JPH0244345A - Method for processing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve the picture stability after processing the subject material and the desilverization of the material, and to make it possible to rapidly processing the material by incorporating at least one kind of a polymer coupler in the material, and processing the obtd. material with a specified processing solution. CONSTITUTION:At least one kind of the polymer coupler is incorporated in the photosensitive material, and the processing solution having bleaching ability contains a ferric salt of a 1,3-diaminopropane tetraacetic acid of >=0.2mol/l and has pH of a range of 2.5-5.5. The polymer coupler may be incorporated in any one layer of photographic constituting layers, preferably a photosensitive emulsion layer or its adjacent layer in an amount of 0.01-1.0g per 1m<2> of the photosensitive material. When the additional amount of the ferric salt of 1,3-diaminopropane tetraacetic acid is <0.2mol/l, the bleaching speed of the material rapidly slows down, and the stain of the material increases after processing it. Thus the sharpness of the material is improved, and the processing time of the material makes it possible to shorten, and the stability of a picture after processing the material is improved, and the faulty desilverization of the material is prevented.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for processing silver halide color light-sensitive materials containing polymer couplers.
The present invention relates to a rapid processing method for the photosensitive material, which has good post-processing image stability and desilvering properties.

(Prior Art) In recent years, silver halide color photographic materials, especially shadow-sensitive materials, have become extremely sensitive, such as ultra-high-sensitivity materials such as ISO 1600 films, and 110-sized cameras and disk cameras. There is a growing demand for photosensitive materials with high image quality and high sharpness that are suitable for such small format cameras.

As a technique to improve sharpness, attempts have been made to thin the emulsion film to reduce the blurring effect caused by light scattering. Kosho 45-4
No. 0155, No. 46-22513, JP-A-57-94
No. 752, No. 58-28745, No. 52-15063
No. 1 and No. 59-42543 have been proposed. It is certainly possible to reduce the thickness of the emulsion film with these polymer couplers, and the thinning improves sharpness to some extent.

On the other hand, in recent years in this industry, processing has become faster.

That is, there is a strong demand for shortening the time required for processing, and in particular, shortening the desilvering step, which occupies nearly half of the conventional processing time, is a major issue. Therefore, the desilvering process has been simplified, with two steps each for bleaching and fixing baths.
Improvements have been made in each of the cases in which the bleach-fixing bath containing a bleaching agent and a fixing agent is used in the lea process.

As a bleaching agent, a bleaching treatment method based on a ferric ion complex salt (for example, an aminopolycarboxylic acid ferric ion complex salt, etc., especially an ethylenediaminetetraacetic acid iron(III) complex salt) is used.

However, since ferric ion complex salts have a relatively small oxidizing power and a bleaching blade is insufficient, products using this as a bleaching agent are, for example, low-sensitivity silver halide color photographs based on silver chlorobromide emulsions. If the material is bleached or bleach-fixed, it is possible to achieve the desired purpose, but it is possible to achieve the desired purpose if the material is bleached or bleach-fixed. When processing silver color photographic materials, especially color reversal photographic materials and color negative photographic materials that use high-silver emulsions, the bleaching effect may be insufficient and desilvering may fail, or the bleaching may fail. It has the disadvantage of requiring a long time.

In color light-sensitive materials, sensitizing dyes are generally used for the purpose of color sensitization. In particular, when tabular grains with high silver or high aspect ratio are used with the aim of achieving high sensitivity, there is a problem that the sensitizing dye adsorbed on the silver halide surface inhibits the bleaching of the silver produced during development of the silver halide. arise.

Persulfates are known as bleaching agents other than ferric ion complex salts, and persulfates are usually used as a bleach solution by adding chloride. However, a disadvantage of bleaching solutions using persulfates is that they have a weaker bleaching edge than ferric ion complexes and take a significantly longer time to bleach.

In general, bleaching agents that are not polluting or corrosive to equipment are associated with weak bleaching blades, and therefore bleaching agents with weak bleaching blades, especially bleach solutions or bleach-fix solutions using ferric ion complexes or persulfates. It is desired to increase the bleaching capacity of.

In contrast, Research Disclosure 24023
(April 1984), JP-A No. 60-230653, etc., describe treatment methods that use two or more of various aminopolycarboxylic acid ferric salts in combination, but these methods are also insufficient. It has not yet reached the point where it exhibits a significant bleaching promoting effect.

(Problems to be Solved by the Invention) The first object of the present invention is to process a silver halide photosensitive material with excellent sharpness and strong film strength in a short time.
Second, the photosensitive material should be processed to provide excellent image stability after processing, and third, it should prevent defective desilvering of the photosensitive material.

(Means for Solving the Problems) These objects of the present invention have been achieved by the following method for processing a sensitive material.

A method of processing an imagewise exposed silver halide color photographic light-sensitive material with a processing solution having bleaching ability after color development, wherein the silver halide color photographic light-sensitive material contains at least one polymer coupler and has the bleaching ability. The treatment solution containing 1,3-diaminopropanetetraacetic acid ferric salt has a concentration of 0.
A method for processing a silver halide color photographic light-sensitive material, characterized in that it contains 2 mol/β or more and has a pH in the range of 2.5 to 5.5.

The mechanism by which photosensitive materials containing polymer couplers have better desilvering properties and less fluctuation in density after processing than photosensitive materials containing ordinary couplers is not clear, but so far we have considered the following. ing.

The reason why the desilvering property is good is that the film thickness of the sensitive material can be made thin by using a polymer coupler, and the diffusion of the processing solution into the film and the diffusion of waste products from the film are fast, and the stain after processing is small. This is probably due to the fact that there is little residual or uptake of processing solution components such as developing agents into the film.

The polymer coupler of the present invention will be described in detail below.

The polymer coupler used in the present invention has the following general formula (
At least one ethylene group derived from a coupler monomer represented by CI) and having a repeating unit represented by the general formula (C1l) or having no ability to oxidatively couple with an aromatic-grade amine developer. Preferably, it is a copolymer with one or more non-color-forming monomers containing. Two or more types of coupler monomers may be polymerized at the same time.

General formula (CI) General formula (Cll In the formula, R1 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a chlorine atom, and Ll represents -CON- (R2 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms) or a substituted alkyl group having 1 to 6 carbon atoms), -COO--NHCO-1-
0CO- independently represents hydrogen, hydroxyl, halodane atom, or substituted or unsubstituted alkyl, alkoxy, acyloxy or aryloxy -N-It'
-(R5 has the same meaning as above, R6 has 1 carbon number),
R2 represents a linking group connecting Ll and Q, and i is 0 or 1
, j represents 0 or l, and Q represents a coupler residue that couples with an oxidized aromatic primary amine developer to form a dye.

Specifically, the linking group represented by R2 is 1+x'÷J'
-X''l-7-fJ2-x'+-4J2)←.

J , J , and J may be the same or different, −
co-1-3O--CON- (R5 is a hydrogen atom, an alkyl group (having 1 to 6 carbon atoms), a substituted alkyl group (having 1 to 6 carbon atoms)
), R5 -3O2N- (R5 is the same as above □□□, is the same as above,
R' represents a hydrogen atom, an alkyl group (having 1 to 6 carbon atoms), or a substituted alkyl group (having 1 to 6 carbon atoms). ), -〇-1-
5- R5R7 -N-C0-N- (R5R' has the same meaning as above), -N
CO- (R5 has the same meaning as above), and the like.

Xl and x 2 x 5 may be the same or different and represent an alkylene group, a substituted alkylene group, an arylene group, a substituted arylene group, an aralkylene group, or a substituted aralkylene group.

9, "and S represents O or 1.

In the general formula (C-1) above, X , X , X
may be the same or different, and have 1 to 10 carbon atoms
Represents an unsubstituted or substituted alkylene group, aralkylene group, or phenylene group, and the alkylene group may be linear or branched. Alkylev groups include, for example, methylene, methylmethylene, dimethylmethylene, dimethylene, trimethylene, tetramethylene, pencumethylene, hexamethylene, decylmethylene, and aralkylene groups include, for example, pennolidene and substituted or unsubstituted phenylene groups. For example, p-phenylene, m-phenylene, methylphenylene natocal.

Also, as a substituent of the alkylev group, aralkylene group or phenylene group represented by xI, X2,
Substituted alkyl group, alkoxy group, substituted alkoxy group, -
A group represented by NHCOR8 (R8 is alkyl, lRm
Furkyl, phenyl, fLi [phenyl, aralkyl,
(represents substituted aralkyl), -NH3O2R8 (R8 has the same meaning as above), -3OR8 (R8 has the same meaning as above), -3
o2R8 (R8 has the same meaning as above), the represented group (-R9
RlG may be the same or different, and may be a hydrogen atom, alkyl, substituted alkyl, phenyl, substituted phenyl,
Examples include aralkyl (R10 has the same meaning as above), an amine group (which may be substituted with alkyl), a hydroxyl group, and a group that forms a hydroxyl group by hydrolysis. When there are two or more of these substituents, they may be the same or different.

Examples of substituents for the above-mentioned substituted alkyl group, substituted alkoxy group, substituted phenyl group, and substituted aralkyl group include hydroxyl group, nitro group, alkoxy group having 1 to about 4 carbon atoms, -N
H3O2R8 (R8 has the same meaning as above), -tJHcOR8
A group represented by (R8 has the same meaning as above), a group represented by the general formula (Cp-
3) (same meaning as above), -3o2R8 (R8 has the same meaning as above), -C
Examples thereof include OR8 (R8 has the same meaning as above), a no-logon atom, a cyano group, an amino group (which may be substituted with an alkyl group), and the like.

Q is R51 of the following general formulas (cp-1) to (Cp-9)
Any part of R57, Z, ~Z3 and Y represents a group bonded to general formula (CI) or (C1l).

General formula (Cp-1) General formula (,CJ)-4) General formula (Cp-2) General formula (Cp-5) General formula (Cp-8) General formula (Cp-6) General formula (Cp-9 ) H General formula (Cp-7) H Next, R51- of the general formulas (Cp-1) to (CP-9)
R57, 42m5 and pK will be explained.

In the formula, Rs+ represents an aliphatic group, aromatic group, alkoxy group, or heterocyclic group, and R52 and Rss each represent an aromatic group or a heterocyclic group.

In the formula, the aliphatic group represented by R5 preferably has 1 to 22 carbon atoms, is substituted or unsubstituted, is linear or cyclic,
It may be either. Preferred substituents for aliphatic groups include alkoxy groups, aryloxy groups, amino groups, acylamino groups, etc., and these may themselves have further substituents (・).Aliphatic groups useful as R51 Specific examples of group groups are as follows: isobutyl group, isobutyl group, jerk-butyl group, inamyl group, Lert-amyl group, 1,1-dimethylbutyl group,
■.

neat methylhexyl group, 1. l-diethylhexyl group, dodecyl group, hexadecyl group, octadecyl group, /chlorohexyl group, 2-methoxyino70vir group, 2-phenoxyinoprobyl group, 2-p-jerL-butylphenoxyinoprobyl group, α-amino Isoprobyl group,
These include an α-(diethylamino)inglovir group, an α-(succinimide)inglovir group, an α-(7talimido)inglovir group, an α-(benzenesulfonamide)inglovir group, and the like.

When R51, R52 or R53 represents an aromatic group (especially a phenyl group), the aromatic group may be substituted.

Aromatic groups such as phenyl groups include alkyl groups having 32 or less carbon atoms, alkenyl groups, alkoxy groups, alkoxycarbonyl groups, alkoxycarbonylamino groups, aliphatic amide groups,
It may be substituted with an alkyl sulfamoyl group, an alkyl sulfonamide group, an alkyl ureido group, an alkyl substituted saxonimide group, etc. In this case, the alkyl group may have an aromatic group such as phenylene interposed in its chain. Phenyl group also includes aryloxy group, aryloxycarvinyl group,
Arylcarbamoyl Tj, 7') - has an amide group, arylsulfamoyl group, arylsulfonamide group,
It may be substituted with an aryl ureido group, etc., and the aryl group portion of these substituents further has a total number of carbon atoms of 1 to 2.
2 may be substituted with one or more alkyl groups.

The phenyl group represented by It, R, or R5 can also be an amine group, a hydroxyl group, or a hydroxyl group, including those substituted with a lower alkyl group having 1 to 6 carbon atoms. It may be substituted with a xyl group, a sulfo group, a nitro group, a cyano group, a thiocyano group, or a halodane atom.

Further, R54, R5□ or R55 may represent a substituent in which a phenyl group is fused with another ring, such as a naphthyl group, a quinolyl group, an inquinolyl group, a chromanyl group, a chromanyl group, a tetrahydronaphthyl group, etc. These substituents may themselves have further substituents.

When R5 represents an alkoxy group, the alkyl portion represents a straight or branched alkyl group having 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms, an alknyl group, a cyclic alkyl group, or a cyclic alkenyl group; It may be substituted with a halodane atom, an aryl group, an alkoxy group, etc.

When R51, R5□ or R53 represents a heterocyclic group,
Each of the halogen ring groups is bonded to the carbon atom of the carp-7-menyl group of the acyl group in alpha-acylacetamide or the nitrogen atom of the amide group through one of the carbon atoms forming the ring. Such heterocycles include thiophene, furan, biran, pyrrole, etc. Examples include lazole, pyridine, pyrazine, virimicin, pyritazine, indolizine, imidazole, thiazole, oxazole, trianone, theanoano/oxanone, and the like. These may further have a substituent on the ring.

In the general formula (Cp-3), R55 has 1 to 3 carbon atoms.
2, preferably 1 to 22 linear or branched alkyl groups (e.g. methyl, inclovir, L-butyl, hexyl, dodecyl, etc.), alkenyl groups (e.g. allyl group, etc.), cyclic alkyl groups (e.g. evacyclointi) aralkyl group (e.g., benzyl, β-phenylethyl group, etc.), a cyclic alkyl group (e.g., t-hacyclointenyl, cyclohexenyl group, etc.);・Rogon atom, nitro group, cyano group, aryl group, alkoxy group, aryloxy group, carboxyl group, arylthiocarbonyl group, arylthiocarbonyl group, alkoxycarvinyl group, aryloxyhydromenyl group, sulfo group, sulfamoyl group group, carbamoyl group, acylamino group, noacylamino group, ureido group, urethane group, thiourethane group,
Sulfo/amide group, heterocyclic group, arylsulfonyl group,
Alkylsulfonyl group, arylthio group, alkylthio group, alkylami 7 group, dialkylamino group, anilino group, N-arylanilino group, N-alkylanilino group, -N-acylanilino group, hydroxyl group, mercapto group, etc. KR55 may represent an aryl group (for example, a phenyl group, an α- or β-naphthyl group, etc.).

The aryl group may have one or more substituents, such as an alkyl group, an alkenyl group, a cyclic alkyl group, an aralkyl group, a cyclic alkenyl group, a halogen atom,
Nitro group, cyano group, aryl group, alkoxy group, aryloxy group, carboxyl group, alkoxycarvinyl group, arylthiocarbonyl group, sulfo group, sulfamoyl group, carbamoyl group, acylamino group, siafuramino group, ureido group, urethane group, sulfonamide group,
Heteromeric Ijj group, arylsulfonyl group, alkylsulfonyl group, arylthio group, alkylthio group, alkylamino group, dialkylamino group, anilino group, N-alkylanilino group, N-arylanilino group, N-acylanilino group, hydroxyl group etc. may be included.

Furthermore, R55 is a heterocyclic group (for example, a 5- or 6-membered heterocyclic ring containing a nitrogen atom, an oxygen atom, or a sulfur atom as a hetero atom, a fused heterocyclic group, such as a pyridyl group, a quinolyl group, a furyl group, a benzothiazolyl group, oxacylyl group, imidazolyl group, naphthoxacylyl group, etc.), heterocyclic group, aliphatic or aromatic acyl group, alkylsulfonyl group, arylsulfonyl group, alkylcarbamoyl group substituted with the substituents listed for the above-mentioned aryl group. ,
It may be an arylcarbamoyl group, an alkylthiocarbamoyl group or an arylthiocarbamoyl group.

In the formula, R54 is a hydrogen atom, 1 to 32, preferably 1 to 22, linear or branched alkyl, alknyl, cyclic alkyl, aralkyl, cyclic alkenyl group (these groups have the substituents listed for R55 above) ), aryl groups and heterocyclic groups (which may have the substituents listed above for R55), alkoxycarbunyl groups (e.g. methoxycarbinyl, ethoxycarvinyl, stear'noroxycarbinyl), (vinyl group, etc.), aryloxycarbonyl group (e.g., phenoxycarbinyl group, naphthoxycarbinyl group, etc.), aralkyloxycarbinyl group (e.g., benzyloxycarbinyl group, etc.)
, alkoxy groups (e.g., methoxy, ethoxy, hegetadecyloxy, etc.), aryloxy groups (e.g., phenoxy, tolyloxy, etc.), alkylthio groups (e.g., ethylthio, dronlthio, etc.), arylthio groups (e.g., phenylthio group, α-naphthylthio group, etc.), carboxyl group, acylamino group (e.g. acetylamino group, 3-C(2,4-amylquenoxy)acetamido]benzamide group, etc.), noacylamino group, N-alkylacylamino group (for example, N-methylcropionamide group, etc.), N-arylacylamino group (for example, N-phenylacetamide group, etc.), ureido group (
(e.g., ureido group, N-arylureido group, N-alkylureido group, etc.), urethane group, thio9-rethane group, arylamino group (e.g., phenylamino group, N-methylanilino group, sophenylamino group, N-acetylanilino group, etc.) group, 2-chloro-5-tetrarcanamideanili7 group, etc.), alkylamine group (e.g. n-butylamino group,
methylamino group, cycloxylamino group, etc.), cycloamino group (e.g. Biyritz group, pyrolituno group, etc.), heterocyclic amino group (e.g. 4-pyrinolamino group, 2-benzoxasilylamino group, etc.), arylcarbinyl group ( For example, methyl carbinyl group, etc.), aryl carbinyl group (for example, evaphenyl carbonyl group, etc.), sulfo/amide group (for example, alkyl sulfonamide group, arylsulfonamide group, etc.), carbamoyl group (for example, ethyl carbamoyl group, dimethyl carbamoyl group) , N-methyl-phenylcarbamoyl group, N-phenylcarbamoyl group), sulfamoyl group (e.g. N-alkylsulfamoyl group, N,N-dialkylsulfamoyl group, N-
71J-Rusulfamoyl group, N-alkyl-N-arylsulfamoyl group, N,N-noarylsulfamoyl group, etc.), cyan group, hydroxyl group, and sulfo group.

In the formula, R56 represents a hydrogen atom or a linear or branched alkyl group having 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms, an alkenyl group, a cyclic alkyl group, an aralkyl group, or a cyclic alkenyl group, and these represent the above-mentioned R55 may have the substituents listed above.

Furthermore, R56 may be an aryl group or a heterocyclic group, and these may have the substituents listed above for R55K.

R56 also represents a cyano group, an alkoxy group, an aryloxy group, a halogen atom, a carboxyl group, an alkylsulfonyl group, an aryloxycarbonyl group, an acyloxy group, a sulfo group, a sulfamoyl group, a carbamoyl group, an acylamino group, a sialamino group, a ureido group, Urethane group, sulfonamide group, arylsulfonyl group, alkylsulfonyl group, arylthio group, alkylthio group, alkylamino group, dialkylamino group, anilino group, N
-arylanilino group, N-alkylanilino group, N-
An acylanilino group or a hydroxyl group may be present.

R57, R58 and R59 each represent a group used in a typical 4-equivalent phenol or α-naphthol coupler, and specifically R57 is a hydrogen atom,
Examples include halogen atoms, alkoxycarbinylamino groups, aliphatic hydrocarbon residues, N-arylureido groups, acylamino groups, -0-R62 or -5-R62 (where R6□ is an aliphatic hydrocarbon residue), When two or more R57s exist in the same molecule, the two or more R57s may be different groups, and the aliphatic hydrocarbon residues include those having substituents. Also, two R57s may cooperate to form a nitrogen-containing heterocyclic nucleus (.

Further, when these substituents include an aryl group, the aryl group may have the substituents listed for R55 above.

R and R59 may include groups selected from aliphatic hydrocarbon residues, aryl groups and heterocyclic residues, or one of these may be a hydrogen atom; Also includes those having groups. Further, R58 and R59 may jointly form a nitrogen-containing heterocyclic nucleus.

The aliphatic hydrocarbon residues may be saturated or unsaturated (or unsaturated), and may be linear, branched, or cyclic. Preferably, alkyl groups (such as methyl, ethyl, 6 groups such as propyl, inpropyl, butyl, t-butyl, isobutyl, dodecyl, octadecyl, 7-clogyl, cyclohexyl, etc.),
It is an alkenyl group (for example, 6 groups such as allyl and octenyl).

Aryl groups include phenyl groups, naphthyl groups, etc.
Six typical heterocyclic residues include pyridinyl, quinolyl, thienyl, pyridyl, and imidazolyl. Substituents introduced into these aliphatic hydrocarbon residues, aryl groups, and heterocyclic residues include halogen atoms, nitro, hydroxyl, cal? Quizonopeanino, substituted amine,
Sulfo, alkyl, alkenyl, aryl, Dim, alkoxy, aryloxy, arylthio, arylazo, acylamino, carbamoyl, ester, acyl,
Examples include acyloxy, sulfonamide, sulfamoyl, sulfonyl, and morpholino.

t represents an integer of 1 to 4, m represents an integer of 1 to 3, and p represents an integer of 1 to 5.

Among the above Kabra residues, as the yellow Kabra residue, in the general formula (Cp-1), R51 is a t-butyl group or a substituted or unsubstituted aryl group, and R52 is a substituted or unsubstituted aryl group. , and the general formula (Cp -2)Ko(・te, R5□ and R5
It is preferred that 3 represents a substituted or unsubstituted 7-aryl group.

Preferred magenta coupler residues are of the general formula (C'
When R54 in p-3) represents an acylamino group, a ureido group or an arylamino group, and R55 represents a substituted aryl group, R5 in general formula (Cp-4) IC
4 represents an arylamino group, a ureido group, or an arylamino group, and R56 represents water or an atom, and in the bifurcated formulas (Cp-5) and (cp-6), R5
4 and R56 represent a linear or branched alkyl group, alkenyl group, cyclic alkyl group, aralkyl group, or cyclic alkenyl group.

Preferred cyan coupler residues have the general formula (Cp
-7) When R57 in K represents an acylamino group or ureido group at the 2nd position, an acylamino group or an alkyl group at the 5th position, and a hydrogen atom or a chlorine atom at the 6th position, and when R57 in the general formula (Cp-9) 5
hydrogen atom, acylamino group, sulfonamide group, alkoxycarvinyl group, R58 is a hydrogen atom, and K
This is the case where H2 represents a phenyl group, an alkyl group, an alkenyl group, a cyclic alkyl group, an aralkyl group, or a cyclic alkenyl group.

In the polymer Kagura used in the present invention, the general formula (
Z, -z3 and YK of Cp-1) to (Cp-9) will be explained in detail below.

2 represents a hydrogen atom, a halogen atom, a sulfo group, an acyloxy group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, or a dacrocyclic thio group, and these groups further include an aryl group (e.g. phenyl group), nitro group, hydroxyl group, cyan group, sulfo group,
Alcoquine groups (e.g. methoxy groups), aryloxy groups (e.g. phenoxy groups), acyloxy groups (e.g. acetoxy groups), acylamino groups (e.g. acetylamino groups), sulfonamide groups (e.g. methanesulfonamide groups), sulfamoyl groups (e.g. is a methylsulfamoyl group), a halogen atom (e.g. evaporative fluorine, chlorine, bromine, etc.),
It may be substituted with a substituent such as a carpyl group, a carbamoyl group (eg, methylcarbamoyl group), an alkoxycarvinyl group (eg, methoxycarbinyl group, etc.), a sulfonyl group (eg, methylsulfonyl group), etc.

Z2 and Y represent a leaving group bonded to the coupling position with a hydrogen atom, oxygen atom, nitrogen atom or sulfur atom, and z2 and Y are bonded to the coupling position with an oxygen atom, nitrogen atom or sulfur atom; (In the case of
Furthermore, in the case of a nitrogen atom, it also means a group containing the nitrogen atom that can form a 5- or 6-membered negative ring and serve as a leaving group (
For example, imidazolyl group, pyrazolyl group, doriagril group, tetrazolyl group, etc.).

The above-mentioned alkyl groups, aryl groups, and cyclic groups may have substituents. ethoxy group, etc.), aryloxy group (e.g., phenyloxy group, etc.), alkylcarbonyl group (e.g., methoxycarvinyl group, etc.), acylamino group (e.g., acetylamino group), carbamoyl group, alkylcarbamoyl group (e.g., methylcarbamoyl group, ethyl carbamoyl group (nato), noalkylcarbamoyl group (e.g. trimethylcarbamoyl group), arylcarbamoyl group (
Examples include evaphenylcarbamoyl group), alkylsulfonyl groups (e.g. methylsulfonyl group), arylcarbonyl groups (e.g. phenylsulfonyl group), alkylsulfone groups (e.g. methanesulfonamide group), arylsulfonamide groups (e.g. phenylsulfonamide group), sulfamoyl group, alkylsulfamoyl group (e.g. ethylsulfamoyl group), dialkylsulfamoyl group (e.g. dimethylsulfamoyl,!!'), alkylthio group (e.g. methylthio group), arylthio group , (for example, phenylthio group), cyano group, nitro group, and halokene atom (for example, fluorine, chlorine, bromine, etc.), and when there are two or more of these substituents, they may be the same or different.

Particularly preferred substituents include halo/atom, alkyl group, alkoxy group, alkoxycarbonyl group, and cyano group.

Preferred groups for z2 include groups that bond to the coupling site via a nitrogen atom or sulfur atom, and preferable groups for Y include groups that bond to the coupling site via a chlorine or oxygen atom, a nitrogen atom, or a sulfur atom. It is.

z3 is a hydrogen atom or the following general formula (R-1), (R-2)
, (R-3), or (R-4).

child, cardanic acid ester group, amino group, alkyl group, alkylthio group, alkoxy group, alkylsulfonyl group,
It represents an alkylsulfinyl group, a carboxylic acid group, a sulfonic acid group, an unsubstituted or substituted phenyl group, or a heterocycle, and these groups may be the same or different.

on, (R-1) R65 represents an optionally substituted aryl group or heterocyclic group.

W, in the formula, R64 and R65 are a hydrogen atom and a halogen atom, respectively, and 4
Represents a nonmetallic atom required to form a membered ring, 5-membered ring, or 6-membered ring.

Among the general formulas (R-4), (R-5
) to (R-7).

RR68 In the formula, R66 and R67 each represent a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or a humanmixyl group, and R68, R6, and "70 each represent a hydrogen atom, an alkyl group, an aryl group, In the aralkyl group or acyl group, W2 represents an oxygen or sulfur atom.

Typical coupler monomers are summarized in Table 6 below, but are not limited thereto.

Next, non-chromogenic ethylene-like monomers that do not couple with the oxidation products of aromatic-grade amine developing reagents include acrylic acid, α-chloroacrylic acid, α-alkylacrylic acid (e.g., acrylic acid, methacrylic acid, acids), and their esters or amides derived from acrylic acids (e.g., acrylamide, methacrylamide, t-
Butylacrylamide, 2-acrylamido-2-methylpropanesulfonic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, n-furobyl acrylate), igo-propyl acrylate, n-butyl acrylate, 1-butyl acrylate, n-butyl methacrylate, 2 -ethylhexyl acrylate, n-
hequinyl acrylate, n-octyl acrylate, lauryl acrylate, acetoacetoxyethyl methacrylate, glyc7dyl methacrylate and methylenebisacrylamide), vinyl esters (e.g. vinyl acetate, vinyl clopionate, and vinyl laurate), acrylonitrile, methacrylonitrinope aromatic vinyl compounds, such as styrene and its derivatives (
For example, potassium styrene sulfinate, sodium styrene sulfonate, etc.), vinyltoluene, divinylbenzene, vinylacetophenone), vinylidene chloride,
Examples include vinyl alkyl ethers (eg vinyl ethyl ether), maleic esters, N-vinyl-2-pyrrolidone, N-vinylpyridine, and 2- and 4-vinylpyridine. Particularly preferred are acrylic esters, methacrylic esters, acrylamides, methacrylamides, styrene and derivatives thereof. For example,
Butyl acrylate and methyl acrylate, n-butyl acrylate and styrene, methyl acrylate and t-butylacrylamide, ethyl acrylate and methacrylic acid, sodium 2-acrylamido-2-methylpronosulfonate and potassium styrene sulfinate, etc. can be used.

The polymer coupler used in the present invention may be water-soluble or water-insoluble.

The polymer coupler of the present invention may be prepared by taking out a lipophilic polymer coupler or telomer coupler made by polymerizing coupler monomers and then redissolving it in an organic solvent and dispersing it by emulsion, or by emulsion polymerization. Polymer coupler latexes and even layered polymer coupler latexes may be added directly to the gelatin halide emulsion. Alternatively, the removed hydrophilic polymer coupler may be redissolved in water or a water/water-miscible organic solvent and directly added to the gelatin silver halide emulsion.
.

The proportion of the coloring part in the polymer coupler is usually 5 to 5.
Although 80% by weight is desirable, from the viewpoint of color reproducibility, color development and stability, 20 to 70% by weight is particularly preferred. The molecule in this case! (contains 1 mole of coupler monomer, f? I
The number of grams) is approximately 250 to 4000, but is not limited to this.

The polymer Kagura latex is preferably added in an amount of 0.005 to 0.5 mol, preferably 0.01 to 0.05 mol, per mol of silver based on the coupler monomer.

Methods for synthesizing coupler polymers are broadly divided into 1) emulsion polymerization method, 11) seed polymerization method, and 111) solution polymerization method, each of which is 1) polymer coupler latex, it) M-structure polymer coupler latex, and i
ii) Lipophilic polymer couplers, telomer couplers and hydrophilic polymer couplers are obtained. The method of manufacturing these polymers and the method of adding them to emulsions are disclosed in 1) U.S. Pat. No. 4,080,211, 1t)
No. 44, 111) as described in U.S. Pat.

The compositions of polymer couplers synthesized according to these patents are shown in Tables 1 to 5.

Table 6 Specifications of coupler monophages used in the present invention (C-3) (C-7) ('C-8) (C-9) (C-4) (C-5) (C-6) ( C-10) (C-11) (C-12) CH2CH2SCH2COOH (C-13) (C-14) (C (C-19) (C-20) H (C-16) (C-17) (C -18) (M-2) CH2CH2CN H2CF3 (M-4) (M-5) (M (M-8) (M-1 (M-1 t (M-16) OCH5 (M-17) (M- 21 t (M t (M'-23) (M (M-19) (M-20) (M-24) (M-25) t t t (M (M-27) (M-28) (M -31) (M-32) (M-33) t CH3 (M-30) (M (M-35) t (M-36) H CH3 (M-37) CH3 (M-41 (M-42) (M-43) (M-38) (M-39) (M-40) (M-44) (y-i 2115υ H5 (y-2) (Y-3) (Y (Y-7) ( Y (Y-5) (Y-6) (Y-9) (Y-10) (Y-11) (Y-13) (Y-14) (Y-12) NHCOCH=CH2 NHCOCH=CH2 In the present invention Among these polymer couplers, preferably a magenta coupler is used, more preferably a 2-equivalent magenta polymer coupler, and even more preferably a 5-pyrazolone type 2-equivalent magenta polymer coupler with pyrazole elimination.

The polymer coupler of the present invention may be added to any of the photographic constituent layers, but is preferably added to the light-sensitive emulsion layer or a layer adjacent thereto, and the amount added is from 0.01 to 0.0g per layer.
More preferably, it is 0.05 to 0.5 g.

In the bleaching solution of the present invention, 1,3-diaminopropanetetraacetic acid ferric complex salt is used in an amount of 0.3-diaminopropanetetraacetic acid ferric complex salt per bleaching solution IC.
The amount is 2 mol or more, preferably 0.25 mol or more, particularly preferably 0.3 mol or more in terms of speeding up. however,
Excessive use will adversely inhibit the bleaching reaction, so 0.5 mol or less is preferable.
As the iron complex salt, salts such as ammonium, sodium, and potassium salts can be used, but ammonium salts are preferable because they cause the fastest bleaching. In addition, the above-mentioned 1,3-diaminopropanetetraacetic acid secondary
If the amount of iron complex salt is less than 0.2 mol, bleaching will be drastically delayed and the stain after treatment will increase.
The condition is that it contains mol or more.

Next, the pH of the bleaching solution of the present invention will be described.

1. pH containing 3-diaminopropanetetraacetic acid ferric complex salt
The bleaching solution No. 6 is known from the above-mentioned Japanese Patent Laid-Open No. 62-222252. Conventionally, the pH of a bleaching solution containing a ferric aminopolycarboxylic acid complex salt has been considered to be optimal at around pH 6 from the viewpoint of both ensuring a high bleaching speed and preventing poor recoloring of cyan dyes, and this has been widely practiced. That is, although lowering the pH improves the bleaching rate, it causes poor recoloring of the cyan dye, so the optimum balance has been set around pH 6.

On the other hand, the present invention has the characteristic that the effect is expressed by setting the pH of the bleaching solution to 5.5 or less, and also achieves rapid desilvering and complete restoration of the cyan dye, which was considered to be contradictory in the past. solve the problem. The pH of the bleaching solution of the present invention is 5.5 to 2.5, and the preferable range for exhibiting the effect is 5.5 to 2.5.
It is 0 to 3.0, more preferably 4.5 to 3.5. p
To adjust H to this range, organic acids such as acetic acid, citric acid, and malonic acid, and inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid can be used, but the acid dissociation index (pka) is 2.5 to 5. Acids in the range of No. 5 are preferred from the viewpoint of imparting buffering properties to the region of the present invention, in addition to the acetic acid, citric acid, and malonic acid, benzoic acid, formic acid, butyric acid, malic acid, tartaric acid, oxalic acid, propionic acid, and phthalic acid. Various organic acids can be mentioned. Among these, acetic acid is particularly preferred.

The amount of these acids to be used is preferably 0.1 to 2 moles, particularly preferably 0.5 to 1.5 moles, per 1 DEG C. of the bleaching solution.

It is preferable to add 1,3-diaminopropanetetraacetic acid to the bleaching solution in an amount slightly in excess of the amount required for complex formation with ferric ions, and the excess is usually in the range of 1 to 10%. preferable.

Further, the bleaching solution of the present invention can also contain aminopolycarboxylic acid ferric complex salts other than 1,3-diaminopropanetetraacetic acid ferric complex salts, and specifically, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, A ferric complex salt of cyclohexanediaminetetraacetic acid can be mentioned.

Various bleaching accelerators can be added to the bleaching solution of the present invention.

Such bleach accelerators are described, for example, in U.S. Pat. No. 3,893,858, German Pat.
, No. 812, British Patent No. 1.138.842, JP-A-53-95630, Research Disclosure No. 17129 (July 1978 issue). Compounds, thiazolidine derivatives described in JP-A No. 50-140129, thiourea derivatives described in U.S. Pat. No. 3,706,561, iodides described in JP-A-58-16235, German patents Polyethylene oxides described in specification No. 2.748,430, Japanese Patent Publication No. 1974-
Polyamine compounds described in Japanese Patent No. 8836 can be used. Particularly preferred is British Patent Tube 1,138.
Mercapto compounds such as those described in '842 are preferred.

In addition to the bleaching agent and the above-mentioned compounds, the bleaching solution constituting the present invention includes bromides such as potassium bromide, sodium bromide,
Rehalogenating agents such as ammonium bromide or chlorides such as potassium chloride, sodium chloride, ammonium chloride can be included. The concentration of rehalogenating agent is bleach solution 1
The amount is 0.1 to 5 mol, preferably 0.5 to 3 mol per °C.

Moreover, it is preferable to use ammonium nitrate as a metal corrosion inhibitor.

The replenishment amount of the bleaching solution of the present invention is 50 to 50 times per photosensitive material.
2000 rubs, preferably 100 rubs to tooowg.

In addition, during processing, the bleaching solution is aerated,
It is preferable to oxidize the 1,3-diaminopropanetetraacetic acid ferrous complex salt produced.

The photosensitive material after bleaching is then subjected to a fixing process.

As the fixing agent, thiosulfur salts such as sodium thiosulfate, ammonium thiosulfate, sodium ammonium thiosulfate, potassium thiosulfate, thiocyanates such as sodium thiocyanate, ammonium thiocyanate, potassium thiocyanate, thiourea, thioether, etc. may be used. Can be done.

Among them, it is preferable to use ammonium thiosulfate in an amount of 0.3 to 3 mol, preferably 0.3 to 3 mol, per 12 of the fixer.
It is 5 to 2 moles.

In addition, from the viewpoint of promoting fixation, the above-mentioned ammonium thiocyanate (rhodan ammonium), thiourea, thioether (
For example, it is also preferable to use 3,6-cythia-1,8-octanediol) in combination, and the amount of these compounds used in combination is generally about 0.1 mol to 0.1 mol per 12 of the fixer, but depending on the case By using 1 to 3 moles, the fixing promoting effect can be greatly enhanced.

The fixer contains sulfites as preservatives, such as sodium sulfite, potassium sulfite, ammonium sulfite, and
Hydroxylamine, hydrazine, bisulfite adducts of aldehyde compounds, such as acetaldehyde sodium bisulfite, can be included. Furthermore, various optical brighteners, antifoaming agents, surfactants, polyvinylpyrrolidone, organic solvents such as methanol, etc. can be contained, but in particular, as a preservative, Japanese Patent Application No. 60-28383
It is preferable to use the sulfinic acid compounds described in Specification No. 1.

The amount of fixer replenishment is 300w1 per photosensitive material.
3000d is preferred, more preferably 300m
1 to xooomfJ.

Furthermore, it is preferable to add various aminopolycarboxylic acids and organic phosphonic acids to the fixing solution of the present invention for the purpose of stabilizing the solution.

Regarding the total time of the desilvering step of the present invention, the effects of the water-sprinkling invention can be significantly obtained. The preferred time is 1 minute to 4 minutes, more preferably 1 minute 30 seconds to 3 minutes. Also, the processing temperature is 25
° to 50°C, preferably 35°C to 45°C. In a preferred temperature range, the desilvering rate is improved and the occurrence of staining after processing is effectively prevented.

In the desilvering step of the present invention, it is preferable that the stirring be as strong as possible in order to more effectively exhibit the effects of the present invention.

A specific method for strengthening stirring is disclosed in JP-A-62-18346.
No. 0, No. 62-183461, the method of impinging a jet of processing liquid on the emulsion surface of a photosensitive material, and the method of colliding a jet of a processing liquid on the emulsion surface of a photosensitive material, as described in JP-A No. 62-183-1.
No. 83461, a method of increasing the stirring effect using a rotating means, and further improving the stirring effect by moving the light-sensitive material while bringing the emulsion surface into contact with a wiper blade provided in the liquid to create turbulence on the emulsion surface. method, and a method of increasing the circulation flow rate of the entire treatment liquid. Such means for improving agitation is effective for all bleaching solutions, bleach-fixing solutions, and fixing solutions. It is believed that improved agitation speeds up the supply of bleach and fixing agent into the emulsion film, and as a result increases the removal rate.

Further, the agitation improvement means is more effective when a bleach accelerator is used, and can significantly increase the acceleration results and eliminate the fixing inhibiting effect caused by the bleach accelerator.

The automatic developing machine used in the present invention is JP-A-60-191
It is preferable to have the photosensitive material conveying means described in No. 257, No. 191258, and No. 191259. As described in JP-A No. 60-191257, such a conveying means can significantly reduce the carry-over of processing liquid from the front bath to the rear bath, and is highly effective in preventing the performance price of the processing liquid from increasing.
Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.

The effect of the present invention is remarkable when the total processing time is short,
Specifically, this effect is clearly exhibited when the total processing time is 8 minutes or less, and the difference from conventional processing methods becomes even more remarkable when the total processing time is 7 minutes or less. Therefore, in the present invention, the total treatment time is preferably 8 minutes or less, particularly 7 minutes or less.

The color developer used in the present invention contains a known aromatic primary amine color developing agent. Preferred examples are p-phenylenediamine derivatives, and one representative example is shown below, but the invention is 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)amino]aniline D-52-methyl-4-[N-ethyl-N-(β-hydroxyethyl)aminonoaniline D-64-amino-3-methyl-N-ethyl-N −[β
-(methanesulfonamido)ethyl]-aniline D-7N-(2-amino-5-diethylaminophenylethyl)methanesulfonamide D-8N, N-dimethyl-p-phenylenediamine D-94-amino-3-methyl- N-ethyl-N-methoxyethylaniline D-104-amino-3-methyl-N-ethyl-N-β
-Ethoxyethylaniline D-114-amino-3-methyl-N-ethyl-N-β
-Butoxyethylaniline Among the above p-fluorinated diamimino conductors, Exemplified Compound D-5 is particularly preferred.

Further, these p-phenylenediamine derivatives may be salts such as sulfate, hydrochloride, sulfite, p-toluenesulfonate, etc. The amount of the aromatic-grade amino developing agent used is per 142 ml of developer solution. Preferably about 0.1g to about 20g
, more preferably at a concentration of about 0.5 g to about 10 g.

In addition, sulfites such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite, potassium metasulfite, and carbonyl sulfite adducts are added to the color developer as preservatives as necessary. be able to.

The preferred amount added is 0.5 g to liter per 12 color developing solutions.
og, more preferably 1 g to 5 g.

In addition, as compounds that directly preserve the color developing agent, various hydroxylamines, Japanese Patent Application No. 61-18655
Hydroxamic acids described in No. 9, hydrazines and hydrazides described in No. 61-170756, and hydrazides described in No. 61-188
Phenols described in No. 742 and No. 61-203253, α-hydroxyketones and α-aminoketones described in No. 61-188741, and/or 6-A18
It is preferable to add various saccharides described in No. 0616, and in combination with the above compounds, Japanese Patent Application Nos. 61-147823, 61-166674, 61-165621,
Monoamines described in 61-164515, 61-170789, 61-168159, etc., 6I-173595, 61-164515, 6
Diamines described in No. 1-16562, No. 61-16
5621 and polyamines described in 61-169789, polyamines described in 61188619, nitroxy radicals described in 61-197760, alcohols described in 61-186561 and 61-197419, It is preferable to use the oximes described in No. 61-198987 and the tertiary amines described in No. 61-265149.

Other preservatives include various metals described in JP-A-57-44148 and JP-A-57-53749;
Salicylic acids described in No. 180588, JP-A-54-35
Alkanolamines described in No. 32, JP-A-56-94
No. 349, the polyethyleneimines described in U.S. Patent No. 3.
The aromatic polyhydroxy compound described in No. 746,544 and the like may be contained as necessary. Particularly preferred is the addition of an aromatic polyhydroxy compound.

The color developer used in the present invention preferably has a pH of 9
-12, more preferably 9-11.0, and the color developer may contain other known developer component compounds.

In order to maintain the above pH, it is preferable to use various buffers.

Specific examples of buffering agents include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, trisodium phosphate, dipotassium phosphate, sodium borate, potassium borate. , Sodium Tetraborate (Borax), Potassium Tetraborate, 0-
Sodium hydroxybenzoate (sodium salicylate), potassium 0-hydroxybenzoate, 5-sulfo-2
~Sodium hydroxybenzoate (sodium 5-sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate), and the like. However, the present invention is not limited to these compounds.

The amount of the buffer added to the color developer is preferably 0.1 mole/flood or more, particularly 0.1 mole/flood or more. 1 mole #2-0
．． Particularly preferred is 4 mol/β.

In addition, various chelating agents can be used in the color developer as an anti-settling agent for calcium or magnesium or to improve the stability of the color developer.

As the chelating agent, organic acid compounds are preferred, such as aminopolycarboxylic acids, organic phosphonic acids, and phosphonocarboxylic acids. Specific examples are shown below, but the invention is not limited to these.

Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N,N,N-trimethylenephosphonic acid, ethylenediamine-N.

N,N',N'-tetramethylenephosphonic acid, transcyclohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid, hydroxyethyliminodiacetic acid, glycol ether diaminetetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane- 1, 2,
4-) Ricarboxylic acid, l-hydroxyethylidene-1,
1-diphosphonic acid, N,N'-bis(2-hydroxybenzyl)ethylenediamine-N,N'-diacetic acid, and two or more of these chelating agents may be used in combination as necessary.

These chelating agents may be added in an amount sufficient to sequester metal ions in the color developer. For example 12
It is about 0.1g to 10g per serving.

Any development accelerator can be added to the color developer if necessary. However, the color developer of the present invention preferably does not substantially contain benzyl alcohol from the viewpoint of pollution, formulation properties, and prevention of color staining. Here, "substantially" means 2 ml per 12 of the developer. Hereinafter, it means preferably not containing at all.

Other development accelerators include Japanese Patent Publications No. 37-16088, No. 37-5987, No. 38-7826, No. 44-
No. 12380, No. 45-9019 and U.S. Patent No. 3,
813,247, etc., p-phinidine diamino compounds shown in JP-A-52-49829 and JP-A-50-15554, JP-A-50-137726, JP-B-Sho. 44- 30074, JP-A-56-156826 and JP-A-52-43429,
Quaternary ammonium salts represented by U.S. Patent No. 2,
No. 494,903, No. 3,128゜182, No. 4,2
No. 30,796, No. 3,253.919, Special Publication No. 1977
-11431, amine compounds described in U.S. Patent No. 2,482,546, U.S. Pat. Polyalkylene oxides as shown in U.S. Patent No. 3,128,183, Japanese Patent Publications No. 41-11431, No. 42-23883, and U.S. Patent No. 3,532,501, other l-phenyl-3-pyrazolidones, imidazole etc. can be added as necessary.

In the present invention, any antifoggant can be added if necessary. As antifoggants, alkali metal halides such as sodium chloride, potassium bromide, potassium iodide, and organic antifoggants can be used. As an organic antifoggant.

For example, benzotriazole, 6-nidropenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, Representative examples include nitrogen-containing heterocyclic compounds such as indazole, hydroxyazaindolizine, and adenine.

The color developer used in the present invention may contain an optical brightener. As the optical brightener, a 4,4'-diamino-2,2'-disulfostilbene compound is preferable, and the amount added is O to 5 g/β, preferably 0.1 g to 4 g/
! ! , is.

Further, various surfactants such as alkylsulfonic acid, ary-phosphonic acid, aliphatic carboxylic acid, and aromatic carboxylic acid may be added as necessary.

The processing temperature of the color developer of the present invention is 20 to 50°C, preferably 30 to 45°C. The treatment time is 20 seconds to 5 minutes, preferably 30 seconds to 3 minutes. Although it is preferable that the amount of replenishment is small, it is 100 to 1,500 pages, preferably 100 to 800 pages per rrr of photosensitive material. More preferably 1ooy
~400 prints.

Further, the color developing bath may be divided into two or more baths as necessary, and the color developing replenisher may be replenished from the first bath or the last bath, thereby shortening the developing time and reducing the amount of replenishment.

The processing method of the present invention can also be used for color reversal processing. In the present invention, the black and white developer used at this time is commonly known as a black and white first developer used for reversal processing of color photographic light-sensitive materials, or Those used for processing black and white photosensitive materials can be used. In addition, various well-known additives that are generally added to black and white developers can be included.

Typical additives include ■ - developing agents such as Hue and Ru-3-pyrazolidones, metol and hydroquinone, preservatives such as sulfite, and promoters consisting of alkalis such as sodium hydroxide, sodium carbonate, and potassium carbonate. agent,
Inorganic or organic inhibitors such as potassium bromide, 2-methylbenzimidazole, methylbenzthiazole, water softeners such as polyphosphates, and development inhibitors consisting of trace amounts of iodides and mercapto compounds. I can give it to you.

The processing method of the present invention comprises processing steps such as color development, bleaching, bleach-fixing, and fixing as described above. Here, after the bleach-fixing or fixing process, processing steps such as water washing and stabilization are generally performed, but after a bath with fixing ability, stabilization processing is performed without substantial water washing. A simple treatment method can also be used.

The rinsing water used in the rinsing step can contain known additives, if necessary. For example, water softeners such as inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid,
Disinfectants and fungicides (for example, intiazolone, organochlorine disinfectants, benzotriazole, etc.) that prevent the growth of various bacteria and algae, surfactants that prevent drying load and unevenness, and the like can be used. Or L, E
.

West, 'Water Quality Cr1
terta-, Phot, Sci.

and Eng,, vol, 9. No, 6. pa
Compounds described in ge344-359 (1965) and the like can also be used.

As the stabilizing solution used in the stabilization step, a processing solution that stabilizes the dye image is used. For example, a solution having a buffering capacity of pH 3 to 6, a solution containing aldehyde (for example, formalin), etc. can be used. can. The stabilizing liquid may contain ammonium compounds, metal compounds such as Bi and Aj2, optical brighteners, chelating agents (for example, l-hydroxyethylidene-1,l-diphosphonic acid), bactericides, fungicides, A hardening agent, a surfactant, etc. can be used.

In addition, the water washing step and the stabilization step are preferably performed using a multi-stage countercurrent method, and the number of stages is preferably 2 to 4. The replenishment amount is 1 to 50 times the amount brought in from the previous bath per unit area, preferably 2 to 30 times. times, more preferably 2 to 15 times.

The water used in these washing steps or stabilization steps includes tap water, as well as Ca
It is preferable to use water that has been deionized to have a Mg concentration of 5 mg/n or less, water that has been sterilized with halogen, an ultraviolet germicidal lamp, or the like.

In each of the above processing steps for photosensitive materials, when continuous processing is performed using an automatic processor, concentration of the processing solution due to evaporation may occur, especially when the processing amount is small or the opening area of the processing solution is large. becomes. In order to correct such concentration of the processing liquid, it is preferable to replenish an appropriate amount of water or correction liquid.

Further, the amount of waste liquid can be reduced by using a method in which the overflow liquid from the water washing step or the stabilization step flows into a pre-bath having a fixing ability.

The light-sensitive material of the present invention only needs to have at least one silver halide emulsion layer of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer on the support. There are no particular restrictions on the number or order of the emulsion layers and non-light-sensitive layers; a typical example is to create a plurality of silver halides with substantially the same color sensitivity but different sensitivity on the support. A silver halide photographic light-sensitive material having at least one light-sensitive layer consisting of an emulsion layer, the light-sensitive layer being a unit light-sensitive layer sensitive to any of blue light, green light, and red light. In a multilayer silver halide color photographic light-sensitive material, the unit photosensitive layers are generally arranged in the following order from the support: a red-sensitive layer, an edge-sensitive layer, and a blue-sensitive layer. However, depending on the purpose, the above-mentioned order of installation may be reversed, or a more convenient order may be adopted in which different photosensitive layers are placed within the same color-sensitive layer.

Non-photosensitive layers such as various intermediate layers may be provided between the silver halide photosensitive layers and between the uppermost layer and the lowermost layer.

The intermediate layer includes JP-A Nos. 61-43748 and 59-1.
No. 13438, No. 59-113440, No. 61-20
Coupler, DIR compound, etc. as described in No. 037 and No. 61-20038 may be included,
It may also contain a commonly used color mixing inhibitor.

A plurality of silver halide emulsion layers constituting each unit photosensitive layer are composed of a high-speed emulsion layer and a low-speed emulsion layer, as described in West German Patent No. 1,121,470 or British Patent No. 923,045. A two-layer structure can be preferably used9
Usually, it is preferable to arrange the layers so that the photosensitivity decreases toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. Also, JP-A-57-
No. 112751, No. 62-200350, No. 62-2
As described in Nos. 06541 and 62-206543, a low-sensitivity emulsion layer may be provided on the side far from the support, and a high-sensitivity emulsion layer may be provided on the side close to the support.

As a specific example, from the side farthest from the support, low sensitivity blue sensitive layer (BL) / high sensitivity blue sensitive layer (BH) / high sensitivity green sensitive layer (GH) / low sensitivity green sensitive layer (GL) / High-sensitivity red-sensitive layer (RH) / Low-sensitivity red-sensitive layer (RL), or BH/BL/GL/G H/RH/RL, or BH/BL/GH/GL/RL /RH, etc.

Further, as described in Japanese Patent Publication No. 55-34932, the blue-sensitive layer/G H/
They can also be arranged in the order of RH, /GL/RL. Alternatively, as described in JP-A-56-25738 and JP-A-62-63936, the blue-sensitive layer/GL/RL/GH/RH can be arranged in this order from the farthest side from the support. .

In addition, as described in Japanese Patent Publication No. 49-15495, the upper layer is a silver halide emulsion layer with the highest sensitivity, the middle layer is a silver halide emulsion layer with lower sensitivity, and the lower layer is more sensitive than the middle layer. An example is an arrangement consisting of three layers with different photosensitivity, in which a silver halide emulsion layer with a low density is disposed and the photosensitivity gradually decreases toward the support. Even when it is composed of three layers with different photosensitivity, as described in JP-A No. 59-202464,
In the same color-sensitive layer, medium-sensitivity emulsion layer/high-sensitivity emulsion layer/low-sensitivity emulsion layer may be arranged in this order from the side remote from the support.

As mentioned above, various layer structures and arrangements can be selected depending on the purpose of each photosensitive material.

The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide, containing about 30 mol% or less of silver iodide. . Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mole percent to about 25 mole percent silver iodide.

Silver halide grains in photographic emulsions include those with regular crystals such as cubes, octahedrons, and tetradecahedrons, those with irregular crystal shapes such as spherical and plate shapes, and those with 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 microns 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) No. 17643.
(December 1978), pp. 22-23, +1. Emulsion preparation
dtypes)”, and same No. 18716 (19
November 1979), 648 pages, Graphic "Physics and Chemistry of Photography", published by Paul Montell (P, Glafkid
es.

nihemic et Ph1sfque Pho
tographique, PauIMonte
1967), "Photographic Emulsion Chemistry" by Duffin
, Focal Press (G, F, Duffin)
.

Photographic Emulsion Che
mistry (Focal Press (1966+)
, “Manufacture and Coating of Photographic Emulsions” by Zelikman et al., published by Focal Press (V, L.

Making
and Coating Photographic E
mulsion, Focal Press, 196
It can be prepared using the method described in 4).

U.S. Patent No. 3,574,628, U.S. Patent No. 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 in Gutoff, Photographic Science and Engineering.
engineering)
, Vol. 14, pp. 248-257 (1970); U.S. Patent Nos. 4,434.226 and 4,414,310.
No. 4,433.048, No. 4,439,520 and British Patent No. 2,112,157.

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.

Also, mixtures of particles of various crystal forms may be used.

The silver halide emulsion used is usually one that has been subjected to physical ripening, chemical ripening, and spectral sensitization. The additives used in such processes are Research Disclosure No.
17643 and No. 18716, and the relevant parts 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.

1 Chemical sensitizer 2 Sensitivity enhancer 3 Spectral sensitizer, supersensitizer 4 Brightener j 5 Antifoggant and stabilizer 6 Light absorber, filter dye, RD17643 RD1871623 page 6
Page 48 right column Same as above, pages 23-24 Page 648 right column - Page 649 Right column Page 24 Pages 24-25 Page 649 Right column - Pages 25-26 Page 649 Right column - Page 650 Left column Ultraviolet absorber 7 Anti-stain agent 25 Page right column 650 pages left to right column 8
Dye image stabilizer page 25 9 Hardener page 26 page 651 left column 10
Binder, page 26 Same as above II Plasticizer, lubricant, page 27 Page 650, right column 12 Coating aid, pages 26-27 Page 650, right column Surfactant 13 Static, page 27 Same Top stop agent Also, for improving photographic performance with formaldehyde gas In order to prevent deterioration, US Patent No. 4,411.987 and US Pat.
It is preferable to add to the photosensitive material a compound that can be immobilized by reacting with formaldehyde, as described in No. 435,503.

Various color couplers can be used in the present invention, and specific examples thereof can be found in the above-mentioned Research Disclosure (
RD) No. 17643, ■-C to G are described here.

As a yellow coupler, for example, U.S. Patent No. 3.93
No. 3,501, No. 4,022,620, No. 4,3
No. 26,024, No. 4,401.752, No. 4.
No. 248,961, Japanese Patent Publication No. 5g-10739, British Patent No. 1,425°020, No. 1,476.760, U.S. Patent No. 3,973,968, No. 4,314,
No. 023, No. 4,511,649, European Patent No. 24
9.473A, etc. are preferred.

Among these, the benzoylacetanilide type is more preferable because it has a high ε and can be formed into a thin layer, thereby improving the desilvering property.

As magenta couplers, 5-pyrazolone and pyrazoloazole compounds are preferred, and US Pat.
No. 0,619, No. 4.351897, European Patent No. 7
No. 3,636, U.S. Patent No. 3,061,432, U.S. Patent No. 3,725,064, Research Disclosure No. 2422 (June 1984), JP-A-60-3
No. 3552, Research Disclosure No. 24
230 (June 1984), JP-A-60-43659
No. 61-72238, No. 60-35730, No. 55-118034, No. 60-185951, U.S. Patent No. 4,500,630, No. 4,540,654
No. 4,556,630, WO (PCT 881)
Particularly preferred are those described in No. 04795 and the like.

Cyan couplers include phenolic and naphthol couplers, and are disclosed in U.S. Pat. No. 4,052,212.
No. 4,146,396, No. 4,228,233
No. 4,296,200, No. 2,369,92
No. 9, No. 2.801.171, No. 2,772.1
No. 62, No. 2.895,826, No. 3,772,
No. 002, No. 3,758,308, No. 4.334
．． No. 011, No. 4,327,173, West German Patent Publication No. 3,329,729, European Patent Cylinder 121.365A
No. 249,453A, U.S. Patent No. 3,446,
No. 622, No. 4.333.999, No. 4,753
, No. 871, No. 4,451,559, No. 4,42
No. 7,767, No. 4,690,889, No. 4,2
No. 54.212, No. 4,296,199, Japanese Unexamined Patent Publication No. 1983
1-42658 and the like are preferred.

Colored couplers for correcting unnecessary absorption of coloring dyes are available in Research Disclosure No. 17643.
Section ■-G, U.S. Patent No. 4 163.670, Japanese Patent Publication No. 57-39413, U.S. Patent No. 4,004,929, No. 4.138゜258, British Patent No. 1,146,
The one described in No. 368 is preferred.

Couplers whose colored dyes have appropriate diffusivity include U.S. Patent No. 4,366.237 and British Patent No. 2,125.
, 570, European Patent No. 96,570, and German Patent Publication No. 3,234,533 are preferred.

Typical examples of polymerized dye-forming couplers are U.S. Pat.
No. 4,576.910, British Patent No. 2,102,
It is described in No. 173, etc.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. A DIR coupler releasing a development inhibitor is the aforementioned RD L 764.
3. ■Patents listed in items ~F, Japanese Patent Application Laid-Open No. 57-1519
No. 44, No. 57-154234, No. 60-18424
No. 8, No. 63-37346, U.S. Patent No. 4,248,9
The one described in No. 62 is preferred.

Couplers that release a nucleating agent or a development accelerator in the form of an image during development include British Patent No. 2,097.140;
No. 2,131,188, JP 59-157638
No. 59-170840 is preferred.

Other couplers that can be used in the photosensitive material of the present invention include competitive couplers described in U.S. Pat. No. 4,130,427, U.S. Pat. , DIR redox compound releasing couplers described in JP-A-60-185950, JP-A-62-24252, etc., DIR coupler-releasing coupler D
IR coupler releasing redox compound or DIR redox releasing redox compound, European Patent No. 173,30
No. 2A, R, D, No. 11449, No. 24241. Tokukai Showa 6
Examples include bleach accelerator-releasing couplers described in US Pat. No. 1-201247, ligand-releasing couplers described in U.S. Pat. It will be done.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods.

Examples of high boiling point solvents used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027 and the like.

Specific examples of high-boiling organic solvents with a boiling point of 175°C or higher at normal pressure used in the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, (decyl phthalate, bis(2,4-di-t-amylphenyl) phthalate, bis(2,4-di-t-amylphenyl) isophthalate, bis(l,1-diethylpropyl) phthalate, etc.), phosphoric acid or Phosphonic acid esters (trifel phosphate, tricresyl phosphate, 2-
ethylhexyldiphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexyl phenyl phosphonate, etc.), benzoic acid esters (2-ethylhexylbenzoate,
dodecyl benzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides (N, N-diethyl dodecanamide, N, N-diethyl lauryl amide,
N-tetradecylpyrrolidone, etc.), alcohols or phenols, (stearyl alcohol, 2.4
-di-tert-amylphenol, etc.), aliphatic carboxylic acid esters (bis(2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, instearyl lactate, trioctyl citrate, etc.), aniline derivatives (N, N -dibutyl-2-
butoxy-5-ter't-octylaniline, etc.),
Examples include hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.). Further, as the auxiliary solvent, an organic solvent having a boiling point of about 30°C or higher, preferably 50°C or higher and about 160°C or lower, can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate,
Examples include methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide, and the like.

Specific examples of latex dispersion processes, effects, and latex for impregnation include U.S. Pat. It is described in.

The present invention can be applied to various color photosensitive materials. Typical examples include color negative film for general use or movies, color reversal film for slides or television, color vapor, color positive film, and color reversal vapor.

Suitable supports that can be used in the present invention include, for example.

The aforementioned RD, No. 17643, page 28, and the same No.
, 18716, from the right column on page 647 to the left column on page 648.

In the light-sensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or less, and the film swelling rate Tλ is preferably 30 seconds or less.

The film thickness means the film thickness measured at 25° C. and 55% relative humidity (2 days), and the film swelling rate 734 can be measured according to a method known in the art. For example, Photographic Science and Engineering (P.
Ho, Sci, Eng,), Volume 19, No. 52,
It can be measured by using a swellometer (swelling membrane) of the type described on pages 124-129.

T% is the saturated film thickness, which is 90% of the maximum swelling film thickness reached when treated with a color developer at 30°C for 3 minutes and 15 seconds.
Defined as the time it takes to reach a film thickness of .

The membrane swelling rate T can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating.

Further, the swelling rate is preferably 150 to 400%. The swelling rate can be calculated from the maximum swollen film thickness under the above-mentioned conditions according to the following formula (maximum swollen film thickness - film thickness)/film thickness.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing. For this purpose, it is preferable to use various precursors of color developing agents. For example, U.S. Pat. No. 3,342,59
Indoaniline compound described in No. 7, No. 3,342,
No. 599, Research Disclosure 14,850
Schiff base-type compounds described in No. 15,159 and aldol compounds described in No. 13.924, U.S. Patent No. 3
, 719,492, JP-A-53-1
Examples include urethane compounds described in No. 35628.

The silver halide color light-sensitive material of the present invention may optionally contain various 1-phenyl-3
- Pyrazolidones may be incorporated. Typical compounds are JP-A-56-64339, JP-A-57-144547,
and No. 58-115438.

The various processing solutions used in the present invention are used at a temperature of 10°C to 50°C. Normally, the temperature is 33°C to 38°C, but higher temperatures may be used to accelerate the processing and shorten the processing time, or vice versa. It is possible to improve the image quality and the stability of the processing solution by lowering the temperature. In addition, in order to save silver on photosensitive materials, West German Patent No. 2.226,770 or U.S. Patent No. 3
, 674.499 may be carried out using cobalt intensification or hydrogen peroxide intensification.

Further, the silver halide photosensitive material of the present invention is disclosed in U.S. Patent No. 4,
No. 500,626, JP-A-60-133449, No. 5
It can also be applied to the heat-developable photosensitive materials described in No. 9-218443, No. 61-238056, European Patent No. 210.66OA2, and the like.

EXAMPLE On a subbed cellulose triacetate film support,
Each layer has the composition shown below! Sample 101, which is a multilayer color photosensitive material, was prepared by applying iN.

(Photosensitive FJ & 11 composition) The numbers corresponding to each component indicate the coating amount expressed in g/%, and for silver halide, the coating amount is calculated by 1^ of silver.However, for aggravating dyes, the coating amount is expressed in g/%. The coating amount is expressed in units of 1 mole per mole of silver halide.

(Sample 101) 1st layer (antihalation 1i) Black colloid m daughter 0.18 gelatin 0.40 2nd layer (intermediate layer) 2.5-dipencudecyl hydroquinone 0.18 x
-10,07 E Aggravating dye ■ Aggravating dye ■ EX-2 EX-10 Gelatin 4th layer (second red-sensitive emulsion layer) Emulsion C Sensitizing dye! Sensitizing dye ■ 0.002 0.06 0.08 0.10 0.10 0.02 1.04 il 0.25 1 dye 0.25 6.9X10-'1.8XIO-' 3, lX10-' 0 .335 0.020 0.87 Silver 1.0 5, lX10-'1.4X10-' Exacerbating dye■ EX-2 EX-3 EX-1゜Gelatin 5th layer (3rd red emulsion N) Emulsion thickening Sensitive pigment! Aggravating dye ■ Sensitizing dye ■ EX-3 EX-4 EX-2 5B-1 5B-2 Gelatin 6th layer (middle N) EX-5 B5-1 Gelatin 2.3X10-'' 0.400 o, os.

O,015 1,30 Silver 1.40 5.4X10-' 1.4XIO°5 2.4XlO-' 0.010 0.080 0.097 0.22 0, IO 1,63 0,040 0,020 0,80 71’! i (first green emulsion N) Emulsion A Emulsion B Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ EX-1 EX-7 EX-8 B5-1 B5-3 gelatin No. 871 (second green emulsion layer) Emulsion C Exacerbating pigment■ Sensitizing dye■ Sensitizing dye■ EX-l1l Silver 0.15 S 艮 0.15 3, OX 10-' 1.0X10-' 3.8X10-' 0.260 0.021 0.030 0.025 0.100 0,005 0.63 Silver 0.45 2, lX10-' ? ,0XIO-' 2.6XIO-' 0.094 0.01fl EX-7 IBS-1 B5-3 gelatin 9th layer (3rd green emulsion layer) Emulsion E Exacerbating pigment■ Exacerbating pigment■ Exacerbating pigment■ EX-13 EX-11 EX-1 B5-1 l3S-2 gelatin 1st O layer (yellow filter group) yellow colloid record EX-5 )IBS-1 gelatin 0.026 0, +60 0,003 0.50 Grudge 1.05 3.5XIO-' 8.0X10-' 3.0X10-' 0.015 o,io.

O,025 0,25 0,10 1,54 Limited 0.05 0.08 0.03 0.95 11th layer (first blue-sensitive emulsion layer) Emulsion A Emulsion B Emulsion F Sensitizing dye■ EX-9 EX-8 B5-1 gelatin 12th layer (second blue-sensitive emulsion layer) Emulsion G Exacerbating pigment■ EX-9 EX-1゜ B5-1 gelatin 13th layer (3rd blue emulsion IW) Emulsion H Exacerbating pigment■ Snake X-9 i 艮　　　0.08 Silver 0.07 Resentment 0.07 3.5XlO-' 0.721 0.042 0.28 1.10 Grudge 0.45 2, lX10-' 0.154 0.007 0.05 0.78 Silver 0.77 2.2XlO-' 0.20 B5-1 gelatin 14th floor! (1st protective layer) Emulsion I B5-1 gelatin 15th layer (second protective layer) polymethyl acrylate particles (Diameter approximately 1.5pm) gelatin In addition to the above ingredients, each layer contains H-1 and a surfactant were added.

0.07 0.69 0.5 0.11 O6I7 0.05 1.00 0.54 0.20 1.20 Gelatin hardener X-1 C1 X-2 H X-3 0 mouth X-7 X X- 9 X-4 H X-5 C6H13(nl H C6H13(2) X-11 Ht Tallate B5-3 Sensitizing dye I Sensitizing dye ■ V-5 Sensitizing dye I Sensitizing dye V Sensitizing dye ■ Sensitizing dye ■ X'y"70:30 (wt%) Sensitizing dye ■ H-1 ( Sample 102) P-5 of the seventh and eighth layers of sample 101 was weighed by 1.
Sample 102 was prepared by replacing P-6 with twice the amount of P-6.

(Sample 103) P-5 of the seventh and eighth layers of sample 101 was weighed by 1.
Sample 103 was prepared by adding 1.5 times HBS-1 and gelatin to 5 times P-1.

(Sample 104) P-5 of the seventh and eighth layers of sample 101 was weighed by 1.
Sample 104 was prepared by adding 1.8 times HBS-1 and gelatin to 8 times EX-11.

When these samples were scratched with a sapphire needle with a diameter of 0.1 mm under a continuous load of 0 to 200 g, all of them were 140
It broke at ~150g, and the film strength was almost the same.

The dry film thickness of sample 101.1.02.103.104 is 2
1.6μm, 21.7LLm, 22.2μm, 23.0
It was μm. The swelling rate of each water (25℃) is 1
It was 16-120%.

The color photosensitive material produced as described above was processed using an automatic processor using the following processing steps and processing solution.

Surface processing step main replenishment amount: 351 per 1 meter length of photosensitive material (in addition, the fixing tank of the automatic developing machine used was
The photographic material was equipped with a stirring device described in No. 460, page 3, and the processing was carried out by impinging a jet of the fixing liquid onto the emulsion surface of the light-sensitive material. ) (Color developer) Diethylenetriaminepentaacetic acid Sodium sulfite Potassium carbonate Potassium bromide Potassium iodide Hydroxylamine sulfate 4-[N-ethyl-N-〇-hydroxyethylamino]-2-Methylaniline sulfate Add aqueous solution H ( Bleach M) 1.3-diaminopro mother liquor (g) Replenisher (g) 5.0 4.0 30.0 1.3 1.2+ag 2.0 4.7 1.04 10, DO 3,6 6, 2 1,0 Flood 10, 15 Mother liquor (g) Replenisher (g) Pantetraacetic acid second complex salt 1.3-diaminopropane tetracomplex ammonium bromide acetate ammonium nitrate Add water and adjust pH with acetic acid and ammonia (fixing/ -Hydroxyethicyan-1,1-diphosphonic acid ethylene diamine tetraacetic acid disodium salt Sodium sulfite Sodium bisulfite Ammonium thiosulfate aqueous solution (700 g/flood) Thiourea pH 4.3 Mother liquor (g) 5.0 0.5 1O10 8,0 t7o, om! 3.0 p) 13.5 Replenisher (g) 7.0 0.7 12.0 10.0 200, 0 m1 5.0 3.6-cythia 1.8 mono-octadiol 3 .0 5.0 Add water 1.0β 1.0β Add acetic acid and ammonia and pH 6,56,7 (Stable solution) Mother liquor, replenisher common forma U: / (37%) 1.2m15
-Chloro-2-Methyl-4-isothiazolin-3-one 6.0mg 2-Methyl-4-thiazolin-3-one 3. Surfactant 0.4 [C1oH2□-0-+-CH2CH20-+Tf-H
] Ethylene glycol 1.0 Added water 1.0°C pH 5.0-7.0 First, the photosensitive material was cut into 35 mm width and exposed to standard light in a camera. This was processed for 500 m to make each port a constant running solution, and aqueous ammonia and acetic acid were added to the bleaching solution. The pH of the bleaching solution was changed as shown below, and the photosensitive material was processed under each pH condition. A comparative evaluation was made.

Table 2 Test Conditions Samples 101 to 104 were exposed to 40 CMS at 4800 DEG and subjected to treatments No. 1 to No. 7, and the amount of silver remaining in the treated samples (Aug/crr?) was measured.

In addition, the same treatment was performed without exposing the treated sample to 60°C.
It was stored for 3 days under conditions of relative humidity of 70%, and the yellow density before and after was evaluated as treated stain (B).

Further, exposure for MTF measurement was applied and processing No. 4 was performed, and the MTF value of a cyan image of 25 cycles/mm was measured.

From Table 1, it can be seen that the combination of the sample and treatment of the present invention provides a processed sample with high sharpness, fewer desilvering defects, and less staining.

Example 2 Samples 101 to 104 were processed using the same automatic processor as in Example 1, using the same processing steps, but changing the amount of 1,3-diaminopropanetetraacetic acid ferric salt in the bleaching solution as shown below. Similarly, the amount of residual silver (μg/crtr) was measured. (Table 2) From Table 2, it can be seen that in the bleaching treatment using a ferric 1,3-diaminopropanetetraacetic acid amount other than that of the present invention, the residual silver of the sample of the present invention was particularly large. In addition, the treated sample has unevenness observed due to the reflection of the sample, but the bleaching treatment of the present invention has little residual silver and there is no unevenness in the treated sample (the finish is uniform, so the effectiveness of the present invention is It has been shown.

Example 3 Samples 101 to 107 were processed using the automatic developing machine in the same manner as in Example-1, using the following processing steps and processing solution.

Table - Processing steps () are m o Q / 12 Table 2 (The automatic developing machine used was
It is equipped with an n-flow stirring device. ) (Color developer) Diethylenetriaminepentaacetic acid Sodium sulfite Potassium carbonate Potassium bromide Potassium iodide Hydroxylamine sulfate 4-[N-ethyl-N-β-hydroxyethylamino]-2- Methylaniline sulfate 1-Hydroxylamine sulfate 1. Add 1-diphosphonic acid water to pH Mother liquor (g) Replenisher 5.0 4.0 30.0 1.3 1.2 mg 2.0 4.7 3.0 10,05 4.0 6.5 4.0 1.0℃ 10, 20 (g) (Bleach solution) 1.3-Diaminopropanetetraacetic acid second complex salt 1.3-Diaminopropanetetraacetic acid ammonium bromide acetate ammonium nitrate Add water and dilute with acetic acid and ammonia. pH (Fixer) Ethylenediaminetetraacetic acid disodium salt sodium sulfite ammonium thiosulfate aqueous solution (700g) Rhodanammoniumthiourea mother liquor (g) 1.5 17.0 00ml 5.0 Replenisher (g) Replenisher (g) ) 2.0 24.0 40m1 7.0 Add water 1.0I 21.0℃ Add ammonia acetate to pH 6,36,3 (washing water) Mother liquor and replenisher Common tap water to H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and a hotbed column filled with OH type anion exchange resin (Amberlite IR-400) to reduce the concentration of calcium and magnesium ions to 3 mg/Q or less. Then, 20 mg/n of sodium incyanurate dichloride and 0.15 g/j2 of sodium sulfate were added.

The pH of this solution was in the range of 6.5-7.5.

(Stable solution) Polmarine (37%) Polyoxyethylene-p-monononylphenyl ether mother liquor (g) Replenisher (g) 2.0mi! 3.0 d (Average degree of polymerization 10) 0゜3 0.45 Ethylenediaminetetraacetic acid disodium salt 0.05 Add 0.0g water 1. oj2 1. OApH5,0-
8,05,o-g,.

Thereafter, the same operation as in Example 1 was carried out to adjust the running liquid, and the pH of the bleaching liquid was adjusted to 6.0.5, 5.4.8.4.3.
．． 3.5.2.0 was prepared and the residual silver amount and yellow stain of each sample were evaluated and measured. The results obtained were similar to Example 1.

Procedural amendment (December 27, 1988 6, number of claims increased by amendment 07, full text of the specification to be amended 8, and detailed statement of the contents of the amendment are written as attached).

(No change in content) Patent Application No. 194643 filed in 1988 2, Title of the invention: Method for processing silver halide color photographic light-sensitive materials 3, Relationship with the person making the amendment case Patent applicant address: 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Name (52
0) Fuji Photo Film Co., Ltd. Representative Minoru Ohnishi 4゜

Claims (1)

[Claims] A method of processing an imagewise exposed silver halide color photographic light-sensitive material with a processing solution having bleaching ability after color development, wherein the silver halide color photographic light-sensitive material contains at least one polymer coupler and has the bleaching ability. The treatment solution containing 1,3-diaminopropanetetraacetic acid ferric salt has a concentration of 0.
A method for processing a silver halide color photographic material, characterized in that it contains 2 mol/l or more and has a pH in the range of 2.5 to 5.5.