JPH0244351A - Method for processing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To make it possible to rapidly desilverize the subject material, and to reduce the tendency for generating a stain in the material by processing the material with a specified processing solution, and incorporating a specified magenta coupler in the photosensitive material. CONSTITUTION:The processing solution having bleaching ability contains a ferric complex salt of 1,3-diaminopropane tetraacetic acid of >=0.2mol/l, and has pH of a range of 2.5-5.5. The photosensitive material contains at least one kind of compds. shown by formulas I and/or II, as the magenta coupler. In formula I, R<1> is carboxylic acid amide or sulfonamide group, etc., R<2> is phenyl group, Z is a group capable of being released an anion by a coupling reaction with the oxidation of an aromatic primary amine developing agent. In formula II, R10 is hydrogen atom or a substituting group, Y2 is hydrogen atom or a group capable of being released by a coupling reaction, Za, Zb and Zc are each methine or a substd. methine group, etc. Thus, the photosensitive material is subjected to the rapid desilverization and has a less tendency for generating the stain, and the subject method does not have adverse effects upon a photograph.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for processing exposed silver halide color photographic materials (hereinafter referred to as color photographic materials). The present invention relates to an improved processing method that shortens processing time, performs sufficient bleaching, and forms color photographic images with good stain and image quality.

(Prior Art) Generally, the basic steps in processing color photosensitive materials are a color development step and a desilvering step. That is, the exposed halogenated scissors color photographic material is subjected to a color development process. Here, silver halide is reduced by a color developing agent to produce silver, and the oxidized color developing agent reacts with a color former to provide a dye image. Afterwards, the color photographic material is subjected to a desilvering process. Here, the silver produced in the previous step is oxidized by the action of an oxidizing agent (commonly called a bleaching agent), and then dissolved and removed by a silver ion complexing agent, commonly called a fixing agent. Therefore, only dye images are produced in photographic materials that have undergone these steps. In addition to the two basic steps of color development and desilvering mentioned above, the actual development process includes auxiliary steps to maintain the photographic and physical quality of the image, or to improve the storage stability of the image. Contains. For example, a hardening bath to prevent excessive softening of the photosensitive layer during processing, a stop bath to effectively stop the development reaction, an image stabilizing bath to stabilize the image, or a support nozzle.
Examples include a film removal bath for removing the packing layer.

In addition, the desilvering process mentioned above is carried out in two steps, with the bleaching bath and fixing bath being separate baths, and in other cases, the processing process is simplified for the purpose of speeding up processing and labor saving, and bleaching agent and fixing agent are used together. Sometimes it is carried out in one step using a bleach-fixing bath.

In recent years, with the spread of small in-store processing service systems called minilabs, there has been a strong demand for shortening the time required for the above-mentioned processing in order to quickly respond to processing requests from customers.

In particular, the highest demand was to shorten the desilvering step, which conventionally occupied most of the processing time.

However, the ferric complex salt of ethylenediaminetetraacetic acid, which is the mainstream bleaching agent used in bleach-fix solutions, has a fundamental drawback of strong oxidizing power, so various improvements have been made, such as the use of bleach accelerators. Despite this, the above requirements have not been met.

On the other hand, red blood salt is a bleaching agent with strong oxidizing power.

Dichromate, ferric chloride, persulfate, bromate, etc. are known, but they are environmentally friendly and safe to handle.

The reality is that they each have many drawbacks from the viewpoint of metal corrosion, etc., and cannot be widely used for over-the-counter treatments.

Under these circumstances, the bleaching solution containing a ferric complex salt of 1,3-diaminopropanetetraacetic acid described in JP-A No. 62-222252 is a bleaching solution containing a ferric complex salt of ethylenediaminetetraacetic acid. It has a higher oxidizing power and can bleach silver more quickly, but it has the disadvantage that if it is bleached directly without using a bath during the color development process, it will generate a color capri called bleach capri. .

In addition to this problem with bleaching capri, it is also clear that if the bleaching time is shortened using this bleaching solution, a new problem will occur: a large increase in staining will occur during storage of the photographic material after processing. Became.

(Problems to be Solved by the Invention) The present inventors found that among many aminopolycarbonate powdered ferric complex salts, when a bleaching solution containing 1,3-diaminoprononetetraacetic acid ferric complex salt was used, halogen It has been found that silver oxide photographic materials can be rapidly desilvered. However, when processing with the above-mentioned bleaching solution, staining occurs and photographic properties are impaired.

%, the 2-equivalent magenta coupler has a leaving group at the coupling active position, and by making it 2-equivalent, the amount of silver halide required can be reduced, making it possible to make the layer thinner, and it also improves the drawback of gas fog caused by formalin gas, etc. However, the above-mentioned rapid processing has the problem of causing significant staining.

Therefore, a first object of the present invention is to provide a processing method for rapidly desilvering silver halide color photographic materials.

A second object of the present invention is to prevent staining.

To provide a desilvering method that does not adversely affect photographs.K
be.

(Means for Solving the Problems) In order to solve the above problems, the inventors of the present invention have worked hard day and night.
As a result of research, it was found that in a method of processing an imagewise exposed silver halide color photographic light-sensitive material with a processing solution having bleaching ability after color development, the processing solution having bleaching ability is
．． Contains 0.2 mol/1 or more of ferric 3-diaminoprono-tetraacetic acid salt and is in the range of ≠25 to pHs, s,
and the silver halide color photographic light-sensitive material contains the following as a magenta coupler - Monna, CI) and/or (II)
It has become clear that the object can be achieved by a method for processing a silver halide color photographic material, which is characterized by containing at least one of the compounds shown below.

The present invention will be explained in detail below.

The 2-unit i5-pyrazolone coupler used in the present invention is preferably represented by the following symbol (1).

In the formula, R1 is a carbonamide 9 group, a sulfo/amide group,
Anilino group or ureido group, R2 is a phenyl group,
Z represents a group capable of leaving as an anion (hereinafter referred to as a leaving group) through a coupling reaction with an oxidized aromatic primary amine developer.

Hereinafter, the -monhole (1) will be explained in detail.

As R□, a carbonamide group is preferable.

2 is an active carbon coupled via an oxygen atom, nitrogen atom, sulfur atom or carbon atom and an aliphatic group, an aromatic group,
Groups that bond with heterocyclic groups, aliphatic/aromatic or heterocyclic sulfonyl groups, aliphatic/aromatic or heterocyclic carbonyl groups, carbamoyl groups, alkoxycarbonyl groups, and aryloxycarbonyl groups, halogen atoms, aromatic groups These include an azo group and a heterocyclic group. Aliphatic contained in Z,
The aromatic or heterocyclic groups R1 and R2 may be further substituted, examples of which include halogen atoms (e.g.
fluorine atom, chlorine atom, bromine atom, etc.), alkyl groups (e.g., methyl group, t-octyl group, dodecyl group, trifluoromethyl group, etc.), alkenyl groups (e.g., allyl group, octadecenyl group, etc.).

Aryl group (e.g. phenyl group, p-)! (fluor group, naphthyl group, etc.), alkoxy group (e.g., methoxy group, (
phenoxy group, methoxyethoxy group, etc.), aryloxy group (e.g., phenoxy group, 2,4-di-tart
-aolphenoxy group, 3-tert-butyl-4-hy)-"cXoxyphenoxy group, etc.), acyl group (e.g.,
acetyl group, indiyl group, etc.), sulfonyl group (e.g. Eva, methanesulfonyl group, toluenesulfonyl group '4)
, carboxy group, sulfo group, cyano group, hydroxy group,
Amino group (e.g. amino group, dimethylamino group, etc.),
Carbonamide ° group (e.g., acetamide group, driburooacetamide group, tetradecanamide group, benzamide group, etc.), sulfonamide 9 groups (e.g., methanesulfonamide 9 group, hexadeca/sulfonamide group, p
-) Based on luenesulfonamide 1. Acyloxy group (e.g., acetoxy group, etc.), sulfonyloxy group (e.g.,
methanesulfonyloxy7 groups, etc.), alkoxycarbonyl groups (e.g., to9decyloxycarbonyl groups, etc.), aryloxycarbonyl groups (e.g., phenoxycarbonyl groups, etc.), carbamoyl groups (e.g., dimethylcarbamoyl groups, tetradecycarbamoyl groups, etc.) ), sulfamoyl groups (e.g., methylsulfamoyl group, hexadecylsulfamoyl group, etc.), imide groups (e.g., succinimide group, phthalimide group, octadecenylsuccinimide group, etc.), heterocyclic groups (e.g., 2- pyridyl group, 2-furyl group, 2-thienyl group, etc.), alkylthio groups (eg, methylthio group, etc.), and arylthio groups (eg, phenylthio group, etc.). To give a specific example of 2, halogen atoms (e.g. fluorine atoms, chlorine atoms,
bromine atom, etc.), alkoxy groups (e.g., indyloxy group, etc.), aryloxy groups (e.g., 4-chlorophenoxy group, 4-methoxy group, etc.), acyloxy groups (e.g., acetoxy group, tetrazocallyoxy group, benzoyl group), (oxy group, etc.), aliphatic or aromatic sulfonyloxy group (e.g., methanesulfonyloxy group, toluenesulfonyloxy group, etc.), carbonamide group (e.g., dichloroacetamide group, trifluoroacetamide group)
groups), aliphatic or aromatic sulfo/amide groups (e.g., methanesulfonamide groups, p-toluenesulfonamide groups, etc.), alkoxycarbonyloxy groups (e.g., ethoxycarbonyloxy groups, benzyloxycarbonyloxy groups, etc.) , aryloxycarbonyloxy group (e.g., phenoxycarbonyloxy group, etc.), aliphatic/aromatic or heterocyclic thio group (e.g., ethylthio group, hexadecylthio group, 4-dodecylphenylthio group,
pyridylthio group, etc.), ureido group (e.g., methylureido group, phenylureido group, etc.), 5- or 6-membered nitrogen-containing heterocyclic group (e.g., imidazolyl group, pyrazolyl group, triazolyl group, tetrazolyl group, 1, 2-dihyto30-2-oquine-1-pyridyl group, etc.), imide groups (e.g., succinimide group, phthalimide group, hydantoinyl group, etc.). In addition, aldehydes or ketones can be used as leaving groups bonded via a carbon atom.
So-called bis-type Cub 2 obtained by condensing equivalent couplers
-There is.

When the coupler of the present invention represents a polymer, it is derived from a monomer coupler represented by the following symbol (?'p-1), and has a repeating unit represented by the symbol (Op-2). 18 of a non-chromogenic monomer containing at least one ethylene group that does not have the ability to coalesce or couple with an oxidized form of an aromatic primary amine developing agent.
It means a copolymer with the above. Here, two or more monomeric couplers may be simultaneously polymerized.

General formula (Cp-1) CH2 = C + A2 catties (As striking 6 Al tank Q' - Mon hole (C
p-2) In the formula, R represents a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, or a chlorine atom, and A1 is 100NR"--N
R3CONR3--NR3COO--COO--3o
--CO--NR3GO-1-5ONR3--NR3C
OO--oc〇-1-0CONR3--NR3-1-8
-1 or -〇-, A2 is -CONR3- or -
Coo-, R3 represents a hydrogen atom, an aliphatic group, or an aryl group, and when there are two or more R3's in the molecule, they may be the same or different. A3 has 1 or more carbon atoms
Represents 10 unsubstituted or substituted alkylene groups, aralkylene groups or unsubstituted or substituted arylene groups,
The alkylene group may be linear or branched. (Alkylene groups include, for example, methylene, methylmethylene, dimethylmethylene, dimethylene, trimeprene, tetramethylene, pentamethylene, hexamethylene, decylmethylene, and aralkylene groups include, for example, benzylidene,
Examples of arylene groups include eva, phenylene, naphthylene, etc.).

Q' represents a coupler residue bonded to the general formula (Op-1) or (Op-2) at any part of R1, R2 or Z of the -pattern (1).

1,'' and k represent 0 or 1.

Examples of substituents for the alkylene group, aralkylene group, or arylene group represented by A3 include aryl group (e.g., phenyl group), nitro group, hydroxyl group, cyano group, sulfo group, alkoxy group (e.g., methoxy group), aryl group, Oxy group (e.g. phenoxy group), acyloxy group (
(e.g., acetoxy group), acylamino group (e.g., acetylamino group), sulfonamide group (e.g., methanesulfo/amide group), sulfamoyl group (e.g., methylsulfamoyl group), halogen atom (e.g., fluorine, chlorine, bromine), etc.), carboxy group.

Carbamoyl group (e.g., methylcarbamoyl group), alkoxycarbonyl group (e.g., methoxycarbonyl group, etc.), sulfonyl group (e.g., methylsulfonyl group)
can be mentioned. When there are two or more of these substituents, they may be the same or different.

Examples of non-chromogenic ethylene-like monomers that do not couple with the oxidation products of aromatic-grade amine developers include acrylic acid,
α-chloroacrylic powder, α-alkyl acrylic acids (such as methacrylic acid), and esters or amides derived from these acrylic acids (such as acrylamide, n-butylacrylamide, t-methylacrylamide, diacet/acrylamide 9, methacrylamide) , methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl acrylate, 1So-butyl acrylate, 2-
ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and β-hydroxy methacrylate), methylene dibis acrylamide.

Vinyl esters (e.g. vinyl acetate, vinyl propionate and vinyl laurate), acrylonitrile, methacrylonitrile, aromatic vinyl compounds (e.g. styrene and its derivatives, vinyltoluene, sivinylinzene, vinylacetophenone and sulfostyrene), itaconic acid , citraconic acid, crotonic acid, vinylidene chlorreich, vinyl alkyl ether (e.g. ethyl ethyl ether), maleic acid, maleic acid, maleic acid ester, N-vinyl-2-pyrrolidone, N-vinylpyridine, and Examples include 2- and 4-vinylpyridine. Two or more kinds of the non-color-forming ethylenically unsaturated monomers used here can also be used together. For example, n
-butyl acrylate and methyl acrylate, styrene and methacrylic acid, methacrylic acid and acrylamide, methyl acrylate and diacetate/acrylamide, etc.

The effects of the present invention are particularly significant when a polymer coupler having an Op-2 unit is used. This is due to the contribution of the thinner layer to improved sharpness.

General formula (1) and methods for synthesizing polymer couplers having coupler residues thereof are disclosed in, for example, JP-A No. 49-111
631, 54-48540, 55-62454, 55-118034, 56-38043, 56-8
0045, 56-126833, 57-4044
, 57-35858, 57-94752, 5B-
17440, 58-50537, 58-85432
, 58-117546, 58-126530, 5
8-145944, 58-205151, Japanese Unexamined Patent Publication No. 1973
-170, 54-10491, 54-21258.
53-46452, 53-46453, 57-3
6577, patent application No. 58-110596, No. 58-13
2134, 59-26729, U.S. Patent No. 322755
4, 3432521, 4310618, 4351
897. 4264723, 4310619, 43
01235, 4308343, 4367282, W
o 88104795 etc.

Specific examples of typical magenta couplers and their vinyl monomers are shown below, but the present invention is not limited thereto.

Below, the 5-pyrazolone series 2 represented by -Momonana (1)
Preferred examples of equivalent magenta couplers are shown.

(M-1) C (M-2) (M-5) (M-10) Q is C (M-23) C1 (M-24) (M-25) O (M-32) (M -31) (M-34) Next, specific examples of the 2-equivalent magenta monomer coupler forming the repeating unit of the general formula (Op-2) of the present invention will be given, but the invention is not limited thereto. (・.

CH3 (J Next, examples of polymer couplers used in the present invention will be given, but the invention is not limited thereto.

Next, the pyrazoloazole magenta coupler represented by the general formula (II) related to the present invention will be explained in detail.

In the general formula (If), Rlo represents a hydrogen atom or a substituent (including substituent atoms), Y2 represents a hydrogen atom or a coupling-off group (including a separation atom; the same applies hereinafter), and Z, , Zb and ZC are methine, substituted methine, =
Represents N- or -NH-. Za-Zb bond and Zb
One of the -Zc bonds is a double bond, and the other is a single bond. The case where Zb - Zc is a carbon-carbon double bond includes the case where it is part of an aromatic ring. Plus R10
1Y2 and Za, Zb or Z representing the substituted methi/
A dimer or more multimer may be formed by one group in the group consisting of c.

Here, the aliphatic group refers to a linear, branched, or cyclic alkyl group, alkenyl group, or alkynyl group, and may be substituted or unsubstituted. The aromatic group refers to a substituted or unsubstituted 7-aryl group, and may be a fused ring. The term "heterocycle" refers to a substituted or unsubstituted monocyclic or condensed ring heterocyclic group.

Next, the general formula ([) will be explained in detail.

- Monna (I[) represents a magenta dye-forming coupler with a pyrazoloazole skeleton.

- In the bracket [''], R10 represents any group that can be substituted at the 3-position of the pyrazole ring, and includes a hydrogen atom or any group described below.

The optional substituents are as follows, and these substituents may be further substituted with one or more groups selected from the substituent group.

R10K allowable optional substituents include aliphatic groups, aromatic groups, heterocyclic groups, aliphatic oxy groups (e.g. methoxy,
2-methoxyethoxy, 2-proynyloxy), aromatic oxy groups (e.g. 2,4-tert-amylphenoxy, 2-chlorophenoxy, 4-cyanophenoxy), acyl groups (e.g. acetyl, benzoyl) ), ester groups (e.g. suthoxycarbonyl, phenoxycarbonyl, indiyloxysulfonyl, toluenesulfonyloxy), amides (e.g. acetylamino, methanesulfonamide, ethylcarbamoyl, diethylcarbamoyl, butylsulfamoyl), imides (e.g. succinimide, hydanthrinyl), ureido 3 (e.g. phenylureido, dimethylureide 9), sulfamoylamino groups (e.g. dipropylsulfamoylamino), aliphatic, aromatic or heterocyclic sulfonyl groups (e.g. methanesulfonyl, phenylsulfonyl) ), aliphatic, aromatic or heterocyclic thio groups (e.g. ethylthio, phenylthio), aliphatic/aromatic or heterocyclic thiooxy groups, aliphatic/aromatic or heterocyclic oxyamide groups,
Substituted amino groups (e.g. diethylamino, anilino), silyl groups (e.g. trimethylsilyl), hydroxyl groups,
Cyano group, carboxyl group, sulfo/acid group, nitro group,
Thioquanato group, halogen atom (fluorine, chlorine, bromine,
iodine), etc. Note that two or more substituents further substituting these substituents may form one or more cyclic structures (for example, 3,4-dimethyleneoxyphenyl, 1,2,3,4-tetrahydronaphthyl Such).

- When Y2 in the pattern (If) is not a hydrogen atom and represents a coupling-off group, the leaving group is oxygen, nitrogen,
Coupling activated carbon via sulfur or carbon atoms, aliphatic groups, aromatic groups, heterocyclic groups, aliphatic/aromatic or heterocyclic sulfonyl groups, aliphatic/aromatic or heterocyclic carbonyl groups, aliphatic/aromatic or heterocyclic carbonyl groups, Aromatic or heterocyclic oxycarbonyl groups, groups that bond with aliphatic/aromatic or heterocyclic carpamoyl groups, halogen atoms, aromatic azo groups, etc., and aliphatic groups included in these leaving groups,
The aromatic or heterocyclic group may be substituted with a substituent allowed by Rlo (and when there are two or more of these substituents, they may be the same or different).

Specific examples of leaving groups include halogen atoms (e.g. fluorine atom, chlorine atom, bromine atom, etc.), alkoxyl groups (
For example, ethoxy, dodecyloxy, methoxyethylcarbamoylmethoxy, carboxylpropyloxy, methylsulfonyl ethoxy, etc.), aryloxy groups (such as 4-chlorophenoxy, 4-methoxyphenoxy, 4
-carboxyphenoxy, etc.), acyloxy groups (e.g. acetoxy, tetrazokyloxy, benzoyloxy, etc.), aliphatic or aromatic sulfonyloxy groups (IJ evamethanesulfonyloxy, toluenesulfonyloxy, etc.), acylamino groups (e.g. dichloroacetyl amino, heptafluorobutyrylamino, etc.), aliphatic or aromatic sulfonamide groups (e.g. methanesulfonamino, p-)luenesulfonylamino)
, alkoxycarbonyloxy groups (e.g., ethoxycarbonyloxy, benzyloxycarbonyloxy, etc.), aryloxycarbonyloxy groups (e.g., phenoxycarbonyloxy, etc.), aliphatic/aromatic or heterocyclic thio groups (e.g., ethylthio, phenylthio, tetrazolylthio, etc.) , carbamoylamino group (e.g. N
-methylcarbamoylamino, N-phenylcarbamoylamino, etc.), 5- or 6-membered nitrogen-containing heterocyclic groups (e.g. imidazolyl, pyrazolyl, triazolyl, tetrazolyl, 1,2-dihyP-rho-2-oxo-1-pyridyl, etc.) , an imide group (eg, succinimide, hydantoinyl, etc.), an aromatic azo group (eg, phenylazo, etc.), and these groups may be further substituted with any group represented by Rlo described above. Furthermore, there are bis-type couplers obtained by condensing a four-equivalent coupler with an aldehyde or a ketone as a leaving group bonded via a carbon atom.

The leaving group of the present invention may contain photographically useful groups such as development inhibitors and development accelerators.

In the present invention, the aliphatic group may be saturated or unsaturated, substituted or unsubstituted, linear or branched, or cyclic,
Typical examples include methyl group, ethyl group, butyl group, cyclohexyl group, allyl group, propargyl group, methoxyether, n-decyl group, n-dodecyl group, n-hexadecyl group, trifluoromethyl group, heptafluoro Propyl group, todecyloxypropyl group, 2,4-di-t
Included are ert-amylphenoxypropyl group, 2,4-di-tert-amylphenoxybutyl group, and the like.

Further, the aromatic group may be substituted or unsubstituted,
Typical examples include phenyl group, tolyl group, 2-tetradecyloxyphenyl group, interfluorophenyl group,
2-chloro-5-rdecyloxycarbonylphenyl group, 4-chlorophenyl group, 4-cyanophenyl group, 4-
Includes human 90xyphenyl group, etc.

In addition, the heterocyclic group may be substituted or unsubstituted,
Typical examples include 2-pyridyl group, 4-pyridyl group,
Included are 2-furyl group, 4-thienyl group, quinolinyl group, and the like.

When the aliphatic/aromatic or heterocyclic group has one or more substituents, that substituent may further have one or more substituents.

Among the pyrazoloazole compounds represented by the general formula (II), a preferred photographic coupler is the following general formula (II-
IH-imidazo-(1,2-b) pyrazoles represented by 1), IH-pyrazolo(r,5-b) pyrazoles represented by -Momonya (II-2), -Momonya (ff-3) )
te table b h6 lH-hit solo (5,1-c) (1
,2,4)) Liazoles, IH-pyrazolo(1,5-b) (1,2,4) represented by -Momonana (It-4)
) lyazoles, -I expressed as n-s
H-pyrazolo(1,5-d)tetrazoles and IH-pyrano(1,5-d) represented by general formula (II-6)
a) Be/dimidazoles.

(II-1) (If-2) CM-3) Cm-4] (II-5) (n-6) (II-
The substituents in the general formulas 1) to (I[-6) will be explained in detail. R21, R12 and R13 represent an aliphatic group, an aromatic group or a heterocyclic group, and these groups are R1o
K may be substituted with at least one of the permissible substituents (the above substituent groups (i.e., substituted or unsubstituted aliphatic, aromatic, and heterocyclic groups) are referred to as R).

R, R and a hydrogen atom, a halogen atom, a cyano group, or an imide 9 group may be used. R11, R12 and R13 are further a carbamoyl group, a sulfamoyl group, or a ureido group.

or a sulfamoylamino group, and these groups may be substituted with permissible substituents for Rlo. X□ is synonymous with Y2, and R11, R12
.

Preferred Hll, HLI and R13 are hydrogen atom, halogen atom, substituent defined by R, RO-1RCONH
-1R8O2-1 Group H-, Paste- or PIOCON
It is an H group. Preferred Xl is a hydrogen atom, a halogen atom,
These include an acylamino group, an imide group, an aliphatic or aromatic sulfonamide group, a 5- or 6-membered nitrogen-containing heterocyclic group bonded to the coupling active position via a nitrogen atom, an aryloxy group, and an alkoxy group.

- The coupler of Monka (I[) may be a dimer, a multimer or a polymer.

Hll, R12 in the general formula from [Tol] to [Toro]
Any group selected from the group consisting of R13 and Xl,
It may also serve as a divalent or higher polyvalent group.

Alternatively, they may form a polymer chain with each other and contain a chromophore in the side chain or in the polymer main chain. Polymer couplers can make the coupler-containing layer thinner and improve sharpness.

General formula (I[) preferably (II-1) to (I[-6
It is desirable that the magenta coupler, which is represented by a hole up to ), usually has a ballast group that makes the coupler itself diffusion resistant. It is also possible to improve the graininess by designing the coloring dye formed from a coupler whose leaving group is a ballast group to have appropriate diffusivity.

Synthesis methods and compound examples of couplers represented by the general formulas (II-1) to Roto 6] are described in the following documents. - Compound of Monna (II-1) is patent application filed in 1988-
23434, and 58-145331.

-The compound of Monna (It-2) is patent application No. 58-15135.
4, etc., the compound of -Momonena [1l-3] was published in
27411 and Japanese Patent Application No. 58-103336, etc., the compound of -monna (n-4) is disclosed in Japanese Patent Application No. 58-45512, No. 58-103336, etc.
9-27745, 59-45601, 59-534
43 and 59-70146, etc., -monana (I[-
The compound of 5) is disclosed in Japanese Patent Application No. 58-142801, etc., and the compound of -Monken (If-6) is disclosed in U.S. Patent No. 3,061,432.
There are detailed descriptions in .

In addition, as a ballast group for maze/ri of the present invention, JP-A-58
-402045. Patent application No. 58-88940, No. 58-5
2923. 58-52924 and 58-52927
By using the highly color-forming ballast group described in et al., it is possible to obtain a high coloring density or a high coloring speed.

Examples of specific compounds of the magenta coupler represented by the general formula (II) are shown below, but the invention is not limited thereto.

(M-101) (M-102) (M-105) (M-103) (M-106) (M-104) (M-107) Ii3 (M-108> (M-109) (M- 110) (M-114) (M-115) (t)C81i17 (M-111) (M-113) (M-117") (M-118) (M-119) H3 (M-120) (M -123) (M-121) (M-124) (M-125) Le = 50150 (Weight) (M-126) (M-128) x/y= 40/60 (!Amount) (M-127 ) X/'!=50150 (weight) The preferred petro ring skeleton structure of the pyrazoloazole coupler represented by the general formula f"II) is the general formula (fl-1)
or I[-6:], but among these, the general formula (U-13, (n-
2), (II-3) and [G4], and the hue improves in this order. -More than Monana [G3] and (I[-6)-Momonana (If-1), [G2], CM-4] and [G5
] The coloring dye of the compound has higher fastness, and is particularly excellent in fastness to light. In particular, the compound Monna (It-4) is excellent in both hue and fastness.

- The coupler represented by Monna [■] has less unnecessary absorption of yellow in the color-forming magenta dye compared to the conventionally known 5-pyrazolo y-based couplers (particularly from - Monna (II-1) to (
Compounds up to If-4) exhibit even less absorption on the longer wavelength side.

In the bleaching solution of the present invention, 1,3-diaminopropane ferric acetate complex salt is used in an amount of 0.0000000 per 10 bleaching solutions.
The amount is 2 mol or more, preferably 0.25 mol or more, particularly preferably 0.3 mol or more for speeding up the process. However, excessive use will adversely inhibit the bleaching reaction, and the upper limit is 0.5 mol. The ferric complex salt of 1,3-diaminoprononetetraacetic acid can be used in the form of ammonium, sodium, potassium, etc. salts, but ammonium salts are preferred because they bleach the fastest. In addition, if the amount of the 1,3-diaminopropanetetraacetic acid ferric complex salt is less than 0.2 mol, bleaching will be rapidly delayed and the stain after treatment will increase. The condition is that it contains.

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

Voice 6 containing 1.3-diaminopropanetetraacetic acid ferric complex salt
The bleaching solution is known from the above-mentioned Japanese Patent Laid-Open No. 62-222252. Conventionally, a bleaching solution containing a ferric aminopolycaric acid complex salt has been widely used since it has been considered optimal to use a bleaching solution containing a ferric aminopolycaric acid complex salt at around 16% from the viewpoint of both ensuring a high bleaching speed and preventing poor recoloring of cyan dyes. That is, although the bleaching speed can be improved by lowering the pH, the optimum balance has been set at around pH 6 because it causes poor recovery of shea/dye.

On the other hand, the present invention has the characteristic that the effect is expressed by setting the - of the bleaching solution to 5.5 or less, and also achieves rapid desilvering and complete restoration of the cyan dye, which is contrary to the conventional art. solve the problem.

- of the bleaching solution of the present invention is 5.5 to 2.5, and the preferable range for effect expression is 5.0 to 3.0, more preferably 4.
5 to 3.5. K that adjusts - to this region is acetic acid,
Organic acids such as 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 preferably in the range of z5 to 5.5 from the viewpoint of imparting buffering properties to the region of the present invention, and in addition to the acetic acid, citric acid, and malonic acid, benzoic acid, formic acid, butyric acid, malic acid, and 11-talaric acid are preferred. ,
Various organic acids can be mentioned, such as cylinoxic acid, propionic acid, and 7-talic acid. Among these, acetic acid is particularly preferred.

The amount of these acids used is preferably 0.1 to 2 mol, particularly preferably 0.5 to 1.5 mol, per 11 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 it is preferable to apply overpressure usually in the range of 1 to 10 hours. .

Further, the bleaching solution of the present invention can also be used in combination with an aminopolycarboxylic acid ferric complex salt other than the 1,3-diaminopropanetetraacetic acid ferric complex salt, and specifically, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, etc. , a ferric complex salt of cyclohexanediaminetetraacetic acid.

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

For such bleach accelerators, see, for example, US Pat. No. 3,893,858, German Patent No. 1.29.
Specification No. 0,812, British Patent No. 1,138,842, Japanese Patent Application Laid-Open No. 1983-95630, Research Disclosure No. 17129 (July 1978 issue)
Compounds having a mercapto group or disulfide group described in JP-A-50-140129, thiazolidine derivatives described in U.S. Pat. No. 3,706,561, JP-A-58-16235 Iodide described in German Patent No. 2,748,430
The polyethylene oxide type 1 described in the specification of No. 1, the polyamine compound described in Japanese Patent Publication No. 45-8836, etc. can be used. Particularly preferably British patent ail,
Mercapto compounds such as those described in US Pat. No. 138,842 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 chloride 1 such as potassium chloride, sodium chloride, ammonium chloride, etc. can be included.

The concentration of the rehalogenating agent is between 0.1 and 5 mol, preferably between 0.5 and 3 mol per bleach solution.

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

The amount of replenishment of the bleaching solution of the present invention is 50 d to 2
000d, preferably 100d to 1000-.

In addition, when processing, the bleaching solution is subjected to an aeration eye,
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.

The fixing process is performed with a fixer or a bleach-fixer.

Fixing agents that can be used in the present invention include thiosulfates such as sodium thiosulfate, ammonium thiosulfate, sodium ammonium thiosulfate, and potassium thiosulfate, thiocyanates such as sodium thiocyanate, ammonium thiocyanate, and potassium thiocyanate, thioureas, and thioethers. etc. can be used. Among them, it is preferable to use ammonium iosulfate, and the amount thereof is 0.3 to 37 moles, preferably 0.5 to 2 moles, per 12 moles of the fixer.

Father, from the viewpoint of promoting retention, ammonium thiocyanate (rhodan ammonium), chi? Urine X, 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 0.01 mol to 0.1 mol per 1 ft of fixer. By using 1 to 3 moles, the fixing promoting effect can be greatly enhanced.

The fixing solution contains sulfites as preservatives, such as sodium sulfite, potassium sulfite, ammonium sulfite,
Hydroxylamine, hydroxide, bisulfite adducts of aldehyde compounds, such as acetaldehyde sodium bisulfite, can be included. Furthermore, various fluorescent whitening agents, antifoaming agents, surfactants, polyvinylpyrrolidone, organic solvents such as methanol, etc. can be contained, but in particular, as preservatives, it is possible to contain them.
It is preferable to use the sulfinic acid compounds described in Specification No. 1.

The fixing solution replenishment amount is 300 per m” of photosensitive material.
m1 to 3000 d is preferable, more preferably 3
00d to 1000d.

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.

The total time of the desilvering process of the present invention is short, and the effect of the basic 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 treatment temperature is 25°C to 50°C, preferably 35°C to 4°C.
The temperature is 5°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 Japanese Patent Application Laid-Open No. 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.
A method of increasing the stirring effect using a rotating means of No. 83461, and further improving the stirring effect by moving the photosensitive material while bringing the emulsion surface into contact with a wiper plate 9 provided in the liquid to create turbulence on the emulsion surface. For example, a method of increasing the circulation flow rate of the entire processing liquid can be mentioned. Such means for improving agitation is effective for all bleaching solutions, bleach-fixing solutions, and fixing solutions. Improving agitation is achieved by adding bleach into the emulsion film,
It is believed that this speeds up the supply of the fixing agent 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 amount of processing liquid brought into the post bath from the front 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 developer used in the present invention contains 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-I N, N-u ethyl-p-phenylenediamine D-22-amino-5-diethylaminotoluene D-3
2-amino-5-(N-ethyl-N-lacrylamino)
Toluene D-44-(N-ethyl-N-(β-hydroxyethyl)amine)anili/D-52-methyl-4-[N-ethyl J・-N-(β-hydroxyethyl)aminocoaniline D- 64-amino-3-methyl-N-ethyl~N-[β
-(methanesulfonamido)ethyl]-aniline D-7N-(2-amino-5-diethylaminophenylethyl)methanesulfonamide D-8N,N-dimethyl-p-phenylenediami/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
-Ptoxyethylaniline Among the above p-phenylenediamine derivatives, Exemplified Compound D-5 is particularly preferred.

Moreover, these p-phenylenediamide/derivatives may be salts such as sulfate, hydrochloride, sulfite, and p-)luenesulfonate. The amount of the aromatic-grade amine developing agent to be used is preferably about 0.19 to about 209% per 1a of developer solution.
More preferably about 0. ! The concentration ranges from 1 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 preferable addition amount is 0.5g to 1.0g per 11 color developer.
0g, more preferably 1g to 5g.

In addition, various human 90 xylamines, patent application No. 1865-1988, are used as compounds that immediately preserve the aforementioned power 2-developing agent.
Hydroxamic acids described in No. 59, No. 61-170756
Hydrazines and hydrazides described in No. 61-18
Phenols described in No. 8742 and No. 61-203253, α-hibiloxyketones and α-aminoketones described in No. 61-188741, and/or No. 61-1
It is preferable to add various saccharides described in No. 80616.

In addition, in combination with the above compounds, patent application No. 147823/1986
No. 61-166674, No. 61-165621, No. 61-164515, No. 61-170789,
and monoamines described in No. 61-168159, etc.
Diamines described in No. 61-173595, No. 61-164515, No. 61-186560, etc., No. 61-186560, etc.
No. 165621 and polyamines described in No. 61-169789, polyamines described in No. 61-188619, nitroxy radicals described in No. 61-197760, No. 61-186561, and No. 61-9741
It is preferable to use alcohols described in No. 9, oximes described in No. 61-198987, and 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
Polyethyleneimines described in US Pat. No. 349, US Pat.
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 IJ hydroxy compound.

The color developer used in the present invention is preferably -9 to
12, more preferably 9 to 11.0, and the color developer may contain other known developer component compounds.

In order to maintain the above..., it is preferable to use each residual buffering agent for K.

Specific examples of buffering agents include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, disodium phosphate, tripotassium sulfate, disodium phosphate,
Dipotassium phosphate, sodium borate, potassium phonate, sodium tetraborate (1 ml of boric acid, potassium tetraborate, sodium 0-hydroxybenzoate (sodium salicylate), potassium 0-hydroxybenzoate, 5-sulfo-2 ~Human 90 Sodium xybenzoate (sodium 5-sulfosalicylate)% Potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate), etc. However, the present invention is limited to these compounds. It's not a thing.

The power of the buffer 2 - the amount added to the developer is 0.1 mol 1
It is preferable that the amount is more than 0.1 mol/1-0.
Particularly preferred is 4 mol/1.

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.

The chelating agent is preferably an organic acid compound, 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-)rimethylenephosphonic acid, ethylenediamine-N,N,N-N'-tetramethylenephosphonic acid, transcyclohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid, hydroxyethylimino Diacetic acid, glycol ether diamine tetraacetic acid, ethylenediamine orthohibiroxyphenylacetic acid, 2-phosphonobutane-1°2.4-11 carbonacetic acid,
1-hydroxyethylidene-1,1-diphosphonic acid, N
, N'-bis(2-hydroxyindyl)ethylenediamine-N,N-)acetic 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 11
It is about 0.19 to 109 per unit.

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 indyl alcohol from the viewpoints of pollution, formulation properties, and prevention of color staining. Here, "substantially" means that the developer contains 2 or less, preferably not at all, per 11 parts of the developer.

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, p-phenylenediamine compounds as shown in JP-A-52-49829 and JP-A-50-15554.

Japanese Patent Publication No. 50-137726, Special Publication No. 44-30074
No. 56-156826 and JP-A No. 52-4342
Quaternary ammonium salts represented by No. 9, etc., U.S. Pat. No. 2,494,903, U.S. Pat. No. 3,128,182, U.S. Pat. 11431, U.S. Patent No. 2.482,546
No. 2,596,926 and No. 3,582,346
Amine compounds described in Japanese Patent Publication No. 37-16088
No. 42-25201, U.S. Patent No. 3,128,1
No. 83, Special Publication No. 41-11431, No. 42-2388
Polyalkylene oxide 9 shown in No. 3 and US Pat. No. 3,532,50f, etc., 1-phenyl-3-pyrazolidones, imidazoles, etc. can be added as necessary.

In the present invention, any anti-capri agent can be added as required. As an anti-capri agent.

Alkali metal halides such as sodium chloride, potassium bromide, potassium iodide and organic anti-capri agents can be used. Examples of organic anti-capri agents include benzotriazole, 6-nitro-enzimidazole, 5-nitroisoindazole, 5-methylbencitriazole, 5-nitroisoindazole, and 5-nitroisoindazole.
nido cl incitriazole, 5-chloro-incitriazole, 2-thiacylyl-;/zimidazole, 2
Typical examples include nitrogen-containing heterocyclic compounds such as -thiazolylmethyl-benzimidazole, indazole, human-90xiazaindolizine, and adenine.

The color developer used in the present invention may contain a fluorescent brightener. As the fluorescent whitening agent, 4°4-diamino-2,2-disulfostilbene compounds are preferred. The amount added is 0 to 59/l, preferably α19 to 4 g/l.

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. The amount of replenishment is preferably small, but is 100 to 1500 ml, preferably 100 to 800 ml, per 1 m'' of photosensitive material. More preferably 1
00d~400m.

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 can be a so-called black-and-white first developer used in the reversal processing of color photographic light-sensitive materials, which is commonly known, or a developer used in the processing of black-and-white light-sensitive materials. It may also contain one or more of the well-known additives commonly added to black and white developers.

Typical additives include developing agents such as 1-phenyl-3-virazolidone, metol and hydroquinone, preservatives such as sulfites, and accelerators consisting of alkalis such as sodium hydroxide, sodium carbonate, and potassium carbonate. ,
Development inhibitors consisting of potassium bromide, inorganic or organic inhibitors such as 2-methylynraimidazole, methylbenzthiazole, water softeners such as poly-1717 salts, trace amounts of iodide, and mercapto compounds. I can give you some medicine.

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,
Bactericides and antifungal agents (for example, intiazolone, organic chlorine fungicides, 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
teria”, Phot, Sci.

and Eng, , vol, 9.46, page
344-359 (1965) and the like can also be used.

As the stabilizing liquid used in the stabilizing step, a processing liquid that can stabilize a dye image is used. For example, a solution having a buffering capacity of -3 to 6, a solution containing aldehyde 9 (for example, formalin), etc. can be used. The stabilizing liquid may contain ammonium compounds, metal compounds such as B1 and Afi, fluorescent whitening agents, chelating agents (for example, 1-hydroxyethylidene-1,1-diphosphonic acid), bactericides, and fungicides as necessary. , a hardening agent, a surfactant, etc. can be used.

Further, the water washing step and the stabilization step are preferably carried out by a multistage countercurrent method, and the number of stages is preferably 2 to 4 stages. The amount of replenishment is 01 to 50 times, preferably 2 to 30 times, more preferably 2 to 15 times the amount brought in from the front bath per unit area.

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 an Mg concentration of 511v/41 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 may occur due to evaporation, 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 has a blue-sensitive layer, a green-sensitive layer, a red-sensitive layer, and a silver rhodanide emulsion layer on the support.
There are no particular restrictions on the number and order of the silver rhodanide emulsion layer and the non-photosensitive layer. A typical example is a silver halide photographic light-sensitive material having on a support at least one photosensitive layer consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different photosensitivity. The photosensitive layer is a unit photosensitive layer that is sensitive to blue light, green light, or red light, and in a multilayer silver halide color photographic light-sensitive material, generally the unit photosensitive layer is The arrangement is, in order from the support side, a red sensitive layer,
A green sensitive layer and a blue sensitive layer are installed in this order. However, depending on the purpose, the order of installation may be reversed, or different photosensitive layers may be 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.

The plurality of silver halide emulsion layers constituting each unit photosensitive layer are high-sensitivity emulsion layers, as described in West German Patent @t, tzx, 4'yo or British Patent No. 923,045.
A two-layer structure of low-speed emulsion layers can be preferably used. 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. In addition, JP-A-57
-112751, 62-200350, 62-
As described in No. 206541, No. 62-206543, etc., 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/BI, /GL/GH/RH/RL, or BH/BL/GH/CL/RL/ It can be placed on bookmarks, etc.

Further, as described in Japanese Patent Publication No. 55-34932, K, blue-sensitive layer/GH/R from the side farthest from the support.
They can also be arranged in the order of H/GL/RL.

Alternatively, as described in JP-A-56-25738 and JP-A-62-63936, the blue-sensitive layer/GL/RL/GH/GH 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 logenide emulsion layer with the highest sensitivity, the middle layer is a silver halide emulsion layer with lower sensitivity, and the lower layer is a silver halide emulsion layer with a lower sensitivity than the middle layer. In addition, a silver halide emulsion layer having a low sensitivity is disposed, and an arrangement consisting of three layers having different sensitivities, the sensitivities of which are successively lowered toward the support, can be mentioned. Even when the layer is composed of three layers with different photosensitivity, as described in JP-A-59-202464, medium-sensitivity emulsions are added from the side remote from the support in the same color-sensitive layer. They may be arranged in the following order: layer/high-speed emulsion layer/low-speed emulsion layer.

Various layer configurations and arrangements can be selected depending on the purpose of each of the above-mentioned 51C1 photosensitive materials.

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 mole or less silver iodide. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 moles of silver iodide to about 25 moles of 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) 417643 (1
December 978), 22-23 Sada, @1. Emulsion production (E
mulsion preparation and t
ypes)', and same 18716 (1979
January), 648 Sada, Glafkides, “Physics and Chemistry of Photography”, Paul Montel Column (P, Glafkides,
Chemic et PhysiquePhotogr
aphique, Paul MonteL 196
7), "Photographic Emulsion Chemistry" by Duffin, Focal Press Column (G, F, Duffin, Photogr.
aphic Emulsion Chemistry (
Focal Press, 1966), "Manufacture and Coating of Photographic Emulsions" by Zelikman et al., Focal Press Column (1966);
V.L., Zellkman at al., Mak.
ing and coating photography
ic Emulsion, Focal Press.

(1964) and others.

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 an ast ratio of about 5 or more can also be used in the present invention. Tabular grains are described by Gutoff, 7 Photographic Science and Engineering (Gutoff, Photographic Sci.
ence and Engineering), No. 14
Volume 248-257 (1970); U.S. Patent No. 4,4
No. 34,226, No. 414,310, No. 4,43
3,048, 4,439,520, and British Patent No. 2,112,157.

The crystal structure may be --like, or it may have a layered structure in which the inside and outside have different halogen compositions, or it may have 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 crystalline forms may be used.

The silver halide emulsion used is usually one that has been subjected to physical ripening, chemical ripening, and spectral sensitization. Additives used in such processes are subject to Research Disclosure 417.
643 and Dorotsu 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 increasing agent 3 Spectral sensitizer, supersensitizer 4 Brightener 5 Anti-fogging agent Page 23 Page 648 Right column Same as above 23-24 648 Shell right column ~ 649 Right column 24 Pages 24-25 649 Negative right column ~ and stabilizers light absorbers, filter dyes, ultraviolet absorbers stain inhibitors dyes image stabilizers hardeners pi/goo plasticizers, lubricant coating aids, surfactants 25-26 Sada 649 shell right column ~ 650 page left column 25 page right column 25 Sada page 651 page left column 26 page 27 same as above 650 page right column 26-27 Sada 650 page right column 650 page left to right column 13 Static 27 page same as above In addition, in order to prevent the deterioration of photographic performance due to formaldehyde gas, compounds that can react with and fix formaldehyde as described in U.S. Pat. Nos. 4,411,987 and 4,435,503 are used. It is preferable to add it to a photosensitive material.

Various color couplers can be used in the present invention, specific examples of which can be found in the above-mentioned Research Disclosure (
RD) 417643, ■-〇-G.

As a yellow coupler, for example, U.S. Pat.
No. 3,501, No. 4,022,620, Same! 4,3
No. 26,024, No. 4,401,752, No. 4,
No. 248,961, Japanese Patent Publication No. 58-10739, British Pat.
No. 023, No. 4,511,649, European Patent No. 4
9.473 A, etc. are preferred.

The magenta coupler may be used in combination with 5-pyrazolone and pyrazoloazole compounds other than the magenta couplers mentioned above, and US Pat. No. 73.636,
U.S. Pat. No. 3,061,432, U.S. Patent No. 3.725,0
No. 64, Research Disclosure Consideration 2422 (1)
(June 1984), JP 60-33552, Research Disclosure 24230 (June 1984), JP 60-43659, JP 61-72238, JP 60-35730, JP 55-118034 No. 60-185951, U.S. Patent No. 4,500.630
No. 4,540.654, No. 4,556,63
Particularly preferred are those described in No. 0, WO (PCT) No. 88104795, and the like.

Cyan couplers include phenolic and 7-tole type carboxylates, and are described in U.S. Patent No. 4,052,212.
No. 4,146,396, No. 4.228233
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,
002 issue, riiJMs, 7ss, aog issue, 777
371g4.334,011, same No.4,327,17
3, West German Patent Publication No. 3,329,729, European Patent No. 121,365A, European Patent No. 249.453A, US Pat.
No. 9, No. 4,753,871, No. 4,451,5
No. 59, No. 4,427,767, No. 4,690,
No. 889, No. 4.254, 212, No. 889, No. 4.254, 212, No. 889, No. 4.254, No. 212, No. 889, No. 4.254, 212, No. 889, No. 4.254, No. 212, No. 4. 4,29
6,199, JP-A-61-42658, etc. are preferred.

Colored couplers for correcting unnecessary absorption of coloring dyes are listed in Research Disclosure Section 17643.
Section G, U.S. Pat. No. 4,163,670.

Special Publication No. 57-39413, U.S. Patent No. 4,004,9
No. 29, No. 4,138,258, British Patent No. 1,1
46,368 is preferred.

Couplers whose colored dyes have appropriate diffusivity include U.S. Patent No. 4.36,6,237 and British Patent No. 2.12.
No. 5,570, European Patent No. 96,570, West German Patent (
The one described in Japanese Publication No. 3,234,533 is preferred.

Typical examples of polymerized dye-forming couplers are U.S. Pat.
No. 4.576.9 I 0, British Patent @2,1
No. 02,173, etc.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. DIR couplers that release development inhibitors include the aforementioned RD 17643.
．． Patent described in Sections 4-2, JP-A-57-15194
No. 4, No. 57-154234, No. 60-184248
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 imagewise 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 the competitive couplers described in U.S. Patent No. 4,130,427, etc.; , multi-equivalent couplers described in JP-A No. 4,310,618, etc., DIR retox compound releasing couplers described in JP-A-60-185950, JP-A-62-24252, etc., DIR coupler-releasing couplers =
DIR Coupler-Releasing Retox Compound or DIR
Redox-releasing redox compound, European Patent No. 173,
302A, a coupler releasing a dye that after separation after separation, R, D, scrap 11449, 24241.

Bleach accelerator-releasing couplers described in JP-A No. 61-201247, ligand-releasing couplers described in U.S. Pat. etc.

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 U.S. 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, y-2-ethylhexyl phthalate, (decyl phthalate, bis(2,4-)-t-amylphenyl) phthalate, bis(2゜4-)-t-amylphenyl) isophthalate, bis(1,1-diethylpropyl) phthalate, etc.), phosphoric acid or Phosphonic acid esters (tri-7-el phosphate, tricresyl phosphate, 2-
Ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri2-ethylhexyl phosphate, tricresyl phosphate, tryptoxyethyl phosphate, trichloropropyl phosphate, -
, ;-2-ethylhexylphenylphosphonate, etc.)
, benzoic acid esters (2-ethylhexyl benzoate, dodecylbenzoate, 2-ethylhexyl p-
hydroxybenzoate, etc.), amides (N,N-diethyl P-decane amibi, N,N-diethyl laurylamide 0.N-tetradecylpyrrolito 97, etc.), alcohols or phenols (instearyl 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- diptyl-2-cytoxy-5-tert-octylaniline, etc.), hydrocarbons (halafine, r-decylyne, diimpropylnaphthalene, etc.), and the like. In addition, as an auxiliary solvent, the boiling point is about 50°C or higher, preferably 50°C or higher.
An organic solvent having a temperature of 160°C or higher can be used, and typical examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, and dimethylformamide.

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 eeper, color positive film, and color reversal R-Se.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, page 417643, and 64 of 18716
It is described from the right column on page 7 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 TI4 is preferably I seconds or less. Film thickness is δ℃ relative humidity 5
It means the film thickness measured under 5-inch humidity control (2 days), and the film swelling rate TI4 can be measured according to a method known in the art.

For example, A. Green et al., Photographic Science Ant9 Engineering (Pho, Sci, Eng.), 19
Volume, No. 2.

It can be measured by using a swellometer (swelling film) of the type described on pages 124 to 129, and TI4 is the maximum swelling film thickness of 901s that is reached when treated with a color developing solution at 30°C for 3 minutes and 15 seconds. The saturated film thickness is defined as the time required to reach the film thickness of TI4.

The membrane swelling rate T14 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 inches. 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.

EXAMPLES The present invention will be explained in detail below using Examples, but the present invention is not limited thereto.

Example 1 (Preparation of Sample 101) Sample 1 is a multilayer color photosensitive material consisting of an undercoated cellulose triacetate film support and each layer having the composition shown below.
01 was created.

(Composition of photosensitive layer) The coating amount is silver halide and colloid) #For silver, the amount expressed in units of 9/m' of silver, and for the coupler additive and gelatin, the amount expressed in units of g/m'. For sensitizing dyes, the number of moles is expressed per mole of silver halide in the same layer.

1st layer (Halesh anti-scratch N) Black colloidal silver ・・・・・・ 0.2 Gelatin ・・・・・・ 1.3EX
M-8...α06 UV-1...0. l UV-2...0.2 Solv-1...Mark 0.01 Solv-2--0,01 2nd layer (middle layer) Fine grain silver bromide (average grain size 0.07ttm)・・・・・・
0.10 gelatin ・・・・・・
1.5UV-1...0.06 UV-2...0.03 ExC-2-...0.02 ExF-1-"・0.004 Solv-1... ...αl 5olv -2" ・Fist j0.09 3rd layer (first red-sensitive emulsion layer) Silver iodobromide emulsion (All 2 molti, internal height Ag i type, equivalent sphere diameter 0.3 μm, equivalent to a sphere Coefficient of variation in diameter 29%, normal crystal, mixed twin grains, diameter/thickness ratio 2.5) Coated silver amount... Gelatin ExS-I EXS-2 ExS-3 ExC-3 ExC-4 ExC-7 ExC- 2 Solv -l 5olv -3 4th layer (second red-sensitive emulsion layer) Silver iodobromide emulsion (Ag 15 molar ratio, internal height Ag type I, equivalent sphere diameter 0.7μ, coefficient of variation of equivalent sphere diameter 25μ) , normal crystal, twinned mixed particles.

Diameter/thickness ratio 4) Coated silver amount... Gelatin 0.4 0.6 1, OX 10-' 3, OX 10-' I X 10= 0.06 α06 0.04 0.03 0. 03 0.012 0.7 0.5 xE3-1 X5-2 ExS-3 ExC-3 XC-4 ExC-7 ExC-2 Solv-1 Solv-3 X5 layer (third red-sensitive emulsion layer) Iodobromide Silver emulsion (Agl 10 molti, internal high Ag I
Model, equivalent ball diameter to 0.8 μ, coefficient of variation of ball equivalent diameter to 16 μ,
Normal crystal, mixed twin grain, diameter/thickness ratio 143) Coated silver amount ...... Gelatin ...
・・ExS-1・・・・・・ ExE3-2 ・・・・・・ExS
-3-= ExC-5... ExC-6... 1 X 10-'3X10-' I X 10-5 0.24 0.24 0.04 0.04 0.15 0.02 1.0 1.0 1 X 10-4 3×10″4 1 X 10-5 0.05 0.1 Solv-1...5olv-2...6th Layer (middle layer) Gelatin...Cpd-1.
...5olv-1... Seventh layer (first green-sensitive emulsion layer) Silver iodobromide emulsion (AgI 2 molti, internal high Agl type,
Equivalent sphere diameter 0.3 μm, coefficient of variation of equivalent sphere diameter 28%, normal crystal, twin crystal mixed particles, diameter/thickness ratio 2.5) Coated silver amount
...EXS-4... ExS-5... E, S-5... Gelatin ......T! ,xkA
-9... KXY -14... ExM-8... 5olv-1... 0, Ol 0.05 1.0 0.03 0.05 0.30 5 X 10-' 0.3 X 10-' 2 , internal high Agl type 1
Coefficient of variation of 1 sphere equivalent diameter to 0.6μ, normal crystal, twin crystal mixed particle.

Diameter/thickness ratio 4) Coated silver amount ・・・・・・ α4 gelatin ・・・・・・ 0.5ExS-4・
・=-5xlO-' Er5-5 ...-2X1
0-'E):S-6・・・0.3X10-'ExM-
9=-0,25 ExM-8...0.03 ExM-10-"...0.015 ExY-14"/0.01 Solv-1=0.2 9th layer (3rd green Sensitive emulsion layer) Silver iodobromide emulsion (Ag 16 molten, internal high Agl type, equivalent sphere diameter 1.0 μm, coefficient of variation of equivalent sphere diameter 80%, normal crystal, twin crystal mixed grain, diameter/thickness ratio 1.2) coating Amount of silver...
・ 1.20 gelatin ・・・・・・
1.0ExS-7... ExS-8... EXM-12... EXM-8... ExY-15... 5olv-1 ...... So lv -2... 10th layer (yellow filter layer) gelatin
・・River・ L2 yellow colloidal silver
・・・・・・ 0.08Cpd-2・・・・・・ 0.
l 5olv-1・-” 0.3 11th layer (11th r-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol ratio, internal high AgI type 1
(Equivalent sphere diameter 0.5μ groove, coefficient of variation of sphere equivalent diameter 15%, octahedral particles) Coated silver amount ...... 3.5 X 10-4 1.4 X 10"-' 0.25 α02 α02 0.20 0.05 Gelatin MS-9 ExY-16 ExY-14""" α07 Solv-1= 0.2 12th layer (second blue-sensitive emulsion layer) Silver iodobromide emulsion (Ag110 molti, internal height Agl Type, equivalent sphere diameter 1.3μ, coefficient of variation of equivalent sphere diameter 6chi, normal crystal,
Twinned mixed grains, diameter/thickness ratio 4.5) Coated silver amount...
・・・ 0.5 gelatin ・・・・・・
・0.6ExS-9...1×1o" ExY-16=-0,25 Solv-1"...0.07 13th layer (first protective layer) Gelatin...0 .8UV
-1...0. l UV-2...0.2 Solv-1''=0.01 Solv-2-''・0.01 14th layer (second protective layer) Fine grain silver bromide (average particle size 0.07 μm ) ・・・・・・ 0.5
Gelatin ・・・・・・ 0.45 Polymethyl methacrylate particles (diameter 1.5 μm) ・・・・・・ 0.2
H-1... 0.4 Cpd-3... 0.5 Cpd-4・Mountain... 0.5 In addition to the above ingredients, a surfactant was added to each layer as a coating aid. It was added as an agent. Sample 10 was prepared using the above procedure.
It was set to 1.

Next, the chemical structural formulas or chemical names of the compounds used in the present invention are shown below.

UV-1: x/y=773 (weight ratio) UV-22 ExF-1: 5olv-1 tricresyl diphosphate 5olv-2: Diptyl phthalate 5olv-3: Bis(2-ethylhexyl) phthalate ExC-2: ExM-8: EXC-3: ExC-4: ExY-15: ExY-14: gxc-5: C(CH3)3 ExC-6: EXC-7: ExM-12: EXY-16 Cpci-1: H H ExM-9: ExM-10: Cpd-2: ExS-1: ExS-2: H ExS-3: KXS-4: ExS-5: ExS-9: H-1: Cpd-3: Cpd-4 : 2H5 EXS-6: 'F, xE3-7: ExS-8: Cp-1: (Creation of sample 102) Magenta coupler ExM-12 in the 9th layer of sample 101
Sample 102 was prepared in the same manner as Sample 101 except that the comparative coupler Cp-1 was substituted in equimolar amounts in place of Cp-1.

(Creation of samples 103 to 107) In place of magenta coupler ExM-12 in the 9th layer of sample 101, couplers M-8, M-59, M-10 of the present invention were used.
1゜M-105 and M-114 were each replaced in equal moles,
Samples 103 to 107 were prepared in the same manner as sample 101 except that the amount of coated silver was changed to 0.809''.

The above samples 101 to 107 were subjected to white imagewise exposure and color development treatment A shown below was performed using an automatic processor.

Table 3 summarizes the results of the amount of residual silver measured by a fluorescent X-ray measuring device, the amount of remaining silver, and the change in gradation due to formalin gas.

Samples 103-10 containing magenta couplers of the present invention
It was found that the amount of residual silver was low, the magenta tin was low, and the influence of formalin was low from the results obtained by treating No. 7 with a bleaching solution within the range of the present invention.

Color Development Process A> First, the photosensitive material was cut into 35 m wide pieces and exposed to standard light in a camera. This was processed for 500 m to make each method into a steady porcelain/ninda solution, and aqueous ammonia and acetic acid were added to the bleaching solution, and the bleaching pI (pI) was changed as follows, and the photosensitive material was processed.

*Amount of replenishment: per 1 length of photosensitive material 35 m wide (color developer) Diethylenetriaminepentaacetic acid Sodium sulfite Potassium carbonate Potassium bromide Potassium iodide Hydroxylamine sulfate Add sulfate water... (Bleach solution) 1.3- Diaminopropanetetraacetic acid ferric complex salt 1.3-Diaminopropanetetraacetic acid ammonium bromide Ammonium acetate nitrate Add water and adjust p)'l with acetic acid and ammonia Mother liquor (9) 5.0 4.0 30.0 1.3 1621η 2.0 1.0fi 10.00 Replenisher (9) 6.0 5.0 37.0 C5 3,6 1,0! 10.15 Mother liquor (g) Replenisher (9) 3.0 1.01 pJ (4,3 4,0 1,01 pH 3,5 (Fixer) Replenisher (9) 7.0 Mother liquor (g) 1- Hydroxyeilidene-1,1 pH5.0 diphosphonic acid ethylenediaminetetraacetic acid disodium salt 0.5 Sodium sulfite 10.0 Sodium bisulfite 8.0 Ammonium thiosulfate aqueous solution (
700Vl) 170.0d Rodan ammonium
100.0 Thiourea 10 3.6-thiourea 1,8-octanediol 3.
Add 0 water and 1.0ffi acetic acid,
Add ammonia to pH 6.5 (Stable solution) Mother solution, replenisher Common formalin (37%) 1.21 5-chloro-2-methyl-4-iso 6.0M
gThiazolin-3-one 2-methyl-4-isothiazolin-3-one 3.0■
Surfactant 0.4 (C1, H21
-0+CH2CH2O+1oH) ethylene glycol
1.0 Add water 1
．． Olkan 5.0-7.0
0.7 ZO 10,0 200,0d 150.0 5.0 5, O ON 6.7 Example 2 (Preparation of Sample 201) On a subbed cellulose triacetate film support, the following coating was applied. Sample 201, which is a multilayer color photosensitive material, was prepared by applying layers of each composition.

(Photosensitive layer composition) The numbers corresponding to each component indicate the coating amount expressed in 9/- units, and for silver halide, the coating amount is expressed in terms of silver. However, for sensitizing dyes, silver halide 1 in the same layer
The coating amount is expressed in moles.

(Sample 101) 1st layer (anti-scratch layer) Black colloidal silver $ 0.18 Gelatin 0.40 2nd layer (intermediate layer) 2.5-di-t-interdecylhydroquinone 0.18
EX-10,07 EX-30,02 X-12 BS-1 B5-2 Third layer of gelatin (first red-sensitive emulsion layer) Emulsion A Emulsion B Sensitizing dye ■ Sensitizing dye ■ Sensitizing dye m X-2 X-10 Gelatin 4th layer (second red-sensitive emulsion layer) Emulsion C Sensitizing dye I Sensitizing dye ■ 0°002 0.06 0.08 0.10 0.10 0.02 1, O4 Silver 0.25 Silver 0.25 6.9 X 10= 1.8 X 10-5 3, I 5 Sensitizing dye ■ EX-2 EX-3 11i: X -10 Gelatin 5th layer (third red-sensitive emulsion layer) Emulsion sensitizing dye I Sensitizing dye ■ Sensitizing dye ■ F, X-3 EX-4 EX-2 5B-1 5B-2 Gelatin 6th layer (intermediate layer) EX-5 B5-1 Gelatin 2,.3 X IF' 0.400 o, os.

O,015 Silver 1,60 5.4X10-5 1.4X10-' 2.4 X 10-' 0,010 0.080 0.097 0.22 0.10 1.63 0.040 0°020 O, SO 7th layer (first green-sensitive emulsion layer) Emulsion A Emulsion B Sensitizing dye V Sensitizing dye ■ Sensitizing dye ■ EX-6 EX-1 EX-7 EX-8 B5-1 B5-3 Gelatin 8th layer (Second green-sensitive emulsion layer) Emulsion C Sensitizing dye ■ Sensitizing dye ■ Sensitizing dye ■ EX-6 EX-8 Silver 0.15 Silver 0.15 3, OX 10-'LOXIO-' 3.8 X 10 -' 0.260 0.021 0,030 0, O25 0,100 0,010 0,63 Silver 0.45 ZIXIO-'7.0X10' Z6 X 10-' α094 0,018 EX-7 B5-1 B5 -3 Gelatin 9th layer (third green-sensitive emulsion layer) Emulsion E Sensitizing dye V Sensitizing dye ■ Sensitizing dye ■ 1i:X-11 EX-1 B5-1 B5-2 Gelatin 10th layer (yellow filter layer ) Yellow Colloidal 9 Silver EX-5 B5-1 Gelatin 0.026 0.160 o, oos O950 Silver 1.2 3.5 X 10-5 8.0X10-'3.0X10-' 0.12 0,025 0 .25 0.10 1.54 Silver 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 Sensitizing dye ■ EX-9 EX-10 B5-1 Gelatin 13th layer (third blue-sensitive emulsion layer) Emulsion H Sensitizing dye ■ EX-9 Silver α08 Silver 0.07 Silver α07 3.5 -' α20 HBS-1 Gelatin 14th layer (first protective layer) Emulsion I B5-1 Gelatin 15th layer (second protective layer) Polymethyl acrylate (diameter approx. 1.5μ) To particles 0.07 0 .69 0.5 0.11 0.17 0.05 1.00 0.54 0.20 Gelatin 1.20 In addition to the above ingredients, gelatin hardening agent H-1 and surfactant were added to each layer. .

X-1 X-4 X-5 X-2 X-6 X-3 C6H13 (nl mol, wt, approx. 000 ) C4H9 B5-1 Tricresyl phosphate B5-2 Di-lobe tylphthalate sensitizing dye I (t) C4H9 Sensitizing dye ■ x : y = 70:30 (wt, %) Sensitizing dye ■ Sensitizing dye ■ Sensitizing dye Sensitizing dye V Sensitizing dye■ Sensitizing dye■ (Preparation of samples 202 to 204) Replace the magenta coupler EX-11K in the 9th layer of sample 201 with couplers of the present invention M-8, M-59, M-105, etc. Sample 2 was prepared in the same manner as Sample 201 except that the moles were replaced.
204 was created from 02.

After applying white imagewise path light to the above samples 201 to 204, the following color development treatment B was performed using an automatic processor.

<Color development process B> Same process as process A except that the fixer in color development process A was changed to the following composition.

-204 was less affected by formalin and had a small amount of residual silver (and low stain) by bleaching within the scope of the present invention.

Disodium salt O゛50°7 Sodium sulfite 10.0 12.0 Sodium bisulfite ao io,.

Ammonium thiosulfate aqueous solution (700 Vl) Add aqueous rhodanammonium thiourea, add acetic acid and ammonia, and make 170.0M1 200.0d 100.0 150.0 1.5 10 11 1fl pH6.5pi (6.7 Same as Example 1) Table 4 summarizes the amount of residual Ag and the stain when the bleaching solutions were changed.

Sample 202 containing the magenta coupler of the present invention Example 3 (Preparation of sample 301) Sample 301 is a multilayer color photosensitive material consisting of each layer having the composition shown below on an undercoated cellulose triacetate film support. was created.

(Composition of photosensitive layer) The coating amount is the amount expressed in units of silver for silver halide and colloidal silver, and the amount expressed in units of g/♂ for coupler additives and gelatin. For dyes, the number of moles is expressed per mole of silver halide in the same layer.The symbols indicating additives have the meanings shown below.However, if they have multiple effects, one of them should be used as a representative. I posted it.

Uv; ultraviolet absorber, 5olv; high boiling point organic solvent, EX
F: Dye, Ext: Sensitizing dye, ExC rainbow coupler, ExM: Magenta coupler, EXY: Yellow coupler, Cpa: Additive 1st layer (antihalation layer) Black colloid @ 0.15 gelatin 2. ．． 9UV-10
,03 UV-20,06 UV-30,07 Solv 2
0.08ExF-10,01 ExF-20,01 2nd layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (Agl 4 molti, uniform Agl type, equivalent sphere diameter 0.4μ, equivalent sphere diameter Coefficient of variation 37ch.

Plate-like particles, diameter/thickness ratio 3.0) Coated silver amount 0.4 0.8 2.3 X 10-'1゜4XIO-' 2.3 X 10-'&OX 10-6 0.17 0.03 0.13 Gelatin/ Ext-1 X5-2 Internal high Agl type with a ratio of 2:1, equivalent ball diameter of 0.65μ.

Coefficient of variation of equivalent sphere diameter 25%, plate-like particles, diameter/thickness ratio 2
0) Coated silver amount 0.65 silver iodobromide emulsion (A
gl 4 molti, homogeneous AgJ type.

Equivalent sphere diameter 0.4μ, coefficient of variation of 1 sphere equivalent diameter 37%, plate-shaped particles, diameter/thickness ratio 3.0) Coated silver amount 0.1 Gelatin 1.0ExS-1
2X10-' ExS -21,2X10-'ExS-52X10-' EXS-77X10-6 ExC-10,31 ExC-20,01 ExC-30,06 4th layer (high sensitivity red-sensitive emulsion layer) Silver iodobromide Emulsion (Ag 16 mole, internal high AgI type with core-shell ratio 2:1, equivalent sphere diameter 0.7 μm, coefficient of variation of equivalent sphere diameter 25 μm, plate-like grains, diameter/thickness ratio 2.5)
Silver amount gelatin xE3-s xE3-2 Ex S-5 xS-7 Ex C-1 XC-4 olv-1 olv-2 pd-7! ! 5th layer (intermediate layer) Gelatin V-4 V-5 pd-1 Polyethyl acrylate latex olv-1 6th layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (Ag1 4 molti, 0.9 0.8 1.6 X io-'!, 6X10-' 1.6 X 10-' 6 0.1 0.08 0.05 Uniform Agl type, equivalent sphere diameter 0.4 μ, coefficient of variation of equivalent sphere diameter 37 mm, plate-shaped particles, diameter/thickness ratio 2.0) Coated silver amount 0.18 Gelatin 0.4ExS-3
2X10-'EMS-47xlO-' ExS -51XIO"-' ExM-50,11 ExM-70,03 ExY-80,01 Solv-10,09 Solv-40,01 7th layer (medium-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (Agl 4 molti, core shell ratio l:
1 surface height Agl type, equivalent sphere diameter 0.5μ.

Coefficient of variation of equivalent sphere diameter: 20 cm, plate-shaped particles, diameter/thickness ratio: 4
．． 0) Coated silver amount 0.27 gelatin
0.6ExS-32X10-'ExS-47X10-'ExS-51Xl0-' Ext-50,17 EXM-70,04 ExY-80,02 Solv-10,14 Solv-40,02 8th layer (high sensitivity green feeling Emulsion layer) Polymerized emulsion (AgI 8.7 molti, silver ratio 3:4:
2 multilayer structure particle, Agl content from inside u mole, 0 mole, 3 mole i sphere tlo, 7 μlo, coefficient of variation of sphere equivalent diameter 2
5%, plate-shaped particles, diameter/thickness ratio 1.6) Gelatin xS-4 X5-5 XX5- 8Ex -5 xM-6 xY-8 Coated silver amount 0.7 0.8 5.2 X 10"-' 0.3 X 10-' 0.1 0.03 0.02 KxC-1 KXC-4 olv-1 olv-2 olv-4 Cpa -7 9th layer (middle layer) Gelatin 0.6 cpa -1
0.04 Polyethyl acrylate latex 0. Technique 2Solv-10,02 10th layer (donor layer for interlayer effect on red-sensitive layer) Silver iodobromide emulsion (Agl 6 molti, internal high Agl type with core-shell ratio 2:1, equivalent sphere diameter 0.7μ poison.

Plate-shaped particles with a coefficient of variation of equivalent sphere diameter of 25 cm.

Diameter/thickness ratio 2.0) 0.02 0.25 0.06 0.01 1XIO"-' Coated silver amount 0.68 Silver iodobromide emulsion (Agl 4 molti, uniform Agl type, equivalent sphere diameter 0. 4μ, coefficient of variation of equivalent sphere diameter 3'7%, plate-shaped particles, diameter/thickness ratio 3.0) Coated silver amount 0.19 Gelatin i.

ExE3-3 8X10-'Ex
M-100,19 Solv-10,20 11th layer (yellow filter layer) Yellow colloidal silver 0.06 gelatin o, 5Cpd-20,13 Solv-10,L3 Cpd-10,07 cpa-60,002 H-10 , 13 12th layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (Ag1 4.5 molti, uniform-Agl type,
Equivalent sphere diameter 0.7 μm, coefficient of variation of equivalent sphere diameter 15 mm, plate-like grains, diameter/thickness ratio 7.0) Coated silver amount 0.3 Silver iodobromide emulsion (Agra morch, uniform Agl type, Equivalent sphere diameter 0.3 Am, coefficient of variation of equivalent sphere diameter a30%, plate-like particles, diameter/thickness ratio 7.0) Coated silver amount 0.15 Gelatin l, 8ExS-6
9X10-' ExC-10,06 EXC-40,03 ExY-90,14 ExY-11089 Solv-10,42 13th layer (middle layer) Gelatin 0.7ExY-1
20, 20 Solv-10, 34 14th layer (high sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (AgllO morch, internal high Agl type, equivalent sphere diameter 1.0 Am, coefficient of variation of equivalent sphere diameter various, multiple Twin platelet particles, diameter/thickness ratio ZO) Coated silver amount 0.5 Gelatin 0.5EXS-6
1XIO″″4 E x Y -90,01 ExY-110,20 EXC-10,02 Solv-10,10 15th layer (first protective layer) Fine grain silver iodobromide emulsion (Agl 2 molti, uniformly
Mold, equivalent sphere diameter 0.07μqTL) Coated silver amount 0.12 Gelatin 0.9 UV-40,11 TIV-50,16 Solv-50,02 H-10,13 0pd-50,10 Polyethyl acrylate latex 0 .09 1st
6 layers (second protective layer) Fine grain silver iodobromide pores (Agl 2 molti, uniform Agl type, equivalent sphere diameter 0.07 μm) Coated silver amount 0.36 Gelatin 0.55 polymethyl methacrylate particles (diameter 1.5 μm) 0.2 V-4 0.17 In addition to the above ingredients, each layer contains emulsion stabilizer cpa-3 (0,079/♂) and surfactant Cpd-4 (0,03
9/inert2) was added as a coating aid.

x:y=70:30 (wt) V-5 v-1 olv-1 Tricresyl phosphate (t)C,H9 olv-2 Diptyl phthalate V-2 olv-5 Trihexyl phosphate (t)04) 1g xF-1 Ex S-2 E: cF ”-2 E): S-4 xS-1 xS-5 gxs-6 EXS=7 gxs-8 ExC-1 ExC-4 XC-2 ExC-3 xM-10 C horse fl H3 EXY -9 Cpd-7 Cpa -1 xY-11 A3 xY-12 Cpa-6 N-m-N cpa -5 <Color development process C> Cpa-3 Cpa-4 (Color developer and mother liquor ( 9) Replenisher (IJ) Diethylenetriaminepentaacetic acid 5.0 7.0 Sodium sulfite 4.0 6.0 0M2=CH-So□-CH2-C0NH-Cki2 Potassium carbonate 30.0 35, O Potassium bromide 1 .3 0.2 Potassium iodide 1.2 ~ Human 90 Kifluamine sulfate 2.0 4.0 4-(N-ethyl-N-β-hydroxyethylamino)-2-methylaniline sulfate 1-hydroxyethylidene- Add 1,1-diphosphonic acid water (IN'i white liquor) 1.3-diaminopronosone tetraacetic acid ferric complex salt 1.3-diaminopropane tetraacetic acid ammonium bromide acetic acid ammonium nitrate Add water to make acetic acid and ammonia (Fixer) 1-Hydroxyethylidene-1,1-diphosphonic acid ethylenediaminetetraacetic acid disodium salt 3.0 1.0 base 10.05 Mother liquor (91 3,0 1, Ol 4.0 6.5 4. 0 1.0Q 10.20 Replenisher (g) Mother liquor (9) Replenisher (9) 7,0 10.0 10.0 Ammonium sulfite ammonium thiosulfate solution (7009/fl) 16.0 25.0 240d 280tj 3. 6-:) Thia-1,8-octane 5.0
Add 7.0 diol water 1.0 pm 1.0ρ
pH 6.5e, s with acetic acid and ammonia (washing water) Common tap water for mother liquor and replenisher with H-type strongly acidic cation exchange resin (A/Pearlite IR-I20B manufactured by Rohm and Haas).

OH type anion exchange resin (Amberlite IR-40)
Water is passed through a mixed bed column filled with 0) to reduce the concentration of calcium and magnesium ions to 31q/fi or less,
Then sodium dichloride isocyanurate 20119/
fi and 0.159/υ of sodium sulfate were added.

The field of this liquid was in the range of 6.5-7.5.

(Stabilizing solution) Formalin (37 g) Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) Add ethylenediaminetetraacetic acid disodium salt solution to close the mother solution (9) 2,0-0,3 gl 3, Od 0.45 0.05 0.08 1.0°C 1, (l! 5.0-8.0 5.0-8.0 After subjecting the above sample 301 to white imagewise exposure, the following After carrying out the color development treatment C shown below, the amount of residual Ag and stain were measured.The results are summarized in Table 5K.

From Table 6, in the treatment of bleaching solutions within the range of the present invention,
The amount of residual Ag was low, and the magenta tin was also low.

Next, 1.3 of the composition of the bleaching solution in color development treatment C
- A similar experiment was conducted by changing the amount of ferric complex salt of diaminopropane tetraacetic acid as follows.

Bleach solution (pH 4,8) 1. Amount of ferric complex salt of 3-diaminopropanetetraacetic acid (mol/l) 120 (0,33 mol/l) 101
(0,28r) 83 (0,23) 65 (0,18) The results are summarized in Table 7K.

<Table 7> (Effect of the invention) By implementing the present invention, Stay/less

Claims (1)

[Scope of 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 processing solution having bleaching ability is 1,3-diaminopropane tetrafluoride. Contains 0.2 mol/l or more of ferric acetate complex salt and has a pH of
2.5 to 5.5, and that the silver halide color photographic light-sensitive material contains at least one compound represented by the following general formula [I] and/or [II] as a magenta coupler. Characteristic processing method for silver halide color photographic materials. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [I] In the formula, R^1 is a carbonamide group, a sulfonamide group,
R^2 represents a phenyl group, and Z represents a group capable of leaving as an anion (hereinafter referred to as a leaving group) through a coupling reaction with an oxidized aromatic primary amine developer. [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the general formula [II], R_1_0 represents a hydrogen atom or a substituent (including a substituent atom), and Y_2 represents a hydrogen atom or a coupling-off group (including a separation atom). The same applies hereinafter), and Za, Zb and Zc are methine, substituted methine,
=N- or -NH-. Za-Zb bond and Zb-
One of the Zc bonds is a double bond and the other is a single bond. When Zb-Zc is a carbon-carbon double bond, it includes when it is part of an aromatic ring. Furthermore, R_
A dimer or more multimer may be formed by one group from the group consisting of 1_0, Y_2 and Za, Zb or Zc representing a substituted methine.