JPS62177550A - Method for processing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To prevent the lowering of a coloring property and the color turbidity in the title material by using a color developer contg. a specific coupler and having pH of >=10.3 and by inserting a non-photosensitive layer contg. a hydroquinone type compd. between two layers of silver halide emulsion layers contg. an antidispersible hydrophobic coupler. CONSTITUTION:The silver halide color photographic sensitive material which has at least two layers of the silver halide emulsion layers contg. the non-diffusive hydrophobic coupler and is formed on the substrate, is developed with the color developer which contains 10<-4>-4X10<-3>mol/l of the compd. shown by the formula, and does not substantially contain benzyl alcohol, after image-wisely exposing it. The non- photosensitive layer contg. the hydroquinone compd. is inserted between the two layers of the silver halide emulsion layers contg. the non-diffusive hydrophobic coupler. In the formula, R1 is an aryl group, R2-R5 are each hydrogen atom, an alkyl group, X is hydrogen atom or a group capable of an alkaline hydrolysis. The amount of adding the compd. shown by formula to the color developer is preferably 2X10<-4>-1X10<-3>mol per 1l of the color developer. Thus, the titled material having a less tendency for generating the color turbidity is obtd.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for processing silver halide color photographic materials (hereinafter referred to as color photographic materials), and in particular, to a method for processing silver halide color photographic materials (hereinafter referred to as color photographic materials), and in particular, to a method for processing silver halide color photographic materials (hereinafter referred to as color photographic materials), and in particular to methods for processing silver halide color photographic materials (hereinafter referred to as color photographic materials). This invention relates to a method for processing color photosensitive materials using a developer.

[Prior Art 1] Benzyl alcohol has traditionally been preferably added to color-forming carrier solutions for light-sensitive materials for color photographic paper, for example, for the purpose of promoting image formation or improving the reactivity between photographic couplers and quinone diimines. I've been exposed to it. It is known that when benzyl alcohol is added to a color developing solution, it is possible to increase the rate of penetration of a color developing agent into a color photosensitive material, thereby increasing the development rate of a silver halide emulsion.

The benzyl alcohol also has the effect of promoting the coupling reaction between a quinone diimine, which is an oxidized product of a color developing agent, and a photographic coupler as a result of color development. This is particularly preferable from the viewpoint of silver saving, since the use of benzyl alcohol maximizes the use of quinone diimine.

On the other hand, the amount of benzyl alcohol commonly used in color development processing of photosensitive materials for current color photographic paper is 10
n+2//! When used in such amounts, the solubility of benzyl alcohol in color developing solutions decreases significantly, and to improve this, auxiliary solvents such as ethylene glycol, diethylene glycol, and It is necessary to add a considerable amount of ethylene glycol, triethanolamine, etc. to dissolve benzyl alcohol.

Benzyl alcohol is a useful substance for color development processing, but it and polyhydric alcohols have high pollution load values such as BOD (biochemical oxygen demand) and COD (chemical oxygen demand). From the perspective of environmental pollution, it is desirable to reduce or not use it at all, and if benzyl alcohol is not substantially used, the use of its co-solvent and polyhydric alcohol in () can also be avoided. The pollution load can be further reduced.

For this reason, a photographic processing method or silver halide color photographic light-sensitive material is developed in which silver halide color photographic light-sensitive materials are color-developed with a color developing solution containing as little or no benzyl alcohol as possible, and the color-forming properties of the coupler are not impaired. The development of materials is desired, and research for this purpose is being conducted. For example, in Japanese Patent Application Laid-Open No. 58-50536, 1
-A photosensitive material containing aryl-3-pyrazolidone,
It has been proposed to add benzyl alcohol in an amount of 2 to 81 β per 12 color developing solutions. however,
Although the technology described in this publication can speed up the diffusion of the color developing agent into the emulsion layer of the light-sensitive material during color development, it cannot improve the color development, and a certain amount of developed silver cannot be improved. There is no improvement in terms of dye density relative to quantity, and this drawback is particularly significant in the middle density region of the characteristic curve.

Also, add 2 to 8 benzyl alcohol per 12 parts of the color developing solution.
Since Th12 is added, the reduction in pollution load cannot be said to be sufficient.

On the other hand, it is well known that 1-aryl-3-pyrazolidone is contained in a color developing solution and color development is rapidly carried out using superadditive development. However, although its development promoting effect is extremely high, two serious problems arise when benzyl alcohol is substantially absent from the color developing solution. The first problem is that when 1-aryl-3-pyrazolidone is added to a color developing solution that does not substantially contain benzyl alcohol,
The dye formation efficiency decreases, resulting in a significant decrease in gradation and maximum density. The second problem is that clouding occurs significantly between silver halide emulsion layers containing two or more diffusion-resistant couplers. Generally 1-aryl-
It is known that when 3-pyrazolidone is added to a color developer, it tends to cause clouding, but this problem is greatly exacerbated when there is substantially no benzyl alcohol in the color developer. I end up.

In both of the above two problems, when 1-aryl-3-virazolidone is added to the color developing solution, the silver development speed of silver halide is dramatically increased, and 1-aryl-3-virazolidone is
The formation of the oxidized form of the color developing agent through the cross-oxidation reaction with the oxidized form of pyrazolidone is so rapid that the oxidized form of the color developing agent may be deactivated by the 01 reaction before it reacts with the coupler, or may be deactivated by other adjacent substances. This is thought to be due to diffusion into the coupler-containing layer.

[Object of the Invention] Therefore, the object of the present invention is to substantially remove benzyl alcohol from a color developing solution and add a 1-aryl-3-pyrazolidone compound to achieve low pollution and rapid processing. Another object of the present invention is to provide a method for processing a silver halide color photographic light-sensitive material that does not reduce color development or cause clouding.

[Structure of the Invention] The object of the present invention is to imagewise expose a silver halide color photographic material having at least two silver halide emulsion layers containing a diffusion-resistant hydrophobic coupler on a support. After that, in a method of processing a compound represented by the following general formula [11] with a color developer containing 10-4 mol/l-4X 10-3 mol/l and substantially free of benzyl alcohol, a color developing solution A non-photosensitive layer containing a hydroquinone compound is provided between two silver halide emulsion layers having a pH of 10.3 or higher and containing a diffusion-resistant hydrophobic coupler. This is achieved by a method for processing silver halide color photographic materials.

General formula [I] r In the formula, R1 represents an aryl group, R2, R3, R4
and R5 represent a hydrogen atom or an alkyl group, and each may be the same or different. X represents a hydrogen atom or an alkali-hydrolyzable group. ] Hereinafter, the present invention will be explained in more detail.

In the treatment method of the present invention, the general formula [I]
In the general formula [I], examples of the aryl group represented by R1 include phenyl group, naphthyl group, tolyl group, and xylyl group. However, phenyl group or tolyl group is preferable. These aryl groups may have substituents, and the substituents include:
For example, halogen atoms (e.g. chlorine atoms, bromine atoms, etc.),
Alkyl groups (e.g. methyl group, ethyl group, etc.), alkoxy groups (e.g. methoxy group, ethoxy group, etc.), sulfonyl groups (e.g. methylsulfonyl group, ethylsulfonyl group, etc.), amide groups (e.g. amide group, methylamide group, ethylamide group) etc.) Kasana can be mentioned.

Further, the alkyl group represented by R2, R3, R+ and R5 is preferably an alkyl group having 1 to 4 carbon atoms, such as a methyl group, ethyl group, propyl group, butyl group, etc., and the substituent is, for example, hydroxyl. group, amino group,
Examples include acyloxy groups (eg, acetyloxy groups), sulfonyloxy groups, and the like.

In the present invention, R2 and R3 are preferably hydrogen atoms.

In general, in the general formula [I], the alkali-hydrolyzable group represented by X is preferably an acetyl group.

In the present invention, it is preferable that X is a hydrogen atom.

Typical specific examples of the compound represented by the general formula [11] according to the present invention are listed below, but the present invention is not limited to these.

The following margins (exemplary compounds) (1-11) (l-12) (
+-131 (1-14) (1-15> (1-16)
) Margin below Cl The amount of the compound represented by the general formula [E] according to the present invention added to the color developer is 10-4 mol - 4X10-3 mol per 11 color developer, preferably 2X10-→ Mol-
In the range of 1X 10-3 moles.

From the viewpoint of pollution, it is preferable that the color developing solution of the present invention does not substantially contain benzyl alcohol. Here, "substantially not contained" means that it may be contained in an amount that does not substantially promote the reaction between the color developing agent and the coupler, and such amount is about 1
It is preferably 12 or less, preferably 0.511Q or less, and most preferably not contained at all.

The pH of the color developing solution of the present invention needs to be 10.3 or higher, and if it is less than 10.3, 1-aryl-3
- When pyrazolidone is added to the color developer, the maximum density and gradation begin to decrease rapidly, and clouding rapidly begins to occur between two different silver halide emulsion layers. Particularly preferably, pt-+ is set to 10.5 or more.

In the color photographic light-sensitive material of the present invention (hereinafter simply referred to as color light-sensitive material), between the silver halide emulsion layers containing two different diffusion-resistant hydrophobic couplers, there is a non-photosensitive material containing a hydroquinone compound. It is necessary to provide a gender layer. Preferred hydroquinone compounds include those represented by the following general formula, which are hydrophobic hydroquinone compounds having at least one substituent having a total number of carbon atoms of 8 or more.

General formula [wherein R is a substituted or unsubstituted alkyl group having 1 or more carbon atoms, and n represents an integer of 1 to 3. However, n
is 2 or more, R may be the same or different. The total number of substituents on hydroquinone is 8 or more. ] Specifically, the compounds shown below are mentioned.

HH o, osg to 2 g, preferably 0.1 (
It is used in the range of 1 to 1 g. In this case, it is also possible to add a quinone compound, which is an oxidized product of the hydroquinone compound, to the non-photosensitive layer together with the hydroquinone compound.

In the color light-sensitive material of the present invention, the effect of the present invention is particularly large when the at least two spread-resistant hydrophobic coupler-containing layers are a yellow coupler-containing layer and a magenta coupler-containing layer. In the case of a coupler represented by formula [1[] or [II[]], it is particularly preferable to use a yellow coupler having a relative coupling reaction rate of 0.3 or more as described below.

The following is a blank general formula [Il, ] General formula [I [[] In the formula, R++, R+2.8 days are a hydrogen atom, a halogen atom (e.g., a chlorine atom, a bromine atom, etc.), and an alkyl group having 1 to 4 carbon atoms, respectively. Or it represents an alkoxy group having 1 to 4 carbon atoms. Z is -NH-L, -NHCO-L, -N
Represents HCHNH-L or -○R20. Here, R20 represents a phenyl group which may have a substituent, and R20 represents an alkyl group or an aryl group. Q represents a hydrogen atom or a group that can be separated upon coupling with an oxidized product of the color developing herbal medicine. Examples of detachable groups include halogen atoms (for example, chlorine atoms, bromine atoms, etc.), -COR21, -O
R22, -0COR23, -0SO2R23, -8R2
Do not express your feelings.

Here, R21 represents an alkyl group, an alkoxy group, an aryl group, or an aryloxy group, and these groups may have a substituent. R22 represents an alkyl group, an alkenyl group, an aryl group or a trialkylsilyl group, and these groups may have a substituent. R23 represents an alkyl group or a heterocyclic group, and these groups may have a substituent.

R24, R25, R26, R27 are each a hydrogen atom,
Represents an alkyl group or a halogen atom (eg, chlorine atom, bromine atom, etc.). W represents a group of nonmetallic atoms necessary to form a 5-membered ring together with the nitrogen atom.

In the formula, R15 and R16 are each a hydrogen atom, an argyl group, an aryl group, a heterocyclic group, an amino group having a substituent,
represents an acylamino group, hydroxyl group, alkoxy group, carboxyl group or esterified carboxyl group,
At least one of R15 and R+s is not a hydrogen atom.

Q' represents a hydrogen atom or a group that can be separated upon coupling with an oxidized product of a color developing agent. Examples of this detachable group include halogen atom (chlorine atom, bromine atom, iodine atom, etc.), -3Oa Hl-COOH, -OR3
0, -S R30, -N = N -R31. R30 represents an aryl group, and this aryl group may have a substituent. R31 represents an acyloxy group, a sulfonyloxy group, a thiocyano group, an imido group or a benzoyltriazolyl group.

Specific examples of the magenta coupler represented by the above general formula [II] or [I[l] that are preferably used in the present invention are shown below, but the invention is not limited thereto.

Exemplary magenta coupler (M-1) t (iVI2) t (iVI-3) (M-4) C:, 4t (M-5) H3 (M-7) 2H5 t (M-9) C,j M- 10) C M-15) CL (IVI-1
7) C1 B Ct (M-19) CL (M, -20
) t (M-21) t (M-221 (M-23) t (M -24-) ct <M-26) (M-3(1)) (M-311 1] (M 32) (M -331 CM-34) (M-3ぢ) (M-36) (M-37) (M-31S) (M-391 (M+0) (M-4-1) J-()H (M-+2 ) (Ivy-431 (M-44-) C+zH2s (M-4';) (IVI-461 (M-47) H3 (M-d) 2H5 (M-Y1) (',,/.

C15H3+ (!■-ta3) (M-54) - H3 (M-55) H3 CM-56) (M-57) r/ (IVI-5g) (M-591 (IVI-60) (M-611 (M-62) (4I(+ (M-63) 2H5 (M-64-) C2H5 (IVI-(55) zHs (M-66i) (M-67) (M-6g) (M65) ('1 (u(Ll (M-70+ (M-77) (M 72) I6H31 (M-'73) r/ C15H3t +M-74-) (M-711;) (M-76) (M-77) (M -71?) (M-7) (M-go) (Mi+ 1 2H5 (M-82) :H3 (M-84-) (M-8S) (M-86) O8O2CH3 (M-8'7) 1”/- CM-88) (K15H]I (M-89) H3 (M-90) Ha (M-9/) r/ OC2us (iVl-3TI NH302Cl6H33 Cl6H33(L C8H+7(t) (M-9r ) (M96) H3 (M-97) (M-qs) (M-99) C7H+s (M-+01) (M-102) (M-1(J?) (M-104) 2H5 (M-10r) (M-10'7) (M-108) (M-10'3) C,5H3゜The magenta couplers used in the color photographic material of the present invention may be used alone or in combination of two or more. In addition, some couplers such as pyrazolinobenzimidazole and indasilone may also be used.

The fast-reactive yellow coupler is a yellow coupler having a relative coupling reaction rate of 0.3 or more, preferably a yellow coupler having a relative coupling reaction rate of 0.5 or more.

The coupling kinetics of the couplers is such that the two couplers M and N give different dyes that can be clearly separated from each other.
It can be determined as a relative value by measuring the amount of each dye in the color image obtained by mixing them, adding them to a silver halide emulsion, and carrying out color development.

If the maximum concentration (DM) max of coupler M is expressed as the color development at the concentration DM in the middle stage, and the color development of coupler N is expressed as (DN) max, respectively, then the reaction activity of the bipolar puller is The ratio RM/RN is expressed by the following formula.

That is, in a silver halide emulsion containing mixed couplers,
The value of the coupling activity ratio RM/RN can be determined from the slope of the straight line obtained by plotting several pairs of DM and ON obtained by applying various stages of exposure and color development as two orthogonal axes. .

If the value of RM/RN is determined as described above for various couplers using a constant coupler N, the value of the relative coupling reaction rate can be determined.

In the present invention, the above coupler N refers to the RM/RN value when the following coupler is used.

Ct The addition temperature of the fast-reacting yellow coupler of the present invention is not limited, but is preferably from 2X10' to 5X10'' mole, more preferably from lX10-2 to 5X10-1 per mole of silver in the blue-sensitive silver halide emulsion layer. It is a mole.

The fast-reacting yellow coupler preferably used in the present invention is represented by the following general formula (2).

General formula (2) [wherein, Z represents a substituent that can be separated by reaction with an oxidized product of a color developing agent, J represents an alkylene group, and R
represents an alkyl group or an aryl group. ] Specific examples of the fast-reacting [f]-couplers of the present invention are listed below, but the present invention is not limited thereto.

The following margins [Example compounds] (Y-1) ("f'-2) (Y-3) (Y-4) ('Y-5) (Y-6) ρl (Y-7) (Y-8) (RM/RN=0.65) (Y-9) (Y-10) (Y-11) (Y-12) .6(Y-13
) , :t('Y-14) t (RM/RN=0.96 ) (Y-151 t (Y-16) t (Y-17) .E(Y-19) L (Y-20) ct (RM, / RN= 0.88': (Y-21) (2 ('Y-22) )CH
2 (Y-30) t O2 H (Y-35) ('Y-36) (RJIIi/RN=0.80) (Y-37) U (Y-38) (RM/RN=0.6) ( Y-39) NHCOC13H27 (RM/RN=0.9) (Y-41) L (Y-43). 6 (Y-44) r/ (Y-45) c4 (Y-48). 6 (Y-49) c4 (Y-50) ct]) (Y-51). The yellow coupler, magenta coupler, and hydroquinone compounds used in the color light-sensitive material of the present invention are generally oil-soluble, and are generally oil-soluble. No. 2,801,171;
2.272.191 and 2.304.94
According to the method described in Publication No. 0, etc., in a high boiling point organic solvent,
It is preferable to dissolve, disperse and add to a hydrophilic colloid solution such as gelatin, using a low boiling point organic solvent if necessary.

For such oil-in-water emulsion dispersion method, conventionally known methods for dispersing hydrophobic additives are applied, such as N
-High boiling point organic solvents with a boiling point of about 170°C or higher, such as n-butylacetanilide, diethyl laurylamide, dibutyl phthalate, dioctyl phthalate, dilauryl phthalate, cyamyl phthalate, tricresyl phthalate, dibenzyl phthalate, and N-dodecylpyrrolidone. The hydrophobic compounds described above are dissolved in the colloid, optionally together with a low boiling point solvent such as ethyl acetate, and finely dispersed in a hydrophilic colloid such as gelatin in the presence of a surfactant.

An image stabilizer that prevents deterioration of dye images can be used in the light-sensitive material using the silver halide emulsion of the present invention.

Examples of image stabilizers include hydroquinone derivatives, gallic derivatives, phenol derivatives and their bis forms, hydroxycoumarans and their spiro forms, hydroxychroman and their spiro forms, piperidine derivatives, aromatic amine compounds, benzodioxane derivatives, and penzdioxane derivatives. Preferred are sole derivatives, silicon atom-containing compounds, thioether compounds, and the like. As a specific example, British Patent No. 1,410,8
No. 46, JP-A-49-134326, JP-A No. 52-356
No. 33, No. 52-147434, No. 52-15063
No. 0, No. 54-145530, No. 55-6321,
No. 55-21004, No. 55-124141, No. 59-3432, No. 59-5246, No. 59-1
No. 0539, Special Publication No. 48-31625, No. 49-20
No. 973, No. 49-20974, No. 50-23813
No. 52-27534, U.S. Patent No. 2,360,2
No. 90, No. 2,418,613, No. 2,675,31
No. 4, No. 2.701.197, No. 2.704.7
No. 13, No. 2.710.801, No. 2.728.
No. 659, No. 2.732.300, No. 2, 735.7
No. 65, No. 2,816,028, No. 3.069.26
No. 2, No. 3.336.135, No. 3.432.300
No. 3,457,079, No. 3,573,050, No. 3,574,627, No. 3,698.909,
3.700.455, 3.764.337, 3.935,016, 3.982.994,
4,013.701, 4,113,495, 4.120.723, 4.155.765, 4
, No. 159,910, No. 4,254,216, No. 4.
No. 268.593, No. 4.279.990, No. 4
．． No. 332.886, No. 4, No. 360.589, No. 4.
430.425, 4.452.884, etc.

Hydrophilic colloid layers such as the protective layer and intermediate layer of the photosensitive material of the present invention are used to prevent fogging due to discharge caused by charging of the photosensitive material due to friction, etc., and to prevent image deterioration due to U light. It may also contain an absorbent.

In the photographic material of the present invention, when dyes, ultraviolet absorbers, etc. are contained in the hydrophilic colloid layer, they may be mordanted with a mordant such as a cationic polymer.

A light-sensitive material using the silver halide emulsion of the present invention can be provided with auxiliary layers such as a filter layer, an antihalation layer, and/or an antiirradiation layer. These layers and/or the emulsion layer may contain dyes that are washed out or bleached from the light-sensitive material during the development process.

The color photosensitive material of the present invention preferably has at least one yellow, magenta, and cyan coupler-containing layer as a constituent layer on a support, and each of these image forming layers is formed of two or more layers. You can leave it there.

In the present invention, the light-sensitive silver halide emulsion used in each of the above-mentioned dye image forming layers includes photosensitive components such as silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide, and silver iodobromide. silver chemical,
Silver chloroiodide or the like can be used.

Particularly preferred silver halides in the present invention are silver chloride and silver chlorobromide, which have excellent silver developability.

Further, the emulsion used in the present invention can be subjected to various chemical sensitization methods that are applied to general emulsions. Namely, active gelatin, noble metal sensitizers such as water-soluble gold salts, water-soluble platinum salts, water-soluble palladium salts, water-soluble rhodium salts, water-soluble iridium salts; sulfur sensitizers; selenium sensitizers; reduction sensitizers, etc. Chemical sensitization can be carried out using a chemical sensitizer or the like alone or in combination. Furthermore, the silver halide described above can be optically sensitized to a desired wavelength range. There are no particular restrictions on the optical sensitization method, and for example, optical sensitizers such as cyanine dyes such as zeromethine dyes, monomethine dyes, dimethine dyes, trimethine dyes, or merocyanine dyes are used alone or in combination (for example, supercolor sensitization). can be sensitized.

The emulsion used in the present invention can contain various commonly used additives depending on the purpose. Examples of these additives include stabilizers such as azaindenes, triazoles, tetrazoles, imidazolium salts, tetrazolium salts, polyhydroxy compounds, and antifoggants: aldehyde-based, aziridine-based, isoxazole-based, and nylsulfone-based, Examples include acryloyl-based, albodiimide-based, maleimide-based, methanesulfonic acid ester-based, triazine-based hardeners, surfactants, antistatic agents, matting agents, development accelerators, and the like.

As the hydrophilic colloid binder forming the constituent layers of the color photographic light-sensitive material according to the present invention, gelatin is preferable, but not only gelatin but also phthalated gelatin,
Gelatin derivatives such as phenylcarbamoylated gelatin, albumin, agar, gum arabic, alginic acid,
Casein, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, etc. can be used.

Supports for the color photographic material according to the present invention include, for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass paper, cellulose acetate, cellulose nitrate, polyvinyl acetal, polypropylene, and polyester films such as polyethylene terephthalate. , polystyrene, etc., and these supports are appropriately selected depending on the intended use of each silver halide photographic material.

These supports are subjected to undercoat processing if necessary.

The color developing agent used in the processing of the color photographic light-sensitive material according to the present invention includes a developing agent with l) H of 10.3 or more;
Preferably it is an alkaline aqueous solution having I)H of 10.5 to 12.0. This aromatic primary amine developing agent as a developing agent has a primary amine group on an aromatic ring and forms a compound capable of developing exposed silver halide, or such a compound. means precursor.

The above-mentioned developing agent is typically p-phenylenediamine-based, and the following are preferred examples.

4-amino-N, N-diethylaniline, 3-noble 4-amino-N, N-diethylaniline, 4-amino-
N-ethyl-N-β-hydroxyethylaniline, 3-
Methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-
Methyl-4-amino-N-ethyl-N-β-methoxyethyl-4-amino-N, N-diethylaniline, 3-methoxy-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3- Methoxy-4-amino-N-ethyl-N-β-methoxyethylaniline, 3-acetamido-4-amino-N,N-diethylaniline, 4-amino-N,N-dimethylaniline, N-ethyl-N- β−
[β-(β-methoxyethoxy)ethoxy]ethyl3
-Methyl-4-aminoaniline, N-ethyl-N-β-
(β-methoxyethoxy)ethyl-3-methyl-4-aminoaniline and salts thereof such as sulfates, hydrochlorides, sulfites, and p-toluenesulfonates. Especially 3
-Methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline sulfate is most preferred.

These aromatic primary amine color developing agents are used in an amount of 0.02 mol or more, preferably 0.025 mol or more per 12 of the color developing solution.
It is necessary to add mol or more to obtain the effect of the present invention.

Moreover, various additives can be added to these color developing solutions as necessary.

Main examples include alkaline agents (e.g. alkali metal and ammonia cum hydroxides, carbonates, phosphates, etc.), pH
Conditioning or buffering agents (e.g. weak acids and weak bases such as acetic acid and boric acid, their salts, etc.), development accelerators (e.g. pyridinium compounds, cationic compounds, potassium nitrate, sodium nitrate, polyethylene glycol condensates and their derivatives) nonionic compounds such as polythioethers, polymer compounds with sulfide esters, other pyridine, ethanolamine, organic amines, hydrazines, etc.), antifoggants (e.g. alkali bromide,
Including alkali iodides and nitrobenzimidazoles, mercaptobenzimidazole, 5-methylbenzotriazole, 1-phenyl-5-mercaptotetrazole, compounds for rapid processing liquids, thiosulfonyl compounds, phenazine N oxides, benzo nitrobenzoates. thiazolium derivatives), stain or sludge inhibitors, interlayer effect promoters, preservatives (e.g. sulfites, acid sulfites,
hydroxylamine hydrochloride, form sulfide, alkanolamine sulfide adducts, etc.).

After the color development process, the silver halide color photographic light-sensitive material according to the present invention can be subjected to a bleaching process in a conventional manner.

This treatment may be done simultaneously with fixing or separately. This processing solution can also be used as a bleach-fixing bath by adding a fixing agent if necessary.

In the present invention, it is preferred to use bleach-fix baths suitable for rapid processing.

The metal complex salt of an organic acid used as a bleaching agent in the bleach-fixing solution used in the bleach-fixing process is a complex salt of an organic acid such as aminopolycarboxylic acid or an organic acid such as oxalic acid or citric acid that coordinates metal ions such as iron, cobalt, or copper. This is what I did. The most preferred compounds used to form such metal complexes of organic acids are:
Examples of acids include polycarboxylic acids. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts. Specific examples of these include the following.

[1] Ethylenediaminetetraacetic acid [2] Diethylenetriaminepentaacetic acid [3] Ethylenediamine-N-(β-oxyethyl)-N,N'
, N'-tri'acetic acid [4] Propylenediaminetetraacetic acid [5] Nitrilotriacetic acid [6] Cyclohexanediaminetetraacetic acid [71 Iminodiacetic acid [8] Dihydroxyethylglycine citric acid (or tartaric acid) [9] Ethyl ether diamine tetraacetic acid [10] Glycol ether diamine tetraacetic acid [11] Ethylenediaminetetrapropionic acid [12] Phenylenediaminetetraacetic acid [13] Ethylenediaminetetraacetic acid disodium salt [14] Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt [15] Ethylenediaminetetraacetic acid Tetrasodium salt [16] Diethylenetriaminepentaacetic acid pentasodium salt [17] Ethylenediamine-N-(β-oxyedyl'
) -N,N',N'-triacetic acid sodium salt [18] Propylene diamine tetraacetic acid sodium salt [19] Nitriloacetic acid sodium salt [20] Cyclohexanediamine tetraacetic acid sodium salt These bleaches have a concentration of 5 to 450 g/l, More preferably, it is used at 20 to 250(]/Q.The bleach-fixing solution contains a silver halide fixing agent in addition to the above-mentioned bleaching agent,
If necessary, a solution containing sulfite M salt is applied as a preservative. In addition, iron ethylenediaminetetraacetate (II
I) 1) A bleach-fix solution consisting of a salt bleach and a small amount of a halide such as ammonium bromide other than the above-mentioned halogenation-limiting adhesive, or conversely a large amount of a halide such as ammonium bromide. A bleach-fix solution consisting of the added composition, iron ethylenediaminetetraacetate (I[[
) A special bleach-fix solution having a composition consisting of a combination of a complex salt bleach and a halide such as ammonium bromide can also be used. As the halides, in addition to ammonium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, etc. can also be used. can.

The silver halide fixing agent contained in the bleach-fix solution includes compounds that react with silver halide to form water-soluble complex salts, such as potassium thiosulfate, sodium thiosulfate, and thiosulfate, which are used in ordinary fixing processes. Typical examples include thiosulfate such as ammonium sulfate, thiocyanine MJW such as potassium thiocyanate, sodium thiocyanate, ammonium thiocyanate, thiourea, and thioether. These fixing agents are used in an amount of 5 g/2 or more, within the range that can be dissolved, but generally 70 to 250 g.
Use with /f.

In addition, various pH buffers such as tllll, fat sand, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide are added to the bleach-fix solution. Alternatively, two or more kinds can be contained in combination. Furthermore, various optical brighteners, antifoaming agents, or surfactants can be contained. In addition, preservatives such as hydroxylamine, hydrazine, bisulfite adducts of aldehyde compounds, organic chelating agents such as aminopolycarboxylic acids, stabilizers such as nitroalcohols and nitrates, and organic A solvent and the like can be contained as appropriate.

Bleach-fix solutions include JP-A No. 46-280 and JP-A No. 45-Sho.
No. 8506, No. 46-556, Belgian Patent No. 770
．． No. 910, Special Publication No. 45-8836, No. 53-985
No. 4, JP-A No. 54-71634 and JP-A No. 49-4234
Various bleaching accelerators such as those described in No. 9 can be added.

The temperature of the color developing solution of the present invention is preferably 30°C or higher and 45°C or lower, most preferably 32°C or higher and 42°C or lower.

The OH of the bleach-fix solution is about 4.0 or more and 9.0 or less,
Preferably it is between about 5.0 and 8.0. Also, the temperature of the bleach-fix solution is 20°C or higher and 50°C or lower, preferably 25°C.
C or higher and 40°C or lower is most preferable.

After bleach-fixing the color photosensitive material of the present invention, it is necessary to remove unnecessary processing chemicals by washing with water.
No. 5145, No. 5fl-134634 and No. 5g-
No. 18631 and Japanese Patent Application No. 58-2709 and No. 59
A stabilization treatment as an alternative to water washing as shown in Japanese Patent Application No.-89288 may also be performed.

The processing time for the color photosensitive material of the present invention varies depending on the type of photosensitive material, the temperature of each processing solution, 11H, etc., but the color development process is generally within 2 minutes, preferably within 1 minute and 30 seconds, and most preferably within 1 minute and 30 seconds. takes place within 1 minute. The bleach-fixing process is preferably carried out within 60 seconds, particularly preferably within 5 seconds.
Done within 0 seconds. Furthermore, water washing or stabilization treatment is carried out within 2 minutes, preferably within 1 minute and 30 seconds.

When processing the color photosensitive material of the present invention while continuously replenishing the replenisher, it is preferable to use a color developer replenisher that has a processing chemical concentration of about 10% to 50% more concentrated than that of the color developer. , and preferably does not contain bromide ions.

Further, the pH of the color developer replenisher is preferably about 0.1 to 0.5 higher than the l)H of the color developer, and the pH of the bleach-fix replenisher is about 0.5 to 0.5 higher than the pH of the continuously processed bleach-fix solution. 3
Preferably, the I)H is between 1.5 and 1.5 lower.

When processing is performed while continuously replenishing the color image, bleach-fixing, and stabilizing liquids of the present invention, the replenishment rate of each replenisher is 100 to 1.0001.
C, preferably 150 to 500 d.

[Example] Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited to these.

Example-1 The following layers were formed on the titanium dioxide-containing polyethylene side of a 170g7.2 paper support laminated with polyethylene on one side and polyethylene containing 11 weight percent anatase titanium dioxide on the other side. Silver halide color photographic light-sensitive materials Nos. 081 to 11 were prepared by sequential coating. Incidentally, the amount added is expressed as the amount per 112 unless otherwise specified.

Layer 1...1.2q of gelatin, 0.30o (in terms of silver,
Blue-sensitive silver chlorobromide emulsion of o, sog di-2-ethylhexyl phthalate (hereinafter abbreviated as DOP).

) and the yellow couplers shown in Table 1 dissolved in 0.
A layer containing the color stain inhibitor HQ-11 of 04Q.

Layer 2...0.7 (J gelatin, 15 Il 1 g anti-irradiation dye (AI-1), 10 mg (AI
-2) and an intermediate layer containing 005 g of DOP in which the hydroquinone compounds shown in Table 1 are dissolved.

Layer 3...1.25+) gelatin, 0.26(l green sensitive silver chlorobromide emulsion, 0.30g dissolved in DOP)
, 45g magenta coupler (M-9) and 0.01
(layer containing 1 HQ-11.

Layer 4...1.2 g gelatin, 0.08 (l HQ-
11 and 0.35 with 0.5g of ultraviolet absorber (UV-1) dissolved in it! An intermediate layer containing a DOP of J.

Layer 5...1.4 g gelatin, 0.21 CI red-sensitive silver chlorobromide emulsion, 0.20 g DOP I: Dissolution 1. , tc O, 25g' (1) Cyan coupler (C-
1>, 0.25 (l cyan coupler (C-2) and o
, a layer containing HQ-11 of oig.

Layer 6...1.0g gelatin and 0.20g DOP
A layer containing 0.30 g of IJV-1 dissolved in.

Layer 7: Layer containing 0.5 g of gelatin.

As a hardening agent, 0.041 J of sodium 2,4-dichloro-6-hydroxy-s-triazine was added to each of the above H4 and layer γ immediately before coating.

t Below margin UV-I I-I I-2 Each of the above photosensitive materials was exposed to white light through an optical wedge and then processed in the following steps.

Processing step (A) Color development (A) 3 minutes 30 seconds 38℃ bleach fixing
1 minute 38°C water wash
Dry for 1 minute at 30-34℃
45 seconds 80-90℃ processing steps (B) to (E) Color development (B) to (E) 1 minute each 38℃ bleach-fixing
Wash with water at 38℃ for 1 minute
Dry for 1 minute at 30-34℃
45 seconds 80-90°C The composition of the color developing solution (A> is as follows).

Pure water 800112 Hydroxylamine sulfate 2.4g Benzyl alcohol 151g Triethanolamine 151g Potassium bromide
1.35 (sodium monochloride
1.0 g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-amine aniline sulfate 4.50 1-hydroxyethylidene-1,1-diphosphonic acid 1.0 g anhydrous potassium carbonate 35 g Kaykoll
PK-ConC2, Oa (fluorescent brightener, manufactured by Shin Nisso Co., Ltd.) Add pure water to make 11, and add 20% potassium hydroxide or 10
Adjust the pH to 10.1 with % dilute sulfuric acid.

The compositions of the color developing solutions (B) to (E) are as follows.

Pure water 8001 (hydroxylamine 1 sulfate 2.4 g Potassium bromide 1.35 G Sodium chloride 1.0 g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-amine aniline sulfate 9.2 g Anhydrous potassium carbonate Afternoon 2g Kaykoll
PK-ConC2, Oa (fluorescent brightener, manufactured by Shin Nisso Co., Ltd.) Add pure water to make 12, and add 20% potassium hydroxide or 10% dilute sulfuric acid to I) H-IQ, 1(B), 10.
Adjust to 4(C), 10.7(D>, 11.0(E)).

The composition of the bleach-fix solution is as follows.

Pure water eootc Iron ethylenediaminetetraacetate (Ill) Ammonium 65 (J ethylenediaminetetraacetic acid 2-sodium salt 5g Ammonium thiosulfate 85 (1 Sodium bisulfite 101J Sodium metabisulfite 2g Sodium ethylenediaminetetraacetic acid 20 G Sodium bromide 10 g phenomenon liquid
Add 200 d of pure water to make 12, and adjust to I)H=7.0 with dilute sulfuric acid.

Reflection density measurements were performed on each of the obtained samples using blue, green, and red color lights to determine the gradation and maximum density. The results are shown in Table-1. In the table, gradation represents the slope of reflection density from 0.8 to 1.5, and B, G, and R indicate that the density was measured using monochromatic light of blue, green, and red, respectively. show.

On the other hand, each of the samples 1 to 11 was exposed to blue monochromatic light through an optical wedge, and then the processing step (A) was performed.
Each treatment of ~(E) was performed.

However, in addition to each of the processing steps (A) to (E), Example 1 is added to the color developing solution for each of (A) to (E).
- Treatment in which 100111 g of aryl-3-pyrazolidone compound (I-4> was added per y of color developer [processing steps (A)', (B)', (C)', (D)',
(E)'. ] was also carried out.

The density of each of the obtained samples was measured using monochromatic blue and green light, and the green temperature at a location where the blue reflection density was 1.2 was determined. The results are shown in Table-2.

Comparative Yellow Coupler Below Margin From the results shown in Table 1, Samples 3 to 11 using the high-speed yellow coupler were color developed for 1 minute in color developing solutions (8) to (E) containing no benzyl alcohol at all. When the treatment is carried out, good gradation and maximum density can be obtained in color developing solutions (C), (D), and (E) having a pH of 10.4 or higher. On the other hand, when the comparative yellow coupler was used (sample 1.2), the p
Even if H is raised to 11 or O, the gradation and maximum density remain unchanged from the standard treatment (
This is significantly lower than A).

On the other hand, looking at the color turbidity in the case of blue monochrome exposure from the results in Table 2, Sample 1 using the comparative yellow coupler
．． 2 is an example of 1-aryl-3-pyrazolidone <l-4)
Due to the presence of , the green component increases significantly and a magenta dye image is formed. On the other hand, Sample 4.5.7.9 was prepared using the high-speed yellow coupler of the present invention and added a hydroquinone compound (HQ-17) to the second layer.
11, even when 1-aryl-3-pyrazolidone is added to the color developer, the pH of the color developer is 10.4.
The samples treated above contained only the same level of green components as the standard treatment (A), indicating that there was almost no color turbidity.

Example-2 In Example-1, the hydroquinone compound was added to HQ-1
1 to HQ-18, and changed the magenta coupler (M-
9) to (M-18), and the green-sensitive silver chlorobromide emulsion used in the third layer was changed from o, zeg to o, 19 (7), samples 12 to 22 were created and carried out. The same experiment as in Example 1 was repeated. The results are shown in Table 3. In Table 3, the gradation and maximum density indicate that the density was measured using monochromatic blue light.

From the results shown in Table 3, it is clear that in this example as well, by adding a high-speed yellow coupler and a hydroquinone compound to the non-photosensitive layer, good color development was achieved and 1-
It can be seen that even when aryl-3-pyrazolidone is added to the color developer, color turbidity hardly occurs when the pH of the color developer is set to 10.4 or higher.

Example-3 In Example-2, 1, magenta coupler (M-18
) to (M-45>) and conducted the same experiment as in Example-2, the same effects of the present invention as in Example-2 were obtained.

Patent Applicant Roku Konishi Photo Industry Co., Ltd. Agent Patent Attorney Ichinose Miyao Procedural Procedures (Ichiyoshisho) % Formula % 2. Name of the Invention Method for Processing Silver Halide Color Photographic Light-sensitive Materials 3. Case of Person Who Makes Amendments Relationship Patent applicant address 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name
(127) Representative Director of Konishiroku Photo Industry Co., Ltd.
Keio Benko 4, Agent 102 Address: 1-11 Kudankita 4-chome, Chiyoda-ku, Tokyo (Shipping date) April 22, 1986 6, Subject to amendment

Claims (1)

[Scope of Claims] A silver halide color photographic light-sensitive material having at least two silver halide emulsion layers containing a diffusion-resistant hydrophobic coupler on a support is prepared by the following general formula [ I
] 10^-^4 mol/l ~ 4 x 10
^-^ In the method of processing with a color developer containing 3 mol/l and substantially free of benzyl alcohol, the pH of the color developer is 10.3 or more, and a diffusion-resistant hydrophobic coupler. 1. A method for processing a silver halide color photographic light-sensitive material, characterized in that a non-photosensitive layer containing a hydroquinone compound is provided between two silver halide emulsion layers containing. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1 represents an aryl group, R_2, R_3
, R_4 and R_5 represent a hydrogen atom or an alkyl group, and may be the same or different. X represents a hydrogen atom or an alkali-hydrolyzable group. ]