound (2) and θri described in No. 565.777, No. 4,
Compound (4) described in No. 124.396, No. 4,613
Examples include the compound (1-19) described in No. 564.

As a phenolic cyan coupler, U.S. Pat.
, No. 372,173, No. 4,564,586, No. 4,
There are compounds in which a nitrogen-containing heterocycle is fused to a phenol nucleus, as described in U.S. Pat. The coupler described in No. 173 (
1) and (3), the compounds (3) and 06) described in No. 4,564,586, the compounds (1) and (3) described in No. 4,430.423, and the following compounds. I can do things.

H3 In addition to the above-mentioned types of cyan couplers, diphenylimidazole cyan couplers such as those described in European Patent Application Publication EP 0,249.453A2 can also be used.

Those with a C4H9 group (e.g., U.S. Pat. Nos. 2,474.293 and 4,282,312), and those with an arylcarbamoyl group at the 2-position (e.g., Japanese Patent Publication No. 14523/1983).
, those having a carbonamide or sulfonamide group at the 5-position (for example, JP-A-60237448, JP-A No. 61-145)
No. 557, No. 61-153640), and those having an aryloxy leaving group (for example, U.S. Pat. No. 3,476.5).
63), those with a substituted alkoxy leaving group (for example, US Pat. No. 4,296.199), and those with a glycolic acid leaving group (for example, Japanese Patent Publication No. 60-39217).

These couplers can be contained in the dispersed emulsion layer in the coexistence of at least one type of high boiling point organic solvent. Preferably, a high boiling point organic solvent represented by the following formula (A) to E) is used.

Formula (A) w.

W2-0-P=0 Other examples of phenolic cyan couplers include U.S. Pat.
, 444.872, 4,427.767, 4,
No. 579,813, European Patent No. (EP) 067.689
There are ureido couplers described in US Pat. No. 4,333,999, and coupler (1) described in US Pat. No. 4,451.559. , the coupler (+4) described in No. 4,444,872, the coupler (3) described in No. 4,427.767, the couplers (6) and (24) described in No. 4,609,619, Coupler (1) and (11) described in 4,579,813, European Patent No. (EP) 067
Examples include couplers (45) and (5o) described in No. 689B1, coupler (3) described in JP-A-61-42658, and the like.

Examples of naphthol-based cyan couplers include those having an N-alkyl-N-arylcarbamoyl group at the 2-position of the naphthol nucleus (for example, U.S. Pat. No. 2,313,586);
Alkylcarbamoy formula (B) W, - at the 2nd position
COO-W2 formula (C) W, -CON/ (in the formula, W, , W2 and W3 are each substituted or unsubstituted alkyl group, cycloaxyl group, alkenyl group,
Represents an aryl group or a heterocyclic group, W4 is W, OW
, or S-W, where n is an integer from 1 to 5, and when n is 2 or more, W4 may be the same or different from each other, and -i in formula (E), Wl and W2 are condensed. (may form a ring).

These couplers can also be synthesized with rhodapul latex polymers (
For example, it can be emulsified and dispersed in an aqueous hydrophilic colloid solution by impregnating it with a polymer (for example, US Pat. No. 4,203,716) or by dissolving it in a water-insoluble but organic solvent-soluble polymer.

Homopolymers or copolymers described on pages 12 to 30 of International Publication No. WO 313100723 are preferably used, and acrylamide polymers are particularly preferred from the viewpoint of color image stabilization.

The light-sensitive material produced using the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, etc. as a color antifoggant.

Various anti-fading agents can be used in the light-sensitive material of the present invention. That is, as organic antifading agents for cyan, magenta and/or yellow images, hydroquinones, 6
-Hydroxychromans, 5-hydroxycoumarans,
Spirochromans, p-alkoxyphenols, hindered phenols centered on bisphenols, gallic acid derivatives, methylenedioxybenzenes, amine phenols, hindered amines, and each of these No. 09 and No. 3,764.337 , Japanese Patent Publication No. 52152225
Spiroindanes are disclosed in U.S. Patent No. 4,360.
No. 589, p-alkoxyphenols are disclosed in U.S. Patent No. 2,735,765 and British Patent Box 2,066.975.
No., JP-A-59-10539, JP-A-57-1976
No. 5, etc., and hindered phenols are disclosed in U.S. Patent No. 37.
Gallic acid derivatives, methylenedioxybenzenes, and amine phenols are disclosed in U.S. Patent No. 3. 457,07
No. 9, No. 4.332.886, Special Publication No. 56-211
No. 44, etc., hindered amines are disclosed in U.S. Patent No. 3.3.
No. 36°135, No. 4,268,593, British Patent Box 1.32. No. 889, No. 1.354,313,
No. 1,410,846, Japanese Patent Publication No. 511420, Japanese Patent Publication No. 58-114036, Japanese Patent Publication No. 59-53846, Japanese Patent Publication No. 59-78344, etc., disclose the use of ethers of phenolic hydroxyl groups and phenolic hydroxyl groups of ester derivative compounds. Typical examples include silylated or alkylated ether or ester derivatives. Further, metal complexes such as (bissalicylaldoximado)nickel complex and (bis-NN dialkyldithiocarbamado)nickel complex can also be used.

Specific examples of organic antifade agents are described in the following patent specifications:

Hydroquinones are disclosed in U.S. Patent No. 2,360.290,
2.418,613, 2,700.453, 2,701,197, 2,728.659
No. 2,732,300, No. 2,735,76
No. 5, No. 3,982.944, No. 4,430,4
25, British Patent Box 1,363,921, U.S. Patent No. 2,710.801, U.S. Patent No. 2,816,028, etc. U.S. Patent No. 3432.300
No. 3,573,050, No. 3,574,62
No. 7, No. 3,698.9 is U.S. Patent No. 4,155,7
No. 65, No. 4.174.220, No. 4,254.
No. 216, No. 4,264.720, Japanese Unexamined Patent Publication No. 1983-1
No. 45530, No. 55-6321, No. 5B-1051
No. 47, No. 59-10539, Special Publication No. 57-3785
No. 6, U.S. Patent No. 4.279.990, Special Publication No. 1979-
No. 3263, metal complexes are disclosed in U.S. Patent No. 4.050,
No. 938, No. 4.241155, British Patent Box 2,0
27,731 (A), etc., respectively. The purpose of these compounds can be achieved by co-emulsifying them with the couplers and adding them to the photosensitive layer, usually in an amount of 5 to 100% by weight based on the respective color couplers. In order to prevent the cyan dye image from deteriorating due to heat and especially light, it is more effective to introduce an external ray absorber into the layers on both sides adjacent to the cyan coloring layer.

Among the above antifading agents, spiroindanes, hindered amines, and the like are particularly preferred.

In the present invention, it is preferred to use the following compounds together with the above-mentioned couplers, especially with the pyrazoloazole couplers.

That is, a compound (F) that chemically bonds with the aromatic amine developing agent remaining after color development processing to produce a chemically inert and substantially colorless compound and/or an aroma remaining after color development processing. For example, in storage after processing, the compound (G) that chemically bonds with the oxidized form of a group amine color developing agent to produce a chemically inert and substantially colorless compound may be used simultaneously or singly. This is preferable in order to prevent staining and other side effects caused by the formation of coloring dyes due to the reaction between the color developing agent or its oxidized product remaining in the film and the coupler.

A preferable compound (F) has a second-order reaction rate constant with p-anilidine of 2 (in trioctyl phosphate at 80°C) of 1.0ffi/mol·sec to
IX 10-51! /mol sec.

When R2 is larger than this range, the compound itself becomes unstable and may react with gelatin or water, decompose and combine to form a cyclic structure.

Among the methods of chemically bonding with the residual aromatic amine developing agent, the typical ones are substitution reaction and addition reaction.

For specific examples of compounds represented by general formulas (Fl) and (FII),
No. 58643, No. 62-212258, No. 62-21
No. 4681, No. 62-228034 and No. 62-279
It is described in No. 843, etc.

Further, details of the above-mentioned compound (G) and its combination with compound (F) are described in Japanese Patent Application No. 18439/1983.

The photosensitive material produced using the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, benzotriazole compounds substituted with an aryl group (for example, those described in U.S. Pat. No. 3,533,794), 4-thiazolidone compounds (for example, those described in U.S. Pat. No. 3,314,794 and 3.352681), ), hensifenone compounds may be stored. On the other hand, if R2 is smaller than this range, the reaction with the remaining aromatic amine developing agent will be slow, and as a result, it may not be possible to prevent the side effects of the remaining aromatic amine developing agent, which is the objective of the present invention.

A more preferable compound (F) can be represented by the following general formula (Fl) or (FII).

General formula (Fl) R1-(A), -X General formula (FIG) R2-C=Y In the formula, R1 and R2 each represent an aliphatic group, an aromatic group, or a heterocyclic group. n represents 1 or 0. B represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, or a sulfonyl group, and Y promotes the addition of an aromatic amine developing agent to the compound of general formula (FIG). represents a group that

Here, R1 and X, Y and R2, or B are bonded to each other (for example, as described in JP-A No. 46-2784), or a cinnamic acid ester compound (for example, as described in U.S. Pat. No. 3,705.805,
No. 3,707,375), butadiene compounds (e.g., those described in U.S. Pat. No. 4,045,229), or benzoxidole compounds (e.g., those described in U.S. Pat. No. 3,700,455). ) can be used. An ultraviolet absorbing coupler (for example, an α-naphthol cyan dye-forming coupler) or an ultraviolet absorbing polymer may be used. These ultraviolet absorbers may be mordanted in specific layers.

The photosensitive material produced according to the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes, hemioxonol dyes and merocyanine dyes are useful.

As the binder or protective colloid that can be used in the emulsion layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used alone or together with gelatin.

In the present invention, the gelatin may be either lime-treated or acid-treated. Details of the method for producing gelatin are described in The Macromolecular Chemistry on Gelatin, written by Arthur Vuis (Academic Press, published in 1964).

As the support used in the present invention, transparent films such as cellulose nitrace film and polyethylene terephthalate, which are usually used in photographic materials, and reflective supports can be used. For purposes of the present invention, the use of reflective supports is more preferred.

The "reflective support j" used in the present invention refers to a material that enhances the reflectivity and makes the dye image formed in the silver halide emulsion layer clear. It can be determined by measuring the occupied area ratio (%) (R4) of the particles.The coefficient of variation of the occupied area ratio (%) is the standard deviation S of R1 with respect to the average value (T?) of R1.
It can be determined by the ratio S/π. The number (n) of target unit areas is preferably 6 or more. Therefore, the coefficient of variation s/R can be determined.

In the present invention, the coefficient of variation of the occupied area ratio (%) of fine pigment particles is 0.15 or less, particularly 0.15 or less. 12 or less is preferable. If it is 0.08 or less, the dispersibility of the particles is substantially
It can be said that it is uniform.

The body may be a support coated with a hydrophobic resin containing dispersed light-reflecting substances such as titanium oxide, zinc oxide, calcium carbonate, or calcium sulfate, or a support coated with a hydrophobic resin containing dispersed light-reflecting substances. Includes those used as For example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, transparent supports with a reflective layer or a reflective material, such as glass plates, polyester films such as polyethylene terephthalate, cellulose triacetate or cellulose nitrate, There are polyamide films, polycarbonate films, polystyrene films, vinyl chloride resins, and the like, and these supports can be appropriately selected depending on the purpose of use.

As a light-reflecting substance, it is best to thoroughly knead a white pigment in the presence of a surfactant, and also coat the surface of the pigment particles with
It is preferable to use one treated with a tetrahydric alcohol.

The occupied area ratio (%) of white pigment fine particles per defined unit area is most typically determined by dividing the observed area into adjacent unit areas of 6 μm x 6 μm.Example-1 Paper support laminated on both sides with polyethylene A multilayer color photographic paper having the layer structure shown below was prepared. The coating solution was prepared as follows.

150 g of ethyl acetate was added to 60.0 g of yellow coupler (Ex Y) and 28.0 g of antifading agent (Cpd-1) to prepare the coating solution for the first layer.
cc and solvent (So Iv-3) 1.0cc and solvent (
S.

1v-4) 3.0 cc was added and dissolved, and this solution was added to 450 cc of a 10% gelatin aqueous solution containing sodium dodecylhenzensulfonate, and then dispersed with an ultrasonic homogenizer. 420 g of silver chlorobromide emulsion containing blue-sensitive sensitizing dye (silver bromide 0.7 mol%)
A first layer coating solution was prepared by mixing and dissolving the above ingredients. Coating solutions for the second to seventh layers were also prepared in the same manner as the coating solution for the first layer. 1,2-bis(vinylsulfonyl)ethane was used as the gelatin hardening agent for each layer.

The following spectral sensitizing dyes were used in each layer.

Blue-sensitive emulsion layer; anhydro-5-5'-chloro3.3'
-disulfoethyl thiacyanine hydroxide green-sensitive emulsion layer; anhydro-9-ethyl-5,5' diphenyl-331-disulfoethyl oxacarbocyanine hydroxide red-sensitive emulsion layer; 3,3'-diethyl-5- Methoxy-9
9'-(2,2'-dimethyl-13-propano)thiarubocyanine yossite The following was also used as a stabilizer for each emulsion layer.

Support Paper support laminated on both sides with polyethylene First layer (blue sensitive layer) Silver chlorobromide emulsion (AgBr: 0.7 mol%, cubic average grain size 0.9μ) 0.27 Gelatin 1.80 IxRho Coupler (ExY) 0.60 Antifading agent (Cpd-1) 0.28 Solvent (So
l v-3) 0.01? Container (
Sol v-4)
0.03 Second layer (color mixing prevention layer) Gelatin 0.80 Color mixing prevention agent (Cpd-2) 0.055 Solvent (Solv-1) 0.03 Solvent (
Solv-2) 0.015 Third layer (green sensitive layer) Silver chlorobromide emulsion (AgBr: 0.7 mol%, cubic grain size 0.45 μ) 0.28 Gelatin 1.40 Magenta coupler (ExM) 0. 6797= Also, the following was used as an irradiation-preventing dye.

[3-Carboxy-5-hydroxy-4-(3(3-carboxy-5-oxo-1-(2,5disulfonatophenyl)-2-pyrazolin-4ylidene)-1-propenyl)-1-bira Zolylcobenzene-2,5-disulfonate-disodium salt N,N'-(4,8-dihydroxy-9,10dioxo-3,7-cissulfonatoanthracene 1,5-diyl)bis(aminomethanesulfonate) )-tetrasodium salt [3-cyano-5-hydroxy-4-(3-(3cyano-5-oxo-1-(4-sulfonatophenyl)-2-
Pyrazolin-4-ylidene)-1pentanyl)-1-pyrazolyl]Hensen-4-sulfonato sodium salt (layer structure) The composition of each layer is shown below. The numbers represent the coating amount (g/rd). The silver halide emulsion represents the coated amount in terms of silver.

Antifading agent (Cpd-3) Antifading agent (Cpd-4) ? Container (Solv-1)? Container (Solv-2) Fourth layer (color mixing prevention layer) Gelatin color mixing prevention agent (Cpd-2) Ultraviolet absorber (UV-1) Ultraviolet absorber (UV-2) Solvent (Solv-1) Solvent (S01■ -2) Fifth layer (red-sensitive layer) Silver chlorobromide emulsion (AgBr: 2 mol%, child size 0.5μ) Gelatin cyan coupler (ExC-1) Cyan coupler (ExC-2) Antifading agent (Cpcl- 1)? Container (Solv-1)? Container (Solv-2) 0.23 0.11 0.20 0.02 1.70 0.065 0.45 0.23 0.05 0.05 Cube, grain 0.19 1.80 0.26 0 .12 0.20 0.16 0.09 Sixth layer (ultraviolet absorption layer) Gelatin 0.70 ultraviolet absorber (UV-1) 0.26 ultraviolet absorber (UV-2) o, o'7 solvent (
Solv-1) 0.30 solvent (S
olv-2) 0.09 Seventh layer (protective layer) Gelatin 1.07 (E
x Y) Yellow coupler α-Vivalyl α-(3-benzyl-1-hydantoynyl)-2-chloro-5[β-(dodecylsulfonyl)-
butylamide] acetanilide (ExM) magenta coupler 1-(2,4,6-1-dichlorophenyl)-3[2
-chloro-5(3-octadecenylsuccinimide)anilino]-5-pyrazolone (ExC-1) cyan coupler 2-pentafluorobenzamide-4-ria.

5[2-(2,4-di-tCrt-amylphenoxy)
-3-methylbutyramidophenol (Solv-4)
Solvent NN-diethylcarbonamidomethoxy-24-amylhenzene (UV-1) UV absorber 2-(2-hydroxy-3,5-di-terL-amyl phenyl)benzotriazole (tJV-2) UV absorber 2- (2-Hydroxy-3,5-di-tertbutylphenyl)hensotriazur (Solv-1) Solvent di(2-ethylhexyl) phthalate (Solv-2)? The sample obtained in the above manner was designated as A. Next, sample A
Samples were prepared in which the halogen composition of the silver chlorobromide emulsion in the red-sensitive emulsion layer was changed as shown in Table 1, and these were designated as samples BE.

(ExC-2) Cyan coupler 2.4-dichloro-3-methyl-6-[α-(24-di-tert-amylphenoxy)butyramide]phenol (Cpd-1) Antifading agent 25-di-tert-amyl phenyl 35 ter
t-butyl hydroxyhenzoate (Cpd-2) Color mixing inhibitor 25-tert-octylhydroquinone (Cpd
-3) Antifading agent ■, 4-di-tert, -amyl-25-dioctyloxybenzene (Cpd-4) Antifading agent 2.2'-methylenebis(4-methyl-6-tertbutylphenol) (Cpd -5) p-(p-)luenesulfonamide) phenyldodecane (Solv-3) Solvent di(i-nonyl)phthalate Table 1 In order to investigate the photographic properties of these coated samples, the following experiments were conducted. I did it.

First, a coated sample was subjected to gradation exposure for sensitometry using a sensitometer (Model FWH manufactured by Fuji Photo Film Co., Ltd., color temperature of light source: 3200 K). The exposure at this time was carried out at an exposure time of 1/10 second and an exposure amount of 250 CMS.

The coating sample was subjected to the following treatment process and the following treatment composition,
Processed with an automatic processor. However, the composition of the color developer was changed as shown in Table 2.

Missing "4" LUL name - Plate color development
Bleach and fix at 38°C for 45 seconds 30-36°
Rinse for 45 seconds at C ■ Rinse for 30 seconds at 30-37°C ■
Rinse for 30 seconds at 30-37°C 30-37°
Dry at C for 30 seconds. Dry at 70-80°C for 60 seconds. The composition of each treatment solution is as follows.

left i two tan one wisteria water Edgelenediamine-N.

N, N, N-tetramethylenebosphonic acid organic preservative A ([-1) Thorium chloride Potassium bromide Potassium carbonate N-ethyl-N-(β methanesulfonamidoethyl)-3-methyl 00ml 3.0g 0.03 mo+ See Table 2 See Table 2 5 g Yuuke 2 (liquid ion exchange water (calcium, magnesium each 3 ppm
Below) Red sensitivity S of the above-treated sample (sensitivity is the reciprocal of the exposure amount required to bring about a cyan density of 0.5, expressed as a relative value with the sensitivity to the sample as 100), maximum cyan density Dmax and minimum flow rate Dmin were measured and the results are shown in Table 2.

Furthermore, the aperture ratio (opening area/liquid volume) of the above color developer
After aging at room temperature for 2 weeks at 0.02CT11-', sensitometric evaluation was performed using it. The increase ΔDmin in the minimum cyan density of the developer over time was measured, and the results are shown in Table 2.

4-aminoaniline sulfate triethanolamine fluorescent brightener (4,4' diaminostilhene type) Add sodium sulfite water to pH (25°C) Ammonium thiosulfate (70%) Sodium sulfite Ethylenediaminetetraacetic acid 1 (III) Ammonium Ethylenediaminetetraacetic acid monosodium Ammonium bromide Glacial acetic acid Add water and pH (25°C) 5.0g 10.0g 2.0g 0.01 g 000mj 10.05 400m! 100 relatives 7g 5g g 0g g 1000% 5.40 As is clear from the results in Table 2, the image forming method of the present invention has high sensitivity, high maximum density, low minimum density, and continuous processing. The feature is that there is little variation in photographic properties (minimum density) associated with .

Example 2 A multilayer color photographic paper having the layer structure shown below was prepared on a paper support which was laminated on both sides with polyethylene. The coating solution was prepared as follows.

19.1 g of yellow coupler (Ex Y), 4.4 g of color image stabilizer (Cpd-1) and color image stabilizer (Cp
d-7) Add and dissolve 27.2 cc of ethyl acetate and 8.2 g of solvent (Solv-3) to 0.7 g, and dissolve this solution in 1
The mixture was emulsified and dispersed in 185 cc of a 10% gelatin aqueous solution containing 8 cc of 0% sodium dodecylbenzenesulfonate.

On the other hand, bulk silver bromide emulsion (cubic average grain size 0.88μ,
Particle size distribution coefficient of variation 0.08, silver bromide 0.2 mol%
(contains on the particle surface) and the blue-sensitive sensitizing dye shown below is added to silver 1.
Sulfur sensitization was prepared after addition of 2.0 x 10-' moles per mole of each.

Green-sensitive emulsion layer (4.OXl0-' mol per mol of silver halide)
The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a first layer coating solution having the composition shown below. Coating solutions for the second to seventh layers were also prepared in the same manner as the coating solution for the first layer. The gelatin hardening agent for each layer is 1-oxy-3
,5-dichloro-S triazine sodium salt was used.

The following spectral sensitizing dyes were used in each layer.

Blue-sensitive emulsion layer SO3H.N(CJs)3 (CH2)4 (CL)3 503)IN(C2H5)3 (2.0 x 104 moles each per mole of silver halide) Red-sensitive emulsion layer C2)15 ■ C31) (0.9 Xl0-' mol per 1 mol of silver halide)
The following compound was added to the red-sensitive emulsion layer in an amount of 2.6 Xl0-3 mol per mol of silver halide.

In addition, for the blue-sensitive emulsion layer, the green-sensitive emulsion layer, and the red-sensitive emulsion layer, 1-(5-methylureidophenyl)5-mercaptotetrazole was halogenated at 8.5 x 10-5 mol per 1 mol, respectively. .7X10-'mol, 2.5
X10-' moles were added.

The following dyes were added to the emulsion layer to prevent irradiation.

and third layer (green-sensitive layer) silver chlorobromide emulsion (1:3 mixture (Ag mole ratio) of cubic average grain size of 0.55μ and 0.39μ). Coefficient of variation of particle size distribution 0.10.0.08゜A g B r
0.8 mol% was locally contained on the particle surface.

Gelatin magenta coupler (ExY) Color image stabilizer (Cpd-3) Color image stabilizer (Cpd-8) Color image stabilizer (Cpd-9) Solvent (Solv-2) Fourth layer (ultraviolet absorption layer) Gelatin ultraviolet absorption Agent (LJV-1) Color mixing inhibitor (Cpd-5) Solvent (Solv-5) 0.12 1.24 0.27 0.15 0.02 0.03 0.54 1.58 0.47 0.05 0.24 (Layer structure) The composition of each layer is shown below. The numbers represent the coating amount (g/po). The silver halide emulsion represents the coated amount in terms of silver.

Support polyethylene laminate paper [The polyethylene on the first layer side contains a white pigment (TiOz) and a blue dye (ulmarine blue)] Layer - (blue sensitive layer) Silver chlorobromide emulsion 0.30 Gelatin 1.86 Yellow coupler (ExY) 0.82 Color image stabilizer (Cpd-1) 0.19 Solvent (So
lv-3) 0.35 color image stabilizer (
Cpd-7) 0.06 Second layer (color mixing prevention layer) Gelatin 0.99 Color mixing prevention agent (Cpd-5) 0.08 Solvent (
Solv-1) 0.16 solvent (S
o I v-4) 0.08 Fifth layer (red sensitive layer) Silver chlorobromide emulsion (cubic, average grain size 0.23 s.
14 mixtures of 58μ and 0.45μ (Ag molar ratio). A particle size distribution coefficient of variation of 0.09.0.11° A g Br 0.6 mol % was locally contained in a part of the particle surface.

Gelatin 1.34 Cyan coupler (ExC) 0.32 Color image stabilizer (Cpd-6) 0.17 Color image stabilizer (Cp d -10) 0.04 Color image stabilizer (Cpd-7) 0.40 Solvent (So I v-6) 0.15 6th layer (ultraviolet absorption layer) Gelatin 0.53 ultraviolet absorber (UV-1'IO, 16 color mixing inhibitor (Cpd-5) 0.02 solvent (
Solv-5) 0.08 7th layer (
Protective layer) Gelatin 1.33 Acrylic 0.1 fully modified copolymer of polyvinyl alcohol (degree of modification 17%) Liquid paraffin 0.03 = 115 (ExC) Cyan coupler R = C2H5°C, H7 (Cpd ■) Color image Stabilizer (ExY) Yellow coupler (Ex M) Magenta coupler (Cpd 3) Color image stabilizer (Cpd 5) Color mixture inhibitor 1B (Cpd 6) Color image stabilizer Cp.

2:4 =4 mixture (weight ratio) (Cpd 7) Color image stabilizer (CH2-CIf +□ C0NHCJ9(t) Average molecular weight 60,000 (Solv 1) Solvent (Solv 2) Solvent (Solv 3) Solvent (Solv 4) Solvent (Cpd-9) Color image stabilizer (Cpd 10) Color image stabilizer H (UV-1) Ultraviolet absorber l 4:2 :4 mixture (weight ratio) (Solv-5) Solvent C00CaH+y (CHI)II COOC++H+.

The sample obtained as above was designated as F.

After imagewise exposure of the sample F in the same manner as in Example 1, continuous processing (running test) was performed using a paper processing machine in the following processing steps until twice the tank capacity of the color developer was replenished.

Processing degree star-degree rich-plate week, tJL"-seg 猌 amount color development 3B"C45 seconds 100 relatives 4! Bleach fixing 30~36°C 45 seconds 61d 41 stable ■30~
37°C 30 seconds -2r stable ■ 30~37°C 30 seconds -21 stable ■ 30~37°C 30 seconds 364m1 21 dry
Drying at 70-85°C for 60 seconds *Replenishment amount per 1M of photosensitive material The composition of each processing solution is as follows.

[Tank liquid]

water 00mf triethanolamine potassium chloride potassium bromide potassium carbonate N-ethyl-N-(β-methyl Tansulfonamidoethyl )-3-methyl-4 Aminoaniline sulfate Organic preservative (n-19) Fluorescent brightener (manufactured by Sumitomo Chemical) WH [TEX-4) add water pH (25°C) (3 rounds with KCH or H2SO4) Tora Moroshi 1 release [Tank liquid] water Ammonium thiosulfate (70X) ammonium sulfite Iron ethylenediaminetetraacetate 12g/l See table 3 See table 3 26g/f 9g/N 7g/1 2.5g # 000m1 IQ, 55 400m flood 100mff1 8g Ethylenediamine-N.

N,N'N'-tetramethylenephosphonic acid triethanolamine sodium chloride potassium bromide potassium carbonate N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4 aminoaniline sulfate organic preservative A (n-19) Fluorescent brightener (WHrTEX-4 manufactured by Sumitomo Chemical) Add water to pH (25°C) [Replenisher] Ethylenediamine-N N,N'N'-tetramethylenephosphonic acid 3.0 g 8. 0g See Table 3 See Table 3 5g 5.0g 0.03mol 1.0g 1000mff 10.05 3g/E (III) Ammonium 55g Disodium ethylenediaminetetraacetic acid 5g Glacial acetic acid
Add 9g water
1000m! pH (25°c)
5.40 [Replenishment solution] 2.5 times concentrated solution of tank solution Water drained (tank solution and replenishment solution are the same) Ion exchange water (calcium and magnesium are 3p each)
pm or less) In addition, for color developing solution, bleach-fixing solution, and washing solution,
Distilled water was added in the same amount as the evaporated water, and continuous treatment was carried out while evaporating and concentrating under pressure.

The maximum cyan density Dmax, the minimum density Dmin at the start of the running test, and the increase Dmin in the minimum cyan density until the end of the running test were measured, and the results are shown in Table 3.

As is clear from the results in Table 3, the effect of the image forming method of the present invention is also recognized in the system of the multilayer coating sample used in Example-2.

(Effects of the Invention) The present invention provides an image forming method with high sensitivity, high maximum density, low minimum density, and significantly suppressed fluctuations in photographic properties (particularly minimum density) due to continuous processing.

Patent applicant: Fuji Photo Film Co., Ltd. Procedural Amendment (,
) Indication of the case Showa t3 year patent application no. The engraving of the A document (no changes to the contents)'t-t-submission.

name of invention A person who corrects the image forming method of silver halide color photographs. Relationship with the incident

Claims (1)

[Claims] A silver halide color photographic light-sensitive material comprising at least one blue-sensitive silver halide emulsion layer, one green-sensitive silver halide emulsion layer, and one red-sensitive silver halide emulsion layer coated on a support. In an image forming method that involves processing with a color developer containing a type of aromatic primary amine color developing agent, the red-sensitive silver halide emulsion layer has a silver bromide content of 0.5 mol % or more and 6 mol % or more. A silver halide color light-sensitive material containing a high silver chloride silver halide emulsion with a mole % or less of chloride ions of 3.5 x 10^-^2 to 1.5 x 1
Contains 0^-^1 mol/l and 3.0x bromide ions
An image forming method for silver halide color photography, characterized by processing with a color developer containing 10^-^5 to 1.0 x 10^-^3 mol/l.