JPS6311941A - Processing method for silver halide color photosensitive material - Google Patents

Abstract

PURPOSE:To shorten the time for respective processes by incorporating substantialy no benzyl alcohol into a liquid color developer and specifying all of the time for bleach fixing and rinsing to <=70 seconds. CONSTITUTION:An exposed silver halide color photosensitive material is subjected to a color developing process then to a bleach fixing process and further to a rinsing process. The processing soln. for the color developing process contains substantially no benzyl alcohol and all of the time for the bleach fixing process and the rinsing process is <=70 seconds. The prepn. of the liquid color developer is facilitated by removing the benzyl alcohol from the liquid color developer, by which the contamination of a color developing tank of a processing machine is decreased and the stains sticking to the photosensitive are decreased as well.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for processing silver halide color light-sensitive materials, and more particularly to a processing method in which the processing time after color development is shortened. Another object of the present invention is to provide a color photographic material that has excellent color reproducibility and color image stability.

(Prior Art) In general, the standard processing steps for silver halide color light-sensitive materials include a color development section (about 3 minutes and 30 seconds) that forms a color image, a bleach-fixing (or bleach-fixing) section that is a desilvering step (
(approximately 1 minute and 30 seconds), a water washing section, and/or an image stabilization section (2 to 3 minutes).

Incidentally, with the recent shortening of finishing delivery times and the reduction of laboratory work, it has been desired to shorten the processing time.

Many studies have been made to shorten the color development process. For example, a method using a development accelerator (U.S. Patent No.
No. 950970, No. 2515147, No. 249690
No. 3, No. 2304925, No. 4038075, No. 4
119462, British Patent No. 1430998, British Patent No. 145
5413, JP-A-53-15831, JP-A No. 55-62
No. 450, No. 55-62451, No. 55-62452
U.S. Pat.
No. 3342597, JP 56-6235, JP 56-16133, JP 57-97531, JP 57-
83565, etc.), a method using silver chloride emulsion (JP-A-58-95345, JP-A-59-232)
342, No. 60-19140, etc.), or a method of increasing the temperature or pH of a color developer.

Next, when shortening the desilvering step, it is clear that a -bath bleach-fixing step is more advantageous than a bleach-fixing step having two baths because of the reduction in the number of processing baths. However, there are few prior art methods for accelerating the bleach-fixing process, and only a limited number of accelerators have been studied.
Examples include compounds having a mercapto group or a disulfide group as described in No. 812, etc.; thiourea derivatives as described in U.S. Pat. However, none have a sufficient promoting effect.

By the way, when the bleach-fixing time is set to 70 seconds or less as described in the present invention, desilvering failure and cyan dye leucoization (decolorization failure) often occur during continuous processing, making it impractical. Ta.

Furthermore, conventional techniques for shortening the washing time include adding a chelating agent, foaming, and strengthening stirring, but the effects are not sufficient.

By the way, if the washing time is 70 seconds or less, the image preservation will deteriorate, and if the amount of water used for washing is significantly reduced, the image preservation will not only deteriorate, but also floating particles will be present in the washing bath. is generated and adheres to photosensitive materials, causing malfunctions. Conventionally, various antifading agents have been added to color photosensitive materials for the purpose of improving image storage stability (for example, U.S. Pat. Nos. 2,816,028, 3,457,079, and 369).
No. 8909, No. 3764337, No. 3700455, etc.), these anti-fading agents become ineffective if the water washing process time is 70 seconds or less.

Furthermore, although the magenta coupler shown by the general formula (1) has the advantage of providing a pigment with very good hue, when it is processed normally, magenta tint is generated after processing. In particular, when the processing time of the bleach-fixing step and the water-washing step is shortened as in the present invention, the coupler has the disadvantage that the generation of stain becomes more noticeable and cannot be used for rapid processing.

(Problems to be Solved by the Invention) Therefore, the purpose of the present invention is to simultaneously solve all of the above-mentioned problems, and more specifically, to provide a processing method in which each processing time is shortened. It is intended to provide
Furthermore, it is an object of the present invention to provide a photosensitive material and a processing method with excellent processing stability.

(Means for Solving the Problems) The above aspects of the present invention include a silver halide color light-sensitive material,
In a method in which bleach-fixing and water washing are performed after color development, the color developer substantially does not contain benzyl alcohol, and the bleach-fixing and water washing are both 70 seconds or less. Preferably, the silver halide color photosensitive material contains a magenta coupler of the following general formula (1). This was achieved by a method of processing color photographic materials.

General formula (1) (In the formula, Rb represents a hydrogen atom or a substituent, Y represents a group that can be separated by a coupling reaction with an oxidized aromatic primary amine developing agent, and Za, Zb or Zc is Represents a methine group, substituted methine group, =N- or -NH-, Z
One of the a-Zb bond and the Zb-Zc bond is a double bond, and the other is a single bond. ) By removing benzyl alcohol from the color developer, it becomes easier to prepare the color developer, and
The amount of dirt in the color developing tank of the processing machine has been reduced. In addition, stains adhering to photosensitive materials were also reduced. Furthermore, the occurrence of magentastin described above was also prevented, and a stable image with good hue could be obtained.

Each treatment step in the present invention will be explained in detail below.

In the color development process of the present invention, the processing time is 30 seconds to 3 minutes and 30 seconds. Preferably 45 seconds to 2
The duration is 30 seconds, and the shorter the better if sufficient color density can be obtained.

The color developing solution used in the development process of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. As this color developing agent, p-phenylenediamine compounds are preferably used, and typical examples thereof include 3-methyl-4-amino-N, N-diethylaniline, and 3-methyl-4-amino-N-ethyl-N. −
β-hydroxylethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N
-β-methoxyethylaniline and their sulfates,
hydrochloride, phosphate or p-toluenesulfonate,
Examples include tetraphenylborate and p-(t-octyl)benzenesulfonate.

Aminophenol derivatives are also useful, e.g.
These include aminophenol, p-aminophenol, 4-amino-2-methylphenol, 2-amino-3-methylphenol, 2-oxy-3-amino-1,4-dimethylbenzene, and the like.

In addition, "Photographic Processing Chemistry" by F. A. Meson, Focal Press (
1966) (L, F, A, Mason.

”Photographic Processing
Chemistry”, FocalPress
), pages 226-229, U.S. Pat. No. 2,193.015, U.S. Pat. If necessary, two or more color developing agents may be used in combination.

The processing temperature of the color developer in the present invention is 30°C to 5°C.
The temperature is preferably 0°C, more preferably 33°C to 45°C.

The development accelerator does not substantially contain benzyl alcohol, but various other known compounds may also be used. For example, U.S. Pat.
-9503, various pyrimidilam compounds and other cationic compounds represented by U.S. Patent No. 3,171,247, cationic dyes such as phenosafranin, neutral salts such as thallium nitrate, Japanese Patent Publication No. 9304/1983, Nonionic compounds such as polyethylene glycol, derivatives thereof, and polythioethers described in U.S. Patent Nos. 2,533.990, 2,531.832, 2.95Q, 970, 2.577, and 127; Patent 3,201
, 242, and other compounds described in JP-A-58-156934 and JP-A-60-220344.

In the present invention, substantially not containing benzyl alcohol means that the benzyl alcohol concentration in the color developer is 2. Om j! / Il, preferably less than 0.5 m (l, more preferably not at all).

Antifoggants in color development include alkali metals such as potassium bromide, electrified sodium, and potassium iodide;
Halides and organic antifoggants are preferred. Examples of organic antifoggants include benzotriazole, 6-
Nidropenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-
Nitrogen-containing heterocyclic compounds such as thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, adenine, and hydroxyazaindolizine; and mercapto compounds such as 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole, and 2-mercaptobenzothiazole. Substituted heterocyclic compounds can also be used, as well as mercapto-substituted aromatic compounds such as thiosalicylic acid. Particularly preferred are halides. These antifoggants may be eluted from the color photosensitive material during processing and accumulated in the color developer.

In addition, the color developer according to the present invention includes pH buffering agents such as carbonates, borates or phosphates of alkali metals; hydroxylamine and triethanolamine; preservatives such as sulfites or bisulfites; organic solvents such as diethylene glycol; dye-forming couplers; competitive couplers; nucleating agents such as sodium boron hydride; such as 1-phenyl-3-pyrazolidones. Auxiliary developer: viscosity imparting agent; ethylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, N-hydroxymethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, and JP-A-58-195845
Aminopolycarboxylic acid, 1-hydroxyethylidene-1,1'-diphosphonic acid, typified by the compounds described in No.
isclosure ) NIL 18170 (197
organic phosphonic acid, aminotris (methylene phosphonic acid), ethylenediamine-N, N, N',
Aminophosphonic acids such as N'-tetramethylenephosphonic acid, JP-A-52-102726, JP-A-53-42730
No. 54-121127, No. 55-4024, No. 55-4025, No. 55-126241, No. 55-
No. 65955, No. 55-65956, and Research Disclosure.
chelating agents such as phosphonocarboxylic acids described in No. N118170 (May 1979).

In addition, the color developing bath can be divided into two or more parts as necessary.
Replenish color developer replenisher from the first bath or last bath,
The development time may be shortened or the amount of replenishment may be reduced.

In the present invention, after the color development process, the developed silver is subjected to a bleach-fixing process. The bleach-fixing time is as short as 70 seconds or less, preferably 1 minute or less, and more preferably 20 seconds to 1 minute.

Bleaching agents that can be used include, for example, organic complex salts of iron (III) or cobalt (■) (e.g., aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, and organic phosphonic acid). complex salts) or organic acids such as citric acid, tartaric acid, and malic acid; persulfates; hydrogen peroxide, etc.

Can be used. Among these, iron(III) organic complex salts are preferable from the viewpoint of rapid processing and prevention of environmental pollution.
Aminopolycarboxylic acids or aminopolyphosphonic acids or salts thereof useful for forming organic complex salts of iron (In) are listed as follows: ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediamine-N-(β-oxyethyl)-N , N
',N'-triacetic acid, 1,3-diaminopropanetetraacetic acid, triethylenetetraminehexaacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, nitrilotripropionic acid, cyclohexanediaminetetraacetic acid, 1,3-diamino-2-propanol Tools Tetraacetic acid, Methyliminodiacetic acid, Iminoniacetic acid, Hydroxyliminodiacetic acid, Dihydroxyethylglycine ethyl ether diamine tetraacetic acid, Glycol ether diamine tetraacetic acid, Ethylenediaminetetrapropionic acid, Ethylenediamine nipropionic acid, Phenylendiaminetetraacetic acid, 2-phosphonobutane-1 , 2,4-triacetic acid, 1,3-diaminopropanol-N, N, N'.

N'-tetramethylenephosphonic acid, ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid, 1,3-propylenediamine-N,N,N'.

N'-tetramethylenephosphonic acid, 1-hydroxyethylidene-1,1'-diphosphonic acid, etc. can be mentioned.

Among these compounds, iron (I[[
) Complex salts are preferred because they have a high bleaching edge.

The iron (I [ Ferric ammonium, ferric phosphate, etc.) and a chelating agent (aminopolycarboxylic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.) may be reacted in a solution to form a ferric ion complex salt. When forming a pre-formed complex salt, one or both of the ferric salt and the chelating agent may be used in combination of two or more;
In either case of complex salt formation, the chelating agent may be used in an amount greater than the stoichiometric amount, and the bleach or bleach-fix solution containing the ferric ion complex may contain metal ions other than iron, such as cobalt and copper, and metal ions such as cobalt and copper. may contain a complex salt of or hydrogen peroxide.

The amount of bleach per bleach-fix solution 11 is 0.075 to 2
．． 0 mol is suitable, preferably 0.1 to 0.5 mol.

The fixing agent used in the present invention is a known fixing agent, namely, thiosulfates such as sodium thiosulfate and ammonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate; ethylene bisthioglycolic acid; Thioether compounds such as s-dithia-1,8-octanediol and water-increasing silver halide shaving agents such as 1,000 urea, which can be used alone or in combination of two or more. . Furthermore, in the bleach-fixing process, a special bleach-fixing solution consisting 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 can also be used.
In the present invention, the use of thiosulfates, particularly ammonium thiosulfates, is preferred.

The amount of fixing agent per bleach-fix solution IAI is preferably from 0.3 to 3 mol, more preferably from 0.5 to 15 mol.

The pH range of the clean fixer in the present invention is preferably 4-9, more preferably 5-7.5. If pll 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. When the reverse pH is higher than this, desilvering is delayed and staining is 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. Qtk+v Q l z-%'f M &r
In addition, the bleach-fix solution of the present invention may contain bromides (e.g., potassium bromide, sodium bromide, ammonium bromide) or chlorides (e.g., potassium chloride, sodium chloride, ammonium chloride) or iodide (e.g. ammonium iodide)
rehalogenating agents. Boric acid, borax, sodium metaborate, acetic acid, sodium acetate, as required
p) One or more inorganic acids, organic acids and their alkali metal or ammonium salts having buffering capacity, such as sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, etc.; Corrosion inhibitors such as ammonium nitrate and guanidine can be added.

Furthermore, in addition to the above-mentioned additives that can be added to the bleach-fix solution, preservatives such as sulfites (e.g., sodium sulfite, potassium sulfite, ammonium sulfite), bisulfites, hydroxylamine, hydrazine, bisulfite of aldehyde compounds, etc. A chloride (eg, acetaldehyde sodium bisulfite) or the like may be included. Furthermore,
Various fluorescent brighteners, antifoaming agents, surfactants, polyvinylpyrrolidone, organic solvents such as methanol, etc. can be contained.

1. Also, a bleach accelerator can be used in the bleach-fix solution and its pre-bath, if necessary. Specific examples of useful bleach accelerators are described in Meiji II: U.S. Pat. No. 3.893.858, German Patent No. 1.290.8.
No. 12, No. 2,059,988, JP-A-53-327
No. 36, No. 53-57831, No. 37418, No. 5
No. 3-65732, No. 53-72623, No. 53-9
No. 5630, No. 53-95631, No. 53-1042
No. 32, No. 53-124424, No. 53-14162
No. 3, No. 53-28426, Research Disclosure N [No. L17129 (July 1978), etc. Compounds having a mercapto group or disulfide group; Thiazolidine derivatives such as those described in JP-A-50-140129 ;Special Publication No. 45-8506, Japanese Patent Publication No. 1973
Thiourea derivatives described in West German Patent No. 2-20832, West German Patent No. 53-32735, and US Pat. West German Patent No. 966.410, 2,
Polyethylene oxides as described in No. 748.430;
Polyamine compounds described in JP-A-45-8836; other JP-A-49-42434, JP-A-49-59644, JP-A-53-94927, JP-A-54-35727, JP-A-5
Compounds described in No. 5-26506 and No. 5B-163940 and iodine and bromide ions can also be used. Among these, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large promoting effect, and are particularly preferred in US Pat.
No. 93.8513, West German Patent No. 1.290.812,
Compounds described in JP-A-53-95630 are preferred.

In the processing method of the present invention, the amount of bleach-fix solution to be replenished to the bleach-fix bath is arbitrary, but is 5 to 100 times the weight of the pre-bath solution attached to the photosensitive material, preferably 1 It is preferable to increase the amount by ~10 times.

In the present invention, the bleach-fixing process is followed by the washing process.

In the present invention, instead of the usual "washing process", a more convenient processing method may be used, such as not providing a substantial washing process and only performing a so-called "stabilization process" that achieves image stability better than washing with water. can.

As described above, the term "water washing treatment" as used in the present invention is used in the broad meaning described above.

The washing time in the present invention is 70 seconds or less, preferably 20 seconds to 1 minute, and more preferably 30 seconds to 1 minute. The washing time here refers to the period of time from when the photosensitive material comes into contact with the washing water until it reaches the drying zone, which is the final process, during which the photosensitive material is substantially in contact with the washing aqueous solution, etc. in a broad sense. It represents time and does not include air time for movement. The above definition is also applicable when a so-called "stabilization treatment" is carried out instead of ordinary water washing, and represents the contact time with the stabilizing liquid.

The amount of aqueous solution used in the water washing in the broad sense of the present invention is difficult to specify because it varies depending on the number of baths in the multistage countercurrent washing and the amount of pre-bath components brought into the photosensitive material. It is sufficient if the bleach-fixing solution component is 1X10-' or less. For example, in the case of simple water washing with 3 tanks countercurrent, it is preferable to use about 1,000 mj or more per 1 resistant light material, more preferably 5,000 mj! That's all.

On the other hand, in the case of water-saving processing, 0.1 to 50 times the weight of the bleach-fix solution that adheres to the photosensitive material and is brought into the first washing bath.
Preferably 1 to 10 times (for example, 100 times per 1 d of photosensitive material)
It is advisable to replenish the washing bath with ~1000 rrj of aqueous solution.

The water washing temperature is 15°C to 45°C, more preferably 20°C to 3°C.
The temperature is 5°C.

In the washing process, for the purpose of preventing precipitation and stabilizing the washing water,
Various known compounds may be added. For example, chelating agents such as inorganic phosphoric acid, aminopolycarboxylic acid, and organic phosphonic acid; bactericides and anti-inflammatory agents that prevent the growth of various bacteria, algae, and molds (for example,・Antifungal Agents” (J.

Antibact, ^ntifung, Agents
) vol, 115N15, p207-223 (
(1983) and compounds described in Hiroshi Horiguchi's "Chemistry of Antibacterial and Antifungal", metal salts such as magnesium salts and aluminum salts, alkali metal and ammonium salts, or to prevent dry load and unevenness. A surfactant and the like can be added as necessary. Or West's ``Photograph Inc. Science and Engineering Magazine J (Pho, t, Sci.
Eng.), No. 6S, pp. 344-359 (1965
) etc. may be added.

Furthermore, chelating agents, bactericides, and anti-piping agents are added to the washing water.
The present invention is particularly effective when the amount of washing water is significantly reduced by multistage countercurrent washing using two or more tanks. It is also particularly effective when carrying out a multi-stage countercurrent stabilization process (so-called stabilization process) as described in JP-A-57-8543 instead of the usual water washing process. In these cases, the bleach-fix components of the final bath should be less than or equal to 5X10-'', preferably 1X
It is sufficient if it is less than 10-''.

Various compounds are added to the stabilizing bath after water washing, preferably a stabilizing bath substituted for the water washing bath, for the purpose of stabilizing the image. For example, various compounds are added to adjust the membrane pH (for example, pH 3 to 8). Buffers (for example, borates, metaborates, borax, phosphates, carbonates, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acids, dicarboxylic acids, polycarboxylic acids, etc., used in combination); Aldehydes such as formalin can be cited as a representative example.

In addition, chelating agents (inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphonic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), fungicides (thiazole type, isothiazole type, halogenated phenol, sulfanilamide,
benzotriazole, etc.), surfactants, fluorescent brighteners,
Various additives such as hardening agents may be used, and two or more compounds for the same or different purposes may be used in combination.

In addition, it is preferable to add various ammonium salts such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate to improve the image storage stability.

In this treatment step, during continuous treatment, a constant finish can be obtained by using a replenisher for each treatment solution to prevent fluctuations in the liquid composition. The replenishment amount can be reduced to half or less than the standard replenishment amount to reduce costs.

Each treatment bath may be provided with a heater, a temperature sensor, a liquid level sensor, a circulation pump, a filter, various floating pigs, various squeegees, nitrogen stirring, air stirring, etc., as necessary.

Next, details of the magenta coupler represented by general formula (I) will be explained.

In the general formula (1), R5 represents a hydrogen atom or a substituent, and Yl represents a hydrogen atom or a group that can be separated by a camping reaction with an oxidized aromatic primary amine developer. Za , Zb and Zc are methine, substituted methine, =
Represents N- or -NH-, and combines Za-Zb bond and Zb-
One of the Zc bonds is a double bond and the other is a single bond.

When Zb-Zc is a carbon-carbon double bond, it includes the case where it is a part of an aromatic ring, and also includes the case where R1 or Yl forms a dimer or more multimer. Also Za SZ
When b or Zc is a substituted methine, the substitution thereof (including the case where a multimer of 2ffi or more is formed with negative methine).

-a In formula (1), multimer means one having two or more groups represented by general formula (1) in one molecule, and this also includes bis-forms, oligomers, and polymer couplers. included. Here, the polymer coupler may be a homopolymer consisting only of a monomer having a moiety represented by the general formula [1] (preferably one having a vinyl group, hereinafter referred to as vinyl carmer), or an aromatic-class amine. Copolymers may be made with nonchromogenic ethylene-like monomers that do not camp with the oxidation products of the developer.

-FIQ The compound represented by formula (1) is a 5-membered ring-5-membered ring fused nitrogen heterocyclic coupler, and its color-forming nucleus exhibits isoelectronic aromaticity with naphthalene, and is usually collectively referred to as azapentalene. It has a chemical structure. Preferred compounds among the couplers represented by the formula (1) are IH-imidazo(1,2-b) bilasie, IH-imidazo(1,5-b) pyrazole, IH-pyrazolo(5 ，
1-C)(1,2,4) triazoles, IH-pyrazolo(1,5-b)(1,2,4) triazoles, IH-pyrazolo(1,5-d)tetrazoles and IH-pyrazolo (1,5-a) benzimidazoles, each having the general formula (n) (III) CI'
/)(V) Among these compounds represented by (Vl) and [■], particularly preferred compounds are (IV) and (V).

Substituents Rt, Rz and R of general formulas (II) to [■]
1 is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an acyloxy group, a carbamoyloxy group, a silyloxy group, a sulfonyloxy group, an acylamino group, Anilino group, ureido group, imido group, sulfamoylamino group, carbamoylamino group, alkylthio group, arylthio group, heterocyclic thio group, alkoxycarbonylamino group, iri-oxycarbonylamino group, sulfonamide group, carbamoyl group , acyl group,
Represents a sulfamoyl group, sulfonyl group, sulfinyl group, alkoxycarbonyl group, oryloxycarbonyl group, and Y represents a hydrogen atom, a halogen atom, a carboxy group, or a coupling position via an oxygen atom, nitrogen atom, or sulfur atom. Represents a group that is coupled to and decoupled from the carbon of .

The case where R1, R2, R1 or Y becomes a divalent group and forms a bis body is also included. Moreover, general formula (II) ~
When the moiety represented by [■] is present in the vinyl monomer, R,, R1 or R2 represents a simple bond or linking group, and through this, the moiety represented by the general formula (n) to [■] The moiety and the vinyl group are bonded together.

More specifically, R1, Rt and R11 are hydrogen atoms, halogen atoms (e.g. chlorine atom, bromine atom, etc.), alkyl groups (e.g. methyl group, propyl group, t-butyl group, trifluoromethyl group, tridecyl group, 3- (2,
4-di-t-amylphenoxy)propyl group, 2-dodecyloxyethyl group, 3-phenoxypropyl group, 2-
hexylsulfonyl-ethyl group, cyclopentyl group, benzyl group, etc.), aryl group (e.g. phenyl group, 4
-t-butylphenyl group, 2.4-di-t-amylphenyl group, 4-tetradecanamidophenyl group, etc.), heterocyclic groups (e.g., 2-furyl group, 2-chenyl group, 2-tetradecanamidophenyl group, etc.),
-pyrimidinyl group, 2-benzothiazolyl group, etc.), cyano group, alkoxy group (e.g. methoxy group, ethoxy group, 2-methoxyethoxy group, 2-dodecyloxyethoxy group, 2-methanesulfonylethoxy group, etc.), −
(e.g., phenoxy group, 2-methylphenoxy group, 4-t-butylphenoxy group, etc.), heterocyclic oxy group (e.g., 2-benzimidazolyloxy group,
), acyloxy groups (e.g., acetoxy, hexadecanoyloxy, etc.), carbamoyloxy groups (e.g., N-phenylcarbamoyloxy, N-ethylcarbamoyloxy, etc.), silyloxy groups (e.g., trimethylsilyloxy), group, etc.), sulfonyloxy group (e.g., dodecylsulfonyloxy group, etc.), acylamino group (e.g., acetamido group, benzamide group, tetradecanamide group, α-(2゜4-di-t-amylphenoxy)butyramide group) , γ-(3-t-butyl-4-hydroxyphenoxy)butyramide group, α-(
4-(4-hydroxyphenylsulfonyl)phenoxy)decaneamide group, etc.), anilino group (e.g., phenylamino group, 2-chloroanilino group, 2-chloro-5-
Tetradecanamide anilino group, 2-chloro-5-dodecyloxycarbonylanilino group, N-acetylanilino group, 2-'Frollo 5-(α-(3-t-butyl-4
-hydroxyphenoxy)dodecanamido)anilino group, etc.), ureido group (e.g., phenylureido group, methylureido group, N, N dibutylureido group, etc.),
Imide groups (e.g. N-succinimide group, 3-penzylhydantoinyl!, 4-(2-ethylhexanoylamino)phthalimide group, etc.), sulfamoylamino groups (
For example, N,N-dipropylsulfamoylamino M,
N-methyl-decylsulfamoylamino group, etc.), alkylthio group (e.g., methylthio group, octylthio group,
Tetradecylthio group, 2-phenoxyethylthio group, 3
-phenoxypropylthio group, 3-(4-t-butylphenoxy)propylthio group, etc.), -ruthio group (e.g., phenylthio group, 2-butoxy-5-octylphenylthio group, 3-pentadecylphenyl Thio group, 2
-carboxyphenylthio group, 4-tetradecanamidophenylthio group, etc.), heterocyclic group (e.g., 2-
benzothiazolylthio group, etc.), alkoxycarbonylamino group (e.g., methoxycarbonylamino group, tetradecyloxycarbonylamino group, etc.), aryloxycarbonylamino group (e.g., phenoxycarbonylamino group, 2.4-di-tert- butylphenoxycarbonylamino group, etc.), sulfonamide group (e.g.
(methanesulfonamide group, hexadecanesulfonamide group, benzenesulfonamide group, p-)luenesulfonamide group, octadecanesulfonamide group, 2-methyloxy-5-1-butylbenzenesulfonamide group, etc.), carbamoyl! (For example, N-ethylcarbamoyl group, N,N-dibutylcarbamoyl group, N-(2-dodecyloxyethyl)carbamoyl group, N-methyl-N-
dodecylcarbamoyl group, N(3-(2,4-te
rt-amylphenoxy)propyl)carbamoyl group,
etc.), acyl groups (e.g., acetyl group, (2,4-di-tert-amylphenoxy)acetyl group, benzoyl group, etc.), sulfamoyl groups (e.g., N-ethylsulfamoyl group, N,N-diprosulfamoyl group, Pyrsulfamoyl group, N-(2-dodecyloxyethyl)sulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, N, N
-diethylsulfamoyl group, etc.), sulfonyl group (e.g. methanesulfonyl group, octanesulfonyl group, benzenesulfonyl group, toluenesulfonyl group, etc.), sulfinyl group (e.g. octanesulfinyl group, dodecylsulfinyl group, phenylsulfinyl group) ,etc),
Alkoxycarbonyl group (e.g., methoxycarbonyl group, butyloxycarbonyl group, dodecylcarbonyl group, octadecylcarbonyl group, etc.), aryloxycarbonyl group (e.g., phenyloxycarbonyl group, 3
-pentadecyloxy-carbonyl group, etc.),
X is a hydrogen atom, a halogen atom (e.g., chlorine atom, bromine atom, iodine atom, etc.), a carboxyl group, or a group connected by an oxygen atom (e.g., acetoxy group, propanoyloxy group, benzoyloxy group, 2.4- Dichlorobenzoyloxy group, ethoxyoxaroyloxy group, pyruvinyloxy group, cinnamoyloxy group, phenoxy group, 4-cyanophenoxy group, 4-methanesulfonamidophenoxy group, 4-methanesulfonylphenoxy group, α
- Naphthoxy group, 3-pentadecylphenoxy group, benzyloxycarbonyloxy group, ethoxy group, 2-cyanoethoxy group, benzyloxy group, 2-phenethyloxy group, 2-phenoxyethoxy group, 5-phenyltetrazolyloxy group , 2-benzothiazolyloxy group, etc.)
, a group linked via a nitrogen atom (e.g., benzenesulfonamide group, N-ethyltoluenesulfonamide group, heptafluorobucunamide group, 2.3.4.5.6-pentafluorobenzamide group, octane sulfonamide group,
p-Cyanophenylureido M, N, N-diethylsulfamoylamino group, 1-piperidyl group, 5,5-dimethyl-2,4-dioxo-3-oxazolidinyl Li
-benzyl-ethoxy-3-hydantoynyl group, 2N-
1,1-dioxo-3(2H)-oxo-1,2-benzisothiazolyl group, 2-oxo-1,2-dihydro-
1-pyridinyl group, imidazolyl group, pyrazolyl group, 3
．． 5-diethyl-1,2,4-1-riazol-1-yl, 5- or 6-promobenzotriazol-1-
yl, 5-methyl-1,2,3,4-1-riazole-
1-yl group, benzimidazolyl group, 3-benzyl-1
-hydantoinyl group, 1-benzyl-5-hexadecyloxy-3-hydantoinyl group, 5-methyl-1-tetrazolyl group, 4-methoxyphenylazo group, 4-pivaloylaminophenylazo group, 2-hydroxy-4 -propanoylphenylazo group, etc.), a group linked by a sulfur atom (e.g., phenylthio group, 2-carboxyphenylthio group, 2-methoxy-5-t-octylphenylthio group, 4-methanesulfonylphenylthio group, 4-octanesulfonamidophenylthio group, 2-butoxyphenylthio group, 2-(2-hexanesulfonylethyl)-5
-tert-octylphenylthio group, benzylthio group, 2-cyanoethylthio group, 1-ethoxycarbonyltridecylthio group, 5-phenyl-2,3,4,5-tetrazolylthio group, 2-benzothiazolylthio group, 2 -dodecylthio-5-thiophenylthio group, 2-phenyl-
3-dodecyl-1,2,4-)riazolyl-5-thio group, etc.).

When R+, Rz, R3 or is a divalent group to form a bis body, this divalent group can be described in more detail as a substituted or unsubstituted alkylene group (for example, a methylene group, an ethylene group, a 1. 10-decylene group, -CHt
CHt-0-CHz CHt-1, etc.) substituted or unsubstituted phenylene group (e.g. 1°4-phenylene group, 1
．． 3-phenylene group, -NHCO-R? , -〇〇NH
- group (R'l represents a substituted or unsubstituted alkylene group or phenylene group).

When those represented by general formulas (II) to [■] are present in the vinyl monomer, the linking group represented by R, R, or R1 is an alkylene group (substituted or unsubstituted alkylene group, For example, methylene group, ethylene group, 1.10 decylene group, -CHzCHzOCHzCHz-1, etc.), phenylene group (substituted or unsubstituted phenylene group, e.g. 1.4
-phenylene group, 1,3-phenylene group, -NHCO-
It includes groups formed by combining groups selected from 1-CONH-1-〇-1-OCO- and aralkylene groups (eg, etc.).

In addition, the vinyl group in vinyl * is -C formula (n) ~
It also includes cases where it has substituents other than those represented by [■]. Preferred substituents are a hydrogen atom, a chlorine atom, or a lower alkyl group having 1 to 4 carbon atoms.

Acrylic acid, α
- Chloroacrylic acid, α-alacrylic acid (e.g., methacrylic acid, etc.) and esters or amides derived from these acrylic acids (e.g., acrylamide, n-butylacrylamide, t-butylacrylamide, diacetone acrylamide, methacrylamide) , methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl acrylate, 1so-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n- Butyl methacrylate and β
-hydroxymethacrylate), methylene dibis acrylamide, vinyl esters (e.g. vinyl acetate, vinyl propionate and vinyl laurate), acrylonitrile, methacrylateryl, aromatic vinyl compounds (e.g. styrene and its derivatives, vinyltoluene, divinylbenzene) , vinylacetophenone and sulphostyrene), itaconic acid, citraconic acid, crotonic acid, vinylidene, loride, vinyl alkyl ethers (e.g. vinyl ethyl ether), maleic acid, maleic anhydride, maleic esters, N-vinyl-2-pyrrolidone , N-vinylpyridine, and 2- and 4-
Examples include vinylpyridine. It also includes cases where two or more of the non-color-forming ethylenically unsaturated monomers used herein are used together.

Compound examples and synthesis methods of couplers represented by the general formulas (n) to [■] above are described in the documents listed below.

The compound of general formula (n) is disclosed in JP-A-59-162548, etc., and the compound of general formula (Ill) is disclosed in JP-A-60-436.
59 etc., the compound of general formula (IV) is disclosed in Japanese Patent Publication No. 47-2
7411 etc., the compound of general formula (V) is disclosed in JP-A-59-
171956 and Japanese Patent Application No. 59-27745, etc., the compound of general formula (Vl) is disclosed in Japanese Patent Application Laid-Open No. 60-33552, etc.
In addition, the compound of general formula [■] is disclosed in U.S. Patent No. 3.061,
432 etc., respectively.

Also, JP-A-58-42045, JP-A-59-21485
4, No. 59-177553, No. 59-177554, and No. 59-177557, etc., are applicable to any of the compounds of the above general formulas (n) to [■].

Specific examples of the pyrazoloazole coupler used in the present invention are shown below, but the invention is not limited thereto.

(M-1) (Pvl-2) (M-3) (M-4) (M-5) CM-1) Shig (M-8) (M-10) CM-11) (M-12) (M-13) I Lllll co (M-14) 2 (M-15) C11! n-[;ill13 (M-16) (M-17) n-CJ* (M-19) (M-20) n-C, Il, Co (M-22) (M-23) (M-24) 1M (M-25) (M-27) Shi11I7111 (M-28) (M-29) (M-30) (M-31) CM-32) (M-33) (M-35) x:y=50:50 (M-36) x: y −55: 45 (M-37) x: y-50: 50 (M-38) C1l* (M-41) (M-42) Shin@La1l*-11 (M-44) CH.

(M-47) (M-48) C.B.

CM-49) (M-50) CI+2 11.7 tons.

(M-51) (M-52) L;, 11. ([) CM-53) CM-54) (M-55) (M-57) (M-59) In the present invention, various color couplers may be used in addition to the magenta coupler of general formula (I). Can be done. Useful color couplers are cyan, magenta and yellow colored couplers, typical examples of which include naphthol or phenolic compounds, pyrazolones and closed or heterocyclic ketomethylene compounds. , magenta and yellow couplers are listed in Research Disclosure (RD) 1764.
3 (December 1978)■-D Section and 18717
(November 19'79).

The color coupler incorporated in the light-sensitive material is preferably diffusion-resistant by having a ballast group or being polymerized. A two-equivalent color coupler substituted with a leaving group can reduce coated silver (■) more than an equivalent color coupler whose coupling active position is a hydrogen atom. Couplers in which the color-forming dye has adequate diffusivity, non-color-forming couplers, or DIR couplers that release a development inhibitor or couplers that release a development accelerator upon coupling reaction can also be used.

A representative example of the yellow coupler that can be used in the present invention is an oil-protected acylacetamide coupler. A specific example is U.S. Patent No. 2.40
7. ．． No. 210, US Pat. No. 2.875.057 and US Pat. , No. 3.447.928, No. 3.933.501 and No. 4.022.6
20, etc., or Japanese Patent Publication No. 5B-10739, U.S. Patent No. 4
．． No. 401.752, No. 4.326.024, RD
18053 (April 1979), British Patent No. 1.425
．． 020, West German Application No. 2.219,917, West German Application No. 2.261.361, West German Application No. 2,329,587 and West German Application No. 2.433.812, etc. Yellow coupler is a typical example. α-pivaloylacetanilide couplers have excellent color fastness, particularly light fastness, while α-penzoylacetanilide couplers provide high color density. .

As a magenta coupler that can be used in combination with the magenta coupler of general formula (1) of the present invention, an oil-protected indacylon type or cyanoacetyl type, preferably a 5-pyrazolone type, may be used in combination.

The 5-pyrazolone coupler is preferably a coupler in which the 3-position is monosubstituted with an arylamino group or an acylamino group from the viewpoint of the hue and color density of the coloring dye, and a representative example thereof is U.S. Pat. , same No. 2,343,
No. 703, No. 2.600.788, No. 2, 908
．． No. 573, No. 3.062.653, No. 3.15
No. 2.896 and No. 3.936.015, etc.

As the leaving group for the two-equivalent 5-pyrazolone coupler, the nitrogen atom leaving group described in U.S. Pat. No. 4,310,619 or the arylthio group described in U.S. Pat. No. 4,351,897 is preferred; European Patent No. '73.
The 5-pyrazolone coupler having a ballast group described in No. 636 provides high color density.

Cyan couplers that can be used in the present invention include oil-protected naphthol-based and phenolic couplers, such as the naphthol-based couplers described in U.S. Pat. No. 2.474.293, preferably U.S. Pat.
．． No. 212, No. 4.146.396, No. 4.22
Typical examples include two-equivalent naphthol couplers of the oxygen atom elimination type described in No. 8.233 and No. 4.296.200. Further, specific examples of phenolic couplers are given in U.S. Patent Nos. 2,369,929 and 2.8.
No. 01.171, No. 2.772.162, No. 2.
895.826, etc. Humidity and temperature robust cyan couplers are preferably used in the present invention, exemplified by U.S. Pat. No. 3,772.
．． Phenolic cyan coupler having an alkyl group of ethyl group or higher at the meta-position of the phenol nucleus described in US Pat. No. 002, US Pat.
8.308, 4,126.396, 4.3
No. 34.011, No. 4.327,173, West German Patent Publication No. 3,329.729, and Patent Application No. 1983-426
2,5-diacylamino substituted phenolic couplers such as those described in US Pat. No. 71 and U.S. Pat.
No. 2, No. 4.333.999, No. 4.451.5
These include phenolic couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position, which are described in No. 59 and No. 4.427.767.

A coupler in which the coloring dye has appropriate diffusivity can be used in combination. Such couplers are described in U.S. Patent No. 4.3.
Examples of magenta couplers are found in European Patent No. 66,237 and British Patent No. 2.125.570, and European Patent No. 96.237.
Specific examples of yellow, magenta or cyan couplers are described in German Patent No. 570 and DE-A-3.234.533.

Dye-forming couplers and the above-mentioned special couplers, except for couplers in which the color-forming dye has diffusivity, may form a dimer or higher polymer.A typical example of a polymerized dye-forming coupler is disclosed in U.S. Pat. .451.820 and 4,080,211. Specific examples of polymerized magenta couplers are given in British Patent No. 2.102.
No. 173 and US Pat. No. 4,367,282.

The various couplers used in the present invention can be used in combination in the same layer of the photosensitive layer in order to satisfy the characteristics required for the photosensitive material, or in two or more different layers using the same compound. It can also be introduced into

The coupler used in the present invention can be introduced into the photosensitive material by various known dispersion methods, such as a solid dispersion method, an alkali dispersion method, preferably a latex dispersion method, and more preferably an oil-in-water dispersion method. be able to. In the oil-in-water dispersion method, after dissolving either a high-boiling organic solvent with a boiling point of 175°C or higher and a so-called auxiliary solvent with a low boiling point, either alone or in a mixture of both, water or gelatin is dissolved in the presence of a surfactant. Finely dispersed in aqueous media such as aqueous solutions. Examples of high boiling point organic solvents are U.S. Pat.
．． The zero dispersion described in No. 021 may be accompanied by phase inversion, and if necessary, the auxiliary solvent may be removed or reduced by distillation, noodle washing, or ultrafiltration before being used for coating. Good too.

Specific examples of high-boiling organic solvents include phthalate esters (dibutyl phthalate, dicyclohexyl phthalate,
esters of phosphoric or phosphonic acids (triphenyl phosphate, tricresyl phosphate, 2-
Ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, triptoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenyl phosphonate, etc.), benzoic acid esters (2-ethylhexylbenzoate, etc.) ,
dodecyl benzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides (diethyl dodecanamide, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4-jerk-aminophenol) ), aliphatic carboxylic acid esters (dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N
, N-dipyl-2-butoxy-5-tert-octylaniline, etc.), hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.), and the like. In addition, as an auxiliary solvent, those with a boiling point of about 30°C or higher,
Preferably, an organic solvent having a temperature of 50° C. or more and about 160° C. or less 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.

Specific examples of latex dispersion processes, effects, and latex for impregnation include U.S. Pat. It is described in.

Typical amounts of color couplers used range from 0.001 to 1 mole per mole of photosensitive halogenated S, preferably from 0.01 to 0 for yellow couplers.
．． 5 moles, 0.003 to 0.00 for magenta couplers.
3 mol, and for cyan couplers 0.002 to 0.
It is 3 moles.

The silver halide emulsion used in the present invention is silver bromide, silver chlorobromide, or silver chloride that does not substantially contain silver iodide, and the silver halide preferably used contains 10 mol% or more of silver chloride. Silver chlorobromide.

In order to obtain an emulsion with sufficient sensitivity without increasing fog, it is preferable that the silver bromide content is 20 mol% or more, but if particularly quickness is required, it is 20 mol% or less or 10 mol% or less. It may be preferable to use

Reducing the silver bromide content not only improves the speed of development, but also reduces the equilibrium accumulation amount in the developing solution, which is determined by the relationship with the amount of replenisher, when a photosensitive material containing it is run in a processing solution. Bromine ions are present at a low concentration, and the rapid developability of the developer itself can be set high, which is preferable.

The silver halide grains used in the present invention may have different phases inside and on the surface, may have a multiphase structure such as a bonded structure, or may consist of a uniform phase throughout the grain. Moreover, they may be mixed.

Average grain size of silver halide grains used in the present invention (
In the case of spherical or nearly spherical particles, the particle diameter is the particle size, and in the case of cubic particles, the particle size is the particle size, and the average particle size is based on the projected area) is preferably 2 μ or less and 0.1 μ or more, but it is particularly preferable. is 1μ or less 0.15μ
That's all. The grain size distribution may be narrow or wide, but the value (variation rate) obtained by dividing the standard deviation value of the grain size distribution curve of the silver halide emulsion by the average grain size is 20.
% or less, particularly preferably 15% or less, is preferably used in the present invention, and in order for the light-sensitive material to satisfy the target gradation, substantially the same color sensitivity. It is possible to mix two or more types of monodisperse silver halide emulsions with different grain sizes (preferably those having the above-mentioned fluctuation rate as monodispersity) in the same layer or to coat them in separate layers. can. Furthermore, two or more types of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion may be mixed or layered for use.

The shape of the silver halide grains used in the present invention is regular (cubic, octahedral, dodecahedral, dodecahedral, etc.).
), or may have an irregular crystal shape such as a spherical shape, or may have a composite shape of these crystal shapes, or may have a tabular grain shape. In particular, an emulsion consisting of a mixture of these various crystal forms may be used, in which tabular grains having a length/thickness ratio of 5 or more, particularly 8 or more account for 50% or more of the total projected area of the grains. These various emulsions may be either a surface latent image type in which a latent image is formed mainly on the surface or an internal latent image type in which a latent image is formed inside the grains.

The photographic emulsion used in the present invention is described in "Chemistry and Physics of Photography J" by Glafktdes, Ch.
imieet Physique Pho, togra
phique (published by Paul Monte1, 196
7th year)], “Photographic Emulsion Chemistry” by Duffin (G, F,
Photographic Emulsi by Duffin
onChemistry (Focal Press
[Published, 1966)], Zelikman et al., "Production and Coating of Photographic Emulsions J (V, L.

Making and by Zelikman et al.
CoatingPotographic E+oul
sin (Focal Press, 1964)]. That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. It is also possible to use a method in which good 0 grains are formed in an excess of silver ions (so-called back-mixing method). As one form of the simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called Chondrald double jet method can also be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

Furthermore, emulsions prepared by the so-called conversion method, which involves a process of converting silver halide that has already been formed before the silver halide grain formation process is completed, into silver halide with a smaller solubility product, and Emulsions which have undergone similar halogen conversion after the completion of the silver grain formation process can also be used.

In the process of silver halide grain formation or physical ripening,
A cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present.

After grain formation, silver halide emulsions are usually subjected to physical ripening, desalting and chemical ripening before being used for coating.

Known silver halide solvents (e.g. ammonia, rhodankali or U.S. Pat. No. 3,271.157;
1-12360, JP-A-53-82408, JP-A-53-144319, JP-A-54-100717, JP-A-54-155828, etc.) by precipitation, physical Can be used in ripening 9 and chemical ripening. In order to remove soluble silver salts from the emulsion after physical ripening, Nudel water washing, flocculation sedimentation method, ultraleakage method, etc. are used.

The silver halide emulsion used in the present invention contains active gelatin and sulfur-containing compounds that can react with silver (for example, thiosulfate,
Sulfur sensitization method using reducing substances (e.g. stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds); metal Compounds (for example, kumquat salt, Pt5IrSPds Rh5Fe
A method of increasing capital gI using complex salts of metals of group 1 of the periodic table, such as complex salts of metals of group 1 of the periodic table, etc., can be used alone or in combination. ◆The claustral, chlorotic and red malignant emulsions of the present invention are each spectrally sensitized with a methine dye or the like so as to have chromochromic properties. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar-cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes.

Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. Namely, viroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, lysine nucleus, etc.; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and Nuclei in which aromatic hydrocarbon rings are fused to these nuclei, namely, indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benz Imidazole nuclei, quinoline nuclei, etc. can be applied. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or complex merocyanine dyes include ketomethylene, pyrazolin-5-one nucleus, thiohydantoin nucleus, 2-thioxazolidine-
2,4-dione nucleus, thiazolidine-2,4-dione nucleus,
A 5- to 6-membered heterocyclic nucleus such as a rhodanine nucleus or a thiobarbic acid nucleus can be applied.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. A typical example is US Patent 2
．． No. 688.545, No. 2,977.229, No. 3,
No. 397.060, No. 3,522.052, No. 3.5
No. 27,641, No. 3.617.293, No. 3.62
No. 8,964, No. 3.666, No. 480, No. 3.672
．． No. 898, No. 3,679.428, No. 3,703.
No. 377, No. 3,769.301, No. 3.814.6
No. 09, No. 3,837.862, No. 4,026.70
7, British Patent No. 1,344.281, British Patent No. 1.507.
No. 803, Special Publication No. 43-4936, No. 53-1237
No. 5, JP-A-52-110618, JP-A No. 52-1099
It is described in No. 25.

Along with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
A substance exhibiting supersensitization may also be included in the emulsion.

The light-sensitive materials produced using the present invention may contain hydroquinone derivatives, 7-minophenol derivatives, amines, gallic acid derivatives, catechol derivatives, ascorbic acid derivatives, colorless couplers, sulfone as color antifogging agents or color mixing inhibitors. It may also contain amidophenol derivatives and the like.

Known anti-fading agents can be used in the light-sensitive material of the present invention. Organic anti-fading agents include hydroquinones,
6-hydroxychroman 1.5-hydroxycoumarans, spirochroman li, p-alkoxyphenols, hindered phenols mainly including bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, Typical examples include hindered amines and ether or ester derivatives obtained by silylating or alkylating the phenolic hydroxyl group of each of these compounds. Further, metal complexes such as (bissalicylaldoximado)nickel complex and (bis-N,N-dialkyldithiocarbamado)nickel complex can also be used.

To prevent yellow dye images from deteriorating due to heat, humidity and light.
As described in U.S. Pat. No. 4,268,593,
Compounds having a hindered amine and a hindered phenol structure in the same molecule give good results. In addition, in order to prevent deterioration of the agenta dye image, especially deterioration caused by light, spiroindanes described in JP-A-56-159644 and hydroquinone diethers or monoethers as described in JP-A-55-89835 are used.・Converted chromans give favorable results.

In order to improve the storage stability of cyan images, especially the light fastness, it is preferable to use a benzotriazole ultraviolet absorber in combination. This UV absorber may be co-emulsified with the cyan coupler.

The amount of ultraviolet absorber applied should be sufficient to impart photostability to the cyan dye image, but if too much is used, it may cause yellowing of the unexposed areas (white areas) of the color photographic light-sensitive material. Therefore, it is usually preferably lXl0-'mol/m! ~2X10-3 mol/m! , in particular in the range of 5XiO-'mol/m" to 1.5 x 10-3 mol/m".

In the conventional color paper layer structure, an ultraviolet absorber is contained in every layer on both sides adjacent to the cyan coupler-containing red-sensitive emulsion layer, preferably in both layers. When an ultraviolet absorber is added to the intermediate layer between the green-sensitive layer and the red-sensitive layer, it may be co-emulsified with a color mixing inhibitor, and when an ultraviolet VA absorber is added to the protective layer, it may be co-emulsified as the outermost layer. Another protective layer may be applied, and this protective layer can contain a matting agent of any particle size.

In the photosensitive material of the present invention, an ultraviolet absorber can be added to the hydrophilic colloid layer.

The light-sensitive material of 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 or halation.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material of the invention may contain a stilbene-based, triazine-based, oxazole-based, or coumarin-based brightener.

Water-soluble brighteners may be used, and water-insoluble brighteners may be used in the form of dispersions.

The present invention, as described above, is applicable to multilayer, multicolor photographic materials having at least two different spectral sensitivities on the support.

Multilayer natural color photographic materials usually have a red-sensitive emulsion layer on a support,
Each of the green-sensitive emulsion layer and the blue-sensitive emulsion layer has a small number (each has one. The order of these layers can be arbitrarily selected as required. Also, each of the above emulsion layers is composed of two or more emulsion layers having different sensitivities. Alternatively, a non-light-sensitive layer may be present between two or more emulsion layers having the same sensitivity.

The light-sensitive material according to the present invention includes, in addition to the silver halide emulsion layer,
Protective layer, intermediate layer, filter layer, antihalation layer,
It is preferable to appropriately provide an auxiliary layer such as a back layer.

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

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein;
Cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, etc.; Pi derivatives such as sodium alginate, starch derivatives; polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyvinyl alcohol; A wide variety of synthetic hydrophilic polymeric materials can be used, such as single or copolymers of acrylamide, polyvinylimidazole, polyvinylpyrazole, and the like.

In addition to lime-processed gelatin, gelatin includes acid-processed gelatin, Bull, Soc, Sci, Phot, and J.
apan.

Enzyme-treated gelatin as described in NCL, page 16.30 (1966) may be used, and gelatin hydrolysates and enzymatically decomposed products may also be used.

In addition to the above-mentioned additives, the photosensitive material of the present invention further contains various stabilizers, anti-staining agents, developers or their precursors,
Development accelerators or their precursors, lubricants, mordants, matting agents, antistatic agents, plasticizers, and other various additives useful in photographic materials may be added.Research provides typical examples of these additives.・Disclosure 1764
3 (December 1978) and 18716 (19
(November 1979).

The "reflective support" that can be used in the present invention is one that enhances the reflectivity and makes the dye image formed in the silver halide emulsion layer clearer. Includes those coated with a hydrophobic resin containing dispersed light-reflecting substances such as titanium, zinc oxide, calcium carbonate, and calcium sulfate, and those using a hydrophobic resin containing dispersed light-reflecting substances as a support. 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, polyamide film, polycarbonate film,
There are polystyrene films and the like, and these supports can be appropriately selected depending on the purpose of use.

[Example IJ Table A was placed on a paper support laminated on both sides with polyethylene.
A multilayer color photographic paper with the layer structure shown below was prepared. The coating solution was prepared as follows.

Preparation of first layer coating solution 27.2 ml of ethyl acetate and 7.9 ml of solvent (C) were added to 19.1 g of yellow coupler (a) and 4.4 g of color image stabilizer (b) and dissolved, and this solution was dissolved. 10%
1 containing 8 ml of sodium dodecylbenzenesulfonate
0% gelatin aqueous solution 185mj! It was emulsified and dispersed. On the other hand, silver chlorobromide emulsion (silver bromide 80moβ%, 8g70g/
1 m of silver chlorobromide and the following blue-sensitizing aggravating dye (containing)
oj! Win 7.0 x 10-'moj! In addition, 90 g of a blue-sensitive emulsion was prepared. The emulsified dispersion and emulsion were mixed and dissolved, and the gelatin concentration was adjusted to have the composition shown in Table I to prepare a first layer coating solution. The coating solutions for the second to seventh layers were also prepared in the same manner as the first layer coating solution. The gelatin hardening agent for each layer is 1-oxy-3,5-dichloro-s-
Triazine sodium salt was used.

The following spectral sensitizers were used in each emulsion.

Blue-sensitive emulsion layer (1.OX 10-' mo per mol of silver halide)
l addition) Green-sensitive emulsion layer (4.OX per mo1 silver halide 10-' mo
1 addition) (7.Q-x per 11 mo1 of halogenated i
10-' mol added) red-sensitive emulsion layer (1.OX per 1 mol of silver halide 10-' +a
ol addition) A si;'< dye was used as an irradiation-preventing dye in each emulsion layer.

The structural formulas of the compounds used in this example, such as the coupler in the green-sensitive emulsion layer and the red-sensitive emulsion layer, are as follows.

(al Yellow coupler (C)? Vehicle H (e) Magenta coupler (M-53) CJ+tm (fl Color image stabilizer (g) Solvent (hl 1:5:3 mixture of ultraviolet absorbers (molar ratio) (1 ) Color mixing inhibitor il ('') Solvent (iso CJ+m0h-P -0 (k) Cyan coupler - (1) Color image stabilizer (e) Solvent The multilayer color photographic paper obtained as described above is subjected to the following processing step A -C, continuous processing was carried out until three times the amount of each color developing tank was replenished.

4 k% iq @ h No. 5 Sakeha i, the rinse bath was a three-stage countercurrent water washing from rinse 3 to rinse 1.

The color developer used in processing steps A and B is as follows.

Color developer tank liquid replenisher water
800 ca1800 mf
f1 diethyltriamine 5 3. Og 3.0
g Benzyl acetate alcohol 15nl '19ml Diethylene glycol Ion/4 10ml Sodium sulfite 2.0g 2.3g Potassium bromide 0.5g - Potassium carbonate
30.0 g 25.0 g N-ethyl-N-(β 5.5 g 7.5 g-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate hydroxylamine sulfate 4.0 g 4.5 g acid salt firefly Optical brightener (Stilbe 1.0g 1.5g type) Add water 1000 rail 10
00 rth Adjust pH with βKOH pH 10,201
For the 0,60 treatment step C, the above treatment liquid from which benzyl alcohol was removed was used.

The composition of the bleach-fix solution used in processing steps A, B and C is as follows.

Water 400mj!
40Orail ammonium thiosulfate 150 m
l 300mj! (70%) Sodium sulfite 18 g 36 g
Ethylenediamine 4-section 55 g 110
g Iron acid (■) ammonium ethylenediamine sg Add 10g acid water 1000 ml 100
0 ml pH 6,756,30 The formulation of the rinse liquid used in treatment steps A, B, and C is as follows.

1-hydroxyethylide 2.5 ml 2.5
Tall-1.1-diphosphonic acid (60%) Aqueous ammonia (28%) 1.8 tall
Add 1.8 ml water and make 1000
Tall 1000 mI! KO) (at p
H7, 07, 0 color developer, bleach-fix solution and rinse solution each 200mj! Met.

In processing steps A, B, and C, changes in cyan density during continuous processing were measured at an exposure dose with a cyan density of 2.0 at the start. Table 1 shows the cyan density at the end of continuous processing.

Also, at the end of continuous processing, unexposed photographic paper is processed and 100
The concentrations of yellow stain and magenta stain were measured after being left for 6 days at ℃.

Further, at the end of the continuous processing, the automatic developing machine was stopped, and the number of days until floating matter appeared on the surface of each rinse solution 1 to 3 was determined.

The above results are shown in Table 1.

After measuring the cyan concentration, the samples obtained in processing steps A and B were treated with a bleaching solution (manufactured by Fujifilm ■, CN-16N).
2-R) for 2 minutes, and after washing with water, the cyan density was measured again and found to be 2.02 and 2.01, respectively, indicating that cyan color recovery failure had occurred.

In addition, in processing step B, in which the bleach-fixing and water washing times are shortened from processing step A, the post-processing stain worsens and furthermore, floating matter is more likely to occur in the rinse bath, whereas processing step In treatment step C (invention) in which benzyl alcohol was simply removed from B, all items were significantly improved, and the effect of benzyl alcohol removal was remarkable.

(Example 2) Instead of the rinsing liquid in Example 1, the following rinsing liquids (a) to (
The samples were treated in the same manner as in Example 1 except that d) was used, and the changes in the resulting treatment stains and the number of days until floating matter appeared in Rinse 2 are shown in Table 2.

Rinse liquid (a) Tank liquid Replenisher ethylenediamine 2.0g 2.0g acid, ZN
a Add water 1000 mf 1000
tallpH7,07,0 Rinse solution (b) 1.2.3-bensito 1.0g 1.0g
Riazole ethylenediamine-2.0g 2.0gN,N,
N', N' 1-tetramethylenephosphonic acid (NH4)z SO32,Og Add 2.0g water 1000 rail 1000 l
ll1lpH7,07,0 Rinse solution (c) Sulfanilamide 1.0g Add 1.0g water 1000 nj! 1000
mj! pH 7,07,0 Rinse solution (d) 5-chloro-2-methy 30 ■ 30 ■ Ru 4
-Isothiazolin-3-one Add water and 1000m! ! 100
0 ml pH 7,07,0 According to the present invention, the increase in stain after treatment and the generation of suspended matter are significantly suppressed.

(Example 3) In the multilayer color photographic paper in Example 1, the emulsion of each layer was changed as shown in Table B below, the yellow coupler and cyan coupler were changed as shown below, and the magenta coupler was changed as shown in Table 3. Multilayer color photographic paper (a) - (Shu) were created.

The magenta couplers used are as follows.

m-1 II l Yellow coupler C11° cyan coupler 1:1 mixture (molar ratio) of the following two couplers l The obtained color photographic paper was exposed to light in a wedge pattern and then processed in the following processing steps.

end Processing process Time Temperature Color phenomenon 45 seconds 35℃ Bleach fixing 45 seconds 35℃ Rinse ■ 20 seconds 35℃ Rinse ■ 20 seconds 35℃ Rinse ■ 20 seconds 35℃ Drying 60 seconds 80℃ (*Excluding air travel time) The composition of each treatment liquid used is as follows.

Mutual two rules 1 dish water 800
m11-hydroxyethylidene-1,1,5m11
-Diphosphonic acid (60% solution) Lithium chloride 1.0g Diethylenetriaminepentaacetic acid 1g 4.5-dihydroxy-m-pene 1.0g Zendisulfonic acid benzyl alcohol Table 3 Diethylene glycol Table 3 Sodium sulfite
0.5g potassium bromide
0.1g sodium chloride 1.
5g adenine 30 ■ Potassium carbonate 40 g N-ethyl-N-(β-methane 4.5g sulfonamidoethyl)-3-methyl-4-aminoaniline sulfate Hydroxylamine sulfate 3.0g Fluorescent brightener (Sumitomo) Chemistry n 1.OgWhi
tex 4) Poly(ethyleneimine) 3.0 g
(50% aqueous solution) Add water to 1000 tal
At lKOH pH 10,25 bleach-fix solution water 400
ml ammonium thiosulfate (70%) 150
ml sodium sulfite 15
g Ethylenediamine tetranodic acid i & (In) 55g
Ammonium ethylenediaminetetraacetic acid 5g Color developer above 200mj! add water
1000 ml pH 7,0 1-Hydroxyethylidene-1,1,5m21-diphosphonic acid (60%) Nitrilotriacetic acid 1.0 g Ethylenediaminetetraacetic acid 0.5 g NNN'N'-
Tetramethylene 1.0 g Phosphonic acid BiCj! 5 (40% aqueous solution) 0.50
gMgSO4・711zO0.20g ZnSO40.3g Ammonium light pan 0.5g5-chloro-2-methyl-4-30■ Isothiazolin-3-one 2-methyl-4-isothiacylyl 10■-3-
2-octyl-4-isothiazo 10 phosphorus-3-
Ethylene glycol 1.5 g Sulfanilamide 0.1 g 1.2.3-benzotriacyl 1.0 g Ammonium sulfite 1.0 g (40%
Aqueous solution) Ammonia water (26%) 2.6 m
l Polyvinylpyrrolidone 1.0 g Fluorescent brightener (4,4'-diami 1.Og nostilbene type) Add water 1000 nII
For rinsing with KOH at pH 7.0, the above rinse solution was added with tlO% of the above bleach-fix solution. In addition, a bleach-fixing solution was added to the rinse solution (1) at a concentration of 1% and the rinse solution (2) at a concentration of 0.1% to simulate a running rinse solution.

The Dam in of each treated photographic paper was measured using a Macbeth densitometer, and the increase in magentastin after aging at 80° C. for 30 days is shown in Table 3.

In the present invention, when processing with a color developer that does not contain benzyl alcohol, increase in magentastin after processing is prevented, and when the magenta coupler of the present invention is used, (M-30, M-53 , M-55, M
-57) The effect is more pronounced.

Example 4 The first layer (bottom layer) to the seventh layer (
Sample 44 was prepared by coating the uppermost layer).

The coating liquid for the first layer was prepared as follows. That is, 200 g of yellow coupler shown in Table C, 93.3 g of antifading agent, 10 g of high boiling point solvent (p) and (q)
5 g and 600 ml of ethyl acetate as a co-solvent.
After heating and dissolving the mixture to 60℃, alkanol B (
Alkylnaphthalene sulfonate (manufactured by DuPont) 5
3300ml of gelatin aqueous solution containing 330ml of % aqueous solution
1 and emulsified using a colloid mill to prepare a coupler dispersion. Ethyl acetate was eluted from this dispersion under reduced pressure, and 1400 g of an emulsion (Ag as 96.7g,
(containing 170 g of gelatin), and further added 2,600 g of a 10% gelatin aqueous solution to prepare a coating liquid.

The coating liquids for the second layer to the seventh layer were prepared according to 1N.

In addition, the following substances were used as aggravating dyes in each emulsion layer.

Blue-sensitive emulsion layer; anhydro-5-methoxy-5'-methyl-3,3'-disulfoprobyl selenacyanine hydroxide; green-sensitive emulsion layer; anhydro-9-ethyl-5°5'-diphenyl-3-3' - Disulfoethyloxacarbocyanine hydroxy red-sensitive emulsion layer; 3,3'-diethyl-5-methoxy-9
, 9'-(2,2-dimethyl-1,3-propano)thiadicarpocyanine iodide.The following substances were also used as stabilizers for each emulsion layer.

1-Methyl-2-mercapto-5-acetylamino-1
, 3,4-) lyazole and the following were used as anti-irradiation dyes.

4-(3-carboxy-5-hydroxy-4-(3-(
3-Carboxy-5-oxo-1-(4-sulfonatophenyl)-2-pyrazolin-4-ylidene-1-propenyl)-1-pyrazolyl)benzenesulfonate-di-
Potassium salt N,N'-(4,8-dihydroxy-9゜10-dioxo-3,7-cissulfonatoanthracene-1,5-diyl)bis(aminomethanesulfonate)-tetrasodium salt Also as a hardening agent 1.2-bis(vinylsulfonyl)ethane was used.

The couplers used are as follows.

Yellow coupler magenta coupler cyan coupler j2 tCsH++ After the multilayer color photographic paper obtained as described above was imagewise exposed, it was subjected to the following processing steps: E, F, Q-, H.

In and I, continuous processing was carried out until three times the amount of the color developing tank was replenished.

This was a countercurrent water wash to Rinse 4-1.

The color developer used in processing steps DG is as follows.

800ml water
800 mA diethyleneamine 5 3. Og
3.0g Acetic acid 1, Hydroxyethyl 1.5 m# 1.5
meden-1.1-diphosphonic acid (60%) Lithium sulfate 1.0g 1.0g Benzyl alcohol 15n/! 15m1 diethylene glycol 10mj! 10mJ Sodium sulfite 1.7g 1.7g Sodium chloride 1.5g 0.7g Adenine 30■ 30■1.2.
3-bensito 2■ 5■ Riazole potassium carbonate 40 g 40 g
N-ethyl-N-(β-5,5g 9.0gmethanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate fluorescent brightener (Sumitomo Chemical 1.0g 2.5gO@
Whitex 4) Add water to 1000 ml 100
At 0 ml K O11 pH 10,50
11,0 Note that in treatment steps H and I, the above treatment liquid from which benzyl alcohol was removed was used.

The bleach-fix used in processing step D-1 was the same as in Example 1. Regarding the rinsing liquid, the replenisher and tank liquid were the same, and the following ones were used.

Ethylenediaminetetraacetic acid/2Na 200 ■ Sulfanilamide 100 ■ 1-Hydroxyethylidene-1,2,5m11-diphosphonic acid (6
0%) Anmore water (26%) 2mj! Add ammonium light bread 0.5g water and 1000m! At KOH
The replenishment amounts of pH 7.0 color developer, bleach-fix solution, and rinse solution were 160 ml each per color photographic paper.

60ml, 120mm! Met.

At the end of continuous processing, heat the white part of the photographic paper to 70°C.
/70%, and the increase in concentration of yellow stain was measured after standing for 20 days.

Furthermore, the highest density portion of the photographic paper (approximately 2.0 on a reflection densitometer) was irradiated with xenon light of 80,000 Lux, and the photofading rate of yellow was determined after being left for 14 days.

Furthermore, at the end of the continuous processing, the automatic developing machine was stopped and the number of days until floating matter appeared on the surface of each rinse solution 1 to 4 was determined.

The above results are shown in Table 4.

In contrast to the process in which the bleach-fixing process and the rinsing process are sufficiently long, in process G where both process times are shortened, the image storage stability is significantly deteriorated and floating particles are more likely to occur. In the present invention H1① which does not contain alcohol, there is no performance deterioration, and floating matters are less likely to be generated than in the process.

(Example 5) A multilayer color photographic paper similar to that of Example 1 was prepared except that (i) to ω shown below were changed.

(1) The first layer coating solution uses the following silver halide emulsion (1) containing 1.0 mol% of silver bromide, and contains a blue-sensitive sensitizing dye of 5.0 x 10 - per mol of silver chlorobromide. It was prepared in the same manner as in Example 1, except that the molar ratio was 1.

Preparation of silver halide emulsion (1) (1 part) (2 parts) Sulfuric acid (IN>20 gloss (3 parts) Silver halide solvent below (1%) 3 mN Hs (4 parts) (5 parts) (6 parts) (Liquid) (Liquid 7) (Liquid 1) was heated to 75°C, and (Liquid 2) and (Liquid 3) were added. Thereafter, (Liquid 4) and (Liquid 5) were added simultaneously over a period of 60 minutes. After 10 minutes, add (6 liquid) and (7 liquid) to 2
The simultaneous additions took 5 minutes. After 5 minutes of addition, the temperature was lowered and desalted. Add water and dispersed gelatin and adjust pH to 6.2
The average particle size is 1.02 μm, and the variation coefficient (standard deviation divided by the average particle size; s/d) is 0.
08, a monodispersed cubic silver chlorobromide emulsion containing 1 mol % of silver bromide was obtained. This emulsion was sensitized with gold and sulfur. Money is LOX
1 mol of IO-' Ag was added, and chemical sensitization was optimally performed with sodium thiosulfate.

([l) The following silver halide emulsion (2) containing 0.5 mol% silver bromide was used as the silver halide emulsion in the coating solution for the third layer, and as the silver halide emulsion in the coating solution for the fifth layer. , using the following silver halide emulsion (3) containing 1.0 mol% silver bromide,
and 0.9 red-sensitive spectral sensitizer per mole of silver halide.
Coating solutions for the second to seventh layers were prepared in the same manner as in Example 1, except that X10-' moles were added.

Preparation of silver halide emulsions (2) and (3) (8 liquids) (9 liquids) Sulfuric acid (IN) 24 liters (10 liquids) (2 liquids) Silver halide solvent (1%) 3rn1 (11 liquids) ( Liquid 12) (Liquid 13) (Liquid 14) (Liquid 8) was heated to 56°C, and Liquid (9) and (Liquid 10) were added. Thereafter, (Liquid 11) and (Liquid 12) were added simultaneously over 100 minutes.

After another 10 minutes, (Liquid 13) and (Liquid 14) were added simultaneously over a period of 8 minutes. After 5 minutes of addition, the temperature was lowered and desalted.

Add water and dispersed gelatin, adjust pH to 6.2, average particle size 0.45 μm, coefficient of variation 0.08, silver bromide 0.
．． A 5 mol % monodisperse cubic silver chlorobromide emulsion was obtained. 4. Add chloroauric acid to this emulsion. 1 x 10-' mol of Ag was added, and gold sensitization was performed.

In the same manner, by changing the composition and temperature of (Liquid 11) and (Liquid 13), a monodisperse cubic silver chlorobromide emulsion with an average grain size of 0.51 μm and a coefficient of variation of 0.07 and 1 mol% of silver bromide was obtained. was subjected to gold and sulfur sensitization to obtain emulsion (3). Gold is 4:1
×10 −4 mol 1 mol Ag was added, and chemical sensitization was optimally performed using sodium thiosulfate.

(Incorporated) As a cyan coupler, K2 was changed to the following among a mixture of K and 2.

The color photographic paper made as described above is processed by JS.
Continuous processing was performed using K, LSM, N, and O until three times the amount of the color developing tank was replenished.

The composition of the treatment liquid used in each treatment method is as follows.

Color developer tank liquid Replenisher triethanolamine 8.0g 10.0gN
, N-diethylhydro 4.2 g 6.
0 g Xylamine optical brightener (4,4'-3,0 g 4.0 g diaminostilbene type) Ethylenediaminetetraacetic acid 1.0 g 1.
5 g Potassium carbonate 30.0 g
30.0g Sodium chloride 1.4g
0.1 g4-amino-3-methyl-N-ethyl-N-(β-5.0g 7.0g (methanesulfonamide) ethyl)-p-phenylenediamine sulfate benzyl alcohol 15Tn120rnI! Add water and 1000 if! 1000
rrlpH 10, 1010, 50 In treatment methods N and 0, the above formulation with benzyl alcohol removed was used.

Bleach-fix solution (tank solution and replenisher are the same) εDTAFe
(III) NH4-2H2060gEDTA ・2N
a ・2Hz0 4g ammonium thiosulfate (70%) 12OrrLI! Sodium sulfite 16g glacial acetic acid
Add 7g water
1000ml! pH 5.5 Rinse solution (tank solution and refill solution are the same) EDTA ・2Na ・2HzO Add 0.4g water
1000mj! p1
7.0 The replenishment amount of each solution is 1 for the photosensitive material.
Per m', it is as follows.

Color developer 160-bleach-fixer 100mj? rinse liquid
2001 In the same manner as in Example 4, the increase in yellow stain and magenta stain after treatment and the yellow photofading rate were determined. Furthermore, the number of days until floating matter appeared was also determined.

The results are summarized in Table 5.

As is clear from the results in Table 5, in the comparative examples, shortening the bleach-fixing time and/or rinsing time increases staining and increases photobleaching, but the method of the present invention does not contain benzyl alcohol. It can be seen that when processing with a color developer, the stability of the image and the stability of the rinsing solution are significantly improved, even though the processing time is shortened.

Claims (2)

[Claims] (1) In a method for processing a silver halide color light-sensitive material in which the exposed silver halide color light-sensitive material is color-developed, then bleach-fixed and further washed with water, the processing solution for the color development processing is substantially 1. A method for processing a silver halide color light-sensitive material, which does not contain benzyl alcohol and is characterized in that the bleach-fix treatment and the water washing treatment are both 70 seconds or less. (2) The silver halide color photographic light-sensitive material according to claim 1, wherein the silver halide color photographic light-sensitive material contains a magenta coupler of the following general formula (I). Processing method. General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. , Za, Zb or Zc represents a methine group, a substituted methine group, =N- or -NH-,
One of the Za-Zb bond and the Zb-Zc bond is a double bond, and the other is a single bond. )