JPH0359654A - Color development replenishing solution composition and method for processing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To prevent coloring of a color development replenishing solution and production of tarry stained matter by incorporating substantially no benzyl alcohol in the replenishing solutionbut bromione ions in an amount of 3X10<-5> -5X10<-4> mol/l and a specified compound. CONSTITUTION:The silver halide color photographic sensitive material has at least one photosensitive emulsion layer containing silver chloride grains in an amount of <= 95 mol %, and the development replenishing solution substan tially does not contain benzyl alcohol but contains bromine ions in an amount of 3X10<-5> -5X10<-4>mol/l, and at least one of the compounds represented by formula l in an amount of >= 100 ml/m<2> of the photosensitive material. In formu la l, A is -SO3M or -SO4M; M is H or an alkali metal atom, such as Li or Na; R is a straight chain or branched alkyl, or each of A and R may be H; p is 1, 2, or 3; and q is an integer of 0 - 6, thus permitting the color development replenishing solution to be prevented from coloring, and producing, and produc ing tarry stained matter and precipitates.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a color development replenisher composition for silver halide color photographic light-sensitive materials and a processing method using the same. More specifically, it relates to a color developer replenisher with improved stability, in particular, which prevents liquid coloring, tar-like contaminants, and precipitate generation, and also relates to a color developer replenisher that has improved stability and is particularly effective in rapid development processing using the above-mentioned color developer replenisher. The present invention relates to a color development processing method for obtaining photographic images with excellent whiteness without contaminating parts of processing equipment or causing trouble in feeding replenisher fluid.

(Prior Art) It is known that a color developing solution containing an aromatic primary amine developing agent is autooxidized when it comes into contact with air (T,
The Theory of the Photographic Process by T. H. James.

James+ 'The Theory of the
Photographic Propoess, 1 (4th ed.) P, 315 (1979)), resulting in the color developer being colored dark brown and further producing black tar-like contaminants. This black tar-like contaminant may adhere to the photosensitive material and cause processing (contamination), or when processing continuously while replenishing the developer with an automatic processor, the processing solution tank, piping, etc.
It adheres to parts of the developing machine that come into contact with the color developer, such as the conveyor roller, and seriously contaminates the developing machine. In particular, if parts that come into contact with the photosensitive material become contaminated, the dirt will be transferred to the photosensitive material.
This will destroy the commercial value of the photosensitive material.

) Recently, along with the simplification of processing, the amount of color developer replenishment is being reduced. Replenishment of the color developer is generally performed with a color developer replenisher having a higher concentration than the mother solution. As the amount of replenishment to the color developer decreases, the residence time in the replenishment tank, which has a relatively large contact area with air, increases, and color development In particular, liquid contamination due to deterioration of the main drug,
It occurs significantly in color developer replenishers and has become a major problem.

As a method of preventing air oxidation of color developing solutions, a method has been used in which a compound called a preservative is added to the color developing solution. Compounds such as sulfites and hydroxylamine salts have been known as preservatives (L, F
, A. Mason, Photographic Processing Chemistry (L.

F, A, Mason, rPhotography
c Processing Chewf-try”)
ρ, 34 (1966), as well as alkanol-amine compounds (US Pat. No. 4,170,478), polyalkyleneimine compounds (US Pat. No. 4,252,892), aromatic polyhydroxy compounds (Research Disclosure, 18843, December 1979), Dihydrobovine diacetones (US Pat. No. 3,615,503) are known as preservatives for color developing solutions, and many compounds known as metal ion chelating agents are also important for the preservation of developing solutions. (Research Disclosure, Nl1m27048.19)
June 1978, etc.)].

All of the above compounds suppress air oxidation of the color developer,
Although it is highly effective in preserving photographic performance, it cannot completely prevent air oxidation, and in order to prevent liquid coloring and the formation of tar-like contaminants, the contact area with air per unit liquid volume (
It was necessary to take measures such as significantly reducing the aperture ratio (hereinafter abbreviated as aperture ratio).

However, even if a floating pig or a floating ball is used to reduce the opening ratio of the replenishment tank, the opening ratio will increase as the amount of replenisher in the tank decreases. Therefore, compared to processing tanks, they are more susceptible to air oxidation.
Even when the above-mentioned preservatives are used, coloring of the color developer replenisher and the generation of tar-like contaminants have been a serious problem.

In addition, as a technology to prevent the generation of tar-like pollutants, it has been published internationally.
No. 087104534 discloses a rapid development process that does not contain benzyl alcohol and uses dialkylhydroxylamine as a preservative for color developing agents.

However, although this method prevents the generation of tar-like contaminants to some extent, it does not improve the coloring of the color developer replenisher, and furthermore, precipitates are generated in the color developer replenisher.
A new problem has arisen in which refilling problems occur due to accumulation in filters and pipes, and a solution to this problem has been strongly desired.

Also, JP-A-62-56961 and JP-A-62-421
No. 54 describes a technique for improving whiteness after processing and preventing contamination of automatic processors by using a polyoxyethylene nonionic surfactant or a polyalkylene nonionic surfactant in a color developer. However, these effects were insufficient. Furthermore, although removal of benzyl alcohol prevents the generation of tar-like contaminants to some extent, the coloring of the liquid and the whiteness of the photosensitive material are insufficient, new precipitates are generated in the color developer replenisher, and furthermore, However, due to the removal of benzyl alcohol, the coloring property was decreased and it was not suitable for practical use.

(Problems to be Solved by the Invention) Therefore, the first object of the present invention is to provide a color developer replenisher that prevents the coloring of a color developer replenisher and the formation of tar-like contaminants, or that makes the effects harmless. Wi, to provide a composition.

A second object of the present invention is to provide a color developer replenisher composition in which the generation of precipitates is prevented.

A third object of the present invention is to provide a method for processing silver halide photographic materials that can quickly produce color photographic images with good whiteness.

A fourth object of the present invention is to prevent tar-like contaminants from adhering to developing equipment or parts of automatic processors (e.g., processing tanks, piping, conveyance rollers, etc.), thereby causing these equipment to become contaminated. It is an object of the present invention to provide a method for processing a silver halide color photographic light-sensitive material, which can prevent such problems from occurring.

A fifth object of the present invention is to provide a) a method for processing silver halide color photographic materials, which prevents the occurrence of precipitates in the color developer replenisher and prevents replenishment troubles due to the accumulation of precipitates in filters and piping. It is to provide.

(Means for Solving the Problems) An object of the present invention is to provide a color developer replenisher containing an aromatic primary amine developing agent, substantially free of benzyl alcohol, and containing 3XIO-5 to bromine ions. 5×10
−'mol/1, and contains the following general formula (1) or the general formula (
Color development replenishment W1. containing at least one of the compounds represented by II). &ll A method in which a silver halide color photographic light-sensitive material is continuously processed using a color developer containing an aromatic primary amine developing agent, wherein the silver halide color photographic light-sensitive material contains silver chloride. It has at least one layer of a photosensitive emulsion containing high silver chloride grains with a content of 95 mol% or more, substantially does not contain benzyl alcohol, and contains bromine ions from 3xto-5 to
A color developer replenisher containing at least one compound represented by the following general formula (1) or general formula (II) was added at a concentration of 100% per m2 of the silver halide color light-sensitive material. The present invention has been achieved by using a method for processing silver halide color photographic materials characterized by the above-mentioned replenishment.

General formula (1) In the formula, A represents -3OJ, -5OaFI, M represents a hydrogen atom or an alkali metal atom such as a lithium atom, a sodium atom, a potassium atom, and R represents a linear or branched alkyl group. preferably carbon number 2-I
O represents a straight chain or branched alkyl group, A and R may be substituted with any hydrogen atom of the naphthalene ring, P is 1
an integer of ~3, q represents an integer of O~6, preferably p
is 1. q represents an integer from 1 to 3.

General formula (n) CHgCOOCJ寞1.1 1 NaOs-CHCOOC5Hta*+ In the formula, m and n represent integers of 4 to 18, preferably m and n are 5 to 9.

Next, specific examples of compounds represented by general formulas (1) and (II) are shown. Compounds in which the substitution position is not specified are compounds with different substitution positions. The present invention is not limited to these. isn't it.

Hs Hs Hs L (1-21) CH.

Chzcoo -ISOCAHQ NA03S -CHCOO -ISOCDL (U -2) CHGCOO -ISOCJ + 1 NAZS -CHCOO -ISOCJ ■ (N -3) CHICOOC6HI3 -N NA01S -CHCOOCJ ( + 5 -N )
CI! ClbCOOCHgCHgC
HCH*CHgCHsNa0sS-CHCOOCHzC
H*CHCHtCHzCHsCH.

(II-5) CHgCOO-CHtCII(Coh5)C4H19■ Na0sS-CI(Coo-CHtCIl (Ctfl
s) Ca'H+ *(II-6) CtllCOO-CsHly y-n Na0sS-CHCOO-CsH+y-n (II-7) CHxCOOCJ+w-n Na0sS-CHCOOCJ+*-n (n-9) CHgCOOC+eHt+-n Na03S-C HCOOC+aHi+ -n All of the above compounds are known compounds and can be obtained from many surfactant manufacturers.

-a The compounds represented by formulas (1) and (II) need to be present in the color developer replenisher. Here, as a method for making it present in the color developer replenisher, it may be added directly to the color developer replenisher, or it may be eluted from the photosensitive material. This is the case, for example, when the overflow solution of a color developer used to process a photosensitive material containing a compound represented by formula (1) or (n) is recycled and reused as a replenisher.

The method of regenerating the overflow solution of color developer is to analyze the missing components, such as color developing agent, preservative, optical brightener, etc., add the required amount, and adjust the pH to an appropriate value by adding an alkaline agent. This refers to a method of adjusting the color and reusing it as a color developer replenisher, with or without using an ion exchange resin and electrodialysis to remove specific components.

However, even when the above removal method is used, the color developer replenisher must contain bromine ions at the concentration of the present invention and the compound of general formula (1) or (n) of the present invention.

In the present invention, from the viewpoint of reducing the amount of waste liquid, it is preferable to regenerate the overflow liquid of the color developer and use it as a replenisher.In particular, it is preferable not to use a specific removal means for ease of use and stability of processing. This is preferable in terms of compatibility.

The amount of the compound represented by general formula (1) or (II) in the color developer replenisher is preferably the same as that of the color developer replenisher tQ.
0.01g to 20g, more preferably 0.1 to Lo
It is preferable to contain g.

In the present invention, it is necessary that the color developer replenisher does not substantially contain benzyl alcohol. here,
"Substantially free" means 2 dt/I.

Indicates the following, preferably 0.5d#! or less, and it is particularly preferable that it is not contained at all.

In the present invention, it is necessary that the color developer replenisher contains 3×10 −5 to 5×10 −′ mol/l of bromide ion. More preferably 8X10-' to 3X10
-'mol/1m2. As a method for incorporating bromine ions into the color developer replenisher, it may be added directly to the color developer replenisher, or it may be eluted from the photosensitive material. This is the case, for example, when the overflow solution of a color developer used to process a photosensitive material containing ions is recycled and reused as a replenisher.

A silver halide color photographic light-sensitive material suitable for the processing method using the color development replenisher of the present invention is a color light-sensitive material having at least one layer of a light-sensitive emulsion containing high silver chloride grains having a silver chloride content of 95 mol% or more. It is. The silver chloride content is preferably 98 mol % or more, particularly 99% or more. However, a silver chloride content of 100% is disadvantageous in terms of decreased sensitivity.

Because the color developer replenisher contains a small amount of bromide ion, a strong developer inhibitor, and the absence of benzyl alcohol, a color accelerator, a silver chloride content of 95 mol% is required for rapid development. It is preferable to use the above-mentioned high silver chloride silver halide photosensitive materials.

In the processing method of the present invention, it is necessary to replenish the color developer replenisher at a rate of 100 or more per m 2 of the silver halide color light-sensitive material. Preferably it is 100-200d.

The replenishment amount of the color developer is 100 per m” of photosensitive material.
- If the concentration is below, the concentration of the replenisher will increase and the pH will further increase, making it impossible to completely prevent the formation of precipitates in the replenisher. The white background after processing is contaminated and the object of the present invention cannot be achieved.

In the color developer replenisher of the present invention, ■ Contains substantially no benzyl alcohol.

(2) Contains 3 x 10-5 to 5 x 10' mol/l of bromine ion.

(2) Contains at least one compound represented by the general formula (1) or (If).

When the above conditions (■ to ■) are simultaneously satisfied, the generation of tar-like contaminants and precipitates can be prevented, and the replenisher and 95%
The fact that by combining a photosensitive material with a high silver chloride content of mol % or more and processing it while replenishing 100% or more of the above-mentioned replenisher per mol% of the photosensitive material, the white background after processing can be rapidly and significantly improved is expected. It was difficult and truly surprising.

JP-A No. 62-275259 discloses that silver chlorobromide containing silver chloride of 50 mol % or more is a color developer that does not substantially contain benzyl alcohol and contains bromine ions of 4×10-” mol/1 or less. A method of processing a photosensitive material is disclosed.However, the general formula (1) or (If
) is not described, nor is there any description of the above-mentioned problems with the replenisher, so the present invention is not inferred.

JP-A-62-42154 discloses bromine ion 0.7X10-
A method of processing with a color developer containing "~3.5XIO-" mol/l and a polyalkylene nonionic surfactant is disclosed; is completely different, and furthermore, it contains benzyl alcohol and is a processing method using silver chlorobromide, which is mainly composed of silver bromide, and the description of precipitation of color developer replenisher and rapid development processing when benzyl alcohol is removed is This is not an analogy to the present invention.

The color developer and color developer replenisher used in the present invention will be explained in detail below.

Color developer replenisher usually has 1.05 to 3 times higher concentration of consumable components such as developing agents, preservatives, and optical brighteners than the color developer (in the processing tank); pn of
It is also designed to be 0.1 to 1.5 higher.

The reason why the color developer replenisher deteriorates more than the tank liquid is because
This is largely due to the above reasons.

In the present invention, in order to suppress the deterioration of the color developer and color developer replenisher, it is necessary not to use the color developer and color developer replenisher for a long time, to use a floating pig to suppress the influence of air oxidation, and to prevent the color developer and color developer replenisher from deteriorating. Physical means such as reducing the aperture of the film can be used, or chemical means such as reducing the developer temperature or adding an organic preservative can be used.

Among these, the method using an organic preservative is advantageous in terms of simplicity.

The organic preservative described in the present invention refers to any organic compound that reduces the deterioration rate of aromatic primary amine color developing agents when added to the processing solution of color photographic light-sensitive materials. These are organic compounds that have the function of preventing oxidation by air, etc. Among them, hydroxylamine derivatives (excluding hydroxylamine, the same applies hereinafter), hydroxamic acids, hydrazines, hydrazides, phenols, α-hydroxyketones , α-anogatones, sugars, monoamines, siatones, boria fruits, quaternary ammonium salts, nitroxy radicals,
Particularly effective organic preservatives include alcohols, oximes, diamide compounds, and fused ring amines. These are Japanese Patent Application No. 61-147823 and Japanese Patent Application No. 63-3084.
No. 5, No. 63-21647, No. 63-44655,
Patent application No. 197760/1983, Japanese Patent Application No. 43140/1983
No. 61-198987, Patent Application No. 61-20186
No. 1, Japanese Patent Publication No. 63-43138, European Patent Publication No. 254
No. 280, JP 6344657, JP 63-4465
No. 6, U.S. Patent No. 3,615.503, U.S. Patent No. 2,494
, No. 903, JP-A No. 52-143020, JP-A No. 1973
-30496, etc.

Regarding the preferred organic preservative, its general formula and specific compounds are listed below, but the present invention is not limited thereto.

In addition, the amounts of the following compounds added to the color developing solution are o, oo
s mol/l to 0.5 mol/l, preferably 0.03 mol/l to 0.1 mol/l! It is desirable to add it to a concentration of .

It is preferable to add 1.05 to 2.0 times the amount of the tank liquid to the color replenisher.

Particularly preferred is the addition of hydroxylamine derivatives and/or hydrazine derivatives.

The hydroxylamine derivative is preferably represented by the following general formula (III).

General formula (III) R'-N-R" ■ H In the formula, R1 and Rt are a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted aryl group, or a heteroaromatic eRI and R8, which represent group groups, do not become hydrogen atoms at the same time, and may be linked to each other to form a heterocycle with a nitrogen atom.The ring structure of the heterocycle is a 5- to 6-membered ring. , carbon atom, hydrogen atom, halogen atom, oxygen atom, nitrogen atom,
It is composed of sulfur atoms, etc., and may be saturated or unsaturated.

171, pt is preferably an alkyl group or an alkenyl group, and preferably has 1 to 10 carbon atoms, particularly 1 to 10 carbon atoms.
5 is preferred. +1. The nitrogen-containing heterocycle formed by linking and Rt includes a piperidyl group, a pyrolisilyl group, a N
Examples include -alkylpiperazyl group, morpholyl group, indolinyl group, and benztriazole group.

L and R may be connected to form a ring.

Specific examples of the compound of general formula (II) in the present invention are listed below, but the present invention is not limited thereto.

Compound 1l-1 CtHs-N-CtHs H 1l-2 CutocHa-N-CtH4-OCH30)1-3 CtHsOCtHa-N-CH-CH=CHtO■ Among the compounds represented by the general formula (III), A compound represented by the following general formula (I[[-a)] is particularly preferred in terms of preventing fluctuations in photographic properties and preventing the above-mentioned streaky capri.

General formula (Ill-a) In the formula, L represents an alkylene group that may be substituted, A is a carboxy group, a sulfo group, a phosphono group, a phosphinic acid residue, a hydroxy group, an amino group that may be substituted with alkyl,
It represents an alkyl-substituted ammonio group, an alkyl-substituted carbamoyl group, an alkyl-substituted sulfamoyl group, and R represents a hydrogen atom or an optionally substituted alkyl group.

The general formula (t[[-a) will be explained in detail below.

In the formula, L represents a linear or branched optionally substituted alkylene group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, specifically, methylene, ethylene, trimethylene,
Propylene is mentioned as a preferred example. Examples of the substituent include a carboxy group, a sulfo group, a phosphono group, a phosphinic acid residue, a hydroxy group, and an alkyl-substituted ammonio group, and preferred examples include a carboxy group, a sulfo group, a phosphono group, and a hydroxy group. . A is a carboxy group, a sulfo group, a phosphono group, a phosphinic acid residue, a hydroxy group, an amino group which may be substituted with alkyl,
An ammonio group which may be substituted with alkyl (preferably 1 to 5 carbon atoms), a carbamoyl group which may be substituted with alkyl (preferably 1 to 5 carbon atoms), and a carbamoyl group which may be substituted with alkyl (preferably 1 to 5 carbon atoms). Represents a good sulfamoyl group,
Carboxy group, sulfo group, hydroxy group, phosphono group,
Preferred examples include carbamoyl groups which may be substituted with alkyl. Examples of -L-'A include carboxymethyl group, carboxyethyl group, carboxypropyl group,
Sulfoethyl group, sulfopropyl group, sulfobutyl group,
Preferred examples include a phosphonomethyl group, a phosphonoethyl group, and a hydroxyethyl group, and particularly preferred examples include a carboxymethyl group, a carboxyethyl group, a sulfoethyl group, a sulfopropyl group, a phosphonomethyl group, and a phosphonoethyl group. R represents a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, and preferably has 1 to 5 carbon atoms, X
-t* groups include carboxy groups, sulfo groups, phosphono groups, phosphinic acid residues, hydroxy groups, amino groups that may be substituted with alkyl, ammonio groups that may be substituted with alkyl, and carbamoyl groups that may be substituted with alkyl. , represents a sulfamoyl group which may be substituted with alkyl, and there may be two or more substituents. Preferred examples of R include a hydrogen atom, a carboxymethyl group, a carboxyethyl group, a carboxypropyl group, a sulfoethyl group, a sulfopropyl group, a sulfobutyl group, a phosphonomethyl group, a phosphonoethyl group, and a hydroxyethyl group. Particularly preferred examples include a carboxymethyl group, a carboxyethyl group, a sulfoethyl group, a sulfopropyl group, a phosphonomethyl group, and a phosphonoethyl group.

-4 1[1-6 -7 ■-8 1m2-9 Js-NH H ll-10 CH30CJ4-NH H ■-1m2 ■-12 ■-13 H3 Hs ■-14 xHS Js ■-15 aL Cal'l drop ■-16 L H3 ■-17 ■-18 H H ■-19 ■-20 ■ 1 ■ 2 CI+.

■-23 ■ 4 ■-25 ■-26 ■-27 ■ 8 1m2 H ■-29 ■-30 ll-31 HO-NH-C1hCO□H HO-NH-C1m2gCHzCO□H80-NH-i
-C(hH CHKO■-33 III-34 ll-35 ■-36 HO-NH-C)I-COgH C,Hg )IQ-NH-CI-CHg-COJ CH3 IO-Nu-(:Hz-CH -COgHCHg [0-NH-CHiCHtSOsH ■-37 No-NO-CHtCHCHiSOJ H ■-38 ■-39 ll-40 -41 -42 ■-43 ■-44 ■-45 HO-NH-(CHz) 5sOJ IO-NH -(CIlri 4SOsH HO-NH-CHtPOJz No-NH-CH-POJt C1f word +1O-NH-CHICHtPOsHlHO-NO-C
HxCH*0H )10-N)I-(CIlyo), OH HO-NO-CHg-POJt ■-46 ■-47 υH ■-48 ■-49 ■-50 ll-51 ■-52 ■-53 ■- 54 ll-55 ll-56 HONHCHtCH(Poses)! ■-57 ■-58 ■-59 ■-60 ■-61 ■-62 ■-63 ■-64 80-N) lcLclhc-N) Ic (CHs) gc
) It-3Osl+1 The compound represented by the general formula (m) can be obtained by alkylation reaction (nucleophilic substitution reaction,
addition reaction, Mannich reaction). West German Patent No. 1m259634, “
Inorgan Power, Chemi Power, Acta J (Inorgan
ica Chimica, Acta)+ 93+ (1
984) 101-108, etc., and the specific method is described below.

Synthesis Example Synthesis of Exemplified Compound (7) To 200jd of an aqueous solution of 20g of hydroxylamine hydrochloride, add 1m2.5 g of sodium hydroxide and 96g of sodium chloroethanesulfonate, and keep at 60°C and add 40I1m2 of an aqueous solution of 23g of sodium hydroxide over 1 hour. I added it slowly. Furthermore, the reaction mixture was kept at 60°C for 3 hours, concentrated under reduced pressure, and 200 ml of concentrated hydrochloric acid was added thereto and heated to 50°C. Insoluble materials were filtered, and 500 g of methanol was added to the filtrate to obtain the desired product (exemplified compound (7)) as crystals of monosodium salt.

41g (yield 53%) Synthesis of Exemplary Compound (21) Hydroxylamine hydrochloride 7.2g and phosphorous acid 18.0g
32.6 g of formalin was added to the aqueous hydrochloric acid solution and heated under reflux for 2 hours. The resulting crystals were recrystallized from water and methanol to obtain 9.2 g (42%) of the exemplary compound (1 m2).

As the hydrazines and hydrazides, the following are preferred.

General formula (■> In the formula, Rjl, 1731, R33 represents a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, or a heterocyclic group, and R24 represents a hydroxy group, a hydroxyl group, a substituted or unsubstituted The heterocyclic group representing an alkyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, carbamoyl group, or amino group is 5 to 6
It is a membered ring, composed of C1H1O1N, S and halogen atoms, &! Can be either sum or unsaturated, xe
lba-CO-1-SO! - or 1. In particular, when n-0, R34 represents a group selected from an alkyl group, an aryl group, and a heterocyclic group, and R33 and R34 may jointly form a heterocyclic group.

In general formula (V), Rjl, )23! , R33 is preferably a hydrogen atom or a C5-C1° alkyl group, especially H! + and R2H are most preferably hydrogen atoms.

-a In the formula (V), 1lff4 is preferably an alkyl group, an aryl group, an alkoxy group, a carbamoyl group, or an amine salt, particularly preferably an alkyl group or a substituted alkyl group, and a substituent of the alkyl group is preferred here. is a carboxyl group, a sulfo group, a nitro group, an amino group, a phosphono group, etc. x3- is preferably -CO- or -5O1-, most preferably -CO-.

(Compound example) V-1 V-2 NHJ)InCHz)-r-3OsH V-3 NHtNH-(CHzl"OH V-4 ■-5 1i1-6 NHJHCOCHs ■7 NH!NHCOOCOH3 IV-8 nυ [V -9 ■-1O NHJHCONHz IV-1m2 ■-12 NHtNH5OsH ■ 3 HI NHJHCNHg IV-14 NHJHCOCONHNHt ■-15 NHJHCHtCHtCHiSOiH V-16 IV-17 NHfNHCHCOOH C aHw(n) IV-18 NHxNHCI(tcHgcOOH ■-19 ■-20 ■ -21 ■-22 υ The combination of the compound represented by the above-mentioned -formation ([[) or (IV)] and the amines represented by the following -formation (V) or (Vl) is useful for color developing solutions. It is more preferable from the viewpoint of improving stability and, furthermore, improving stability during continuous processing.

General formula (V) tt l? 'H-N-R? ! In the formula, R1, R"Q'L2 are hydrogen atoms, alkyl groups,
represents an alkenyl group, an aryl group, an aralkyl group, or a heterocyclic group, where R1 and H'rtHti and R1
m2 or Rfft and R? 2 may be connected to form a nitrogen-containing heterocycle.

Here, R? I, R? ! and R? 3 may have a substituent R? l, Rat, R? Particularly preferred as 1 are a hydrogen atom and an alkyl group. Examples of the substituent include a hydroxyl group, a sulfo group, a carboxyl group, a halogen atom, a nitro group, and an amino group.

(Compound example) -1 N→C1hCHgOH) x -2 HtNCHtCHtOH -3 NH→CHtCHtOH)z -4 H CJ+sN (CIIgCICIIiOH)g-5 -6 -7 V-8 -10 (HOCHiCflg)rNcHtcH*5OtcHs
-1m2 NH-(CHtCOOH) t ■-12 HOOC[tCHtCRCOOH NH□ ■-13 1m21Nc old CHtSOtNHz ■-14 -15 HtN-C-4CI! OH)! ■ 6 HOCH, CHCOOH NH2 ■-17 ■-18 ■-19 -20 General formula () In the formula, X represents a trivalent atomic group necessary to complete the condensed ring, R1 and RZ are alkylene groups, arylene group,
Represents an alkenylene group or an aralkylene group.

Here, R1 and yt may be the same or different.

Among general formulas (Vl), particularly preferred ones are general formulas (V
1-a) and (Vl-b).

In the formula, x1 represents N or >cn.

R1 and Rt are defined in the same manner as in general formula (Vl), and 1 R represents the same group as R1 and R1, or -CHtC-.

- During the formation (Vl-a), xl is preferably )N. ill, ll+! , R1 preferably has 6 or less carbon atoms, more preferably 3 or less carbon atoms, and most preferably 2 carbon atoms.

R1, R1, and R3 are preferably an alkylene group or an arylene group, and most preferably an alkylene group.

In the formula, R1 and RZ are defined in the same manner as in general formula (Vl).

In the general formula (Vl-b), the number of carbon atoms in R and RZ is preferably 6 or less. R1,91 is preferably an alkylene group or an arylene group, and most preferably an alkylene group.

Among the compounds of general formulas (Vl-a) and (Vl-b), the compound represented by -formation (■-a) is particularly preferred.

Vl-1 Vl-2 Vl-3 Vl-4 Vl-5 H Vl-6 Vl-7 Vl-8 Vl-9 1-10 ■-1m2 r-12 r-13 ■-14 1-15 Vl-16 1 -17 1-18 The organic preservatives mentioned above can be obtained as commercially available products.
The bottom can also be formed by the method described in No. 74 or the like.

The color developer and color developer replenisher used in the present invention contain a known aromatic primary amine color developing agent. Preferred examples are P-phenylenediamine derivatives, representative examples of which are shown below, but are not limited thereto.

D-IN, N-diethyl-p-phenylenediamine D-22-amino-5-diethylaminotoluene D-32-amino-5-(N-ethyl-N-laurylamino)toluene D-44-(N-ethyl -N-(β-hydroxyethyl)aξno]aniline D-52-methyl-4-[N-ethyl-N-(β-hydroxyethyl)aξno]aniline D-64-amino-3-methyl- N=ethyl-N-(β
(Methanesulfonamide) Ethyltwoaniline D-7N-(2-amino-5-diethylaminophenylethyl)methanesulfonamide D-88,N-dimethyl-P-phenylenediamine D-94-amino-3-methyl-N- Ethyl-N-methoxyethylaniline D-104-amino-3-methyl-N-ethyl-N-β
-Ethoxyethylaniline D-1m24-acuno-3-methyl-N=ethyl-N-
β-ethoxyethylaniline Among the above-mentioned -phenylenecyan derivatives, 4-amino-3-methyl-N-ethyl-N-(β-(
methanesulfonamide) ethyl-aniline (exemplary compound D-6) and 2-methyl-4-[N-ethyl-N-
(β-hydroxyethyl)aniline (exemplified compound D-5).

Further, these p-phenylenediamine derivatives may be salts such as sulfate, hydrochloride, sulfite, p-toluenesulfonate, etc. The amount of the aromatic-grade amine developing agent used is 1 m2 of color developer. preferably about 0.1 to about 2
0g, more preferably from about 0.5g to about 15g.

The concentration during color developer replenishment is preferably 1.2 to 3 times the concentration in the color developer.

In the color developer and color developer replenisher according to the present invention, the compounds represented by the following formations (B-1) and (B-1m2) are used, since the effects of the present invention can be better exhibited.
More preferably used.

-Formation (Bi) (III General formula (B-n) In the formula, RI4, Ls, R1& and R1? are each a hydrogen atom, a halogen atom, a sulfonic acid group, an alkyl group having 1 to 7 carbon atoms, -OR+* , -GOOR+w,
Rls, R+drop, R*a and R□ each represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. However, when Rls represents 0 or a hydrogen atom, Ro represents a halogen atom, a sulfonic acid group , an alkyl group having 1 to 7 carbon atoms, -OR+s, -COOR+q, the above R+a,
The alkyl groups represented by Rls s R+h and R include those having substituents, such as methyl group, ethyl group, 1
so-propyl group, n-propyl group, t-butyl group, n
-butyl group, hydroxymethyl group, hydroxyethyl group, methylcarboxylic acid group, benzyl group, etc., and Rls, R1? % Rz.

The alkyl group represented by R□ has the same meaning as above, and further includes an octyl group.

Examples of the phenyl group represented by R14, Ls5RIG and R1'l include a phenyl group, a 2-hydroxyphenyl group, and a 4-aminophenyl group.

Typical specific examples of the chelating agent of the present invention are listed below, but the invention is not limited thereto.

(Bi-1) 4-isopropyl-1,2-dihydroxybenzene (B-1-2) 1,2-dihydroxybenzene-3,5-disulfonic acid (B-1-3) 1.2,3-trihydroxy Benzene-5-carboxylic acid (B-1-4) 1.2.3-trihydroxybenzene-5-carboxymethyl ester (B-1-5) 1.2.3-1-lyhydroxybenzene-5-carboxy -n-butyl ester (B-1-6) 5-t-butyl-1°2°3 trihydroxybenzene (B-1-7) l.

2-Dihydroxybenzene-3゜4゜-trisulfonic acid (B-■-1) 2゜3-dihydroxynaphthalene-6-sulfonic acid (B-1m2-2) 3゜8-trihydroxynaphthalene-6-sulfonic acid ( B-If-3) 2゜3-dihydroxynaphthalene-6 carboxylic acid (B-It-4) 2゜dihydroxy-8 isopropyl-naphthalene (B-u-5) 2゜3-dihydroxy-8-chloro-naphthalene- 6-sulfonic acid Among the above compounds, compounds particularly preferably used in the present invention include 1,2-dihydroxybenzene-3,
Examples include 5-disulfonic acid, and it can also be used as alkali metal salts such as sodium salts and potassium salts. (Specific exemplary compound (B1-2)).

In the present invention, the general formula (B-1) and (B-I[
) is 5 to 1 compound per 12 color developing solutions.
It can be used in a range of 5g, preferably 15~
It is desirable to use 10g, more preferably in the range of 251m2g to 7g.

The color developer used in the present invention preferably has a pH of 9
-12, more preferably 9-1 m2.0, and the color developer replenisher is 0.1-1.5 m2.
It is preferable to design it high.

The color developer and color developer replenisher may contain other known developer component compounds. For example, in order to maintain the above pH, various buffering agents may be used. 5) 2.3-dihydroxy-8-chloro-naphthalene-6-
Among the above sulfonic acid compounds, compounds particularly preferably used in the present invention include 1,2-dihydroxybenzene-3,
Examples include 5-disulfonic acid, and it can also be used as alkali metal salts such as sodium salts and potassium salts. (Specific exemplary compound (B-1-2)).

In the present invention, the general formulas (B-1) and (B-1m
2) The compound shown in
Can be used in a range of 15g, preferably 15g
It is desirable to use the amount in the range of 10 g to 10 g, more preferably 25 g to 7 g.

The color developer used in the present invention preferably has a pH of 9
-12, more preferably 9-1 m2.0, and the color developer replenisher is 0.1-1.5 m2.
It is preferable to design it high.

The color developer and color developer replenisher may contain other known developer component compounds.6 For example, in order to maintain the above pH, it is preferable to use various buffers. Sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate,
Sodium tetraborate (borax), potassium tetraborate, 0
-Sodium hydroxybenzoate (sodium salicylate)% O-Potassium hydroxybenzoate, 5-sulfo-
Examples include sodium 2-hydroxybenzoate (sodium 5-sulfosalicylate) and potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate).

The amount of the buffer added to the color developer is 0.1 mol/1
It is preferably 0.1 mol/l to 0.1 mol/l or more.
Particularly preferred is 4 mol/l.

In addition, various caloric acid agents can be used in the color developer as agents for preventing precipitation of calcium and magnesium, or for improving the stability of the color developer.

Specific examples are shown below, but the invention is not limited to these. Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenedianetetraacetic acid, triethylenetetraminehexaacetic acid, nitriloN,N,N-1-lis(methylenephosphonic acid),
Ethylenediamine-N.

N, N, N'-tetrakis (methylenephosphonic acid)
, 1,3-diamino-2-propatoltetraacetic acid, transcyclohexanediaminetetraacetic acid, nitrilotripropionic acid, 1,2-diaminopropanetetraacetic acid, hydroxyethyliminodiacetic acid, glycol ether diaminotetraacetic acid, hydroxyethylenediaminetriacetic acid , ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1, 2゜4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N,M-bis(2-hydroxybenzyl)ethylenediamine-N,N-diamine acetic acid,
Catechol 3,4.6-trisulfonic acid, Catechol-
3,5-disulfonic acid, 5-sulfosalicylic acid, 4-sulfosalicylic acid.

These chelating agents are preferably ethylenediaminetetraacetic acid, ethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, 1,3-cyanobanoltetraacetic acid, ethylenecyamine-N, N, N',
N'-tetrakis (methylenephosphonic acid) and hydroxyethyliminodiacetic acid are good.

Two or more of these chelating agents may be used in combination, if necessary.

The amount of these chelating agents added may be sufficient to sequester metal ions in the color developer. For example, II
The amount is about 0.1 to 10 g per liter.

Any development accelerator can be added to the color developer if necessary.

As a development accelerator, Japanese Patent Publication No. 37-16088 and No. 3
No. 7-5987, No. 3B-7826, No. 44-123
No. 80, No. 45-9019 and U.S. Patent No. 3,813
．． 247, etc., p-phenylenediamine compounds shown in JP-A-52-49829 and JP-A-50-15554, JP-A-Sho 50
-137726, Japanese Patent Publication No. 44-30074, Japanese Patent Publication No. 56-156826 and Japanese Patent Publication No. 52-43429, etc., U.S. Patent No. 2,61
p described in No. 0.122 and No. 4,1m29,462
-Agonobenols, U.S. Patent No. 2.494.903
No. 3, No. 128.182, No. 4.230.796, No. 3,253,919, Special Publication No. 41-1m2431
No. 2,482,546, U.S. Pat. No. 2,596.
Amine compounds described in Japanese Patent Publication No. 37-16088 and Japanese Patent Publication No. 42-25
No. 201, U.S. Patent No. 3.128.183, Special Publication No. 4
Polyalkylene oxides shown in 1-1m2431, 42-23883, U.S. Patent No. 3,532,501, etc., 1-phenyl-3-pyrazolidones, hydrazines, meso-ionic compounds, ionic compounds, indazoles , etc. can be added as necessary.

In the present invention, any antifoggant such as chlorine ion or bromide ion can be added as required. As antifoggants, alkali metal halides such as potassium iodide and organic antifoggants can be used. Examples of organic antifoggants include benzotriazole, 6-nidrobenziξdazole, 5-nitroisoindazole, and 5-nitroisoindazole.
Representative examples include nitrogen-containing heterocyclic compounds such as methylbenzotriazole, 5-nitrobenzotriazole, 5-chlorobenzotriazole, 2-thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine. It can be given as follows.

The color developer used in the present invention preferably contains a fluorescent brightener.
Diamino-2,2'-disulfostilbene compounds are preferred, the amount added is 0 to Log/Il, preferably 0.1
~6 g/j! It is.

The above buffering agents, anti-settling agents, chelating agents, development accelerators,
It is preferable that antifoggants, fluorescent brighteners, and the like be added to the color developer replenisher in an amount of 1.2 to 3 times the amount of the color developer tank solution.

The processing time of the color developer of the present invention is 10 seconds to 120 seconds,
Preferably, the processing time is 20 seconds to 60 seconds from the viewpoint of rapidity and processing stability, and the processing temperature is 33 to 60 seconds.
45°C, preferably 35-40°C.

Furthermore, the color developer of the present invention has relatively superior performance in its liquid opening ratio (air contact area (e)/liquid box (d)) than combinations other than those of the present invention under any conditions. From the viewpoint of the stability of the developer, the opening ratio of the solution should be O~0.1.
cm-' is preferred. In continuous processing, the range of O,OOlcm-' to 0.05c+s-' is preferred from a practical standpoint, and more preferably 0.002CI-' to 0.03
CI-'.

The aperture ratio of the color developer replenishment tank is preferably smaller, particularly preferably 0 to 0.01 cm-'.

- If hydroxylamine or the like is used as a preservative in a, even if the aperture ratio of the color developer is reduced,
It is widely known that decomposition occurs due to heat or trace metals. However, in the color developer of the present invention,
These decompositions are extremely small, and the color developer can be sufficiently put to practical use even when the color developer is stored or used for a long period of time. Therefore, in this case, the smaller the liquid aperture ratio is, the more preferable it is, and the most preferable is 0 to 0.002 CI.

In the present invention, desilvering treatment is performed after color development. The desilvering step generally consists of a bleaching step and a fixing step, but it is particularly preferable that they are carried out simultaneously.

The bleach or bleach-fix solutions used in the present invention may contain bromides (e.g., potassium bromide, sodium bromide, ammonium bromide), or chlorides (e.g., potassium chloride, sodium chloride, ammonium chloride), or iodides. (eg, ammonium iodide).

If necessary, it has pH buffering capacity for boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, etc. 1!1! The above inorganic acids, organic acids, alkali metal or ammonium salts thereof, or corrosion inhibitors such as ammonium nitrate and guanidine can be added.

The fixing agent used in the bleach-fixing solution or fixing solution according to the present invention is a known fixing agent, namely sodium thiosulfate,
Thiosulfates such as ammonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate; thioether compounds such as ethylene bisthioglycolic acid and 3,6-cythia-1,8-octanediol; Halogenation 1! These are solubilizing agents, and these can be used alone or in combination of two or more. Further, a special bleach-fixing solution consisting of a combination of a fixing agent and a large amount of a halide such as potassium iodide as described in JP-A-55-155354 can also be used. In the present invention, thiosulfate,
Particularly preferred is the use of ammonium thiosulfate, 1ff
The amount of fixing agent per i is preferably 0.3 to 2 mol, more preferably 0.5 to 1.0 mol.

The p)IeI range of the bleach-fix solution or fixing solution in the present invention is preferably 3 to 8, and particularly preferably 4 to 7.If the pH is lower than this, the desilvering property is improved, but the deterioration of the solution and the cyanide Leukization of pigments is promoted. On the other hand, if pi is higher than this, desilvering is delayed and staining is more likely to occur.

In order to adjust the pH, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, bicarbonate, ammonia, caustic potash, caustic soda, sodium carbonate, potassium carbonate, etc. can be added as necessary.

Further, the bleach-fix solution may contain various other optical brighteners, antifoaming agents, surfactants, and organic solvents such as polyvinylpyrrolidone and methanol.

The bleach-fix solution and fixer solution used in the present invention contain sulfites (e.g., sodium sulfite, potassium sulfite,
ammonium sulfite, etc.), bisulfites (e.g. ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.), metabisulfites (e.g. potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.) > Contains sulfite ion-releasing compounds such as
The content is preferably 2 to 0.50 mol/l, more preferably 0.04 to 0.40 mol/l! , is.

Particularly preferred is the addition of ammonium sulfite.

Sulfites are commonly added as preservatives, but other preservatives include ascorbic acid, carbonyl bisulfite adducts,
Sulfinic acids, carbonyl compounds, sulfinic acids, etc. may be added.

Furthermore, buffering agents, optical brighteners, chelating agents, antifungal agents, etc. may be added as necessary.

The bleach-fix solution of the present invention has a processing time of 10 seconds to 120 seconds, preferably 20 seconds to 60 seconds. Also, the replenishment amount is 1m of photosensitive material.
30M1-250m per 2, preferably 40Id-15
Generally speaking, an increase in staining and poor desilvering tend to occur as the replenishment amount decreases, but according to the present invention, such problems do not occur and the replenishment amount of the bleach-fix solution is reduced. can be reduced.

In the silver halide color photographic light-sensitive material of the present invention, after desilvering treatment such as fixing or bleach-fixing, washing and/or stabilizing steps are generally reduced.

The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (the number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set over a wide range. this house,
The relationship between the number of flushing tanks and the amount of water in the multi-stage countercurrent system is described in the Journal of the Society op Mausillane.
Picture and Television Engineers (J
our own of the 5ociety of
Motion Picture and Television
ion Engineers) No. 641', p. 2
48-253 (May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria will breed, and the generated suspended matter will adhere to the photosensitive material. In the processing of the color photosensitive material of the present invention, as a solution to such problems, the method for reducing calcium and magnesium described in Japanese Patent Application No. 131631/1988 can be used very effectively. can. In addition, chlorine-based disinfectants such as isothiazolone compounds, cyabendazole, chlorinated sodium isocyanurate, and other benzotriazoles described in JP-A No. 57-8542, "Chemistry of Antibacterial and Antifungal Agents" by Hiroshi Horiguchi It is also possible to use the disinfectants described in ``Microorganism Sterilization, Disinfection, and Anti-Mold Techniques'', a complete collection of sanitary techniques, and ``Encyclopedia of Anti-Bacterial and Anti-Mold Agents'' edited by the Japanese Society of Anti-Bacterial and Anti-Mold.

The pH of the washing water in the processing of the photosensitive material of the present invention is 4 to 9.
and preferably 5 to 8. The washing water temperature and washing time can also be set variously depending on the characteristics of the photosensitive material, its use, etc., but generally it is 20 seconds to 2 minutes at 15 to 45°C, preferably 25 to 45°C.
A range of 30 seconds to 1 minute and 30 seconds at 0°C is selected.

Even in such short-time water washing, according to the present invention, 5
Good photographic properties can be obtained without an increase in stain.

Furthermore, the photosensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water. In such stabilization treatment, Japanese Patent Application Laid-open Nos. 57-8543 and 58-1
No. 4834, No. 59-184343, No. 60-220
No. 345, No. 60-238832, No. 60-2397
The known methods described in No. 84, No. 60-239749, No. 61-4054, No. 61-1m28749, etc.
All can be used. In particular, a stabilizing bath containing 1-hydroxyethylidene-1,1-diphosphonic acid, 5-chloro-2-methyl-4-isothiazolin-3one, a bismuth compound, an ammonium compound, etc. is preferably used.

Further, following the water washing process, a further stabilization process may be performed, such as a stabilizing bath containing formalin and a surfactant, which is used as a final bath for color photosensitive materials for photography. .

The processing time of the present invention is defined as the time from when the photosensitive material comes into contact with the color developer until it exits the final bath (generally water washing or stabilization bath).
The effects of the present invention can be significantly exhibited in a rapid treatment process in which the processing time is 30 seconds or less, preferably 3 minutes or less.

Next, details of the silver halide color photographic material used in the present invention will be explained.

The silver halide emulsion of the present invention consists essentially of silver chloride.

Here, "substantially" means that the content of silver chloride based on the total amount of halogenated roots is 95 mol% or more, more preferably 98 mol% or more. From the viewpoint of rapidity, the higher the silver chloride content, the more preferable it is, and the high silver chloride of the present invention may also contain a small amount of silver bromide or silver iodide. This increases the amount of light absorption in terms of photosensitivity, strengthens the adsorption of spectral sensitizing dyes,
Alternatively, it may have many useful benefits, such as weakening the desensitization caused by spectral sensitizing dyes.

The amount of coated silver in the silver halide emulsion of the present invention is preferably 0.8 g/- or less, more preferably 0.75 g/-.
is" or less. 0.3 g/bo or more. The amount of coated silver is 0°8
g/l or less is very preferable from the viewpoint of rapidity.

The silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention may have different phases inside and on the surface, may have a multiphase structure such as a bonded structure, or may have a uniform grain structure as a whole. You may precept from phase to phase, or they may be mixed.

Silver halide grains in photographic emulsions include those with regular crystal shapes such as cubes, octahedrons, and tetradecahedrons, those with variable speed crystals such as spherical and plate shapes, and twin planes. may have crystal defects, or a composite form thereof.

The grain size of the silver halide may be fine grains of about 0.2 Gron or less, or large grains with a projected area diameter of up to about 10 microns, and may be a polydisperse emulsion or a monodisperse emulsion.

Silver halide photographic emulsions that can be used in the present invention include, for example, Research Disclosure (RD), Sou 17643
(December 1978), pp. 22-23, 1. Emulsion manufacturing (
Emulsion preparation and
It can be adjusted using the method described in ``Ttypes'', etc.

U.S. Patent Nos. 3,574,628 and 3,655,39
Monodisperse emulsions such as those described in No. 4 and British Patent No. 1,413,748 are also preferred.

Tabular grains having aspect ratios of about 5 or more can also be used in the present invention. Tabular grains are described by Gutoff, Photographic Science and Engineering.
ence and Engineering), No. 14
Vol. 248-257 (1970); U.S. Patent No. 4,
No. 434,226, No. 4,414.310, No. 4,4
33,048, 4,439.520, and British Patent No. 2.1m22.157.

The crystal structure may be --like, the inside and outside may have different halogen compositions, it may be a layered structure, or silver halides with different compositions may be joined by epitaxial bonding. It may also be bonded with a compound other than silver halide, such as silver rhodan or lead oxide.

Further, the silver halide emulsion which may contain a mixture of grains of various crystal forms is usually used which has been subjected to physical ripening, chemical ripening and spectral sensitization. Additives used in such processes are Research Disclosure N1m
27643 and Nα18716,
The relevant sections are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the relevant descriptions are shown in the table below.

RD764 RD 7 1 Chemical sensitizer page 23 Page 648 Right column 2 Sensitivity enhancer Same as above 4 Brightener Page 24 Anti-stain agent Dye image stabilizer Hard film binder Plasticizer, lubricant Page 25 Right column 25 page 26 Page 26 Page 27, page 650, left to right column, page 651, left column, same as above, page 650, right column 13 Static prevention, page 27, same as above agent When the present invention is applied to a color light-sensitive material, the color light-sensitive material is prepared by the oxidation of an aromatic amine color developer. Yellow couplers, magenta couplers, and cyan couplers, which produce yellow, magenta, and cyan colors respectively when coupled with the body, are commonly used.

In the present invention, as cyan coupler, magenta coupler and yellow coupler, the following general colors (C-1),
(C-1m2), (M-I), (M-■) and (Y)
It is preferable to use one shown in the following from the viewpoint of processing stability.

General color (C-1) H Y' General color (C-1m2-) lJ General color (Ml) General color (M-u) General color (Y) In general color (C-1) and (C-1m2) , R1
, R2 and R4 represent a substituted or unsubstituted aliphatic, aromatic or heterocyclic group, R1, Rs and R& represent a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group or an acylamino group, and R1 is e may represent a group of nonmetallic atoms that together with Rt form a nitrogen-containing 5- or 6-membered ring.
el and Y2 represent a hydrogen atom or a group that can be separated during a coupling reaction with an oxidized developing agent; n represents 0 or 1;

1-5 in the general color (C-n) is preferably an aliphatic group, such as methoxy group, ethyl group, propyl group, butyl group, pentadecyl group, tert-butyl group, cyclohexyl group, cyclohexyl group. Examples thereof include a methyl group, a phenylthiomethoxymethyl group, a dodecyloxyphphenylthiomethyl group, a butaneamitomethyl group, and a methoxymethyl group.

A preferred example 1 of the cyan coupler represented by the general color (C-1) or (C-1m2) is as follows.

In general color (C-1), R1 is preferably an aryl group,
A heterocyclic group, such as a nor\logen atom, an alkyl group, an alkoxy group, an aryloxy group, an acyfuramino group, an acyl group, a carbamoyl group, a sulfonado group, a sulfamoyl group, a sulfonyl group, a sulfaξdo group, an oxycarbonyl group, More preferably, it is an aryl group substituted with a cyano group).

In general color (C-1), when R and Rt do not form a ring, h is preferably a substituted or unsubstituted alkyl group or aryl group, particularly preferably t is a substituted aryloxy-substituted alkyl group, R.

is preferably a hydrogen atom.

In the general formula (C-It), R4 is preferably a substituted or unsubstituted alkyl group or aryl group, and particularly preferably a substituted aryloxy-substituted alkyl group.

In the general formula (C-1m2), preferable R2 has 2 carbon atoms.
It is a methyl group having a to 15 alkyl group and a substituent having 1 or more carbon atoms, and the substituent is preferably an arylthio group, an alkylthio group, an azilamino group, an aryloxy group, or an alkyloxy group.

In general formula (C-1m2), Rs is more preferably an alkyl group having 2 to 15 carbon atoms, and preferably 2 to 4 carbon atoms.
Particularly preferred is an alkyl group.

In the general formula (C-I[), R1 is preferably a hydrogen atom or a halogen atom, and chlorine atom and fluorine atom are particularly preferred. In the general formulas (c-B and (C-If), preferred Yl and Y2 are, respectively, These are a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, and a sulfonamide group.

In general formula (M-1), R? and R9 represents an aryl group, R6 represents a hydrogen atom, an aliphatic or aromatic acyl group, an aliphatic or aromatic sulfonyl group,
Y represents a hydrogen atom or a leaving group.

Aryl groups of R7 and R9 (preferably phenyl 1&
) are the same as the substituents allowed for substituent R2, and when there are two or more substituents, they may be the same or different, R. is preferably a hydrogen atom , an aliphatic acyl group or a sulfonyl group, and particularly preferably a hydrogen atom.

preferable! , is of the type that leaves off with either sulfur, oxygen or nitrogen atoms; for example, US Pat. No. 4.3
Particularly preferred are sulfur atom dissociative types such as those described in No. 51,897 and International Publication No. WO88104795.

- In the formula (M-1m2), Ro represents a hydrogen atom or a substituent, Y represents a hydrogen atom or M degrouping, and a halogen atom or a ruthio group is particularly preferred, Za,
Zb and Zc are methine, substituted methine, .N- or -
Nfl- is represented, one of the Za-Zb bond and the Zb-Zc bond is a double bond, and the other is a single bond. zb
- When the Zc bond is a carbon-carbon double bond, including when it is part of an aromatic ring, when it forms a dimer or more multimer with R1° or Y, and when Za, Zb or When Zc is a substituted methine, it includes the case where the substituted methine forms a dimer or more multimer.

Among the pyrazoloazole couplers represented by the general formula (M-If), Ijudashi (1), which is described in U.S. Pat. , 2-b) pyrazoles are preferred,
Pyrazolo (1
, 5-b)(1,2,4)triazoles are particularly preferred.

In addition, a branched alkyl group as described in JP-A No. 61-65245 is directly connected to the 2.3 or 6-position of the pyrazolotriazole ring to create a pyrazolotriazole coupler, which is described in JP-A No. 61-65246. pyrazoloazole couplers containing a sulfonamide group in the molecule, pyrazoloazole couplers having an alkoxyphenylsulfonamide ballast group as described in JP-A-61-147254, European Patent Publication No. 226, It is preferred to use pyrazolotriazole couplers having an alkoxy or aryloxy group at the 6-position, such as those described in No. 849 and No. 294,785.

In the general formula (Y), Ro represents a halogen atom, an alkoxy group, a trifluoromethyl group or an aryl group,
Lz represents a hydrogen atom, a halogen atom or an alkoxy group, A is -NHCORI3, -NIISOOR+x
, -5OJHR+s , -GOOR+3, -5OtN-
Rls14, where Ro and R14 are each an alkyl group,
e YS representing an aryl group or an acyl group represents a leaving group. The substituents for R1, R13, and H□ are the same as those allowed for Ro, and the leaving group V is preferably oxygen. It is a type in which either an atom or a nitrogen atom is released, and a nitrogen atom-eliminating type is particularly preferred.

General formula (C-1), (C-1m2), (M-I), (M
-1m2) and (Y) are listed below.

(C 1) 1 (C-2) I;1 (C-3) L1! (C-4) H (C-5) 1 (C-6) ShiE (C-7) (C-8) (C-9) (C-10) (C-1m2) (C-12) H (C-13) (C-14) (C-15) (C-16) (C-17) (C 18〉 (C-19) zns (C 20) (C-21) (C-22) (1m2; H.

(M-1) (M-2) (M-3) (M 4) (M-5) l (M-7) C■.

(Y-1) (Y-2) (Y 3) (Y-4) (Y-5) (Y 6) (Y-7) (Y-8) (Y-9) Above - Shape (Cl) The coupler represented by ~(Y) is usually present in the silver halide emulsion layer constituting the photosensitive layer in an amount of 0.1 to 1.0 mol per mol of halide 1i, preferably 0.
．． It is contained in an amount of 1 to 0.5 mol.

In the present invention, in order to add the coupler to the photosensitive layer, various known techniques can be applied.Usually, the coupler can be added by an oil-in-water dispersion method known as an oil protection method. After dissolving, it is emulsified and dispersed in an aqueous gelatin solution containing a surfactant. Alternatively, water or an aqueous gelatin solution may be added to a coupler solution containing a surfactant to form an oil-in-water droplet dispersion with phase inversion.

Alkali-soluble couplers can also be dispersed by the so-called Fischer dispersion method. From the coupler dispersion,
By methods such as distillation, noodle washing, or ultrafiltration,
After removing the low-boiling organic solvent, it may be mixed with the photographic emulsion.

As a dispersion medium for such couplers, the dielectric constant (25°C
)2~20, refractive index (25°C)! , 5 to 17 high boiling point organic solvents and/or water-insoluble polymer compounds are preferably used.

As the high boiling point m solvent, preferably the following general formula (A) ~
A high boiling point organic solvent represented by (E) is used. In particular, the general formulas (C-1), (C-If), (M-1), (
Particular preference is given to couplers represented by M-1m2) and (Y).

-Shape (A) u.

Wff-0-P=O ! Ago General formula (B) h, -Coo-In.

General formula (C) General formula (D) W+ Hz\/ General formula (E) wt-o-wt (In the formula, -1, -8 and H are respectively substituted or unsubstituted alkyl groups, cycloalkyl groups, alkenyl group,
Represents an aryl group or a heterocyclic group.

represents Hl, Okh or S-2, n is an integer from 1 to 5, and when n is 2 or more, -4 may be the same or different from each other, and in -form power (E), h and H8 may form a fused ring).

The high boiling point organic solvent that can be used in the present invention has a melting point of 100°C or less and a boiling point of 140°C or less, even in forms other than -form (A) or E).
Compounds that are immiscible with water at temperatures above ℃ and can be used as long as they are good solvents for couplers. The melting point of the high-boiling organic solvent is preferably 80°C or lower. The boiling point of the high boiling point organic solvent is preferably 160°C or higher, more preferably 170°C or higher.

For details on these high boiling point organic solvents, please refer to JP-A-62
-215272 Publication Specification, page 137, lower right column ~ 14
It is written in the upper right column of page 4.

Additionally, these couplers can be synthesized with loadable latentx polymers (
For example, the emulsion can be dispersed in an aqueous solution of a hydrophilic colloid by impregnating it with a polymer (eg, US Pat. No. 4,203,716) or by dissolving it in a water-insoluble but organic solvent-soluble polymer.

Preferably, the homopolymers or copolymers described on pages 12 to 30 of International Publication No. 1m2088100723 are used, and the use of acrylamide polymers is particularly preferred from the viewpoint of color image stabilization.

The light-sensitive material produced using the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, etc. as a color anti-capri agent.

Various anti-fading agents can be used in the photosensitive material of the present invention. That is, hydroquinones, 6
-Hydroxychromans, 5-hydroxycoumarans,
Spirochromans, p-alkoxyphenols, hindered phenols centered on bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines, and silylation and alkylation of the phenolic hydroxyl groups of these compounds. Typical examples include ether or ester derivatives. Further, metal complexes such as (bissalicylaldoximado)nickel complex and (bis-N,N-dialkyldithiocarbamado)nickel complex can also be used.

Specific examples of organic antifade agents are described in the following patent specifications:

Hydroquinones are disclosed in U.S. Patent No. 2,360,290;
No. 2,418,613, No. 2,700.453, No. 2.701.197, No. 2,728,659
No. 2.732.300, No. 2.735,76
No. 5, No. 3.982.944, No. 4,430,4
25, British Patent No. 1.363,921, U.S. Patent No. 2,710,801, U.S. Pat. U.S. Patent No. 3.432,30
No. 0, No. 3.573.050, No. 3.574.6
No. 27, No. 3,698,909, No. 3,764.
No. 337, JP-A No. 52-152225, spiroindanes are described in U.S. Patent No. 4,3 SO, SS9, and p-alkoxyphenols are disclosed in U.S. Pat. No. 2,735.765.
No. 2.066, British Patent No. 975, Japanese Patent Application No. 1983-1
No. 0539, JP-A-57-19765, etc., and hindered phenols are disclosed in U.S. Patent No. 3,100.455,
JP-A No. 52-72224, U.S. Patent No. 4.228.23
No. 5, JP-A No. 52-6623, etc., gallic acid derivatives, methylenedioxybenzenes, and ataphenols are disclosed in U.S. Pat.
No. 32,886, Special Publication No. 56-21m244, etc.
Hindered amines are disclosed in US Pat. No. 3,336,135, US Pat. No. 4,268,593, British Patent No.
No. 889, No. 1.354.313, No. 1,410
．． No. 846, Japanese Patent Publication No. 51-1420, Japanese Patent Publication No. 58-1
m24036, 59-53846, 59-
No. 78344, etc., and metal complexes are disclosed in U.S. Patent No. 4,050.
, No. 938, No. 4,241.155, British Patent No. 2
, 027, 731 (A), etc., respectively. The purpose of these compounds can be achieved by co-emulsifying them with a coupler and adding them to the photosensitive layer, usually in an amount of 5 to 100% by weight based on the corresponding color coupler. In order to prevent the cyan dye image from deteriorating due to heat and especially light, it is more effective to introduce an ultraviolet absorber into the cyan coloring layer and the layers on both sides adjacent to it.

As ultraviolet absorbers, benzotriazole compounds substituted with aryl groups (for example, U.S. Pat. No. 3,533,7
94), 4-thiazolidone compounds (e.g., U.S. Pat. No. 3,314,794, U.S. Pat. No. 3,352.
681), benzophenone compounds (e.g., those described in JP-A-46-2784), cinnamic acid ester compounds (e.g., as described in U.S. Pat. Nos. 3.705.805 and 3.707,395), ), butadiene compounds (as described in U.S. Pat. No. 4,045,229), or benzoxidol compounds (e.g., U.S. Pat. Nos. 3,406,070, 3,677,672, and 4). , 271, 30T) can be used. An ultraviolet-absorbing coupler (for example, an α-naphthol-based cyan dye-type power coupler), an ultraviolet-absorbing polymer, or the like may be used. These ultraviolet absorbers may be mordanted in specific layers.

Among these, benzotriazole compounds substituted with the aforementioned aryl group are preferred.

In addition, it is particularly preferable to use the following compounds together with the couplers described above, particularly in combination with pyrazoloazole couplers.

That is, a compound (F) that chemically bonds with the aromatic amine developing agent remaining after color development processing to produce a chemically inert and substantially colorless compound and/or an aroma remaining after color development processing. For example, in storage after processing, the compound (G) that chemically bonds with the oxidized form of a group amine color developing agent to produce a chemically inert and substantially colorless compound may be used simultaneously or singly. This is preferable in order to prevent staining and other side effects caused by the formation of coloring dyes due to the reaction between the color developing agent or its oxidized product remaining in the film and the coupler.

A preferred compound (F) has a second-order reaction rate constant Kt (in trioctyl phosphate at 80°C) with p-aningine of 1. Oj! /5ol-sec~l
X10-' I! /mol-sec. In addition, the second-order reaction rate constant is based on JP-A-63-
It can be measured by the method described in No. 158545.

If K8 is larger than this range, the compound itself becomes unstable and may react with gelatin or water and decompose. On the other hand, if N is smaller than this range, the reaction with the remaining aromatic amine developing agent will be slow, and as a result, side effects of the remaining aromatic amine developing agent may not be prevented.

A more preferable compound (F) can be represented by the following form (Fl) or (FIG).

General formula (Fl) R + - (A) - - represents 1 or 0.

A represents a group that reacts with an aromatic amine developer to form a chemical bond, X represents a group that reacts with an aromatic amine developer and leaves, B represents a hydrogen atom, an aliphatic group, an aromatic group group, heterocyclic group, acyl group, or sulfonyl group,
Y represents a group that promotes the addition of an aromatic agonist developing agent to the compound of general formula (Fil), where R,
and X, Y, and R2 or B may be bonded to each other to form a cyclic structure.

Among the methods of chemically bonding with the residual aromatic amine developing agent, the typical ones are substitution reaction and addition reaction.

For specific examples of compounds represented by general formulas (FT) and (Fff), see JP-A-63-158545 and JP-A-62-158545.
283338, European Patent Publication No. 298321, European Patent Publication No. 27
Those described in specifications such as No. 7589 are preferred.

On the other hand, more preferable compounds (G) that chemically bond with the oxidized aromatic amine developing agent remaining after color development processing to produce a chemically inert and colorless compound are as follows: CI).

General formula (Gl) -Z In the formula, R represents an aliphatic group, an aromatic group, or a heterocyclic group, and Z is a nucleophilic group or a nucleophilic group that is decomposed in a photosensitive material to release a nucleophilic group. A compound represented by the -form (Gl), which represents a group, has a Z value of Pearson's nucleophilicity "CHsl value (
R.G., Pearson, et al., J.
As.

Chew, Soc, Hammer, 319 (196B)
) is preferably 5 or more, or a group derived therefrom.

- For specific examples of compounds represented by the form GI, see European Patent Publication No. 255722 and Japanese Patent Application Laid-Open No. 1430-1983.
No. 48, No. 62-229145, patent application No. 63-136
No. 724, No. 62-214681, European Patent Publication 29
Those described in No. 8321, No. 277589, etc. are preferred.

Further, details of the combination of the above-mentioned compound (G) and compound (F) are described in European Patent Publication No. 277589.

The photosensitive material produced using the present invention contains a hydrophilic dye or a dye that becomes water-soluble through photographic processing as a filter dye in the hydrophilic colloid layer or for various purposes such as preventing irradiation or halation. You can leave it there. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes, hemioxonol dyes and merocyanine dyes are useful.

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

In the present invention, the gelatin may be either lime-treated or acid-treated. Details of the method for producing gelatin are described in The Macromolecular Chemistry of Gelatin, written by Arthur Vuis (Agademik Press, published in 1964).

As the support used in the present invention, transparent films such as cellulose nitrate film and polyethylene terephthalate, which are usually used in photographic light-sensitive materials, and reflective supports can be used. For the purpose of the present invention, reflective supports are used. is more preferable.

The "reflective support" used in the present invention is one that enhances the reflectivity and makes the dye image formed in the silver halide emulsion layer clearer. Includes those coated with a hydrophobic resin containing a dispersed light-reflecting substance such as titanium oxide, zinc oxide, calcium carbonate, and calcium sulfate, and those using a hydrophobic resin containing a dispersed light-reflecting substance as a support. For example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, transparent supports with a reflective layer or a reflective material, such as glass plates, polyester films such as polyethylene terephthalate, cellulose triacetate or cellulose nitrate, polyamide film, polycarbonate film,
Examples include polystyrene film and vinyl chloride resin.

As other reflective supports, supports having a specular reflective or second type diffuse reflective metal surface can be used. The metal surface has a spectral reflectance of 0.5 in the visible wavelength range.
The above is preferable, and it is also preferable to roughen the metal surface or use metal powder to make it diffusely reflective.The metal should be aluminum, tin, silver, magnesium, or an alloy thereof, and the surface should be rolled. It may be the surface of a metal plate, metal foil, or gold 11KI layer obtained by , vapor deposition, plating, or the like.

Among these, it is preferable to obtain the metal by vapor-depositing it on another substrate.It is preferable to provide a layer of water-resistant resin, especially a thermoplastic resin, on the metal surface. For details of such a support, which is preferably provided with an antistatic layer on the opposite side, see, for example, JP-A-61-210.
No. 346, No. 63-24247, No. 63-24251
No. 63-24255, etc.

These supports can be appropriately selected depending on the purpose of use.

As a light-reflecting substance, it is best to thoroughly knead a white pigment in the presence of a surfactant, and also coat the surface of the pigment particles with
It is preferable to use one treated with a tetrahydric alcohol.

The occupied area ratio (%) of white pigment fine particles per defined unit area is most typically calculated by dividing the observed area into adjacent unit areas of 6μ-×6μ- and projecting onto that unit area. It can be determined by measuring the occupied area ratio (%) (Ri) of the fine particles. The coefficient of variation of the occupied area ratio (%) can be determined by the ratio s/R of the standard deviation S of Rj to the average value (T) of Ri. The number of target unit areas (n) is preferably 6 or more, and therefore the coefficient of variation s/R can be determined by s/R.

In the present invention, the variation coefficient of the occupied area ratio (%) of pigment fine particles is preferably 0.15 or less, particularly 0.12 or less. If it is 0.08 or less, the dispersibility of the particles is substantially "uniform". It can be said that.

(Example) Examples of the present invention will be specifically shown below, but the present invention is not limited thereto.

Example-1 As shown below, a color developer replenisher was prepared, and the color developer replenisher had an aperture ratio of 0.0 IC1 m2-' and room temperature (25
C) for 30 days, and after the aging, the color development replenisher was observed for coloring, the presence or absence of tar-like contaminants, and the presence or absence of precipitates. The results are shown in Table 1.

Table j 2"I" Liquid water benzyl alcohol diethylene glycol additive 60〇 - See Table 1 See Table 1 0, 1g Potassium bromide triethanolamine Potassium carbonate preservative (DI-1m2) Fluorescent brightener ( WRITEX4B manufactured by Sumitomo Chemical) Refer to Table 1 13, (Ig 28.0゜7.0g 3.0g Add water and potassium hydroxide, 000m pH (25℃) 10.70 From the results shown in Table 1, this Only the color developer replenisher that does not contain the benzyl alcohol of the invention, contains the compound of -1m2 formula (r) or (rl), and contains bromide ions at the concentration of the invention has less liquid coloring and is tar-like. The generation of contaminants and precipitates was prevented, and good results were obtained.

When benzyl alcohol is contained in the color developer replenisher, the generation of colored tar-like contaminants in the solution is significant, and the object of the present invention cannot be achieved.

When the color developer replenisher does not contain benzyl alcohol, the generation of colored tar-like contaminants is improved;
-5 to 5 x 10-'mol/I! , if not contained, the occurrence of precipitates was significant and the object of the present invention could not be achieved.

Example 2 A multilayer color photographic paper having m layers as shown below was prepared on a paper support laminated on both sides with polyethylene. The coating solution was prepared as follows.

19.1 g of yellow coupler (Ext), 4.4 g of color image stabilizer (Cpcl-1) and color image stabilizer (Cp
d-7) Add and dissolve 27.2 cc of ethyl acetate and 8.2 g of solvent (Solv-1) to 0.7 g, and dissolve this solution in 8 cc of 10% sodium dodecylbenzenesulfonate.
The mixture was emulsified and dispersed in 185 cc of a 10% aqueous gelatin solution. On the other hand, silver chlorobromide emulsion (cubic, average grain size 0.8
A 3-nia mixture of 8μ and 0.70-(fl
I molar ratio) 0 The coefficient of variation of the particle size distribution is 0.08 and 0.
．． 10. Each emulsion contains 0.2 mol % of silver bromide locally on the grain surface), and the following blue-sensitive sensitizing dyes are added to each emulsion (2.0 x 10-' mol for large emulsions per ml mol). , and 2.5 for small emulsions, respectively.
A sample was prepared in which sulfur sensitization was performed after adding 10-' moles of X. The above-mentioned emulsified dispersion and this emulsion were mixed and dissolved to prepare a first coating solution having the following &1 m2 precept.

The coating solutions for the second to seventh layers were also prepared in the same manner as the coating solution for the first layer. l-oxy-3,5-dichloro-5-) riazine sodium salt was used as the gelatin hardening agent for each layer.

The following spectral sensitizing dyes were used in each layer.

Blue sensitive emulsion layer SO2θ 503H-N(CtHs)s (2.0XIO-' moles each for large size emulsions and 2.5X10-' moles each for small size emulsions per m2 mole of halide i) Green-sensitive emulsion layer (per mole of silver halide, 4.0 x 10-' moles for large size emulsions, 5.0 x 10-' moles for small size emulsions).
6X10-'mol> and (per m21 mol of halide, ?, 0X10-' mol for large size emulsions and 1.0XIQ-' mol for small size emulsions) red-sensitive emulsion layer (silver halide 0.9 x 10-' mol for large size emulsions and 1.1 x 10-' mol for small size emulsions). 2.6.times.10@-3 moles were added per mole of silver halide.

In addition, 1-(5-methylureidophenyl)=5-mercaptotetrazole was added in s per mole of silver halide to the blue-sensitive emulsion layer, green-sensitive emulsion layer, and red-sensitive emulsion layer.
, 5xio-'mol, ? , 7X10-'mol, 2.5X
10-'mol was added.

In addition, for the blue-sensitive emulsion layer and the green-sensitive emulsion layer, 4-hydroxy-6-methyl-1,3,3a,7-titrazaindene was added per mole of silver halide, respectively, at l×10−'
mol and 2X10-' mol were added.

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

and (layer structure) The composition of each layer is shown below. The numbers represent the coating amount (g/m''), and the silver halide emulsion represents the coating amount in terms of silver.

Support polyethylene laminate (the polyethylene on the first layer side contains a white pigment (TiOz) and a bluish dye (ulmarine)) No.-N (blue-sensitive layer) Said silver chlorobromide emulsion 0.30 Gelatin 1.86 Yellow Coupler (ExY) 0.82 Color image stabilizer (Cp
d-1) 0.19 solvent (Solv-
1) 0.35 color image stabilizer (C
plv-7) 0.06 Second layer (mixing prevention layer) Gelatin 0.99 Color mixing prevention agent (Cpd-5) 0.08 Solvent (S
olv-1) 0.16 solvent (
Solv-4) 0.08 Third layer (green sensitive layer) Silver chlorobromide emulsion (cubic, average grain size 0.551!m)
The coefficient of variation of the particle size distribution of a 1:3 mixture (Ag molar ratio) of 0.39 and 0.39 is 0. lO and 0.0
8. Each emulsion contained 0.8 mol% of HegBr locally on the grain surface) 0.12 Gelatin
1.24 magenta coupler (
T! xM) 0.20 color image stabilizer (Cpd
-2) 0.03 color image stabilizer (Cpd
-3) 0.15 color image stabilizer (Cpd
-4) 0.02 color image stabilizer (Cpd
-9) 0.02 solvent (Solv-2
) 0.40 Fourth layer (ultraviolet absorption layer) Gelatin 1.58 Ultraviolet absorber (UV-1) 0.47 Color mixing inhibitor (Cpd-5) 0.05 Solvent (S
olb-5) 0.24 Fifth layer (red sensitive layer) Silver chlorobromide emulsion (cubic, 1:4 mixture of one with an average grain size of 0.58 m and one with an average grain size of 0.45 m (Ag molar ratio) The coefficient of variation of particle size distribution is 0.09 and 0.1 m2
, each emulsion contained 0.6 mol% of AgBr locally on a part of the grain surface) 0.23 gelatin
1.34 cyan coupler (ExC
) 0.32 color image stabilizer (Cpd-6
) 0.17 color image stabilizer (Cpd-7
) 0.40 color image stabilizer (Cpd-8
) 0.04 Solvent (Solv-6)
0.15 Fifth layer (ultraviolet absorption layer) Gelatin ultraviolet absorber (υv-1) Color mixing inhibitor (Cpd-5) Solvent (Solv-5) Seventh l? ! (Protective layer) Gelatin polyvinyl alcohol scum (denaturation degree 17%) The above seven layers were applied per liter of liquid paraffin light-sensitive material.

(ExY) Yellow coupler 1.33 Lyle modified copolymer 0.17 0.03 Add 0.3g of (1-3), 0.53 0.16 0.02 0, l:l mixture with O8 ( Molar ratio) (ExM) Magenta coupler 1:1 mixture (molar ratio) (ExC) Cyan coupler α-ctns, C4H* and H mixture at a ratio of 2:4:4 by weight, respectively (Cpd-1) Color image stabilizer ( Cpd-2) Color image stabilizer (Cpd-3) Color image stabilizer (Cpd-4) Color image stabilizer (Cpd-5) Color mixture inhibitor H (Cpd-6) Color image stabilizer 2 = 4:4 Mixture (weight ratio) (Cpd-7) Color image stabilizer 1→Cl! -C elbow r CONHCJw (t) Average molecular weight 60.000 (Cpd-8) Color image stabilizer H (Cpd-9) Color image stabilizer (UV-1) 4 = 2:4 mixture of ultraviolet absorbers (weight ratio ) (Solv-1) Solvent (Solv-2) Solvent 2: ■Mixture (volume ratio) (Solv-4) Solvent (Solv-5) Solvent C00CsH+t (CIri1 COOCJ+t (Solv-6) Solvent Image of the above sample After exposure, continuous processing (running test) was carried out using an automatic paper processing machine using the following processing steps and processing composition until three times the tank capacity of the color developer was replenished.

The composition of the color developer was changed as shown in Table 3.

Color development 38℃ 45 seconds Bleach fixing 30-36°C 45 seconds Stable ■ 30-37°C 20 seconds Stable■　　30~37℃　20 seconds Stability 0 30-37°C 20 seconds Drying 70~85"C60 seconds Replenishment amount per 1rrf of 1photosensitive material See Table 3 20f 215m lOf 01 01 364 composition 101 (3-tank countercurrent force type for stable ■ → ■).

) The &I power of each treatment solution is as follows.

Color developer water 00I 1m2 Potassium chloride 3.1g Triethanol 10.0g Potassium carbonate 7g Preservative (m 1m2 - 50 ramol) Add 4-aminoaniline sulfate solution to 000Id pH (25°C> 10.05) Wadingho liquid (tank liquid and refill liquid are the same) water
40〇-Ammonium thiosulfate (70X) 100m Sodium sulfite 17g Ethylenediaminetetravinegar H
flc (III) ammonium
Add 55g ethylenediaminetetraacetic acid disodium glacial acetic acid water and pH (25°C) Chichi production (tank liquid and replenisher are the same) Formalin (372) Formalin-sulfite adduct 5g 5g 000td 5.40 0, 1g 0. 7g -one 2-methyl-4-isothiazolin-3-one cupric ammonium sulfate water (2B Add water to pH (25°C)) 0.02g 0.01g 0.005g 2.0d 000m 4.0 Above coated sample was processed at the start and end of running, and the minimum density difference of yellow (at N1 - at start) was measured, and the degree of contamination of the white background accompanying running was evaluated. The results are shown in Table 3.

Furthermore, at the end of the run, contamination of the rollers in the color development processing tank and clogging of the filter in the color development replenishment tank were observed, and the results are shown in Table 3.

From the results shown in Table 3, only when the color developer replenisher of the present invention is continuously processed at a replenishment amount of 100 d/n or more of the present invention, contamination of the white background of the photosensitive material after processing is significantly prevented; Good results were obtained without contaminating the rollers of the automatic processor or clogging the filter of the color replenishment tank.

If the color development replenishment amount is less than 100 ml per photosensitive material, the rollers are seriously contaminated and the filters in the color replenishment tank are also clogged, so that the object of the present invention cannot be achieved.

Example-3 Using the same coating sample as in Example-2, the overflow liquid of the color developer was supplemented with insufficient components as shown below.
A running test was conducted while reusing it as a color developer replenisher.

The treatment steps and treatment liquid composition are shown below.

Color development 38℃ 45 seconds 161H1m20f
fi bleach fixing 35℃ 45 seconds 215d
5Il rinse ■ 35℃ 30 seconds
5N rinse ■ 35℃ 30 seconds
5N rinse ■ 35℃ 30 seconds 364id
i Drying 80° C. 60 seconds Amount of replenishment per 1M of photosensitive material (rinsing was performed using a 3-tank countercurrent flow method from ■→■→■) The composition of each processing solution is as described above.

Gen J: "Drama 4 attack water 00d potassium bromide potassium chloride triethanolamine potassium carbonate Fluorescent brightener 01HIT [! X, 4B.

Preservative ■-1m2 0,015g 3.1g 10.0g 7g Sumira Chemical) 1.0g 5.0g Add water to 000d pH (25℃) 10.05 Bleach-fix solution, bleach-fix replenisher, rinse The liquid was the same as in Example-2.

As the replenisher for the color developer, the overflow solution of the color developer was reused as shown below.

color developing chemicals in the overflow solution of color developer;
Preservatives and optical brighteners were analyzed using liquid chromatography, and color developing agents, preservatives, and optical brighteners were each 7g/j! , 7g/j! , the insufficient amount was added to make it 2 g/l. Also, adjust the pH by adding potassium hydroxide and i.o.
, so, and used as a color developer replenisher.

The overflow liquid from the above operation is 5j! A running test was repeated each time the amount of color development was accumulated until the total amount of color development replenishment reached 401. During this period, the overflow liquid is reused, so the amount of waste color developer liquid becomes substantially zero.

Furthermore, when the amounts of bromide ions and I-3 in the regenerated solution were analyzed by fluorescent X-ray and liquid chromatography, they were 3 x 10-' mol/l and 0.08 g/l, respectively. It was confirmed that bromine ions and compound I-3 were not added to the color developer replenisher.

At the end of the running test conducted in this way, in the same manner as in Example-2, white background contamination after processing the coated sample, roller contamination in the color developing tank of the automatic processor, and filter holes in the color replenishment tank were detected. Observation of clogging revealed good results similar to those of N1m25 in Example-2.

(Effects of the Invention) The color developer replenisher of the present invention has excellent stability without causing liquid coloring, tar-like contaminants, or precipitates. In addition, even in color development using it, there is no replenishment trouble, no roller stains, and white background stains are excellent.

(3 others) hand Continued Supplementary Positive book October 1999

Claims (2)

[Claims] (1) A color developer replenisher containing an aromatic primary amine developing agent, containing substantially no benzyl alcohol and containing bromine ions of 3 x 10^-^5 to 5 x 10^-^
4 mol/l, and has the following general formula (I) or general formula (
A color developer replenisher composition containing at least one of the compounds represented by II). General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, A represents -SO_3M, -SO_4M, M represents a hydrogen atom or an alkali metal atom, and R represents a linear or branched alkyl group. represent. A and R may be substituted with any hydrogen atom of the naphthalene ring. Also, p is 1 to 3
q represents an integer from 0 to 6. General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ m and n represent integers from 4 to 18. (2) In a method of continuously processing a silver halide color photographic light-sensitive material using a color developer containing an aromatic primary amine developing agent, the silver halide color photographic light-sensitive material contains silver chloride. Contains at least one photosensitive emulsion containing high silver chloride grains with a ratio of 95 mol % or more, substantially no benzyl alcohol, and bromine ions of 3 x 10^
-^5 to 5 x 10^-^4 mol/l, and a color developer replenisher containing at least one compound represented by the following general formula (I) or general formula (II) is added to the silver halide. A method for processing a silver halide color photographic material, characterized in that 100 ml or more is replenished per 1 m^2 of the color photographic material. General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ In the formula, A represents -SO_3M, -SO_4M, and M represents a hydrogen atom or an alkali metal atom. R represents a straight chain or branched alkyl group. A and R may be substituted with any hydrogen atom of the naphthalene ring. Also, p is 1 to 3
q represents an integer from 0 to 6. General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ m and n represent integers from 4 to 18.