JPH0830872B2 - Processing method of silver halide color photographic light-sensitive material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a so-called slit developing method for processing a silver halide color photosensitive material such as a color film or a color paper in a slit-like processing path. .

[Conventional technology]

In general, a silver halide photosensitive material is developed through a rectangular processing tank containing processing solutions such as a developing solution, a bleaching solution, a fixing solution, and a stabilizing solution one after another. At this time, in order to obtain a uniform and uniform finish performance, the photosensitive material is dipped in a large amount of processing solution for processing, but if a large amount of processing solution is stored in the processing tank, halogenation will be processed. When the amount of silver light-sensitive material is small, the components in the processing liquid may deteriorate due to air oxidation or absorption of carbon dioxide, or the pH of the processing liquid may fluctuate, causing the fluctuation of the performance of the processing liquid photosensitive material. It was. Further, if the amount of the replenisher is reduced in order to achieve a simple and quick process, the retention time of the treatment liquid is extended, and thus these problems are remarkable. As an effective means for solving the problem, there is known a slit developing method in which the treatment liquid is brought into contact with air as much as possible and the treatment is performed in a slit-shaped treatment tank in which a treatment is performed with a required minimum amount of liquid. In the bleaching tank and the bleach-fixing tank, since the opening area is small, there is a problem that the concentration of Fe ²⁺ increases and a cyan color restoration failure occurs. Especially in the rapid processing, when the bleaching processing was performed at a low pH, the color restoration failure was particularly remarkable. In some cases, the above problems can be solved by making only the bleach-fixing tank into a conventional open tank or by carrying out forced oxidation by aeration, but it has not been able to meet the demand for reduction in size and weight of the apparatus.

Cyan couplers that are less likely to cause such color restoration defects are disclosed in US Pat. Nos. 3772002, 2772162, and 375830.
In some cases, the color recovery failure can be improved by using the couplers described in No. 8, No. 4327173, No. 4334011, and No. 4427767. In many cases, it has been desired to develop a light-sensitive material which does not cause defective color restoration in the slit developing process.

[Problems to be Solved by the Invention]

Therefore, it is an object of the present invention to provide a color development processing method which does not cause a cyan color restoration failure in the slit processing method and enables simple processing.

[Means for solving the problem]

The present invention has been completed based on the finding that the above problems can be solved by using a cyan coupler with less recoloring failure in the photosensitive material in performing slit development processing, and by combining it with a specific surfactant. It was

That is, the present invention relates to a method of processing a silver halide color photographic light-sensitive material by using an automatic developing device, in which bleaching and / or bleach-fixing treatment is carried out in a slit-shaped processing path of the automatic developing device. Includes (a) a coupler selected from the general formulas [I] to [IV], and (b) a surfactant having the following composition and having a solubility in a developing solution of 0.005% by weight or more at 35 ° C .: Processing method of silver halide color photographic light-sensitive material Developer 3 g of sodium chloride, 8 g of triethanolamine, 3 g of ethylenediaminetetramethylenephosphonic acid, potassium carbonate
26 g, N, N-bis (carboxymethyl) hydrazine 5 g, sodium sulfite 0.1 g, N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 5 g and potassium bromide 0.02 Developer having 1 added by adding water to g General formula [I] General formula (II) (In the formulas [I] and [II], R ¹ , R ⁴ and R ² each represent an aliphatic group, an aromatic group, a heterocyclic group, an aromatic amino group or a heterocyclic amino group, and R ⁵ is a fat represents groups (excluding methyl group), R ³ and R ⁶ are each a hydrogen atom, a halogen atom, an aliphatic group, an aliphatic oxy group or an acylamino group, Y ^1, Y ² is a halogen atom or a developing agent Represents a group capable of splitting off during a coupling reaction with an oxidant of the formula (I) and formula (II), wherein R ² and R ³ and R ⁵ and R ⁶ form a 5-, 6- or 7-membered ring, respectively. R ¹ , R ² , R ³ or Y ¹ ; R ⁴ , R ⁵ , R ⁶ or Y ² ;
May form a dimer or higher polymer. ) General formula [III] (In the formula [III], R ⁷ represents an aliphatic group, an aromatic group or a heterocyclic group, Ar is a substituted or unsubstituted aryl group or heterocyclic group, and Z is a hydrogen atom or an aromatic primary amine. And a general formula [IV], which represents a group capable of splitting off by a coupling reaction with an oxidized product of a developing agent. (In the formula [IV], R ²¹ represents a halogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an amidino group, a guanidino group or -COR.
²⁴ , -SO ₂ R ²⁴ , -SOR ²⁴ , -NHCOR ²⁴ , -NHSO ₂ R ²⁴ , -NHSOR ²⁴ , And R ²² represents a group capable of substituting for the aromatic ring. T represents a hydrogen atom or a group capable of splitting off by a coupling reaction with an oxidized product of an aromatic primary amine developing agent.

When l'is plural, R ^{22 s} may be the same or different, and they may be bonded to each other to form a ring. R ²²
And R ²³ or R ²³ and T may be bonded to each other to form a ring. Further, any of R ²¹ , R ²² , R ^{23 and} T may form a dimer or multimer (oligomer or polymer) which is bonded to each other via a divalent or divalent or higher valent group. ).

The slit-shaped processing path used in the development processing of the present invention is defined such that when a path in a processing tank through which a photosensitive material passes is cut at a right angle to a traveling direction of the photosensitive material, its cross section has a lateral width (width direction of the photosensitive material). Means a so-called slit shape having a small thickness. The slit-shaped cross section may be rectangular or oval.

The shape of the processing tank having such a slit processing path is defined as follows.

V / L ≦ 20 Particularly preferably, V / L ≦ 10. Here, V is the volume (cm ³ ) of the processing liquid contained in the processing passage, and L is the central passage (processing) of the photosensitive material from the photosensitive material inlet side liquid level to the outlet side liquid level of the processing tank. The length of the road (cm).

Therefore, the slit processing path is characterized in that the amount of liquid accommodated with respect to the length of the path is small. That is, since the amount of the solution is small, the replacement of the solution in the processing path (processing tank) by replenishment of the processing solution is quickened, in other words, the residence time of the solution in the processing tank can be shortened, and the fatigue of the processing solution over time can be avoided. Can be. However, the lower limit of V / L is practically preferably 0.1, particularly preferably 0.5.

In the processing path, V is preferably 10000～100Cm ³ Specifically, particularly preferred 5000～200Cm ^3, most preferably
It is 1000 to 300 cm ³ . L is preferably 300 to 10 cm,
Particularly preferably, it is 200 to 20 cm, most preferably 100 to 30 cm.

When processing is performed through a slit processing path, the liquid volume V (cm
^It is preferable to use a treatment tank having a small liquid area S (cm ² ) in contact with air (hereinafter referred to as “opening area”) with respect to ³ ). Specifically, it is preferable that V and S have the following relationship.

S / V ≦ 0.05 Particularly preferably, S / V ≦ 0.01. That is, the smaller the S / V, the less likely it is to undergo air oxidation, and the less the liquid evaporates, the more stable the liquid can be stored for a long period of time. However, practically, the lower limit is preferably 0.0005, and particularly preferably 0.001.

In the above rules, the thickness of the slit-like processing path is 1 to 50
mm, particularly preferably 3 to 30 mm.

Also, the conveying speed of the photosensitive material in the slit processing path is 10 cm /
The range of minutes to 1000 cm / min is preferable, and the range of 20 to 600 cm / min is preferable and the most preferable range is 30 to 400 cm / min in order to obtain a uniform and even finish.

When processing is performed in the above slit processing path, changes in processing liquid in the processing tank, specifically, oxidation of developing agents and preservatives, lowering of PH due to absorption of carbon dioxide in the air, concentration due to evaporation of moisture , Various decomposition of processing liquid components due to long-term retention in the tank,
The great advantage is that it is possible to eliminate the variable factors of the conventional processing such as mutual unfavorable reactions. Therefore, even in the light-duty processing in which the processing amount of the photosensitive material is small, it is possible to perform the processing in which the finishing performance of the photosensitive material such as gradation, fog, sensitivity, and the like is hard to fluctuate. Further, it is easy to achieve the compactness of the processing apparatus, and since the opening area is small, it is possible to avoid the complexity of using a conventional floating lid.

In the present invention, the slit-shaped processing path includes those in which at least a part of the portion other than the photosensitive material transporting roller is slit-shaped, and the length of the slit-shaped processing path between the transporting roller and the roller is 5cm or more, preferably 10c
It should be m or more. A flexible member (nylon, polyester, or the like) may be provided on the inner wall of the slit-shaped processing path so as to protrude toward the inside.

In the present invention, when performing slit development,
It is preferable to use a processing tank in which the ratio of the liquid surface area to the liquid volume is small. In this processing tank, the cross-sectional area of the processing liquid path is preferably substantially the same as the surface area of the liquid surface, and so-called thin layer development is preferable.

Further, the liquid flow path of the main part of the developing tank and the conveying path of the photosensitive material are substantially parallel to each other, and in the main part, the direction perpendicular to the emulsion tank of the photosensitive material and the support layer (thickness direction). Is less than 200 times the thickness of the light-sensitive material, and further 2
It is preferable that the processing liquid path is up to 100 times, especially 5 to 50 times. In this case, the gap between the processing tank and the photosensitive material in the thickness direction is 0.3 to 30 mm, preferably 0.5 to 10 mm, and particularly preferably 0.5 to 3 mm.

In the present invention, the slit processing path is filled with a developing solution, a bleaching solution, a bleach-fixing solution, a fixing solution, washing water, a stabilizing solution, and the like,
A development process is carried out by passing a silver halide light-sensitive material as an exposure agent between them. Examples of the developing solution include a black-and-white developing solution and a color developing solution (including a reversal color developing solution). The following steps are specifically exemplified as the slit developing method of the present invention.

(1) Development-bleach-fix-wash-dry (2) Development-bleach-fix-stabilize-dry (3) Development-bleach-fix-wash-dry (4) Development-bleach-fix-stabilize-dry (5) ) Development-bleaching-fixing-washing-stabilization-drying (6) Development-bleaching fixing-washing-stabilization-drying (7) Black-white development-washing-reversal-Color development-washing-bleaching-fixing-washing-stabilization A washing with water can be provided between development and bleaching in the above processing step. Further, if necessary, steps such as stopping, adjusting, and neutralizing can be appropriately provided. In the case of a black-and-white light-sensitive material, the bleaching step and the stabilizing step can be omitted in the above (3) to (5).

In the above-described slit developing method, it is preferable that the processing liquid is divided and supplied into the processing path along the traveling direction of the silver halide photosensitive material in the slit processing path. Here, at least one of the above-mentioned processing liquids can be given as the processing liquid to be dividedly supplied, but all the processing liquids can also be dividedly supplied. Further, the term “divided supply” means that, for example, when a developing solution is supplied, the developing solution is introduced into a slit processing path in which the developing solution is contained in at least 2 parts along the traveling direction of the silver halide photosensitive material.
It means to supply at two places, preferably two to five times.

When the developer is supplied in divided portions, a supply port is provided at a position where the photosensitive material enters the developer in the developing tank, and the supply port provides 30 to 70%, preferably 40 to 60% of the total replenishment amount of the developer. %, The remainder is divided according to the number of supply ports, and supplied from a supply port provided downstream of a position where the photosensitive material enters the developing solution. On the other hand, the bleaching solution, the bleach-fixing solution, the fixing solution, the washing water, the stabilizing solution, and the like are different from the supply order of the developing solution. 30-70%, preferably 40-60%, of the replenishment amount of the processing solution is supplied from a supply port provided at a position where the material exits, and the remainder is divided according to the number of supply ports, and upstream of the position where the photosensitive material exits It is preferable to supply from a supply port provided in the hopper.

The slit development can be carried out by using, for example, an automatic developing machine shown in FIG. 1 in which all processing paths for introducing the processing solution (developing solution, bleach-fixing solution, washing water, etc.) are formed as slit-shaped processing paths. .

 The light-sensitive material is usually subjected to the following development processing.

Color developing treatment The color developing solution used in the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. Although aminophenol compounds are also useful as the color developing agent, p-phenylenediamine compounds are preferably used, and a typical example thereof is 3
-Methyl-4-amino-N, N-diethylaniline, 3-
Methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-
Methyl-4-amino-N-ethyl-N-β-methoxyethylaniline and their sulfates, hydrochlorides or p-
Toluene sulfonate may be mentioned. Two or more of these compounds can be used in combination depending on the purpose. Of these, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethyl-p-phenylenediamine sulfate is preferable.

The color developing solution used in the present invention is prepared as a solution containing the above-mentioned color developing agent in an amount of 0.1 to 2.0 wt%, preferably 0.3 to 1.5 wt%.

To adjust the pH of the solution, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate is used,
Preferably an alkaline agent such as potassium hydroxide and a pH such as an alkali metal carbonate, borate or phosphate.
Buffering agents can be used. Usually the former is 0.3-2.0wt
%, Preferably 0.5 to 1.5 wt%, the latter being 1 to 5 wt%
To use. These pH adjusters may be added to the composition in advance, or the pH may be adjusted to a desired value by adding an alkaline agent to the solution.

The pH of the developer used in the processing method of the present invention is usually 9.5 or higher, preferably 9.8 or higher. PH of developer
If it exceeds 12, fog will increase, so it is desirable not to exceed pH 12. However, when the slit-shaped processing machine of the present invention is used, it has a feature that the preservative of the processing liquid is good even if the pH is high because the opening is small. Therefore, it is preferable to have a high pH within the range where the fog does not significantly increase, because the development is quicker.

The developer added as a replenisher to the mother liquor initially filled in the slit processing tank as the developer preferably has a pH of about 0.2 to 1.0 higher so as to maintain the pH.

The color developing solution used in the present invention generally contains a development inhibitor such as bromide salt, iodide salt, benzimidazole, benzothiazole or mercapto compound, or an antifoggant. Also, if necessary,
Various preservatives such as hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenylsemicarbazide, triethanolamine, catecholsulfonic acid, triethylenediamine (1,4-diazabicyclo [2,2,2] octane), ethylene Organic solvents such as glycol, diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, fogging agents such as sodium boron hydride, 1-phenyl-3 -An auxiliary developing agent such as pyrazolidone, a viscosity-imparting agent, aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid, various chelating agents represented by phosphonocarboxylic acid, for example, ethylenediaminetetraacetic acid, nitrite B triacetate, diethylenetriaminepentaacetic acid, cyclohexane diamine tetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,
1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof Can be included.

The color developer used in the present invention preferably does not contain a sulfite. Usually, when sulfite is not present, tar formation due to the oxide of the color developing agent is likely to occur, but in the slit processing tank, the opening area is small, and the developer is less likely to be polymerized by being oxidized by oxygen in the air. The tar formation does not occur.

 The light-sensitive material is usually subsequently subjected to the following processing.

Bleaching and / or fixing treatment (desilvering treatment) Usually, bleaching treatment is carried out after color development. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. Further, in order to speed up the processing, a processing method of bleach-fixing processing after bleaching processing may be used. Further, it is possible to optionally carry out the treatment in two continuous bleach-fixing baths, or to perform the fixing treatment after the bleach-fixing treatment according to the purpose. Examples of the bleaching agent include iron (III) and cobalt (II
Compounds of polyvalent metals such as I), chromium (VI) and copper (II), peracids, quinones, nitro compounds and the like are used.
Typical bleaching agents are ferricyanide; dichromate; organic complex salts of iron (III) or cobalt (III) such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3- Aminopolycarboxylic acids such as diaminopropane tetraacetic acid and glycol ether diamine tetraacetic acid or complex salts such as citric acid, tartaric acid and malic acid; persulfates; bromates; permanganates; nitrobenzenes and the like can be used. Of these, aminopolycarboxylic acid iron (III) complex salts such as ethylenediaminetetraacetic acid iron (III) complex salts and persulfates 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. The pH of a bleaching solution or a bleach-fixing solution containing these aminopolycarboxylic acid iron (III) complex salts is usually
5.5-8 but lower p due to faster processing
H can also be processed.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath. As a useful bleaching accelerator, specifically, U.S. Patent No. 3,893,858, West German Patent No. 1,290,812, JP-A-53-95,630, Research
Compounds having a mercapto group or a disulfide bond described in Disclosure No. 17,129 (July 1978) and the like; Thiazolidine derivatives described in JP-A No. 50-140,129; Thiourea derivatives described in US Pat. No. 3,706,561;
Iodide salt described in JP-A-58-16,235; West German Patent No. 2,74
Polyoxyethylene compounds described in No. 8,430; Japanese Patent Publication No. 4
Examples thereof include polyamine compounds described in 5-8836; bromide ions and the like. Among them, a compound having a mercapto group or a disulphide group is preferable because of its large accelerating effect, and particularly, US Pat. No. 3,893,858, West German Patent No. 1,290,812, JP
The compounds described in Nos. 53-95,630 are preferred. Further, the compounds described in US Pat. No. 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color photographic material for photography.

Examples of the fixing agent include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but the use of thiosulfates is common,
In particular, ammonium thiosulfate can be used most widely. As a preservative for the bleach-fix solution, sulfite, bisulfite or carbonyl bisulfite adduct is preferable.

Washing and / or stabilizing treatment After the desilvering treatment, a washing and / or stabilizing step is generally performed. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), application, and further, the rinsing water temperature, the number of rinsing tanks (number of stages), replenishment method such as countercurrent, forward flow, and various other conditions It can be set in a wide range. Of these, the relationship between the number of washing tanks and water volume in the multi-stage countercurrent method is described in the Journal of the Society of Motion Pictu
re and Television Engineers Volume 64, P.248-253 (1955
May issue).

According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate, and the suspended matter produced adheres to the photosensitive material, etc. Problem arises. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, the method of reducing calcium ion and magnesium ion described in Japanese Patent Application No. 61-131632 can be very effectively used. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8,542, chlorine-based bactericides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., Hiroshi Horiguchi "Chemistry of antifungal agents" The sterilizing agents described in "Microbial Sterilization, Sterilization, and Antifungal Technologies" edited by the Society of Hygiene Technology and "Encyclopedia of Antibacterial and Antifungal Agents" edited by Japan Society for Antibacterial and Antifungal Agents can also be used.

The pH of the washing water used is 4-9, preferably 5
-8. Washing water temperature, washing time, the characteristics of the photosensitive material,
Although various settings can be made according to the application, generally, a range of 20 seconds to 10 minutes at 15-45 ° C, and preferably 30 seconds to 5 minutes at 25-40 ° C is selected. Further, the light-sensitive material of the present invention, instead of the above water washing,
It is also possible to treat directly with the stabilizing solution. In such a stabilization treatment, JP-A-57-8,543, 58-14,834
All the known methods described in No. 60-220,345 can be used.

Further, there is a case where a stabilizing treatment is further performed after the water washing treatment, and an example thereof is a stabilizing bath containing formalin and a surfactant, which is used as a final bath of a color light-sensitive material for photographing. . Various chelating agents and fungicides can also be added to this stabilizing bath.

The overflow solution accompanying the above washing with water and / or supplementation of the stabilizing solution can be reused in other steps such as the desilvering step.

The light-sensitive material processed by the method of the present invention may be any material known as a color light-sensitive material. For example, in addition to color paper, color reversal paper, color negative film for photographing, color reversal film, negative or positive film for motion picture, direct positive color photosensitive material, meley film, photosensitive material for printing, microfilm and the like can be mentioned. .

Any of the known silver halide emulsions for light-sensitive materials can be used. Silver chlorobromide emulsions for color printing photographic materials (silver chloride is preferably 90 mol% or more for rapid processing), and silver iodobromide emulsions (silver iodide content for photographic color photographic materials) The amount is preferably 2 to 15 mol%). In particular, in the slit development, it is preferable to use a silver chloride photosensitive material because there is no release of bromine ions into the developing solution, so that uneven development of the bromine ions is less likely to occur. In addition, since the developing speed is high, the length of the slit processing path can be shortened, the processing apparatus can be easily made compact, and the non-uniform distribution of the processing solution concentration is eliminated. The silver halide grains are spherical, cubic,
It is an octahedron, a rhombohedron, a tetrahedron, or the like, and a flat plate shape (preferably an aspect ratio of 5 to 20) is preferable for the high-sensitivity light-sensitive material. These particles may be particles having a uniform phase or particles having a multilayer structure. Further, the particles may be surface latent image type particles or internal latent image type particles. The particle size distribution may be polydisperse or monodisperse (preferably standard deviation /
The average particle size may be ≤15%), but the latter is preferable. These silver halide grains may be used alone or in combination according to the purpose.

The above photographic emulsion is available from Research Disclosure (R
D) vol.176 Item No.17643 (I, II, III)
(February).

Emulsions which have been usually subjected to physical ripening, chemical ripening and spectral sensitization can be used. Additives used in such processes are known as RESERT DISCLOSURE No. 176
Volume, No. 17643 (December 1978) and Volume 187, No. 1871
6 (November 1979), and the relevant parts are summarized in the table below.

Further, known photographic additives that can be used are also described in the above two Research Disclosures, and the locations described in the table below are shown.

The color light-sensitive material can contain various color couplers, and specific examples thereof are disclosed in the patents described in Research Disclosure (RD) No. 17643, VII-C to G. As the dye-forming coupler, a coupler that gives the three primary colors of the subtractive color method (that is, yellow, magenta and cyan) by color development is important, and specific examples of the diffusion resistant 4-equivalent or 2-equivalent coupler are described above.
In addition to the yellow and magenta couplers described in the patents of 17643, VII-C and D, the following can be preferably used.

Typical examples of usable yellow couplers include known oxygen atom-releasing yellow couplers and nitrogen atom-releasing yellow couplers. α-
Pivaloyl acetanilide type couplers are excellent in color fastness of color forming dyes, especially light fastness, while α-benzoyl acetanilide type couplers can obtain high color density.

Examples of magenta couplers that can be used include hydrophobic 5-pyrazolone and pyrazoloazole couplers having a balance group. The 5-pyrazolone-based coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamino group, from the viewpoint of the hue and color density of the color forming dye.

The present invention is characterized in that, in the slit developing treatment, the above-mentioned light-sensitive material is used in combination with a cyan coupler having less color reversion defects and a surfactant having a solubility in a developing solution of 0.005% by weight or more.

The surfactant used in the present invention has a solubility in the developing solution of 0.05% by weight or more at 35 ° C., preferably 0.
It is at least 01% by weight, preferably at most 50% by weight.

The surfactant has a substitution of 4 or more carbon atoms as a hydrophobic group,
It has unsubstituted alkyl, alkenyl, aralkyl, and aryl groups, and the hydrophilic group has anion, cation, betaine, and nonion groups.

The preferred hydrophobic group is a substituted or unsubstituted alkyl, alkenyl, aralkyl or aryl group having 6 to 40 carbon atoms, for example, hexyl, octyl, nonyl, decyl,
Dodecyl, cetyl, stearyl, oleyl, nonylphenyl, octylphenyl, dit-amylphenyl, dinonylphenyl, dodecylphenyl, dodecylbiphenyl, bis (di-t-butylphenyl) methylene, bis (di-t-butylphenyl) Examples include phenylmethylene, perfluorooctyl, perfluorodecyl, perfluorohexyl, perfluorononileil, perfluorododecyl and the like.

The hydrophilic group is preferably a carboxylate salt, a sulfonate salt, a phosphate salt, a sulfuric acid ester salt or a borate salt as the anion group, and a tertiary amine, a quaternary amine, phosphonium or sulfonium salt as the cationic group. The betaine group is an amino acid, carboxybetaine, sulfoxybetaine, phosphobetaine, and the nonionic group is polyoxyalkylene, hydroxy, sorbitan,
Examples thereof include sugar and polyhydric alcohol. Particularly preferred hydrophilic groups are carboxylates, sulfonates, phosphates, sulfates, tertiary or quaternary amines, carboxybetaines, sulfobetaines, polyoxyalkylenes (alkylene groups preferably having 1 to 6 carbon atoms. , For example ethylene,
Propylene, hydroxypropylene, etc.), hydroxy, sorbitan, and polyhydric alcohols. The anion salt is preferably hydrogen, alkali metal, alkaline earth, ammonium or lower amine. When the hydrophilic group is anion, cation, or betaine, it is preferable that the hydrophilic group further contains polyoxyalkylene (wherein alkylene has 1 to 6 carbon atoms) at the same time.

 These specific compounds are listed below as examples.

Compound example W-7 C ₁₂ H ₂₅ OCH ₂ CH ₂ O ₅ CH ₂ COOK The amount of the surfactant of the present invention added is preferably 1 to 2000 mg, and more preferably 3 to 500 mg, per 1 m ² of the photographic light-sensitive material.
5-300 mg is particularly preferred.

Further, these surfactants may be used alone or in combination of two or more kinds.

The addition place of the surfactant used in the present invention is at least one layer on the silver halide emulsion side of the photographic light-sensitive material.

Examples of constituent layers to be added include a surface protective layer, an emulsion layer,
An intermediate layer, an undercoat layer and the like can be mentioned, but an emulsion layer, and among them, a cyan coupler-containing layer is most preferable.
When the surface protective layer is composed of two or more layers, any of these layers may be used, and the surface protective layer may be further used as an overcoat.

In this case, a surfactant having a solubility of less than 0.005% may be used together for coating suitability unless the effects of the present invention are lost.

Although they are used as coating aids, they are sometimes applied for other purposes such as emulsion dispersion, sensitization and other improvement of photographic characteristics.

These surfactants are natural surfactants such as saponin,
Cationic surfactants such as higher alkyl amines, quaternary ammonium salts (eg cetyltrimethyl ammonium chloride), pyridine and other heterocycles (eg dodecylpyridinium bromide), phosphonium or sulfonium compounds; carboxylic acids (eg potassium laurate) , Oleic acid ammonium), sulfonic acid (eg dodecylbenzene sulfonic acid Na salt, triisopropylnaphthalene sulfonic acid Na salt, dioctyl α-sulfosuccinic acid)
Na salt, etc.), phosphoric acid, sulfate ester (for example, dodecyl sulphate Na salt, oleyl sulfate K salt, etc.),
Anionic surfactants containing acidic groups such as phosphoric acid esters (eg, sodium salt of nonylphenylphosphate, K salt of polyoxyethyleneoleylphosphate, etc.), amino acids (eg, dodecyldimethylammoniomethylenecarboxylate), aminosulfonic acids ( For example, hexyldimethylammoniobutane sulfonate), and amphoteric surfactants such as sulfuric acid or phosphoric acid esters of amino alcohol.

Further, in the present invention, a slip activating composition, for example, U.S. Patent Nos. 3,079,837, 3,080,317, and 3,545,970.
Nos. 3,294,537 and Japanese Laid-Open Patent Publication No. 52-129520 may be incorporated in the photographic constituent layers.

In the present invention, the cyan coupler which can be used in combination with the above-mentioned surfactant is represented by the general formula (I) General formula (II) The couplers represented by can be mentioned.

In the formula, R ¹ , R ⁴ and R ² are each an aliphatic group, an aromatic group,
Represents a heterocyclic group, an aromatic amino group or a heterocyclic amino group, R ⁵ represents an aliphatic group (excluding a methyl group), R ³
And R ⁶ are each a hydrogen atom, a halogen atom, an aliphatic group,
Represents an aliphatic oxy group or an acylamino group, Y ¹ , Y ²
Represents a halogen atom or a group capable of splitting off during a coupling reaction with an oxidized product of a developing agent (hereinafter abbreviated as splitting group), and in the general formula (I) and the general formula (II), R ² , R ³ and R ⁵ And R ⁶ may form a 5-, 6- or 7-membered ring, respectively.

Furthermore, R ¹ , R ² , R ³ or Y ¹ ; R ⁴ , R ⁵ , R ⁶ or Y ² ;
May form a dimer or higher polymer.

The term "aliphatic group" as used herein refers to an aliphatic hydrocarbon group and includes a linear, branched or cyclic alkyl, alkenyl or alkynyl group, which may be substituted or unsubstituted.

Hereinafter, R ^{1 to} R ⁶ and Y ^{1 to} Y ^{2 in} the general formulas (I) and (II)
Will be described in detail.

In the general formulas (I) and (II), when Y ¹ and Y ² represent a coupling leaving group (hereinafter referred to as a leaving group), the leaving group is a cupping group via an oxygen, nitrogen, sulfur or carbon atom. The ring activated carbon is bonded to an aliphatic group, an aromatic group, a heterocyclic group, an aliphatic / aromatic or heterocyclic sulfonyl group, an aliphatic / aromatic or heterocyclic carbonyl group, at a coupling position. A nitrogen-containing heterocyclic group linked by a nitrogen atom, a halogen atom, an aromatic azo group, etc., and the aliphatic, aromatic or heterocyclic group contained in these leaving groups may be substituted by R ¹ (described later). It may be substituted with a group, and when these substituents are two or more, they may be the same or different, and these substituents may have a substituent permissible in R ^1. .

Specific examples of the coupling-off group include a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, an aliphatic or aromatic sulfonyloxy group, an acylamino group, an aliphatic or aromatic sulfonamide group, an alkoxycarbonyloxy group, Aryloxycarbonyloxy group, aliphatic / aromatic or heterocyclic thio group (eg ethylthio group, phenylthio group, tetrazolylthio group etc.), carbamoylamino group (eg N-methylcarbamoylamino group, N-phenylcarbamoylamino group etc.), 5- or 6-membered nitrogen-containing heterocyclic group (for example, imidazolyl group, pyrazolyl group, triazolyl group, tetrazolyl group, 1,2-dihydro-2-oxo-1-pyridyl group, etc.), imide group, aromatic azo group, etc. location is located, these groups may be further substituted R ¹ It may be substituted with allowed group as group. Further, there is a bis-type coupler obtained by condensing a 4-equivalent coupler with an aldehyde or a ketone as a leaving group bonded via a carbon atom. The leaving group of the present invention may contain a photographically useful group such as a development inhibitor and a development accelerator. A preferred combination of leaving groups in each general formula will be described later.

In the general formula (I) and the general formula (II), R ¹ , R ² and R ⁴ are each preferably an aliphatic group having 1 to 36 carbon atoms, preferably an aromatic group having 6 to 36 carbon atoms, or a heterocycle. Represents a group (eg, 3-pyridyl group, 2-furyl group, etc.) or an aromatic or heterocyclic amino group (eg, anilino group, naphthylamino group, 2-benzothiazolylamino group, 2-pyridylamino group, etc.) , These groups are further alkyl groups, aryl groups, heterocyclic groups, alkoxy groups, aryloxy groups, alkenyloxy groups, acyl groups, ester groups, amide groups, sulfamide groups, imide groups, ureido groups, aliphatic groups or Aromatic sulfonyl group (eg, methanesulfonyl group, phenylsulfonyl group, 2-butoxy-5-tert-octylphenylsulfonyl group, etc.), aliphatic or aromatic Oh group (for example,
Ethylthio group, phenylthio group, etc.), hydroxy group,
It may be substituted with a group selected from a cyano group, a carboxy group, a nitro group, a sulfo group, a halogen atom and the like.

As the aliphatic group, a methyl group, an ethyl group, a butyl group,
Dodecyl group, octadecyl group, eicosenyl group, iso-
Propyl group, tert-butyl group, tert-octyl group, tert
-Dodecyl group, cyclohexyl group, cyclopentyl group,
There are allyl group, vinyl group, 2-hexadecenyl group, propargyl group and the like.

In the general formula (I) R ⁵ preferably represents an aliphatic group having 2 to 20 carbon atoms and may be substituted with permissible substituents on R ^1.

In the general formula (I) and the general formula (II), R ³ and R ⁶
Are each a hydrogen atom, a halogen atom, preferably an aliphatic group having 1 to 20 carbon atoms, preferably an aliphatic oxy group having 1 to 20 carbon atoms, or an acylamino group having 1 to 20 carbon atoms, and these aliphatic groups R ^{1 for} an aliphatic oxy group or an acylamino group
It may be substituted with a substituent allowed by the above.

In the general formula (I), R ² and R ³ may form a 5- to 7-membered ring together.

In the general formula (II), R ⁵ and R ⁶ may form a 5- to 7-membered ring together.

Any ^one of R ¹ , R ² , R ³ or Y ^{1 in} the general formula (I),
Further, in the general formula (II), any one of R ⁴ , R ⁵ , R ⁶ or Y ²
The two groups may independently or jointly form a dimer or higher multimeric coupler. In the case of a dimer, those groups are used as a mere bond or a divalent linking group (for example, an alkylene group, an arylene group, an ether group,
A divalent group such as an ester group or an amide group and a divalent group combining these groups, and when forming an oligomer or a polymer, those groups are described as a polymer main chain or a dimer. It is preferred to attach to the polymer backbone through such divalent groups. When forming a polymer, even if it is a homopolymer of a coupler derivative, other non-color-forming ethylene-like monomers (for example, acrylic acid, methacrylic acid, methyl acrylate n-butyl acrylamide, β-
Hydroxymethacrylate, vinyl acetate, acrylonitrile, styrene, crotonic acid, maleic anhydride,
(N-vinylpyrrolidone, etc.), and one or more of them may form a copolymer.

Preferred R ² in the general formula (I) and the general formula (II)
In preferred R ⁴ is a substituted or unsubstituted alkyl group, an aryl group, an optionally substituted phenoxy group as a substituent of the alkyl group, a halogen atom is particularly preferable (the substituent of the phenoxy group is an alkyl group). Group, alkoxy group, halogen atom, sulfonamide group,
(Sulfamoyl group and carboxyl group are more preferable),
The aryl group is particularly preferably a phenyl group substituted with at least one halogen atom, an alkyl group, a sulfonamide group, a sulfamoyl group, a carboxyl group or an acylamino group.

Preferred R ¹ in the general formula (I) is a substituted alkyl group or a substituted or unsubstituted aryl group, a halogen atom is particularly preferable as a substituent of the alkyl group, and the aryl group is a phenyl group or a halogen atom, a sulfonamide group, Particularly preferred is a phenyl group substituted with at least one sulfamoyl group.

In formula (II), preferred R ⁵ is an optionally substituted alkyl group having 2 to 20 carbon atoms. The substituent for R ⁵ is preferably an alkyl or aryloxy group, an acylamino group, an alkyl or arylthio group, an imide group, a ureido group, an alkyl or arylsulfonyl group.

In the general formula (II), R ⁶ is preferably a hydrogen atom, a halogen atom (particularly a fluorine atom or a chlorine atom) or an acylamino group, and particularly preferably a halogen atom.

In formula (I), R ³ is preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an alkenyl group, and particularly preferably a hydrogen atom.

In the general formula (I), it is preferable that R ² and R ³ form a 5- or 6-membered nitrogen-containing heterocycle.

In the general formula (II), R ⁵ is more preferably an alkyl group having 2 to 4 carbon atoms.

In the general formulas (I) and (II), Y ¹ and Y ² are each preferably a halogen atom, more preferably a chlorine atom.

The couplers represented by the general formulas (I) and (II) can be used alone or as a mixture of a plurality of couplers.

The cyan couplers represented by the general formulas (I) and (II) can be synthesized by a known method. For example, the general formula (I
The cyan coupler represented by I) is described in US Pat. No. 2,423,730.
No. 3,772,002 and the like.
The cyan coupler represented by the general formula (I) is described in US Pat.
2,895,826, 4,333,999, 4,327,173 and the like.

Hereinafter, general formulas (I) and (II used in the present invention will be described.
The coupler of I) will be specifically shown as an example.

In the general formulas (I) and (II), examples of the coupler in which R ² and R ³ and R ⁵ and R ⁶ form a condensed ring include the following.

Other cyan couplers that can be used in the present invention are represented by the following general formula [III]. Phenolic couplers may be mentioned.

(In the formula, R ⁷ represents an aliphatic group, an aromatic group or a heterocyclic group, Ar is a substituted or unsubstituted aryl group or heterocyclic group, Z is a hydrogen atom or an aromatic primary amine developing agent oxidation Group represents a group capable of splitting off by a coupling reaction with a compound.) The aromatic group represents a substituted or unsubstituted aryl group, and may be a condensed ring. The heterocycle means a substituted or unsubstituted monocyclic or condensed ring heterocyclic group.

Specific examples of the substituent in the general formula [III] will be described in detail below.

R ⁷ represents an aliphatic group having 1 to 36 carbon atoms, an aromatic group having 6 to 36 carbon atoms or a heterocyclic group having 2 to 36 carbon atoms, and preferably 3 to 4 carbon atoms which may be substituted 3 Primary alkyl group,
It is an optionally substituted cycloalkyl group or cycloalkenyl group having 3 to 36 carbon atoms or a group represented by the following general formula [V].

(In the formula, R ⁸ is an aliphatic group having 1 to 30 carbon atoms, and 6 to 30 carbon atoms.
Represents an aromatic group or a heterocyclic group having 2 to 30 carbon atoms, R ⁹
And R ¹⁰ may be the same or different and each represents a hydrogen atom, an aliphatic group having 1 to 30 carbon atoms or an aromatic group having 6 to 30 carbon atoms, and L represents —O—, —S—, —SO— or -SO ₂ - represent. In the general formula [II], R ⁸ is more preferably a group represented by the following general formula [VI].

(In the formula, R ¹¹ represents a monovalent group, k represents an integer of 0 to 5, and when k is plural, plural R ¹¹ may be the same or different.) Preferred R ⁹ and R ¹⁰ As a linear or branched alkyl group having 1 to 18 carbon atoms, preferable R ¹¹ is a halogen atom, an aliphatic group, an aliphatic oxy group, a carbonamido group, a sulfonamide group, a carboxyl group, a sulfo group, a cyano group. , A hydroxyl group, a carbamoyl group, a sulfamoyl group, an aliphatic oxycarbonyl group and an aromatic sulfonyl group, and preferable L is —O— and —SO ₂ —.
Each can be listed. Where the carbon number of R ¹¹ is 0
Is about 30 and k is preferably 1 to 3.

Ar is a substituted or unsubstituted aryl group or heterocyclic group (4-pyridyl, 4-quinolyl, 2-pyrimidyl, 4
-Piperidyl, morpholino, etc.) and may be a condensed ring. Typical substituents for Ar include halogen atom, cyano group, nitro group, trifluoromethyl group, -CO
^{OR 12 -, - COR 12 -} , - SO 2 OR 12, -NHCOR 12, -OR ⁵ , _{^{-SO 2 R 7, -SOR 14,}} -OCOR 14 and Can be mentioned. R ¹² and R ¹³ may be the same or different and each represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group, and R ¹⁴ represents an aliphatic group, an aromatic group or a heterocyclic group. The carbon number of Ar is 6 to 30 in the case of an aryl group and 2 to 30 in the case of a heterocyclic group. As Ar, a phenyl group having the above substituent is preferable.

Z represents a hydrogen atom or a coupling-off group (including a leaving atom; the same applies hereinafter). Representative examples of coupling-off group, a halogen atom, -OR ^15, -SR ¹⁵ -NHCOR ¹⁵ , -NHSR ¹⁵ , Aromatic azo group having 6 to 30 carbon atoms, heterocyclic group having 1 to 30 carbon atoms and linked to the coupling active position of the coupler by a nitrogen atom (succinimide group, phthalimido group, hydantoinyl group, pyrazolyl group, 2- Benzotriazolyl group etc.)
And so on. Where R ¹⁵ has 1 to 30 carbon atoms
Aliphatic group, aromatic group having 6 to 30 carbon atoms or 2 to 2 carbon atoms
30 heterocyclic groups are shown.

As described above, the aliphatic group may be saturated / unsaturated, substituted / unsubstituted, linear / branched / cyclic, and typical examples thereof include methyl, ethyl, butyl, cyclohexyl and allyl. , Propargyl, methoxyethyl, n-decyl, n-dodecyl, n-hexadecyl, trifluoromethyl, heptafluoropropyl, dodicyloxypropyl, 2,4-di-tert-pentylphenoxypropyl,
A 2,4-di-tert-pentylphenoxypentyl group and the like are included.

The aromatic group may be substituted or unsubstituted, and typical examples thereof include phenyl, tolyl, 2-tetradecyloxyphenyl, pentafluorophenyl, 2-
Chloro-5-dodecyloxycarbonylphenyl, 4-
It includes chlorophenyl, 4-cyanophenyl, 4-hydroxyphenyl groups and the like.

Further, the heterocyclic group may be substituted or unsubstituted, and typical examples include 2-pyridyl, 4-pyridyl,
It includes 2-furyl, 4-thienyl, quinolinyl and the like.

Preferred Z is a hydrogen atom, a halophen atom, an aliphatic oxy group having 1 to 30 carbon atoms, an aromatic oxy group, an aliphatic thio group, a heterocyclic thio group or an aromatic azo group, and particularly a hydrogen atom and an aromatic group. Group oxy groups are preferred.

Preferred R ⁷ is 1- (2,4-di-tert-pentylphenoxy) pentyl, 1- (2,4-di-tert-pentylphenoxy) heptyl, t-butyl, 1- (2-chloro-4-). tert-pentylphenoxy) heptyl, 1-hexadecylsulfonylpropyl, 2-hexadecyloxycarbonyl-1-cyclohexyl group and the like.

Particularly preferred Ar is a cyano-substituted phenyl group (4-
Cyanophenyl, 3,4-dicyanophenyl, 3-cyanophenyl, 3-chloro-4-cyanophenyl, 4-chloro-3-cyanophenyl group, etc., halogen-substituted phenyl group (4-chlorophenyl, 3,4-dichlorophenyl) ,
2,4,5-trichlorophenyl group, etc.), alkylsulfonyl-substituted phenyl group (4-methylsulfonylphenyl,
4-propylsulfonylphenyl, 4-butylsulfonylphenyl, 3-chloro-4-ethylsulfonylphenyl group, etc.), 4-trifluoromethylphenyl group, 3-
There are methanesulfonamidophenyl groups and the like, and more preferably 4-cyanophenyl groups, 4-chloro-3-cyanophenyl groups, 3,4-dicyanophenyl groups, and 4-butylsulfonylphenyl groups.

Further, the coupler represented by the general formula [III] forms a dimer, an oligomer or a multimer or a polymer which are bonded to each other through a divalent or divalent group at R ⁷ or Z. Good. In this case, the carbon number range shown in each of the above substituents may be out of the range.

Next, specific examples of the coupler represented by the general formula [III] are shown below.

The couplers represented by the general formula [III] of the present invention are disclosed in JP-A-56-65134, JP-A-57-204543, JP-A-57-204544 and 57-2.
04545, 58-33249, 58-33250, 60-35731
No. 60-49336, European Patent Organization (EP) No. 0254151A2
No. 0271323A2, No. 0271324A2, No. 0271325A
It can be synthesized according to the method described in No. 2 and the like.

The addition amount of these couplers, 0.05~1.0g / m ^2, preferably 0.1~0.7g / m ^2, more preferably 0.2-0.5 g / m ^2.

Other cyan couplers can be used together with these couplers.

The coupler of the present invention is preferably added to the red-sensitive silver halide emulsion layer group, and when these are divided into two or more layers, a low-sensitivity layer, an intermediate-sensitivity layer, an intermediate layer (a high-sensitivity layer and a low-sensitivity layer). It is preferred to use mainly 4 equivalent couplers for the non-photosensitive layers between the layers and mainly 2 equivalent couplers for the sensitive layers. As the 4-equivalent coupler, it is preferable to use two or more types of couplers in the present invention.

Further, other couplers that can be used in the present invention include general couplers [IV] (In the formula, R ²¹ represents a halogen atom, an aliphatic group, an aromatic group,
A heterocyclic group, an amidino group, a guanidino group or -COR ²⁴ ,
-SO ₂ R ^24, -SOR ^24, -NHCOR ²⁴ , -NHSO ₂ R ²⁴ , -NHSOR ²⁴ , Represents a group represented by, R ²² is a halogen atom, a hydroxyl group, a carboxyl group, a sulfo group, an amino group, a cyano group, a nitro group, an aliphatic group, an aromatic group, a carbonamido group, a sulfonamide group, a carbamoyl group, Sulfamoyl group, ureido group, acyl group, acyloxy group, aliphatic oxy group, aromatic oxy group, aliphatic sulfonyl group, aromatic sulfonyl group, aliphatic sulfinyl group, aromatic sulfinyl group, aliphatic oxycarbonyl group, aromatic It represents an oxycarbonyl group, an aliphatic oxycarbonylamino group, an aromatic oxycarbonylamino group, a sphamoylamino group, a heterocyclic group or an imide group, l'represents an integer of 0 to 3, and R ²³ represents a hydrogen atom or R It represents ²⁶ U, T is the coupling reaction with hydrogen atom or an aromatic primary amine developing agent oxidized form It represents a leaving group capable of Te. However, R ²⁴ and R ²⁵ are each independently an aliphatic group, an aromatic group,
Represents a heterocyclic group, an amino group, an aliphatic oxy group, or an aromatic oxy group, R ²⁶ is a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, -OR ²⁷ , -SR ²⁷ , -COR ²⁸ , -PO (R ²⁷ ) ₂ , -PO (-OR ²⁷ ) ₂ , _{^{-CO 2 R 27, -SO 2 R}} 27, represents -SO ₂ OR ²⁷ or imide group, U is _{^{NR 29, -CO-, SO 2 -}} , - SO- or a single bond. Here, R ²⁷ represents an aliphatic group, an aromatic group or a heterocyclic group, R ²⁸ represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group, and R ²⁹ and R ³⁰ each independently represent a hydrogen atom. Represents an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, an aliphatic sulfonyl group or an aromatic sulfonyl group.

When l'is plural, R ^{22 s} may be the same or different, and they may be bonded to each other to form a ring. R ²²
And R ²³ or R ²³ and T may be bonded to each other to form a ring. Further, any of R ²¹ , R ²² , R ^{23 and} T may form a dimer or multimer (oligomer or polymer) which is bonded to each other via a divalent or divalent or higher valent group. ) Can be mentioned.

The coupler represented by the formula [IV] will be described below.

As described above, the aliphatic group means a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group, which may be substituted or unsubstituted. The aromatic group means a substituted or unsubstituted aryl group, and may be a condensed ring. The heterocycle means a substituted or unsubstituted monocyclic or condensed ring heterocyclic group.

Next, examples of preferable substituents in the compound represented by the general formula [IV] will be described below.

In the general formula [IV], R ²¹ is preferably a halogen atom, —COR ²⁴ or —SO ₂ R ^{24, and} more preferably R ²⁴ is an amino group. Examples of —COR ²⁴ include carbamoyl group, N-ethylcarbamoyl group, Nn-butylcarbamoyl group, N-cyclohexylcarbamoyl group and N-
(2-Ethylhexyl) carbamoyl group, N-dodecylcarbamoyl group, N-hexadecylcarbamoyl group, N
-(3-decyloxypropyl) carbamoyl group, N-
(3-dodecyloxypropyl) carbamoyl group, N-
[3- (2,4-di-t-pentylphenoxy) propyl] carbamoyl group, N- [4- (2,4-di-t-pentylphenoxy) butyl] carbamoyl group, N, N-dimethylcarbamoyl group, N, N-dibutylcarbamoyl group,
N-methyl-N-dodecylcarbamoyl group, morpholinocarbabonyl group, N-methyl-N-phenylcarbamoyl group, N- (2-tetradecyloxyphenyl) carbamoyl group, N-phenylcarbamoyl group, N- (4-tetra Decyloxyphenyl) carbamoyl group, N- (2
-Propoxyphenyl) carbamoyl group, N- (2-chloro-5-dodecyloxyphenyl) carbamoyl group,
N- (2-chlorophenyl) carbamoyl group and the like,
Examples of —SO ₂ R ²⁴ include sulfamoyl group, N-methylsulfamoyl group, N, N-diethylsulfamoyl group, N, N
-Diisopropylsulfamoyl group, N- (3-dodecyloxypropyl) carbamoyl group, N- [3- (2,4
-Di-t-pentylphenoxy) propyl] carbamoyl group, N- [4- (2,4-di-t-pentylphenoxy) butyl] carbamoyl group, pyrrolidinosulfonyl group, N-phenylsulfonyl group, N- (2 -Butoxyphenyl) carbamoyl group, N- (2-tetradecyloxyphenyl) carbamoyl group and the like. Particularly, R ²¹ is preferably —COR ²⁴ (R ²⁴ is an amino group).

In the general formula [IV], (R ²² ) l 'is preferably l' = 0 and then l '= 1. When l ′ = 1, R ²² is preferably a halogen atom, an aliphatic group, an aliphatic oxy group, a carbonamido group, a sulfonamide group, a cyano group or the like, and among them, a fluorine atom, a chlorine atom, a trifluoromethyl group, a methoxy group. Alternatively, a cyano group is particularly preferable. The substitution position of R ²² is preferably 2-position or 4-position with respect to R ²³ NH-.

In R ²³ of the general formula [IV], R ²⁶ is preferably an aliphatic group, an aromatic group, —OR ²⁷ or —SR ²⁷ , and U is preferably —CO— or —SO ₂ —. As examples of the aliphatic group, methyl group, trifluoromethyl group, trichloromethyl group, ethyl group, heptafluoropropyl group, t-butyl group, 1-ethylbenzyl group, cyclohexyl group, penzyl group, undecyl group, tridecyl group, 1- (2,4-the-
t-pentylphenoxy) propyl group and the like, and examples of aromatic groups include phenyl group, 1-naphthyl group, 2-naphthyl group, 2-chlorophenyl group, 4-methoxyphenyl group, 4-nitrophenyl group, pentafluorophenyl. There are groups such as a methoxy group, an ethoxy group as an example of -OR ^27,
Isopropoxy group, n-butoxy group, isobutoxy group,
t-butoxy group, n-pentyloxy group, n-hexyloxy group, n-octyloxy group, 2-ethylhexyloxy group, n-decyloxy group, n-dodecyloxy group, 2-methoxyethoxy group, benzyloxy group, There are a trichloroethoxy group, a trifluoroethoxy group, a phenoxy group, a p-methylphenoxy group, and the like, and examples of -SR ²⁷ include a methylthio group, an ethylthio group, an allylthio group, and n.
-Butylthio group, benzylthio group, n-dodecylthio group, phenylthio group, pt-octylphenylthio group, p-dodecylphenylthio group, p-octyloxyphenylthio group and the like. R ²³ is more preferably an aliphatic oxycarbonyl group (R ²⁶ is R ²⁷ O— and U is —CO—) and an aliphatic or aromatic sulfonyl group (R ²⁶ is an aliphatic group or an aromatic group and U is —SO). _2- ), particularly preferably an aliphatic oxycarbonyl group.

In the general formula [IV], T is preferably a hydrogen atom, a halogen atom, an aliphatic oxy group, an aromatic oxy group, an aliphatic thio group or a heterocyclic thio group. Examples of the aliphatic oxy group include a methoxy group, an ethoxy group, a 2-hydroxyethoxy group, a 2-chloroethoxy group, a carboxymethoxy group, a 1-carboxyethoxy group, a methoxyethoxy group,
2- (2-hydroxyethoxy) ethoxy group, 2-methylsulfonylethoxy group, 2-methylsulfonyloxyethoxy group, 2-methylsulfonamidoethyl group, 2-
Carboxyethoxy group, 3-carboxypropoxy group,
2- (carboxymethylthio) ethoxy group, 2- (1-
Carboxytridecylthio) ethoxy group, 1-carboxytridecyl group, N- (2-methoxyethyl) carbamoylmethoxy group, 1-imidazolylmethoxy group, 5-phenoxycarbonylbenzotriazol-1-ylmethoxy group, etc. Examples of the oxy group include 4-nitrophenoxy group, 4-acetamidophenoxy group, 2-
There are acetamidophenoxy group, 4-methylsulfonylphenoxy group, 4- (3-carboxypropanamide) phenoxy group and the like, and examples of the aliphatic thio group include methylthio group, 2-hydroxyethylthio group, carboxymethylthio group, 2 -Carboxyethylthio group, 1-carboxyethylthio group, 3-carboxypropylthio group, 2-
There are dimethylaminoethylthio group, benzylthio group, n-dodecylthio group, 1-carboxytridecylthio group and the like, and examples of the heterocyclic thio group include 1-phenyl-1,2,3,4.
-Tetrazol-5-ylthio group, 1-ethyl-1,2,3,
4-tetrazol-5-ylthio group, 1- (4-hydroxyphenyl) -1,2,3,4-tetrazol-5-ylthio group, 4-phenyl-1,2,4-triazol-3-ylthio group, 5-methyl-1,3,4-oxadiazole-2-
Ylthio group, 1- (2-carboxyethyl) -1,2,3,4
-Tetrazol-5-ylthio group, 5-methylthio-1,
3,4-thiadiazol-2-ylthio group, 5-methyl-
1,3,4-thiadiazol-2-ylthio group, 5-phenyl-1,3,4-oxadiazol-2-ylthio group, 5-
Amino-1,3,4-thiadiazol-2-ylthio group, benzoxazol-2-ylthio group, 1-methylbenzimidazol-2-ylthio group, 1- (2-dimethylaminophenyl) -1,2,3, 4-tetrazol-5-ylthio group, benzothiazol-2-ylthio group, 5- (ethoxycarbonylmethylthio) -1,3,4-thiadiazol-2-ylthio group, 1,2,4-triazol-3-ylthio group , 4-pyridylthio group, 2-pyrimidylthio group and the like. T is more preferably a hydrogen atom, a chlorine atom, an aliphatic oxy group or an aliphatic thio group, and particularly preferably a hydrogen atom or an aliphatic oxy group.

The coupler represented by the general formula [IV] has a substituent R ²¹ ,
Each of R ²² , R ^{23 and} T may form a dimer or a multimer which is bonded to each other via a divalent or divalent or higher valent group. In this case, the carbon number range shown in each of the above substituents may be out of the range.

When the coupler represented by the general formula [IV] forms a multimer, a typical example is a homopolymer or copolymer of an addition-polymerizable ethylenically unsaturated compound (cyan color-forming monomer) having a cyan dye-forming coupler residue. In this case, the multimer contains repeating units of the general formula [VII]
The cyan color repeating unit represented by the formula (1) may be contained in one or more kinds in the multimer, and may be a copolymer containing one or more non-color-forming ethylene-like monomers as a copolymerization component. .

General formula (VII) (In the formula, R ³¹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a chlorine atom, G represents —CONH—, —COO— or a substituted or unsubstituted phenylene group, and J represents a substituted or unsubstituted group. Represents an alkylene group, a phenylene group or an aralkylene group, and L is -CONH-, -NHCONH-, -NHCOO.
-, -NHCO-, -OCONH-, -NH-, -COO-, -OCO
-, - CO -, - O -, - SO 2 -, - NHSO 2 - or -SO ₂ N
Represents H-. a ', b', and c 'represent 0 or 1. ) Q represents a cyan coupler residue obtained by removing a hydrogen atom other than the hydrogen atom of the hydroxyl group at the 1-position from the compound represented by the general formula [IV].

As the multimer, a copolymer of a cyan color-forming monomer giving a coupler unit of the general formula [VII] and the following non-color-forming ethylene-like monomer is preferable.

Examples of the non-color-forming, ethylenic monomer that does not couple with the oxidation product of the aromatic primary amine developing agent include acrylic acid, α-chloroacrylic acid, α-alkylacrylic acid and esters or amides derived from these acrylic acids. , Vinyl ester, acrylonitrile, methacrylonitrile, aromatic vinyl compounds (for example, styrene and its derivatives, itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ether,
Maleic acid ester, N-vinyl-2-pyrrolidone, N
-Vinyl pyridine and 2- and -4-vinyl pyridine and the like.

Particularly preferred are acrylic acid ester, methacrylic acid ester, and maleic acid esters. Two or more kinds of non-color-forming ethylenic monomers used here can be used together. For example, methyl acrylate and butyl acrylate, butyl acrylate and styrene, butyl methacrylate and methacrylic acid, and the like can be used.

As well known in the field of polymer couplers, the above general formula [VI
I] is an ethylenically unsaturated monomer for copolymerization with a vinyl monomer, and the physical and / or chemical properties of the copolymer formed, such as solubility, binding of photographic colloid composition. The compatibility with agents such as gelatin, its flexibility, thermal stability, etc. can be selected to be favorably influenced.

In order to obtain a lipophilic polymer coupler soluble in an organic solvent, a lipophilic non-color-forming ethylenic monomer (eg, acrylic acid ester, methacrylic acid ester, maleic acid ester vinylbenzenes, etc.) is mainly selected as a copolymerization component. preferable.

Even when a lipophilic polymer coupler obtained by polymerization of a vinyl-based monomer which gives a coupler unit represented by the general formula [VII] is dissolved in an organic solvent, it is emulsified and dispersed in an aqueous gelatin solution in the form of a latex. Alternatively, it may be prepared directly by an emulsion polymerization method.

U.S. Pat. No. 3,45, for a method of emulsifying and dispersing a lipophilic polymer coupler in the form of a latex in an aqueous gelatin solution.
1,820, U.S. Pat.
No. 3,370,952.

To obtain a neutral or alkaline water-soluble hydrophilic polymer coupler, N- (1,1-dimethyl-
2-2 sulfonate ethyl) acrylamide, 3-sulfonate propyl acrylate, sodium styrenesulfonate, potassium 2-styrenesulfinate, acrylamide, methacrylamide, acrylic acid, methacrylic acid, N-vinylpyrrolidone, N-vinylpyridine, etc. It is preferable to use a hydrophilic non-color forming ethylene-like monomer as a copolymerization component.

The hydrophilic polymer coupler can be added to the coating solution as an aqueous solution, and a lower alcohol, tetrahydrofuran, acetone, ethyl acetate, lecrohexane,
It can also be added by dissolving it in a mixed solvent of water and an organic solvent miscible with water such as ethyl lactate, dimethylformamide, and dimethylacetamide. Further, it may be added after being dissolved in an alkaline aqueous solution or an alkali-containing organic solvent. A small amount of surfactant may be added.

Specific examples of the coupler represented by the general formula [IV] used in the present invention will be shown below.

Examples of couplers represented by the general formula [IV] other than the above used in the present invention are disclosed in JP-A-60-237448, 61-153640,
No. 61-145557 and Japanese Patent Application No. 62-42090. In addition to the above-mentioned patent specifications, the synthesis of these couplers is described in Japanese Patent Application Nos. 60-259752, 60-259753 and 61-205.
It can be carried out by the method described in the specification of No. 344.

The coupler represented by the general formula [IV] of the present invention can be added to the emulsion layer and the non-photosensitive intermediate layer. It is preferably contained in the emulsion layer. When it is added in a large amount, it is possible to reduce side effects such as sensitivity decrease by adding it to the non-photosensitive intermediate layer.

The addition amount is 0.01 mol% to 100 mol%, preferably 0.1 mol% to 50 mol%, and particularly preferably 1 mol% to 20 mol% of the total coated silver amount.

In the above-mentioned coupler, the graininess can be improved by using a coupler in which the color forming dye has an appropriate diffusibility. Specific examples of such couplers are described in U.S. Pat. No. 4,366,237 and the like, and specific examples of yellow, magenta or cyan couplers are described in the European Patent 96,570 and the like.

The dye-forming coupler and the above-mentioned special coupler may form a dimer or higher polymer. Typical examples of polymerized dye forming couplers are described in US Pat. No. 3,451,820. Specific examples of the polymerized magenta coupler are described in US Pat. No. 4,367,282 and the like.

Couplers that release a photographically useful residue upon coupling can also be preferably used in the present invention. As the DIR coupler releasing the development inhibitor, the couplers of the patents described in the above-mentioned RD17643, VII to F are useful.

The light-sensitive material processed according to the present invention may contain a coupler which imagewise releases a nucleating agent or a development accelerator or a precursor thereof during development. Specific examples of such compounds include British Patent Nos. 2,097,140 and 2,131,188.
No. In addition, a DIR redox compound releasing coupler described in JP-A-60-185950, European Patent No. 1
The couplers described in No. 73,302A, which release a dye that recovers color after separation, can be used.

〔The invention's effect〕

According to the present invention, it is possible to provide a processing method of a silver halide color light-sensitive material which enables simple processing without causing color restoration failure in the slit processing method.

 Next, the present invention will be described with reference to examples.

〔Example〕

Example 1 The exposed silver halide photosensitive material was processed using a slit type automatic developing machine 1 shown in FIG. 1 (showing a sectional view). In FIG. 1, a processing tank 2 includes a processing housing 4.
A lid (8) with a comb-shaped upper lid (6) suspended therein was put into the processing passage (15) to form a narrow (slit-shaped) processing passage (15). A handle 10 is provided on the lid 8. The upper cover 6 has a plurality of upper covers 12 made of vinyl chloride, each having a rectangular cross section, arranged substantially vertically.
Is arranged.

Inside the processing housing 4, a tank wall member 14 that forms a processing path 15 (3 mm in width) in combination with the top lid member 12 is disposed. Therefore, the upper lid member 12 and the tank wall member 14 form a processing path 15 which is continuous in a wavy form, and the photosensitive material feed reels 16 are disposed at the upper and lower bent portions, respectively.
In FIG. 1, two photosensitive material feed reels 16 are provided above and three below.

The processing path 15 is provided with replenishing ports 3, 9, 13 and overflow ports 5, 7, 11 so that the processing liquid replenished from the replenishing port is discharged from the overflow port. In the portion (D) from the replenishing port 3 to the overflow port 5, a color developing solution,
The part from the refill port 9 to the overflow port 7 (B
F) Bleaching fixer, replenishment port 13 to overflow port 11
The portion (W) up to is filled with washing water, the color developing solution necessary for processing is replenished from the replenishing port 3, the bleach-fixing solution from the replenishing port 9, and the rinsing water is replenished from the replenishing port 13. . Each replenishing port is provided at a position slightly higher than each overflow port. A photosensitive material supply reel 17 and a take-up reel 18 are arranged on the upper left side and the upper right side of the processing path 15, and the ends of the take-up reels are connected to a drying section 19. A photosensitive material take-up reel 21 is further arranged on the upper right side of the drying section 19. Further, warm water was put in the developing housing 4 in order to keep the developing solution at a constant temperature. Then, the photosensitive material S is supplied to the processing path 15 via the photosensitive material supply reel 17, and a plurality of photosensitive material feed reels are provided.
The photosensitive material is developed while being transported by the photosensitive material 16, dried through a photosensitive material take-out reel 18, and taken out.

Next, a multilayer color photographic paper having the following layer structure was prepared on a paper support laminated on both sides with polyethylene.
The coating liquid was prepared as follows.

Preparation of 1st layer coating solution Yellow coupler (ExY) 19.1g and color image stabilizer (Cp
d-1) 4.4 g and 0.7 g of color image stabilizer (Cpd-7) in ethyl acetate
27.2 cc and 8.2 g of solvent (Solv-3) were added and dissolved, and this solution was dissolved in 10% sodium dodecylbenzenesulfonate (EXW-
1) Emulsified and dispersed in 18.5 cc of 10% gelatin aqueous solution containing 8 cc. On the other hand, silver chlorobromide emulsion (cubic mean grain size 0.88
μ, the coefficient of variation of the grain size distribution is 0.08, and 0.2 mol% of silver bromide is contained on the grain surface as a proportion of the whole grain), and the following blue-sensitive sensitizing dyes were added at 2.0 × 10 ⁻⁴ mol per mol of silver. What was later subjected to sulfur sensitization was prepared. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a coating liquid for the first layer having the composition shown below. The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer.
As the gelatin hardening agent for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used.

 The following were used as the spectral sensitizing dye in each layer.

(Each 2.0 × 10 ^-4 mol per mol of silver halide) (4.0 × 10 ⁻⁴ mol per mol of silver halide) and (7.0 × 10 ^-5 mol per mol of silver halide) (0.9 × 10 ⁻⁴ mol per mol of silver halide) The following compounds were added to the red-sensitive emulsion layer in an amount of 2.6 × 10 ⁻³ mol per mol of silver halide.

Further, 1- (5-methylureidophenyl) -5-mercaptotetrazole was added to each of the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer per mol of silver halide.
8.5 × 10 ^-5 mol, 7.7 × 10 ^-4 mol and 2.5 × 10 ^-4 mol were added.

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

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

Support Polyethylene laminated paper [Polyethylene on the first layer side contains white pigment (TiO ₂ ) and bluish dye (ultraviolet)] First layer (blue-sensitive layer) Silver chlorobromide emulsion 0.30 Gelatin 1.86 Yellow coupler ( ExY) 0.82 Color image stabilizer (Cpd-1) 0.19 Solvent (Solv-3) 0.35 Color image stabilizer (Cpd-7) 0.06 Second layer (color mixing prevention layer) Gelatin 0.99 Color mixing inhibitor (Cpd-5) 0.08 Solvent (Solv-1) 0.16 Solvent (Solv-4) 0.08 Third layer (green sensitive layer) Silver chlorobromide emulsion (cubic, with average grain size 0.55μ
(0.39μ is mixed 1: 3 (Ag molar ratio), the coefficient of variation of particle size distribution is 0.10 and 0.08, respectively, and AgBr 0.8mol% is contained locally on the surface of each particle)
0.12 Gelatin 1.24 Magenta coupler (ExM) 0.27 Color image stabilizer (Cpd-3) 0.15 Color image stabilizer (Cpd-8) 0.02 Color image stabilizer (Cpd-9) 0.03 Solvent (Solv-2) 0.54 Fourth layer ( UV absorber layer) Gelatin 1.58 UV absorber (UV-1) 0.47 Color mixture inhibitor (Cpd-5) 0.05 Solvent (Solv-5) 0.24 Fifth layer (red sensitive layer) Silver chlorobromide emulsion (cubic, average grain size) With 0.58μ
0.45μ is mixed 1: 4 (Ag molar ratio), the coefficient of variation of particle size distribution is 0.09 and 0.11, respectively, and AgBr 0.6mol% as a proportion of the whole particle is locally localized on the particle surface. 0.23 Gelatin 1.34 Cyan coupler (ExC) 0.32 Color image stabilizer (Cpd-6) 0.17 Color image stabilizer (Cpd-10) 0.04 Color image stabilizer (Cpd-7) 0.40 Solvent (Solv-6) 0.15 Sixth Layer (UV absorbing layer) Gelatin 0.53 UV absorbing agent (UV-1) 0.16 Anti-color mixing agent (Cpd-5) 0.02 Solvent (Solv-5) 0.08 Seventh layer (protective layer) Gelatin 1.33 Acrylic modified copolymer of polyvinyl alcohol (Degeneration degree
17%) 0.17 Liquid paraffin 0.03 Surfactant EXW-2 0.01 2: 4: 4 mixture (weight ratio) 2: 4: 4 mixture (weight ratio) Average molecular weight 60,000 4: 2: 4 mixture (weight ratio) 2: 1 mixture (weight ratio) (Solv-3) solvent O = PO-C ₉ H ₁₉ (iso)) ₃ The sample manufactured as described above was used as Comparative Example 101.

(Preparation of Samples 102 to 105) Samples 102 to 105 were prepared in the same manner as in Sample 101, except that the coupler ExC added to the fifth layer in Sample 101 was replaced with the couplers shown in Table I in equimolar amounts. It was made.

(Preparation of Samples 106 to 120) As the product of the present invention or a comparative example, a surfactant added as an emulsifying dispersant and a coating aid when preparing the coating liquids (1st to 6th layers) of Samples 101 to 105. EXW-1 of the present invention or Comparative Example 106-12 in which the surfactant shown in Table 1 was changed to the same weight.
0 was prepared in the same manner as Samples 101 to 105.

The same surfactants were used as the 7th layer in the same amount.

Samples 101 to 120 thus obtained were cut to a width of 8.25 cm, uniformly exposed to 10 CMS at a color temperature of 2854K, and the following processing solutions were used according to the slit development processing method of FIG. And continuously processed for 2 rounds.

To the above color developer, potassium hydroxide (10% aqueous solution) was added to adjust the pH, and the color developer was used. At that time, the replenisher was prepared so that the pH was increased by 0.6.

(Washing water) Deionized water (conductivity 3 μs / cm) The replenishing amount was 8.25 cm per 1 m width, and the color developing solution was 2.2 ml, the bleach-fixing solution was 5 ml, and the washing water was 10 ml.

The shape of each tank in this embodiment is 12 cm in width and 0.3 c in thickness
m, path length below liquid level (L) 200 cm, liquid volume (V) 720 cm ³ ,
The opening area (S) was 7.2 cm ² , V / L = 3.6, S / V = 0.01, and the transport speed was 340 cm / min. Due to this speed, the processing time was 45 seconds in each step.

 The treatment temperature was 38 ° C in each process.

Samples 101-120 exposed to 1000 CMS of white light were treated with the resulting running solution. The pH of the bleach-fix bath after running was also measured.

The cyan image densities of these samples were measured with an X-Rite 301 type photographic densitometer.

Next, the sample after the above measurement was immersed in a red blood salt solution having the following formulation, washed with water and dried, and then the concentration was similarly measured. These cyan color image density differences were evaluated as defective color restoration.

The above experiment was carried out by adjusting the pH of the bleach-fix bath to 5.0, 4.5, 4.0.
Then, the defective color restoration after the running process was evaluated in the same manner.

Red blood salt 40 g NaBR 25 g water (pH 6.5) 1 The results are shown in Table 1.

As is clear from Table 1, in the comparative examples, the color restoration failure becomes large when the pH is lowered and the desilvering rate is improved, whereas the degree of the color restoration failure is small in the processing method of the present invention.

In particular, it can be seen that the use of a highly hydrophilic surfactant in the treatment method of the present invention greatly improves the color restoration failure.

Example 2 Sample 201, which is a multi-layer color light-sensitive material including each layer having the following composition, was prepared as a comparative example on an undercoated cellulose triacetate film support.

The amount coated amount (Composition of photosensitive layer) is represented in units of g / m ² of silver for silver halide and colloidal silver, also couplers, the amount for the additives and gelatin, expressed in units of g / m ^2, The sensitizing dye is shown by the number of moles per mole of silver halide in the same layer.

1st layer (antihalation layer) Black colloidal silver ・ ・ ・ 0.2 Gelatin ・ ・ ・ 1.3 ExM-9 ・ ・ ・ 0.06 UV-1 ・ ・ ・ 0.03 UV-2 ・ ・ ・ 0.06 UV-3 ・ ・ ・ 0.06 Solv- 1 ・ ・ ・ 0.15 Solv-2 ・ ・ ・ 0.15 Solv-3 ・ ・ ・ 0.05 Second layer (intermediate layer) Gelatin ・ ・ ・ 1.0 UV-1 ・ ・ ・ 0.03 ExC-4 ・ ・ ・ 0.02 ExF-1 ・ ・・ 0.004 Solv-1 ・ ・ ・ 0.1 Solv-2 ・ ・ ・ 0.1 Third layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, uniform AgI type, equivalent spherical diameter 0.5)
μ, coefficient of variation of equivalent sphere diameter 20%, plate-like particles, diameter / thickness ratio
3.0) Coating silver amount: 1.2 Silver iodobromide emulsion (AgI 3 mol%, uniform AgI type, spherical equivalent diameter 0.3
μ, coefficient of variation of spherical equivalent diameter 15%, plate-like particles, diameter / thickness ratio
1.0) Silver coating amount ・ ・ ・ 0.6 Gelatin ・ ・ ・ 1.0 ExS-1 ・ ・ ・ 4 × 10 ^-4 ExS-2 ・ ・ ・ 5 × 10 ^-5 ExC-1 ・ ・ ・ 0.05 ExC-2 ・ ・・ 0.50 ExC-3 ・ ・ ・ 0.03 ExC-4 ・ ・ ・ 0.12 ExC-5 ・ ・ ・ 0.01 4th layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 6 mol%, core shell ratio 1: 1) Internal height of
AgI type, equivalent sphere diameter 0.7μ, coefficient of variation of equivalent sphere diameter 15%, plate-like particles, diameter / thickness ratio 5.0) Coating amount of silver ・ ・ ・ 0.7 Gelatin ・ ・ ・ 1.0 ExS-1 ・ ・ ・ 3 × 10 ^-4 ExS-2 ・ ・ ・ 2.3 × 10 ^-5 ExC-7 ・ ・ ・ 0.13 ExC-4 ・ ・ ・ 0.05 Solv-1 ・ ・ ・ 0.05 Solv-3 ・ ・ ・ 0.05 Fifth layer (intermediate layer) Gelatin・ ・ ・ 0.5 Cpd-1 ・ ・ ・ 0.1 Solv-1 ・ ・ ・ 0.05 6th layer (low sensitivity green emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, surface height 1: 1 core shell ratio)
AgI type, equivalent sphere diameter 0.5μ, variation coefficient of equivalent sphere diameter 15%, tabular grains, diameter / thickness ratio 4.0) Coating silver amount: 0.35 Silver iodobromide emulsion (AgI 3 mol%, uniform AgI) Mold, equivalent sphere diameter 0.3
μ, coefficient of variation of sphere equivalent diameter 25%, plate-like particles, diameter / thickness ratio
1.0) Coating silver amount ・ ・ ・ 0.20 Gelatin ・ ・ ・ 1.0 ExS-3 ・ ・ ・ 5 × 10 ^-4 ExS-4 ・ ・ ・ 3 × 10 ^-4 ExS-5 ・ ・ ・ 1 × 10 ^-4 ExM -8 ・ ・ ・ 0.4 ExM-9 ・ ・ ・ 0.07 ExM-10 ・ ・ ・ 0.02 ExY-11 ・ ・ ・ 0.03 Solv-1 ・ ・ ・ 0.3 Solv-4 ・ ・ ・ 0.05 7th layer (high sensitivity green emulsion Layer) Silver iodobromide emulsion (AgI 4 mol%, core shell ratio 1: 3
AgI type, equivalent sphere diameter 0.7μ, coefficient of variation of equivalent sphere diameter 20%, plate-like particles, diameter / thickness ratio 5.0) Silver coating amount ... 0.8 Gelatin ... 0.5 ExS-3 ... 5 × 10 ^-4 ExS-4 ・ ・ ・ 3 × 10 ^-4 ExS-5 ・ ・ ・ 1 × 10 ^-4 ExM-8 ・ ・ ・ 0.1 ExM-9 ・ ・ ・ 0.02 ExY-11 ・ ・ ・ 0.03 ExC-2 ・・ ・ 0.03 ExM-14 ・ ・ ・ 0.01 Solv-1 ・ ・ ・ 0.2 Solv-4 ・ ・ ・ 0.01 Eighth layer (intermediate layer) Gelatin ・ ・ ・ 0.5 Cpd-1 ・ ・ ・ 0.05 Solv-1 ・ ・ ・ 0.02 Ninth layer (donor layer having a multilayer effect on the red-sensitive layer) Silver iodobromide emulsion (AgI 2 mol%, core shell ratio 2: 1, internal height)
AgI type, equivalent sphere diameter 1.0μ, variation coefficient of equivalent sphere diameter 15%, plate-shaped particles, diameter / thickness ratio 6.0) Silver coating amount: 0.35 Silver iodobromide emulsion (AgI 2 mol%, core shell ratio) 1: 1 internal height
AgI type, sphere equivalent diameter 0.4μ, variation coefficient of sphere equivalent diameter 20%, plate-like particles, diameter / thickness ratio 6.0) Coating silver amount 0.20 Gelatin 0.5 ExS-3 8x 10 ^-4 ExY-13 ・ ・ ・ 0.11 ExM-12 ・ ・ ・ 0.03 ExM-14 ・ ・ ・ 0.10 Solv-1 ・ ・ ・ 0.20 10th layer (yellow filter layer) Yellow colloidal silver ・ ・ ・ 0.05 Gelatin ・ ・ ・0.5 Cpd-2 ・ ・ ・ 0.13 Solv-1 ・ ・ ・ 0.13 Cpd-1 ・ ・ ・ 0.10 11th layer (low-sensitivity blue emulsion layer) Silver iodobromide emulsion (AgI 4.5 mol%, uniform AgI type, sphere equivalent) Diameter 0.
7μ, coefficient of variation of equivalent sphere diameter 15%, plate-like grain, diameter / thickness ratio 7.0) Coating silver amount: 0.3 Silver iodobromide emulsion (AgI 3 mol%, uniform AgI type, equivalent sphere diameter 0.3)
μ, coefficient of variation of sphere equivalent diameter 25%, plate-like particles, diameter / thickness ratio
7.0) Coating silver amount ・ ・ ・ 0.15 Gelatin ・ ・ ・ 1.6 ExS-6 ・ ・ ・ 2 × 10 ^-4 ExC-16 ・ ・ ・ 0.05 ExC-2 ・ ・ ・ 0.10 ExC-3 ・ ・ ・ 0.02 ExY- 13 ・ ・ ・ 0.07 ExY-15 ・ ・ ・ 1.0 Solv-1 ・ ・ ・ 0.20 12th layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (AgI 10 mol%, internal high AgI type, equivalent spherical diameter)
1.0μ, 25% variation coefficient of equivalent spherical diameter, multiple twin plate-like particles,
Diameter / thickness ratio 2.0) Amount of coated silver ・ ・ ・ 0.5 Gelatin ・ ・ ・ 0.5 ExS-6 ・ ・ ・ 1 × 10 ^-4 ExY-15 ・ ・ ・ 0.20 ExY-13 ・ ・ ・ 0.01 Solv-1 ・ ・・ 0.10 13th layer (first protective layer) Gelatin ・ ・ ・ 0.8 UV-4 ・ ・ ・ 0.1 UV-5 ・ ・ ・ 0.15 Solv-1 ・ ・ ・ 0.01 Solv-2 ・ ・ ・ 0.01 14th layer (2nd Protective layer) Fine grain silver bromide emulsion (AgI 2 mol%, uniform AgI type, equivalent spherical diameter 0.07μ) ...
5 Gelatin ・ ・ ・ 0.45 Polymethylmethacrylate particles 1.5μ ・ ・ ・ 0.2 H-1 ・ ・ ・ 0.4 Cpd-5 ・ ・ ・ 0.5 Cpd-6 ・ ・ ・ 0.5 In addition to the above components in each layer, emulsion stability Agent Cpd-3 (0.0
4 g / m ² ) was added.

EX as an emulsifying dispersant for oil-soluble substances such as couplers in each layer
W-1 was used. The amount used is 3 per weight of oil-soluble substance
Was ~ 5%.

Cpd-4 was added to the 14th layer as a coating aid in an amount of 0.03 g / m ² .

Solv-1 Tricresyl phosphate Solv-2 Dibutyl phthalate (Preparation of Samples 202 to 205) Samples 202 to 205 are the same as Sample 201 except that EXC-2 of the third layer and EXC-7 of the fourth layer in Sample 201 were replaced by the equimolar amounts of the couplers shown in Table 2. It produced similarly.

(Production of Samples 206 to 220) As the products of the present invention or comparative examples, first to first samples 201 to 205
When emulsifying and dispersing the oil-soluble substance added to the 13th layer, the surfactant EXW-1 used in the present invention or Comparative Examples 206 to 220 in which the surfactants shown in Table 2 were changed to equal weight was used as Sample 201. Was prepared in the same manner as ~ 205. The same amount of the coating aid added to the 14th layer was used.

The above color photographic light-sensitive materials 201 to 220 are cut into a width of 35 m / m, and a uniform exposure of 1 CMS is applied at a color temperature of 4800 ° K. Fig. 1 A slit developing machine is used to continuously process for 2 rounds by the method described below. did.

Process Treatment time Treatment temperature Replenishment amount ¹⁾ Color development 3 minutes 00 seconds 40 ℃ 10ml Bleach fixing 3 minutes 00 seconds 40 ℃ 20ml Stability 60 seconds 40 ℃ 20ml Dry 50 seconds 65 ℃ ¹⁾ Replenishment amount is 35mm width 1m length Next, the composition of the treatment liquid is shown.

1.0l 1.0l by adding water pH (prepared with acetic acid) 6.3 6.0 (stabilizer) mother liquor and replenisher common formalin (37%) 2.0ml polyoxyethylene-p-0.1g monononylphenyl ether (average degree of polymerization 10) Ethylenediaminetetraacetic acid 0.05 g Disodium salt Water was added to 1.0 l pH 5.0-8.0 Running liquid thus obtained
Twenty processed. In the same manner as in Example 1, the difference between the cyan color image density obtained immediately after drying and the color image density after the treatment with the red blood salt solution was determined, and evaluated as defective color restoration.

The above experiment was performed in the same manner by changing the pH of the bleach-fix bath to 5.0, 4.5 and 4.0. The results are shown in Table 2.

As is clear from Table 2, in the comparative example, when the pH of the bleach-fixing bath becomes low, the color restoration failure becomes extremely large.
In the processing method of the present invention, the color restoration defect is extremely slight.

In particular, it can be seen that the use of a highly hydrophilic surfactant results in a marked improvement.

[Brief description of drawings]

FIG. 1 shows an automatic developing device used when the present invention is carried out. In the figure, 15 ... Processing path S ... Photosensitive material D ... Color development tank BF ... Bleach-fixing tank W ... Washing and / or stabilizing tank.

Claims (1)

[Claims] 1. A method of processing a silver halide color photographic light-sensitive material using an automatic developing device, wherein bleaching and / or bleach-fixing treatment is carried out in a slit-shaped processing path of the automatic developing device. And (a) a coupler selected from the general formulas [I] to [IV], and (b) a surfactant having a solubility of 0.005% by weight or more at 35 ° C. in a developer having the following composition: Processing method of silver halide color photographic light-sensitive material. Developer: Sodium chloride 3g, triethanolamine 8g, ethylenediaminetetramethylenephosphonic acid 3g, potassium carbonate 26
g, N, N-bis (carboxymethyl) hydrazine 5 g, sodium sulfite 0.1 g, N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 5 g and potassium bromide 0.02 Developer having 1 added by adding water to g General formula [I] General formula (II) (In the formulas [I] and [II], R ¹ , R ⁴ and R ² each represent an aliphatic group, an aromatic group, a heterocyclic group, an aromatic amino group or a heterocyclic amino group, and R ⁵ is a fatty group. Represents a group (excluding a methyl group), R ³ and R ⁶ each represent a hydrogen atom, a halogen atom, an aliphatic group, an aliphatic oxy group or an acylamino group, and Y ¹ and Y ² represent a halogen atom or a developing agent. Represents a group capable of splitting off during a coupling reaction with an oxidant of the formula (I) and (II), and R ² and R ³ and R ⁵ and R ⁶ form a 5-, 6- or 7-membered ring, respectively. In addition, R ¹ , R ² , R ³ or Y ¹ ; R ⁴ , R ⁵ , R ⁶ or Y ² ; may form a dimer or higher multimer.) General Formula (III) (In the formula [III], R ⁷ represents an aliphatic group, an aromatic group or a heterocycle, Ar is a substituted or unsubstituted aryl group or heterocyclic group, and Z is a hydrogen atom or an aromatic primary amine developing agent. And a general formula [IV], which represents a group capable of splitting off by a coupling reaction with an oxidized form of the main agent. (In the formula [IV], R ²¹ is a halogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an amidino group, a guanidino group or —COR ²⁴ , —SO ₂ R ²⁴ , -NHCOR ²⁴ , -NHSO ₂ R ²⁴ , -NHSOR ²⁴ , R ²² represents a group capable of substituting on an aromatic ring, l ′ represents an integer of 0 to 3, R ²³ represents a hydrogen atom or R ²⁶ U, and T represents a hydrogen atom or aromatic. Represents a group capable of splitting off by a coupling reaction with an oxidized group 1 primary amine developer. However, R ²⁴ and R ²⁵ each independently represent an aliphatic group, an aromatic group, a heterocyclic group, an amino group, an aliphatic oxy group, or an aromatic oxy group, and R ²⁶ is a hydrogen atom, an aliphatic group, or an aromatic group. Group group, heterocyclic group, -OR ²⁷ , -SR ²⁷ , -COR ²⁸ , _{^{-PO (R 27) 2, -PO}} (-OR 27) 2, _{^{-CO 2 R 27, -SO 2 R}} 27, represents -SO ₂ OR ²⁷ or imide group, U is ^{NR 29, -CO -, - SO} 2 -, - SO- or a single bond. Here, R ²⁷ represents an aliphatic group, an aromatic group or a heterocyclic group, R ²⁸ represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group, and R ²⁹ and R ³⁰ each independently represent a hydrogen atom. Represents an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, an aliphatic sulfonyl group or an aromatic sulfonyl group. When a plurality of l's are present, R ^22's may be the same or different, and may combine with each other to form a ring. R
²² and R ²³ or R ²³ and T may be bonded to each other to form a ring. Further, any of R ²¹ , R ²² , R ^{23 and} T may form a dimer or multimer (oligomer or polymer) which is bonded to each other via a divalent or divalent or higher valent group. )