JPS6332550A - Method for processing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To prevent the deterioration of a magenta dye as well as to accelerate bleaching by processing a silver halide color photographic sensitive material contg. a prescribed magenta coupler in a silver halide emulsion layer with a bleaching soln. contg. a compound represented by a specified general formula. CONSTITUTION:A silver halide color photographic sensitive material contg. at least one kind of two-equiv. magenta coupler in at least one of the silver halide emulsion layers is bleached with a bleaching soln. contg. at least one kind of compound represented by formula I, II or III after development. Even when such sensitive materials are continuously processed in large quantities, rapid bleaching can be carried out and a rise in the contrast of an image and the deterioration of a magenta dye during storage are prevented. In the formulae I-III, each of R1, R2, R4 and R5 is H, halogen, amino or alkyl and each of R3 and R6 is H, amino or alkyl.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for processing silver halide color photographic light-sensitive materials, and more particularly to an improvement in the bleaching process of silver halide color photographic light-sensitive materials.

[Back of invention f! 'l In general, the processing of silver halide color photographic materials (hereinafter also referred to as single-litter photographic materials) basically consists of two steps: color development and desilvering. In some cases, it is carried out in a single bleach-fixing bath. In addition to this, additional processing steps such as rinsing treatment and stabilization treatment are added.

In the color development process, the exposed silver lodenide is reduced and becomes a metal compound, and at the same time, the color developing agent represented by the oxidized aromatic primary amine compound reacts with the coupler to form a dye. form.

In the desilvering step, metallic silver produced by reduction is bleached with an oxidizing agent, and then all silver salts are removed from the photographic material as soluble silver salts with a fixing agent.

Conventionally, Kuroiso's oxidizing agents such as red blood salt and dichromate have been widely used as oxidizing agents for bleaching reduced metallic silver in processing solutions with bleaching ability in the desilvering process of photographic light-sensitive materials. was.

However, the above-mentioned red salts and dichromates are said to be self-sharpening of metallic silver.However, they decompose in the presence of light and produce cyanide ions and hexavalent chromium ions, which are harmful to the human body. In addition, the processed liquid containing these oxidizing agents has the disadvantage that it is extremely difficult to recycle the waste liquid after treatment. are doing.

In contrast, metal complex salts of organic acids, such as amide/polycarboxylic acid metal complex salts, have come to be used as oxidizing agents that have bleaching ability and meet the requirements of recyclability and less pollution problems. . However, processing solutions using metal complex salts of organic acids have low oxidizing power, and their bleaching ability for gold and silver formed during the development process was not necessarily sufficient6.
For example, iron ethylenediaminetetraacetate (II
I) Complex salts can achieve the purpose when bleaching low-sensitivity photographic materials with a small amount of silver, such as color vapor, which are mainly composed of silver chlorobromide emulsions.
Bleaching blades are insufficient for high-sensitivity photographic materials based on filled silver iodide or silver iodobromide emulsions, especially color negative films and color reversal films for photography that contain silver iodide as silver halide and have a high silver content. However, it has the disadvantage that the bleaching process takes a long time.

On the other hand, a method has been proposed in which a bleaching accelerator is added to an i-bleaching bath, a bleach-fixing bath, or a pre-bath thereof in order to enhance the whitening edge of the above-mentioned amide/polycarboxylic acid metal complex.

As a bleach accelerator, for example, U.S. Pat. No. 3,893°8
No. 58, British Patent No. 1,138,842, JP-A-53
No.-141623, No. 54-52534, JP-A No. 1973
Various mercapto compounds described in JP-A-95631, etc., compounds having disulfide bonds as described in JP-A-53-95630, thiazolidine derivatives as described in JP-A-53-9854, and thiazolidine derivatives as described in JP-A-53-94927. Isothiourea derivatives, Japanese Patent Publication No. 45-8506, No. 49-20
1,000 urea conductor described in No. 586, JP-A-49-423
Thioamide compound described in No. 49, JP-A-55-265
Examples include notiocarbamate salts described in No. 06.

These bleaching accelerators were used in combination with the aminopolycarboxylic acid metal complex salt to enhance the bleaching edge and to some extent achieved the purpose of speeding up the bleaching process.

However, when the above-mentioned bleaching accelerator is applied to a development method in which a large amount of photographic material is continuously processed using an automatic processor, etc., a phenomenon of high contrast is observed in the dye image of the processed photographic material. When a photographic light-sensitive material is stored over time, especially under high temperature conditions, a phenomenon of a decrease in magenta dye density has been observed.

The present inventors conducted various studies to solve the above problems, and as a result, they processed a silver halide color photographic light-sensitive material having a 2-equivalent magenta coupler using a bleach solution containing a specific bleach accelerator. We have discovered that this method has the advantage of speeding up the bleaching process even when large quantities of light-sensitive materials are processed continuously, and that there is no increase in image contrast or deterioration of magenta dye during storage. It has arrived.

[Objective of the Invention 1 Therefore, the object of the present invention is to speed up the bleaching process when processing large quantities of photographic light-sensitive materials continuously, and to eliminate halogenation that does not increase the contrast of images or reduce the magenta dye during storage. An object of the present invention is to provide a method for processing silver color photographic materials.

[Configuration 1 of the Invention] The above object of the present invention is to carry out at least a color development step, a bleaching step and In a method for processing a silver halide color photographic light-sensitive material which is subjected to processing including a fixing step, the whitening liquid (used in the whitening step) has the following formula [1], [I[] and l,' [1Itl A method for processing a silver halide color photographic light-sensitive material containing at least one compound selected from the compounds shown in the following, and containing at least one 2-equivalent magenta coupler in at least one of the silver halide emulsion layers. .

General formula [+1 -N R3-CC-R.

\S' General formula [11] % formula %] (-In formula [+] ~ [III], R,, R2, R,
and (7R3 each represents a hydrogen atom, a halogen atom, an amine group, or an alkyl group, and R1 and R each represent a hydrogen atom, an amine group, or an alkyl group.) [Specific structure of the invention] The bleaching accelerator used in the whitening solution (in the present invention) is at least one compound selected from the compounds represented by the formulas Ill, NTI, and [III] (hereinafter referred to as the bleaching accelerator of the present invention). .

In general 2, [11], [lI [], R1,
R, , R, and R9 each represent a hydrogen atom, a halogen atom, and an alkyl group;
Examples include a bromine atom and an iodine atom, and examples of the alkyl group include those having a substituent, and examples of the substituent include an amide group. The alkyl group preferably has a carbon atom r
11.1-5 alkyl group, examples of which include methyl group, ethyl group, propyl group, butyl group, pentyl group, and aminoethyl group. R3 and VF6 are hydrogen atoms,
It represents an ami7 group or an alkyl group, but the alkyl group also includes those with a substituent, and the substituent is an ami7 group or an alkyl group.
Examples include groups. The alkyl group is preferably an alkyl group having 1 to 5 carbon atoms, such as a methyl group, an ami/methyl group, an ethyl group, an ami 7 ethyl group, a propyl group, an ami 7 brobyl group, a butyl group, an ami/ Examples include butyl group and pentyl group.

Typical specific examples of the bleach accelerator of the present invention are listed below.
The present invention is not limited to these -1° Exemplary Compound (S) (6) (19)
<20)+HsN t
it NH2
ri4INI"12U2Hs The bleaching accelerator of the present invention is partially described in JP-A No. 54-52534, but for example,
rnal of tl+e American CI+
en+1calS ocieLy) No. 69 $PIS2
674 pages (1947), Journal of Organic Chemistry
rganic CheIIIstry) PI
S3 Volume 3 fIS 1275 pages (1968), Journal of the Society of Chemical Ingestion: Transaction (Journal
of tbe 5ocietyor Chemica
l Indusjry: Transaction
n) No. 528, p. 272 (19:13) and The Chemistry of Functional Groups: The Chemistry of FuncLio
nal Groups: TIIeCI+eni
sLry or T l+iol G roupes)
(Jol+nWiley & 5ons I
nc, + published in 1974), pages 163-269 (
6, which can be easily obtained according to the method described in Preparation of Thiols).
Among the bleach accelerators of the present invention, compounds represented by the general formula [111] are preferred, and exemplary compound No.
, (11), (12), (7), (1) etc. are preferred,
Particularly preferred are No and (li).

The bleaching accelerator (1f1) of the present invention may be used alone or in combination of two or more, and the amount of the bleaching accelerator added to the bleaching solution is 0.0 per 11
1-0,30. Good results can be obtained within the range of 0.05 to 0.05 ZOg.

When adding the bleaching accelerator of the present invention to a bleaching solution, it may be added and dissolved as is, but it is common to dissolve it in water, an alkali, an organic acid, etc. before adding it, and add methanol as necessary. Even if it is dissolved and added using an organic solvent such as , ethanol, or acetone, there is no effect on its bleaching accelerating effect or the effect of the present invention.

The bleaching solution containing the bleaching accelerator of the present invention (hereinafter referred to as the bleaching solution of the present invention) contains organic acids such as aminopolycarboxylic acid, oxalic acid, citric acid, and polyphosphonic acid, and iron, cobalt, etc. It is preferable to use a bleaching agent coordinating a metal ion such as copper or the like, with an angle of -1° or less. Preferred specific examples of the bleaching agent used in the bleaching solution of the present invention are given below.

[Example Compound 1 [11 Ethylenenoaminetitraacetic acid [2] Diethylenetriaminepentaacetic acid [3] Ethylenediamine-N-(β-hydroxyethyl)-N,N'
, N'-) diacetic acid [4] propylenenoamine titraacetic acid [51 triethylenetetramine hexaacetic acid [61 cyclohexanoamine titraacetic acid [7] 1,2-diaminopropane tetraacetic acid [8] 1,3-noami7proban- 2
-All-tetraacetic acid [91 Ethyl ether diamine tetraacetic acid [10] Glycol ethernoamine tetraacetic acid [11] Ethylene7minetetraprobionic acid [12] Phenylenenoamine titraacetic acid [13] Ethylenenoamine titraacetic acid disodium salt [141 Ethylenenoamine titraacetic acid tetra(trimethylammonium) salt [151 Ethylenenoamine titraacetic acid tetrasodium salt [16] Noethylenetriamine pentaacetic acid pentasodium salt [17] Ethylenediamine-N-(β-hydroxyethyl)-N,N' , N'-) Sodium acetate [181 Propylene 7M Sodium tetraacetate [1
9] Ethylenenoamine titramethylene phosphonic acid [20 [cyclohexanediamine tetraacetic acid sodium salt] [21] diethylenetriamine pentamethylene phosphonic acid [22] cyclohexanenoamine titramethylene phosphonic acid [231 nitrilotriacetic acid [24] imi-7noacetic acid [251 hydroxy Ethylimi7) Acetic acid [26] Nitrilotripropionic acid [27] Nitrotrimethylenephosphonic acid [28] Iminodimethylenephosphonic acid [29] Hydroxyethyliminonomethylenephosphonic acid [30] 2) Lilotriacetic acid trisodium salt [311
Among these aminocarboxylic acid compounds and aminophosphonic acid compounds, compounds particularly preferably used from the viewpoint of the desired effects of the present invention include (1), (2), (5),
(8), (19), (23), (25), (27
).

The amounts of these amine/carboxylic acid compounds and aminophosphonic acid compounds used in the present invention are determined by the bleaching method. 1111
preferably 20 to 300 g, more preferably 4
0-200. It is.

The bleaching solution of the present invention may optionally contain various additives commonly used in bleaching solutions in addition to the bleaching accelerator of the present invention and the bleaching agent.

Additives that can be added to the bleaching solution of the present invention include halogen ion releasing compounds such as ammonium bromide, sodium bromide, potassium bromide, ammonium chloride, ammonium iodide, raiN&, borax, sodium hydroxide, potassium hydroxide. , sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide, and the like can be contained alone or in combination of two or more. Furthermore, various optical brighteners, antifoaming agents, surfactants, and antifungal agents can be contained.

The bleaching solution of the present invention can be used at a pH of 0.2 to 9.5, preferably 4.0 to 7.0, more preferably 5.
．． Used between 0 and 6.8. The temperature of the treatment is 20'
It is used at a temperature of 80°C to 80°C, preferably 40°C or higher.

The processing time for bleaching a silver halide color photographic material containing a 2-equivalent magenta coupler used in the present invention, which will be described in detail later, using a bleach solution containing a bleach accelerator of the present invention is 30 seconds to The time is preferably 6 minutes 30 seconds, more preferably 1 minute to 4 minutes 20 seconds.

In the treatment method of the present invention, as described above! By using a 2-equivalent magenta coupler and a bleaching accelerator in combination, an excellent processing method is provided that speeds up bleaching and does not cause a decrease in magenta density during storage of the obtained dye image, and also does not cause a sharpening of the characteristic curve. and
The effects of the present invention were unexpected from the prior art.

In the treatment using the bleaching solution of the present invention, a color development treatment is performed prior to the bleaching treatment of the present invention.

That is, in the processing power method of the present invention, a color development treatment, then a bleaching treatment using the bleaching solution of the present invention, a fixing treatment are performed, and then a treatment with water or a water-washing substitute stabilizing solution is performed.

Aromatic primary amine color developing agents preferably used in the color developing solution of the present invention include various types that are widely used in various color photographic processes.

These developers include ami/7er/-el derivatives and D-phenylenenoamine derivatives. These compounds are generally used in the form of salts, such as hydrochlorides or sulfates, since they are more stable than in the free state. Additionally, these compounds are generally used at a concentration of about 0.18 to about 308 g per 1N color developer, and more preferably from about 1 g to about 15 g per 1N.

Examples of amino 7-el/-based developers include 〇-amino/
7er/-er, p-7mi/phenol, 5-amine-2-
Included are oxy-toluene, 2-7-7-3-oxy-toluene, 2-oxy-3-ami/-1,,4-tumethyl-benzene, and the like.

The aromatic primary amine color developer which is particularly useful from the viewpoint of the effects of the present invention is an aromatic primary amine color developer having an amide group having at least one water-soluble group, Particularly preferred is a compound represented by the following formula [X].

General formula [X] In the formula, R13 represents a hydrogen atom, a halogen atom, or an alkyl group, this alkyl group represents a linear or branched alkyl group having 1 to 5 carbon atoms, and r! It also includes those having an i substituent. R11 and [Ls represent a hydrogen atom, an alkyl group, or an aryl group, and these groups include those having a substituent, and in the case of a furkyl group, an alkyl group substituted with an aryl group is preferable. and at least one of R14 and RIS is a hydroxyl group, a carboxylic acid group, a sulfonic acid group,
It is an alkyl group or +(CH2)q-0+5-Rlg substituted with a water-soluble group such as an amine 7 group or a sulfonamide group. This alkyl group also includes those having further substituents.

In addition, Rlg represents a hydrogen atom or an alkyl group, the alkyl group represents a linear or branched alkyl group having 1 to 5 carbon atoms, and p and q represent integers of 1 to 5.

Next, list the compounds represented by the formula [χ1] (Example compounds) (E-2) (E-3) (E-4) (E-5) (E-6) (E-7) (E -8) (, E-9) (E-10) (E-11) (E-12) (E-13) (E-14) (E-15) (E-16) These - formulas [X] +17 indicated by! Nylennoamine derivatives can be used as salts of organic acids and non-diabolic acids, such as hydrochloride, sulfate, phosphate, P-)luenesulfonate, sulfite, oxalate, benzenosulfonate, etc. be able to.

In the present invention, among these 9-phenylenediamine derivatives represented by formula [X], those in which R+4 and/or RI5 are represented by 10 (CH, gradient 0+5R1g (p, Q and R+s are the same as above) are used. In certain cases, the effects of the present invention can be particularly well achieved.

Preferred compounds for use in the color developer of the present invention include sulfites, hydroxylamines, and development inhibitors.

Examples of sulfites include sodium sulfite, sodium hydrogen sulfite, potassium sulfite, potassium hydrogen sulfite, etc., and it is preferable to use them in a range of 0.1 to 40 g/l, more preferably in a range of 0.5 to 10 g/l. It is to be used within a range.

Hydroxylamine is used as a salt for hydrochloride, sulfate, etc., and is preferably used in a range of 0.1 to 40 g/l', more preferably 0.5 to 10°/1! Use within the range.

As the suppressor, halides such as sodium bromide, potassium bromide, sodium iodide, potassium iodide, etc., and a photographic suppressor can be used, and the amount added is 0.005 to 20
g/l, preferably 0.01 to 5 g/l! is within the range of

The color developing solution used in the present invention further contains various commonly added components, such as alkali extracts such as sodium hydroxide and sodium carbonate, alkali metal thiocyanates, alkaline earth metal halides, benzyl alcohol, and water. A softener, a thickener, a development accelerator, and the like may optionally be included.

Additives other than those mentioned above that may be added to the color developing solution include anti-stinting agents, anti-surano agents, preservatives, interlayer effect promoters, chelating agents, and the like.

The color developing solution of the present invention has a pH of 9 or higher, particularly a pH of 9 to 13.
It is preferably used in

The silver halide fixing agent to be included in the fixing solution of the present invention is a compound that reacts with silver halide to form a water-soluble complex salt, such as potassium thiosulfate, sodium thiosulfate, Typical examples include thiosulfates such as ammonium sulfate, thiocyanates such as potassium thiocyanate, sodium thiocyanate, ammonium thousocyanate, thiourea, thioethers, and high concentrations of bromide and iocyanide. Their fixing agent is 5
It can be used in an amount that can dissolve 7 g/1 or more, preferably 50 g/1 or more, more preferably 7 (1 g/1 or more).

- Note that the fixing solution of the present invention contains boric acid, as well as the bleaching solution.
Borax, hydroxide) IJ zum, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide, and other pH buffers, either alone or in combination. A combination of two or more types can be contained. Furthermore,
It is also possible to contain various optical brighteners, antifoaming agents, surfactants, and antifoaming agents. In addition, preservatives such as hydroxyloxyamine, hydrazine, sulfites, isomeric bisulfites, bisulfite adducts of aldehydes and ketone compounds, acetylacetone, phosphonocarboxylic acids, polyphosphoric acids, organic phosphonic acids, oxycarboxylic acids, polycarboxylic acids, etc. Acids, organic chelating agents such as dicarboxylic acids and aminopolycarboxylic acids, stabilizers such as nitro alcohols and nitrates, solubilizers such as alkanolamines, stain inhibitors such as organic amines, other additives, and metal/alcohols. , dimethylformamide, dimethyl sulfoxide, and other organic solvents may be appropriately contained.

In the processing method using the processing solution of the present invention, the most preferable processing method is to perform bleaching immediately after color development.
After color development, bleaching may be performed directly after washing or after undergoing treatments such as rinsing and stopping.

Processing temperatures of the silver halide color photographic material of the present invention other than bleaching, such as color development, fixing, and various processing steps such as washing with water or stabilization as an alternative to water washing, may range from 20°C to 20°C. The temperature is preferably 80°C, more preferably 40°C or higher.

In the present invention, JP-A-58-14834, JP-A-58-14834;
No. 105145, No. 58-134634, No. 58-1
No. 8631, No. 59-126533 and No. 60-23
It is preferable to carry out a stabilization treatment in place of water washing as shown in No. 3651 and the like.

At least one of the silver halide emulsion layers of the silver halide color photographic light-sensitive material used in the processing of the present invention contains a 2-equivalent magenta coupler.

The two-equivalent magenta couplers used in the present invention are as follows:
The couplers shown can be preferably used.

General formula [M,] [Z represents a nonmetallic atomic group necessary to form a nitrogen-containing polycyclic ring, and the ring formed by Z may have a substituent.

X represents a substituent that can be separated by reaction with the oxidized product of the color developing agent.

Further, R represents a hydrogen atom or a substituent. Examples of the substituent represented by R include a halogen atom, an alkyl group,
Cycloalkyl group, alkenyl group, cycloalkenyl group, alkynyl group, aryl group, heterocyclic group, acyl group,
Sulfonyl group, sulfinyl group, phosphonyl group, carbamoyl group, sulfamoyl group, Schiff 7 group, spiro compound residue, bridged hydrocarbon compound residue, alkoxy group, aryloxy group, heterocyclic oxy group, siloxy group, acyloxy group, Carbamoyloxy group, amine 7 group, acylami 7 group, sulfonamide group, imide group, thureido group, sulfamoylamif group, alkoxycarbonyl amide/group,
Examples include aryloxycarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkylthio group, arylthio group, and heterocyclic thio group.

Examples of the halogen atom include a chlorine atom and a bromine atom, with a chlorine atom being particularly preferred.

The alkyl group represented by R has 1 to 32 carbon atoms, and the alkenyl group and alkynyl group have 2 to 3 carbon atoms.
2, cycloalkyl groups and cycloalkenyl groups preferably have 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms, and the alkyl groups, alkenyl groups and alkynyl groups may be linear or branched.

In addition, these alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, and cycloalkenyl groups are substituents [e.g., aryl, cyano, halogen atoms, heterocycles, cycloalkyl, cycloalkenyl, spiro compound residues, bridged carbonized In addition to hydrogen compound residues, such as acyl, carboxy, carbamoyl, alkoxycarbonyl, and aryloxycarbonyl (those that are moxibusted via the device 1 via a carbonyl group, and those that are substituted via a heteroatom (specifically, hydroxy, Alkoxy, aryloxy, heterocyclic oxy, siloxy, acyloxy, carbamoyloxy, etc. substituted via an oxygen atom, nitro, amino (including dialkylami7?), sulfamoylami/, alkoxycarbonylamino, aryl Oxycarbonyl amide/, acylamino, sulfonamide, imide, ureido etc. substituted via nitrogen atom, alkylthio,
arylthio, heterocyclic thio, sulfonyl, sulfinyl, sulfamoyl, etc., which are substituted via a sulfur atom, and phosphonyl, which is substituted via a phosphorus atom, etc.).

Specifically, for example, a methyl group, an ethyl group, an isopropyl group, a butyl group, a bentatecyl group, a heptadecyl group,
1-hexyl/nyl group, 1.1'-noventylnonyl group, 2-chloro-butyl group, trifluoromethyl group,
1-Ethoxytridecyl group, 1-methoxyisopropyl group, methanesulfonyl ethyl group, 2,4-non-monoamyl7ethyl/oxymethyl group, anilino group, 1-phenylinpropyl group, 3m-butanesulfonamide/7ethyl group /xypropyl, 3-4'-10-[4''(p-hydroxybenzenesulfonyl)7ヱ/xy]tripyrol/ilami/
+7enylprovir i, 314'-[α-(2”, 4”
-di-amylphenoxy)butanamido]phenyl)-propyl group, 4-[α-(0-chlorophenoxy)
Examples include a tetradecaneamide phenoxyfupropyl group, a 7lyl group, a cyclopentyl group, a cyclohexyl group, and the like.

The aryl group represented by R is preferably a phenyl group, and may have a substituent (for example, an alkyl group, an alkoxy group, an acylamino group*).

Specifically, 7enyl group, 4-t-butylphenyl group,
2.4-no-L-7 mylphenyl group, 4-tetradecanamidophenyl group, hexatesiloxyphenyl group, 4
'-[α-(4″-t-butyl7eth/oxy)tetrabutycanamido]phenyl group, and the like.

The convex heterocyclic ring represented by R preferably has 5 to 7 rings, and may be substituted or fused.
Specific examples include 2-7lyl group, 2-thienyl group, 2-biriminonyl group, and 2-benzothiazolyl group.

Examples of the acyl group represented by R″C include an acetyl group,
Furkylcarbonyl groups such as phenylacetyl group, dodecamyl group, α-2,4-cyamyl727xybutaphyll group, arylsulfonyl group such as benzoyl 7A, 3-pentadecyloxybenzoyl group, p-chlorobenzoyl group, etc. etc.

The sulfonyl group represented by R includes an alkylsulfonyl group such as a methylsulfonyl group and a dodecylsulfonyl group,
Examples include arylsulfonyl groups such as benzenesulfonyl group and p)luenesulfonyl group.

Examples of the sulfinyl group represented by R include 1, an alkylsulfinyl group such as an ethylsulfinyl group, an octylsulfinyl group, and a 3-phenoxybutylsulfinyl group, an arylsulfinyl group such as a phenylsulfinyl group, and an I#-pentadecylphenylsulfinyl group. Can be mentioned.

The phosphonyl group represented by R includes an alkylphosphonyl group such as a butyloctylphosphonyl group, an alkoxyphosphonyl group such as an octyloxyphosphonyl group, an aryloxyphosphonyl group such as a 7e/xyphosphonyl group, and a phenylphosphonyl group. +7) arylphosphonyl groups and the like.

The carbamoyl group represented by R′c may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as N-methylcarbamoyl group, N,N-butylcarbamoyl M, N-(2 -Bentatecyloctylethylethyl-N-dodecylcarbamoyl group. N-13-(
Examples include 2.4-cy-7-ethyl-7eth/xy)propyl)carbamoyl group.

The sulfamoyl crystal represented by the margin R below is an alkylaryl group (
Preferably phenyl group) etc. may be present, for example, N-pro and rusul 7T moyl groups, N,N-butylcarbamoyl groups, N-(2-pentadecyloxyethyl)
Examples include sulfamoyl group, N-ethyl-N-1'decylsulfTmoyl group, ps-7enylsulf7γmoyl group, and the like.

Examples of the spiro compound residue represented by R″C include spiro[3.3]hebutan-1-yl.

Examples of the bridged carbonized compound residue represented by R include bicyclo[2, 2.11butan-1-yl, tricyclo[3
, 3.1.1co(7)decane-1-yl, 7,7-dimethyl-bicyclo(2,2.11butan-1-yl, etc.).

The alkoxy group represented by R″c may be further substituted with the following substituents for the alkyl group, such as methoxy group, propoquine group, 2-ethoxyethoxy group, pentadecyloxy group, 2- Examples include dodecyloxyethoxy group and 7enethyloxyethoxy group.

The 7-aryloxy group represented by R is preferably 7-enyloxy, and the aryl nucleus further includes r1 to the aryl group.
It may be monosubstituted or substituted with those listed as atoms, such as phenoxy group, p-L-butylphenoxy group, t#-pentadecyl 72/xy MvP.

The heterocyclic oxy group represented by R is preferably one having a May to July heterocycle, and the heterocycle may further have a substituent, for example, 3゜4 +5 +6-tetrahydrobilanyl. -2-oxy group, 1-phenylnato2
A sol-5-oxy group is mentioned.

The siloxy group to be quenched by RT may be further substituted with an alkyl group, and examples thereof include trimethylsiloxy group, triethylsiloxy group, trimethylbutylsiloxy group, and the like.

Examples of the 7-syloxy group represented by R''C include an alkylcarbo-;ruoxy group, a 7-arylcarbonyloxy group, and may further have 110 groups, specifically a 7-cetyloxy group, Examples include α-talolacetyloxy group and benzoyloxy group.

The carbamoyloxy group represented by R is an alkyl group, 7
It may be substituted with a lyl group, and examples thereof include an N-ethylcarbamoyloxy group, an N,N-v ethylcarbamoyloxy group, and an N-phenylcarbamoyloxy group.

The amino group represented by R may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as an ethyl group, an anilino group, a aryl group,
Examples thereof include 3-pentadecyloxyluponyl 7-nylino group, 2-chloro-5-hexadecane 7-mido 7-nylino group, and the like.

Examples of the 7-sylamine group represented by R include 7 alkylcarbonylamino groups, arylcarbonylamino groups (preferably 7 phenylcarbonylamino groups), and may further have a substituent (specifically, Acetamide group, α-ethylpropanamide group, N-7enyl acetamide group,
dodecanamide group, 2.4-di[-7milphenoxyacetamide group, α-3-L-butyl 4-hydroxy 7
Examples include eth/xybutanamide group.

Examples of the sulfonamide group represented by R include 7 furkylsulfonylamide groups and 7 arylsulfonylamide groups, and may further have a substituent.

The three bodies are 7 methylsulfonylamide groups, 7 bentatecylsulfonylamide groups, benzenesulfonamide group, p-)
Examples thereof include a luenesulfonamide group, a 2-7toxy-5-7-methylbenzenesulfonamide group, and the like.

The imide group represented by R may be open-chain or cyclic, and r! It may have one substituent, for example, a succinimide group, a 3-heptadecylsuccinimide group,
Examples include a 7-talimide group, a glutarimide group, and the like.

The ureido group represented by R is an alkyl group, an aryl group (
(preferably phenyl group) may be substituted with vP, for example N-ethylureido group, N-methyl-N-decylureido group, N-phenylureido group, N-p-)
Examples include a lylureido group.

The 7 sulfoylamine groups represented by R are an alkyl group,
It may be substituted with a 7-aryl group (preferably a phenyl group), etc., such as N,N-dibutylsulfTmoyl 7mi/group, N-methylsulfo7amoylami 7M, N-7enylsulfo7γmoylamide 7 group, etc. .

The phenoxycarbonylamide 7 group represented by R is:
It may further have a substituent, for example, a methoxycarbonylamino group, a methoxyethoxycarbonylamino group,
Examples include 7 octatecyloxycarbonylamide groups.

Even if the aryloxycarbonylamino group represented by R has a substituent, examples thereof include a phenoxycarbonylamino group and a 4-methylphenoxydicarbonylamino group.

The alkoxycarbonyl group represented by R may further have a substituent, for example, a methoxycarbonyl group, a butyloxycarbonyl group, a dodecyloxycarbonyl group, an octatecyloxycarbonyl group, an ethoxymethoxycarbonyloxy group, a benzyloxycarbonyl group. etc.

The carbonyl group represented by R may further have a substituent, for example, a 7-carbonyl group,
Examples thereof include p-chlorophenoxycarbonyl group, and pentatecyloxy72/oxycarbonyl group.

The alkylthio group represented by R may further have a substituent, and examples thereof include an ethylthio group, a dodecylthio group, an octadecylthio group, a 7enethylthio group, and a 3-72/xypropylthio group.

The arylthio group represented by R is preferably a phenylthio group and may further have a substituent, for example, a phenylthio group,
Examples include p-7 toxyphenylthio group, 2-octylphenylthio group, 3-octadecylphenylthio group, 2-carboxyphenylthio group, and p-7cetoami7phenylthio group.

The heterocyclic thio group represented by R is preferably a 5- to 7-true heterocyclic thio group, which may further have a condensed ring, or may have an Fi conversion, for example, 2- Examples include a pyridylthio group, a 2-benzothiazolylthio group, and a 2,4-no7-/xy-1115-triazole-6-thio group.

Examples of substituents that can be separated by reaction with the oxidized product of the color developing agent represented by Examples include groups that are substituted via atoms.

Examples of the group substituted via a carbon atom include carboxyl group, 1r-formula (R,' is the same as the above R, Z' is the same as the above Z, R2' and VR *' are hydrogen atoms , a group represented by ) representing an aryl group, an alkyl group or a heterocyclic group, a hydroxymethyl group, and a triphenylmethyl group.

Examples of groups substituted via an oxygen atom include alkoxy groups, aryloxy groups, heterocyclic oxy groups, acyloxy groups, sulfonyloxy groups, alphkydicarbonyloxy groups, aryloxycarbonyloxy groups, alkyloxalyloxy groups, and alkoxyoxalyloxy groups. Examples include groups.

The alkoxy group may further have a substituent, for example,
Examples include ethoxy group, 2-phenoxyethoxy group, 2-cyanoethoxy group, 7enethyloxy group, p-70 lupencyloxy group, and the like.

The aryloxy group is preferably a 7e/oxy group, and the aryl group may further have a substituent, specifically a phenoxy group, a 3-methyl 7e/oxy group, a 3-
Dodecyl 72/xy group, 4-7 tansulfonamide 72/xy group, 4-[α-(3'-pentadecylphenoxy)butanamide] 71/xy group, hequindecyl rubamoylmethoxy group, 4-sia/ 7eth/oxy group, 4-methanesulfonylphenoxy group, 1-s7tyloxy group, p-
Examples include methoxy7e/oxy group.

The heterocyclic oxy group is preferably a 5- to 7-shell heterocyclic oxy group, which may be a condensed ring or may have a substituent. Specific examples include 1-phenyltetrazolyloxy group, 2-benzothiazolyloxy group, and the like.

Examples of the acyloxy group include acetoxy groups, alkylcarbonyloxy groups such as butanoloxy groups, alkenyloxy groups such as cinnamoyloxy groups,
Examples include arylcarbonyloxy groups such as benzoyloxy groups.

Examples of the sulfonyloxy group include a butanesulfonyloxy group and a methanesulfonyloxy group.

Examples of the alkoxycarbonyloxy group include ethoxycarbonyloxy group and benzyloxycarbonyloxy group.

Examples of the alkyloxalyloxy group include a methyloxalyloxy group.

Examples of the alkoxyoxalyloxy group include a hydroxyoxalyloxy group and the like.

Examples of the group substituted via a sulfur atom include an alkylthio group, an arylthio group, a heterocyclic thio group, and an alkyloxythiocarbonylthio group.

Examples of the alkylthio group include a butylthio group, a 2-cyanoethylthio group, a 7ethylthio group, a benzylthio group, and the like.

The arylthio group includes a 7enylthio group, a 4-7thanesulfonamidophenylthio group, a 4-dodecyl7enethylthio group, a 4-/sufluoropentane7mido7enethylthio group, a 4-carboxyphenylthio crystal, and a 2-ethoxy- Examples include 5-L-butylphenylthio group.

Examples of the heterocyclic thio group include 1-722-1.
Examples include 2.3.4-nato2zolyl-5-thio group and 2-benzothialtruthio group.

Examples of the alkyloxythiocarbonylthio group include dodecyloxythiocarbonylthio group.

Examples of the formula-N include aryl groups, heterocyclic groups, sulfo-moyl groups, carbamoyl groups, 7-syl groups, sulfonyl groups, carbonyl groups, alkoxycarbonyl groups, and R4 ' and R! ' may be combined to form a heterocycle, provided that R4' and Rs
' cannot both be hydrogen atoms.

The alkyl group may be linear or branched, and preferably has 1 to 22 carbon atoms. Further, the alkyl group may have a substituent, and examples of the substituent include an aryl group, an alkoxy group, an aryloxy group, a furkylthio group,
7 arylthio group, 7 alkylamides, 7 arylamides, 7 acylamides, sulfonamide group, imino group, acyl group, alkylsulfonyl group, arylsulfonyl group,
Carbamoyl group, sulfyl moyl group, alkoxycarbonyl group, ryoroxycarbonyl group, fluoryloxycarbonyl 7 group, sulfyloxycarbonyl group 7
group, hydroxyl group, carboxyl group, cyano group, and halogen atom.

Specific examples of the furkyl group include ethyl group, oxytyl group, 2-ethylhexyl group, and 2-lylolethyl group.

The oryl group represented by R4' or R%' has 6 to 32 carbon atoms, and phenyl and naphthyl groups are particularly insectophilic;
The 7-aryl group may have a substituent (ra substituents include those listed above as substituents for the alkyl group represented by R, 7 or R5', and an alkyl group. Specific examples of the group include a phenyl group, a 1-su7tyl group, and a 4-methylsulfonylphenyl group.

The heterocyclic group represented by R, J or R5' is 5 to 6
A simple one is preferable, and it may be a condensed ring or may have a substituent. Specific examples include a 2-7lyl group, a 2-quinolyl group, a 2-pyrimidyl group, a 2-benzothiazolyl group, and a 2-benzothiazolyl group. -Birinol group and the like.

The sulf 1 moyl group represented by R4' or R5' includes N-furkylsulfamoyl group, N,N-dialkylsulfamoyl group, N-7 lylsul 7T moyl group, N-furkylsulfamoyl group,
, N-diarylsul77 moyl group, etc., and these alkyl groups and aryl groups may have the substituents listed for the alkyl groups and aryl groups. Specific examples of the sulf1 moyl group include, for example: N, N-diethylsul77 moyl group, N-methylsulfamoyl group, N
-dodecylsulfamoyl group and N-p-tolylsulfamoyl group.

The carbamoyl group represented by R4' or R1' is
N-furkylcarbamoyl group, N,N-noalkylcarbamoyl group, N-7lylcarbamoyl group, N,N-)
7-arylcarbamoyl group, etc., and these alkyl groups and aryl groups may have the substituents listed for the alkyl group and 1-aryl group. Examples of consortiums of carbamoyl groups include N,N-diethyl, etc. Carbamoyl group, N-methylcarbamoyl group, N-dodecylcarbamoyl, N1+-cya/phenylcarbamoyl group, N
-p-)lylcarbamoyl group.

Examples of the acyl group represented by R,/or R, and 7 include an alkylcarbonyl group, a 7-arylcarbonyl group, and a heterocyclic carbonyl group, and the alkyl group, aryl group, and heterocyclic group may have a substituent. Specific examples of the acyl group that may be present include hexafluorobutanoyl group, 2I3.4.5.6-penta7fluorobenzo4) group, acetyl group, benzoyl group, naphthonyl group, -furyl carbonyl group, etc.

Examples of the sulfonyl group represented by R4' or R5' include an alkylsulfonyl group, an arylsulfonyl group, and a heterocyclic sulfonyl group, which may have a substituent (for example, an ethanesulfonyl group) , benzenesulfonyl group, octanesulfonyl group, naphthalenesulfonyl Ii, p?lorbenzenesulfonyl group, and the like.

The aryloxycarbonyl group represented by R4' or R5' may have one of the substituents listed in -1 for the aryl group, and specific examples include a 7-enoxycarbonyl group, etc. do.

The alphkidicarbonyl group represented by R4' or Rs' may have a substituent listed for the alkyl group, and specific examples include a methoxycarbonyl group, a dodecyloxycarbonyl group, and a pennoloxycarbonyl group. Examples include groups.

The heterocycle formed by combining R, / and R1' is preferably one with a 5 to G shell, and may be saturated or unsaturated, and may have aromaticity, even if it is ~1, without ν1. Good too,
Further, the heterocycle may be a condensed ring, for example, N-7
Talimide group, N-cono)phosphoric acid imide group, 4-N-urazolyl, 1-N-hyguntoynyl group, 3-N-2,4
-Nookineoxazolinonyl group, 2-N-1,1-dioxo-3-(2H)-oxo-1,2-benzthiazolyl group, 1-pyrrolyl group, 1-pyrrolidinyl group, 1-pyrazolyl group, 1- Pyrazolidinyl group, 1-piperinonyl group, 1-pyrrolinyl group, 1-imidazolyl group, 1-indolyl group, 1-indolyl group, 1-isoindolinyl group,
2-isoindolyl group, 2-ineindolinyl group, 1-
Pencyto+77 zolyl group, 1-pencyimigzolyl group,
1-(1,2,4-)riazolyl) group, i-<1.2.
3-) riazolyl) group, 1-(1,2,3,4-tetrazolyl) group, N-morpholinyl group, 1.2.3.4-tetrahydrocucifuryl group, 2-oxo-1-pyrrolinonyl group, Examples include 2-IH-pyridone group, 7-tafunone group, and 2-oxo-1-piperidinyl group, and these heterocyclic groups include alkyl group, aryl group, alkyloxy group, aryloxy group, 7-syl group, and sulfonyl group. , alkylamino group, arylamino group, 7 acylamino groups, 7 sulfonamide groups, carbamoyl group, sulfamoyl group, alkylthio group, arylthio group, ureido group, alkoxycarbonyl group, aryloxycarbonyl group, imido group, nitro group, sia/group , a carboxyl group, a halogen atom, etc.

Examples of the nitrogen-containing heterocycle formed by Z or Z' include a pyrazole ring, imidazole ring, triazole ring, or tetrazole ring, and substituents that the ring may have include The above-mentioned R can be mentioned.

Also, -mathematical formula [C] and general formula (M-1) to be described later ~ [Yu-
7] on the heterocycle (for example, R1R1 to R
Where s) is a part, R'', X and VZ'' are the same a'c as R, X and Z in the general formula [Iris]. ), it forms a so-called screw-type coupler, which is, of course, included in the present invention. In addition, the ring formed by z, z', z'' and 71 described below may be further fused with another ring (for example, 5 to 7 cycloalkenes). In the mathematical formula, Rt and R may be combined with each other to form fi (for example, 5 to 7 cycloalkenes, benzene).

More specifically, what is represented by the general formula [C] is represented by, for example, the following formulas (M-1) to (M-&).

-Mathematical formula CM-1) General formula CM-2) General formula (M-3) General formula [Ryori general formula [Iris] General formula (M-4) Above-mentioned -Math formula CM-1) ~ (M- 6) In R1-R1
and (/X has the same meaning as R and X above.

Moreover, among the -mathematical formulas [Lu], the following -mathematical formulas (
M-'F).

-Formula (M-7) In the formula, R, , X and (/Z) are -R in the formula [c].

It is synonymous with X and Z.

A particularly preferable width of the magenta coupler represented by the above-mentioned formula (M-1)-(M() is a magenta coupler represented by the general formula (M-13).

Regarding the substituents on the heterocycle in formulas [O] to (M-'l), R is in formula [C], and R is in formula (C) -(M-7). It is preferable that R1 satisfies the following conditions ff, 1, more preferable is the case that it satisfies the following conditions 1 and 2, and particularly preferable is the case that it satisfies the following conditions 1.2 and 3.

Condition 1: The root atom directly connected to the heterocycle is a carbon atom.

Condition 2: Only one hydrogen atom or no hydrogen atom is bonded to the carbon atom.

Condition 3 All bonds between the carbon atom and adjacent atoms are single bonds.

The most preferred substituents R and R5 on the biplane seat are those represented by the following formula CM-8).

General formula (M-8) R1 R9゜-〇- In the formula, R,,R,. and VR,, are hydrogen atoms, /”
10 denene atoms, alkyl groups, cycloalkyl groups, alkenyl groups, cycloalkenyl groups, alkynyl groups, aryl groups, heterocyclic groups, acyl groups, sulfonyl groups, sulfinyl groups, phosphonyl groups, carbamoyl groups, sulfamoyl groups, cyano groups, spiro Compound residue, bridged hydrocarbon compound residue, flukoxy group, aryloxy group, heterocyclic oxy group, siloxy group, acyloxy group, carbamoyloxy group, amine 7 group, acylami 7 group, sulfone 7 mido group,
Represents an imido group, a ureido group, a sulf7 amoylami group, a 7 alkoxycarbonyl amine group, an aryloxycarbonyl amine 7 group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylthio group, an arylthio group, a heterocyclic thio group, R9TRto and R8 , at least two of which are not hydrogen atoms (1.

Also, the above R,,R,. and 1/ R+ + For example, R9 and Rto may be combined to form a saturated or unsaturated ring (e.g. dichloroflucan, dichloflukene, heterocycle), and R1+ may be further bonded to the chain ring to form a ring. Bridge hydrocarbon compound residues may also be implanted.

The group represented by R9-R1 may have a substituent,
Specific examples of the group represented by R, to R11 and substituents that the group may have include specific examples of the group and substituents represented by R in the above-mentioned general formula [Jiku].

Also, for example, a ring formed by combining R1 and R1゜ and R1
- fi! formed by R1! Specific examples of hydrocarbon compound residues and flE substituents that they may have include specific examples of cycloalkyl, cycloalkenyl, and heterocyclic group-containing hydrocarbon compound residues represented by R in the aforementioned general formula [Ro]. and its r! One substituent may be mentioned.

Among the general formulas CM-8), (i) R*~
When two in R are alkyl groups, (ii) R, ~R
One of the eyes, for example R11, is a hydrogen atom, and the other two
When R1 and R1° combine to form a cycloalkyl together with the root carbon atom, the following is true.

Furthermore, among (i), 2 of R9-R1 is preferable.
One is a furkyl group and the other is a hydrogen atom or an alkyl group.

Here, the alkyl and the cycloalkyl may further have a substituent (specific examples of the alkyl, the cycloalkyl, and the substituent thereof include the alkyl, cycloalkyl, and its Specific examples of substituents are listed.

Also, - the ring formed by Z in the formula [邑] and -
Substituents that the ring formed by Zl in W3 in the formula CM-Tl may have, and -Formula CM-1) ~ [R1-R1 in Ou-Gen are those represented by the following -Formula CM-91 is preferred.

-Formula CM-'I) -R'-8Ot-12 In the formula, R+ represents alkylene and R'' represents alkyl, dichlorofurkyl or aryl.

The alkylene represented by R1 preferably has 2 or more carbon atoms in the straight chain portion, more preferably 3 to 6 carbon atoms, and the straight chain portion has 1 or more carbon atoms.
Regardless of branching, this alkylene may have a substituent.

Examples of the substituent include R in the above general formula [c]
When is an alkyl group, the substituents that the alkyl group may have include those shown below.

Preferred substituents include phenyl.

Preferred specific examples of alkylene represented by R1 are shown below.

The alkyl group represented by R2 has a straight ζi1 branch.
1° Specific examples include methyl, ethyl, propyl, 1so-propyl, butyl, 2-ethylhexyl, octyl, dodecyl, tetradecyl, hexadecyl, oftagyl, 2-hexyldecyl, and the like.

The cycloalkyl group represented by R2 is preferably 5-6ji, such as cyclohexyl.

The alkyl and cycloalkyl represented by R2 may have a substituent, and examples thereof include those exemplified as the substituent for R1 above.

Specific examples of the aryl represented by R1 include phenyl and naphthyl. The aryl group may have a substituent, and examples of the substituent include linear or branched furkyl, as well as those exemplified as the substituent for R1 described above.

Moreover, when there are two or more substituents, those substituents may be the same or different.

-Among the compounds represented by the formula [Iris], particularly preferred are those represented by the following formula (M-10).

General formula (M-IQ) In the formula, R and X have the same meaning as R and X in the general formula.
It is synonymous with IR2.

Below is a specific example of ``27ka70ra'' in 1 book [M].

However, the numbers in the table represent the following groups.

-F -CI-
Br-CHs-CF3
-C* Hs-C, Ht -(i)
C3Ht - (L) C4H12021 deficiency 2 (-r 12 mountain 5 11'1s I 13 shi -I'i+7 (LJ - (CH2) 30 C1z H2srσ CH* CHz CH* S O2CH* CH* S
O* C+ s H* sG9 -CH-CH, CH25○2C1, H2°CH.

-CHCH,CH,SO,C,,H2%C,H.

-CHCH,CH,5O2C,4H,.

CH.

-CHCH,CH,5o2C,,H,3C,H.

2O -C)(CH2CH,SO,C,,H,.

CH.

2l -CHCH,CH,502C,,H,.

Hs -C-CH2CH,5OtC,H2S CH.

-CCH,CH25O,C,gH,2 CH.

sound CH.

Shimonko Cσ −NHCOCF, −NHCOC,F,
-NHC○(CF,),)1to-OCH,C0NHCHICH20CH,-0C2Hs
-OCOC, Hz* 08Oz
CHs-9 C-H, t-
S C, a H□- S O-C1-Hs - Formula [MJ I Δr:lii A phenyl group including one having a substituent, C is necessary, and an ffi+ negative phenyl group is particularly preferred.

Examples of the substituent include a halogen atom, an alkyl group, an alkyl group, an aryl AI'', a cy group, an alkoxycarbonyl group, a cyano group, a carbamoyl group, a sulfonyl group, a sulfonyl group, a sulfonamido group, and an acylamino group. In this case, the substituents may be the same or present.

A specific example of WllIIIJl& is given below.

Halogen atom: J! ! Prime, bromine, fluorine alkyl group:
Examples include a methyl group, an ethyl group, a 1so-butyl group, a butyl group, a t-butyl group, a t-pentyl group, and an alkyl group having 1 to 5 carbon atoms is particularly preferred.

Alfuxi! %: Methoxy group, ethoxy group, ゛ group, butoxy group, 5ec-butyloxy group, +SO-pentyloxy group, etc., and particularly preferred is an alkoxy group having 1 to 5 carbon atoms.

Aryloxy group = phenoxy group, β-naphthoxy group, etc., but this aryl moiety may further have the same substituents as listed for the phenyl group represented by A.

Alkoxycarbonyl W: The above-mentioned carbonyl group with an alkoxy group attached, preferably those in which the alkyl moiety has 1 to 5 carbon atoms, such as a methoxycarbonyl group or a pentyloxycarbonyl group.

Carbamoyl group: Carbamoyl group, alkylcarbamoyl sulfamoyl group such as dimegylcarbamoyl group W: Sulfamoyl group, furkylsulfamoyl group such as methylsulfamoyl group, dimethylsulfamoyl group, ethylsulfamoyl group Sulfonyl group: Methanesulfonyl group, ethanesulfonyl group, alkylsulfonyl group such as butanesulfonyl group, arylsulfonyl group such as phenylsulfonyl group Sulfonamide group: Alkylsulfonamide group such as methanesulfonamide group, 1-luenesulfonamide group, arylsulfonamide group Acylamino group: acetamino group, pivaloylamino group, benzamide group, etc. Particularly preferred are halogen atoms, among which chlorine is most preferred.

Y: represents a group that leaves when a dye is formed by coupling with an oxidized product of a color developing agent J'.

Specifically, it represents an atomic group required to form a 5- or 6-membered ring with an atom selected from, for example, a halogen atom, an alkoxy group, a child, and a hydrogen atom. ) Specific examples are given below.

Halogen atom: i! A, bromine, fluorine alkoxy group:
1-oxy group, benzyloxy group, methoxyedylrubamoylmethoxy group, tetradecylcarbamoylmethoxy group, 1-
Aryloxy group such as xy group = phenoxy group, 4-methoxyphenoxy group, 4-21-a phenoxy JIJ Acyloxy group: ace1-oxy group, myristoyloxy group, benzoyloxy group, etc. Arylthio group: phenylthio group, 2-butoxy group -5-
octylphenylthio group, 2.5-dihexyloxyphenyldiΔii 1 alkyldio JA = medildio group, octylphenylthio group, octylphenylthio group, hexadecylthio group, benzylthio group, 2-(diethylamino)edylthio group, 1-oxycarbonylmethylthio group 7
1 group, phenoxyethylthio acyl group, tetrazolyl group, etc. R: When R is an acylamino group, examples thereof include acetamide group, isoptylamino L benzamide group, 3-[α
-(2,4-di-tert-amylphenoxy)butylamido]benzamide group, 3-[α-(2,4-tert-amylphenoxy)butylamido]
O "[-amylphenoxy)acetamido]benzamide group, 3-[α-(3-pentadecylphenoxy)butylamidej benzamide group, α-(2,4-di[e"
(-amylphenoxy)butyrami I'll, CI-
(3-pentadecylphenoxy)butyramide group, power 1nadecaneamide group, isostearylamim, 3-
(3-octadecenylsuccinimide) benzamide group or pivaloylamino group, etc., and when R is anilino group, examples thereof include anilino group, 2-chloroanilino group, 2,4-dichloro7nilim L2.5-dichloro 7
Nilim! 1,2.4.5-1-lichloroanilino base, 2
-Chloro-5-tetradecanamide anilino group, 2-chloro-5-(3-octadecenylsuccinimide) ayurim 1,2-chloro-5-[α-(3-tert-butyl-4-hydroxy) Te1-ladecanamido)anilimL2-chloro5-tetradecyloxycarbonylanilisulfamoyl)anilino group, 2,4-dichloro-5
- Tetradecyloni 1; Cyanirim L2 - Ri O "Ko 5
-(Butrabcyloxycarbonylamino 2anilim L
2-Roleau 5-71tadecylthiaanilino group or 2-chloro-5-(N-deradecylcarpalyl)
Anilino group, etc. When R is a ureido group, examples include 3-((2,4-di-tart-7minophenoxy)aretamide) phenylureido group, phenylureido group, methylureido group, A phtadecylureido group. , 3-
Te! ~ Radecanamidophenylureido or N,N
-Geokujiru Ureid! ! There is a first prize. -Cost of clothing [M'
Among the compounds represented by the above formula, a particularly preferred compound is represented by the general formula [M'-IJ.

In the formula, Y and Δr have the same meanings as in the general formula IM'J, 1°X: halogen atom, alkoxy group: or Al: 1-nyl group.

Specific examples are listed below.

Pigeon 1 gene atom: chlorine, bromine, fluorine alkoxy! 3: me(-xyki, ethoxy group, butoxy group, 5aC-1 toxy group, 1so-pentyl 2t=1-
An alkoxy group having 1 to 5 carbon atoms, such as a silica group, is preferred.

Al4nyl group: medyl group, edyl group, 1so-bu[copyl group, bubour group, t-pudyl group, (-pendel!!!
Preferred are aru4nyl groups having 1 to 5 carbon atoms, such as . Particularly preferred is a halogen atom, and "11r:" is also preferably chlorine.

R1: represents a group capable of TIJ substituted on the bembin ring, n is 1
Or when 1°11 is 2 to represent 2, then l? + may be the same or different °
[Ji Olji 1ji 11・+? ', +1'', and 1 may each be ml- or different, and each may be a hydrogen atom, or each may be a diagonal. Among these, preferable examples of magenta couplers are shown below, but the shells are not limited to these.

Examples of R in the above formula include the following.

M J NHCOC+slJ*y M
2-NH(':0CnHz.

C,,H,.

t Examples of Y in the above formula include the following.

M-12M-13 -3CH,CO,C,H,-8C)12COO)JM-
16M-17 -8CH,CH,0Ct)I, -5CH
,C)1. OHM-: 10 M-27 C(J
Null Op the Chemical Fusaiety 1 Perkin I
(Journal or tbe CI+em
icalSociety, Perkin I + 1
977) 2047-2052, U.S. Pat. No. 3,725.
No. 067, JP-A-59-99437 and JP-A-58-
It can be synthesized by referring to No. 42045 and the like.

Moreover, the magenta coupler indicated by the above-mentioned -clothing cost [M'1 is disclosed in Japanese Patent Application Laid-open Nos. 58-38043 and 57-14837,
It can be easily synthesized according to the methods described in Japanese Patent Nos. 57-204036 and 58-14833.

The amount of the 2-equivalent magenta coupler of the present invention added is preferably 0.005 to 2 mol, more preferably 0.01 to 1 mol, per 1 mol of silver denide.

The magenta couplers according to the present invention may be used alone or in combination of two or more, and may also be used in combination with other magenta couplers outside the present invention.

Photographic magenta couplers that may be used in combination include compounds other than those of the present invention, such as pyrazolone, pyrazolotriazole, pyrazoli/benraimigzole, and ingzolone.

As pyrazolotriazole magenta couplers, U.S. Patent No. 1,247,493, Belgian Patent No. 792,
The couplers described in US Pat.
No. 71, tpJ2,983,608, tpJ 3.00
No. 5,712, No. 3,684,514, British patent fi
Examples thereof include compounds described in No. 937゜621, VF No. 49-123625, and No. 49-31448.

Furthermore, a colored magenta coupler of the type in which the dye flows out into the processing solution by the reaction of the oxidized product of the developing agent as described in US Pat. No. 3,419,391 can also be used.

In addition to the 2-equivalent magenta coupler of the present invention, a yellow coupler and a cyan coupler can be used, and each of the yellow and cyan couplers may be a so-called 2-equivalent type coupler or a 4-equivalent type coupler, or In combination with these couplers, it is also possible to use diffusible dye-releasing couplers and the like.

The yellow coupler may be a closed ketomethylene compound or a so-called two-equivalent type coupler.
〇-7 aryl substituted coupler, active point -〇-acyl substituted coupler, active point hyguntoin compound substituted coupler, active point urazole compound substituted coupler, active point dinolyl imide compound substituted coupler, active point fluorine substituted coupler, active point chlorine Alternatively, bromine-substituted couplers, active site -0-sulfonyl-substituted couplers, etc. can be used as effective yellow couplers. Specific examples of yellow couplers that can be used include U.S. Patent No. 2,875,057, U.S. Pat. No. 3,265,506, U.S. Pat. ,
No. 3,725,072, No. 3.891,445,
West German Patent No. 1,547,868, West German Application Publication No. 2,21
9.917, 2,261,361, 2,41
4,006, British Patent No. 1,425,020, Japanese Patent Publication No. 51-10783, Japanese Patent Publication No. 47-26133, 4
B-73147, No. 51-102636, No. 50-
No. 6341, No. 50-123342, No. 50-130
No. 442, No. 51-21827, No. 50-87650
No. 52-82424, No. 52-115219,
Examples include those described in No. 58-95346.

Further, useful cyan couplers used in the present invention include, for example, phenol couplers, naphthol couplers, and the like. These cyan couplers may be not only 4-equivalent type couplers but also 2-equivalent type couplers like the yellow couplers.Specific examples of cyan couplers include US Pat. : No. 369,929, No. 2,434.272, No. 2.474,293, No. 2
, No. 521,908, No. 2,895.826, No. 3,
No. 034,892, No. 3,311,476, No. 3,4
No. 58,315, No. 3,476.563, No. 3,58
No. 3,971, No. 3,591,383, No. 3,767
．． No. 411, No. 3,772,002, No. 3,933,
No. 494, No. 4,004,929, West German patent application (O
L S ) No. 2,414,830, No. 2,454,3
No. 29, JP-A-48-59838, JP-A No. 51-2603
No. 4, No. 48-5055, No. 51-146827,
No. 52-69624, No. 52-90932, No. 58
-95346, Japanese Patent Publication No. 49-11572, and the like.

A coupler such as a colored magenta or cyan coupler or a polymer coupler may be used in combination in the silver halide emulsion layer of the present invention and in its photogroove layering.

Regarding colored magenta or cyan couplers, reference may be made to the description in JP-A-81-72235, and regarding polymer couplers, reference may be made to JP-A-61-50143.

The method of adding the above coupler used in the present invention to the photographic constituent layer of the present invention is the same as before, and the amount of the above coupler added is not limited, but I x 1 per mole of silver.
0-' to 5 mol is preferable, more preferably I X 1
0-'' to 5 x 10-'.

The silver halide color photographic light-sensitive material of the present invention may contain various other photographic additives.For example, as described in Research Disclosure Magazine No. 176439, J l) Inhibitors, stabilizers, and ultraviolet absorbers. , a color stain inhibitor, a fluorescent whitening agent, a color image fading inhibitor, an antistatic agent, a hardening agent, a surfactant, a plasticizer, a wetting agent, etc. can be used.

In the silver halide color photographic light-sensitive material of the present invention, the hydrophilic colloids used to prepare the emulsion include gelatin, derivative gelatin, graft polymers of gelatin and other polymers, proteins such as albumin and casein, and hydroxyl colloids. Ethyl cellulose derivatives, cellulose derivatives such as carboxymethyl cellulose, starch derivatives, polyvinyl alcohol, polyvinyl alcohol, polyacrylic 7
Any single or copolymer synthetic hydrophilic polymers such as amide and the like are included.

Examples of the support for the silver halide color photographic light-sensitive material of the present invention include a glass plate, a polyester film such as cellulose acetate, cellulose nitrate, or polyethylene terephthalate, a polyamide film, a polycarbonate film, and a polystyrene film. The body is appropriately selected depending on the intended use of the photosensitive material.

In the photosensitive material of the present invention, it is optional to provide an intermediate layer with an appropriate thickness depending on the purpose, and a filter layer,
Anti-curl layer, protective layer, anti-halation/r! Various layers such as No. 1 can be used in appropriate combinations as constituent layers. Hydrophilic colloids that can be used in the emulsion layers as described above can be used as binders in these constituent layers, and various types of colloids that can be contained in the emulsion layers as described above can be used in these layers. Photographic additives may be included.

The processing method of the present invention can be applied to silver halide color photographic light-sensitive materials such as color negative film, color positive film, color reversal film for slides, color reversal film for movies, color film for TV use, and films.

[Specific Effects of the Present Invention] In the processing power method of the present invention having the configuration as explained above, bleaching is speeded up, there is no decrease in magenta density during storage of the obtained dye image, and the characteristic curve is improved. An image without high contrast can be obtained.

[Community Embodiment 1 of the Invention The present invention will be specifically explained below with reference to Examples, but the embodiments of the present invention are not limited thereto.

Example 1 Following the layer structure adopted in the industry for high-sensitivity halogenated nail color photographic light-sensitive materials, an antihalation layer, a red-sensitive silver halide layer, and a red-sensitive silver halide layer were coated from the support with various auxiliary layers interposed. An emulsion layer, a green-sensitive silver halide emulsion layer, and a blue-sensitive silver halide emulsion layer were provided, and a monodisperse high-sensitivity silver halide emulsion layer was disposed on the outermost side of the blue-sensitive silver halide emulsion layer.

The amount of coated silver is approximately 13 in the blue-sensitive silver halide emulsion layer.
mH/di2. 7fI was prepared so that the green-sensitive silver halide emulsion layer was approximately 18 m ((/d+a2) and the red-sensitive silver halide emulsion layer was approximately 13 mg/dm2.

Wil...Hydroquinone is reduced using Nitl112 silver as a reducing agent, and 0.8 g of black colloidal silver, which exhibits high absorption of light in the wavelength range of 400 to 700 nm, is added to gelatin 3.
A dispersion liquid was prepared in step g, and an antihalation layer was applied.

Layer 2: Middle layer consisting of gelatin.

(Dry film thickness 0.8 μm) Layer 3: 1.5 g of low-sensitivity red-sensitive silver iodobromide 7 detergent (
AgI: 6 mol %), 1.9 Fi of gelatin and 0.98 g of 1-hydroxy-4-(β-7toxyethylami7carponylmethquine)-N-[δ-(2,4
-No-amyl 7ヱ/xy)butyl 1-2-su7amide (hereinafter referred to as cyan coupler (C-1)), 0
．． 0281? 1-Hydroquine-4-[4-(1-hydroxy-8-7cetamido-3,6-nosulfo-2-su7tylazo)7eth7xy]-N-[δ-(2,4-noamylphenoxy) butyl]-2-su7tamide nonodium (hereinafter referred to as colored cyan coupler (CC-1)
A low-sensitivity red-sensitive silver halide emulsion layer containing 0.4 g of triphrenor phosphate (hereinafter referred to as TCP) dissolved therein.

N4... Bow, 1 [1 high-sensitivity red-sensitive silver iodobromide emulsion (A
gI; 8 mol%) 1.2 g of gelatin and 0
．． 41g cyan coupler (C-1), 0.026g
A high-sensitivity red-sensitive silver halide emulsion layer containing O, 1.5H TCP in which colored cyan coupler (CC-1) is dissolved.

7ffl 5...0.08. 2,5-not-t-octylhydrogen (hereinafter referred to as anti-staining agent) (Q-1
) dissolved in 0,04. of butyl 7-talate (hereinafter referred to as DBP) and 1.2 g of gelatin.

Layer 6...low-sensitivity green-sensitive silver iodobromide emulsion (AgI: 15
mol %), 1.7 g of gelatin and magenta coupler, 1-(2,4,6-)cyclo-7enyl)-4-(1-su7tylazo)-3-(2-chloro-
5-octadecenyl succinimide anilino)-5-pyrazolone (hereinafter referred to as color-magenta coupler (CM-
A low-sensitivity green-sensitive silver halide emulsion layer containing 0.38 TCP dissolved in 1).

Layer 7: Highly sensitive green-sensitive silver iodobromide emulsion (A, I; 11
mol%), 1.9g of gelatin-containing magenta coupler, 0.049g of colored magenta coupler ('CM
-1) A high-sensitivity green-sensitive silver halide emulsion layer containing 1 to 2 g of TCP dissolved therein.

N8...0.2g1f) Yellow colloidal silver, 0.11H DBP in which 0.2g of antifouling agent (HQ-1> was dissolved)
and a layer of yellow filter containing 2.1 g of gelatin.

Layer 9...0.95 FI of low-speed blue-sensitive silver iodobromide (A!lI: 6 mol %), 1.9 g of gelatin and 1.84 g of α-[4-(1-bentrue) 2-phenyl-3,5-]]oxo1.2.4-triaziridinyl)]-]C-pipiparoyl--chloro5 [γ-(2
A low-sensitivity blue-sensitive silver halide, 7L agent layer containing 0.93 g of DBP in which ,4-no-17 milphenoxy)butanamide 1-acetanilide (hereinafter referred to as yellow coupler (Y-1)) was dissolved.

lto...1.2g of highly sensitive single-component blue-sensitive silver iodobromide emulsion (Agl; 7 mol%), 2.0g of gelatin and 0.48g of yellow coupler (Y-1>) were dissolved. A highly sensitive blue-sensitive silver halide emulsion layer containing a DBP of 0.0 and 23.

(ε Layer 11: second protective F1 layer made of gelatin.

Layer 12: first protective layer containing 2.3 g of gelatin.

Samples Nos. 1 to 11 were prepared by changing the type and amount of magenta coupler used in layers 6 and N7 of the photographic constituent layers and the amount of coated silver as shown in Table 1 below.

Comparison coupler (1) rθ C! Comparative coupler (2) Each of the samples Nos. 011 to 11 obtained above was exposed to a tungsten light source and the color temperature was adjusted to 4800° using a filter to give an exposure value of 20 CMC.

The exposed photosensitive material was subjected to the following treatments.

Processing steps include color development for 3 minutes and 15 seconds, bleaching for 3 minutes and 15 seconds, fixing for 3 minutes and 15 seconds, washing with water for 3 minutes, tlS1 stabilization for 2 minutes, and second stabilization for 3 minutes.
It was set to 0 seconds.

Each treatment was carried out at 37.8°C, and each treatment liquid was prepared according to the following formulation.

[Color development e,] Potassium carbonate 30g Sodium bicarbonate cum 2.5g Potassium sulfite 5g Sodium bromide 1.3g Potassium iodide
211g hydroxylamine sulfate 2.5g sodium chloride
o, 6. i Sodium diethylenetriaminepentaacetate 2.5g N-ethyl-N-β-hydroxyethyl-3-methyl-4-7 minoaniline sulfate 4.8g Potassium hydroxide 1.2g Add water and 1
p with potassium hydroxide or 20% sulfuric acid.
Adjust to H10,06.

[Color developer replenisher] Potassium carbonate 35g Sodium bicarbonate 3g Potassium sulfite 7g Sodium bromide
0.9g hydroxylamine sulfate 3.1g noethylenetriaminepentaacetic acid sodium worm 3.2gN-
Ethyl-N-β-hydroxyethyl-3-methyl-4-7 minoaniline sulfate 5.4g Potassium hydroxide 2g Add water to 1
! and p using potassium hydroxide or 20% sulfuric acid.
Adjust to H10,12.

[) Vote white liquid・) Vote white 7i! Replenishment i Good 1 Ethylenediaminetetraacetic acid ferric salt 120Fi Ethylenediaminetetraacetic acid 58 Ammonium bromide 140g Bleach acceleration reduction (listed in Table 2) Add 0.15g water to 11, pH 5.8 using acetic acid or aqueous ammonia Adjust to.

[Fixer/fixer replenishment? [l] Ammonium 1000sulfate 1808 Sodium metabisulfite 4g Sodium sulfite 13g Add water to 11 and adjust the pH to 7.0 by 1:4 using acetic acid or aqueous ammonia.

[Stabilizer 1 Formalin (37% aqueous solution) 3vll Funiguncus (
5111 (manufactured by Konishiroku Photo Industry Co., Ltd.) Add water to make 11.

[Stabilizer Replenisher 1 Formalin (37% aqueous solution) 3ml Funig 7x (manufactured by Konishiroku Photo Industry Co., Ltd.) 7ml! Add water to make 1i.

Color development liquid replenisher is color negative film 100c-
15mj per m2! The color developing bath is replenished and bleaching a
The replenisher was added to the bleach bath at 10 ml per 100 cm2, and at a constant rate of 10+s per 100 cm2.
The fixing bath is replenished and the water is 150 ml per 100 cm.
III l flowed.

Regarding the above photosensitive material samples No. 1 to 11, respectively,
The treatment was carried out continuously for 40 days at a rate of 7.0 m' per day while replenishing the treatment solution from the time of preparation.

For the processed sample, the average gradation (slope at +0.2 density area and 1.50 density area from the lowest density area) of the dye image obtained using the processing solution immediately after preparation is calculated. Using the obtained value as a reference, the average gradation of the dye image obtained as the processing liquid ages was determined in the same manner, and the difference from the average gradation of the reference was determined to examine the degree of contrast enhancement of the image. *Ta,
The residual silver concentration of the dye image obtained using the processing solution immediately after preparation was determined as follows.

The results are shown in Table-2.

The residual silver concentration was determined by determining the amount of silver remaining in the film using the fluorescence X and Jil methods.

As is clear from Table 2, in photosensitive materials No. 1 and 2 using couplers other than the present invention, when treated with white liquor (which does not contain bleaching slurry), there was no high contrast, but there was no desilvering. It is insufficient. However, in the bleach solution treatment containing the bleaching accelerators of the present invention and those other than the present invention, the desilvering performance is improved compared to Experiment No. 001, but it is still insufficient, and furthermore, continuous processing over time causes the image to become sharper. In addition, even when a light-sensitive material sample using the coupler of the present invention is processed using a comparative bleaching accelerator, the desilvering property is still insufficient and the improvement in high contrast is also insufficient. In contrast, only the method of the present invention in which a light-sensitive material sample using the coupler of the present invention is treated with the FJA solution containing the bleaching accelerator of the present invention has good desilvering properties and good prevention of high contrast. I can see that it is being done.

Comparative bleach accelerator I N142-CN)(.

Comparative Bleach Accelerator 2 HSCH2CH, OI (In addition, the decrease in the maximum magenta concentration was investigated when each sample was stored under air conditioning conditions of 75° C. and 165% for 8 days. The results are shown in Table 3.

From Table 3 below, it is clear that when using a bleaching solution containing the bleaching accelerator of the present invention, if the magenta coupler of the present invention is not used, it will fail under high temperature and high humidity conditions after processing. 7 when saving in
It is easy to understand the percentage of people who say that the decline in agricultural yield is young.0
From the above results, when using the bleaching solution according to the present invention,
By using the coupler according to the present invention in the green sensitive layer, stable maintenance of average gradation and high temperature during long-term large-scale processing, which could not be achieved with the bleaching solution according to the present invention alone, can be achieved. It is easy to understand that the major problem of stable storage of magenta dye without a decrease in density under these conditions has been solved at the same time.

Example 2 The bleaching accelerator according to the present invention of Example 1 was varied as shown in Table 4, and the treatment was carried out in the same manner as in Example 1. Fluctuations and high temperatures (65°C7)
The variation in the maximum magenta density after storage for 8 days under conditions (5% RH) was measured using sample No. 1°3.7, 9.11. According to the table, all the bleaching accelerators according to the present invention have similar problems, but it is also clear that they can be solved by using the magenta couplers according to the present invention. There is.

Table 4 Example 3 The effects of various changes in the 12-iron complex salt were confirmed in the same manner as in Example 2. The results are shown in Table-5.

As is clear from Table 5, even if the organic acid tpJ2 iron complex salt is changed in various ways, the effect is sufficient to generate nitrogen.

Claims (1)

[Claims] After imagewise exposing a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support,
In a method for processing a silver halide color photographic light-sensitive material that includes at least a color development step, a bleaching step, and a fixing step, the bleaching solution used in the bleaching step has the following general formulas [I], [II], and [III]. Contains at least one compound selected from the compounds respectively shown in
A method for processing a silver halide color photographic material, characterized in that at least one of the silver halide emulsion layers contains at least one type of 2-equivalent magenta coupler. General formula [I] ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ General formula [II] ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ General formula [III] ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (General formula [I ] ~ [III] Medium, R_1, R_2, R_4
and R_5 each represent a hydrogen atom, a halogen atom, an amino group or an alkyl group, and R_3 and R_6
each represents a hydrogen atom, an amino group or an alkyl group. )