JPH01223458A - Method for processing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To shorten the time of the desilvering step of the sensitive material by processing the silver halide photographic sensitive material contg. a specified coupler capable of releasing a development retarder and a specified gelatin hardening agent with a bleaching solution contg. a specified ferric complex salt and a specified diacetate in a specified ratio. CONSTITUTION:The silver halide color photographic sensitive material contains one or more kinds of the gelatin hardening agent shown by formula I and one or more kinds of the coupler capable of releasing the development retarder. The retarder releases the compd. capable of controlling the development of silver halide by an electron transfer reaction of a releasing body via ethylenic dienes, and said releasing body releases a precursor of a compd. capable of controlling the development of the silver halide by allowing the compd. to react with the oxidant of a developing main agent at the time of developing. The sensitive material is processed with the processing solution contg. the diacetate of 1,3-diaminopropane tetra-acetic acid and one or more kinds of the ferric complex salt of a compd. shown by formulas II-V in a mol. ratio of <=3 and having bleaching ability. Thus, the desilvering step of the sensitive material is effected for a short period without generating a pollution and maintaining high sharpness of the sensitive material. In the formula, X<1> and X<2> are each -CH=CH2 or -CH2CH2 Y group, Y is a group capable of substituting with a nucleophilic group or a group capable of being released a group HY with a base, L is two binding groups.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention relates to an exposed silver halide color photographic light-sensitive material (
This technology relates to the development processing method (hereinafter simply referred to as processing) for developing, bleaching, and fixing color photosensitive materials (hereinafter referred to as color photosensitive materials).In particular, it accelerates the bleaching action, shortens processing time, and performs sufficient bleaching to improve image quality. The present invention relates to an improved development processing method capable of forming good color photographic images.

(Prior Art) -m. The basic steps of processing color photosensitive materials are a color development step and a desilvering step. That is, the exposed silver halide color photographic material is subjected to a color development process. Here, silver 10genide 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. 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 bath. Examples include a membrane removal bath for removing the backing layer.

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

In recent years, in color photographic materials, from the viewpoint of quick and simple processing and prevention of environmental pollution, ferric ion complex salts (e.g., ferric aminopolycarboxylic acid ion complex salts, etc.), especially iron ethylenediaminetetraacetate ( I[I]
Bleaching prescription methods based on complex salts are mainly 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 emulsions with a high silver content, the bleaching effect may be insufficient and desilvering may fail, or the bleaching may take a long time. It has the disadvantage of being time consuming.

In color light-sensitive materials, sensitizing dyes are generally used for the purpose of color sensitization. In particular, when parallel 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 bleaching solution by adding chloride. However, the disadvantage of bleaching solutions using persulfates is that they have a weaker bleaching edge than ferric ion complex salts 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 desirable 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 complex salts in combination, but these methods also do not require sufficient treatment. It has not reached the point where it exhibits a bleaching accelerating effect.

On the other hand, in recent years, advances in color photographic materials have significantly improved the image quality of color photographs, and print quality from small formats (110 size, disk size) has become acceptable.

To improve image quality, U.S. Patent Nos. 3,227,554 and 3
, No. 701,783, No. 3,615.506, No. 3,
It is a well-known fact that the so-called DIR coupler described in No. 617.291 plays a major role in improving sharpness. However, JP-A-54-1451 improved these.
Although the use of the DIR coupler having a timing group described in No. 35 provides even higher sharpness, it was not optimal due to problems such as stability of the compound.

Also, JP-A-56-114946 and JP-A No. 58-98728
The timing type DIR described in No. 5B-209738, No. 58-209739, and No. 5B-209740
The coupler has been improved in these shortcomings, but this DIR
It has become clear that the use of couplers slows down the desilvering step in processing and requires sufficient time for desilvering, particularly for the oxidation process by bleaching the reduced silver.

Therefore, it has been desired to develop a new method that can shorten the desilvering process in the processing of photosensitive materials whose sharpness has been increased using the timing-type DIR coupler.

(Problems to be Solved by the Invention) Therefore, the first object of the present invention is to provide a method for processing a color photographic material that has high sharpness and allows a desilvering process to be performed in a short time.

The second object is to provide a method for processing a silver halide color photographic light-sensitive material that uses a timing type DIR coupler and has excellent desilvering properties even in a running state.

(Means for solving the problem) The above problem could be solved by the method described below.

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 silver halide color photographic light-sensitive material reacts with an oxidation product of a developing agent during development. , a development inhibitor release in which a precursor of a compound that inhibits the development of silver halide is released, and then the precursor releases a compound that inhibits the development of silver halide by an electron transfer reaction via an ethylenic conjugated chain. A processing solution containing at least one coupler and at least one gelatin hardener represented by the following general formula (H) and having the bleaching ability contains the following compound group (A) as a bleaching agent.
) and 1,3-diaminopropanetetraacetic acid ferric acetate in a molar ratio of the former to the latter of 3 or less. A method for processing silver halide color photographic materials.

General formula (H) 2. Description of the Related Art In order to increase the water resistance and mechanical strength of a gelatin layer used as a binder in photographic materials, methods of hardening gelatin using various compounds are conventionally known.

For example, aldehyde compounds such as formaldehyde and glutaraldehyde, compounds containing reactive halogens as described in U.S. Pat. No. 3,288,775 and others, U.S. Pat.
Compounds with reactive ethylenically unsaturated bonds described in No. 13563 and others, U.S. Pat. No. 3,017,2
aziridine compounds described in U.S. Pat. Additionally, chromium alum, zirconium sulfate, etc. are known as inorganic hardening agents.

Among these many hardening agents, when the compound represented by the general formula below is used in combination with the bleaching agent of the present invention, the delay in bleaching when using the timing-type DIR compound can be prevented. This finding is surprising even to those skilled in the art.

Next, a precursor of a compound that inhibits development of silver halide is released by a coupling reaction with the oxidized aromatic primary amine developer used in the present invention, and then the precursor is released via an ethylenic conjugated chain. A development inhibitor-releasing coupler that releases a compound that inhibits silver halide development through an intramolecular electron transfer reaction will be described in detail.

The development inhibitor-releasing coupler is represented by the following general formula (1).

General formula [1] R1 A' -Q-(L)r-C-W R≧ In the formula, A' is an aromatic primary amine group (& a coupler that releases Q or less by coupling reaction with folate) the residue,
Q is an oxygen atom, a sulfur atom or a substituted imino group, L is a vinylene group, l is an integer of 1 or 2, R1 and R1 are each independently a hydrogen atom, an alkyl group or an aryl group, W is a silver halide component (compound) that inhibits the development of
respectively, provided that when 1 is 2, the vinylene groups may be the same or different.The vinylene group represented by these is preferably a component of a benzene ring or a heterocycle.

Further, when Q represents a substituted imino group, it is preferable that the substituted wA group is bonded to L to form a 5- to 7-membered nitrogen-containing ring together with the nitrogen atom and L.

Further, among the compounds represented by the general formula (''[), compounds represented by the following general formulas (π] to ('73) are preferable.

General formula [English] General formula [U] I2 General formula (1F) ", ■, ... z -1Q formula CI) ~ ("7) Nitij I T-2A',
R1゜R2 and W are A゛, R1% in the general formula [Engine]
They are synonymous with Ryo and W, respectively, and vl and V! represents a nonmetallic atomic group necessary to form a 5- to 7-membered nitrogen-containing tri ring (which may have a substituent or be a fused ring) together with the bonding atomic group; Forms a 5- to 7-membered heterocycle (which may have a substituent or be a fused ring) or a benzene ring (which may have a substituent or be a fused ring) with the bonding atomic group 2 represents a substituted or unsubstituted methine group or a nitrogen atom, R1 represents a hydrogen atom or a monovalent group, and R11 and R+2 each independently represent a monovalent group. However, R3 may be bonded to v2 to form a ring.

Next, A゛, R1, RL in general formulas CI) to (T)
, Rs, R/l, RI2, Z and W will be described in detail. Couplers 85 represented by A' include yellow image-forming couplers, magenta image-forming couplers, cyan image-forming couplers, and so-called colorless couplers in which the campling reaction product is substantially colorless.

The yellow image-forming coupler residue represented by A' includes pivaloylacetanilide type, benzoylacetanilide type, malondiester type, malondiamide type, dibenzoylmethane type, benzothiazolylacetamide type, malone ester monoamide type, and benzoylacetanilide type. Eight couplers of the thiazolyl acetate type, benzoxacylylacetamide type, benzoxa/' IJ acetate type, malon diester type, benzimidazolylacetamide type or benzimidazolylacetate type, U.S. Patent 3,
Coupler residues derived from heterocyclic substituted acetamides or heterocyclic disubstituted acetates contained in US Pat. No. 841,880, or U.S. Pat.
No. 459,171, West German Patent (OLS) 2.503.0
No. 99, Japanese Patent Publication No. 5G-139,738 or Research, Disclosure No. 15737, coupler residues derived from acylacetamides, or
Examples include the heteroprototypical coupler residues described in US Pat. No. 4,046,574.

The magenta image-forming coupler residue represented by A' includes pyrazolo-(1,
5-a) Coupler residues having a benzimidazole nucleus, a pyrazoloimidazole nucleus, a pyrazolotriazole, a pyrazolotetrazole or a cyanoacetophenone type coupler residue are preferred.

The cyan image-forming coupler residue represented by A' is preferably a coupler residue free of phenol or containing α-naphthol.

Furthermore, the effect as a DIR coupler is the same even if the coupler does not substantially form a dye after coupling with the oxidized form of the developing agent and releasing the development inhibitor. A'
This type of coupler residue represented by
．． No. 052.213, No. 4.088.491, No. 3,
No. 632.345, No. 3.958,993 or No. 3,
Examples include the coupler residues described in No. 961.959.

Preferred examples of the coupler residue represented by A' are represented by general formulas (Cp-1) to (Cp-9> described below).

R1 and R2 are each independently a hydrogen atom, carbon atom number 1
~36 alkyl groups (e.g. methyl, ethyl, benzyl, dodecyl, cyclohexyl, etc.) or aryl groups having 6 to 36 carbon atoms (e.g. phenyl, 4-
methoxyphenyl group, 4-chlorophenyl group, 4-nitrophenyl group, naphthyl group, etc.), and hydrogen atom is most preferred.

R1 is bonded to 1lhVo of the group represented by R1 and R2 to form a benzene ring or a 5- to 7-membered heterocycle (e.g. pyrrole, pyrazole, 1.2.3-) riazole, pyridine,
Represents a group capable of forming pyridazine, pyrimidine, thiophene, furan, etc.).

R1 and R+h each independently represent a hydrogen atom, an aliphatic group having 1 to 30 carbon atoms (for example, a methyl group, an ethyl group, an n-
undecyl group, aromatic group having 6 to 30 carbon atoms (e.g. phenyl group, p-t') group, 1-naphthyl group, p
-nitrophenyl group, etc.), halogen atoms (e.g., fluorine atom, chlorine atom, bromine atom, etc.), aliphatic groups having 1 to 30 carbon atoms (e.g., methoxy group, ethoxy group, benzyloxy group, dodecyloxy group) etc.), number of carbon atoms 1~
36 unsubstituted or substituted amino groups (e.g. amino group, dimethylamino group, pyrrolidino group, piperidino group, morpholino group, anilino group, n-dodecylamino group, octadecylmethylamino group, 2-chloro-5-tetradecanamide phenylamino group) groups), nitro groups, cyano groups, carboxy groups, carbonamide groups having 1 to 36 carbon atoms (e.g. acetamide groups, benzamide groups, tetradecanamide groups, etc.), sulfonamide groups having 1 to 36 carbon atoms (
R5, which represents an alkoxycarbonyl group having 2 to 36 carbon atoms (for example, a methoxycarbonyl group, a dodecyloxycarbonyl group, etc.); and Rrz is preferably a hydrogen atom or an aliphatic group.

Z represents a monosubstituted or unsubstituted methine group or a nitrogen atom, and when Z represents a substituted methine group, R as a substituent
11 and R11! The A wound can be cited as an example.

W is a triazolyl group, a tetrazolyl group, 1.3.
4-oxadiazol-2-ylthio group, 1.3.4-
Thiadiazol-2-ylthio group, 1-indazolyl group, l-benzimidazolyl group, l-benzotriazolyl group, 2-benzotriazolyl group, 2-benzimidazolylthio group, 2-benzoxazolylthio group, 2 -benzothiazolylthio group, 2-pyrimidylthio group, 2-pyridylthio group, 4-quinolylthio group, 1.3.5-) riazin-2-ylthio group, 2-imidazolylthio group, 1.2
．． 4-triazol-5-ylthio group, l.

3.4-tri7zol-2-ylthio group, 1.2°3.
4-tetrazol-5-ylthio group, etc., and these groups may have a substituent group. Preferred groups as W include 1,2.3.4-tetrazole-5-
ylthio group, 1,3.4-oxadiazol-2-ylthio group, 1,3.4-thiadiazol-2-ylthio group, 1-benzotriazolyl group, 2-benzothiazolylthio group, 2-benzo These include an oxazolylthio group, a 1,3.4-triazol-2-ylthio group, and a 2-pyrimidylthio group, and are more preferably represented by the following general formula 1] to α-plane.

General formula (m) General formula [τ] R general formula [■] General formula (W) General formula [x] υ General formula (1m) General formula (X] [[) General formula [π] ~ (311) , R9 has 1 carbon atom
-16 alkyl groups (e.g. methyl group, ethyl group, hexyl group, benzyl group, octyl group, etc.) or carbon atom B
6 to 24 aryl groups (e.g. phenyl group, 4-hydroxyphenyl group, 3-hydroxyphenyl group, 3-sulfamoylphenyl group, 3-succinimidophenyl group, 4-methylphenyl group, 4-methoxyphenyl group, 3
-nitrophenyl group, 3-acetamidophenyl group, 3
-methylsulfonamidophenyl group, 4-methoxycarbonylphenyl group, etc.), and R represents a hydrogen atom, a halogen atom, an amino group, an alkyl group having 1 to 16 carbon atoms (e.g., a methyl group, an ethyl group, a hydroxyethyl group). , methoxyethyl group, butyl group, etc.).

Aryl groups having 6 to 24 carbon atoms (e.g. phenyl group,
4-methoxyphenyl group, 4-chlorophenyl group, etc.),
Carbonamide groups having 1 to 24 carbon atoms (e.g. acetamide group, benzamide group, etc.), furkylthio groups having 1 to 16 carbon atoms (e.g. methylthio group, ethylthio group,
benzylthio group, octylthio group, methoxycarbonylmethylthio group, etc.).

Arylthio groups having 6 to 24 carbon atoms (e.g. 4-acetamidophenylthio group, 4-methylsulfonamidophenylthio group, etc.), or sulfonamide groups having 1 to 24 carbon atoms (e.g. methylsulfonamide group, tolylsulfonamide group) , octyl sulfodiamide group, etc.), and R6 represents a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group having 1 to 16 carbon atoms (for example, a methyl group, an ethyl group, a butyl group, etc.), or an alkoxy group having 81 to 16 carbon atoms. groups (e.g. methoxy group, ethoxy group, butoxy group, methoxyethoxy group, benzyloxy group, etc.), nitro group, cyano group, amino group, carbonamide group having 1 to 24 carbon atoms (e.g. acetamide group, benzamide group, etc.) , sulfonamide group having 1 to 24 carbon atoms (e.g. methylsulfonamide group, phenylsulfonamide group, etc.), alkoxycarbonyl group having 2 to 16 carbon atoms (e.g. methoxycarbonyl group, ethoxycarbonyl group, etc.), number of carbon atoms Aryloxycarbonyl group having 6 to 16 carbon atoms (e.g., phenoxycarbonyl group, 4-methylphenoxycarbonyl group, etc.) or sulfamoyl group having 0 to 16 carbon atoms (e.g., sulfamoyl group, dimethylsulfamoyl group, butylsulfamoyl group, etc.) represents R7 and R#
is a hydrogen atom, a hydroxy group, an amino group, and a carbon atom number of 1 to
8 alkyl group (e.g. methyl group, ethyl group, etc.) or an alkoxy group having 1 to 8 carbon atoms (e.g. methoxy group,
ethoxy group, methoxyethoxy group, etc.).

Among the compounds represented by the general formulas (π) to [7], particularly preferred are the compounds represented by the general cutting degree C), and among the compounds represented by the general formula [2], the following are particularly preferred: It is represented by the general formula αL.

In General Geki-α Town, A', R+, R7 and W have the same meanings as A', R,, R2 and W in the general formula [Eng], respectively, and R2 is an alkyl group having 1 to 24 carbon atoms (e.g. methyl group, benzyl group, dodecyl group, etc.) or an aryl group having 6 to 36 carbon atoms (e.g. phenyl group, 4-
(tetradecyloxyphenyl group, 4-methoxyphenyl group, 4-70 lophenyl a, 2 + 5-'; chlorophenyl group, 4-methylphenyl group, 4-nitrophenyl group, etc.), R1+1 is a hydrogen atom, the number of carbon atoms 1~
24 alkyl groups (e.g. methyl group, ethyl group, tundecyl group, etc.), C6-C36 alkyl groups (e.g. phenyl group, 4-methoxyphenyl group, etc.), at-24 carbon atoms
alkoxy groups (e.g. methoxy, ethoxy, dodecyloxy, etc.), cyano groups, amino groups having 0 to 36 carbon atoms (e.g. amino, dimethylamino, piperidino, dimethylamino, anilino, etc.), carbon Numbers 1-24
carbonamide group (e.g. acetamide group, benzamide group, tetradecanamide group, etc.), sulfonamide group having 1 to 24 carbon atoms (e.g. methylsulfonamide group, phenylsulfonamide group, etc.), carboxy group, carbon number 2
-24 alkoxycarbonyl group (e.g. methoxycarbonyl group, dodecyloxycarbonyl group, etc.) or a C1-24 carbamoyl group (e.g. carbamoyl group,
dimethylcarbamoyl group, pyrrolidinecarbamoyl group, etc.).

In the general formula [mi], 8 is a cyan dye-forming coupler residue (e.g. phenolic cyan coupler residue, α
-naphthol cyan coupler α group, etc.) are preferable, and R
, and RL are preferably hydrogen atoms, Ry is preferably an aryl group, R1゜ is preferably a furkyl group, and W is represented by the general formulas [anal], [■] and [≧]
A group represented by is preferred.

A precursor of a compound that inhibits development of silver halide is released by a coupling reaction between the aromatic primary amine used in the present invention and an oxidized placebo, and then the precursor is released via an ethylenic conjugated chain. Specific examples of development inhibitor-releasing couplers that release a compound that inhibits the development of silver halide through an intramolecular electron transfer reaction are shown below, but the present invention is not limited thereto.

(D-1) One column (D-3) H3 (D-4) (D-5) H (D-6) (D-7) nIJ (D-8) nIJ (D-9) 1l (D- 10) ni station (D-11) nIJ (D-12) nIJ (D -13) 1l (D-14) IJ (D-15) nu (D-16) 0■ (D-17) nu (D - 18) 1l (D-19) (D-20) II (D-21) (D-22) COOC4He(n) These development inhibitor-releasing couplers are described, for example, in U.S. Pat.
US) No. 4.421.845, JP 57-1880
No. 35, No. 58-98728, No. 5B-209736
No. 58-209737, No. 58-209738, No. 38-209740, etc.

The amount of the development inhibitor-releasing coupler used in the present invention is lXl0-'mol-lXl for the entire coated ill.
0-'10-mol% is preferred. The amount of these additives is determined by the coupling speed of the coupler, the release rate of the development inhibitor from the precursor, the silver development inhibition degree of the released development inhibitor, and those with a slow rate or weak inhibition should be added in large amounts. It is necessary.

The coupler of the present invention may be added to any layer such as the emulsion layer or the non-malignant intermediate protective layer. Moreover, two or more types may be used in combination, or there is no problem in using them in combination with couplers described below.

Next, the hardening agent represented by the following general formula (H) used in the present invention will be explained in more detail.

In the general formula, Xl and X'' bar C H = C H
”or CHg CHx Y, Xl
and X8 may be the same or different. Y represents a group that is substituted with a nucleophilic group or can be removed in the form of HY with a base (eg, a halogen atom, sulfonyloxy, sulfuric acid monoester group).

L is a divalent linking group and may be substituted.

The amount of hardener added in the present invention ranges from 0.01 to 20% by weight, particularly preferably from 0.1 to 10% by weight, based on dry gelatin.

Specific examples of x' and x- include the following.

(X 1) CH=CHx (X-2) -cHi cHt cIl(X-3)
-CH. CH. Br (X 4) CHt CHz 030oCH.

(X-6) (X-7) -CHg CHz 0SOs N
a(X-8) CHz CHz 03Os
K(X-9) -CH. CHz 0COCH.

(X-10) -CHg CHg 0COCF! (
X-11) -CHg CHg 0CoCHCL Among these, (X-1), (X-2), (X-4), (
X-7) and (X-12) are preferred, and (X-1) is particularly preferred.

The divalent linking group is an alkylene group, an arylene group, or these groups and -〇-1-N-1-CO-1-1-3O-1-SO. -1-SO, -1-sox N-1
R is a divalent group formed by combining one or more bonds represented by - N CO *-
1 represents a hydrogen atom, an alkyl group containing 1 to 15 carbon atoms, or an aralkyl group.

Fortune-telling/ R1 may be used by bonding together to form a ring.

Furthermore, L may have a substituent, and as a substituent
Examples of '' include a hydroxy group, an alkoxy group, a carbamoyl group, a sulfamoyl group, an alkyl group, an allyl group, and an amino group. Moreover, those substituents may be further substituted, and may contain one or more groups represented by x'-sow- in their chemical structure.
S has the same meaning as XI and XS described above.

The following can be cited as representative examples of L.

(L-1) -(-CHOter (L-2) +CHt+-rO+CHx+y(L-
6) ÷ C11t given Coo (C1lzLTOCO-
C1laT(L-7) -(-CH,→-rsot
-+cHz] In the formula, a "-r is an integer from 1 to 6, and only e may be 0. Among these, a, e, j,
k.

It is preferable that n is 1 to 32, and b, c, and d.

f, g, h, i, j! , m, p, q
, r is preferably 1 or 2 R1-R8 are a hydrogen atom, or a substituent or unsubstituted alkyl group having 1 to 6 carbon atoms, and R1 and R2 and R4 and R
R1 to R6, which may be bonded together to form a ring, are preferably a hydrogen atom, a methyl group, or an ethyl group.

Further, these groups may have a substituent.

Representative examples of cases where L has a substituent and cases where the above R1 and Rz are combined include the following.

CI! So□CH, C11゜-C11□-C-CU, - ■ CHzSOxCIlgCHtNIICIlzCIIzS
OJa (L-10) (L-11) ■ CO+CHt-)+-8O□C1(, CH.

In the formula, s-"-w represents 1 or 2.

Among these L, (L-1), (L-2), (L-3)
, (L-8), (L-9) are preferred; (L-1), (
L-9) is particularly preferred.

Next, specific examples of the hardening agent used in the present invention will be listed, but the present invention is not limited thereto.

(H-1) Cut” CHS O* CHt S Ot CH Tomi C
Ht (H-2) CH1 Snow Cll5OtCHtC1ltC1l□5OtC
H""' CIlg (H-3) CIlOSO□
CH-Cut" Cll*=CH3OtCHtCCHtSOtCIIIC
HthCHxSOxCHzCHtNHClllxCHzSO
Ja(H-4) C11□-CH3Oz-CH30zCIIiOClbS
O (H-5) C! lt+Icll5(hCIl*C1bOC1lzC
HzSOxCHIICHz (H-6) CHxCHx (H-7) CONHCHxCHx NHCO (H-8) CHtClhCHt (H-9) (H-10) C0CIItC1ltSOiCH=CHz (H-11) CONHCHzCHxNHCo SOJa (H-13) COHs 0 COCH30zCHiCHzCj ! tHs (H-14) CIIt=CH5O□CHxCHCHtSO□C11-
CLH These hardening agents used in the present invention are known ones,
For example, the synthesis method is described in Japanese Patent Publication Nos. 47-2429 and 50-3.
No. 5807, JP-A-49-24435, JP-A No. 53-41
It is described in detail in publications such as No. 221 and No. 59-18944.

In the present invention, even if the hardening agent is added to the coating solution in advance,
It may be mixed with the coating liquid immediately before coating.

Hereinafter, the processing bath having bleaching ability of the present invention will be explained.

In the present invention, immediately after color development, processing is carried out in a processing bath having bleaching ability.

A processing bath having bleaching ability generally refers to a bleaching solution and a bleach-fixing solution, but in the present invention, a bleaching solution is preferable because it has an excellent bleaching blade, or the desilvering process of the present invention includes, for example, the following steps. However, it is not limited to these.

■ Bleach □ Fixing ■ Bleach-bleach-fix ■ Bleach-fix ■ Bleach-fix □ Bleach-fix ■ Bleach □ Washing □ Fixing In particular, steps □ and □ are preferred in order to exhibit the effects of the present invention.

The bleaching agent of the present invention comprises at least one ferric complex salt of a compound selected from the compound (A) group and a ferric complex salt of 1゜3-diaminopropanetetraacetic acid in a molar ratio of 3 or less. Used together with. The preferred molar ratio is 1.8 to 0.5.
It is. When the molar ratio exceeds 3, the bleaching strength decreases, resulting in poor desilvering. Furthermore, if the ratio of the ferric complex salt of 1,3-diaminopropanetetraacetic acid becomes extremely high, slight bleaching fog may occur.

The amount of the bleaching agent of the present invention added is 0 per liter of bath having bleaching ability.
．． 05 mol to 1 mol, preferably 0.1 to 0.5 mol.

In addition, an aminopolycarboxylic acid salt can be added to the treatment solution having bleaching ability of the present invention in addition to the above-mentioned aminopolycarboxylic acid iron (I[) 11 body. In particular, it is preferable to add a compound of compound group (A).

The preferred amount added is 0.0001 mol to 0.1 mol/f
, more preferably 0.003 mol to 0.05 mol/2.

Aminopolycarboxylic acids and their ferric complex salts are usually preferably used in the form of alkali metal salts or ammonium salts, and ammonium salts are particularly preferred because they have excellent solubility and bleaching properties.

Further, the bleach solution or bleach-fix solution containing the above-mentioned ferric ion complex may contain a metal ion complex salt other than iron, such as cobalt or copper.

Various bleach accelerators can be added to the bath having bleaching ability of the present invention.

Such bleach accelerators are described, for example, in US Pat. No. 3,893,858, German Patent No. 1,290.
, 812, British Patent No. 1 138.842, JP-A-53-95630, and 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 preferably British Patent No. 1.138,
Mercapto compounds such as those described in '842 are preferred.

In particular, in the present invention, the following bleaching agents are preferably used because they have excellent bleaching ability and little bleaching fog.

BA-I BA-2 BA-4 BA-5 BA-6N -N ■ BA-7 H BA-8 BA-9 BA-11 BA-12 The amount of bleaching accelerator added is O per 11 bleaching liquids. ,O
1g to 20g, preferably 0.1g to 10g.

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 the rehalogenating agent is 0.00% per 11 parts of the bleaching solution. 1-5
mol, preferably 0.5 to 3 mol. In addition, nitrates such as sodium nitrate and ammonium nitrate, boric acid, borax,
One or more types of inorganic acids and organic acids having pH buffering ability such as sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, and tartaric acid, and these Additives known to be commonly used in bleaching solutions, such as salts, can be added.

The pH of the bath having bleaching ability of the present invention is generally 6-1, preferably 5.8-1.5, most preferably 5.8-1.5.
It is 3-2. In the preferred pH range, there is little bleaching fog and the desilvering performance is excellent.

The replenishment amount of the bath having bleaching ability of the present invention is 50 to 2,000 m, preferably 100 to 1,000 m per pot of photosensitive material.
It is.

In the present invention, after treatment with a bath having bleaching ability, treatment is generally performed with a bath having fixing ability.

However, this does not apply when the bath having bleaching ability is a bleach-fixing solution.

The bath having the fixing ability of the present invention includes a bleach-fixing bath and a fixing bath.

Fixing agents for baths having these fixing abilities include thiosulfates such as sodium thiosulfate, ammonium thiosulfate, sodium ammonium thiosulfate, and potassium thiosulfate; thiocyanates such as sodium thiocyanate, ammonium thiocyanate, and potassium thiocyanate; urea,
Thioether etc. can be used. The amount of these fixing agents is 0.3 mol to 3 mol, preferably 0.3 mol to 3 mol per 11 processing liquids.
It is 5 moles to 2 moles.

Baths with fixing ability contain sulfites as preservatives, such as sodium sulfite, potassium sulfite, ammonium sulfite, and bisulfite adducts of hydroxylamine, hydrazine, and aldehyde compounds, such as acetaldehyde (sodium bisulfite). can be done.

Furthermore, various optical brighteners, antifoaming agents, surfactants,
Organic solvents such as polyvinylpyrrolidone and methanol can be contained, but in particular as preservatives,
It is preferable to use the sulfinic acid compound described in Japanese Patent No.-283831.

The amount of replenishment of the bath with fixing ability is 300 to 3000 ml per photosensitive material! is preferred, and more preferably 30 (ld to 10001).

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

The shorter the total time of the desilvering step of the present invention, the more remarkable the effects of the present invention can be obtained. The preferred time is 1 minute to 4 minutes, more preferably 1 minute 30 seconds to 3 minutes.

Furthermore, the treatment temperature is 25 to 50°C, preferably 35 to 45°C.
It is ℃. In a preferred temperature range, the desilvering rate is improved and the occurrence of staining after treatment 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.

The color 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-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)aminocoaniline D-52-methyl-4-[N-ethyl-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-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-phenylenediamine derivatives, 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 amine developing agent used is per 12 of the developer solution. Preferably about 0.1 g to about 20 g,
More preferred is 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 carboxysulfite adducts are added as preservatives to the color developer as necessary. be able to.

The preferred addition amount is 0.5 g per 12 color developer = 1
0 g, 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 No. 61-18
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 No. 61-164515, No. 61-170789, No. 61-168159, etc., No. 61-173595, No. 61-164515, No. 6
Diamines described in No. 1-186560, etc., No. 61-1
65621 and polyamines described in 61-169789, polyamines described in 61-188619, nitroxy radicals described in 61-197760, alcohols described in 61-186561 and 61-197419. It is preferable to use the oximes described in Japanese Patent No. 61-198987, and the tertiary amines described in Japanese Patent 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, Special JM 1973-3
Alkanolamines described in No. 532, JP-A-56-9
Polyethyleneimines described in No. 4349, U.S. Patent No. 3
, 746,544, etc., may be included if necessary, and addition of aromatic polyhydroxy compounds is particularly preferred.

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, disodium 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.

Applicable! 1 The amount of equilibrating agent added to the color developer is 0. It is preferably 1 mol/1 or more, particularly 0. 1 mol/f
It is particularly preferable that the amount is 0.4 mol/2.

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 1 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.

Nihalirotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N,N,N-)rimethylenephosphonic 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 -) recarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N,N'-bis(2-hydroxybenzyl)ethylenediamine-N,N'-diacetic acid, two types of these chelating agents as necessary The above may be used in combination.

The amount of these chelating agents added may be sufficient as long as it is sufficient to sequester metal ions in the color developer.For example, II
It is about 0°Ig-10g per liter.

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

Other development accelerators include Japanese Patent Publications No. 37-16088, No. 37-5987, No. 3 B-7826, No. 44
-12380, No. 45-9019 and U.S. Patent No. 3
．． 813,247, etc., JP-A-52-49829 and JP-A-50-15554
P-phenylenediamine-based compounds represented by Nos., JP-A-50-137726, JP-B-Sho 44-30074,
Quaternary ammonium salts disclosed in JP-A-56-156826 and JP-A-52-43429, etc., U.S. Patent No. 2
, No. 494,903, No. 3,128゜182, No. 4,
No. 230.796, No. 3.253.919, Special Publication No. 4
No. 1-11431, U.S. Patent No. 2.482.546,
Same 2. Amine compounds described in Japanese Patent Publication No. 37-16088, Japanese Patent Publication No. 42-25201, U.S. Patent No. 3,128,18, etc.
No. 3, Special Publication No. 41-11431, No. 42-23883
and U.S. Pat. No. 3,532,501, etc., and other 1-phenyl-3-
Pyrazolidones, imidazoles, 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. Examples of organic antifoggants include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2 Typical examples include nitrogen-containing heterocyclic compounds such as -thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine.

The color developer used in the present invention may contain a fluorescent brightener, and the preferable fluorescent brightener is a 4°4'-diamino-2,2'-disulfostilbene compound. The amount added is O~5 g/1. Preferably 0. 1-4
g/j! It 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 1500 m1, preferably 100 to 800 m1, per 1 nf of light-sensitive material. More preferably 10
01-400m.

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 is commonly known as the black and white first developer used for the reversal processing of color photographic light-sensitive materials, or Those used for processing black and white photosensitive materials can be used. It can also contain various well-known additives that are commonly added to black and white developers.

Typical additives include developing agents such as 1-phenyl-3-pyrazolidone, metol and hydroquinone, preservatives such as sulfites, and accelerators consisting of alkalis such as sodium hydroxide, sodium carbonate, and potassium carbonate. ,
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 process may contain known additives as required. For example, water softeners such as inorganic phosphoric acid, aminopolycarboxylic acid, and organic phosphoric acid;
Disinfectants and anti-fungal agents (for example, isothiazolones, organochlorine disinfectants, benzotriazole, etc.) to prevent the growth of algae and various bacteria, surfactants to prevent drying load and unevenness, etc. can be used. Or L, E.

! Aest, “Iplater Quality C
r1teria”, Phot, Scj.

and Eng,, vol, 9. N1161 pa
Compounds described in GE 344-359 (1965) and the like can also be used.

As the stabilizing liquid used in the stabilization step, a processing liquid that stabilizes the dye image is used. For example, a liquid having an a-equilibrium of pH 3 to 6, a liquid containing an aldehyde (for example, formalin), etc. may be used. Can be done. The stabilizing liquid may contain ammonium compounds, metal compounds such as Bi and Al2, optical brighteners, chelating agents (for example, 1-hydroxyethylidene-1,1-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 reduce the Mg%Mg to 14 degrees below 5/2, or that has been sterilized with halogen, ultraviolet killing lights, 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 bath having a fixing ability, which is a pre-bath.

Next, the automatic processor used in the present invention will be described.
In the automatic processor used in the present invention, it is preferable that the agitation of the processing liquid in the desilvering process be as strong as possible, so that the time required for derailment can be shortened. A specific method for strengthening stirring is described in Japanese Patent Application Laid-open No. 1983-
183460 and 62-183461, a method of impinging a jet of processing liquid on the emulsion surface of a photosensitive material, a method of increasing the stirring effect using a rotating means as described in JP-A No. 62-183461, and a method of improving the stirring effect in liquid. Examples include a method in which the photosensitive material is moved while the emulsion surface is in contact with a wiper blade provided on the emulsion, thereby creating turbulence on the emulsion surface to improve the stirring effect, and a method in which the circulation flow rate of the entire processing liquid is increased. Such means for improving agitation is effective for all bleaching solutions, bleach-fixing solutions, and fixing solutions. It is believed that the improvement in N1 agitation speeds up the supply of bleaching agent and fixing agent into the emulsion film, and as a result increases the desilvering rate.

Further, the agitation improving means is more effective when used to accelerate bleaching, and can significantly increase the accelerating effect 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
257, No. 191258, and No. 191259. As described in JP-A-60-191257, such a conveying means is used to transfer from the front bath to the post bath. It is possible to significantly reduce the amount of processing liquid carried into the process, and it is highly effective in preventing the performance price of the processing liquid from increasing.This effect is particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.

The swelling ratio of the color light-sensitive material used in the present invention in a bleaching bath is particularly preferably 2.8 or more, and more preferably 3.0 or more.

The larger the swelling ratio is, the more preferable it is for the purpose of the present invention, but if it is too large, a new problem arises in that the film strength etc. become weaker.

Therefore, the practical upper limit of the swelling ratio is preferably 5.0 or less.

An easy way to control the swelling rate is to change the ratio of hardener to gelatin. In addition, as a method that does not impair the film strength as much as possible, it is possible to increase the swelling rate of the emulsion layer close to the support, and to lower the swelling rate of the layers located far from the support (especially the top layer, the protective layer). It is preferable to use it as a means.

For this reason, the specific method is to use a hardening agent with low diffusivity (
For example, methods known to those skilled in the art can be used, such as using polymeric hardening agents (Hwi) or dura inhibitors.

In the present invention, the swelling ratio in a bleaching bath is defined as the value obtained by dividing the film thickness after swelling in a bleaching bath (thickness of all layers on the side with the photosensitive layer with respect to the support) by the dry film thickness. say.

Measurement of swollen film thickness in a bleach bath is performed using A, Green and
G.1. P, Leveson+ J, Phot, Sci.
, +l., 205 (1972). That is, it can be determined from the equilibrium value of the swollen film thickness in a bleach bath kept at 38°C. The bleaching solution used had the formulation shown in Example 1.

The dry film thickness means a value measured at 25°C and 55% humidity. The measurement can be performed using a commercially available film thickness meter.

The silver halides contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention are silver chloride, silver bromide, silver chlorobromide, silver iodochloride, silver chloroiodobromide, and silver iodobromide.

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), Nal 764
3 (December 1978), pp. 22-23. ! .

Emulsion preparation (E+mulsion preparation)
n and types)”s and the same Nal 871
6 (November 1979), p. 648, by Grafkide, “
"Physics and Chemistry of Photography", published by Beaumontel (P, Gla
fkides, Chemical at Phisiqu
ePhotographiqutr Paul Mon
tel., 1967), "Photographic Emulsion Chemistry" by Duffin.
, published by Focal Press (G.

F. Duffin, Photographic E.
Mulsion Chemistry (Focal P
ress, 1966), Zelikman et al., “Manufacture and Coating of Photographic Emulsions”, Focal Press (V, L.).

Zalik+*an at al, Making a
nd Coating Photographic Em
ulsion+ Focal Press+ 1964
), etc.).

U.S. Patent Nos. 3,574.628 and 3.655.39
No. 4 and British Patent No. 1. 413. Monodispersed emulsions such as those described in No. 748 are also preferred.

Tabular grains having aspect ratios of about 5 or more can also be used in the present invention. Tabular grains are described by Gutoff, Photographic Sci.
ence and Engineering), No. 14
-1', pp. 248-257 (1970); U.S. Patent No. 4,434,226, U.S. Pat. No. 4,414.310, U.S. Pat. It can be easily prepared by the method described in 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 of 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. Additives used in such processes are listed in Research Disclosure 7 Fish 17
643 and Questionnaire 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.

Additive type [RD17643 RD187161 Chemical sensitizer Page 23 Page 648 Right column 2 Sensitivity enhancer
Same as above 4 Brightening agent page 24 8 Dye image stabilizer page 25 9 Hardening agent page 26 page 651 left column 10
Binder, page 26 Same as above 11 Plasticizer, lubricant, page 27, page 650, right column A wide range of color couplers can be used in the present invention, specific examples of which can be found in the Research Disclosure (RD) Nal mentioned above.
No. 7643, Vl-C-G.

As a yellow coupler, for example, U.S. Patent No. 3.93
3.501, 4,022,620, 4.3
No. 26.024, No. 4.401゜752, Special Publication No. 5
No. 8-10739, British Patent No. 1.425.020,
Preferably, those described in the same No. 1°476.760, etc.

As magenta couplers, 5-pyrazolone and pyrazoloazole compounds are preferred, and US Pat.
No. 0.619, No. 4.351°897, European Patent No. 73,636, US Patent No. 3.061,432, US Patent No. 3.725.067, Research Disclosure 1 No. 24220 (1984) June), Japanese Patent Application Publication No. 1986-
No. 33552, Research Disclosure Na24
230 (June 1984), JP-A No. 60-43659, U.S. Patent No. 4,500,630, No. 4. 540
．． Particularly preferred are those described in No. 654 and the like.

Cyan couplers include phenolic and naphthol couplers, and are disclosed in U.S. Patent No. 4°052.212.
No. 4,146.396, No. 4,228,23
No. 3, No. 4. z9s, No. 200, No. 2,369
, No. 929, No. 2.801゜171, No. 2,772
．． No. 162, No. 2゜895.826, No. 3,77
No. 2.002, No. 3.758,308, No. 4.
334. No. 011, No. 4.327, 173, West-
German Patent Publication No. 3,329,729, European Patent No. 121
No. 365A, U.S. Patent No. 3,446,622, U.S. Patent No. 4,333,999, U.S. Patent No. 4. 451. 559, European Patent No. 4,427,767, European Patent No. 161.62
Those described in No. 6A etc. are preferred.

Colored couplers for correcting unnecessary absorption of coloring dyes are described in Research Disclosure 117643.
- Section G, U.S. Patent No. 4,163゜670, Special Publication No. 1983
-39413, U.S. Patent No. 4,004,929, same jf! 4. No. 138.258, British Patent No. 1.146
．． The one described in No. 368 is preferred.

Couplers whose coloring dyes have appropriate diffusivity include U.S. Patent No. 4.366.237 and British Patent No. 2.12.
5.570, European Patent No. 96,570, West German Patent (
Preferred are those described in U.S. Pat. No. 3,234,533; typical examples of polymerized dye-forming couplers are U. 4.3'67.282 Calyx, British Patent No. 2.102
．． It is described in No. 173, etc.

Couplers that release photographically useful residues upon camping are also preferably used in the present invention. DIR couplers that release development inhibitors include the aforementioned RD17643.
Patent described in paragraphs 1 and 2, JP-A-57-151944
Preferred are those described in No. 57-154234, No. 60-184248, and U.S. Pat.

As a coupler that releases a nucleating agent or a development accelerator imagewise during development, 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. , long equivalent couplers described in JP-A No. 4.310.618, DIR redox compound releasing couplers described in JP-A-60-185950, etc., and dyes that fade after separation as described in European Patent No. 173.302A. Examples include couplers that emit light.

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 Patent No. 2.322.027 and the like.

There is also a method of using a polymer as a coupler dispersion medium, as described in Japanese Patent Publication No. 4B-30494, U.S. Patent No. 3.619,
No. 195, West German Patent No. 1.957゜467, Special Publication No. 1977
There are various descriptions in No.-39835.

The steps and effects of latex dispersion methods, and specific examples of latex for impregnation, can be found in U.S. Pat. It is written in the number etc.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, page 28 of l1h17643, and the same 18716
It is described from the right column on page 647 to the left column on page 648.

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

A multilayer color photosensitive material 101 was prepared by coating each layer having the composition shown below on a cellulose acetate film support coated with one layer and a top layer.

(Photosensitive layer composition) The number corresponding to each component indicates the coating amount expressed in g/rd unit, and for silver halide, it indicates the coating amount in terms of silver.However, for sensitizing dyes, the coating amount in the same layer The coating amount is shown in moles based on 111 moles of halogenide.

-th layer (Haley silane prevention layer) Black colloidal silver 0.2 gelatin 1. 0 UV absorber UV
-10゜05 Same UV-20,i Same UV-30,1 Dispersion oil 0IL-10,02 2nd layer (intermediate layer) Fine grain silver bromide (average particle size 0.07μ) 0.15 Gelatin 1.0th 3 layers (
1st red-sensitive emulsion layer) Monodisperse emulsion (1N iodide 6 mol%, average grain size 0.4 μm, coefficient of variation 15%) 1.42 gelatin
0.9 sensitizing dye A
2.4X10-' sensitizing dye B
1.0X10-' Sensitizing dye C0,3X10-' Cp-b 0.35Cp-
co, 052 Cp-do, 047 DA 0.060HBS
-10,10 HBS-20,10 4th layer (middle layer) Gelatin 0.8Cp-d
O,10HBS-10,0
5 5th layer (second red-sensitive emulsion layer) Monodispersed emulsion (116 mol% iodide, average grain size 0.5 am, coefficient of variation 15%) 1.38 gelatin
1. 0 sensitizing dye A
1.5X10-' sensitizing dye B
2.0XIO-' Sensitizing dye CO, 5X104 Cp-b 0.150Cp-
dO,027DA
00010HBS-10,05
0 1 (BS-20,060 6th layer (third red-sensitive emulsion layer) Monodisperse emulsion (silver iodide 7 mol%, average grain size 1.1.un, coefficient of variation 16%) 2.08 Ceratin 1. 5cp-a
o, 060Cp-co, 024Cp-d 0.038DA
0.006)I
BS-10,12 7th layer (middle layer) Gelatin 1.0Cpd-A
O,05HBS-20,0
5 Single 8 layer (first green sensitive layer) Monodisperse silver iodobromide emulsion (iodide! I3 mol%, average grain size 0.4 Bm.

(coefficient of variation 19%) 0.64 Monodisperse silver iodobromide emulsion (silver iodide 6 mol%, average grain size 0.7 μm, coefficient of variation 18%) 1.12 Gelatin 1. .

Sensitizing dye D lXl0-' Sensitizing dye E 4X10-' Sensitizing dye F lXl0-'cp-h
o, 20cp-rQ, 61 cP-go, 084Cp-
0.035 (:, -10,036 DA O,0
50HBS-10,25 HBS-20,45 9th layer (second green-sensitive emulsion layer) Monodispersed silver iodobromide emulsion (silver iodide 7 mol%, average grain size 1.0am, coefficient of variation 18%) 2. 07 Gelatin 1.5 Sensitizing dye D
1.5X10-' sensitizing dye E
2.3XIO-'sensitizing dye F
1.5X10-'Cp-f
-0,007Cp-h, 0
．． 012cp-g o, 00
9HBS-20,088 10th layer (intermediate layer) Yellow colloidal silver 0.06 Seratin 1. 2Cpd-A
O,3HBS-10,3 11th layer (first blue-sensitive emulsion layer) Monodispersed silver iodobromide emulsion (iodide!!6 mol%, average grain size 0.4 μm, coefficient of variation 20%) 0.31 unit Dispersed silver iodobromide emulsion (silver iodide 5 mol %, average grain size 0.9 μm.

Coefficient of variation 17%) 0.38 Gelatin 2.0 Sensitizing dye G
lXl0-' Sensitizing dye HlXl0-' 0p-i 0.65Cp
-jO,57 DA 0.037HB
S-10,05 12th layer (second blue-sensitive emulsion layer) Monodisperse silver iodobromide emulsion (silver iodide 8 mol%, average grain size 1.3 μm, coefficient of variation 18%) 0.77 Gelatin 0.5 Sensitizing dye 0
5X10-' Sensitizing dye H5X10-' Cp-1o, t.

Cp-jO,lo DA O,005HBS
-20,10 13th layer (middle layer) Gelatin 0.5Cp-mO
, I UV-IQ・l UV-20,l UV-30,1 HBS-10,05 )IBS-20,05 14th layer (protective layer) Monodisperse silver iodobromide emulsion (silver iodide 4 mol%, Average particle size 0.05μ, coefficient of variation 10%) 0.1 Gelatin 1.5 Polymethyl methacrylate particles (average 1.5μ) 0. l 5-1 0・2S-20
, 2 HA O, 35 and -1 were added to other surfactants.

Same D Same G Same H CH! 1L-1 LIL; 11gM1iUυNHUtltUthU圀1s
p-r ShiL p-g ShiL p-h Cp-3 CaH*(b) ■ Cp-K Cp-7! B5-1 CaHS B5-2 -1 Compound cp dA H Preparation of Samples 102 to 104 In place of DA added to No. 3.5.6.8.11.12N in Sample 101, as shown in Table 1 was used. Sample 101 was prepared in the same manner as Sample 101, except that the coupler of the invention was used in an equal molar amount and the hardener of the invention was used once.

After processing the sample prepared as described above into a 35 mm size, a standard subject was photographed, and continuous processing was performed in the following processing steps until twice the tank capacity of the color developer was replenished. However, the composition of the bleaching solution was changed as shown in Table 1, and each test was conducted.

The automatic developing machine used was JP-A-60-191257.
The belt conveyance method described in the issue is used, and each treatment bath is manufactured by JP-A-62
The jet stirring method described in No. 183460 was used.
′ The processing steps are shown below.

Color development 3 minutes 15 seconds 38℃ 381d drift
White 1 minute 38°C 4Id fixing 1 minute 38°C 3011 Stable 1 20 seconds 38°C - Stable 220 seconds 38°C - Stable 320 seconds 38°C 35m" Drying 1 minute 15 seconds 50-70°C - Formula.

The composition of each treatment liquid used is shown below.

(Color developer) Mother solution (6) Replenisher (barrel diethylenetriaminepentaacetic acid 5.0 6.0 Sodium sulfite 4.0 4.4 Potassium carbonate
30.0 37.0 Potassium bromide
1.3 0.9 Potassium iodide
1.2aL-hydroxyamine sulfate
2.0 2.84-(N-ethyl-N-β-hydroxyethylamino)-2-methylaniline sulfate 4.7 5.
3 Add water! , 011. On! P
H10,0010,00 (Bleach solution) Mother liquor Replenisher 1.
3-diaminopropanetetraacetic acid 4.0. 5.0゜Ammonium bromide 100.0 g 160.0
g Ammonium nitrate 30.0g 50.0g Ammonia water (27χ) 20. Od 23. O
am acetic acid (98χ) 9.0ad
Add 15.0d water 1. Of 1
．． Oj! Refer to pH Table 1 (stable solution) Mother liquor, replenisher common formalin (37%) 1.2d5-
Chloro-2-methyl-4-inthiazolin-3-one 6.0d2-Methyl-4-isothialin-3-one 3. 0 ■ Surfactant 0. 4 Ethylene glycol 1.0 Add water
1.0ffi pH5,0-7,0 After exposing the sample to 20 CMS, it was treated with each running equilibrium solution, and residual ill was determined by the fluorescence XfiljI method.

(Fixer) Mother solution Replenisher l-hydroxyethylidene-1,1-diphosphonic acid 5. 0g 6. 0g sodium sulfite? , Og8.0g Sodium bisulfite 5.0g5.5g Ammonium thiosulfate sulfate aqueous solution 70%) 170.0■ 200.
0 ■ Add water 1. Oj! 1.0
1pH6,76,6 The results are shown in Table 2.0 As is clear from Table 2, when the timing DIR coupler of the present invention is used, the amount of residual silver increases, but the bleaching solution with the bleaching ratio of the present invention and the hardness The amount of residual silver that is said to not be a practical problem when using a film agent3
It can be seen that it is less than μg/cd.

This effect can only be obtained by the combination of the present invention.

Example 2 Compounds BA-1, BA-16, and BA-9 were added in equimolar amounts instead of the bleach accelerator in the bleach bath used in Example 1, and compared with a bleaching solution without additives. The experimental method was the same as in Example 1.

As a result, the amount of residual II in all of the products using a bleaching accelerator was lower than that in the products without additives. Among these, BA-
1 showed the best effect.

Example 3 In samples 101 to 10B, the hardening agent DA was changed to comparative compounds DB and DC, respectively, and samples 301 to 308.309
~318 were produced. The amount added was adjusted to match the swelling ratio. When the desilvering properties were similarly tested using the treatment liquid of Example 1, almost the same results as Samples 101 to 108 in Table 2 were obtained.

Comparative compound DC (compound described in JP-A No. 60-237445) l Example 4 Bleach A-1 (ethylenediaminetetraacetic acid) used in Example 1 was mixed with bleach A-2 (diethylenediaminepentaacetic acid) in equimolar amounts. A bleach bath was prepared in a similar manner except for the substitution.

This bleach bath was replaced with the bleach bath used in Example 1,
Samples 101-120 were processed in the same manner.

The amount of residual silver in the sample after treatment was almost the same as the results obtained in Example 1.

Patent applicant: Fuji Photo Film Co., Ltd. Date of 1963

Claims (1)

[Scope of Claims] 1) A method of processing an imagewise exposed silver halide color photographic light-sensitive material with a processing solution having bleaching ability after color development, in which the silver halide color photographic light-sensitive material is used as a developing agent during development. A precursor of a compound that inhibits the development of silver halide is released by reacting with the oxidation product of A processing solution containing at least one development inhibitor-releasing coupler that releases a compound and at least one gelatin hardener represented by the following general formula (H) and having the bleaching ability is a bleaching agent as shown below. At least one ferric complex salt of a compound selected from compound group (A)
1. A method for processing a silver halide color photographic light-sensitive material, comprising a seed and ferric acetate of 1,3-diaminopropanetetraacetic acid, the molar ratio of the former to the latter being 3 or less. General formula (H) [X^1-SO_2-L-SO_2-X^2 In the formula, X^
1 and X^2 are -CH=CH_2 or -CH_2CH
_2Y, and X^1 and X^2 may be the same or different. Y represents a group that can be substituted by a nucleophilic group or can be eliminated in the form of HY by a base. L is a divalent linking group and may be substituted. ] Compound group (A) A-1: Ethylenediaminetetraacetic acid A-2: Diethylenetriaminepentaacetic acid A-3: Cyclohexanediaminetetraacetic acid A-4: 1,2-propylenediaminetetraacetic acid 2) Swelling rate in the bleach bath is 2 A method for processing a silver halide color photographic light-sensitive material according to claim 1, characterized in that a light-sensitive material having a molecular weight of .8 or higher is processed.