JPH0822110A - Method for processing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To enable common processing for washing or stabilizing process for various kinds of photographic sensitive materials by using a common washing or stabilizing liquid having specified surface tension in the process succeeding to developing and desilverizing processes. CONSTITUTION:In the continuous processing method of two or more kinds of silver halide color photographic sensitive materials, these materials are processed with a common cleaning or stabilizing liquid after developing and desilverizing processes. The washing or stabilizing liquid is specified to have 20 to 60 dyne/cm, preferably 25 to 50 dyne/cm surface tension. It is preferable that these photographic materials contain couplers selected from those expressed by formula I or II. In formula I, R1 is a hydrogen atom or substituent, Z is a nonmetal atomic group necessary to form a five-member azole ring containing 2-4 nitrogen atoms, and X is a hydrogen atom or a group which can be released in the coupling reaction with the oxidizing group in a developing agent. In formula II, R11 is a substituent, R12 is an electron with drawing group, (m) is an integer 1 to 5, and (n) is an integer 2 to 5.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide color photographic light-sensitive material, and to provide a simple processing method in which washing or stabilizing baths are used in common, and a processing apparatus capable of miniaturization. The purpose is. BACKGROUND OF THE INVENTION Silver halide color photographic light-sensitive materials are roughly classified into photographic films typified by color negative films and print materials typified by color paper. In order to maximize the performance of these light-sensitive materials, the coated silver halide composition, the amount of silver, the coupler or the support, etc. are optimized, and the individual characteristics are maximized. In order to exert the effect, it is general that they are processed by different processing recipes. Therefore, in the conventional method, for example, a processing machine and processing solution dedicated to color negative film and a processing machine and processing solution dedicated to color paper are prepared,
For the first time, it will be possible to obtain practical prints. By the way, in recent years, a small-scale in-store processing system called a so-called minilab, which performs simultaneous print processing at a store such as a photo store, is becoming popular. In many cases, these small-scale processing systems are installed in a small store, so that a processing system as small as possible is desirable. Furthermore, since there is a shortage of skilled workers, it is desirable that the work itself be as simple as possible.

Therefore, since the processing of both the color negative film and the color paper is made common, not only the processing equipment can be used in common and the size can be reduced, but also the rack, circulation pump, heater and temperature sensor attached to the equipment. It is also possible to reduce the amount and so on, which also saves costs. Furthermore, if the replenisher for each treatment liquid can be made common, the burden of liquid preparation work and treatment liquid management can be reduced, which is a very preferable mode. In this sense, JP-A-60-129747 proposes an automatic developing machine for common processing, and JP-A-1-154154.
In No. 3, a method of commonly treating the desilvering process is proposed. Further, JP-A 1-154153 discloses a technique for commonly performing washing or stabilizing treatment after bleach-fixing treatment.

The inventors of the present invention have studied a common technique of washing or stabilizing treatment, and although it is possible to obtain a rough performance, a rigorous comparison is made with the performance of each individual treatment so that the running performance can be improved. It was found that new problems such as increase in yellow stain, generation of film stain, and increase in fading of magenta dye will occur, and their solution has been eagerly awaited. In particular, it has been found that the above problems are more prominent in the rapid treatment process in which the total time of washing and stabilization is 50 seconds or less.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a processing method in which different photographic light-sensitive materials can be processed by a common washing or stabilizing process.

It has been found that the above object can be achieved by the following method. That is, (1) in a continuous processing method of two or more different types of silver halide color photographic light-sensitive materials, following color development and desilvering processing, at least common washing or stabilizing solution is used, and The surface tension of the stabilizing solution is 20-60 dyn /
cm is a method for processing a silver halide color photographic light-sensitive material. (2) The halogenated silver halide color photographic material as described in the above item (1), which contains at least one coupler selected from the following general formulas (I) and (II). Processing method of silver color photographic light-sensitive material. General formula (I)

[0005]

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(In the formula, R ₁ represents a hydrogen atom or a substituent. Z represents a group of non-metal atoms necessary for forming a 5-membered azole ring containing 2 to 4 nitrogen atoms. May have a substituent (including a condensed ring). X represents a hydrogen atom or a group capable of splitting off upon a coupling reaction with an oxidized product of a developing agent.) General formula (II)

[0007]

[Chemical 6]

(In the formula, R ₁₁ represents a substituent, R ₁₂ represents an electron-withdrawing group. M represents an integer of 1 to 5, and when m is 2 or more, R ₁₁ is the same or different. Is good, n is 2
And R ₁₂ may be the same or different. X ₁ represents a group capable of splitting off upon reaction with an oxidized product of an aromatic primary amine color developing agent. R ₁₁ , R ₁₂ or X ₁
In, a dimer or a multimer having a valence of two or more may be bonded to each other to form a dimer or a multimer. )

(3) The above washing or stabilizing solution has the following general formula:
The method for processing a silver halide color photographic light-sensitive material according to item (1) or (2), which contains the compound (III). General formula (III)

[0010]

[Chemical 7]

(In the general formula (III), L ¹ , L ² , L ³ and L ⁴ may be the same or different, --OR ¹ or-
The four substituents L ^{1 to} L ⁴ represented by NR ² (R ³ ) and in the general formula (III) have a total of two or more substituents in the general formula (IV) group. Here, R ¹ and R ² each represent a hydrogen atom, an alkyl group, or an alkyl group having a substituent in the following general formula (IV) group, and R ³ represents an alkyl group or a general formula (IV) group below. Represents an alkyl group having a substituent of. ) General formula (IV)

[0012]

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In the general formula (IV), X represents halogen and R represents an alkyl group. Further, in the general formulas (III) and (IV), M represents a hydrogen atom, an alkali metal, tetraalkylammonium or pyridinium. (General formula (III)
In the above, L ^{1 to} L ⁴ may be the same or different, and —OR ¹
Alternatively, the four substituents L ¹ and L ² represented by —N—R ² (R ³ ) in the general formula (III) have a total of four or more substituents in the general formula (IV) group. Where R ¹ and R
² represents a hydrogen atom, an alkyl group, or an alkyl group having a substituent in the following general formula (IV) group, and R ³
Represents an alkyl group or an alkyl group having a substituent in the following general formula (IV) group. )

(4) The method for processing a silver halide color photographic light-sensitive material as described in the item (1) or (2), wherein the washing or stabilizing solution contains substantially no formalin. (5) Treatment time of the above washing or stabilizing step is 5 seconds to 50
The processing method of the silver halide color photographic light-sensitive material according to item (3), wherein the processing time is seconds. (6) The method for processing a silver halide color photographic light-sensitive material according to item (1), wherein the two different types of light-sensitive materials are a color negative film and a color negative print material (for example, color paper). (7) The method for processing a silver halide color photographic light-sensitive material according to item (2), wherein two kinds of processing machines for color negative film processing and color negative printing processing are integrated.

The details of the present invention will be described below. In the present invention, two or more different silver halide color photographic light-sensitive materials mean a light-sensitive material having a different purpose of use, for example, a color negative film for photographing, a color paper for printing, a color positive film for photographing, It means color reversal paper. Since these light-sensitive materials are optimized depending on the purpose of use, the coating silver amount,
The silver halide compositions, supports, sensitivities, etc., are generally different and each has its own optimized processing steps. Therefore, common processing was rarely performed. Details of the light-sensitive material used in the present invention will be described later.

In the processing method of the present invention, the different light-sensitive materials described above are subjected to common washing and / or stabilization processing. The difference between the washing step and the stabilizing step here is that the latter contains a chemical that stabilizes the image, and in the present invention, after the washing step, it is treated in the stabilizing step. Also, it may be processed in the reverse process. The surface tension of the washing and / or stabilizing solution of the present invention is 2
It must be 0 to 60 dyn / cm. The more preferable surface tension is 25 to 50 dyn / cm. When the surface tension is smaller than that of the present invention, bubbles are likely to be generated, and sagging unevenness is likely to occur on the film surface, which is not preferable. On the other hand, when the surface tension is higher than that of the present invention, spot-like stains are likely to occur on the film surface, which is not preferable. Here, the surface tension is measured by a conventional method.

The value of the surface tension of the present invention has only to be achieved by at least one bath of the washing and / or stabilizing bath, but more preferably the final value of the washing and / or stabilizing bath is the above value. Is preferably reached. Further, most preferably, all the baths have the above values. In order to achieve the above surface tension value, a method of washing with various surfactants and / or adding it to a stabilizing solution is preferable, but it may be eluted from the light-sensitive material to reach the above value. These surfactants include polyethylene glycol type nonionic surfactants, polyhydric alcohol type nonionic surfactants, alkylbenzene sulfonate type anionic surfactants, higher alcohol sulfate ester salt type anionic surfactants. Agents, alkyl naphthalene sulfonate type anionic surfactants, quaternary ammonium salt type cationic surfactants, amine salt type cationic surfactants, amino salt type amphoteric surfactants, betaine type amphoteric surfactants However, a nonionic surfactant and an anionic surfactant are preferable. Particularly, those having a structure represented by the following general formula (V) are preferable.

[0018]

[Chemical 9]

In the formula, R ¹⁰ is an alkyl group, an alkenyl group,
It represents an aryl group or an alkylcarbonyl group, and p and q represent a numerical value of 0 to 100. However, p + q represents 3 or more. r represents a numerical value of 0 to 50. V represents a hydrogen atom, sulfonic acid, or phosphoric acid when r is 0. Further, when r is 1 or more, it represents a hydroxy group, a sulfonate ester, or a phosphate ester. It is particularly preferred that R ¹⁰ is an aryl group, and p + q is most preferably in the range of 5 to 30. Further, r is most preferably 0 to 10. The general formula (V) below
However, the present invention is not limited to these.

[0020]

[Chemical 10]

[0021]

[Chemical 11]

[0022]

[Chemical 12]

[0023]

[Chemical 13]

[0024]

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In order to obtain the desired surface tension by adding these compounds to washing water or a stabilizing bath, the amount added varies depending on the compound, but is generally 0.01 g to 2.0 g / liter, preferably Is about 0.05 g to 0.5 g / liter. The amount of washing in the washing step in the present invention is the characteristics of the light-sensitive material (for example, depending on the material used such as the coupler), application, and further the washing water temperature, the number of washing tanks (the number of stages), countercurrent, forward replenishment method, etc. It can be set in a wide range according to various conditions. Of these, the relationship between the number of washing tanks and water volume in the multi-stage countercurrent method is described in the Journal of the Society of Motion Pictu
re and Television Engineers Vol. 64, p. 248-
253 (May 1955 issue). In the present invention, it is more preferable to employ a multi-stage countercurrent system of two or more tanks in order to achieve the object of the present invention, and in the multistage countercurrent washing of 2 to 5 tanks, the effect of the present invention is remarkably exhibited. Can be demonstrated.

According to the multistage countercurrent system described in the above-mentioned document,
Although the amount of washing water can be greatly reduced, the increase in the residence time of water in the tank causes problems such as bacteria breeding and adhered floating substances produced to the photosensitive material. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, the method of reducing calcium ion and magnesium ion described in JP-A-62-288838 can be very effectively used. In addition, the antibacterial agents and antifungal agents described below can be used, and Horiguchi Hiroshi "Chemistry of antibacterial and antifungal agents", Hygiene Engineering Society "Sterilization of microorganisms, sterilization, antifungal technology", Japanese antibacterial agent The bactericide described in "Encyclopedia of Antibacterial and Antifungal Agents" edited by the Antifungal Society can also be used.

The pH of the washing water in the treatment of the present invention is 4
-9, preferably 5-8. The washing water temperature and washing time can be variously set depending on the characteristics of the photosensitive material, the application, etc.
The range of 5 to 50 seconds is the most preferable and the range of 15 to 40 seconds is the most preferable range in order to fully exert the effect of the present invention. In particular, in such a short-time water washing step, washing of various processing chemicals from the light-sensitive material is likely to be insufficient, undesired unevenness and stains are likely to occur remarkably, and the effect of the present invention is sufficiently exerted. can do. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such stabilizing treatment, JP-A Nos. 57-8,543 and 58-14,834 have been used.
All known methods described in No. 60-220,345 can be used.

Further, it is preferable that the washing water and the stabilizing solution contain various antibacterial agents and antifungal agents in order to prevent water stains and molds generated on the processed light-sensitive material. Examples of these antibacterial agents and antifungal agents are shown in JP-A Nos. 57-157244 and 58-105145, which are thiazolylbenzimidazole compounds, and JP-A-57-8542. Such isothiazolone compounds, chlorophenol compounds represented by trichlorophenol, bromophenol compounds, organotin and organozinc compounds, acid amide compounds,
Diazine and triazine compounds, thiourea compounds,
Benzotriazole compounds, alkylguanidine compounds, quaternary ammonium salts represented by benzalkonium chloride, antibiotics represented by penicillin, Journal Antibacterial &
Antifungus Agent (J. Antibact. Ant
Ifung. Agents) vol 1. No. 5, p.207 to 223 (1983), general-purpose antifungal agents and the like can be mentioned. You may use these 2 or more types together. Further, various bactericides described in JP-A-48-83820 can also be used.

The washing water and the stabilizing solution may contain various chelating agents as required. Preferred chelating agents include aminopolycarboxylic acids such as ethylenediaminetetraacetic acid nitrilotriacetic acid and diethylenetriaminepentaacetic acid β-alaninediacetic acid, or European Patent 3451.
The hydrolyzate of the maleic anhydride polymer described in 72A1 and the like can be mentioned.

In the stabilizing solution, compounds that stabilize the dye image, such as formalin, hexamethylenetetramine and its derivatives, hexahydrotriazine and its derivatives, N-methylol compounds such as dimethylolurea and N-methylolpyrazole, and organic compounds are used. Acids, pH buffers, etc. are included. The addition amount of these compounds is preferably 0.001 to 0.02 mol per liter of the stabilizing solution, but the lower the free formaldehyde concentration in the stabilizing solution is, the less the formaldehyde gas is scattered, which is preferable. From this point of view, examples of the dye image stabilizer include hexamethylenetetramine and N-methylolpyrazole.
N-methylolazoles described in 318644, N,
Azolylmethylamines described in Japanese Patent Application No. 3-142708 such as N'-bis (1,2,4-triazol-1-yl) piperazine are preferable. In addition, if necessary, ammonium compounds such as ammonium chloride and ammonium sulfite, metal compounds such as Bi and Al, optical brighteners,
It is also preferable to contain a hardener, an alkanolamine described in U.S. Pat. No. 4,786,583, and a preservative that can be contained in the fixing solution or the bleach-fixing solution. Among these, the sulfinic acid compounds described in JP-A No. 1-231051 (for example, benzenesulfinic acid, toluenesulfinic acid, or salts thereof such as sodium and potassium) are preferable, and the addition amount of these is a stabilizing solution. 1
1 × 10 ⁻⁵ to 1 × 10 ⁻³ mol per liter is preferable, and 3 × 10 ^{−5 to} 5 × 10 ⁻⁴ mol is particularly preferable.

The replenishing amount in the washing and / or stabilizing step of the present invention can be set arbitrarily, but in order to effectively exert the effect of the present invention, 30 to 400 ml per square meter of the light-sensitive material is used. , And more preferably 60
A small replenishing amount of about 300 ml is preferable.

Further, the effect of the present invention can be more effectively exhibited when the washing and / or stabilization of the present invention contains the compound of the following general formula (III).

[0033]

[Chemical 15]

Details of the general formula (III) will be described below. In the general formula [III], L ^{1 to} L ⁴ are -OR ¹ or -N-.
It is represented by R ² (R ³ ), and R ¹ , R ² and R ³ represent an alkyl group and may be the same or different. The alkyl group is a linear or branched alkyl group, and the hydrogen atom of the alkyl group may be substituted with another substituent. Here, a hydrophilic group is preferred as the group capable of substituting for a hydrogen atom. Particularly in the present invention, R ¹ , R ² or R
³ is preferably an alkyl group having a strong hydrophilic group selected from among the following general formula [IV] group. The alkyl group preferably has 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms.

[0035]

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In the compound of the general formula [III] in the present invention, the substituents L ^{1 to} L ⁴ have the above-mentioned characteristics.
Specific examples of ^{1 to} L ⁴ include a methoxy group, an ethoxy group,
Propoxy group, isopropoxy group, butoxy group, isobutoxy group, pentyloxy group, hexyloxy group, methylamino group, ethylamino group, propylamino group, isopropylamino group, butylamino group, isobutylamino group, 2-hydroxyethoxy group , 3-hydroxypropoxy group, 4-hydroxybutoxy group, 2-hydroxyethylamino group, 3-hydroxypropylamino group, 4-
Hydroxybutylamino group, 2-hydroxyethylethylamino group, 3-hydroxypropylpropylamino group, 4-hydroxybutylbutylamino group, dimethylamino group, diethylamino group, dipropylamino group, diisopropylamino group, dibutylamino group, diisobutyl Amino group, di2-hydroxyethylamino group, di3-hydroxypropylamino group, dihydroxybutylamino group, 2-sulfoethoxy group, 3-sulfopropoxy group,
4-sulfobutoxy group, 2-sulfoethylamino group, 3
-Sulfopropylamino group, 4-sulfobutylamino group, di2-sulfoethylamino group, di3-sulfopropylamino group, di4-sulfobutylamino group, 2-sulfoethylmethylamino group, 3-sulfopropylmethyl group Amino group, 4-sulfobutylmethylamino group, 2-sulfoethylethylamino group, 3-sulfopropylethylamino group, 4-sulfobutylethylamino group, 2-carboxyethoxy group, 3-carboxypropoxy group, 4-carboxy Butoxy group, 2-carboxyethylamino group, 3-
Carboxypropylamino group, 4-carboxybutylamino group, di2-carboxyethylamino group, di3-carboxypropylamino group, di4-carboxybutylamino group, 2-carboxyethylmethylamino group, 3-carboxypropylmethylamino Group, 4-carboxybutylmethylamino group, 2-carboxyethylethylamino group, 3-carboxypropylethylamino group, 4-carboxybutylethylamino group, 2-sulfoethoxy group,
3-Sulfoxypropoxy group, 4-Sulfoxybutoxy group, 2-Sulfoxyethylamino group, 3-Sulfoxypropylamino group, 4-Sulfoxybutylamino group, Di 2
-Sulfoxyethylamino group, di3-sulfoxypropylamino group, di4-sulfoxybutylamino group, 2-sulfoxyethylmethylamino group, 3-sulfoxypropylmethylamino group, 4-sulfoxybutylmethylamino group Group, 2-sulfoxyethylethylamino group, 3-sulfoxypropylethylamino group, 4-sulfoxybutylethylamino group, trimethylammoniomethylamino group,
Examples thereof include a trimethylammonioethylamino group, a trimethylammoniopropylamino group, a triethylammoniomethylamino group, a triethylammonioethylamino group and a triethylammoniopropylamino group. More preferably, methoxy group, ethoxy group, 2-hydroxyethoxy group, 2-hydroxyethylamino group, 2-
Sulfoethylamino group, di2-sulfoethylamino group,
Examples thereof include 2-carboxyethylamino group, di2-carboxyethylamino group and di2-hydroxyethylamino group.

The compound of the above-mentioned general formula [III] in the present invention is preferably highly hydrophilic, and specifically has a logP value of -30 or more and -4 or less, more preferably -18 or more and -7 or less. . However, here, the logP value is
It represents a value defined by the logarithmic value of the partition ratio P (= [concentration in octanol] / [concentration in water]) of the compound in a binary system of octanol / water. Here, if the logP value is too small, the effect of improving the residual color is deteriorated, and if it is too large, the precipitation of the fluorescent whitening agent may occur, which is not preferable.

The compound of the general formula [III] used in the present invention has at least two or more substituents L having a total of three or more substituents represented by the general formula [IV] group. Furthermore, it is most preferable that the four substituents L have a total of four or more substituents represented by the general formula (IV). Here, the number of the substituents represented by the general formula [IV] group is preferably an even number, and the number thereof is 8 or less, more preferably 6 or less. Specific examples of preferable diaminostilbene compounds are shown below, but the invention is not limited thereto.

[0039]

[Table 1]

[0040]

[Table 2]

[0041]

[Table 3]

In the present invention, the object can be achieved by containing the compound of the general formula [III] in the bath in any of the washing and / or stabilizing steps.
It may be contained in the developer or bleaching solution in the pre-bath, or the bleach-fixing solution or the fixing solution, and brought into the washing and / or stabilizing bath. In this case, it is preferably added to the treatment bath as early as possible in the previous step, and particularly preferably added to the developing solution (color developing solution, black and white developing solution).
The preferred concentration of the compound of the general formula [III] in the treatment liquid is
In the running liquid, 5 × 10 ⁻⁵ to 1 × 10 ⁻² mol / liter, more preferably 1 × 10 ^{−4 to} 5 × 10 ⁻³
Mol / liter, which is the concentration required to keep the set concentration of the running liquid constant in the replenisher, specifically, 1.5 × 10 ^{−4 to} 1.5 × 10 ⁻² mol / liter Is preferred.

The compound of the general formula [III] can be synthesized by a conventionally known method. For example, 4,4'-
Diaminostilbene-2,2'-disulfonic acid and cyanuric chloride are condensed to synthesize 4,4'-bistriazinylaminostilbene-2,2'-disulfonic acid, which is then condensed with alcohols or amines. can do. Specifically, Industrial Chemistry Magazine Vol. 60, No. 5, P.
604 (1957).

An example of the synthesis of the optical brightener is shown below. Synthesis of compound (SR-13) 10.2 g of cyanuric chloride was dissolved in 100 ml of acetone, and 100 g of a 10% sodium diaminostilbenesulfonate aqueous solution was added dropwise over 20 minutes while cooling with ice.
During this period, the pH of the reaction solution was adjusted to 5 to 7 with an aqueous sodium carbonate solution.
Kept at. After continuing stirring for another 30 minutes, 100 g of an 18% taurine aqueous solution was added. Then, the mixture was heated to remove acetone, the internal temperature was adjusted to 95 ° C., and the mixture was stirred for 3 hours. During this period, the pH of the reaction solution was maintained at 6 or higher with an aqueous sodium carbonate solution. After the reaction was completed, the reaction mixture was cooled and salted out to give 12 g of pale yellow crystals.
I got It was confirmed from the mass spectrum and NMR that this compound was the compound (SR-13). λ max = 348 nm (ε = 4.65 × 10 ⁴ , H ₂ O)

Synthesis of Compound (SR-25) 10.2 g of cyanuric chloride was dissolved in 100 ml of acetone, and 100 g of a 10% sodium diaminostilbenesulfonate aqueous solution was added dropwise over 20 minutes while cooling with ice.
During this period, the pH of the reaction solution was adjusted to 5 to 7 with an aqueous sodium carbonate solution.
Kept at. After stirring for another 30 minutes, set the internal temperature to 40 ° C.
Then, 35 g of an 18% aqueous solution of taurine was added. After heating for 1 hour, acetone was distilled off, 50 g of a 20% aqueous solution of N-methyltaurine was added, and the internal temperature was adjusted to 95 ° C, followed by stirring for 3 hours. During this period, the pH of the reaction solution was maintained at 6 or higher with an aqueous sodium carbonate solution. After completion of the reaction, the mixture was cooled and salted out to obtain 8.3 g of pale yellow crystals. It was confirmed from the mass spectrum and NMR that this compound was the compound (SR-25). λ max = 345 nm (ε = 4.38 × 10 ⁴ , H ₂ O) Also, other compounds and comparative compounds were synthesized by the same method as above.

Compound (SR-1) Light yellow powder λmax = 351 nm (ε = 5.10 × 10 ⁴ , H ₂ O) 〃 (SR-2) 〃 〃 = 352 nm (ε = 5.33 × 10 ⁴ , H ₂ O) 〃 (SR-3) 〃 〃 = 348 nm (ε = 4.51 × 10 ⁴ , H ₂ O) 〃 (SR-4) 〃 〃 = 351 nm (ε = 5.23 × 10 ⁴ , H ₂ O) 〃 (SR-5) 〃 〃 = 348 nm (ε = 4.78 × 10 ⁴ , H ₂ O) 〃 (SR-6) 〃 〃 = 348 nm (ε = 4.76 × 10 ⁴ , H ₂ O) 〃 (SR-7) 〃 〃 = 343 nm (ε = 4.86 × 10 ⁴ , H ₂ O) 〃 (SR-8) 〃 〃 = 345 nm (ε = 4.56 × 10 ⁴ , H ₂ O) 〃 (SR-9) 〃 〃 = 343 nm (ε = 4.43 × 10 ⁴ , H ₂ O) 〃 (SR-10) 〃 〃 = 345 nm (ε = 4.99 × 10 ⁴ , H ₂ O) 〃 (SR-11) 〃 〃 = 357 nm (ε = 4.25 × 10 ⁴ , H ₂ O) 〃 (SR -12) 〃 〃 = 343nm (ε = 5.11 × 10 ⁴ , H ₂ O) 〃 (SR-14) 〃 〃 = 352nm (ε = 5.68 × 10 ⁴ , H ₂ O) 〃 (SR-15) 〃 ＝ 353 nm (ε = 5.40 × 10 ⁴ , H ₂ O) 〃 (SR-16) 〃 〃 = 350 nm (ε = 4.98 × 10 ⁴ , H ₂ O) 〃 (SR-17) 〃 〃 = 349 nm (ε = 4.76 × 10 ⁴ , H ₂ O) 〃 (SR -18) 〃 〃 = 348nm (ε = 4.77 × 10 ⁴ , H ₂ O) 〃 (SR-19) 〃 〃 = 349nm (ε = 4.62 × 10 ⁴ , H ₂ O) 〃 (SR-20) 〃 ＝ 352 nm (ε = 4.91 × 10 ⁴ , H ₂ O) 〃 (SR-21) 〃 〃 = 351 nm (ε = 5.21 × 10 ⁴ , H ₂ O) 〃 (SR-22) 〃 〃 = 350 nm (ε = 5.18 ×) 10 ⁴ , H ₂ O) 〃 (SR-23) 〃 〃 = 352 nm (ε = 4.63 × 10 ⁴ , H ₂ O) 〃 (SR-24) 〃 = 350 nm (ε = 4.78 × 10 ⁴ , H ₂ O ) 〃 (SR-26) 〃 〃 = 349 nm (ε = 5.12 × 10 ⁴ , H ₂ O) 〃 (SR-27) 〃 〃 = 353 nm (ε = 4.56 × 10 ⁴ , H ₂ O)

The compound of the general formula [III] may be used alone or in combination with another diaminostilbene compound if necessary. As the fluorescent whitening agent that can be used in combination with the compound of the general formula [III], a known or commercially available diaminostilbene-based fluorescent whitening agent may be used. Examples of commercially available compounds include "Dyeing Note", 19th Edition (Irozen Co., Ltd.)
P. 165-P. 168, among the products described here, Whitex RP, or Whitex
BRF liq. Is preferred.

Next, the color development in the processing method of the present invention will be described. The color developing solution used for the development processing of the light-sensitive material is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. Is. Although aminophenol compounds are also useful as the color developing agent, p-phenylenediamine compounds are preferably used, and a typical example thereof is 3-methyl-4-amino-.
N, N-diethylaniline, 4-amino-N-ethyl-
N-β-hydroxyethylaniline, 3-methyl-4-
Amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-
Amino-N-ethyl-N-β-methoxyethylaniline, 3-methyl-4-amino-N-ethyl-N-δ-hydroxybutylaniline and their sulfates, hydrochlorides or p-toluenesulfonates are mentioned. To be Two or more of these compounds can be used in combination depending on the purpose.

The color developer contains a pH buffering agent such as an alkali metal carbonate, borate or phosphate, a bromide salt, an iodide salt, a benzimidazole, a benzothiazole or a mercapto compound. It is common to include agents or antifoggants. Also, if necessary, various preservatives such as hydroxylamine, N, N-di (sulfoethyl) hydroxylamine, diethylhydroxylamine, sulfite, hydrazines, phenylsemicarbazides, triethanolamine, and catecholdisulfonic acids, ethylene glycol. , Organic solvents such as diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers,
Fogging agent such as sodium boron hydride, 1
An auxiliary developing agent such as -phenyl-3-pyrazolidone,
Various chelating agents represented by viscosity imparting agents, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, phosphonocarboxylic acids, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid. , Hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid, ethylenediamine Add di (o-hydroxyphenylacetic acid) and their salts. The pH of these color developing solutions is generally 9-12.

The replenishing amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but it is generally 1 liter or less per 1 square meter of the light-sensitive material. By reducing the bromide ion concentration in the replenishing solution, It can be 500 ml or less. Particularly, in the case of a film for photography, it is preferable that the volume is 60 to 300 ml per square meter, and in the case of a print sensitive material, it is preferably 30 m.
1 to 100 ml / square meter. When the replenishment rate is reduced, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the processing tank with the air. Further, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developing solution. The processing time for color development is about 5 seconds to 3 minutes and 30 seconds, but about 15 seconds to 90 seconds is preferable for a film for photography. In the case of print photosensitive material, 5 seconds to 3 seconds
About 0 seconds is preferable.

The photographic emulsion layer after color development is usually bleached by a bath having a bleaching ability. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. Further, in order to speed up the processing, a processing method of bleach-fixing processing after bleaching processing may be used. Further, treatment with two continuous bleach-fixing baths, fixing treatment before the bleach-fixing treatment, or bleaching treatment after the bleach-fixing treatment can be optionally carried out according to the purpose. Typical bleaching agents include ferricyanide, dichromate, and iron (trivalent) organic complex salts, with the use of ferric organic acid complex salts being particularly preferred. Particularly preferred organic acids include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, ethyliminodiacetic acid, and 1,3.
-Diaminopropane tetraacetic acid, glycol ether diamine tetraacetic acid, β-alanine diacetic acid, ethylenediamine-
N, N'-disuccinic acid, ethylenediamine-N, N'-
Dimalonic acid, 1,3-diaminopropane-N, N'-
Examples thereof include aminopolycarboxylic acids such as disuccinic acid. These iron (III) complexes are preferably used in the form of ammonium salt, sodium salt or potassium salt.

If necessary, a bleaching accelerator may be used in the bleaching solution, the bleach-fixing solution and their pre-bath.
Specific examples of useful bleaching accelerators are described in the following specifications: U.S. Pat. No. 3,893,858, West German Patent No. 1,290,812, JP-A-53-95,630,
Research Disclosure No. Compounds having a mercapto group or a disulfide bond described in JP-A No. 17,129 (July 1978); JP-A-50-140,
Thiazolidine derivatives described in U.S. Pat. No. 129; US Pat.
Thiourea derivatives described in JP 706561 A;
No. 16,235, the iodide salt; West German Patent No. 2,7.
Polyoxyethylene compounds described in 48,430;
Polyamine compounds described in JP-B-45-8836; bromide ions and the like can be used. Among them, a compound having a mercapto group or a disulfide group is preferable from the viewpoint of a large accelerating effect, and particularly, US Pat. No. 3,893,858, West German Patent No. 1,290,812, and JP-A-53-95,6.
The compounds described in No. 30 are preferable. Further, the compounds described in US Pat. No. 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color photographic material for photography. The treatment time of the bath having a bleaching ability is generally about 10 seconds to 120 seconds. In the case of a photographic film, in the sense that the effect of the present invention is fully exerted, it is 20
Seconds to 60 seconds are preferable, and in the case of a photosensitive material for printing, 10 seconds to 30 seconds are preferable. In addition, photosensitive material 1
The replenishment amount per square meter is 30-
It is about 200 ml, and in the case of a bleach-fixing solution, it is about 30 to 300 ml.

Next, the bath having fixing ability in the present invention will be described in detail. Examples of the fixing agent include thiosulfates, thiocyanates, thioether compounds described in JP-A-4-230749, mercapto compounds described in JP-A-5-72696, mesoionic compounds described in JP-A-4-143755, and thioureas. , A large amount of iodide salt and the like can be mentioned, but thiosulfate is generally used, and ammonium thiosulfate, sodium thiosulfate and potassium thiosulfate are most widely used. As a bleach-fixing solution or a preservative for the fixing solution, sulfite, bisulfite, benzenesulfinic acid or carbonyl bisulfite adduct is preferable. The concentration of the fixing agent is 0.1 mol to 3 mol, preferably 0.2 mol to 2 mol per liter. The concentration of the preservative is about 0.02 to 0.5 mol. The replenishing amount of the fixing solution is 10 to 500 ml, preferably 30 to 2 per square meter of the light-sensitive material.
It is about 00 ml. The processing time of the fixing solution is generally about 5 seconds to 120 seconds. In the sense that the effects of the present invention are fully exhibited, it is preferably 20 seconds to 60 seconds in the case of a photographic film, and is preferably 10 seconds to 30 seconds in the case of a photosensitive material for printing. Processing temperature is 25 ℃
50 ° C, preferably about 30 ° C to 45 ° C.

Next, the silver halide color photographic light-sensitive material of the present invention will be described in detail. In the present invention, as described above, two or more different types of silver halide color photographic light-sensitive materials are used. Here, the different light-sensitive materials mean that the purpose of use is different, and specifically, a color negative film for photographing, a color paper for printing, a color positive film for photographing, a color reversal paper and the like. Particularly, in the present invention, it is preferably applied to a color negative film for photographing (color negative film) and a color paper for printing (color paper). The silver halide emulsion and other materials (additives, etc.) and photographic constituent layers (layer arrangement, etc.) applied in the present invention, and the processing method and processing additive applied for processing the light-sensitive material are The following patent publications, particularly European Patent EP 0,355,660A2 (Japanese Patent Application No. 1-107).
No. 011) is preferably used.

[0055]

[Table 4]

[0056]

[Table 5]

[0057]

[Table 6]

[0058]

[Table 7]

[0059]

[Table 8]

The silver halide emulsion used in the present invention is
Silver iodobromide, silver iodochloride, silver iodochlorobromide, silver chlorobromide, silver bromide,
Emulsions of various halogen compositions such as silver chloride can be used. Particularly, in the case of a color negative film, it is preferable to have a layer containing a silver iodobromide emulsion, and it is preferable to use an emulsion having an iodine content of about 0.1 to 10 mol%. Further, in the case of color paper, it is preferable to have at least one emulsion layer containing silver halide grains of which silver chloride is 90 mol% or more. More preferably 95 to 99.9 mol% or more, still more preferably 98 to 9
It is particularly preferable that the emulsion is 9.9 mol% or more of silver chloride, and the total layer is a silver chlorobromide emulsion of 98 to 99.9 mol% or more of silver chloride. The amount of coated silver is not particularly limited, but it is about ² g to 10 g / m ^{2 in} the case of a color negative film and 0.
It is preferable that the content is about ² to 0.9 g / m ² . Also,
The light-sensitive material used in the present invention may contain various couplers, but the details are as shown in Table 2.

Further, as a cyan coupler, JP-A-2-33
In addition to the diphenylimidazole type cyan couplers described in No. 144, 3-hydroxypyridine type cyan couplers described in European Patent No. A divalent equivalent having a leaving group, couplers (6) and (9) are particularly preferable), and cyclic active methylene cyan couplers described in JP-A-64-32260 (among others, listed as specific examples). (Coupler Examples 3, 8, 34 are especially preferred).

The magenta coupler preferably contains at least one coupler selected from the following general formulas (I) and (II). In particular, this coupler is preferably contained in both of two different light-sensitive materials.

[0063]

[Chemical 17]

(In the formula, R ₁ represents a hydrogen atom or a substituent. Z represents a group of non-metal atoms necessary to form a 5-membered azole ring containing 2 to 4 nitrogen atoms. May have a substituent (including a condensed ring). X represents a hydrogen atom or a group capable of splitting off upon a coupling reaction with an oxidized product of a developing agent.)

[0065]

Embedded image

(In the formula, R ₁₁ represents a substituent, R ₁₂ represents an electron-withdrawing group. M represents an integer of 1 to 5, and when m is 2 or more, R ₁₁ is the same or different. Is good, n is 2
And R ₁₂ may be the same or different. X ₁ represents a group capable of splitting off upon reaction with an oxidized product of an aromatic primary amine color developing agent. R ₁₁ , R ₁₂ or X ₁
In, a dimer or a multimer having a valence of two or more may be bonded to each other to form a dimer or a multimer. ) In the present invention, by using the coupler of the general formula (I) or (II), washing and / or stabilizing bath can be commonly used without impairing image storability (increased yellow stain and photobleaching), At the same time, it is noteworthy that the processing time could be shortened at the same time.

Next, the coupler of the formula [I] will be described in detail. Among the coupler skeletons represented by the formula (I), a preferable skeleton is 1H-imidazo [1,2-b] pyrazole,
1H-pyrazolo [1,5-b] [1,2,4] triazole, 1H-pyrazolo [5,1-c] [1,2,4] triazole, 1H-pyrazolo [1,5-d] tetrazole and 1H-pyrazolo [1,5-a] benzimidazole.

In the above general formula [I], the substituent represented by R ₁ is not particularly limited, but is typically alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, cycloalkyl and the like. Examples of the groups include, halogen atom and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocycleoxy, siloxy, acyloxy, carbamoyl. Oxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclicthio groups, and spiro Compound residues also include an organic hydrocarbon compound residue, or the like.

The alkyl group represented by R ₁ preferably has ₁ to 32 carbon atoms and may be linear or branched.
The aryl group represented by R ₁ is preferably a phenyl group. Examples of the acylamino group represented by R ₁ include an alkylcarbonylamino group and an arylcarbonylamino group. Examples of the sulfonamide group represented by R ₁ include an alkylsulfonylamino group and an arylsulfonylamino group. Examples of the alkyl component and aryl component in the alkylthio group and arylthio group represented by R ₁ include the alkyl group and aryl group represented by R above. The alkenyl group represented by R ₁ has 2 carbon atoms.
To 32, and a cycloalkyl group having 3 to 1 carbon atoms
2, especially 5 to 7, are preferable, and the alkenyl group may be linear or branched. The cycloalkenyl group represented by R ₁ preferably has 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms.

The sulfonyl group represented by R ₁ is an alkylsulfonyl group, an arylsulfonyl group or the like; the sulfinyl group is an alkylsulfinyl group, an arylsulfinyl group or the like; the phosphonyl group is an alkylphosphonyl group, an alkoxyphosphonyl group, an aryl. Oxyphosphonyl group, arylphosphonyl group, etc .; Acyl group, alkylcarbonyl group, arylcarbonyl group, etc .; Carbamoyl group, alkylcarbamoyl group, arylcarbamoyl group, etc .; Sulfamoyl group, alkylsulfamoyl group, arylsulfamoyl group Moyl group and the like; Acyloxy group as an alkylcarbonyloxy group, arylcarbonyloxy group and the like; Carbamoyloxy group as an alkylcarbamoyloxy group, arylcarbamoyloxy group and the like; The idide group is an alkylureido group, an arylureido group, or the like; the sulfamoylamino group is an alkylsulfamoylamino group, an arylsulfamoylamino group, or the like; and the heterocyclic group is preferably a 5- to 7-membered group. Specifically, 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group and the like;
The heterocyclic oxy group is preferably one having a 5- to 7-membered heterocycle, for example, 3,4,5,6-tetrahydropyranyl-2-oxy group, 1-phenyltetrazole-5-
Oxy group, etc .; As the heterocyclic thio group, a 5- to 7-membered heterocyclic thio group is preferable, for example, 2-pyridylthio group, 2-benzothiazolylthio group, 2,4-diphenoxy-1,
3,5-triazole-6-thio group and the like; trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group and the like as siloxy group; succinimide group, 3-heptadecylsuccinimide and phthalimide group as imide group, Glutarimide group etc .; Spiro [3,3] heptan-1-yl etc. as spiro compound residue; Bicyclo [2,2,1] heptan-1-yl, tricyclo [3,3] as organic hydrocarbon compound residue 3,1,1 ^3.7 ] Decan-1-yl, 7,7-dimethyl-bicyclo [2,2,2]
1] Heptan-1-yl and the like.

Examples of the group represented by X which can be removed by the reaction with the oxidation product of the color developing agent include, for example, a halogen atom (chlorine atom, bromine atom, fluorine atom, etc.) and alkoxy, aryloxy, heterocyclic oxy, acyloxy, sulfonyl. Oxy, alkoxycarbonyloxy, aryloxycarbonyl, alkyl oxalyloxy, aloxy oxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxycarbonylthio, acylamino, sulfonamide, nitrogen-containing heterocycle bonded by N atom, alkyl Each group such as oxycarbonylthiamino, aryloxycarbonylamino, carboxyl, and the like can be mentioned, but preferably a halogen atom, particularly a chlorine atom.

Examples of the nitrogen-containing heterocycle formed by Z include a pyrazole ring, an imidazole ring, a triazole ring and a tetrazole ring. As the substituent which the ring may have, the above-mentioned R ₁ may be mentioned. There are things. Among the pyrazoloazole-based couplers represented by the formula [M], the imidazo [1,2-b] described in U.S. Pat. No. 4,500,630 in terms of the absorption characteristics of the coloring dye.
Pyrazoles, pyrazolo [1,5-b] [1,2,4] triazoles described in U.S. Pat. No. 4,540,654, and pyrazolo [5,5] described in U.S. Pat. No. 3,725,067. 1-c] [1,2,4] triazole is preferable, and in view of light fastness, pyrazolo [1,2]
5-b] [1,2,4] triazoles are particularly preferred.

For details of the substituents of the azole ring represented by the substituents R ₁ , X and Z, see, for example, US Pat. No. 4,540,654, column 2, line 41 to column 8, line 27. It is described in. Pyrazoloazole couplers in which a branched alkyl group is directly bonded to the 2, 3 or 6-position of a pyrazolotriazole ring as described in JP-A-61-265167 and JP-A-61-265167. No. 65246, a pyrazoloazole coupler containing a sulfonamide group in the molecule,
Pyrazoloazole couplers having an alkoxyphenyl sulfonamide ballast group described in JP-A-61-147254, JP-A-62-209457 or JP-A-6-209457.
JP-A-3-307453, a pyrazolotriazole coupler having an alkoxy group or an aryloxy group at the 6-position, a pyrazolotriazole coupler having a phenylene group at the 2-position described in JP-A-63-41851, and Japanese Patent Application No. It is a pyrazolotriazole coupler having a carbonamide group in the molecule described in JP-A 1-222279.

Of these couplers, specific examples of the pyrazolotriazole coupler are listed below.

[0075]

[Chemical 19]

[0076]

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[0077]

[Chemical 21]

[0078]

[Chemical formula 22]

[0079]

[Chemical formula 23]

[0080]

[Chemical formula 24]

[0081]

[Chemical 25]

[0082]

[Chemical formula 26]

[0083]

[Chemical 27]

[0084]

[Chemical 28]

[0085]

[Chemical 29]

[0086]

Embedded image

[0087]

[Chemical 31]

The coupler represented by the formula (I) is represented by US Pat. Nos. 4,540,654 and 4,705,863,
JP-A-61-65245, JP-A-62-209457,
62-249155, Japanese Examined Patent Publication No. 47-27411,
It can be synthesized by the method described in US Pat. No. 3,725,067. Next, R ₁₁ , R ₁₂ and X _{1 in the} coupler represented by the formula (II) will be described in detail.

R ₁₁ represents a substituent. Specifically, it is a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxy group, a nitro group, a carboxy group, a sulfo group, an amino group, an alkoxy group or an aryloxy group. Group, acylamino group, alkylamino group, anilino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, hetero Ring oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonylamino group, imide group, heterocyclic thio group, sulfinyl group, phosphonyl group,
It represents an aryloxycarbonyl group, an acyl group or an azolyl group, and R ₁₁ may be a divalent group to form a bis form.

More specifically, R ₁₁ is each a hydrogen atom, a halogen atom (eg, chlorine atom, bromine atom), an alkyl group (eg, a straight chain or branched chain alkyl group having 1 to 32 carbon atoms, an aralkyl group, an alkenyl). Group, alkynyl group,
A cycloalkyl group or a cycloalkenyl group, more specifically,
For example, methyl, ethyl, propyl, isopropyl, t-
Butyl, tridecyl, 2-methanesulfonylethyl, 3
-(3-Pentadecylphenoxy) propyl, 3- {4
-{2- [4- (4-hydroxyphenylsulfonyl)
Phenoxy] dodecanamide} phenyl} propyl, 2
-Ethoxytridecyl, trifluoromethyl, cyclopentyl, 3- (2,4-di-t-amylphenoxy) propyl group), aryl group (eg, phenyl, 4-t-
Butylphenyl, 2,4-di-t-amylphenyl, 4
-Tetradecanamidophenyl), heterocyclic groups (e.g. 2-furyl, 2-thienyl, 2-pyrimidinyl, 2
-Benzothiazolyl), cyano group, hydroxy group, nitro group, carboxy group, amino group, alkoxy group (for example, methoxy, ethoxy, 2-methoxyethoxy, 2-
Dodecylethoxy, 2-methanesulfonylethoxy),
Aryloxy group (eg, phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 3-t-butyloxycarbamoylphenoxy, 3-methoxycarbamoyl), acylamino group (eg, acetamide, benzamide, tetradecane) Amide, 2- (2,4-di-t-amylphenoxy) butanamide, 2- (3-t-butyl-4-hydroxyphenoxy) butanamide, 2- {4- (4-hydroxyphenylsulfonyl) phenoxy} decanamide) , An alkylamino group (eg, methylamino, butylamino, dodecylamino, diethylamino, methylbutylamino), an anilino group (eg, phenylamino, 2-chloroanilino, 2-chloro-5-tetradecaneaminoanilino, 2-chloro-). 5- Decyloxycarbonyl anilino, N- acetyl anilino, 2-chloro-5- {2-
(3-t-butyl-4-hydroxyphenoxy) dodecanamide} anilino), ureido group (for example, phenylureido, methylureido, N, N-dibutylureido), sulfamoylamino group (for example, N, N-dipro). Pilsulfamoylamino, N-methyl-N-decylsulfamoylamino), alkylthio group

(Eg, methylthio, octylthio, tetradecylthio, 2-phenoxyethylthio, 3-phenoxypropylthio, 3- (4-t-butylphenoxy) propylthio), arylthio group (eg, phenylthio, 2-butoxy-). 5-t-octylphenylthio, 3-pentadecylphenylthio, 2-carboxyphenylthio, 4-tetradecanamidophenylthio),
Alkoxycarbonylamino group (eg, methoxycarbonylamino, tetradecyloxycarbonylamino), sulfonamide group (eg, methanesulfonamide, hexadecanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, octadecanesulfonamide, 2-methoxy- 5-t-butylbenzenesulfonamide), a carbamoyl group (eg, N-ethylcarbamoyl, N, N-dibutylcarbamoyl, N-
(2-dodecyloxyethyl) carbamoyl, N-methyl-N-dodecylcarbamoyl, N- {3- (2,4-
Di-t-amylphenoxy) propyl} carbamoyl), sulfamoyl group (for example, N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N- (2
-Dodecyloxyethyl) sulfamoyl, N-ethyl-N-dodecylsulfamoyl), N, N-diethylsulfamoyl), sulfonyl group (e.g., methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl), alkoxycarbonyl group ( For example, methoxycarbonyl, butyloxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl),
Heterocyclic oxy group (for example, 1-phenyltetrazole-5-oxy, 2-tetrahydropyranyloxy), azo group (for example, phenylazo, 4-methoxyphenylazo, 4-pivaloylaminophenylazo, 2-hydroxy-). 4-propanoylphenylazo), acyloxy group (eg acetoxy), carbamoyloxy group (eg N-methylcarbamoyloxy, N-phenylcarbamoyloxy), silyloxy group (eg trimethylsilyloxy, dibutylmethylsilyloxy), aryl Oxycarbonylamino group (for example, phenoxycarbonylamino), imide group, for example, N-succinimide, N-phthalimide, 3-octadecenylsuccinimide, heterocyclic thio group (for example, 2-benzothiazolylthio, 2, Four Di-phenoxy-1,3,5-triazole-6-thio, 2-pyridylthio), sulfinyl group (for example, dodecanesulfinyl, 3-pentadecylphenylsulfinyl, 3-phenoxypropylsulfinyl), phosphonyl group (for example, phenoxyphosphon) Nyl, octyloxyphosphonyl, phenylphosphonyl), aryloxycarbonyl group (for example, phenoxycarbonyl), acyl group (for example, acetyl, 3-phenylpropanoyl, benzoyl, 4-dodecyloxybenzoyl), azolyl group (for example, Imidazolyl, pyrazolyl, 3-chloro-pyrazol-1-yl, triazolyl).

Of these substituents, the group capable of having a substituent may further have an organic substituent or a halogen atom linked by a carbon atom, an oxygen atom, a nitrogen atom or a sulfur atom. Of these substituents, preferred R ₁₁ is a halogen atom, an alkoxy group, an aryloxy group, an acylamino group, a ureido group, a sulfamoylamino group, an alkoxycarbonylamino group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group. , A carbamoyloxy group, an imide group, or an acyl group.

R ₁₂ represents an electron-withdrawing group, specifically, a halogen atom, an aryl group, a heterocyclic group, a cyano group, a nitro group, a carboxy group, a sulfo group, an acylamino group, a ureido group, a sulfamoylamino group, an alkylthio group. Group, arylthio group, alkoxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, imide group, heterocyclic thio group, sulfinyl group, phosphonyl group, acyl group,
Represents an azolyl group. More particularly, these groups are R ₁₁
It is a group having the same meaning as the group specifically shown in. Preferably R ₁₂
Is a halogen atom, an acylamino group, or a carbamoyl group, and more preferably a halogen atom. n is preferably 3-5. m is preferably 1 to 3.

X ₁ represents a group capable of splitting off upon reaction with an oxidation product of an aromatic primary amine color developing agent. The splitting-off group is specifically described by a halogen atom, an alkoxy group,
Aryloxy group, acyloxy group, alkyl or aryl sulfonyloxy group, acylamino group, alkyl or aryl sulfonamide group, alkoxycarbonyloxy group, aryloxycarbonyloxy group,
An alkyl, aryl or heterocyclic thio group, a carbamoylamino group, a 5- or 6-membered nitrogen-containing heterocyclic group,
There are an imide group, an arylazo group and the like, and these groups may be further substituted with a group which is allowed as a substituent for R ₁₁ .

More specifically, a halogen atom (eg, fluorine atom, chlorine atom, bromine atom), an alkoxy group (eg, ethoxy, dodecyloxy, methoxyethylcarbamoylmethoxy, carboxypropyloxy, methylsulfonylethoxy, ethoxycarbonylmethoxy), aryl An oxy group (for example, 4-methylphenoxy, 4-
Chlorophenoxy, 4-methoxyphenoxy, 4-carboxyphenoxy, 3-ethoxycarboxyphenoxy, 3-acetylaminophenoxy, 2-carboxyphenoxy), acyloxy group (for example, acetoxy, tetradecanoyloxy, benzoyloxy), alkyl or aryl. Sulfonyloxy groups (eg, methanesulfonyloxy, toluenesulfonyloxy), acylamino groups (eg, dichloroacetylamino, heptafluorobutyrylamino), alkyl or aryl sulfonamide groups (eg, methanesulfonamino, trifluoromethanesulfonamino, p-toluenesulfonylamino), an alkoxycarbonyloxy group (eg, ethoxycarbonyloxy, benzyloxycarbonyloxy), aryl Oxycarbonyl group (e.g., phenoxycarbonyloxy), alkyl, aryl or heterocyclic thio group (e.g., dodecylthio,
1-carboxydodecylthio, phenylthio, 2-butoxy-5-t-octylphenylthio, tetrazolylthio), carbamoylamino group (for example, N-methylcarbamoylamino, N-phenylcarbamoylamino),
5- or 6-membered nitrogen-containing heterocyclic group (for example, imidazolyl, pyrazolyl, triazolyl, tetrazolyl,
1,2-dihydro-2-oxo-1-pyridyl), an imide group (eg, succinimide, hydantoinyl), an arylazo group (eg, phenylazo, 4-methoxyphenylazo), and the like. In addition to these, X ₁ may take the form of a bis-type coupler obtained by condensing a 4-equivalent coupler with an aldehyde or a ketone as a leaving group bonded via a carbon atom. Further, X ₁ may contain a photographically useful group such as a development inhibitor or a development accelerator. Preferred X
₁ is a halogen atom, an alkoxy group, an aryloxy group, an alkyl or arylthio group, or a 5- or 6-membered nitrogen-containing heterocyclic group bonded to the coupling active position with a nitrogen atom. Most preferably, it is an arylthio group.

When the vinyl monomer contains the one represented by the formula (II), the vinyl group may have a substituent other than the one represented by the formula (II). Preferred substituents are hydrogen atom, chlorine atom, Alternatively, it represents a lower alkyl group having 1 to 4 carbon atoms (eg, methyl group, ethyl group).

Monomers including those represented by formula (II) may form copolymers with non-color forming ethylenic monomers that do not couple with the oxidation products of aromatic primary amine developers.

Non-color-forming, ethylenic monomers that do not couple with the oxidation products of aromatic primary amine developers include acrylic acid, α-chloroacrylic acid, α-alkylacrylic acid (eg methacrylic acid) and their Esters or amides derived from acrylic acids (eg, acrylamide, n-butyl acrylamide, t-butyl acrylamide, diacetone acrylamide, methacrylamide, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl acrylate) , Iso-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and β-. Mud carboxymethyl methacrylate),
Methylenedibisacrylamide, vinyl esters (eg vinyl acetate, vinyl propionate and vinyl laurate), acrylonitrile, methacrylonitrile, aromatic vinyl compounds (eg styrene and its derivatives, vinyltoluene, divinylbenzene, vinylacetophenone and sulfostyrene). , Itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ether (eg vinyl ethyl ether),
Maleic acid, maleic anhydride, maleic acid ester, N
-Vinyl-2-pyrrolidone, N-vinylpyridine, and 2- and 4-vinylpyridine. Two or more non-color-forming ethylenically unsaturated monomers used herein can be used together. For example, n-butyl acrylate and methyl acrylate, styrene and methacrylic acid, methacrylic acid and acrylamide, methyl acrylate and diacetone acrylamide, and the like.

As is well known in the polymer color coupler art, the non-chromogenic, ethylenically unsaturated monomers for copolymerization with the solid water-insoluble monomer coupler are the physical properties and / or chemistry of the copolymer formed. Properties such as solubility,
The compatibility of the binder of the photographic colloidal composition, such as gelatin, its flexibility, thermal stability, etc., can be selected to be favorably influenced. The polymer coupler used in the present invention may be water-soluble or water-insoluble, and among them, a polymer coupler latex is particularly preferable.

Specific examples of the coupler represented by formula (II) of the present invention are shown below, but the present invention is not limited thereto.

[0101]

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[0102]

[Chemical 33]

[0103]

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[0104]

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[0105]

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[0106]

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[0107]

[Chemical 38]

Synthesis of these couplers is described in British Patent 1,5
52,701 and European Patent Publication 348,135. These couplers of the present invention are described in British Patent 1,525,70.
1, European Published Patent No. 348,135, US Pat. Nos. 3,227,554, 4,351,897,
No. 4,556,630, No. 4,584,266, No. 4,264,723, No. 4,308,343, No. 4,367,282 and No. 4,436,808. Can be synthesized by the method described above.

The couplers represented by the formulas (1) and (II) of the present invention have spectral absorption waveforms of a dye obtained from the coupler by color development and a color-forming dye obtained from another coupler used in the same layer. Selected to approximate. With this, color filters with various spectral characteristics, light sources,
The printer suitability in various auto printers of various companies using the density sensor is stably maintained even when the photographing conditions and the exposure amount are changed, and it is possible to supply a print having a constant quality. Furthermore, the formulas (1) and (I
The coupler represented by I) has improved photographic sensitivity and exhibits stable color development processability. The couplers represented by formulas (I) and (II) of the present invention may be used in any layer in the silver halide light-sensitive material, but may be added to the green-sensitive emulsion layer and / or its adjacent layer. preferable. The total amount added is 1 × 10 ^{−3 to} 1.0 g / m ² , preferably 5
× 10 ^{−3 to} 0.8 g / m ² , more preferably 1 × 10 ⁻² to
It is 0.5 g / m ² . The method of adding the coupler of the present invention to the light-sensitive material is based on the method of other couplers described later,
The weight ratio of the high-boiling organic solvent used as the dispersion solvent to the magenta coupler is preferably 0 to 3.0, more preferably 0.3 to 2.0, and even more preferably 0.5 to 1.2.

The couplers represented by the formulas (I) and (II) of the present invention can be used with known magenta couplers. As the known magenta coupler, 5-pyrazolone compounds are preferable, and US Pat. No. 4,310,619
No. 4,351,897, European Patent No. 73,63.
6, U.S. Pat. Nos. 3,061,432 and 3,72.
No. 5,067, Research Disclosure No. Two
4220 (June 1984), JP-A-60-33552.
No., Research Disclosure No. 24230
(June 1984), JP-A-60-43659, 6
1-72238, 60-35730, 55-1
No. 18034, No. 60-185951, U.S. Patent Nos. 4,500,630, 4,540,654, 4,556,630, and International Publication WO88 / 0479.
Those described in No. 5 and the like are particularly preferable.

In the light-sensitive material of the present invention, a hydrophilic colloid layer for the purpose of improving the sharpness of an image can be decolorized by the treatment described in European Patent EP0,337,490A2, pages 27 to 76. Dye (among others, oxonol dye) is added so that the optical reflection density at 680 nm of the light-sensitive material is 0.70 or more, and dihydric alcohol (dihydric alcohol) ( For example, it is preferable to contain 12% by weight or more (more preferably 14% by weight or more) of titanium oxide surface-treated with trimethylolethane or the like. Further, in the color photographic light-sensitive material according to the present invention, it is preferable to use a color image storability improving compound as described in European Patent EP 0,277,589A2 together with a coupler. In particular, it is preferably used in combination with a pyrazoloazole coupler.

That is, compound (F) and // which chemically bond with an aromatic amine type developing agent remaining after color development processing to form a chemically inactive and substantially colorless compound.
Alternatively, the compound (G) which chemically bonds with an oxidized product of an aromatic amine color developing agent remaining after the color developing treatment to form a chemically inactive and substantially colorless compound is used simultaneously or alone. However, it is preferable to prevent the occurrence of stains and other side effects due to the formation of a coloring dye due to the reaction of the residual color developing agent in the film or the oxidant thereof with the coupler during storage after processing. Further, to the light-sensitive material according to the present invention, a fungicide such as that described in JP-A-63-271247 is added in order to prevent various molds and bacteria that propagate in the hydrophilic colloid layer and deteriorate the image. Preferably. In the present invention, it is preferable that the dry film thickness of the silver halide color photographic light-sensitive material excluding the support is 25 μm or less in order to reduce the carryover amount and increase the silver recovery rate. 1 for color negative film
3 to 23 μm, 7 to 12 μ for car paper
About m is preferable. The reduction of these film thicknesses is due to the amount of gelatin,
This can be achieved by reducing the amount of silver, the amount of oil, the amount of coupler, etc., but it is most preferable that the amount of gelatin is reduced. Here, the film thickness can be measured by an ordinary method after allowing the sample to stand at 25 ° C. and 60 RH% for 2 weeks.

In the silver halide color photographic light-sensitive material used in the present invention, the film swelling degree of the photographic layer is 1.5 to.
A value of 4.0 is preferable from the viewpoint of improving stain and improving image storability. Particularly, in the range of 1.5 to 3.0, a further effect can be obtained. The swelling degree of the present invention means a value obtained by dividing the film thickness of the photographic layer after dipping the color light-sensitive material in distilled water at 33 ° C. for 2 minutes by the film thickness of the dried photographic layer.

The photographic layer means a hydrophilic colloid group layer including at least one photosensitive silver halide emulsion layer and having a water-permeable relationship with this layer. The back layer provided on the opposite side of the support from the photographic photosensitive layer is not included. The photographic layer is usually formed of a plurality of layers involved in photographic image formation, and in addition to the silver halide emulsion layer, an intermediate layer, a filter layer, an antihalation layer, a protective layer and the like are included.

Any method may be used to adjust the degree of swelling. For example, the amount and type of gelatin used in the photographic film, the amount and type of hardener, or the drying conditions after coating the photographic layer. And can be adjusted by changing the aging condition. It is advantageous to use gelatin for the photographic layer, 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, sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol. Use of various synthetic hydrophilic polymer substances such as single or copolymers of polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole and polyvinylpyrazole. You can As the gelatin, acid-treated gelatin may be used in addition to lime-treated gelatin, and gelatin hydrolyzate and gelatin enzyme-decomposed product may also be used. Examples of the gelatin derivative include gelatin such as acid halide,
Those obtained by reacting various compounds such as acid anhydrides, isocyanates, bromoacetic acid, alkane sultones, vinyl sulfonamides, maleinimide compounds, polyalkylene oxides and epoxy compounds are used.

As the gelatin-graft polymer, a homopolymer or copolymer of vinyl monomers such as acrylic acid, methacrylic acid, derivatives thereof such as esters and amides, acrylonitrile and styrene are grafted onto gelatin. What was made to use can be used. In particular, a graft polymer with a polymer having a certain degree of compatibility with gelatin, for example, a polymer such as acrylic acid, methacrylic acid, acrylamide, methacrylamide, or hydroxyacyl methacrylate is preferable.
Examples of these are U.S. Pat. Nos. 2,763,625 and 2,8.
31, 767, 2,956, 884 and the like. Typical synthetic hydrophilic polymer substances are, for example, West German patent application (OLS) 2,312,708, US Pat.
No. 620,751, No. 3,879,205, Japanese Patent Publication No. 4
No. 3-7561.

Examples of hardening agents include chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glital aldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane. Derivatives (2,3-dihydroxydioxane, etc.), active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, bis (vinylsulfonyl) methyl ether, N, N'-methylenebis- [β- (vinyl Sulfonyl) propionamide] etc.), active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine etc.), mucohalogen acids (mucochloric acid, mucophenoxycycloric acid etc.), isoxazoles, dialdehyde starch, 2-black And 6-hydroxy-triazinyl gelatin can be used alone or in combination. Particularly preferred hardeners are aldehydes,
They are active vinyl compounds and active halogen compounds.

As the support used in the light-sensitive material of the present invention, a white polyester support for display or a layer containing a white pigment is provided on the support having a silver halide emulsion layer. A support may be used. Further, in order to improve the sharpness, it is preferable to apply an antihalation layer on the silver halide emulsion layer coated side or the back side of the support. In particular, the transmission density of the support is 0.3 so that the display can be viewed with both reflected and transmitted light.
It is preferably set in the range of 5 to 0.8.

The light-sensitive material according to the present invention may be exposed to visible light or infrared light. The exposure method may be low-illuminance exposure or high-illuminance short-time exposure, and in the latter case, a laser scanning exposure method in which the exposure time per pixel is shorter than 10 ⁻⁴ seconds is preferable. Further, it is preferable to use the band stop filter described in U.S. Pat. No. 4,880,726 upon exposure. As a result, light color mixture is removed, and color reproducibility is significantly improved.

The processing method of the present invention can be applied to various light-sensitive materials. Color negative film, color negative paper, color reversal paper, auto positive paper, color reversal film, negative film for movies, positive film for movies, radiographic films, plate making films such as squirrel films, black and white negative films, etc. In particular, application to a color negative film and a color negative paper is preferable.

[0121]

EXAMPLES Specific examples of the present invention will be shown below by way of examples.
The present invention is not limited to these. On the undercoated cellulose triacetate film support, each layer having the composition as shown below is multilayer-coated,
Sample 101, which is a color negative film, was prepared. (Photosensitive layer composition) The main materials used for each layer are classified as follows; ExC: Cyan coupler UV: UV absorber ExM: Magenta coupler HBS: High boiling point organic solvent ExY: Yellow coupler H: Gelatin Curing agent ExS: Sensitizing dye The numbers corresponding to the respective components indicate the coating amount expressed in units of g / m ² , and for silver halide, the coating amount in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown in mol unit per mol of silver halide in the same layer.

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

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

Third Layer (Low Sensitivity Red Sensitive Emulsion Layer) Silver iodobromide emulsion A Silver 0.25 Silver iodobromide emulsion B Silver 0.25 ExS-1 6.9 × 10 ^-5 ExS-2 1.8 × 10 ^-5 ExS-3 3.1 × 10 ^-4 ExC-1 0.17 ExC-3 0.030 ExC-4 0.10 ExC-5 0.020 ExC-6 0.010 Cpd-2 0.025 HBS-1 0.10 Gelatin 0.87

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

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

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

Seventh layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion E Silver 0.15 Silver iodobromide emulsion F Silver 0.10 Silver iodobromide emulsion G Silver 0.10 ExS-4 3.0 × 10 ^-5 ExS-5 2.1 × 10 ^-4 ExS-6 8.0 × 10 ^-4 ExM-2 0.33 ExM-3 0.086 ExY-1 0.015 HBS-1 0.30 HBS-3 0.010 Gelatin 0.73

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

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

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

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

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

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

14th layer (second protective layer) Silver iodobromide emulsion M Silver 0.10 H-1 0.40 B-1 (diameter 1.7 μm) 5.0 × 10 ^-2 B-2 (diameter 1.7 μm) 0.15 B-3 0.05 S-1 0.20 Gelatin 0.70

Further, in order to improve storage stability, processability, pressure resistance, antifungal / antibacterial property, antistatic property and coating property of each layer, W-1 to W-3, B-4 to B- may be used. 6, F
-1 to F-17 and iron salt, lead salt, gold salt, platinum salt,
It contains a palladium salt, an iridium salt, and a rhodium salt.

[0137]

[Table 9]

In Table 9, (1) Emulsions J to L were prepared according to the examples of JP-A-2-91938.
It is reduction-sensitized during grain preparation using thiourea dioxide and thiosulfonic acid. (2) Emulsions A to I were prepared according to the examples of JP-A-3-237450.
Gold sensitization, sulfur sensitization and selenium sensitization are performed in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate. (3) For the preparation of tabular grains, low molecular weight gelatin is used according to the examples of JP-A 1-158426. (4) Dislocation lines as described in JP-A-3-237450 are observed in the tabular grains by using a high voltage electron microscope. (5) Emulsion L is a double structure grain containing an internal high iodine core described in JP-A-60-143331.

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

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

[0141]

[Chemical Formula 39]

[0142]

[Chemical 40]

[0143]

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[0144]

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[0145]

[Chemical 43]

[0146]

[Chemical 44]

[0147]

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[0148]

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[0149]

[Chemical 47]

[0150]

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[0151]

[Chemical 49]

[0152]

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[0153]

[Chemical 51]

[0154]

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[0155]

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[0156]

[Chemical 54]

The above color negative film (Sample 101)
Was cut into a width of 35 mm. Next, a color paper (Sample 102) was prepared as follows. After the corona discharge treatment is applied to the surface of a paper support laminated on both sides with polyethylene, a gelatin subbing layer containing sodium dodecylbenzene sulfonate is provided, and various photographic constituent layers are further coated to form a color paper having the layer constitution shown below. (102) was produced. The coating liquid was prepared as follows.

Preparation of coating solution for first layer Yellow coupler (ExY) 153.0 g, color image stabilizer (C
pd-1) 15.0 g, color image stabilizer (Cpd-2) 7.5 g,
16.0 g of color image stabilizer (Cpd-3) was used as a solvent (Solv-
1) 25 g, solvent (Solv-2) 25 g and ethyl acetate 1
This was dissolved in 80 cc, and this solution was emulsified and dispersed in 1000 g of a 10% gelatin aqueous solution containing 10 cc of 10% sodium dodecylbenzenesulfonate and 10 g of citric acid to prepare an emulsified dispersion A. On the other hand, silver chlorobromide emulsion A (cube, average grain size of 0.
A 3: 7 mixture of 88 μm large size emulsion A and 0.70 μm small size emulsion A (silver molar ratio). Coefficients of variation of grain size distribution are 0.08 and 0.10 respectively, and silver bromide for each size emulsion
0.3 mol% was locally contained on a part of the surface of the grain based on silver chloride) was prepared. In this emulsion, the blue-sensitive sensitizing dyes A and B shown below are large-sized emulsions A per mol of silver.
For, 2.0 × 10 ^-4 mol, respectively, also to the small size emulsion A, are respectively 2.5 × 10 ^-4 mol per mol. The chemical ripening of this emulsion was performed by adding a sulfur sensitizer and a gold sensitizer. The above emulsified dispersion A and this silver chlorobromide emulsion A were mixed and dissolved to prepare a coating solution for the first layer having the following composition. The emulsion coating amount indicates a coating amount equivalent to silver.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. As the gelatin hardening agent for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. Also, Cpd-14 and C are added to each layer.
total amount pd-15 were added to each so that 25.0 mg / m ² and 50.0 mg / m ^2. The following spectral sensitizing dyes were used for the silver chlorobromide emulsion of each photosensitive emulsion layer. Blue-sensitive emulsion layer

[0160]

[Chemical 55]

(2.0 × 10 ^-4 mol for large-sized emulsion and 2.5 × 10 ^-4 mol for small-sized emulsion per mol of silver halide) Green-sensitive emulsion layer

[0162]

[Chemical 56]

(4.0 × 10 ⁻⁴ mol per mol of silver halide for large size emulsion, and for small size emulsion)
5.6 × 10 ^-4 mol) and,

[0164]

[Chemical 57]

(7.0 × 10 ⁻⁵ mol for large size emulsion and 1.0 × 10 ⁻⁴ mol for small size emulsion per mol of silver halide) Red-sensitive emulsion layer

[0166]

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(0.9 × 10 ^-4 mol for large size emulsion and 1.1 × 10 ^-4 mol for small size emulsion per mol of silver halide)

Further, the following compounds were added in an amount of 2.6 × 10 ^-3 mol per mol of silver halide.

[0169]

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For the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer, 1- (5-methylureidophenyl)-
5-Mercaptotetrazole to silver halide 1
8.5 x 10 ^-5 mol, 7.7 x 10 ^-4 mol, 2.5 x 10 per mol
^-4 mol was added. Further, 4-hydroxy-6-methyl-1,3,3a, 7 was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer.
Tetrazaindene was added in an amount of 1 × 10 ^-4 mol and 2 × 10 ^-4 mol per mol of silver halide, respectively. Further, in order to prevent irradiation, the following dye (the amount in parentheses represents the coating amount) was added to the emulsion layer.

[0171]

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(Layer Structure) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents the coating amount in terms of silver.

Support Polyethylene laminated paper [Polyethylene on the first layer side contains a white pigment (TiO ₂ ) and a bluish dye (ultraviolet)]

First Layer (Blue Sensitive Emulsion Layer) Silver Chlorobromide Emulsion A 0.27 Gelatin 1.36 Yellow Coupler (ExY) 0.79 Color Image Stabilizer (Cpd-1) 0.08 Color Image Stabilizer (Cpd-2) 0.04 Color Image stabilizer (Cpd-3) 0.08 Solvent (Solv-1) 0.13 Solvent (Solv-2) 0.13

Second layer (color mixing prevention layer) Gelatin 1.00 Color mixing inhibitor (Cpd-4) 0.06 Solvent (Solv-2) 0.25 Solvent (Solv-3) 0.25 Solvent (Solv-7) 0.03

Third Layer (Green Sensitive Emulsion Layer) Silver chlorobromide emulsion (cubic, 1: 3 mixture of large size emulsion B having an average grain size of 0.55 μm and small size emulsion B of 0.39 μm (Ag molar ratio)) The coefficient of variation of the grain size distribution was 0.10 and 0.08, respectively, and 0.8 mol% of AgBr was locally contained in a part of the grain surface based on silver chloride in each size emulsion).
0.13 Gelatin 1.45 Magenta coupler (ExM) 0.16 Color image stabilizer (Cpd-2) 0.03 Color image stabilizer (Cpd-5) 0.15 Color image stabilizer (Cpd-6) 0.01 Color image stabilizer (Cpd-7) 0.01 Color Image stabilizer (Cpd-8) 0.08 Solvent (Solv-3) 0.50 Solvent (Solv-4) 0.15 Solvent (Solv-5) 0.15

Fourth Layer (Color Mixing Prevention Layer) Gelatin 0.70 Color mixing inhibitor (Cpd-4) 0.04 Solvent (Solv-2) 0.18 Solvent (Solv-3) 0.18 Solvent (Solv-7) 0.02

Fifth layer (red-sensitive emulsion layer) Silver chlorobromide emulsion (cubic, 1: 4 mixture of large size emulsion C having an average grain size of 0.50 μm and small size emulsion C of 0.41 μm (Ag mole ratio)) The coefficient of variation of the grain size distribution is 0.09 and 0.11, and AgBr 0.8 mol% was locally contained in a part of the grain surface based on silver chloride in each size emulsion)
0.20 Gelatin 0.85 Cyan coupler (ExC) 0.33 Ultraviolet absorber (UV-2) 0.18 Color image stabilizer (Cpd-1) 0.33 Color image stabilizer (Cpd-6) 0.01 Color image stabilizer (Cpd-8) 0.01 Color image Stabilizer (Cpd-9) 0.01 Color image stabilizer (Cpd-10) 0.01 Color image stabilizer (Cpd-11) 0.01 Solvent (Solv-1) 0.01 Solvent (Solv-6) 0.22

Sixth layer (UV absorbing layer) Gelatin 0.55 UV absorbing agent (UV-1) 0.38 Color image stabilizer (Cpd-5) 0.02 Color image stabilizer (Cpd-12) 0.15

Seventh layer (protective layer) Gelatin 1.13 Polyvinyl alcohol acrylic modified copolymer (degree of modification
17%) 0.05 Liquid paraffin 0.02 Surfactant (Cpd-13) 0.01

[0181]

[Chemical formula 61]

[0182]

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[0183]

[Chemical formula 63]

[0184]

[Chemical 64]

[0185]

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[0186]

[Chemical formula 66]

[0187] Next, the color negative film sample 101 and the color paper sample 102 obtained as described above.
After the imagewise exposure, was subjected to continuous processing in the following processing steps.
In the color development processing, the film and the paper were processed separately, and a processing machine was prototyped so that they could be processed in a common processing bath after the desilvering step. The daily throughput was 1 m ² for negative film and 8 m ² for paper. Under these conditions, continuous processing (running test) was performed until the tank was replenished with twice the capacity of the color developing tank. Processing process Temperature Time Replenishment amount (ml) * Negative paper Negative paper Negative paper Color development 40 ℃ ---- 3'15 "---- 260 ----- Color development ---- 40 ℃ ---- 30 "---- 40 Bleach-fix 38 ℃ 38 ℃ 3'00" 30 "520 50 Rinse ** 38 ℃ 38 ℃ 15" 10 "---- Rinse 38 ℃ 38 ℃ 15" 10 "---- Rinse 38 ℃ 38 ℃ 15 "10" 260 150 Dry 60 ℃ 70 ℃ 60 "60" * 1 square meter of photosensitive material ** Rinsing is a three-tank countercurrent method to Kara and carryover per 1 square meter of photosensitive material The amount of each bath was 60 ml for the color negative film and 40 ml for the color paper.

The composition of each processing liquid is as follows. [Color developer] Tank liquid (g) Replenisher (g) Diethylenetriaminepentaacetic acid 2.0 2.0 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 2.0 Sodium sulfite 3.9 6.1 Potassium carbonate 37.5 39.0 Potassium bromide 2.0 --- Iodide Potassium 2.0 mg--Hydroxylamine sulfate 2.4 4.0 2-Methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 4.5 11.0 Water was added to 1.0 liter 1.0 liter pH (potassium hydroxide And adjusted with sulfuric acid) 10.05 10.25

[Color developer] [Tank solution] [Replenisher] water 800 ml 800 ml ethylenediaminetetraacetic acid 3.0 g 3.0 g 4,5-dihydroxybenzene-1,3-disulfonic acid disodium salt 0.5 g 0.5 g triethanolamine 12.0 g 12.0 g potassium chloride 11.5 g-potassium bromide 0.03 g-potassium carbonate 27.0 g 27.0 g optical brightener (SR-5) 2.0 g 5.0 g sodium sulfite 0.1 g 0.1 g disodium-N, N-bis (sulfo Natoethyl) hydroxyl amine 5.0 g 12.0 g Sodium triisopropylnaphthalene (β) sulfonate 0.1 g 0.1 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline / 3/2 sulfuric acid・ 1 water salt 5.0 g 20.0 g Add water 1000 ml 1000 ml pH (25 ° C / Adjusted with potassium oxide and sulfuric acid) 10.00 11.80

Further, the fluorescent whitening agent (SR
-5) was changed as follows and a running test was conducted for each of them. [Color developer same as SR-9 except that SR-5 is changed to SR-9. [Same as color developer SR-5 was changed to SR-28. [Same as color developer SR-5 except that the fluorescent whitening agent UV-1 below is used.

[0191]

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(Bleach-fixing solution) Tank solution (g) Replenishing solution (g) 1,2-cyclohexanediamine tetraammonium ferric acetate monohydrate 130 195 Ammonium sulfite 19 57 Ammonium thiosulfate aqueous solution (700 g / l) 200 ml 400 ml Imidazole 15 45 Ethylenediaminetetraacetic acid 5 5 Add water 1.0 liter 1.0 liter pH [Prepared with ammonia water and acetic acid] 6.0 5.45

(Rinse Solution A) Common to Tank Solution and Replenisher (Unit: g) Tap water is used as H type strong acid cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas Co.) and OH type strongly basic anion exchange resin. (The same Amberlite IR-40
0) packed in a mixed bed column to treat calcium and magnesium ions at a concentration of 3 mg / liter or less, and then 20 mg of sodium diisocyanurate dichloride /
L and 150 mg / L of sodium sulfate were added. The pH of this liquid was in the range of 6.5 to 7.5.

Next, the composition of the rinse liquid was changed as follows, and a running test was conducted for each of them. (Rinse solution B) Common tank solution and replenisher solution Rinse solution A 1000 ml V-1 0.2 g Ethylenediaminetetraacetic acid disodium salt 0.5 g with NaOH / sulfuric acid pH 7.0 (Rinse solution C) Tank solution, replenisher solution Common rinse solution A 1000 ml V-15 0.2 g Ethylenediaminetetraacetic acid disodium salt 0.5 g With NaOH / sulfuric acid pH 7.0 (rinse solution D) Tank solution, replenisher common rinse solution A 1000 ml V-18 0 0.2 g Ethylenediaminetetraacetic acid disodium salt 0.5 g With NaOH / sulfuric acid pH 7.0 (rinse solution E) Common for tank solution and replenisher solution Rinse solution A 1000 ml V-21 0.2 g Ethylenediaminetetraacetic acid disodium salt PH 7.0 with 5 g NaOH / sulfuric acid

For each running equilibrium solution, the surface tension of the final rinse solution after the end of running was measured, and the results are shown in Table 10. Further, samples 101 and 102 exposed through a wedge wedge at 10 cms were processed, and the film (sample 101) was measured for photofading of magenta dye. This shows the amount of decrease in density after irradiation with 70,000 Lux xenon light at a magenta density of 2.0 for 3 days.
(ΔD _G 2.0) Further, the dirt on the base surface was judged with the naked eye. Further, the paper (sample 102) has an increased yellow density (ΔD) in the unexposed area at the start and end of running.
_B min) was measured. The results are shown in Table 10.

[0196]

[Table 10]

From the above results, the present invention of 20 to 60 d
When treated in a final rinse bath having a surface tension of yn / cm, the color negative film has improved magenta photofading, and at the same time, the back surface (base surface) of the film is improved in stain and the yellow stain of the color paper is also improved. Has also been reduced. (No.5 ~ 20) Especially the surface tension is 25 ~.
The case of 50 dyn / cm is preferable. Further, particularly preferable results are obtained when the fluorescent whitening agent represented by the general formula (III) is used in the developer.

Example. 2 Example. No. 1 sample 101, the green-sensitive emulsion layer (7th,
Color negative film samples 103 to 106 were prepared by changing the magenta couplers (8 and 9 layers) as follows. Sample 101 103 104 105 105 106 7th layer EXM-2 II-24 I-22 M-1 M-4 EXM-3 EXM-3 EXM-3 M-2 M-2 8th layer EXM-2 II-24 I- 22 M-1 M-4 EXM-3 EXM-3 EXM-3 M-2 M-2 9th layer EXM-1 EXM-1 EXM-1 M-1 M-4 EXM-4 EXM-4 EXM-4 M -2 M-2 EXM-5 EXM-5 EXM-5 M-3 M-3 Magenta couplers The structures of M-1 to M-4 are shown below.

[0199]

[Chemical 68]

[0200]

[Chemical 69]

The above sample was treated with N in the same manner as in Example 1.
O. Treatment with 1 to 12 running solutions was carried out, and the light fading of magenta was measured. The results are shown in Table 11.

[0202]

[Table 11]

From the above, N using the rinse bath of the present invention
o. In Nos. 5 to 12, the fading of magenta was improved, and the effect was remarkable especially in Samples 101, 103 and 104 containing the preferable magenta couplers represented by the general formulas (I) and (II).

[0204]

EFFECTS OF THE INVENTION Different photographic light-sensitive materials can rapidly solve problems in photographic properties (eg, increase in yellow stain, prevention of fading of magenta dye).

Claims (4)

[Claims] 1. A continuous processing method of two or more different types of silver halide color photographic light-sensitive materials, which is followed by color development and desilvering, followed by processing with at least a common washing or stabilizing solution, and The surface tension of the stabilizing solution is 20-60
A method for processing a silver halide color photographic light-sensitive material, characterized in that it is dyn / cm. 2. The silver halide according to claim 1, wherein each of the silver halide color photographic light-sensitive materials contains at least one coupler selected from the following formula (I) or (II). Color photographic light-sensitive material processing method. General formula (I) (In the formula, R ₁ represents a hydrogen atom or a substituent. Z represents a non-metal atom group necessary to form a 5-membered azole ring containing 2 to 4 nitrogen atoms, and the azole ring is a substituent. (Including a condensed ring), X represents a hydrogen atom or a group capable of splitting off upon a coupling reaction with an oxidized product of a developing agent.) General formula (II) (In the formula, R ₁₁ represents a substituent, R ₁₂ represents an electron-withdrawing group. M represents an integer of 1 to 5, and when m is 2 or more, R ₁₂ represents
₁₁ may be the same or different. n represents an integer of 2 to 5, and R ₁₂ may be the same or different. X ₁ represents a group capable of splitting off upon reaction with an oxidized product of an aromatic primary amine color developing agent. A dimer or a multimer of R ₁₁ , R ₁₂ or X ₁ which are bonded to each other via a divalent or divalent or higher valent group may be formed. ) 3. The rinsing water or stabilizing solution is represented by the following general formula (I
2. A compound containing the compound of II).
Or the processing method of the silver halide color photographic light-sensitive material as described in 2 above. General formula (III) (In the general formula (III), L ¹ , L ² , L ³ and L ⁴ may be the same or different; —OR ¹ or —N—R ² (R ³ )
And four substituents L ¹ in the general formula (III)
To L ⁴ have a total of two or more substituents in the general formula (IV) group. Here, R ¹ and R ² each represent a hydrogen atom, an alkyl group, or an alkyl group having a substituent in the following general formula (IV) group, and R ³ represents an alkyl group or a general formula (IV) group below. Represents an alkyl group having a substituent of. ) General formula (IV): In the general formula (IV), X represents halogen and R represents an alkyl group. Further, in the general formulas (III) and (IV), M represents a hydrogen atom, an alkali metal, tetraalkylammonium or pyridinium. 4. The method of processing a silver halide color photographic light-sensitive material according to claim 2, wherein two kinds of processing machines for color negative film processing and color negative printing processing are integrated.