JPH06332127A - Color image forming method - Google Patents

Abstract

PURPOSE:To decrease after-colors without crystallization of a fluorescent whitening agent having specific substituents in spite of low-temp. preservation of a processing liquid and to obtain color images having an excellent image preservable property by using a diaminostilben fluoescent whitening agent. CONSTITUTION:The silver halide emulsion used for a silver halide color photographic sensitive material consists of a high chloride silver emulsion of >=90mol% silver chloride content and the total amt. of the replenishing amts. in processing stages is <=200ml per 1m<2> photosensitive material. Further, at least one of the processing stages are executed in the presence of the compd. expressed by formula. In the formula, L<1> and L<2> are expressed by-OR<1> or-NR<2>R<3> (R<1> to R<3> are hydrogen atoms or alkyl groups) and satisfy the following conditions: the four substituents L<1> and L<2> in the formula have total >=4 substituents selected from -SO3M,-CSO3M,-COOM,-NR3M. As a result, the color images which are less colored in the white ground parts and have excellent image preservable property are obtd.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a color image forming method using a silver halide color photographic light-sensitive material. In particular, the present invention relates to a processing composition which does not cause precipitation and precipitation during the low temperature storage of a processing solution, and a processing method of a silver halide photographic light-sensitive material using the same. The present invention relates to an image forming method capable of providing an excellent color image.

[0002]

2. Description of the Related Art In recent years, silver halide color photographic light-sensitive materials, especially ornamental light-sensitive materials such as printing light-sensitive materials, have been required to provide higher quality images with higher productivity. ing. Therefore, in the development processing, in recent years, for the purpose of increasing the efficiency, the processing has been speeded up and the light-sensitive material has been improved. Further, in recent years, there has been an increasing demand for reducing the amount of replenishment required for processing as well as for speeding up processing, in consideration of the environment by reducing the cost and the amount of waste liquid. As a processing method for shortening the developing time or reducing the replenishment amount as described above, for example, JP-A-3-109
There are methods described in No. 549 and No. 4-443. However, the low replenishment and speeding up of the above processing (hereinafter, referred to as simple speeding up) generally deteriorates image storability,
There was a problem that the color contamination of the light-sensitive material was aggravated. That is,
The processing is completed before the dye or sensitizing dye in the light-sensitive material is sufficiently eluted from the light-sensitive material due to the rapid processing,
A large amount of dyes and sensitizing dyes remaining in the light-sensitive material contaminate the white background, causing a so-called residual color problem. In addition to the contamination of the white background, the simple and speedy processing increases the amount of residues in the light-sensitive material, for example, the amount of residual developing agent, which causes stains during image storage.

To solve the problem of residual color as described above, the residual color due to the sensitizing dye can be reduced to some extent by adding a water-soluble fluorescent whitening agent to a developing solution, a bleach-fixing solution or a washing / stabilizing bath. It is known and is described in, for example, Research Disclosure 20733 (1981, July). Further, for example, a method using a specific sensitizing dye and a fluorescent whitening agent described in JP-A-62-257154, and a specific water-soluble fluorescent whitening agent disclosed in JP-A-4-249243 are used. The method of doing so is disclosed as a method of reducing the residual color. JP-A-62-2571
The methods described in JP-A-54-49243 and JP-A-4-249243 are superior to the conventional ones in that the residual color is reduced to some extent, but the technology using these known water-soluble optical brighteners requires low replenishment and speeding up. There is a problem in that the effect of reducing the residual color is insufficient in the treatment, and crystals are precipitated (crystallization) during storage of the treatment liquid. Compounds that do not crystallize in conventionally known optical brighteners, such as JP-A-62-2571.
No. 54 (I-30) and (I-31), and the compound described in JP-A-4-249243 (Comparative-
1) and the like, these compounds had no or no effect of reducing the residual color.
Further, for the residual color caused by the dye for preventing irradiation or halation remaining in the light-sensitive material, conventional fluorescent whitening agents including the above-mentioned known brightening agents have been found to be effective. Didn't.

[0004]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention
The method disclosed in Japanese Patent No. 243 is superior to the conventional method in that the residual color is reduced to some extent. However, the present inventor has attempted to reduce the replenishment and speed up the processing by using these conventional residual color improving techniques, and as a result, the following problems have occurred. That is, the problem that the residual color is deteriorated by the sensitizing dye after the processing due to the low replenishment and speeding up of the processing, particularly, the deterioration of the residual color is remarkable when the desilvering processing is carried out at a pH of less than 6 of the processing liquid. When the treatment liquid was stored at low temperature, problems such as crystallization occurred. Further, when the processing speed is low and replenishment is rapid, the residual amount of the main agent in the light-sensitive material is increased and the image storability is impaired, but the conventional techniques have not yet solved this problem. Therefore, the object of the present invention is to simplify and speed up, especially in a treatment in which the total amount of replenishment in all treatment steps is significantly reduced, even if the treatment liquid is stored at a low temperature, the optical brightener does not crystallize and the residual color is reduced. An object of the present invention is to provide a method for forming an image of a silver halide color photographic light-sensitive material, which can achieve a color image having excellent image storability.

[0005]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that a diaminostilbene optical brightener having a specific substituent does not crystallize even when stored at low temperature. Furthermore, when a simple and rapid continuous process was carried out, the image forming method of the present invention not only improved the residual color due to the sensitizing dye, but surprisingly was also effective against the residual color due to the dye. Was found. Further, it has been found that the present invention can improve even when a desilvering treatment at a pH of less than 6 which has been conventionally difficult to achieve sufficient residual color improvement is performed. (1) A silver halide color photographic light-sensitive material having a light-sensitive silver halide emulsion layer on at least one side of a support is subjected to imagewise exposure, followed by development, desilvering, washing with water and / or stabilization and drying. In the image forming method, the silver halide emulsion used in the silver halide color photographic light-sensitive material comprises a high silver chloride emulsion having a silver chloride content of 90 mol% or more, and the total replenishment amount of the processing step is 1 m of the light-sensitive material. ²
A color image forming method, wherein the amount is 200 ml or less, and at least one of the processing steps is carried out in the presence of a compound represented by the following general formula SR.

[0006]

[Chemical 8]

In the general formula [SR], L ¹ and L ² may be the same or different, --OR ¹ or --NR ² R
³ (R ¹ , R ² and R ³ are each a hydrogen atom or an alkyl group) and satisfy at least one of the following conditions. Four substituents L ¹ and L in the general formula [SR]
² has a total of 4 or more substituents selected from the general formula [A] group. Four substituents L ¹ and L in the general formula [SR]
² has a total of two substituents selected from the general formula [A] group, and has a total of two or more substituents selected from the general formula [B] group.

[0008]

[Chemical 9]

In the general formula [A] group, X is a halogen atom and R is
Represents an alkyl group. In the general formulas [SR] and [A], M represents a hydrogen atom, an alkali metal, tetraalkylammonium or pyridinium. (2) The color image forming method according to (1), wherein the desilvering step is performed at a pH of the processing solution of 4.0 or more and less than 6.0. (3) The color image forming method as described in (1), wherein the developing agent used in the color developing solution is represented by the following general formula [D].

[0010]

[Chemical 10]

In the general formula [D], R ⁵ represents a linear or branched alkyl group having 1 to 6 carbon atoms, or a linear or branched hydroxylalkyl group having 3 to 6 carbon atoms. R ⁶ represents a linear or branched alkylene group having 3 to 6 carbon atoms or a linear or branched hydroxyl alkylene group having 3 to 6 carbon atoms. R ⁷ represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms or a linear or branched alkoxy group having 1 to 4 carbon atoms. (4) Color image formation according to (1), wherein the processing time of the light-sensitive material is within 25 seconds in the bleach-fixing process and within 120 seconds from the beginning of the developing process to the end of the drying process. Method. (5) The silver halide color photographic light-sensitive material contains at least one compound represented by the following general formula (I), (II), (III), (IV) or (Sa) ( The color image forming method described in 1).

[0012]

[Chemical 11]

[0013]

[Chemical 12]

[0014]

[Chemical 13]

[0015]

[Chemical 14]

The above general formula [SR] will be described in more detail. In the general formula [SR], L ¹ and L ² are -O.
Represented by R ¹ or —NR ² R ³ , R ¹ , R ² and R
³ represents 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 group. Any group can be substituted here, but it is preferably a substituent selected from the general formula [A] group and the general formula [B] group. Also, R ¹ ,
The alkyl group represented by R ² and R ³ has 1 to 1 carbon atoms.
0 is preferable, and 1-5 is more preferable. The substituents in the general formula [A] group and the general formula [B] group are generally known as hydrophilic groups. In particular, the substituent of the general formula [A] group is known as a group having a strong hydrophilicity, that is, a so-called strongly hydrophilic group.

In the present invention, the compound represented by the above general formula [SR] has L ¹ and L ² satisfying at least one of the above conditions or. The general formula [SR] is
The two triazine rings in the molecule have symmetry by having L ¹ and L ² , respectively, and more specifically, have two rotation axes out of the plane of the molecule at the center of the molecule (center point on the double bond). It has symmetry belonging to the C _2h point cloud. Here, the condition means four substituents L ¹ in the general formula [SR].
And L ² is a condition having a substituent selected from the group of the general formula [A] of 4 or more in total. If the conditions are met,
When combined with the number of two sulfo groups of the benzene ring constituting stilbene in the compound of the general formula [SR],
This corresponds to having a total of 6 or more strongly hydrophilic groups in the molecule. Here, the number of substituents selected from the general formula [A] group is preferably an even number, and the number is 8
The number is preferably not more than 6 and is preferably not more than 6. in this way,
If the number of the above-mentioned substituents is too large or too small, the effect of preventing residual color is lowered, which is not preferable. Further, the conditions are that the four substituents L ¹ and L ² in the general formula [SR] are selected from the two [A] groups in total and the substituents selected from the two or more general formula [B] groups in total. It is a condition having a group.
When the conditions are satisfied, the compound of the general formula [SR] has a total of four strongly hydrophilic groups and two or more hydrophilic groups in the molecule when combined with the number of two sulfo groups of the benzene ring constituting stilbene. Equivalent to having a sexual group. Here, as the number of substituents selected from the general formula [B] group,
It is preferably an even number, and the number thereof is preferably 10 or less, more preferably 4 or less. As described above, if the number of the above-mentioned substituents is too large or too small, the effect of preventing residual color is lowered, which is not preferable. Among the compounds represented by the above general formula [SR] related to the present invention, more preferable compounds are those satisfying the above-mentioned conditions or conditions.

The compound represented by the above general formula [SR] having a strongly hydrophilic group under the above-mentioned conditions or the above has a structure generally known as a stilbene optical brightener.
However, for example, (I-30) and (I-31) described in JP-A-62-257154, JP-A-4-24
Conventional fluorescent whitening agents having a total of four or more strongly hydrophilic substituents in the molecule like the compound described in No. 9243 (Comparison-1) usually have two triazine rings in the molecule with an anilino group. There was a characteristic to have. Further, in the conventional stilbene optical brightening agent in which the triazine ring does not have an anilino group, no specific compound has been known that satisfies any of the above conditions and. In the stilbene-based optical brightening agent represented by the above general formula [SR] satisfying any one of the above conditions or the present invention, the triazine ring has a substituent L ¹
And L ² are characterized by not having an anilino group but having a strongly hydrophilic group and having a symmetrical structure as described above, which is different from the fluorescent whitening agent described in JP-A-4-249243.

In the compound of the general formula [SR] in the present invention, the substituents L ¹ and L ² have the characteristics as described above, and specific examples of L ¹ and L ² are methoxy group, ethoxy group and propoxy group. 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, diisobutylamino group, di2-hydroxyethylamino group, di3-hydroxypropylamino group, dihydroxybutylamino group, 2-sulfoethoxy group, 3-sulfopropoxy group 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-sulfopropylmethylamino group, 4-sulfobutylmethylamino group, 2-sulfoethylethylamino group, 3-sulfopropyl Ethylamino group, 4-sulfobutylethylamino group, 2-carboxyethoxy group, 3-carboxypropoxy group, 4-carboxybutoxy 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
-Carboxycarboxymethylamino group, 2-carboxyethylethylamino group, 3-carboxypropylethylamino group, 4-carboxybutylethylamino group, 2-sulfoethoxy group, 3-sulfoxypropoxy group, 4-sulfoxybutoxy group A 2-sulfoxyethylamino group,
3-sulfoxypropylamino group, 4-sulfoxybutylamino group, di2-sulfoxyethylamino group, di3-
Sulfoxypropylamino group, di4-sulfoxybutylamino group, 2-sulfoxyethylmethylamino group, 3-
Sulfoxypropylmethylamino group, 4-sulfoxybutylmethylamino 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, 2-carboxyethylamino group, di2-carboxyethyl group. Examples thereof include an amino group and a di2-hydroxyethylamino group.

The preferred hydrophilicity of the compound of the general formula [SR] in the present invention is that the logP value is -30 or more and -4.
Hereafter, it is more preferably -18 or more and -7 or less. Here, the logP value 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. When the logP value is -4 or more, crystallization of the treatment liquid during storage at low temperature becomes remarkable, and the reason is not clear but is -30.
The following is not preferable because the effect of improving the residual color of the whitening agent becomes small. Further, the compound of the general formula [SR] in the present invention preferably has a large diffusion coefficient in the gelatin film under various processing conditions. For example, the diffusion coefficient in an aqueous solution of pH 5 is preferably 10 × 10 ⁹ cm ² / sec. Or more,
20 × 10 ⁹ cm ² / sec. Or more is more preferable. Also, the pH
In an aqueous solution of 10, 20 × 10 ⁹ cm ² / sec. Or more is preferable, and 50 × 10 ⁹ cm ² / sec. Or more is more preferable.
The diffusion coefficient can be measured by monitoring with a spectrophotometer how the fluorescent whitening agent molecules in the aqueous fluorescent whitening agent solution permeate and diffuse into the adjacent water across the gelatin film. Journal of Polymer Science, Vol. 3
0, 2075 (1985). The diaminostilbene-based optical brightening agent of the general formula [SR] used in the present invention has a specific structure in which L ¹ and L ² are represented by the atomic groups shown below. Is not limited to these.

[0021]

[Table 1]

[0022]

[Table 2]

[0023]

[Table 3]

[0024]

[Table 4]

[0025]

[Table 5]

[0026]

[Table 6]

The compound of the general formula [SR] 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, it can be synthesized by the following method. A synthesis example 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, it was cooled and salted out to give 12 g of pale yellow crystals.
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, 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 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) Further, other compounds and comparative compounds can be easily synthesized by the same method as above. Industrial Chemistry Magazine Vol. 60 No. 5 P. 604 (1957).

The compound of the general formula [SR] is effective both when it is used alone and when it is used in combination with plural kinds of other diaminostilbene compounds. Is it a compound of [SR],
Alternatively, a diaminostilbene compound represented by the following general formula [SR-c] is preferable.

[0030]

[Chemical 15]

In the general formula [SR-c], L ⁵ , L ⁶ ,
L ⁷ and L ⁸ are represented by —OR ⁸ or —NR ⁹ R ¹⁰ and may be the same or different. Here, R ⁸ , R ⁹ and R ¹⁰ represent a hydrogen atom, an alkyl group, or an alkyl group having a substituent. General formula [SR-
Specific examples of the compound represented by c] include the compounds shown in Table 2.

[0032]

[Table 7]

As the fluorescent whitening agent which can be used in combination with the compound of the general formula [SR], a commercially available diaminostilbene type fluorescent whitening agent may be used. Examples of commercially available compounds include Dyeing Note 19th Edition (Color Sensha Co., Ltd.); 165-P. 168
And among the products listed here
Whitex RP or Whitex BRF liq. Is preferred.

The processing method of the present invention is effective in developing any light-sensitive material containing a silver halide emulsion, and is effective in any processing method, but is preferably a color paper processing method, particularly a silver chloride content of 90 mol%. This is effective when the color photographic paper containing the above high silver chloride emulsion is processed in a low replenishment rapid processing. Although the low replenishment of processing in the present invention varies depending on the type of the light-sensitive material,
For example, in the case of color paper development processing, the total replenishment rate in all steps is preferably 70 to 200 ml / m ² , 90 to 160 ml
/ M ² is more preferable. Furthermore, the total amount of replenishment for all processes is 90.
~ 160 ml / m ² and replenishing amount of color developer is 20 ~
50 ml / m ² and replenishing amount of bleach-fixing solution is 20-50 ml /
m ² and the replenishing amount of the washing and / or stabilizing solution is 20 to
It is preferably 130 ml / m ² . As described above, even when the replenishment rate is lower than in the conventional case, the use of the compound represented by the general formula [SR] has an effect of remarkably suppressing the residual color.

Regarding the crystallization when the treatment liquid of the present invention is stored at low temperature, specifically the crystal precipitation of the optical brightening agent, the low temperature at the time of low temperature storage means the temperature range in which the treatment liquid can be practically stored. It refers to a temperature equal to or lower than the average storage condition, and specifically refers to, for example, 18 ° C. or lower and −20 ° C. or higher.

The compound of the general formula [SR] in the present invention can be contained in either the light-sensitive material or the processing solution, but it is preferably contained in the processing solution. When the compound of the general formula [SR] is contained in the processing liquid, the purpose is to include it in the processing liquid of any of the steps of (1) development, (2) desilvering, (3) washing with water and / or stabilization. Although it is possible to achieve the above, it is preferable that the treatment liquid of a plurality of steps is substantially contained. Here, the desilvering step includes any step of bleaching, fixing, or bleach-fixing and a combination thereof. In the present invention, the general formula [S
The compound R] is preferably added to the processing bath as early as possible in all the processing steps, and particularly preferably added to the developing solution. The preferred concentration of the compound of the general formula [SR] in the treatment liquid is 5 in the running liquid.
× 10 ^-5 to 1 × 10 ^-2 mol / liter, more preferably 1 × 10 ^{-4 to} 5 × 10 ^-3 mol / liter, and keep the set concentration of the running liquid constant in the replenisher. Concentration required for this purpose, specifically 1.5 × 10 ^-4 ~
It is preferably 1.5 × 10 ^-2 mol / liter.

The photosensitive material relating to the present invention will be described in detail below. In the light-sensitive material of the present invention, the hydrophilic colloid layer is treated with the treatment described on pages 27 to 76 of European Patent EP 0337490A2 for the purpose of preventing irradiation and halation and improving safety of safelight. Therefore, it is preferable to add a dye that can be decolorized (among others, an oxonol dye and a cyanine dye). In particular, Japanese Patent Application No. 03-310139 discloses a dye that does not deteriorate color separation and safelight safety even if the amount used is increased.
Water-soluble dyes described in the specification are preferred. The preferable coating amount of these water-soluble dyes can be the following coating amount as one guide. Cyan dye: 20 to 100 mg / m ² Magenta dye: 0 to 50 mg / m ² Yellow dye: 0 to 30 mg / m ^{2 In the} present invention, coating or coating of a coloring layer containing solid fine particle dye or colloidal silver as described above or It is preferable to color the hydrophilic colloid layer with / and a water-soluble dye. The optical reflection density of the unexposed light-sensitive material used in the present invention is such that the optical reflection density at a wavelength having the highest optical reflection density in the visible region of 400 nm to 700 nm as a light wavelength is 0.2 or more and 2.0 or less. Is more preferable, 0.2 or more and 1.5 or less, and especially 0.
It is preferably 2 or more and 1.2 or less, and the type and coating amount of the coloring substance (for example, white pigment, solid fine particle dye, anti-irradiation dye, colloidal silver, etc.) can be selected within a range satisfying this condition. In the region where the optical reflection density is less than 0.2, the effect of the coloring substance on the sharpness cannot be substantially expected. The optical reflection density is 2.0
In the above range, the white background is significantly deteriorated due to the residual color, which is not suitable for practical use. The optical reflection density in the present invention is measured by a reflection densitometer generally used in the art, and is defined as follows. However, at the time of measurement, it is necessary to install a standard reflection plate on the back surface of the sample to prevent a measurement error due to light trying to pass through the sample. Optical reflection density = log ₁₀ (F ₀ / F) F ₀ : Reflected light flux of standard white plate F: Reflected light flux of sample

The dye relating to the present invention will be described in detail below. In the general formula (I), the heterocycle formed by the group of non-metal atoms represented by Z ₁ and Z ₂ is preferably a 5- or 6-membered ring, and may be a single ring or a condensed ring, for example, 5-pyrazolone or 6-hydroxy. Pyridone, Pyrazolo [3,4
-B] Pyridine-3,6-dione, barbituric acid, pyrazolidinedione, thiobarbituric acid, rhodanine, imidazopyridine, pyrazolopyrimidine, pyrrolidone, pyrazolone imidazole and the like. A ₁ , A ₂ ,
The methine group represented by A ₃ , A ₄ and A ₅ may have a substituent (for example, methyl, ethyl, phenyl, chlorine atom, sulfoethyl, carboxyethyl, dimethylamino, cyano), Are linked to each other to form a 5- or 6-membered ring (for example, cyclohexene, cyclopentene, 5,5-
Dimethylcyclohexene) may be formed. Monovalent cations other than hydrogen represented by M ⁺ include, for example, Na ⁺ ,
_{^{K +, HN + (C 2}} H 5) may be mentioned _3, Li ⁺ and the like. Among the dyes represented by the general formula (I), particularly preferable dyes are the following general formulas (Ia) and (Ib),
It is a dye represented by (Ic), (Id) or (Ie).

[0039]

[Chemical 16]

[0040]

[Chemical 17]

[0041]

[Chemical 18]

[0042]

[Chemical 19]

Examples of the dye represented by formula (Ia) are shown below, but the invention is not limited thereto.

[0044]

[Table 8]

[0045]

[Table 9]

These dyes are described in British Patent No. 506,38.
No. 5, No. 1,177,429, No. 1,338,799
No. 1, 1,385,371, 1,467,214
Issue No. 1,433,102 Issue 1,553,516
No. 48-85130, 55-161233.
No. 52-20330, No. 59-111640,
It can be synthesized by the method described in JP-A No. 62-273527. Specific examples of the dye represented by formula (Ib) are shown below, but the invention is not limited thereto.

[0047]

[Chemical 20]

[0048]

[Chemical 21]

The dyes represented by formula (Ib) are described in British Patent Nos. 1,278,621 and 1,512,863.
No. 1,579,899. The general formula (Ic) used in the present invention is shown below.
Specific examples of the dye represented by are shown below, but the invention is not limited thereto.

[0050]

[Table 10]

Dyes represented by the general formula (Ic) include, for example, Japanese Examined Patent Publications Nos. 39-22069, 43-3504, and 5-3.
No. 2-38056, No. 54-38129, No. 55-1
No. 0059, JP-A-49-99620 and JP-A-59-16.
No. 834 or the method described in US Pat. No. 4,181,225 and the like can be used for the synthesis. Specific examples of the dye represented by formula (Id) are shown below, but the invention is not limited thereto.

[0052]

[Table 11]

These dyes are described in US Pat. No. 3,247,
No. 127, No. 3,469,985, No. 3,653,9
It can be synthesized by the method described in No. 05, No. 4,078,933 and the like. Next, specific examples of the dye general formula (Ie) used in the present invention are shown, but the present invention is not limited thereto.

[0054]

[Chemical formula 22]

[0055]

[Chemical formula 23]

The compound represented by the general formula (Ie) is described in JP-A-1.
It can be synthesized by the synthetic method described in 183652. Specific examples of the dye represented by formula (II) used in the present invention are shown below.

[0057]

[Chemical formula 24]

[0058]

[Chemical 25]

The dye represented by formula (II) can be easily synthesized by the method described in JP-A-51-3623. Specific examples of the dye represented by formula (III) are shown below.

[0060]

[Chemical formula 26]

[0061]

[Chemical 27]

The dyes represented by the general formula (III) are represented by British Patent Nos. 575,691, 907,125 and 1,3.
It can be synthesized by the method described in No. 53,525. Specific examples of the dye represented by formula (IV) are shown below.

[0063]

[Chemical 28]

[0064]

[Chemical 29]

The dye represented by the general formula (IV) can be synthesized by the method described in US Pat. No. 2,865,752. Among the dyes represented by the general formulas (I), (II), (III) and (IV), particularly preferable ones are the general formula (I),
Above all, it is (I-a), (I-b) or (I-c).

The compound represented by formula (Sa) will be described in detail below. The compound having a chromophore represented by D can be selected from many well-known dye compounds. Examples of these compounds include oxonol dyes, merocyanine dyes, cyanine dyes, arylidene dyes, azomethine dyes, triphenylmethane dyes, azo dyes, anthraquinone dyes and indoaniline dyes. The dissociative proton represented by X or a group having a dissociative proton is non-dissociated when the compound represented by the general formula (Sa) is added to the silver halide photographic light-sensitive material of the present invention. It has a property of making the compound of Sa) substantially water-insoluble, and has a property of making the compound of the general formula (Sa) substantially water-soluble by being dissociated in the step of developing the material. Examples of these groups include a carboxylic acid group, a sulfonamide group, an arylsulfamoyl group, a sulfonylcarbamoyl group, a carbonylsulfamoyl group, and an enol group of an oxonol dye. Among the compounds represented by the general formula (Sa), more preferable compounds are the following general formulas (Sb) and (S
c), (Sd), and (Se).

[0067]

[Chemical 30]

In the formula, A ₁ and A ₂ each represent an acidic nucleus,
B ₁ represents a basic nucleus, Q represents an aryl group or a heterocyclic group, L ₁ , L ₂ and L ₃ each represent a methine group,
m represents 0, 1, 2 and n and p are 0, 1, 2, 3 respectively.
Represents However, the compounds of the general formulas (Sa) to (Se) consist of a carboxylic acid group, a sulfonamide group, an arylsulfamoyl group, a sulfonylcarbamoyl group, a carbonylsulfamoyl group, and an enol group of an oxonol dye in one molecule. It has at least one group selected from the group and does not have more water-soluble groups (for example, sulfonic acid group and phosphoric acid group). The acidic nucleus represented by A ₁ or A ₂ is preferably a cyclic ketomethylene compound or a compound having a methylene group sandwiched between electron withdrawing groups. Examples of the cyclic ketomethylene compound include 2-pyrazolin-5-one, rhodanine, hydantoin, thiohydantoin, 2,4-oxazolidinedione, isoxazolone, barbituric acid, thiobarbituric acid, indandione, dioxopyrazolopyridine, Examples thereof include hydroxypyridone, pyrazolidinedione, and 2,5-dihydrofuran, each of which may have a substituent.
A compound having a methylene group sandwiched by electron withdrawing groups can be represented as Z ₃ CH ₂ Z ₄ , where Z ₃ ,
Z ₄ is CN, SO ₂ R ₁₁ , COR ₁₁ , COOR ₁₂ ,
CONHR ₁₂ , SO ₂ NHR ₁₂ , R ₁₁ represents an alkyl group, an aryl group or a heterocyclic group, R ₁₂ represents a hydrogen atom or a group represented by R ₁₁ , each of which may have a substituent. . Examples of the basic nucleus represented by B ₁ include pyridine, quinoline, indolenine, oxazole, imidazole, thiazole, benzoxazole,
Examples thereof include benzimidazole, benzothiazole, oxazoline, naphthoxazole and pyrrole, each of which may have a substituent.

Examples of the aryl group represented by Q are:
Examples thereof include a phenyl group and a naphthyl group, each of which may have a substituent. Examples of the heterocyclic group represented by Q ₁ include pyrrole, indole, furan, thiophene, imidazole, pyrazole, indolizine, quinoline, carbazole, phenothiazine, phenoxazine, indoline, thiazole, pyridine, pyridazine,
Thiadiazine, pyran, thiopyran, oxadiazole, benzoquinoline, thiadiazole, pyrrolothiazole, pyrrolopyridazine, tetrazole, oxazole,
Examples include coumarin and coumarone, each of which may have a substituent. The methine group represented by L ₁ , L ₂ and L ₃ may have a substituent, and the substituents may be linked to each other to form a 5- or 6-membered ring.

The substituent which each of the above-mentioned groups may have is not particularly limited as long as it does not substantially dissolve the compounds of the general formulas (Sa) to (Se) in water having a pH of 5 to 7. There is no. For example, a carboxylic acid group, a sulfonamide group having 1 to 10 carbon atoms (for example, methanesulfonamide, benzenesulfonamide, butanesulfonamide, n-octanesulfonamide), a sulfamoyl group having 0 to 10 carbon atoms (for example, an unsubstituted group). Of sulfamoyl, methylsulfamoyl, phenylsulfamoyl, butylsulfamoyl), a sulfonylcarbamoyl group having 2 to 10 carbon atoms (for example, methanesulfonylcarbamoyl, propanesulfonylcarbamoyl, benzenesulfonylcarbamoyl), and 1 to 10 carbon atoms. Acylsulfamoyl group (for example, acetylsulfamoyl, propionylsulfamoyl, pivaloylsulfamoyl, benzoylsulfamoyl), an alkyl group having 1 to 8 carbon atoms (for example, methyl, ethyl, isopropyl, butyl) , Hexyl, 2-hydroxyethyl, 4-carboxybutyl, 2-methoxyethyl, benzyl, phenethyl, 4-carboxybenzyl, 2-diethylaminoethyl), an alkoxy group having 1 to 8 carbon atoms (for example, methoxy, ethoxy, butoxy). ,
Halogen atom (for example, fluorine atom, chlorine atom, bromine atom), C0-10 amino group (for example, unsubstituted amino, dimethylamino, diethylamino, carboxyethylamino), C2-10 ester group (for example, ,
(Methoxycarbonyl), an amide group having 1 to 10 carbon atoms (eg, acetylamino, benzamide), 1 to 1 carbon atoms
A carbamoyl group of 0 (eg, unsubstituted carbamoyl,
Methylcarbamoyl, ethylcarbamoyl), carbon number 6
10 aryl groups (eg phenyl, naphthyl, 4
-Carboxyphenyl, 3-carboxyphenyl, 3,
5-dicarboxyphenyl, 4-methanesulfonamidophenyl, 4-butanesulfonamidophenyl), an acyl group having 1 to 10 carbon atoms (eg, acetyl, benzoyl, propanoyl), a sulfonyl group having 1 to 10 carbon atoms (eg, Methanesulfonyl, benzenesulfonyl),
Ureido group having 1 to 10 carbon atoms (for example, ureido, methylureido), urethane group having 2 to 10 carbon atoms (for example,
Methoxycarbonylamino, ethoxycarbonylamino), cyano group, hydroxyl group, nitro group, heterocyclic group (for example, 5-carboxybenzoxazole ring, pyridine ring, sulfolane ring, furan ring) and the like. Next, the general formulas (Sa) to (Se) used in the present invention are used.
Examples of compounds represented by

[0071]

[Chemical 31]

[0072]

[Chemical 32]

[0073]

[Chemical 33]

[0074]

[Chemical 34]

[0075]

[Chemical 35]

[0076]

[Chemical 36]

[0077]

[Chemical 37]

[0078]

[Chemical 38]

The solid fine particles of the above-mentioned dye are prepared by precipitating the dye in the form of fine particles and / or in the presence of a dispersant, by a known grinding means such as ball milling (ball mill,
Vibratory ball mill, planetary ball mill, etc.), sand milling, colloid milling, jet milling, roller milling, etc., in which case a solvent (eg water, alcohol, etc.) may or may not be present. Good. Alternatively, the dye may be dissolved in a suitable solvent, and then a non-solvent for the dye may be added to precipitate fine crystal particles of the dye. In that case, a decomposition surfactant may be used. Alternatively, the dye may be first dissolved by controlling the pH and then crystallized by changing the pH.

As the solid fine particle dye, at least pH
It is preferably water-insoluble at 6 or less, and substantially water-soluble at pH 8 or more. The phrase "the dye is substantially water-insoluble at least at pH 6 or less" means that the fine powder dispersion state is insoluble enough to be retained in a hydrophilic colloid having pH 6 or less, for example, an aqueous gelatin solution. A dye having a solubility in water of pH 6 at room temperature (24 ° C.) of 0.01% by weight or less, more preferably 0.001% by weight or less is preferable. Further, “substantially water-soluble at pH 8 or higher” means that the fine powder dispersion state is at least pH 8
It means that the dye is dissolved to the extent that it cannot be retained in the above aqueous solution, and more specifically, the solubility at room temperature in water of pH 8 exceeds 0.1% by weight, and further exceeds 0.5% by weight. Dyes are preferred. The solid dye used in the present invention may be water-soluble or water-insoluble at pH 7, but is substantially water-insoluble at least at pH 6 or lower, and is substantially water-soluble at pH 8 or higher. Is preferred.

The fine dye particles in the gelatin dispersion preferably have an average particle size of 10 μm or less, more preferably 2 μm or less, particularly preferably 0.5 μm or less, and in some cases 0.1 μm or less. It is more preferable that there is. The compound represented by the general formula (Sa) can be added to any of the photographic constituent layers. However, in order to exhibit the effect of the colored layer satisfactorily, a layer containing the compound represented by the general formula (Sa) of the present invention, which has absorption in the wavelength region similar to the spectral sensitization region of each photosensitive layer, is required. It is preferable that the photosensitive layer is coated below and adjacent thereto. As used herein, "coating adjacent to a layer below" means coating on the side of the support relative to the layer, and the layer is coated via another hydrophilic colloid layer. It can also include a mode.
More specifically, "coating below the light-sensitive silver halide emulsion layer" means that a thin non-light-sensitive hydrophilic colloid layer (a coupler or the like may be added) is added to this emulsion layer. And a hydrophilic colloid layer containing the compound represented by the general formula (Sa) is applied. However, the compound represented by the general formula (Sa) is preferably contained without such a layer. It is preferable that the hydrophilic colloid layer is coated directly below the photosensitive layer. The total amount of the compound represented by formula (Sa) used in the light-sensitive material may be any amount necessary for improving sharpness, but is preferably 10 to 800 mg.
/ M ² , more preferably 10 to 400 mg / m ² , and even 1
Most preferred is 0 to 200 mg / m ² .

The color light-sensitive material according to the present invention comprises at least one yellow color-forming silver halide emulsion layer, magenta color-forming silver halide emulsion layer and cyan color-forming silver halide emulsion layer coated on a reflective support. Can be configured. In general color photographic paper, color reproduction by the subtractive method can be performed by including a color coupler which forms a dye having a complementary color relationship with the light to which the silver halide emulsion is exposed. In a general color photographic paper, silver halide emulsion grains are spectrally sensitized by the blue-sensitive, green-sensitive and red-sensitive spectral sensitizing dyes in the order of the color forming layers described above, and are also formed on the support in the order described above. It can be constructed by coating. However, the order may be different from this. That is, from the viewpoint of rapid processing, it is preferable that the photosensitive layer containing the silver halide grains having the largest average grain size comes to the uppermost layer, or from the viewpoint of storability under light irradiation, the lowermost layer is the magenta color photosensitive layer. In some cases it may be preferable to do so. Further, the light-sensitive layer and the color-developing hue may not have the above correspondence, and at least one infrared-sensitive silver halide emulsion layer can be used.

The silver halide grains used in the light-sensitive material include silver chloride, silver bromide, silver (iodo) chlorobromide and silver iodobromide. In particular, in the present invention, in order to accelerate the development processing time, a silver chlorobromide or silver chloride containing substantially no silver iodide can be preferably used.
The term "substantially free of silver iodide" means that the silver iodide content is 1 mol% or less (including zero), preferably 0.2 mol%.
The following (including zero) is said. On the other hand, for the purpose of enhancing high illuminance sensitivity, spectral sensitization sensitivity, or enhancing storage stability of a light-sensitive material, 0.01 to 3 mol% on the emulsion surface as described in JP-A-3-84545. In some cases, high silver chloride grains containing silver iodide are preferably used. The halogen composition of the emulsion may be different or the same between grains, but if an emulsion having the same halogen composition among grains is used, it is easy to make the properties of each grain uniform. Regarding the halogen composition distribution inside the silver halide emulsion grains, the so-called uniform structure grains having the same composition in any part of the silver halide grains, or the core inside the silver halide grains and the shell surrounding it. (Shell) [a single layer or a plurality of layers] particles having a so-called laminated structure having a different halogen composition, or a structure having a portion having a different halogen composition inside or on the surface of the particle (edge of the particle when present on the particle surface, It is possible to appropriately select and use particles having a structure in which parts having different compositions are bonded to a corner or a surface. In order to obtain high sensitivity, it is advantageous to use either of the latter two rather than the particles having a uniform structure, and it is also preferable from the viewpoint of pressure resistance. When the silver halide grains have the above structure, the boundary between different portions in the halogen composition is an unclear boundary because a mixed crystal is formed due to the composition difference even if the boundary is clear. It may also be one that positively has a continuous structural change.

A so-called high silver chloride emulsion having a high silver chloride content is preferably used for a light-sensitive material applied to rapid processing as in the present invention. In the present invention, the silver chloride content of the high silver chloride emulsion is preferably 90 mol% or more, more preferably 95 mol% or more. In such a high silver chloride emulsion, a structure having a localized silver bromide phase in the inside and / or on the surface of the silver halide grain in the form of layer or non-layer as described above is preferable. The halogen composition of the localized phase is preferably at least 10 mol% in terms of silver bromide content,
More than mol% is more preferable. The silver bromide content of the localized phase of silver bromide can be measured by an X-ray diffraction method (for example, “Chemical Society of Japan”,
New Experimental Chemistry Lecture 6, Structural Analysis "Maruzen. ) Etc. can be used for analysis. These localized phases can be present inside the particles, on the edges, corners, or on the surface of the particles, and one preferable example thereof is that epitaxially grown on the corners of the particles. It is also effective to further increase the silver chloride content of the silver halide emulsion for the purpose of reducing the replenishment amount of the developing solution. In such a case, an almost pure silver chloride emulsion having a silver chloride content of 98 mol% to 100 mol% is also preferably used.

The average grain size of the silver halide grains contained in the silver halide emulsion used for the light-sensitive material (the grain size is determined by the diameter of the circle equivalent to the projected area of the grain and the number average thereof is taken) is 0. .1 μ to 2 μ is preferable. Further, the particle size distribution thereof is preferably a so-called monodisperse coefficient of variation of 20% or less (standard deviation of particle size distribution divided by average particle size), preferably 15% or less, more preferably 10% or less. . At this time, it is also preferable to use the above monodisperse emulsion by blending it in the same layer for the purpose of obtaining a wide latitude, or to perform multi-layer coating. The shape of silver halide grains contained in a photographic emulsion is regular, such as cubic, tetradecahedral or octahedral.
Those having a (regular) crystal form, those having an irregular (eg regular) crystal form such as spheres and plates, or those having a composite form thereof can be used. It may also be a mixture of materials having various crystal forms. In the present invention, 50% or more, preferably 7% or more of the particles having the above-mentioned regular crystal form are used in the invention.
It is preferable to contain 0% or more, more preferably 90% or more. In addition to these, an emulsion having tabular grains having an average aspect ratio (diameter in terms of circle / thickness) of 5 or more, preferably 8 or more as a projected area exceeding 50% of all grains can be preferably used.

The silver chlorobromide emulsion used in the present invention is P. Glafki.
des by Chimie et Phisique Photographique (Paul Mont
published by el, 1967), by GF Duffin Photographic Em
ulsion Chemistry (Focal Press, 1966), V.
Making and Coating Photographic by L. Zelikman et al
It can be adjusted using the method described in Emulsion (Focal Press, 1964) and the like. That is,
Any method such as an acidic method, a neutral method, an ammonia method, etc. may be used.As a method for reacting a soluble silver salt and a soluble halogen salt, any method such as a one-sided mixing method, a simultaneous mixing method, and a combination thereof may be used. Is also good. It is also possible to use a method of forming grains in an atmosphere in which silver ions are excessive (so-called reverse mixing method). As one form of the simultaneous mixing method, a method of keeping pAg in a liquid phase where silver halide is formed constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained.

The localized phase of the silver halide grain of the present invention or its substrate preferably contains a different metal ion or a complex ion thereof. The preferred metal is selected from metal ions or metal complexes belonging to Group VIII and Group IIb of the Periodic Table, and lead ions and thallium ions. Ions mainly selected from iridium, rhodium and iron or their complex ions in the localized phase, and metal ions selected mainly from osmium, iridium, rhodium, platinum, ruthenium, palladium, cobalt, nickel and iron as the substrate. Alternatively, the complex ions can be used in combination. Further, the type and concentration of the metal ion can be changed depending on the localized phase and the substrate. Plural kinds of these metals may be used. In particular, iron and iridium compounds are preferably present in the silver bromide localized phase.

These metal ion-providing compounds are used in a gelatin aqueous solution which becomes a dispersion medium when silver halide grains are formed,
Of the silver halide grains of the present invention by means such as adding in an aqueous solution of a halide, in an aqueous solution of a silver salt or other aqueous solution, or in the form of fine silver halide grains containing metal ions in advance and dissolving the fine grains. It is contained in the localized phase and / or other particle portion (matrix). The metal ion used in the present invention can be incorporated into the emulsion grains either before grain formation, during grain formation, or immediately after grain formation. This can be changed depending on the position of the metal ion contained in the particle.

The silver halide emulsion in the light-sensitive material relating to the present invention is usually chemically and spectrally sensitized. Regarding the chemical sensitization method, chemical sensitization using a chalcogen sensitizer (specifically, sulfur sensitization represented by the addition of an unstable sulfur compound, selenium sensitization with a selenium compound, and tellurium sensitization with a tellurium compound are performed. Noble metal sensitization typified by gold sensitization, reduction sensitization and the like can be used alone or in combination. As the compound used for the chemical sensitization, those described in JP-A-62-215272, page 18, lower right column to page 22, upper right column are preferably used. The emulsion used in the present invention is a so-called surface latent image type emulsion in which a latent image is mainly formed on the grain surface. The silver halide emulsion used in the light-sensitive material according to the present invention includes various compounds or precursors thereof for the purpose of preventing fog during production process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. The body can be added. Specific examples of these compounds are described in JP-A-62-2.
Those described on pages 39 to 72 of the specification of Japanese Patent No. 15272 are preferably used. Furthermore, the 5-arylamino-1,2,3,4-thiatriazole compounds described in EP 0447647 (wherein the aryl residue has at least one electron-withdrawing group) are also preferably used.

Spectral sensitization is carried out for the purpose of imparting spectral sensitivity in a desired light wavelength region to the emulsion of each layer in the light-sensitive material of the present invention. In the photosensitive material according to the present invention,
Examples of spectral sensitizing dyes used for spectral sensitization in the blue, green, and red regions include Heterocyclic compounds- by FM Harmer.
Cyanine dyes and related compounds (John Wiley & S
Ons New York, London, Inc., 1964). Specific examples of compounds and the spectral sensitization method are described in the above-mentioned JP-A-62-215272.
The compounds described on page 22, right upper column to page 38 of the publication are preferable, and more preferable compounds among them are (S-1) to (S-19) and (S-21) in specific compound examples.
(S-23) to (S-38), (S-40) to (S-4
4), (S-46) to (S-48), (S-51),
(S-53), (S-55) to (S-58), (S-6
0), (S-62), (S-63), (S-66),
(S-68), (S-71) to (S-83), (S-8
5) to (S-90) and the like, which do not have a carboxy group in the molecule. Further, as the red-sensitive spectral sensitizing dye for silver halide emulsion grains having a particularly high silver chloride content, the spectral sensitizing dye described in JP-A-3-123340 is stable, has strong adsorption, and has an exposure temperature. It is very preferable from the viewpoint of dependency.

In the case of efficiently spectrally sensitizing the infrared region of the light-sensitive material of the present invention, JP-A-3-15049-1.
Page 2, upper left column to Page 21, lower left column, or JP-A-3-207
No. 30, page 4, lower left column, to page 15, lower left column, EP-0, 420,
011 page 4, line 21 to page 6, line 54, EP-0,420,
012, page 4, line 12 to page 10, line 33, EP-0,44
The sensitizing dyes described in 3,466 and US-4,975,362 are preferably used.

To incorporate these spectral sensitizing dyes in a silver halide emulsion, they may be dispersed directly in the emulsion, or water, methanol, ethanol, propanol, methyl cellosolve, 2,2,2. It may be added to the emulsion by dissolving it in a solvent such as 3,3-tetrafluoropropanol alone or in a mixed solvent. Also, Japanese Patent Publication No.
No. 3389, Japanese Patent Publication No. 44-27555, Japanese Patent Publication No. 57-
As described in 22089 and the like, an acid or a base is allowed to coexist to prepare an aqueous solution, and as described in U.S. Pat. No. 3,822,135 and U.S. Pat. It may be added to the emulsion. Alternatively, the emulsion may be dissolved in a solvent that is substantially immiscible with water, such as phenoxyethanol, and then dispersed in water or a hydrophilic colloid to add to the emulsion. JP-A-53-102733, JP-A-58-105141
Alternatively, the dispersion may be directly dispersed in a hydrophilic colloid, and the dispersion may be added to the emulsion. The time of addition to the emulsion may be any stage of emulsion preparation known to be useful so far. In other words, before preparing the silver halide emulsion grains, during grain formation, immediately after grain formation, before entering the washing step, before chemical sensitization, during chemical sensitization, immediately after chemical sensitization, until the emulsion is cooled and solidified. You can choose from either. Most commonly, it is carried out after the completion of chemical sensitization and before the application, but is described in US Pat.
It is also possible to add spectral sensitization simultaneously with chemical sensitization by adding it at the same time as the chemical sensitizer as described in JP-A No. 628969 and No. 4225666.
It can be carried out prior to chemical sensitization as described in No. 28, or it can be added before the completion of silver halide grain precipitation to initiate spectral sensitization. It is also possible to add the spectral sensitizing dyes separately, as taught in U.S. Pat. No. 4,225,666, i.e. adding some prior to chemical sensitization and the rest after chemical sensitization. It is possible and can be at any time during silver halide grain formation, including the method taught in US Pat. No. 4,183,756. Of these, it is particularly preferable to add a sensitizing dye before the step of washing the emulsion with water or before the chemical sensitization.

The addition amount of these spectral sensitizing dyes is wide depending on the case and is 0.5 per mol of silver halide.
The range of × 10 ^-6 mol to 1.0 × 10 ^-2 mol is preferable.
More preferably, 1.0 × 10 ^-6 mol to 5.0 × 10 ^-3
It is in the molar range. In the photosensitive material according to the present invention,
Particularly when a sensitizing dye having spectral sensitization sensitivity in the red region to the infrared region is used, it is preferable to use the compounds described in JP-A-2-157749, page 13, lower right column to page 22, lower right column. By using these compounds, the storability of the light-sensitive material, the processing stability, and the supersensitizing effect can be specifically enhanced. Among them, the general formulas (IV), (V) and (V
It is particularly preferable to use the compound of I) in combination. These compounds are 0.5 × 10 ^-5 per mol of silver halide.
Mol to 5.0 × 10 ⁻² mol, preferably 5.0 × 10 ⁻⁵
The sensitizing dye 1 is used in an amount of mol to 5.0 × 10 ⁻³ mol.
0.1 times to 10,000 times, preferably 0.5 times per mol
There is an advantageous amount of use in the range of 2 times to 5000 times.

As the binder or protective colloid that can be used in the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can be used alone or together with gelatin. As a preferable gelatin, it is preferable to use low calcium gelatin having a calcium content of 800 ppm or less, more preferably 200 ppm or less. Further, in order to prevent various molds and bacteria which propagate in the hydrophilic colloid layer and deteriorate the image, it is preferable to add an antifungal agent as described in JP-A-63-271247.

Swelling in a color developing solution of a hydrophilic colloid layer composed of an emulsion layer, a non-photosensitive layer and the like coated on a support of a color photographic light-sensitive material according to the present invention achieves the object of the present invention. It is necessary to be prompt in order to do so.
Specifically, the film thickness during color development is 40
The value of the film thickness when immersed in an alkaline aqueous solution at ℃,
It is preferable that the film thickness after 30 seconds reaches 1.5 times or more the dry film thickness. It is preferably 1.5 times or more in 20 seconds, more preferably 1.5 times or more in 10 seconds. Further, it is preferably 5 times or less. Such a magnification can be easily set by a method of changing the type and amount of the hardener used in the hydrophilic colloid layer. The dry film thickness referred to here is 2 when the photosensitive material is at 25 ° C. and a humidity of 55%.
It is the value of the film thickness measured under the conditions after storage for a period of time or more. The alkaline aqueous solution referred to here is 0.2 mol / liter of sodium hydrogen carbonate (pH 1 with sulfuric acid.
Adjusted to 0.0) Represents an aqueous solution.

The light-sensitive material of the present invention may be exposed to visible light or infrared light. The exposure method may be low-illuminance exposure or high-illuminance exposure. As a preferred exposure method for high illuminance exposure, there is a laser scanning exposure method in which the exposure time per pixel is shorter than 10 ⁻⁴ seconds, more preferably shorter than 10 ⁻⁶ seconds. Further, upon exposure, it is preferable to use the band stop filter described in US Pat. No. 4,880,726. As a result, light color mixture is removed, and color reproducibility is significantly improved.

[0097]

[Table 12]

[0098]

[Table 13]

[0099]

[Table 14]

[0100]

[Table 15]

[0101]

[Table 16]

Cyan, magenta, or yellow couplers are impregnated into rollable latex polymers (eg, US Pat. No. 4,203,716) in the presence (or absence) of high boiling organic solvents as listed in the table above. Then, it is preferable to dissolve in a polymer soluble in an organic solvent and to emulsify and disperse in a hydrophilic colloid aqueous solution. Water-insoluble and organic solvent-soluble polymers that can be preferably used are described in US Pat. No. 4,857,449, columns 7 to 15 and International Publication WO88 / 00723, page 12 to.
The homopolymer or copolymer described on page 30 can be mentioned. It is more preferable to use a methacrylate-based or acrylamide-based polymer, particularly acrylamide-based polymer, from the viewpoint of color image stability and the like.

In the light-sensitive material of the present invention, it is preferable to use a color image storability-improving compound as described in European Patent EP 0277589A2 together with a coupler. In particular, it is preferably used in combination with a pyrazoloazole coupler or a pyrrolotriazole coupler. That is, by chemically bonding with the aromatic amine-based developing agent remaining after color development processing,
When chemically bound to the compound (F) in the above-mentioned patent specification which forms a chemically inert and substantially colorless compound, and / or an oxidant of an aromatic amine color developing agent remaining after the color developing treatment. The use of the compound (G) in the above-mentioned patent specification, which forms a chemically inert and substantially colorless compound, simultaneously or alone, is effective in, for example, the residual color developing agent in a film in the storage after processing or its developing agent. It is preferable for preventing the occurrence of stains and other side effects due to the formation of a coloring dye by the reaction of the oxidant and the coupler.

Further, as a cyan coupler, there is disclosed in JP-A-2-
In addition to the diphenylimidazole-based cyan coupler described in Japanese Patent No. 33144, European Patent EP 0333185A2.
3-hydroxypyridine type cyan couplers described in the above specification (in particular, the couplers listed as specific examples (4
(2) 4-equivalent couplers having a chlorine-releasing group to make them 2-equivalent, and couplers (6) and (9) are particularly preferable)
And cyclic active methylene cyan couplers described in JP-A No. 64-32260 (coupler examples 3, 8, and 34 listed as specific examples are particularly preferable), and European Patent No. EP 0456226A1. Pyrrolopyrazole type cyan coupler, European Patent EP044890
Pyrroylimidazole type cyan couplers described in No. 9, European Patent Nos. EP0488248 and EP04911.
Preference is given to using the pyrrolotriazole type cyan couplers described in 97A1. Of these, use of a pyrrolotriazole type cyan coupler is particularly preferable.

Further, as the yellow coupler, in addition to the compounds described in the above table, European Patent EP0447969 may be used.
Acylacetamide type yellow couplers having a 3- to 5-membered cyclic structure in the acyl group described in A1 specification, Malondianilide type yellow couplers having a cyclic structure described in European Patent EP 0482552A1, US Pat. The acylacetamide type yellow coupler having a dioxane structure described in 118,599 is preferably used. Among them, it is particularly preferable to use an acylacetamide type yellow coupler whose acyl group is a 1-alkylcyclopropane-1-carbonyl group and a malondianilide type yellow coupler in which one of the anilide constitutes an indoline ring. These couplers can be used alone or in combination.

As the magenta coupler, 5-pyrazolone type magenta couplers and pyrazoloazole type magenta couplers as described in the above-mentioned publicly known documents are used. Japanese Patent Application Laid-Open No. 61-65245, wherein a pyrazolotriazole coupler having a secondary or tertiary alkyl group directly bonded to the 2, 3 or 6 position of the pyrazolotriazole ring is disclosed.
Pyrazoloazole couplers containing sulfonamide groups in the molecule as described in JP-A-65246;
Pyrazoloazole couplers having an alkoxyphenyl sulfonamide ballast group as described in US Pat. No. 147,254, European Patent Nos. 226,849A and 294,
It is preferable to use a pyrazoloazole coupler having an alkoxy group or an aryloxy group at the 6-position as described in No. 785.

As the processing method of the present invention, in addition to the methods described in the above table, page 26, right lower column, line 1 to page 34, right upper column, line 9 of JP-A-2-207250 and JP-A-4-973.
The processing materials and processing methods described in No. 55, page 5, upper left column, line 17 to line 18, lower right column, line 20 are preferable.

The processing materials and processing methods used in the present invention will be described in detail. In the present invention, the light-sensitive material is color-developed, desilvered, washed with water or stabilized. The color developing solution used in the present invention contains a known aromatic primary amine developing agent. A preferred example is p
-A phenylenediamine derivative, a typical example of which is
N, N-diethyl-p-phenylenediamine, 4-amino-N, N-diethyl-3-methylalinine, 4-amino-N- (β-hydroxyethyl) -N-methylaniline, 4-amino-N-ethyl. -N- (β-hydroxyethyl) aniline, 4-amino-N-ethyl-N- (β-
Hydroxyethyl) -3-methylaniline, 4-amino-N-ethyl-N- (3-hydroxypropyl) -3-
Methylaniline, 4-amino-N-ethyl-N- (4-
Hydroxybutyl) -3-methylaniline, 4-amino-N-ethyl-N- (β-methanesulfonamidoethyl) -3-methylaniline, 4-amino-N, N-diethyl-3- (β-hydroxyethyl) ) Aniline, 4-amino-N-ethyl-N- (β-methoxyethyl) -3-
Methylaniline, 4-amino-N- (β-ethoxyethyl) -N-ethyl-3-methylaniline, 4-amino-
N- (3-carbamoylpropyl) -N-n-propyl-3-methylaniline, 4-amino-N- (3-carbamoylbutyl) -Nn-propyl-3-methylaniline, N- (4-amino -3-Methylphenyl) -3-hydroxypyrrolidine, N- (4-amino-3-methylphenyl) -3- (hydroxymethyl) pyrrolidine, N-
(4-amino-3-methylphenyl) -3-pyrrolidinecarboxamide. Particularly preferred compounds are those represented by the above general formula (D). This specific example is shown, but the present invention is not limited to this.

[0109]

[Chemical Formula 39]

[0110]

[Chemical 40]

[0111]

[Chemical 41]

The most preferred compounds are 4-amino-N-ethyl-N- (3-hydroxypropyl) -3-methylaniline, and 4-amino-N-ethyl-N- (4-hydroxybutyl) -3-methyl. It is aniline. In addition, salts of these p-phenylenediamine derivatives and sulfates, sulfites, hydrochlorides, naphthalenedisulfonates, p-toluenesulfonates and the like may be used. The amount of the aromatic primary amine developing agent used is preferably 0.002 mol to 0.2 mol, and more preferably 0.005 to 0.1 mol, per liter of the developing solution. The developing time of the color developing process which can be generally applied is 45 seconds to 3 minutes, but the shorter one is preferable in the invention for the purpose of achieving speeding up. Specifically, 10 seconds to 25 seconds are preferable. The treatment temperature at that time is 20 to 50 ° C, preferably 30 to 45 ° C, and most preferably 37 to 42 ° C. The replenishment amount is preferably small, but ^{20 to} 600 ml is appropriate per 1 m ^{2 of} the light-sensitive material, preferably 30 to 200 ml, more preferably 4
It is 0 to 100 ml. In the present invention, the processing time (for example, developing time) means the time from when the photosensitive material enters the target processing solution to when it enters the next processing solution. The term "from the beginning of the developing process to the end of the drying process" means the time from entering the developing bath of the developing processing apparatus to passing through the drying step to the outside of the apparatus.

In carrying out the present invention, it is preferable that substantially no benzyl alcohol is contained. The term "substantially free from" means that the concentration of benzyl alcohol is preferably 2 ml / liter or less, more preferably 0.5 ml / liter or less, and most preferably, benzyl alcohol is not contained at all.

The color developing solution used in the present invention suppresses fluctuations in photographic characteristics due to continuous processing, and contains substantially no sulfite ion in order to achieve the effects of the present invention. That is, the sulfite ion concentration is 3.0 × 10 ⁻³ mol / liter or less. Sulfite ion is preferably 1.0 × 10 ⁻³ mol / liter or less, and most preferably contains no sulfite ion. However, in the present invention, however, a very small amount of sulfite ion used for the antioxidant of the processing agent kit in which the developing agent is concentrated before preparing the use solution is excluded. The color developing solution used in the present invention should further contain substantially no hydroxylamine in order to suppress fluctuations in photographic characteristics due to fluctuations in the concentration of hydroxylamine. 5.0 × 10 ⁻³ mol / liter or less) is more preferable. Most preferably, it contains no hydroxylamine at all.

The color developing solution used in the present invention more preferably contains an organic preservative in place of hydroxylamine or sulfite ion. Here, the organic preservative refers to all organic compounds that reduce the deterioration rate of the aromatic primary amine color developing agent by being added to the processing solution of the color photographic light-sensitive material. That is, it is an organic compound having a function of preventing oxidation of a color developing agent due to air or the like, but among them, hydroxylamine derivatives (excluding hydroxylamine), hydroxamic acids, hydrazines, hydrazides, α-amino acids, phenols. , Α-hydroxyketones, α-aminoketones, sugars, monoamines,
Diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, condensed amines and the like are particularly effective organic preservatives. These are disclosed in JP-B-48-30496, JP-A-52-143020, JP-A-63-1235 and JP-A-6-23535.
No. 3-30845, No. 63-21647, No. 63-4
No. 4655, No. 63-53551, No. 63-4314.
0, 63-56654, 63-58346,
63-43138, 63-146041, 6
3-44657, 63-46656, U.S. Pat. Nos. 3,615,503, 2,494,903, JP-A-1-97953, 1-186939, 1-1.
No. 86940, No. 1-187557, No. 2-3062
No. 44, European Patent Publication EP0530921A1 and the like. Other preservatives include JP-A-57
-44148 and 57-53749, various metals, salicylic acids described in JP-A-59-180588, JP-A-63-239447, and JP-A-63-128.
340, JP-A-1-186939 and 1-1875.
Amines as described in JP-A-57-35,
No. 32 alkanolamines, JP-A-56-94
Polyethyleneimines described in U.S. Pat.
You may use the aromatic polyhydroxy compound etc. of 746,544 etc. as needed. Particularly, alkanolamines such as triethanolamine, dialkylhydroxylamine such as N, N-diethylhydroxylamine and N, N-di (sulfoethyl) hydroxylamine, glycine, alanine, leucine, serine, threonine, valine and isoleucine. It is preferable to add such an α-amino acid derivative or an aromatic polyhydroxy compound such as catechol-3,5-disulfonate.

In particular, dialkylhydroxylamine and alkanolamines are used in combination, or dialkylhydroxylamine described in European Patent Publication EP0530921A1 and α-represented by glycine are used.
The combined use of amino acids and alkanolamines is more preferable from the viewpoint of improving the stability of the color developing solution and, in turn, improving the stability during continuous processing. The amount of these organic preservatives added may be an amount having a function of preventing deterioration of the color developing agent, and is preferably 0.01 to 1.0.
The mol / liter is more preferably 0.03 to 0.30 mol / liter.

In the present invention, it is preferable that the color developer contains chlorine ions in an amount of 3.0 × 10 ^{-2 to} 1.5 × 10 ^-1 mol / liter. Particularly preferably 3.5 × 10 ^-2
˜1.0 × 10 ⁻¹ mol / liter. When the chlorine ion concentration is more than 1.5 × 10 ^{-1 to} 1.0 × 10 ^-1 mol / liter, it has a drawback that development is delayed, and in order to achieve the object of the present invention that the concentration is high and the maximum concentration is high. Not preferable. If it is less than 3.0 × 10 ^-2 mol / liter,
It is not preferable for preventing fog. In the present invention,
It is preferable that the color developer contains 0.5 × 10 ⁻⁵ mol / liter to 1.0 × 10 ⁻³ mol / liter of bromine ions. More preferably, 3.0 × 10 ^{−5 to} 5 × 10
^-4 mol / l. Bromine ion concentration is 1 × 10 ^-3
When the amount is more than mol / liter, the development is delayed, the maximum density and the sensitivity are lowered, and when it is less than 0.5 × 10 ⁻⁵ mol / liter, fog cannot be sufficiently prevented.

Here, the chlorine ion and the bromine ion may be directly added to the color developing solution, or may be eluted from the light-sensitive material to the color developing solution during the development processing. When added directly to the color developer, examples of the chloride ion supplying substance include sodium chloride, potassium chloride, ammonium chloride, lithium chloride, magnesium chloride and calcium chloride. Further, it may be supplied from a fluorescent whitening agent added to the color developing solution. As a source of bromide ions,
Examples thereof include sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide and magnesium bromide. When it is eluted from the light-sensitive material during the development processing, both chlorine ions and bromine ions may be supplied from the emulsion or may be supplied from sources other than the emulsion.

The color developing solution used in the present invention preferably has a pH of 9 to 13, more preferably 9 to 12.5, and the color developing solution contains a compound of a known developing solution component. be able to. In order to maintain the above pH, it is preferable to use various buffers. As the buffer, carbonate, phosphate, borate, tetraborate, hydroxybenzoate, glycyl salt, N, N-dimethylglycine salt, leucine salt, norleucine salt, guanine salt,
3,4-dihydroxyphenylalanine salt, alanine salt, aminobutyrate, 2-amino-2-methyl-1,3-
Propanediol salt, valine salt, proline salt, trishydroxyaminomethane salt, lysine salt and the like can be used. Particularly, carbonates, phosphates, tetraborates, and hydroxybenzoates have excellent solubility and buffering ability in a high pH range of pH 9.0 or more, and even when added to a color developing solution, they have excellent photographic performance. It is particularly preferable to use these buffers, since they have the advantages of being free from adverse effects (fogging, etc.) and being inexpensive.

Specific examples of these buffers include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate. , Potassium borate, sodium tetraborate (borax),
Potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), 5-sulfo-
Examples thereof include potassium 2-hydroxybenzoate (potassium 5-sulfosalicylate). The amount of the buffer added to the color developer is preferably 0.1 mol / liter or more, and particularly 0.1 mol / liter to 0.1.
It is particularly preferably 4 mol / liter.

In addition, various chelating agents can be used in the color developing solution as a calcium or magnesium precipitation preventing agent or for improving the stability of the color developing solution. For example, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N,
N ', N'-tetramethylenephosphonic acid, trans-silohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid Acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N'-bis (2
-Hydroxybenzyl) ethylenediamine-N, N'-
Examples thereof include hydroxyethyliminodiacetic acid diacetate.
Two or more of these chelating agents may be used in combination, if necessary. The amount of these chelating agents added may be an amount sufficient to block the metal ions in the color developing solution. For example, it is about 0.1 g to 10 g per liter.

Any development accelerator can be added to the color developing solution if necessary. As a development accelerator, Japanese Patent Publication No. 37
-16088, 37-5987, 38-782.
No. 6, No. 44-12380, No. 45-9019, and thioether compounds represented by US Pat. No. 3,813,247;
P-phenylenediamine compounds represented by JP-A-15554, JP-A-50-137726, and JP-B-44-3.
No. 0074, JP-A Nos. 56-156826 and 52-
Quaternary ammonium salts represented by U.S. Pat. No. 4,434,29, U.S. Pat. Nos. 2,494,903 and 3,128,182.
No. 4,230,796, 3,253,919
No. 4, Japanese Patent Publication No. 41-11431, US Pat. No. 2,48
2,546, 2,596,926 and 3,58
Amine compounds described in 2,346, etc., JP-B-37-
16088, 42-25201, U.S. Pat.
128,183, Japanese Patent Publication Nos. 41-11431, 42
-23883 and U.S. Pat. No. 3,532,501, and the like, polyalkylene oxides, 1-phenyl-3-pyrazolidones, imidazoles, and the like can be added as necessary.

In the present invention, any antifoggant can be added if necessary. As the antifoggant, alkali metal halides such as sodium chloride, potassium bromide and potassium iodide, and organic antifoggants can be used. Examples of the organic antifoggant include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2 Typical examples include nitrogen-containing heterocyclic compounds such as -thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine and adanine.

After color development, desilvering processing is performed. In the desilvering process, the bleaching process and the fixing process may be separately performed,
It may be performed at the same time (bleach-fixing process). In the mode of the desilvering process in the present invention, a bleach-fixing process is preferable for the purpose of simplifying the process and shortening the time. 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. In the present invention, the pH of the bleach-fixing solution or the bleaching solution used in the desilvering step is 4.0 or more and less than 6.0, and more preferably 4.5 or more and 5.5 or less. pH
When it is 4.0 or less, it is not preferable in terms of reduction of residual color and storage stability of the liquid. On the other hand, if the pH is 6.0 or more, the residual main agent may increase and the image storability may deteriorate, which is not preferable.

Examples of the bleaching solution used in the bleaching solution and the bleach-fixing solution include iron salts; compounds of polyvalent metals such as iron (III), cobalt (III), chromium (IV) and copper (II); peracids. Quinones; nitro compounds and the like. Typical bleaching agents are iron chloride; ferricyanide; dichromate; iron (I
II) organic complex salts (for example, metal complex salts of aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid) Persulfate; bromate; permanganate; nitrobenzenes and the like. Of these, iron ethylenediamine tetraacetate
(III) Complex salt, and iron 1,3-diaminopropane tetraacetate (I
II) Complexing salts and other iron (III) aminopolycarboxylic acid complex salts are preferable from the viewpoint of rapid treatment and prevention of environmental pollution. Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in both the bleaching solution and the bleach-fixing solution.

Known additives such as rehalogenating agents such as ammonium bromide and ammonium chloride; pH buffering agents such as ammonium nitrate; metal corrosion inhibitors such as ammonium sulfate are added to the bleaching solution and the bleach-fixing solution. be able to. In the bleaching solution and bleach-fixing solution, in addition to the above compounds,
It is preferable to contain an organic acid for the purpose of preventing bleach stain. A particularly preferred organic acid has an acid dissociation constant (pK
a) is a compound of 2 to 5.5, and specifically, acetic acid, propionic acid and the like are preferable.

Examples of the fixing agent used in the fixing solution and the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas and a large amount of iodide salts. Use of thiosulfates Are generally used, and ammonium thiosulfate is most widely used. Further, the combined use of thiosulfate and thiocyanate, thioether compounds, thiourea and the like is also preferable. As a preservative for the fixing solution and the bleach-fixing solution, sulfites, bisulfites, carbonyl bisulfite adducts or sulfinic acid compounds described in European Patent 294769A are preferable. Further, in the fixing solution and the bleach-fixing solution, various aminopolycarboxylic acids and organic phosphonic acids (for example, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N, N ', N') are used for the purpose of stabilizing the solution. -Ethylenediaminetetraphosphonic acid) is preferred.

The fixing solution and the bleach-fixing solution may further contain various fluorescent whitening agents, defoaming agents, surfactants, polyvinylpyrrolidone, methanol and the like. Bleach,
If necessary, a bleaching accelerator can be used in the bleach-fixing solution and the prebath thereof. Specific examples of useful bleaching accelerators include U.S. Pat. No. 3,893,858, West German Patent 1,290,812, and JP-A-53-95630.
And Research Disclosure No. 17129 (July 1978) and the like having a mercapto group or a disulfide bond;
Thiazolidine derivatives described in No. 29; US Pat. No. 3,7
Thiourea derivatives described in JP-A No. 06,561;
Iodide salt described in 16235; West German Patent No. 2,74
The polyoxyethylene compounds described in No. 8,430; the polyamine compounds described in JP-B-45-8836; the bromide ion 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 in particular, US Pat.
Compounds described in US Pat. Furthermore, US Pat.
The compounds described in No. 552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material.

For the purpose of shortening the processing time, the total time of the bleaching / fixing step in the present invention is preferably as short as possible in the range where desilvering failure does not occur. The preferred time is 5 seconds to 1 minute, more preferably 5 seconds to 25 seconds. The processing temperature is 25 ° C to 50 ° C, preferably 35 ° C to 45 ° C. In the preferred temperature range, the desilvering rate is improved,
In addition, the generation of stains after the processing is effectively prevented. Further, in the treatment step of the present invention, the stirring method in each step may be applied by any known method, but it is preferable that the stirring is strengthened as much as possible. As a concrete method for strengthening stirring, JP-A-62-183460,
No. 62-183461, a method of colliding a jet of a processing liquid with the emulsion surface of a light-sensitive material, and JP-A-62-18343.
A method of increasing the stirring effect by using the rotating means of No. 61, and further moving the light-sensitive material while bringing the emulsion surface into contact with a wiper blade provided in the liquid to make the emulsion surface turbulent, thereby further improving the stirring effect. There are a method of improving the method and a method of increasing the circulation flow rate of the whole processing solution. Such a stirring improving means is effective in any of a developing solution, a bleaching solution, a bleach-fixing solution, a fixing solution, a washing solution and / or a stabilizing solution. Further, in each of the above processing liquids used in the present invention, for example, JP-A-62-183460, specification 3
The method described in the lower right column of page to the lower right column of page 4 and discharging the liquid pumped by a pump from a slit or nozzle provided facing the emulsion surface can be applied. Further, the treatment of the present invention has a relatively excellent performance in any state of the liquid opening ratio [air contact area (cm ² ) / liquid volume (cm ³ )] compared to combinations other than the present invention,
From the viewpoint of stability of liquid components, the liquid opening ratio is 0 to 0.1 cm.
^-1 is preferred. In continuous processing, practically 0.0
The range of 01 cm ^{-1 to} 0.05 cm ^-1 is preferable, and 0.002 to 0.03 cm ^-1 is more preferable.

The color light-sensitive material of the present invention generally undergoes a washing step after desilvering. A stable process may be performed instead of the water washing process. In such stabilization treatment, JP-A-57-8543, JP-A-58-14834,
All the known methods described in JP-A-60-220345 can be used. In addition, a washing process-stabilizing process may be performed in which a stabilizing bath containing a dye stabilizer and a surfactant is used as a final bath. For the washing and stabilizing solutions,
A water softening agent such as inorganic phosphoric acid, polyaminocarboxylic acid or organic aminophosphonic acid; a metal salt such as Mg salt, Al salt or Bi salt; a surfactant; a hardener and the like can be contained.

The amount of rinsing water in the rinsing step depends on the characteristics of the light-sensitive material (for example, depending on the materials used such as couplers), application, and further, the rinsing water temperature, the number of rinsing tanks (the number of stages), the replenishment system such as countercurrent and forward flow, and other various It can be set in a wide range depending on the condition. Further, as a solution to the problems such as the propagation of bacteria and the adherence of the produced suspension to the light-sensitive material, which occurs when the amount of washing water is greatly reduced in the multi-stage countercurrent system, there is disclosed in Japanese Patent Laid-Open No.
The method of reducing calcium ion and magnesium ion described in 2-288838 can be used very effectively. Also, isothiazolone compounds, siabendazoles, chlorine-based bactericides such as sodium chlorinated isocyanurate described in JP-A-57-8542, and benzotriazole, etc., Hiroshi Horiguchi, "Chemistry of Antibacterial and Antifungal Agents"
(1986) Sankyo Publishing, edited by Hygiene Engineering Society, "Microbial sterilization, sterilization, antifungal technology" (1982) Industrial Technology Association, edited by Japan Society for Antibacterial and Antifungal, "Encyclopedia of Antibacterial and Antifungal Agents" (1986) The disinfectants described can also be used.

The pH of the washing or stabilizing solution is 4-9, preferably 5-8. Washing water temperature, washing time,
Although various settings can be made according to the characteristics and uses of the light-sensitive material, it is generally 15 to 45 ° C. for 10 seconds to 5 minutes, preferably 25 to 40 ° C.
The range of 15 seconds to 2 minutes is selected with. Examples of dye stabilizers that can be used in the stabilizing solution include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts. In addition, the stabilizing solution may further include a pH adjusting buffer such as boric acid and sodium hydroxide; 1-hydroxyethylidene-1,1-diphosphonic acid; a chelating agent such as ethylenediaminetetraacetic acid;
Antisulfurization agents such as alkanolamines; optical brighteners;
A fungicide and the like can be included. Washing with water and /
Alternatively, the overflow solution accompanying the supplement of the stabilizing solution can be reused in other steps such as the desilvering step. In the processing using an automatic processor or the like, when each processing solution described above is concentrated by evaporation, it is preferable to add water to correct the concentration. In the present invention, the washing and / or stabilizing water treated with a reverse osmosis membrane can be effectively used. As the material of the reverse osmosis membrane, cellulose acetate, crosslinked polyamide, polyether, polysulfone, polyacrylic acid, polyvinylene carbonate, etc. can be used. The liquid feeding pressure in the use of these membranes is preferably 2 to 10 kg / cm 2 because of the stain prevention effect and the reduction of the permeated water amount.
² , particularly preferable conditions are 3 to 7 kg / cm ² . The washing and / or stabilizing step is preferably connected in a multi-stage countercurrent system with a plurality of tanks, but it is particularly preferable to use 2 to 5 tanks.

The treatment with the reverse osmosis membrane is preferably carried out on the water from the second tank onward of such multi-stage countercurrent washing and / or stabilization. Specifically, in the case of a two-tank configuration, the second tank, in the case of a three-tank configuration, the second or third tank, and in the case of a four-tank configuration, the water in the third or fourth tank is treated with a reverse osmosis membrane and permeated. Same water tank (Tank for collecting water for reverse osmosis membrane treatment; hereinafter referred to as “collection tank”)
Alternatively, it is carried out by returning to a washing and / or stabilizing tank located thereafter. Furthermore, concentrated washing and /
Alternatively, one of the measures is to return the stabilizing solution to the bleach-fixing bath upstream of the sampling tank.

The color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing, and in order to incorporate it, it is preferable to use various precursors of the color developing agent. For example, indoaniline compounds described in U.S. Pat. No. 3,342,597, and No. 3,342,59.
No. 9, RD magazine Nos. 14850 and 15159, Schiff base type compounds, Aldol compounds described in No. 13924, metal salt complexes described in US Pat. No. 3,719,492, JP The urethane compounds described in JP-A-53-135628 can be mentioned. The color light-sensitive material of the present invention may contain various 1-phenyl-3-pyrazolidones in order to accelerate color development, if necessary. A typical compound is JP-A-56-64339.
No. 57-144547 and No. 58-11543.
No. 8 etc.

[0135]

EXAMPLES The present invention will be specifically described below with reference to examples. However, the present invention is not limited to these examples. Example 1 (Production of Photosensitive Material) After corona discharge treatment was applied to the surface of a paper support laminated on both sides with polyethylene, a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided, and various photographic constituent layers were further coated. A photosensitive material (photographic paper A) having the following layer structure was prepared. The coating liquid was prepared as follows. Preparation of coating liquid for first layer Yellow coupler (ExY) 153.0 g, color image stabilizer (Cpd-1) 15.0 g, color image stabilizer (Cpd-2)
7.5 g, color image stabilizer (Cpd-3) 16.0 g, solvent (Solv-1) 25 g, solvent (Solv-1) 25
g and 180 cc of ethyl acetate, and the solution is 10%
An emulsified dispersion A was prepared by emulsifying and dispersing in 1000 cc of 10% gelatin aqueous solution containing 60 cc of sodium dodecylbenzenesulfonate and 10 g of citric acid.

On the other hand, silver chlorobromide emulsion A {cubic, 3: 7 mixture of large size emulsion A with average grain size 0.88 μm and small size emulsion A with 0.70 μm (silver molar ratio), grain size distribution The coefficient of variation was 0.08 and 0.10 respectively, and each size emulsion contained 0.3 mol% of silver bromide localized on a part of the grain surface}. In this emulsion, the blue-sensitive sensitizing dyes A and B shown below were 2.0 × 10 ^-4 mol for each large-sized emulsion A and 2.0 × 10 ^-4 mol for each large-sized emulsion A per mol of silver. 2.5 × 10 ⁻⁴ mol of each is added. 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
And were mixed and dissolved, and a coating solution for the first layer was prepared so as to have the following composition. Preparation of Second Layer to Seventh Layer Coating Liquid The coating liquids for the second to seventh layers were also prepared in the same manner as the first layer coating liquid. The coating liquid for each layer described above was applied onto a support to prepare a sample of a light-sensitive material having a layer structure described below.

The gelatin hardener for each of the above layers is 1
-Oxy-3,5-dichloro-s-triazine sodium salt was used. In addition, Cpd-14 and Cpd-1 are provided in each layer.
Total volume 5 were added to each so that 25.0 mg / m ² and 50 mg / m ^2. The following spectral sensitizing dyes were used for the silver chlorobromide emulsion of each photosensitive emulsion layer.

[0139]

[Table 17]

[0140]

[Table 18]

[0141]

[Table 19]

Further, 1- (5-methylureidophenyl) is added to the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer.
-5-Mercaptotetrazole was added in an amount of 8.5 x 10 ^-5 mol, 7.7 x 10 ^-4 mol and 2.5 x 10 ^-4 mol per mol of silver halide, respectively. For the blue-sensitive emulsion layer and the green-sensitive emulsion layer, 4-hydroxy-6-methyl-1,
3,3a, 7-Tetrazaindene was added at 1 × 10 ⁻⁴ mol and 2 × 10 ⁻⁴ mol per mol of silver halide, respectively. (Layer constitution) The composition of each layer is shown below. Numbers are coating amount (g
/ M ² ). The silver halide emulsion represents the coating amount in terms of silver.

[0143]

[Table 20]

[0144]

[Table 21]

[0145]

[Table 22]

[0146]

[Chemical 42]

[0147]

[Chemical 43]

[0148]

[Chemical 44]

[0149]

[Chemical formula 45]

[0150]

[Chemical formula 46]

[0151]

[Chemical 47]

Further, in the above light-sensitive material (photographic paper A), (photographic paper B) having the same constitution as (photographic paper A) except that the following anti-irradiation dye is added to the emulsion layer,
(Printing paper C), (printing paper D), and (printing paper E) were prepared. Dye No. Coating amount (mg / m ² ) (photographic paper B) (III-1) 10 (a-23) 10 (a-2) 20 (a-13) 40 (photographic paper C) (III-1) 10 (a-23) 20 (a-2) 40 (a-13) 40 (photographic paper D) (a-17) 10 (a-25) 10 (a-19) 60 (photographic paper E) (b- 11) 10 (c-13) 10 (b-8) 50

(Processing Method 1) Using the following processing steps and the color developing solutions (101) to (105), the previously exposed (photographic paper B) was used until the tank was filled with the color developing solution. A continuous process (running test) was performed.

Treatment process Temperature Time Replenishment rate (ml / m ² ) Tank capacity (liter) Color development 40 ° C 25 seconds 35 2 Bleach fixing 40 ° C 25 seconds 35 2 Rinse 35-40 ° C 15 seconds 1 Rinse 35-40 ° C 15 seconds 1 rinse 35-40 ° C 15 seconds 60 1 dry 80 ° C 20 seconds (Rinse → 3 tank countercurrent method)

Color developer (101) Tank solution Replenisher Water 700 ml 700 ml Sodium triisopropylnaphthalene (β) sulfonate 0.1 g 0.1 g Ethylenediaminetetraacetic acid 3.0 g 3.0 g 1,2-dihydroxybenzene-4,6 -Disulphonic acid disodium salt 0.5 g 0.5 g Triethanolamine 12.0 g 12.0 g Potassium chloride 6.5 g-Potassium bromide 0.03 g-Potassium carbonate 27.0 g 27.0 g Sodium sulfite 0.1 g 0.1. 1 g Disodium-N, N-bis (sulfonate ethyl) hydroxylamine 10.0 g 13.0 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 7.0 g 15.0g Add water 1000ml 1000ml pH (25 ℃) 1 .35 11.6

Color developing solutions (102), (103),
(104) and (105) are color developing solutions (10
It was prepared by adding an optical brightener to 1) as follows. Color developer Fluorescent brightener addition amount (g / liter) (102) (B-1) 2.5 (tank liquid) 〃 4.0 (replenisher) (103) (B-4) 2.5 (tank Liquid) 4.0 (replenisher) (104) (SR-13) 2.5 (tank liquid) 〃 4.0 (replenisher) (105) (SR-35) 2.5 (tank liquid) 〃 4 0.0 (Replenisher) (For each processing solution, adjust the pH of the processing solution to the color developing solution (10
The same as the tank solution or replenisher solution of 1) was set)

Bleach-fixing solution Tank solution Replenishing solution Water 600 ml 150 ml Ammonium thiosulfate (700 g / l) 100 ml 250 ml Ammonium sulfite 15 g 30 g Ethylenediaminetetraacetic acid iron (III) ammonium 77 g 150 g Ethylenediaminetetraacetic acid 5 g 12.5 g Ammonium bromide 40 g 75 g Nitric acid ( 67%) 30g 65g Water added 1000ml 1000ml pH (25 ° C) 5.8 5.6 (adjusted with acetic acid or ammonium water)

Rinse solution Ion-exchanged water (calcium and magnesium are each 3 ppm or less)

The previously prepared A3 size light-sensitive material (photographic paper B), which was imagewise exposed using a stretcher, was repeatedly processed by the above (Processing method 1) (this is called a running process). This is continued until the total amount of the replenisher added is 1 times the capacity of each processing tank of the developing machine used (this is referred to as 1 cycle). The running test was carried out with the replenishment amount shown in Table 23 and the color developing solution, and when the ratio of the replenishment amount to the bath volume was different for each bath, it was continued until it was doubled or more in any bath. Here, when the replenishment amount was increased to n times as much as that of the above (treatment method 1), the replenisher was diluted n-fold with water and used as a new replenisher. After the continuous processing, for each processing solution, Fuji Photo Film Co., Ltd., F
Color-exposed photographic printing paper was processed with a W type sensitometer. The reflection densities of yellow, magenta, and cyan of the processed sample were measured to obtain a characteristic curve, and the minimum density (Dmin) at that time was obtained. On the other hand, the developer (101)
A crystallization test was carried out by placing 100 cc of each of the replenishers (1) to (105) in a polyvinyl chloride container, sealing the container, storing at 5 ° C for 5 days, and observing the precipitate. Second result
It is shown in Table 3.

[0160]

[Table 23]

A processing solution containing a conventional optical brightener (10
Compared to the processing solution (101) which does not use the optical brightener, 2) and (103) have Dmi even if the replenishment amount is reduced.
Although it had the effect of reducing the increase in n (yellow), there was a problem that precipitates were formed during low temperature storage. As is clear from the results shown in Table 23, the development processing solution of the present invention was capable of achieving a white background in which precipitation of crystals did not occur during storage under refrigeration and the increase of Dmin (yellow) was further reduced. Further, in the present invention, surprisingly, cyan Dmin
We were able to achieve a white background with little rise.

Example 2 (Treatment Method 2) As a result of carrying out continuous treatment (running test) in the same manner as in Example 1 except that the following treatment steps were performed, the same results as in Example 1 were obtained.

Processing Step Temperature Time Tank Capacity (liter) Color Development 40 ° C. 45 seconds 2 Bleaching Fixing 40 ° C. 45 seconds 2 Rinse 35-40 ° C. 22.5 seconds 1 Rinse 35-40 ° C. 22.5 seconds 1 Rinse 35 ~ 40 ° C 22.5 seconds 1 Rinse 35-40 ° C 22.5 seconds 1 Dry 80 ° C 20 seconds (* replenishment amount per 1 m ^{2 of} light-sensitive material) (Rinsing → 3 tank countercurrent method) In the treatment, the rinse water was pumped through the reverse osmosis membrane, the permeate was supplied to the rinse, and the concentrated water that did not pass through the reverse osmosis membrane was returned to the rinse for use.

Example 3 (Processing Method 3) The following processing steps and color developing solution (3
01) to (305) were used to carry out continuous processing (running test) using the exposed (photographic printing paper B) until the tank was replenished with the color developer.

Treatment process Temperature Time Replenishment amount ^* Tank capacity (liter) Color development 40 ° C. 15 seconds 35 ml 2 Bleach fixing 40 ° C. 15 seconds 35 ml 2 rinse 40 ° C. 3 seconds −1 rinse 40 ° C. 3 seconds −1 rinse 40 ° C. 3 sec - 1 rinse 40 ° C. for 3 seconds - 1 rinse 40 ° C. 6 seconds 60 ml 1 drying 80 ° C. 20 seconds (total 130 ml) (* replenishment rate per photosensitive material 1 m ²⁾ (and the third tank countercurrent system of the rinsing → did)

In the above treatment, the rinse water was pumped through the reverse osmosis membrane, the permeated water was supplied to the rinse, and the concentrated water that did not pass through the reverse osmosis membrane was returned to the rinse for use. In addition,
In order to shorten the crossover time between the rinses, a blade was installed between the tanks, and the photosensitive material was passed between them. As the small-sized developing machine used in this example, a developing machine having the same structure as that shown in FIGS. 1 and 2 on pages 45 to 46 of JP-A-5-66540 was used.

Color developer (301) Tank solution Replenisher Water 700 ml 700 ml Ethylenediaminetetraacetic acid 1.5 g 3.75 g Sodium triisopropylnaphthalene (β) sulfonate 0.01 g 0.01 g 1,2-dihydroxybenzene-4,6 -Disulphonic acid disodium salt 0.25 g 0.7 g triethanolamine 5.8 g 14.5 g potassium chloride 10.0 g-potassium bromide 0.03 g-potassium carbonate 30.0 g 39.0 g sodium sulfite 0.14 g 0.1. 2 g Disodium-N, N-bis (sulfonate ethyl) hydroxylamine 7.4 g 15.0 g 4-Amino-3-methyl-N-ethyl-N- (4-hydroxybutyl) aniline.2-p-toluene sulfone Acid 14.5g 35.0g Add water 1000ml 10 00 ml pH (25 ° C) 10.05 11.60

Color developing solutions (302), (303),
(304) and (305) are color developing solutions (30
It was prepared by adding an optical brightener to 1) as follows. Color developing solution Fluorescent brightening agent addition amount (g / liter) (302) (B-1) 3.0 (tank solution) 〃 5.0 (replenisher) (303) (B-10) 3.0 (tank Liquid) 〃 5.0 (Replenisher) (304) (SR-13) 3.0 (Tank liquid) 〃 5.0 (Replenisher) (305) (SR-35) 3.0 (Tank liquid) 〃 5 0.0 (Replenisher) (For each processing solution, adjust the pH of the processing solution to the color developing solution (30
The same as the tank solution or replenisher solution of 1) was set)

Bleach-fixing solution (a replenishing solution prepared by separating the components into two solutions was used.) [First Replenishing Solution] Water 150 ml Ethylenebisguanidine nitrate 30 g Ammonium sulfite / monohydrate 190 g Ethylenediaminetetraacetic acid 7.5 g Bromide Ammonium 30g Ammonium thiosulfate (700g / l) 340ml Acetic acid (50%) 250ml Add water 1000ml pH (25 ° C) 6.0 [Second replenisher] Water 140ml Ethylenediaminetetraacetic acid 11.0g Ethylenediaminetetraacetic acid iron (III) Ammonium 715 g Acetic acid (50%) 100 ml Water added 1000 ml pH (25 ° C) 3.3 Bleach-fix solution tank solution 1st replenisher 300 ml 2nd replenisher 200 ml Water added 1000 ml pH (25 ° C) 5.0 the replenishing amount of bleach-fixing solution (total 35ml per 1 m ² in the following weight) first replenisher 1ml second replenisher 14ml rinse liquid ion-exchanged water (calcium, magnesium each 3ppm or less)

After the continuous processing according to the above (Processing method 3) was completed, the gradation-exposed color photographic paper was processed with each processing solution. In the same manner as in Example 1, the yellow, magenta, and cyan reflection densities of the processed sample were measured to obtain a characteristic curve, and the minimum density at that time was obtained. Further, the unexposed color photographic paper was processed, and the residual ratio of the sensitizing dye and the dye in the color photographic paper was determined by the following method. (Method of quantifying residual color) The sensitizing dye and the anti-irradiation dye remaining on the color photographic paper after treatment were treated with methanol /
Extract with water (1/1) and quantify by high performance liquid chromatographic analysis, residual rate (100 x residual amount / application amount,%)
Expressed as The results show the residual ratios of sensitizing dyes A and B in Table 17 for the sensitizing dye and (a-2) and (a-13) for the anti-irradiation dye.
In the same manner as in Example 1, the developing replenisher (3
The crystallization tests of 01) to (305) were carried out. The above results are shown in Table 24.

[0171]

[Table 24]

As is clear from the results shown in Table 24, the development processing solution of the present invention did not cause precipitation of crystals during storage under refrigeration.
Moreover, it is possible to provide a white background with little residual color due to the sensitizing dye and dye in the processing.

Example 4 The developer (301) of Example 3 was used, and the same continuous processing as in Example 3 was carried out under other conditions. Using the running liquid obtained after the continuous treatment, the following residual color and crystallization tests were carried out. Two color developer and bleach-fix solution after running
Treatment solutions (401) to (410), each of which was divided into 00 cc and added with a brightening agent as shown in Table 25.
Was prepared. Using the processing solutions in Table 25, unexposed color photosensitive materials (photographic paper A), (photographic paper B), (photographic paper C),
(Printing paper D) and (Printing paper E) were processed in a small developing machine. At that time, the rinse liquid uses the running liquid itself,
The processing temperature and the processing time of each step are as described above (processing method 3).
The same standard was used. The minimum densities (Dmin) of yellow, magenta and cyan of the processed light-sensitive material were determined. After the processing was completed, the above-mentioned developing solution and bleach-fixing solution were observed for the presence or absence of crystallization by the same method as in Example 1.

[0174]

[Table 25]

[0175]

[Chemical 48]

[0176]

[Table 26]

[0177]

[Table 27]

The above results are shown in Tables 26 and 27. In the results of Table 27, the treatment liquids (401), (402), to which the conventional diaminostilbene compound was added,
In (403) and (405), precipitation of crystals occurred during low temperature storage of the replenisher. Further, the treatment liquid (404) in which a conventional diaminostilbene compound having an anilino group as a substituent on the triazine ring was added did not cause precipitation during refrigeration storage, but the residual color was the worst in Table 26. On the other hand, the treatment liquid of the present invention did not cause the precipitation of crystals during storage under refrigeration, and in addition, in the results shown in Table 26, a white background with the least residual color was achieved.

Example 5 The developer (301) of Example 3 was used, and the same continuous treatment as in Example 3 was carried out under other conditions. 4 liters of running liquid after continuous processing was prepared and the following tests of residual color and image storability were carried out. After running, divide the color developing solution and the bleach-fixing solution into 200 cc aliquots, add a fluorescent whitening agent to the developing solution as shown in Table 28, and add a pH of the bleach-fixing solution with aqueous ammonia or acetic acid as shown in Table 28. The modified treatment liquids (501) to (516) were prepared. An unexposed color light-sensitive material (photographic paper B) was processed in a small developing machine using the processing solutions shown in Table 28. At that time, the running liquid itself was used as the rinse liquid, and the processing temperature and the processing time of each step were performed according to the same standard as the above (processing method 3). Minimum density of yellow, magenta, and cyan (Dmi
n) was calculated. Further, in the image storability test, the images after the processing were stored for 10 days under the conditions of 80 ° C. and a humidity of 60%, and the minimum density of the unexposed portion after the storage was measured for comparison.
The result is expressed by the minimum density of magenta (D (M) min), D (M) m
The smaller the value of in, the less the occurrence of stain during storage.

[0180]

[Table 28]

[0181]

[Table 29]

The above results are shown in Table 29. In the results shown in Table 29, although the image storage stability is improved as the pH is lowered in the processing methods (401) to (405) using the conventional diaminostilbene compound, the residual color is yellow when the pH of the bleach-fixing solution is less than 6. And cyan Dmin
Has risen. On the other hand, in the processing methods (406) to (410) using the fluorescent whitening agent of the present invention, Dmin does not increase even when the pH of the bleach-fixing solution is lowered, and particularly when the pH is less than 6, a low Dmin and stain during image storage are obtained. Had achieved a low rise image.

Example 6 In the case of (Processing method 1) of Example 1, the color developing solution (10
1) and the photosensitive material (photographic paper B),
The running treatment (1 cycle) was performed with 5 different replenishment amounts of 1) to (605). Complementary amount (ml / m ² ) Processing solution name Color development Color bleach-fix Water wash Total (601) 90 90 90 240 420 (602) 60 60 120 240 (603) 45 45 120 120 210 (604) 45 45 90 90 (605) ) 35 35 60 130 The running solution after completion of the running treatments of (601) to (605) was divided into 200 ml each, and an optical brightener was added as shown in Table 30. An unexposed light-sensitive material (photographic paper B) was processed with a small developing machine using the prepared processing solution, and Dmin of the light-sensitive material after processing was measured by the same method as in Example 1. Further, the processed developer was refrigerated and stored at 5 ° C. for 5 days, and the presence or absence of deposits after the storage was observed. The above results are summarized in Table 30.

[0184]

[Table 30]

As is clear from the results shown in Table 30, the treatment method using the optical brightener of the present invention has a total replenishment amount of 20.
Even when the replenishment rate is reduced to 0 ml or less, the Dmin of yellow and cyan in the unexposed area of the light-sensitive material is very little increased, and crystals are not precipitated even when the processing solution is stored at low temperature. On the other hand, when the conventional fluorescent whitening agent is used, there is some effect on the Dmin of yellow, but there is no effect on the increase of Dmin of cyan, and there is a problem that crystals are precipitated when the treatment liquid is stored at a low temperature.

[0186]

By carrying out the constitution of the present invention, in a simple and rapid development processing of a color photographic light-sensitive material, no precipitate is generated in the processing solution during low temperature storage, and an image after processing is It is possible to provide a color image forming method with less residual color and excellent image storability. Further, in the development processing method in which the replenisher of the processing solution such as the color developing solution was reduced, the residual color could be remarkably suppressed.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location G03C 7/44

Claims (5)

[Claims] 1. A silver halide color photographic light-sensitive material having a light-sensitive silver halide emulsion layer on at least one side of a support is subjected to image exposure, followed by development, desilvering and washing and / or stabilization steps. In the image forming method of drying,
The silver halide emulsion used in the silver halide color photographic light-sensitive material comprises a high silver chloride emulsion having a silver chloride content of 90 mol% or more, and the total amount of replenishment in the processing step is 200 ml or less per 1 m ^{2 of the} light-sensitive material. A color image forming method, wherein at least one of the above-mentioned processing steps is carried out in the presence of a compound represented by the following general formula [SR]. [Chemical 1] In the general formula [SR], L ¹ and L ² may be the same or different and are represented by —OR ¹ or —NR ² R ³ (R ¹ , R ² and R ³ are each a hydrogen atom or an alkyl group), And, at least one of the following conditions is satisfied. Four substituents L ¹ and L in the general formula [SR]
² has a total of 4 or more substituents selected from the general formula [A] group. Four substituents L ¹ and L in the general formula [SR]
² has a total of two substituents selected from the general formula [A] group, and has a total of two or more substituents selected from the general formula [B] group. [Chemical 2] In the general formula [A] group, X represents a halogen atom and R represents an alkyl group. In the general formulas [SR] and [A],
M represents a hydrogen atom, an alkali metal, tetraalkylammonium or pyridinium. 2. The desilvering step, wherein the pH of the processing solution is 4.0 or more 6.
The color image forming method according to claim 1, wherein the color image forming method is performed at less than 0. 3. The color image forming method according to claim 1, wherein the developing agent used in the color developing solution is represented by the following general formula [D]. [Chemical 3] In the general formula [D], R ⁵ represents a linear or branched alkyl group having 1 to 6 carbon atoms or a linear or branched hydroxylalkyl group having 3 to 6 carbon atoms. R ⁶ represents a linear or branched alkylene group having 3 to 6 carbon atoms or a linear or branched hydroxyl alkylene group having 3 to 6 carbon atoms. R
⁷ represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched alkoxy group having 1 to 4 carbon atoms. 4. The processing time of the light-sensitive material is 2 in the bleach-fixing process.
2. The process is within 5 seconds, and the time from the beginning of the developing process to the end of the drying process is within 120 seconds.
The method for forming a color image according to item 1. 5. A silver halide color photographic light-sensitive material has the following general formula (I), (II), (III), (IV) or (Sa).
The color image forming method according to claim 1, further comprising at least one compound represented by [Chemical 4] [Chemical 5] [Chemical 6] [Chemical 7]