JPS62178254A - Processing method for silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To prevent the generation of magenta processing stains by incorporating a specific magenta coupler and specific magenta dye image stabilizer into >=1 layers of emulsion layers and executing a color developing stage in the presence of an auxiliary developer. CONSTITUTION:>=1 magenta couplers expressed by the formula I and >=1 magenta dye image stabilizers selected from the formula II-formula V are incorporated into at least one layer of silver halide emulsion layers and color developing stage is executed in the presence of the auxiliary developer. Y, Z are a nonmetallic atom group necessary for forming a nitrogenous heterocycle, X is a substituent which can be desorbed by the reaction with the oxidant of the color developing agent. R is an H atom or substituent. In the formula II, R1 is an H atom, alkyl group, etc., R2, R3, R5, R6 are an H atom, halogen atom, etc., R4 is an alkyl group, etc., R1 and R2 may form 5--6-membered rings by ring closure with each other and R4 in such a stage is a hydroxy group, etc., R3 and R4 may form a 5-membered hydrocarbon ring by ring closure and R1 in such a stage is an alkyl, etc. In the formula III, Y is an atom group necessary for forming a cumarone ring. In the formula V, R' is an aliphat. group, etc.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for processing silver halide photographic materials.
More specifically, the present invention relates to a method for color development processing of a silver halide photographic light-sensitive material with reduced pollution.

[Background of the Invention] Generally, silver halide color photographic light-sensitive materials consist of three types of silver halide photographic materials that are selectively spectral sensitized to have sensitivity to blue light, green light, and red light on a support. An emulsion layer is coated. For example, in a color negative light-sensitive material, a blue-sensitive emulsion layer, a green-sensitive emulsion layer, and a red-sensitive emulsion layer are generally coated in this order from the exposed side, and there is a layer between the blue-sensitive emulsion layer and the green-sensitive emulsion layer. A bleachable yellow filter layer is provided to absorb the blue light transmitted through the blue-sensitive emulsion layer. Furthermore, each emulsion layer is provided with other intermediate layers and a protective layer as the outermost layer for various special purposes. Furthermore, for example, in light-sensitive materials for color photographic paper, the layers are generally coated in the order of a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer from the exposed side, and each layer has a special coating, similar to the light-sensitive material for color negatives. For this purpose, intermediate layers including an ultraviolet absorbing layer, protective layers, etc. are provided. It is also known that each of these emulsion layers may be provided in a different arrangement from the above, and each emulsion layer may be provided with a photosensitive layer consisting of two layers that are sensitive to substantially the same wavelength range for each color light. It is also known to use emulsion layers. In these silver halide color photographic materials, exposed silver halide grains are developed using, for example, an aromatic primary amine color developing agent as a color developing agent, and the resulting color developing agent is oxidized. A dye image is formed by reaction of the product with the dye-forming coupler. In this method, phenolic or naphtholic cyan couplers, 5-pyrazolones, pyrazolinobenzimidazoles, pyrazolotriazoles, indacylones or cyanoacetyl couplers are used to form cyan, magenta and yellow dye images, respectively. Magenta couplers and acylacetamide-based or benzoylmethane-based yellow couplers are used. These dye-forming couplers are contained in the light-sensitive color photographic emulsion layer or in the developer solution. The present invention relates to a method for processing a silver halide color photographic light-sensitive material in which these couplers are preliminarily contained in an emulsion layer and rendered non-diffusive.

Incidentally, in recent years, there has been a strong desire to reduce pollution in the development process. One major means of reducing pollution is the use of a color developing solution that does not contain benzyl alcohol.

However, with a color developing solution that does not contain benzyl alcohol, the developability is greatly reduced. Therefore, in order to reduce pollution, it is necessary to use means for improving developability.

As one method, it is known to use an auxiliary developer when developing exposed silver halide color photographic light-sensitive materials using an aromatic primary amine color developing agent, and this is an effective method. It is. For example, as such an auxiliary developer, U.S. Pat.
, No. 515, 147, No. 2.496.903, No. 4,
No. 038,075, No. 4.119.462, British Patent No. 1,430,998, British Patent No. 1,455,413, Japanese Patent Application Publication No. 53-75831, Japanese Patent Publication No. 55-62450, British Patent No. 55
-62451, 55-62452, 55-62
No. 453, No. 51-12422, Special Publication No. 51-124
No. 22, No. 55-49728, No. 57-14454
No. 7, No. 58-50532, No. 58-50533,
No. 58-50534, No. 58-50535, No. 58
- Compounds described in Nos. 50536 and the like were investigated.

However, when these compounds are used, the developability is greatly improved, but magenta stains become noticeable in the white areas during processing, which significantly reduces the product value of the photograph. .

Such magenta coloring is particularly likely to occur in automatic sheet processing machines that require a long time between development and bleach-fixing.

Therefore, in low-pollution development processing, magenta color processing stain (hereinafter referred to as magenta processing stain)
A proposal for a method to reduce this was desired.

[Object of the Invention] In view of the above-mentioned current situation, the inventors of the present invention have conducted various studies and have discovered the present invention.

A first object of the present invention is to provide a method for processing silver halide photographic materials that does not cause magenta processing stains and allows rapid processing.

A second object of the present invention is to provide a method for processing silver halide photographic materials that does not cause magenta processing stains and can be processed with low pollution.

[Structure of the Invention] The object of the present invention is to provide a silver halide photographic material comprising at least the step of imagewise exposure and color development of a silver halide photographic material having at least one silver halide emulsion layer on a support. In the material processing method, at least one of the silver halide emulsion layers contains at least one magenta coupler represented by the following general formula [I] and the following general formulas [I], [I[I], [rV] and [ V], and the color developing step is achieved by a method for processing silver halide photographic materials in the presence of an auxiliary developer.

General Formula [I] [In the formula, 2 represents a non-gold layer atomic group necessary to form a nitrogen-containing polychoric ring, and the ring formed by Z may have a substituent.

X represents a hydrogen atom or a substituent which forms 1iltlH1 by reaction with an oxidized product of a color developing agent.

Further, R represents a hydrogen atom or a substituent. ]The following is a blank general formula []I] (wherein, R1 is a hydrogen atom, an alkyl group, an alkenyl group,
R2, R5, R6,
R represents a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group, an alkenyl group, an aryl group, an alkoxy group or an acylamide group, and R1 represents an alkyl group, a hydroxy group, an aryl group or an alkoxy group.

Further, R4 and R7 may be ring-closed with each other to form a 5-membered or 6-membered ring, in which case R4 may have a hydroxy group or an alkoxy group, or R3 and R4 may be ring-closed to form a 5-membered hydrocarbon ring. In this case, R1 may be an alkyl group, an aryl group, or a heterocyclic group. However, R1
is a hydrogen atom and R4 is a hydroxy group) General formula [I[1 (wherein R- and cFR, respectively, are a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkenyl group) Oxy group, hydroxy group, aryl group, aryloxy group, acyl group, acylamino group, acyloxy group, sulfonamido group, cycloalkyl or alfkyl carbonyl group, R2 is hydrogen atom, alkyl group, alkenyl group, 71J- R1 is a hydrogen atom,
halogen atom, alkyl group, alkenyl group, aryl group, aryloxy group, acyl group, acyloxy group, sulfonamide group, cycloalkyl group or alkoxycarbonyl group) Y is necessary to form a chroman or coumaran ring Hail a group of atoms.

General formula (IV) RI (wherein R' and R3 are a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, a hydroxy group, an aryl group, an aryloxy group, an acyl group, an acylamine group, and an acyloxy group, respectively) , represents a sulfonamide group, a cycloalkyl group or an alkoxycarbonyl group.

R1 represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, a hydroxy group, an aryl group, an acyl group, an acylamine/group, an acyloxy group, a sulfonamide group, a cycloalkyl group, or a 7-rukoxycarbonyl group. General formula ( V) , -1 R -N Y [wherein, R represents an IfWIIJj-M group, a Schiff a, a lekyl group, or an aryl group, and Y together with a nitrogen atom
7 Represents a group of nonmetallic atoms necessary to form a biplane ring, provided, however, that when two or more heteroatoms are turned on among the nonmetallic atoms containing nitrogen atoms forming the heterocycle, at least two
Two heteroatoms are heteroatoms that are not adjacent to each other.

] Margin below [Specific structure of the invention] The present invention will be explained in detail below.

First, the auxiliary developer used in the present invention will be explained. The term "auxiliary developer" as used herein means, when present at the time of color development, having the ability to develop a part of the silver halide grains to be developed, and as a result promoting color development by the color developing agent. Moreover, the compound itself refers to a compound that does not substantially form a dye image through a coupling reaction with a dye-forming coupler.

Some auxiliary developers used in the present invention are already known in the art, and any of them can be used. Particularly preferable auxiliary developers for use in the present invention include the following general formulas [VI], [■],
These are compounds represented by [■] and [IX].

The following is a blank general formula [VI] i'R4 (wherein RI, R2, R3 and R4 each represent an alkyl group, R1 and R2 and/or R3 and R4
may be bonded to each other to form a nitrogen-containing heterocycle with a nitrogen atom. R5 represents a halogen atom, an alkyl group or an alkoxy group, and nl represents an integer of 0 to 4. n
When l is an integer of 2 to 4, R5 may be the same or different. ) The general formula [Vl 1, RI , R2,
The alkyl group represented by R3 and R4 may be linear or branched, and is preferably an alkyl group having 1 to 4 carbon atoms, and this alkyl group also includes those having a substituent,
Examples of substituents include hydroxy group, alkoxy group (
For example, methoxy group, ethoxy group, etc.), sulfonamide group (for example, alkylsulfonamide group such as methanesulfonamide group, arylsulfonamide group such as benzenesulfonamide group, etc.), aryl group (for example, phenyl group, etc.)
etc. Examples of the alkyl group represented by R1, R2, R3 and R4 include methyl group, ethyl group, n
-propyl group, i-propyl group, n-butyl group, 5ec
-butyl group, hydroxymethyl group, β-hydroxymethyl group, β-methoxyethyl group, methanesulfonamidoethyl group, and the like. R1 and R2 and/or R3
The nitrogen-containing heterocyclic nucleus formed by and R4 may further contain an oxygen atom, a nitrogen atom, a sulfur atom, etc., and examples thereof include a pyrrolidine nucleus, a piperidine nucleus, a morpholine nucleus, and the like.

Examples of the halogen atom represented by R5 in the general formula [VI] include a bromine atom, a chlorine atom, etc., and examples of the alkyl group include a methyl group, an ethyl group, etc.
Examples of the alkoxy group include a methoxy group and an ethoxy group. The alkyl group and alkoxy group represented by R5 include those having a substituent.

Specific examples of the compound represented by the general formula [VI] used in the present invention are shown below, but the present invention is not limited thereto.

Below margin TI -I Vl -2
Vl -3vl -4 TI -7TI -8 The following margins These compounds, with some exceptions, are known (for example, they are described in JP-A-50-15554, JP-A-58-120248, etc.). ), can be easily synthesized by those skilled in the art. The synthesis of these compounds can be carried out using methods such as [Bent, Desroches, 77 Sett, James, Laby, Sterner, Pittam, Peaceberger: Journal of the American Chemical Society, (3e
nt, Dcssloch.

Fassett, James, Ruby, 3t
crner, Vittum.

Weissberger: J, An+, Qhe
m, 3oc, ) ] L Yu, 3100 (, 19
51), [Bent, Brown, Gressmanes, Harnisch; Photo Science Engineering, (Be
nt, Brown.

Glesmaness, l-1arnish; P
Hot, Sci.

EnlJ, ) ] 8. 125 (1964) etc.

General formula [■] (In the formula, R6 and R7 each represent a hydrogen atom or an alkyl group, and R6 and R7 may be combined with each other to form a nitrogen-containing heterocycle. R8 is a halogen atom, an alkyl group, or represents an alkoxy group, and R2 represents an integer of 0 to 4. When R2 is an integer of 2 to 4, R8 may be the same or different.) In the general formula [■], an alkyl group represented by R6 and R7. may be linear or branched, and is preferably an alkyl group having 1 to 6 carbon atoms, and these alkyl groups include those having substituents, such as hydroxy groups, alkoxy groups (e.g. methoxy group, ethoxy group, etc.), sulfonamide group (for example, alkylsulfonamide group such as methanesulfonamide group, arylsulfonamide group such as benzenesulfonamide group), and the like. Examples of the alkyl group represented by R6 and R7 include methyl group, ethyl group, butyl group, hexyl group, hydroxymethyl group, β-hydroxyethyl group, methoxymethyl group, β-methanesulfonamidoethyl group, etc. The nitrogen-containing heterocyclic nucleus formed by aRs and R7 may further contain an oxygen atom, a nitrogen atom, a sulfur atom, etc., and examples thereof include a pyrrolidine nucleus, a piperidine nucleus, a piperazine nucleus, a morpholine nucleus, and the like.

Examples of the halogen atom represented by R8 include a bromine atom and a chlorine atom, examples of the alkyl group include a methyl group and an ethyl group, and examples of the alkoxy group include a methoxy group and an ethoxy group. It will be done.

The alkyl group and alkoxy group represented by R8 include those having a substituent.

When R2 is 2 to 4, R8 may be the same or different.

Specific examples of the compound represented by the general formula [■] used in the present invention are shown below, but the present invention is not limited thereto.

Below margin vn −i vu −
2Vll -3Vu -4 Vl+ -5Vll -6 Vl+ -7VII -8 0H0H Vil -11Tl[-12 711-15VII-16 vII-17''-18 (Jl-10H) These compounds are described, for example, in U.S. Pat. 678
No. 2,483,374, No. 2.776, 31
No. 3, No. 3.060,225, British Patent No. 928.
No. 671 Mei 1II, Berichte der Deutschen Chemischen Gesellschaft Vol. 16, p. 724 (13
Erichte der Deutschen Chea
+1schen Ge5ellschaft), 2.125 pages for Spring 34, Chemisier Berichte No. 9
Volume 2, No. 3, page 223 (Chea+1sche 3er
ichte), Photographic Science and Engineering Vol. 12, p. 41 (p hot
graphic3science and engineering
NEERING) and Journal of the Chemical Society Vol. 1947, p. 182 (Jour.
al of the Chemical 5oci
It can be synthesized according to the method described in ety) et al.

General formula [■] t9 (wherein, X represents a hydrogen atom or a hydrolyzable group, R9 represents an aryl group, R1o %R++, R1
2 and R13 each represent a hydrogen atom, an alkyl group or an aryl group. ) In the general formula [■], X represents a hydrogen atom or a hydrolyzable group, and the hydrolyzable group represented by X is preferably an acedel group. x is preferably a hydrogen atom.

As the aryl group represented by R9 in the general formula [■],
For example, phenyl group, naphthyl group, etc. can be mentioned, but phenyl group is preferable. This aryl group includes those having substituents, such as alkyl groups (for example, methyl, ethyl, propyl, etc.), halogen atoms (chlorine, bromine, etc.), alkoxy groups (methoxy, ethoxy, etc.). group, etc.), a sulfonyl group, and an amide group (methylamide group, ethylamide group, etc.).

The alkyl group represented by Rho, R++, R+2, and R13 in the general formula [■] preferably includes an alkyl group having 1 to 10 carbon atoms (eg, methyl group, ethyl group, butyl group, etc.). This alkyl group includes those having a substituent, and examples of the substituent include a hydroxyl group, an amino group, and an acyloxy group.

Further, examples of the aryl group for Rho, Rt+, R+2 and R+3 include a phenyl group and a naphthyl group. This aryl group includes those having substituents, such as alkyl groups (methyl group, ethyl group, propyl group, etc.), halogen atoms (chlorine atom, bromine atom, etc.), alkoxy groups (methoxy group, ethoxy group, etc.). groups, etc.) and hydroxyl groups.

Typical specific examples of the compound represented by the general formula [■] used in the present invention are shown below, but the compound of the present invention is not limited thereto.

Margin below CH3CH3 VIII-11 VIII-19■IU-20 VIII -21Vllll -22 Yell -23VI[l -24 H3 VI[l -25VIII -26 TIrl -27TI[l -28 111-29'7■-3Q VI[ l -31Vul -32TI[lVI[[-3
3VI[l -34 7m-35V''llll-36 -37VIII-38 H3 VTII-43Vllll Ct Vm -45vIII vm -47Vm t Although some compounds represented by the general formula [■] are commercially available, they are disclosed in US patents. No. 2,688,024, same 2,
It can be synthesized according to No. 704,762, JP-A-56-64339, and JP-A-57-211147.

In the general formula [IX] (wherein A and B each represent a secondary amino group bonded to the carbon atom of the mother nucleus through a nitrogen atom, and Y represents a sulfur atom or an oxygen atom), ,A
The secondary amino group bonded to the carbon atom of the mother nucleus by the nitrogen atom represented by and B can contain various aliphatic or aromatic components, and A and B may be the same or different from each other.

Specifically, the above A and B are -N H-R14 and -
Each can be expressed as N H−R+s, where R
14 and R+s are each an aliphatic or aromatic group, and R++ and R+s are preferably electron-donating groups. Specifically, the groups represented by R++ and R15 are:
Examples include alkyl groups, alkenyl groups, aryl groups, etc.
These alkyl groups, alkenyl groups, and aryl groups include those having substituents.

Examples of these substituents include alkoxy groups (eg, mexyl group, ethoxy group, etc.), alkylthio groups (eg, methylthio group, ethylthio group, etc.). R1+ and R+
s is, for example, a methyl group, ethyl group, propyl group, butyl group, methoxymethyl group, β-methoxyethyl group, β-ethoxyethyl group, methylthioethyl group, ethylthiomethyl group, allyl group, phenyl group, methoxyphenyl group , ethoxyphenyl group, methylthiophenyl group, ethylthiophenyl group, etc.

Specific examples of the compound represented by the general formula [rX] used in the present invention are shown below, but the present invention is not limited thereto.

rX-12,5-bis(methylamino)-1゜3.4-
Deadiazole ■χ-22-methylamino-5-ethylamino 1.3
．． 4-thiadiazole■χ-32,5-bis(ethylamino)-1゜3.4-
Thiadiazole lX-42,5-bis(n-butylamino)-1,3,
4-thiadiazole lX-52-allylamino-5-methylamino-1,3
,4-thiadiazole IX-62-(2-ethoxyethylamino)-5-methylamino-1,3,4-thiadiazole IX-72,5-bis(phenylamino)-1,3,4
-thiadiazole rX-82,5-bis(2-methoxyethylamino)-
1,3,4-thiadiazol-rX-92-(2-ethoxyethylamino)-5-(2
-methoxyethylamino> -1,3,4-thiadiazole lX-102,5-bis(2-ethoxyethylamino)
-1,3,4-thiadiazole 112-(2-methoxyethylamino)-5-phenylamino-1,3,4-thiadiazole 122-(p-methoxyphenylamino)-5-
(2-methoxyethylamino)-1,3,4-thiadiazolelX-132-(3-methylthiopropylamino)-5
-(2-methoxyethylamino)-1,3,4-thiadiazole lX-142,5-bis(methylamine)-1°3.4
-Oxadiazole lX-152,5-bis(ethylamino)-1°3.4
-Oxadiazole An example of the method for producing the diazole compound represented by the above general formula [IX] is described in JP-A-53-61334 [
B, C, Guha, Journal of American
Chemical Society, (P, C.

Guha, Journal of Ameri
can Chemica13ociety, )]
Dan, p. 1036 (1928), and [Journal of Medical Chemistry, Journal
or Medical Cbemistry,
Vol, ) ] 15, NO, 3, 11, 315 (
1972) et al.

In the present invention, general formulas [VI], [Vl], [■1
Alternatively, color development is carried out in the presence of a compound represented by [Iχ], but the presence here means that it is present at the time of color development, and it may be contained in the silver halide color light-sensitive material in advance. Alternatively, it may be included in the color developing solution in advance. Furthermore, it may be contained in advance in both the silver halide photosensitive material and the color developing solution.

When adding a compound represented by the general formula [V1], [■], [■] or [IX] to a silver halide color light-sensitive material, the degree of addition depends on the halogen composition of the silver halide emulsion, the amount of silver, etc. Although it varies over a wide range, it is generally from o, ooi mole to 1 mole, preferably from 0.002 mole to 0.2 mole, per mole of silver halide. The amount of two or more photosensitive silver halide emulsion layers is generally within the range of 2 x 10-'' mol to 2 x 10-3 mol, preferably 5 x 10-5:Cl to 5 x 10-3 mol per 11 years of age. can be included in

The compound represented by the general formula [VI], [■], [■] or [IX] can be used in each photosensitive emulsion layer, undercoat layer, intermediate layer, protective layer, etc. ! ! It may be added to any layer constituting a silver halide color photographic light-sensitive material, such as an undercoat layer, the lowest layer in contact with the undercoat layer (the layer closest to the support side), or each photosensitive layer. It is preferable to add it to the lowest emulsion layer (the emulsion layer closest to the support).

General formula [VI], [■], [■J or [IX] of the present invention
] In order to add the compound represented by the above to a predetermined photographic constituent layer of a silver halide color photographic light-sensitive material, it can be directly dispersed in a hydrophilic colloid solution forming the photographic constituent layer, or it can be added to, for example, methanol, ethanol, isopropylene. Patul, acetone, methyl ethyl ketone, dimethyl formamide,
1 g of a suitable solvent such as dioxane, ethyl acetate, etc.! Alternatively, it may be added to the hydrophilic colloid solution after being dissolved in a mixture of two or more. Alternatively, after dissolving in one or a mixed solvent of two or more high boiling point solvents such as dibutyl phthalate, dioctyl phthalate, dimethyl phthalate, tri-0-cresyl phosphate, trioctyl phosphate, etc., a hydrophilic colloid solution is prepared. It may also be emulsified and dispersed. Furthermore, when this compound is added to the photosensitive silver halide emulsion layer, it can be emulsified and dispersed simultaneously with the coupler and then added to the coating solution.

General formula [VI], [■], [■] or [TX
The compound represented by ] may be added to the coating solution at any time after the preparation of the photosensitive silver halide emulsion when this compound is added to the photosensitive silver halide emulsion layer. When the photosensitive silver halide emulsion is a surface latent image type emulsion that mainly forms a latent image on the grain surface, it may be prepared at any time after chemical ripening and optical sensitization. Further, when the photosensitive silver halide emulsion is an internal latent image type emulsion that mainly forms latent images inside the grains, it may be carried out at any time after the silver halide emulsion has been prepared and optically sensitized.

Also, general formulas [VI], [■], [■] and [rX]
When adding the compound represented by the formula to the non-photosensitive emulsion layer, it may be added at any time before coating this emulsion layer, but it is preferably added immediately before coating.

Furthermore, the general formulas [VI], [■], [
■When adding the compound represented by 1 or [IX] to the color developer, the addition range is 1 to 5 per 12 of the color developer.
00II1 g, more preferably in the range of 10 to 300 mg.

[VI], [■ ko, [■] or [
For example, methanol, ethanol, isopropanol,
It may be added to the color developer after being dissolved in one or a mixture of two or more suitable solvents such as acetone and dimethylformamide.

Next, the magenta coupler represented by the general formula [I] according to the present invention will be explained in detail.

In the magenta coupler represented by general formula ('I) below, Z represents a nonmetallic atomic group necessary to form a nitrogen-containing heterocycle, and the ring formed by Z has a substituent. It's okay.

X represents a hydrogen atom or a substituent that can be separated by reaction with an oxidized product of a color developing agent.

R represents a hydrogen atom or a substituent.

Examples of the substituent represented by R include a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a heterocyclic group,
Acyl group, sulfonyl group, sulfinyl group, phosphonyl group, carbamoyl group, 7-ammoyl group, n-a/group, spiro compound residue, bridged hydrocarbon compound residue, alkoxy group, aryloxy group, heterocyclic oxy group, Siloxy group, acyloxy group, carbamoyloxy group, amide 7 group,
7 acylamide groups, sulfonamide group, imide group, ureido group, 7 sulfonylamide groups, 7 alkoxycarbonylamide groups, 7 aryloxycarbonylamide groups, alkoxycarbonyl group, aryloxycarbonyl group, alkylthio group, 7lylthio group, hetero Examples include ring thio groups.

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 include substituents [e.g., aryl, cyano, halogen atoms, heterocycles, cycloalkyl, cycloalkenyl, spiro compound residues, and aromatic hydrocarbon compound residues. In addition to groups, those substituted via a carbonyl group such as acyl, carboxy, car/moyl, alkoxycarbonyl, and aryloxycarbonyl, and those substituted via a heteroatom (specifically, hydroxy, alkoxy, Aryloxy, heterocyclic oxy, siloxy, acyloxy, carbamoyloxy, etc. substituted via an oxygen atom, nitro, ami7 (including dialkylami7, etc.), sul7amoylamino, alkoxycarbonylami/, aryloxycarbonyl7 those substituted via a nitrogen atom such as mino, acylamino, sulfonamide, imide, and ureido; those substituted via a sulfur atom such as alkylthio, arylthio, heterocyclic thio, sulfonyl, sulfinyl, and sulf7moyl;
(e.g., those substituted via a phosphorus atom such as phosphonyl)].

Specifically, for example, methyl group, ethyl group, isopropyl group, t-butyl group, pentadecyl group, heptadecyl group, 1
-hexylnonyl group, 1.1'-dibentyl/nyl group,
2-chloro-butyl group, trifluoromethyl group, 1
-Ethoxytridecyl group, 1-methoxyisopropyl group, methane or sulfonylethyl group, 2.4-nor-17-methylphenoxymethyl group, anilino group, 1-phenylisopropyl group, 3 m-butanesulfonami/7dinoxypropyl group, 3-4'-(ff-(4"(p-hydroxybenzenesulfonyl)fairoxy]dodeca/ylamino)phenylpropyl group, 3-i4'-(α-(2"
, 4''-di-t-amylphenoxy)butane7mi)')
phenyl)-propyl group, 4-Cα-(〇-chloro7e/xy)tetradecanamide72/xy]propyl group,
Examples include allyl group, cyclopentyl group, and cyclohexyl group.

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

Specifically, phenyl group, 4-t-butyl 7-enyl group,
2.4-di-t-7mylphenyl group, 4-tetradecanamidophenyl group, hexadecyloxyphenyl group, 4'
-[α-(4″-L-butylphenoxy)tetradecanamide] phenyl group and the like.

The heterocyclic group represented by R is preferably one with 5 to 7 shells, and may be substituted or fused.
Specific examples include 2-7lyl group, 2-chenyl group, 2-pyrimidinyl group, and 2-pentthiazolyl group.

Examples of the acyl group represented by R include acetyl group, phenylacetyl group, dodeca/yl group, α-2,4-di-
Examples include furkylcarbonyl groups such as t-amyl 7-ethyl/xybutameyl groups, 7-arylcarbonyl groups such as benzoyl groups, 3-pentadecyloxybenzoyl groups, and p-chlorobenzoyl groups.

The sulfonyl group represented by R includes an alkylsulfonyl group such as a methylsulfonyl group and a dodecylsulfonyl group,
Benzenesulfonyl group, ρ-tolux>X)Iz
Examples include arylsulfonyl groups such as honyl groups.

Examples thereof include a sulfinyl group, an octylsulfinyl group, an alkylsulfinyl group such as a 3-phenoxydibutylsulfinyl group, a phenylsulfinyl group, an arylsulfinyl group such as a m-pentadecyl phenylsulfinyl group, and the like.

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 7e7xyphosphonyl group, and a phenylphosphonyl group. Examples include arylphosphonyl groups such as.

The carbamoyl group represented by R may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc.
For example, N-methylcarbamoyl group, N, N −') 1+
carbamoyl group, N-(2-pentadecyloctylethyl)carbamoyl group, N-ethyl-N-dodecylcarbamoyl, N-+3-(2,4-not-7myl7eth/xy)propyl)carbamoyl group, etc. can be mentioned.

The sulfamoyl group represented by R may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc.
For example, N-propylsul77 moyl group, N,N-diethylsulfamoyl group, N-(2=pentadecyloxyethyl)sulfamoyl group, N -x thyl-N -)'
Examples include tethylsul 7T moyl group and N-phenylsul 77 moyl group.

Examples of spiro compound residues represented by R include spiro[
3,3]hebutan-1-yl and the like.

The bridged carbonized compound residues quenched by R include lateral bicyclo[2,2,1]hebutan-1-yl, tricyclo[3
, 3,1,1-7]decane-1-yl, 7,7-dimethyl-bicyclo[2,2,1]hebutan-1-yl, and the like.

The alkoxy group represented by R may be further substituted with the substituents listed above for the alkyl group, such as a methoxy group, a propoxy group, a 2-ethoxyethoxy group,
Examples include pentadecyloxy group, 2-dodecyloxyethoxy group, and 7enethyloxynitoxy group.

The aryloxy group to be reduced by R″C is preferably 722yloxy, and the aryl nucleus may be further substituted as mentioned above as a substituent or atom to the aryl group, and the side light is 7eth/oxy group. , p--butylphenoxy group,
Examples include W-pentadecyl 7-ninoxy group.

The heterocyclic oxy group represented by R preferably has 5 to 7 heterocyclic rings, and the heterocyclic ring may further have a substituent, for example, 1r, 3°4.5.6 -tetrahydrobilanyl-2-oxy group and 1-phenyltetrazole-5-oxy group.

The siloxy group represented by R″Ch may be further substituted with an alkyl group, etc., for example, a trimethylsiloxy group,
Examples include triethylsiloxy group and dimethylbutylsiloxy group.

Examples of the acyloxy group represented by R include a side-light alkylcarbonyloxy group, an arylcarbonyloxy group, etc., and may further have a substituent, specifically an acetyloxy group, an α-carbonyloxy group, etc. , loracetyloxy group, benzoyloxy group, and the like.

The carbamoyloxy group represented by R″C′ may be substituted with an alkyl group, an aryl group, etc., such as N-ethylcarbamoyloxy group, N,N-noethylcarbamoyloxy group, N-phenylcarbamoyloxy group, etc. can be mentioned.

The amine group represented by R may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as an ethyl amine group, an anilino group, a l-chloroanili group,
Examples include 3-pentadecyloxycarbonylanilino group, 2-chloro-5-hexadecaneamide anilino group, and the like.

Examples of the acylamino group represented by R include alkylcarbonylamide 7 groups, arylcarbonylamide 7 groups (preferably phenylcarbonylamide 7M), and may further have a substituent, specifically an acetamido group, Examples thereof include a-ethylpropanamito group, 2,4-not-t-7mil727oxyacetamide group, and α-3-t-butyl 4-hydroxyphenoxybutanamide group.

Examples of the sulfonamide group to be reduced by R″C include 7 alkylsulfonylamide groups and 7 arylsulfonylamide groups, which may further have a substituent.

Specifically, methylsulfonylamide 7 groups, pentadecylsulfonylamide/group, benzenesulfone 7 mido group, p-)
Ruensulfonamide! -12-/) Ki-5-t-7
Examples include milbenzenesulfonamide group.

The imide group represented by R″C″ may be open-chain or cyclic, and may have a 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 RT is an alkyl group, an aryl group (
(preferably phenyl group), etc., such as N-ethylwalate group, N-no4+hada+Ncho+
, Meany H-v''++-11% l-1° ureido group, N-p-)ylcleido group, and the like.

The 7 sulfamoylamide groups represented by R are an alkyl group,
It may be substituted with an aryl group (preferably a fninyl group), etc., and the side light is N, N-butylsul7 amoylami/f, N-methylsul7 amoylami/group, N-7 dinylsul7 amoylami group, etc. can be mentioned.

As the alfkhidicarbonylamino group represented by R,
It may further have a substituent, for example /toxyluponylamide 7 groups, methoxyethoxycarbonylamide 7 groups,
Examples include 7 octadecyloxycarbonylamide groups.

The 7 aryloxycarbonyl amide groups represented by R may have a substituent, and examples thereof include 7 7-ethyl-7-oxycarbonyl amide groups and 7 4-methyl-7-ethyl-7-oxycarponyl amide groups.

The alphoxycarbonyl group represented by R may further have a substituent, such as a methoxycarbonyl group, a butyloxycarbonyl group, a tosyloxycarbonyl group,
Examples include octadecyloxycarbonyl group, nidoxymethoxycarbonyloxy group, benzyloxycarbonyl group, and the like.

The aryloxycarbonyl group represented by R4 may further have a substituent, for example, a 7ethoxycarbonyl group,
Examples include p-chloro7ethycarbonyl group, m-pentadecyloxy72/quinecarbonyl group, and the like.

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 3-7 dinoxyprobylthio group.

The ruthio group represented by R is preferably a phenylthio group and may further have a substituent, for example, a phenylthio group,
Examples include p-methoxyphenylthio group, 2-octylphenylthio group, 3-octatecylphenylthio group, 2-carboxyphenylthio group, and p-7cetaminophenylthio group. .

The heterocyclic thio group represented by R is preferably a 5- to 7-shell heterocyclic thio group, which may further have a condensed ring or a substituent. Examples include 2-pyridylthio group, 2-benzothiazolylthio group, and 2,4-diphenoxy-1,3,5-triazole-6-thio group.

Examples of substituents that can be removed by reaction with the oxidized product of the color developing agent represented by Examples include groups substituted via a nitrogen atom.

Groups substituted via a carbon atom include, in addition to carboxyl groups, for example, those of the general formula (R1' is the same as the above R, Z' is the same as the above Z, R2' and VR,' are hydrogen atoms, aryl group, alkyl group or heterocyclic group)
-1/P? → b knee J! ++-jeLII-y--s,
Examples include z4-n-1t.

An example of a group that substitutes via an oxygen atom! i'Fulkoxy group, aryloxy group, heterocyclic oxy group, acyloxy group, sulfonyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, alkyloxalyloxy group, and alkoxyoxalyloxy group.

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

The aryloxy group is preferably a 7e/xy group, and the aryl group may further have a substituent, specifically a 7e/xy group, a 3-methyl 7e/xy group, 3-
Dodecylphenoxy group, 4-notanesulfonamide 7-ethyl/oxy group, 4-(ff-(3'-pentadecylphenoxy)butanamide] 7-ethyl/oxy group, hexydecylcarbamoyl, /)oxy group, 4-cyano 7eth/oxy group, 4-
Examples include methanesulfonyl 72/oxy group, 1-su7tyloxy group, p-methoxy 72/oxy group, and the like.

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 group, fulkylcarbonyloxy group such as butanoloxy group, alkenylcarbonyloxy group such as cinnamoyloxy group,
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 an ethoxycarbonyloxy group and a benzyloxycarbonyloxy group.

Examples of the aryloxycarbonyl group include a phenoxycarbonyloxy group.

Examples of the alkyloxalyloxy group include methyloxalyloxy group.

Examples of the alkyloxalyloxy group include a nidoxyoxalyloxy group.

Examples of groups substituted via a sulfur atom include side-light alkylthio groups, arylthio groups, heterocyclic thio groups, and flukyloxythiocarbonylthio groups.

As the alkylthio group, butylthio group, 2-thia/
Examples include ethylthio group, 7enethylthio group, and benzylthio group.

The arylthio group includes phenylthio group, 4-notanesulfone7midophenylthio i, 4-)'decyl7enethylthio group, 4-/sufluoropentane7mido7enethylthio group, 4-carboxy7dynylthio group, 2-nidoxy- Examples include 5-t-butyl 7dinylthio group.

Examples of the heterocyclic group include 1-phenyl-1,
Examples include 2,3,4-tetrazolyl-5-thio group and 2-benzothiazolylthio group.

Examples of the alkyloxythiocarbonylthio group include a dodecyloxythiocarbonylthio group.

Examples include those represented by the general formula -N, which represent an aryl group, a heterocyclic group, a sulfonyl group, a carbamoyl group, an acyl group, a sulfonyl group, an aryloxycarbonyl group, and an alkoxycarbonyl group, R, 7 and R9 / may be combined to form a heterocycle. However, R1' and R5
' 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, an alkylthio group,
Arylthio group, 7 alkylamino groups, 7 arylamino groups, acylamino group, sulfonamide group, imino group, acyl group, alpamoyl group, sulfonyl 77 moyl group, alkoxycarbonyl group, aryloxycarbonyl group, 7 fulkyloxycarbonyl amine groups, aryl Examples include oxycarbonylamino group, hydroxyl group, carboxyl group, cyano group, and halogen atom.

Specific examples of the alkyl group include ethyl group, oxytyl group, 2-ethylhexyl group, and 2-chloroethyl group.

The aryl group substituted by R1' or Rs' has 6 to 32 carbon atoms, and is particularly preferably a phenyl group or a naphthyl group, and the aryl group may have a substituent such as those mentioned above. Examples of substituents for the alkyl group represented by R4' or R1' include those listed above and an alkyl group. Specific examples of the aryl group include a phenyl group, a 1-su7tyl group, and a 4-methylsulfonylphenyl group.

The heterocyclic group cyclically substituted by R1' or R5' is 5 to 6
Preferred examples include 2-7yl group, 2-7yl group, 2-7yl group, 2-7yl group, 2-7yl group, etc.
Examples include quinolyl group, 2-pyrimidyl group, 2-benzothiazolyl group, and 2-pyridyl group.

It will be done.

The sul77moyl group represented by R4' or R5' includes N-furkylsulfamoyl group, N,N-dialkylsulfamoyl group, N-arylsul77moyl group, N-furkylsulfamoyl group, N,N-dialkylsulfamoyl group,
, N-diarylsul77 moyl group, etc., and these alkyl groups and aryl groups may have substituents listed for the alkyl groups and aryl groups. Specific examples of the sulfamoyl group include N, N-diethylsulfamoyl group, N-methylsulfamoyl group, N
-dodecylsul77moyl group, N-p-)lylsul7amoyl group.

The carbamoyl group represented by R4' or Rs' is
N-alkylcarbamoyl group, N,N-difurkylcarbamoyl group, N-7lylcarbamoyl group, N,N-diarylcarbamoyl group, etc., and these alkyl groups and aryl groups are the same as those mentioned above for the alkyl group and aryl group. Specific examples of the carbamoyl group which may have a substituent are N, N-cynythylcarbamoyl group, N-methylcarbamoyl group, N-dodecylcarbamoyl i, N-p-cya/phenylcarbamoyl. basis,
N-p-)lylcarbamoyl group is mentioned.

Examples of the 7-sil group represented by R or Rs/ include a furkylcarbonyl group, an arylcarbonyl group, and a heterocyclic carbonyl group, and the alkyl group, the aryl group, and the heterocyclic group include Specific examples of the 6-acyl group which may have a substituent include hexafluorobutameyl group, 2゜3.4.5.6-pentafluorobenzoyl group, acetyl group, benzoyl group, naphthonyl group. , 2-furylcarbonyl group, and the like.

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, and specific examples include an ethanesulfonyl group, Examples include a benzenesulfonyl group, an octanesulfonyl group, a naphthalenesulfonyl group, and a p-chlorobenzenesulfonyl group.

The aryloxycarbonyl group substituted by R47 or R1' may have any of the substituents listed above for the aryl group, and specific examples thereof include a 7e/xycarbonyl group and the like.

The alfkidicarbonyl group represented by R1' or R5' may have a substituent listed for the alkyl group, and specific examples include a methoxycarbonyl group, a dodecyloxycarbonyl group, and a benzyloxycarbonyl group. Examples include groups.

The heterocycle formed by bonding R and R5' is preferably a 5- to 6-membered ring, and may be saturated or unsaturated, and may or may not have aromaticity. It may also be a fused ring. Examples of the heterocycle include N-7 talimide group, N-succinimide group, 4-N-urazolyl group, 1-N-hydantoinyl group, and 3-N-2,4-dioxoxazolidinyl 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-piperidinyl group ,1
-pyrrolinyl group, 1-imidazolyl group, 1-imidazolinyl group, 1-indolyl group, 1-isoindolinyl group,
2-isoindolyl group, 2-isoindolinyl group, 1-
Benzotriazolyl group, 1-pencyimigzolyl group, 1
-(1,2,4-)riazolyl) group, 1-(1,2,3
-)riazolyl) group, 1-(1,2,3,4-tetrazolyl) group, N-morpholinyl group, 1,2,3.4-tetrahydroquinolyl group, 2-oxo-1-pyrrolidinyl group, 2- Examples include IH-pyridone group, 7-talanone group, 2-oxo-1-piperidinyl group, etc., and these heterocyclic groups include alkyl groups, aryol groups, alkyloxy groups, nialyloxy groups, acyl groups, and sulfonyl groups. , alkylamino group, 7-arylamino group, 7 acylamino groups, 7 sulfonamide groups, carbamoyl group, sulfamoyl group, alkylthio group, arylthio group, ureido group, alkoxycarbonyl group, aryloxycarbonyl group, imido group, nido a group, sia / group, carboxyl group, halogen atom, etc. may be substituted.

Also, a nitrogen-containing heterocycle formed by 2 or Z'.

Examples include a pyrazole ring, imidazole ring, triazole ring, or tetrazole ring, and examples of the substituents that the ring may have include those described for R above.

In addition, the substituent on the heterocycle (for example, R9R, -R,) in the general formula [■] and the general formulas [x] to [x■] described later is a moiety (herein R'', X and Z / / has the same meaning as R, Z+ mentioned later
The ring formed by may be further fused with another ring (for example, a 5- to 7-shell cycloalkene). In the general formula [x■], R5 and R5 are bonded to each other, and in the general formula [x], R2 and R6 are bonded to each other to form a ring (for example, 5-7
may form shellfish cycloalkenes, benzene).

Margin below More specifically, what is represented by general formula (1) is:

For example, it is represented by the following general formulas [x] to (XV).

General formula (xl General formula [revised] N -N -N General formula (XI) N -N -N)l General formula [×■] General formula (XIV) N -N -NR General formula [special] The above general formula In [x] to [soot], R5-R8 and X have the same meanings as R and VX above.

Also, among the general formula (1), the following general formula [
].

General formula (Xrl/) In the formula, R, , X and Z are R in general formula (1).

It is synonymous with X and Z.

Among the magenta couplers represented by the general formulas [χ] to (XV), particularly preferred is the magenta coupler represented by the general formula [X].

Regarding substituents, in general formula (1), R is
Further, in general formulas (X) to [XVI:l, it is preferable that R9 satisfies the following condition 1, more preferably the case that the following conditions 1 and 2 are satisfied, and particularly preferable is the case that the following conditions 1, 2 and 2 are satisfied. This is a case where condition 3 is satisfied.

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 VR6 on the bicyclic ring are those represented by the following general formula [Z].

General formula [gourd] R9 R1゜-〇-RIl In the formula, R,,R,. and R11 are each nine elementary atoms, halogen atom, alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkynyl group, oryl group,
heterocyclic group, acyl group, sulfonyl group, sulfinyl group, phosphonyl group, carbamoyl group, sulfamoyl group,
Shea/group, spiro compound residue, bridged hydrocarbon compound residue, alkoxy group, aryloxy group, heterocyclic oxy group, siloxy group, acyloxy group, carbamoyloxy group, ami7 group, 7silami7 group, sulfonamide group, imide group, ureido group, 7 sul7amoylaminyl groups, 7 alkoxycarbonyl 7 groups, 7 aryloxycarbonylami groups, alfkyloxycarbonyl group, 7lyloxycarbonyl group, furkylthio group, arylthio group, heterocyclic group and at least two of R1゜RIo and R1 are not hydrogen atoms (1゜, and two of the above R* - R1゜ and R1+, for example, R
1 and R1° may be combined to form a saturated or unsaturated ring (e.g., cycloalkane, dichloroflukene, heterocycle), and R1+ is further combined to the ring to form a bridged hydrocarbon compound residue. It's okay.

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

Also, for example, a ring formed by combining R9 and R1° and R1
Specific examples of the bridged hydrocarbon compound residue formed by -R11 and its optional substituents include cycloalkyl, cycloalkenyl, and heterocyclic groups represented by R in the general formula CI). Specific examples of hydrogen compound residues and their substituents are listed.

Among the general formula [X■], (i) R, ~R
If two of 7l are alkyl groups, (ii) R9-R
One of 1, for example, R1+, is a hydrogen atom, and the other 2, Rs and R1° combine to form a cycloalkyl group together with the root carbon atom.

Furthermore, among (i), ν· is preferable when two of R4 to R1+ are alkyl groups and the other one is a hydrogen atom or an alkyl group.

Here, the alkyl and cycloalkyl may further have a substituent, and specific examples of the alkyl, the cycloalkyl, and the substituent thereof include the alkyl, cycloalkyl, and its substituent in which R in Il decreases. Specific examples of the group are listed below.

In addition, the substituents that the ring formed by Z in general formula CI) and the ring formed by Z in general formula [X■] may have, as well as general formulas (X) to [S■] R2-R8 are preferably represented by the following general formula.

General formula (XV[] -R1-9Q, -R2 In the formula, R1 represents alkylene, and R2 represents alkyl, cycloalkyl or 7-aryl.

The alkylene represented by R1 is preferably a direct part thtf
1#jL hand'16J-1911tL-tn62+l/I
-) Qs>+, xlC, regardless of linear chain and one branch,
Moreover, this alkyl and lene may have a substituent.

Examples of the substituent include R in the above-mentioned general formula (1)
When is an alkyl group, the substituents that the alkyl group may have include those shown below.

Preferred ra substituents include phenyl.

A preferred Jl-isomer 91 of fullkylene represented by R1 is shown below.

The furkyl group represented by R2 may be a linear, monobranched group.

Specifically, methyl, ethyl, propyl, 1F10-propyl, butyl, 2-ethylhexyl, octyl, dodecyl, tetradecyl, hexadecyl, oftagyl, 2-
Examples include hexyldecyl.

The cycloalkyl group represented by R2 is preferably one having 5 to 6 shells, such as cyclohexyl.

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

Specific examples of the 7 reel represented by R2 include phenyl and naphthyl. The Tetsuko Ryl group may have a substituent, and examples of the substituent include, for example, linear or branched alkyl, as well as those exemplified as the substituent for R16. When there are two or more substituents, those substituents may be the same or different.

Among the compounds represented by the general formula (1), those represented by the following general formula [E] are particularly preferred.

General formula [Megumi] In the formula, R and X have the same meaning as R and X in the general formula [■]'?
A') R' and R2 are represented by the general formula (XVI) l: R'.

It has the same meaning as R2.

Specific examples of compounds used in the present invention are shown below.

Margin below 12H2M E CH.

CH.

CH3 CHyo C2H.

Margin below 4H9 H3 O3 H3 H3 C,I(,.

xHS CHi Cl.

H3 L CJ+s CHs
J+t(tJCI.

06H1゜ H3 C.I.

OCH2CONHC112CH20CH30CR2CH
2SO□CH3 u- "CH3 し2115 6H13 CH.

CH3 C2H5 CH.

C1゜7H15 0(CHz)20ct2t125 N -N -N N -N -N N N Ni1 N N Ni1 CJ+ between 88□ c,,, N N 81
141 8 HH CtRs 6B C□).

) IN □ Song N N NH HN 811 N -H-I+ Below margin ■ ■ しSU,! (t;; N N NH Also, the coupler is Journal Op the Chemica A,
-'/Saiati (Journal of, theC
he-ical Soaiety), t<-Kin I (1977), 204
7-2052. U.S. Patent No. 3,725,067, JP-A-59-99437, JP-A-58-42045, JP-A-59-
No. 162548, No. 59-171956, No. 60-3
No. 3552, No. 60-43659, No. 60-1729
It can be synthesized by referring to No. 8.2 and No. 6G-190779.

The couplers of the invention are typically 1x1 per mole of silver halide.
0-Comole 1 mol, preferably lXl0-'' mol to 8
It can be used in the range of X10-' moles.

The couplers of the present invention can also be used in combination with other types of magenta couplers.

In order to incorporate the magenta coupler used in the present invention into the emulsion, a high-boiling point organic solvent with a dielectric constant of 6.0 or less and a low-boiling point organic solvent such as ethyl acetate, butyl acetate or butyl propionate are used separately. After dissolving the couplers individually or in a mixture of solvents, if desired, the couplers are mixed with an aqueous gelatin solution containing a surfactant and then processed in a speed rotation mixer, colloid mill, or It is preferable to emulsify and disperse using an ultrasonic disperser or the like, and then add silver halide to prepare a silver halide emulsion.

Examples of high boiling point organic solvents with a dielectric constant of 6.0 or less include:
Examples include esters such as 7-talic acid ester and phosphoric acid ester, organic acid amides, ketones, and hydrocarbon compounds having a dielectric constant of 6.0 or less. Preferably vI: electric current of 6.0 or less and 1.9 or more and vapor pressure at 100°C of 0.5118
It is a high boiling point organic solvent of G or less.

Even more preferred are phthalic esters or phosphoric esters in the high-boiling organic solvent.

Note that the organic solvent may be a mixture of two or more types, and in this case, it is sufficient that the dielectric constant of the mixture is 6.0 or less. Note that the dielectric constant in the present invention refers to the dielectric constant at 30°C.

Examples of phthalic acid esters advantageously used in the present invention include those represented by the following general formula [XX].

General Formula [XX] In the formula, Rye and R5 each represent an alkyl group, an alkenyl group or an aryl group. However, R4 and R
The total number of carbon atoms in the groups represented by 5 is 8 to 32. More preferably, the total number of carbon atoms is 16 to 2.
It is 4.

In the present invention, Rs and R5 of the general formula [XX]
The alkyl group represented by is linear or branched, such as butyl group, pendel group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, These include a pentadecyl group, hexadecyl group, heptadecyl group, and octadecyl group. The aryl group represented by R4 and R5 is a phenyl group, naphthyl group, etc., and the alkenyl group is a hexenyl group, heptenyl group, octadecenyl group, etc. These alkyl groups, alkenyl groups and aryl groups may have single or multiple substituents,
Examples of substituents for alkyl groups and alkenyl groups include halogen atoms, alkoxy groups, aryl groups, aryloxy groups, alkenyl groups, and alkoxycarbonyl groups. Examples of substituents for aryl groups include halogen atoms, alkyl groups, and alkoxy groups. , an aryl group, an aryloxy group, an alkenyl group, and an alkoxycarbonyl group. Two or more of these substituted chrysanthemums may have an alkyl group, an alkenyl group, or an aryl group introduced therein.

Phosphate esters advantageously used in the present invention include those represented by the following general formula [X n].

General formula [XXI:1 In formula, Rs, R? and R8 are each an alkyl group,
Represents an alkenyl group or an aryl group.

However, the total number of carbon atoms represented by Rs, R7 and R8 is 24 to 54.

General formula [XX I] (7) R6, R? aJ:HiR
The alkyl group represented by a 1' is, for example, a butyl group 1.
These include pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, and the like.

These alkyl groups, alkenyl groups and aryl groups may have single or multiple substituents. Preferably R6, R7 and R8 are alkyl groups, for example 2-ethylhexyl group, n-octyl group, 3.5.5
-trimethylhexyl group, n-nonyl group, n-decyl group, 5ec-decyl group, 5ec-dodecyl group, t-octyl group and the like.

Specific examples of the organic solvent according to the present invention are shown below, but the present invention is not limited thereto.

Below are the blank examples of organic solvents "-2C:Hs ■ C2Hs H-12C2H5 0C*Hl*(i) 0CJ(l, (n) 0-01゜Hz+(i) O-C,.H2,(n) (J C+oHr+ (n) A-17 0CIzHzs(i) -u-19 Item-21 These organic solvents are used in an amount of 25 to 150% by weight based on the magenta coupler of the present invention.Preferably, the amount is 50 to 100% based on the coupler. Weight%.

As the combination of the magenta coupler and the high-boiling point organic solvent used in the present invention, any combination of high-boiling point organic solvents with a dielectric constant of 6.0 or less can be used, but preferably those of the general formulas [X] and [XI] are used. This is a combination of high boiling point organic solvents shown in

In the present invention, the magenta coupler has the general formula [
At least one of the compounds represented by I[] to [V]
used in combination with

The following is a general formula in which R1 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group, and R2, R1, R7, R
6 is a hydrogen atom, a halogen atom, a hydroxy group,
an alkyl group, an alkenyl group, an aryl group, an alkoxy group or an acylamino group, R1 is an alkyl group,
Represents a hydroxy group, an aryl group, or an alkoxy group.

In addition, R and R2 may be ring-closed with each other to form a 5-membered or 6-membered ring, in which case R4 may have a hydroxy group or an alkoxy group, or R3 and R4 may be ring-closed to form a 5-membered or 6-membered ring. A hydrogen ring may be formed, in which case R5 is an alkyl group, an aryl group, or a heterocyclic group, provided that R
Except when 1 is a hydrogen atom and R4 is a hydroxy group.

In the general formula []r], R1 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group, and examples of the alkyl group include, for example, a methyl group, an ethyl group, a propyl group, n -octyl group, tert
Straight chain or branched alkyl groups such as -octyl group and hexadecyl group can be mentioned. Examples of the alkenyl group represented by R1 include allyl, hexenyl, and octenyl groups. Further, examples of the aryl group R include phenyl and naphthyl groups. Further, specific examples of the heterocyclic group represented by R1 include a tetrahydropyranyl group and a pyrimidyl group. Each of these groups can have a substituent, for example, an alkyl group having a substituent such as a benzyl group, a nidoxymethyl group, and an aryl group having a substituent such as a methoxy7enyl group, a chlorophenyl group, a 4-hydroxy Examples include -3,5-dibutylphenyl group.

In the general formula [1], R2, R5, R6 and R6 are hydrogen atoms, halogen atoms, hydroxy groups, alkyl groups,
Flukenyl group 711-yl certain alkoxy group; Things can be mentioned. Examples of the halogen atoms include fluorine, chlorine, and bromine. ? ! r
Further, specific examples of the alkoxy group include a methoxy group and a nidoxy group. Further, the acylamide 7 group is represented by R'CONH-, where R' is an alkyl group (e.g., methyl, ethyl, n-propyl, n-butyl, n-octyl, tert-octyl, pencil, etc.). ), alkenyl groups (e.g. allyl, octenyl, oleyl, etc.), aryl groups (e.g. phenyl, methoxyphenyl, naphthyl, etc.), or heterocyclic groups (e.g. pyridyl, pyrimidyl). be able to.

Further, in the general formula [111, R4 is an alkyl group,
It represents a hydroxy group, an aryl group or an alkoxy group, and among these, for an alkyl group or an aryl group, the above R
Specific examples include the same alkyl groups and aryl groups shown in 1. As for the alkenyl group of R4, the same alkoxy groups mentioned above for R2, R3, R5 and R, +2 can be mentioned.

Examples of the ring formed by R1 and R2 together with a benzene ring by closing each other include chroman, coumaran, and methylenedioxybenzene.

Furthermore, examples of the ring formed by R1 and R4 together with a benzene ring include bean. These rings may have substituents (eg alkyl, alkoxy, aryl).

In addition, a spiro compound may be formed by using the atom in the ring formed by R1 and R2, or R1 and R4 by ring closure, as a spiro atom, or a bis compound may be formed by using R2, R1, etc. as a linking group. Good too.

Among the phenolic compounds or phenyl ether compounds represented by the general formula []II, preferred are:
It is a biindane compound having four R〇- groups (R represents an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group), and is particularly preferably represented by the following general formula [II-1
].

General formula [11-1] In the formula, R is an alkyl group (e.g. methyl, ethyl, propyl, n-octyl, tert-octyl, benzyl, hexadecyl), an alkenyl group (e.g. allyl, octenyl, oleyl), an aryl group (e.g. , phenyl, naphthyl) or a heterocyclic group (e.g., tetrahydropyranyl, pyrimidyl), R9 and I
/R1o is a hydrogen atom, a halogen atom, (for example, 7
7, chlorine, bromine), an alkyl group (e.g. methyl, ethyl, n-butyl, benzyl), an alkoxy group (allyl, hexenyl, octenyl), or an alkoxy group (e.g. methoxy, ethoxy, benzyloxy) , RII is a hydrogen atom, an alkyl group (e.g. methyl, ethyl, n-butyl, benzyl), an alkenyl group (e.g.
2-7''ropenyl, hexenyl, octenyl), or a ring group (e.g. phenyl, methoxyphenyl, chlorenyl, naphthyl).

The compound represented by the general formula [II] is disclosed in U.S. Patent No. 3,
No. 935,016, No. 3,982,944, No. 4
．． No. 254,216, JP-A No. 55-21004, No. 5
No. 4-145530, British Patent Publication No. 112,077.45
No. 5, No. 2,062, No. 888, U.S. Patent No. 3,76
4,337, No. 3.432300, No. 3,574
, No. 627, No. 3,573,050, Japanese Unexamined Patent Publication No. 1973-
No. 152225, No. 53-20327, No. 53-17
No. 729, No. 55-6321, British Patent No. 1g34, No. 556, Publication No. 2.066.975, Special Publication No. 1973
-12337, No. 48-31825, U.S. Patent No. 3
, 700, 455 and the like.

The amount of the compound represented by the general formula [1] used is preferably 5 to 300 mol%, more preferably 10 to 200 mol%, based on the magenta coupler.

The following is a list of the compounds that can be reduced by the general formula [n]: Type (1) RI Type (2) Type (3) Type (4) Type (5) Type (6) Type (7) Type (4) ・;7″ Pato: Type (5) Below margin Type (6) Below margin A-7 Below margin General formula [II] (R3 and R1 in the formula are a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkenyloxy group, a hydroxy group, an aryl group, an aryloxy group, an acyl group, an acylamino group, an acyloxy group,
a sulfonamide group, cycloalkyl or alfkyl dicarbonyl group, R2 is a hydrogen atom, an alkyl group,
An alkenyl group, an aryl group, an acyl group, a cycloalkyl group, or a heterocyclic group, and R3 is a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, an aryloxy group, an acyl group, an acyloxy group, or a sulfonamide. group, cycloalkyl group or alkoxycarbonyl group.

Each of the groups listed above may be substituted with other substituents, such as an alkyl group, an alkenyl group, an alkoxy group,
Examples include an aryl group, an aryloxy group, a hydroxy group, an alphkidicarbonyl group, an aryloxycarbonyl group, an acylamide 7 group, a 7-syloxy group, a carbamoyl group, a sulfonamide group, and a sulfamoyl group.

Further, R2 and R may be ring-closed with each other to form a 5- or 6-membered ring. Examples of the ring formed by R2 and R3 together with a benzene ring include a chroman ring and a methylenedioxybenzene ring.

Y represents the atomic group necessary to form a chroman or coumaran ring.

As expected from Chroman, the coumaran ring consists of halogen atoms, alkyl groups, dichlorofurkyl groups, alkoxy groups, alkenyl groups,
May be substituted with an alkenyloxy group, hydroxy group, aryl group, aryloxy group, or heterocycle,
Furthermore, a spiro ring may be formed.

Among the compounds represented by the general formula [I]ll, the present invention! 7
Particularly useful compounds are of the general formulas [I[-1], [I[-21
, [[-3], [Melon-4], and [[-5] are now three times the general formula [Ni 1] General formula [I[L-2] 1 General formula [ Dish-31 General formula [[-4] General formula [[-51 to 1 General formula [1] I -1], [I-2], [ff1-31
, [R1, R2, R in [[-41 and [mouse-51]
3 and R1 have the same meaning as in Dish 1, and R2, R6, R7, R8, R9 and R10 are hydrogen atoms, halogen atoms, alkyl groups, alkoxy groups,
Includes hydroxy group, alkenyl group, alkenyloxy group, aryl group, aryloxy group or heterocyclic group.

Furthermore, R5 and R6, R6 and R1, R7 and R8, R6 and R
3, R3, and R2° may be cyclized with each other to form a carbocyclic ring, and the carbocyclic ring may be further substituted with an alkyl group.

The general formula [1[[-1], [I[-2], [I[-3]
], [1-41 and [I[-5], R1 and R1 are hydrogen atoms, alkyl groups, alkoxy groups, hydroxy groups or cycloalkyl groups, R,, R7, R8,
Particularly useful are compounds in which R1 and RIO are hydrogen atoms, alkyl groups, or cycloalkyl groups.

The compound represented by the general formula [IL] is tetrahedron (T
etrahedron), 1970tvo12L474
pp. 3-4751, Journal of the Chemical Society of Japan, 1972. No1O,
pp. 0987-1990, Chemical (chess, Let
t, ), 1972 (4) pp. 315-316, Japanese Patent Publication No. 5
No. 5-139383, which represent and include the compounds described therein, and which can be synthesized according to the methods described therein.

The amount of the compound represented by the general formula [I[I] used is 5 to 3% based on the magenta coupler of the emulsion of the present invention.
The amount is preferably 00 mol%, more preferably 10 to 200 mol%.

Typical specific examples of these compounds are shown below.

The following is a blank general formula (IV) R'R where R1 and R'J are a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, a hydroxy group, an aryl group, a 7-aryloxy group, an acyl group, Represents an acylamide group, an acyloxy group, a sulfonamide group, a cycloalkyl group, or an alkoxycarbonyl group.

R2 represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, a hydroxy group, an aryl group, a 7-syl group, an acylamide group, an acyloxy group, a sulfone 7-mido group, a dichlorofurkyl group, or an alkoxycarbonyl group.

The above-mentioned groups may each be substituted with other substituents, such as alkyl groups, alkenyl groups,
Examples include an alkoxy group, an aryl group, an aryloxy group, a hydroxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acylamide group, a carbamoyl group, a sulfonamide group, and a sulfamoyl group.

Further, R2 and R3 may be ring-closed with each other to form a 5- or 6-membered hydrocarbon ring, and this 5- or 6-membered hydrocarbon ring may be a halogen atom, an alkyl group, a cycloalkyl group,
It may be substituted with an alkoxy group, an alkenyl group, a hydroxy group, an aryl group, an aryloxy group, a heterocyclic group, or the like.

Y represents an atomic group necessary to form an indane ring; an indane ring is a halogen atom or an alkyl group.

It may be substituted with an alkenyl group, an alkoxy group, a cycloalkyl group, a hydroxy group, an aryl group, a 7-aryloxy group, or a hetero:IR group, and may further form a spiro ring.

Among the compounds represented by the general formula (Ill/), compounds of the general formula (IV-1) to [:IV-31
It is included in the compound represented by.

General formula (IV-1) 81 General formula (IV-23 General formula (IV-3) R', R2 in general formula (IV-13 to (IV-3))
and R3 have the same meaning as in the general formula [■], and R
', R', R', R', R'' and R' are each a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkenyl group, a hydroxy group, an aryl group, an aryloxy group, or a heterocyclic group. R4 and R5, R5 and R',
R' and R7, R and R, and R8 and R9 may be ring-closed with each other to form a hydrocarbon ring, and the hydrocarbon ring may be further substituted with an alkyl group.

In the general formulas CIV-1) to [:■-3], R'
and R' is a hydrogen atom, an alkyl group, an alkoxy group, a hydroxy group, or a cycloalkyl group, R'' is a hydrogen atom, an alkyl group, a hydroxy group, or a cycloalkyl group, R'
, R', R', R', R" and R" are hydrogen atoms, alkyl groups or cycloalkyl groups, which are particularly useful.

The amount of the compound to be attenuated by the general formula [IV] is:
It is preferably 5 to 300 mol%, more preferably 10 to 200 mol%, based on the magenta coupler.

Typical specific examples of the compound represented by the general formula [IV] are shown below.

The following is a blank general formula CV) , -1, R'-Y Attenuates the nonmetallic atomic groups needed to form. However, when there are two or more heteroatoms among the nonmetallic atoms containing nitrogen atoms forming the heterocycle, at least two heteroatoms are not adjacent to each other. ] Examples of the aliphatic group substituted by R' include a saturated alkyl group which may have a substituent and an unsaturated alkyl group which may have a substituent. Examples of saturated alkyl groups include methyl group, ethyl group, butyl group, octyl group, dodecyl group, tetradecyl group, hexadecyl group, etc.; examples of unsaturated alkyl groups include ethynyl group,
Examples include propenyl group.

Examples of the cycloalkyl group substituted by R' include a 5- to 7-shell cycloalkyl group that may have a substituent, such as a cyclopentyl group and a cyclohexyl group.

The aryl group represented by R1 is a 7-ninyl group or a naphthyl group, each of which may have a substituent.

Substituents for the aliphatic group, cycloalkyl group, and aryl group represented by R1 include alkyl groups, aryl groups, alkoxy groups, carbonyl groups, carbamoyl groups, and acylamine groups.
group, sulfamoyl group, sulfonamide group, carbonyloxy group, alkylsulfonyl group, arylsulfonyl group, hydroxy group, heterocyclic group, alkylthio group, arylthio group, etc., and these substituents further have a substituent. Good too.

In the general formula (V), Y together with the nitrogen atom is 5 to 7
It represents a group of nonmetallic atoms necessary to form a membered heterocycle, and at least two of the nonmetallic atom groups containing nitrogen atoms forming the bicyclic ring must be heteroatoms, and
At least two heteroatoms must not be adjacent to each other, and if all the heteroatoms are adjacent to each other in the bicyclic ring of the compound represented by general formula (V), the magenta dye image stabilizer can be used as a magenta dye image stabilizer. This is not desirable because it cannot perform its functions.

The 5- to 7-shell heterocycle of the compound represented by the general formula EV) may have a substituent, and examples of the substituent include an alkyl group, an aryl group, an acyl group, a carbamoyl group, and an alkyl dicarbonyl group. group, sulfonyl group, sulfamoyl group, etc., and may further have a substituent. In addition, 5 to 7
The penetrating heterocycle may be saturated, but a saturated heterocycle is preferable, and a benzene ring or the like may be fused to the bicyclic ring to form a spiro ring.

The amount of the compound attenuated by the general formula (V) of the present invention used is preferably 5 to 300 mol%, more preferably 10 to 300 mol%, based on the magenta coupler represented by the general formula (1) of the present invention. It is 200 mol%.

Typical specific examples represented by general formula (V) are shown below.

J-63 J-64 /'-N C++H29N II ■ 12H25 Among the compounds represented by the general formula (V), piperazine compounds and homovivera. Zin-based compounds are particularly preferred, and more preferably, compounds of the following general formula (V-1) or (V
-2).

General Formula (V-1) General Formula (V-21 In the formula, R2 and R3 each represent a hydrogen atom, an alkyl group, or an aryl group. However, R2 and R3 do not become hydrogen at the same time. R4~ R'' represents a hydrogen atom, an alkyl group or an aryl group, respectively.

In the general formulas (V-1) and (V-2), R2 and R1 each represent a hydrogen atom, an alkyl group, or an aryl group, and the furkyl group represented by R2 or R3 is, for example, methyl. Examples of the aryl group subtracted by lR2 or R include phenyl group, etc.R2 or R2. The alkyl group and 7-aryl group represented by R3 may have a substituent, and examples of the substituent include a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, and a heterocyclic group.

The total number of carbon atoms of R2 and R' (including substituents) is 6 to
40 is preferred.

In the general formula (V-'1) or (v-2), %
R' to RI each represent a hydrogen atom, a furkyl group, or an aryl group, and examples of the alkyl group represented by R4 to R'' include a methyl group and an ethyl group.R4 Examples of the aryl group substituted with H in -R1ff include a phenyl group.

Specific examples of the compound represented by the general formula (V-1) or (V-2) include the above-mentioned exemplary piperazine compound (J-
1) to (J-30) and exemplary homopiperazine compounds (
J-51) to (J-62).

Next, a synthesis example of a typical magenta dye image stabilizer of the present invention represented by the general formula (Vl) will be shown.

Synthesis Example-1 (Synthesis of Compound J-2) Piperazine9. 15 g of anhydrous potassium carbonate was added to 100, Q acetone in which 55 g of Og and myristyl bromide were dissolved, and the mixture was boiled and refluxed for 10 hours to react.

After the reaction, the reaction solution was poured into 500 mL of water and extracted with ethyl acetate. The ethyl acetate layer was dried over magnesium sulfate, and the ethyl acetate was distilled off to obtain the desired product as white crystals. Recrystallization with acetone 30011III gave 34 g of white flaky crystals (yield: $70%).

Melting point: 55-58°C Synthesis Example-2 (Synthesis of Compound J-34) 18 g of 4-morpholino-7niline was dissolved in 10 G of ethyl acetate.
! After dissolving the mixture in 12 rr+Ω of acetic anhydride, 12 rr+Ω of acetic anhydride was added little by little while stirring and keeping the reaction solution at 20°C.

After adding acetic anhydride, cooling with water and filtering the precipitated crystals,
Recrystallization from ethyl acetate gave 16.51 white powder crystals (yield 75%).

fusing, α207 to 210° C. or less. As the yellow image-forming coupler, various known couplers can be used, and examples of couplers that can be preferably used include the following.

General formula (A) In the formula, R1 represents an alkyl group or an aryl group, and R
2 represents an aryl group, and X represents a hydrogen atom or a group that is eliminated during the color development reaction.

R1 is a linear or branched alkyl group (e.g. butyl group) or aryl group (e.g. phenyl group), preferably an alkyl group (especially 1-butyl group), and R2 is an aryl group (preferably phenyl group)
The alkyl group and aryl group represented by R1 and R2 include those having substituents, and the aryl group of R2 is preferably substituted with a halogen atom, an alkyl group, etc. X is the following general formula (B) or (C
) are preferable, and among general formula (B), groups represented by general formula (B') are particularly preferable.

General formula (B) In the formula, Zl represents a modern atomic group capable of forming a 4- to 7-membered ring.

General formula (C) -O-R+1 In the formula, Rh represents an aryl group, a heterocyclic group or an acyl group, and an aryl group is preferable.

General formula (B') Represents a group of nonmetallic atoms that can be formed.

A preferred yellow coupler according to the present invention in the general formula (A) is represented by the following general formula (A').

General formula (A') R-heavy 7 In the formula, R14 represents a hydrogen atom, a halogen atom, or an alkoxy group, and a halogen atom is preferable.

R+s, R16 and R17 are each a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an aryl group, a carboxy group, an alkoxycarbonyl group, a carbamyl group, a sulfone group, a sulfamyl group, an alkylsulfonamide group, an acylamide group, It represents a ureido group or an amine group, R+5 and Rls are each a hydrogen atom, and R17 is preferably an alkoxycarbonyl group, an acylamido group, or an alkylsulfonamide group. Further, X represents a group having the same meaning as that shown in the above general formula (A), preferably the above general formula (B) or (C
), (B), the general formula (B'
).

Below margin (Y-11 (Y-2) (Yf3) 0 CCH3 `` Hs (Y-7) (Y-8) (Y-9) (Y-10) (Y-11) ( (Y-12) t Y-13) Y-14) As the cyan image forming coupler, various known couplers can be used, but couplers represented by the following general formulas [El, [F] can be preferably used.

General formula [El In the formula, R1 represents an aryl group, a cycloalkyl group, or a heterocyclic group. R2H represents an alkyl group or a phenyl group. R3 represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group.

71ε represents a hydrogen atom, a halogen atom, or a group that can be eliminated by reaction with an oxidized product of an aromatic primary amine color developing agent.

General formula [F] 2F In the formula, R+r represents an alkyl group (eg, methyl group, ethyl group, propyl group, butyl group, nonyl group, etc.). R5
F represents an alkyl group (eg, methyl group, ethyl group, etc.). RIJ is a hydrogen atom, a halogen atom (e.g. fluorine,
(chlorine, bromine, etc.) or an alkyl group (eg, methyl group, ethyl group, etc.).

72F represents a hydrogen atom, a halogen atom, or a group capable of being removed by reaction with an oxidized product of an aromatic primary absorbing amine color developing agent.

Margin below (n) Cl 2H2S S 02NH C-7 Couplers represented by the general formulas [E] and [F] of the present invention are described, for example, in JP-A-59-146050 and JP-A-1988-60-
No. 117249 and No. 59-31953.

Other cyan couplers used in the present invention include, for example, U.S. Pat.
, No. 356,475, No. 2,362,598, No. 2,367.531, No. 2,369,929, No. 2,423,730, No. 2,474,293 ,
2,476.008, 2,498.466, 2,545,687, 2.728.660
No. 2,772.162, No. 2,895,82
No. 6, No. 2.976, No. 146, No. 3,002, 8
No. 36, No. 3,419,390, No. 3,446,
No. 622, No. 3.476, No. 563, No. 3,737
．． No. 316, No. 3,758,308, No. 3.83
9.044, British Patent No. 478.991, British Patent No. 94
5.542@, same No. 1.084,480, same No. 1, 3
No. 77.233, No. 1,388,024 and No. 1
, 543,040, and JP-A-47-
No. 37425, No. 50-10135, No. 50-252
No. 28, No. 50-112038, No. 50-11742
No. 2, No. 50-130441, No. 51-6551,
No. 51-37647, No. 51-52828, No. 51
-108841, 53-109630, 54-
No. 48237, No. 54-66129, No. 54-131
Examples include those described in publications such as No. 931 and No. 55-32 (No. 171).

The above yellow and cyan couplers are blue sensitive and
Two or more types may be contained in the same red-sensitive silver halide emulsion layer. Also, the same coupler may be included in two or more different layers having the same color sensitivity.

These yellow and cyan couplers are generally used in amounts ranging from 2.times.10@-3 moles to 1 mole, preferably from 1.times.10@-2 moles to 8.times.10@-1 moles per mole of silver in the emulsion layer.

The silver halide photographic light-sensitive material of the present invention can be, for example, a color negative film, a positive film, or a color photographic paper, but especially when used as a color photographic paper for direct viewing, the method of the present invention can be used. The effects of this will be effectively demonstrated.

The silver halide photographic material of the present invention, including this color photographic paper, may be one for monochrome use or one for multicolor use. In the case of multicolor silver halide photographic light-sensitive materials, in order to perform subtractive color reproduction, a silver halide emulsion layer containing magenta, yellow, and cyan couplers as photographic couplers, and a non-light-sensitive layer are usually used. Although it has a structure in which layers are laminated on a support in an appropriate layer order and layer order, the number and layer order may be changed as appropriate depending on the important performance and the purpose of use.

The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention includes conventional silver halides such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride. Any of those used in emulsions can be used.

The silver halide grains used in the silver halide emulsion of the present invention may be obtained by any of the acid method, neutral method, and ammonia method. The particles may be grown all at once, or may be grown after seed particles are created. The method of creating and growing the seed particles may be the same or different.

In the silver halide emulsion, halogen ions and silver ions may be mixed simultaneously, or one may be mixed in the presence of the other. In addition, while considering the critical growth rate of silver halide crystals, we added halide ions and silver ions to
) H and pAQ may be produced by controlling them and adding them sequentially or simultaneously. After growth, a conversion method may be used to change the silver halide composition of the grains.

When producing the silver halide emulsion of the present invention, the grain size, grain shape, grain size distribution, and grain growth rate of silver halide grains can be controlled by using a silver halide solvent as necessary.

The silver halide grains used in the silver halide emulsion of the present invention are prepared in the process of forming and/or growing the grains such as cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or complex salt, rhodium salt or complex salt. Metal ions can be added to the inside of the particles and/or on the surface of the particles by adding iron salts or complex salts, and can be reduced inside the particles and/or on the surface of the particles by placing them in an appropriate reducing atmosphere. Can provide sensitizing nuclei.

In the silver halide emulsion of the present invention, unnecessary soluble salts may be removed after the growth of silver halide grains is completed, or they may be left contained. In the case of removing the salts, it can be carried out based on the method described in Retirement Disclosure No. 17643.

The silver halide grains used in the silver halide emulsion of the present invention may consist of a uniform layer inside and on the surface, or
It may consist of different layers.

The silver halide grains used in the silver halide emulsion of the present invention may be grains in which a latent image is mainly formed on the surface, or grains in which a latent image is mainly formed inside the grains.

The silver halide grains used in the silver halide emulsion of the present invention may have a regular crystal shape or may have an irregular crystal shape such as a spherical shape or a plate shape. In these particles, any ratio of the (100) plane to the (111) plane can be used.

Further, the particles may have a composite form of these crystal forms, or particles of various crystal forms may be mixed.

The silver halide emulsion of the present invention may be a mixture of two or more separately formed silver halide emulsions.

The silver halide emulsion of the present invention is chemically sensitized by a conventional method. That is, compounds containing sulfur that can react with silver ions,
A sulfur sensitization method using activated gelatin, a selenium sensitization method using a selenium compound, a reduction sensitization method using a reducing substance, a noble metal sensitization method using gold or other noble metal compounds, etc. can be used alone or in combination.

The silver halide emulsion of the present invention can be optically sensitized to a desired wavelength range using a dye known as a sensitizing dye in the photographic industry. The sensitizing dyes may be used alone or in combination of two or more. Along with the sensitizing dye, the emulsion contains a dye that itself does not have a spectral sensitizing effect, or a supersensitizer, which is a compound that does not substantially absorb visible light and enhances the sensitizing effect of the sensitizing dye. Also good.

The silver halide emulsion of the present invention includes steps for producing light-sensitive materials,
For the purpose of preventing fog during storage or photographic processing and/or keeping photographic performance stable, silver halide emulsions are used during and/or at the end of chemical ripening, and/or after the end of chemical ripening. Compounds known in the photographic industry as antifoggants or stabilizers can be added prior to coating.

Gelatin is advantageously used as a binder (or protective colloid) for the silver halide emulsion of the present invention, but
In addition, hydrophilic colloids such as synthetic hydrophilic polymer substances such as gelatin derivatives, graft polymers of gelatin and other polymers, proteins, sugar derivatives, cellulose derivatives, and single or copolymers can also be used.

The photographic emulsion layer or other hydrophilic colloid layer of a light-sensitive material using the silver halide emulsion of the present invention can be formed by using, alone or in combination, a hardening agent that crosslinks binder (or protective colloid) molecules and increases film strength. It is hardened. ! i! It is desirable to add all the coating agents that can harden the photosensitive material to such an extent that there is no need to add a hardening agent to the processing solution, but it is also possible to add a hardening agent to the processing solution.

A plasticizer can be added for the purpose of increasing the flexibility of the silver halide emulsion layer and/or other hydrophilic colloid layer of the silver halide photographic material of the present invention.

The photographic emulsion layer and other hydrophilic colloid layers of the silver halide photographic light-sensitive material of the present invention may contain a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability.

In the emulsion layer of the silver halide color photographic light-sensitive material of the present invention, an aromatic primary amine developer (
For example, a dye-forming coupler is used that forms a dye by performing a coupling reaction with an oxidized product of p-phenylenediamine derivatives, aminephenol derivatives, etc.). The dye-forming couplers are typically selected for each emulsion layer such that a dye is formed that absorbs light in the light-sensitive spectrum of the emulsion layer, with a yellow dye-forming coupler for the blue-sensitive emulsion layer and a dye for the green-sensitive emulsion layer. A magenta dye-forming coupler is used in the sensitive emulsion layer and a cyan dye-forming coupler is used in the red-sensitive emulsion layer. However, depending on the purpose, silver halide color photographic materials may be produced using different combinations from the above.

Examples of yellow dye-forming couplers include acylacetamide couplers (e.g., benzoylacetanilides, pivaloylacetanilides); examples of magenta dye-forming couplers include, in addition to the couplers of the present invention, 5-pyrazolone couplers, pyrazolonebenzimidazole couplers, pyrazolone triazoles, There are closed acylacetonitrile couplers and the like, and cyan dye-forming couplers include naphthol couplers and phenol couplers.

These dye-forming couplers preferably have a group called a ballast group in the molecule, which makes the coupler non-diffusive and has 8 or more carbon atoms. Furthermore, even if these dye-forming couplers are 4-equivalent, in which 4 molecules of silver ions need to be reduced in order to form 1 molecule of dye, only 2 molecules of silver ions need to be reduced. Either 2-isomerism is fine.

For hydrophobic compounds such as dye-forming couplers that do not need to be adsorbed onto the silver halide crystal surface, various methods such as solid dispersion, latex dispersion, and oil-in-water emulsion dispersion can be used. can be appropriately selected depending on the chemical structure of the hydrophobic compound, etc. The oil-in-water emulsion dispersion method can be applied to a method of dispersing a hydrophobic compound such as a coupler, and usually a high boiling point organic solvent with a boiling point or <150°C or higher is added with a low boiling point and/or water-soluble cloth as necessary. Dissolve using a combination of solvents and use a stirrer, homogenizer, etc. using a surfactant in a hydrophilic binder such as an aqueous gelatin solution.
It may be emulsified and dispersed using a dispersing means such as a colloid mill, a flow jet mixer, or an ultrasonic device, and then added to the desired hydrophilic colloid layer. A step of removing the low boiling point organic solvent may be included simultaneously with the dispersion or dispersion.

Examples of high boiling point oils include phenol derivatives that do not react with the oxidized form of the developing agent, phthalates, phosphates, citric esters, benzoates, alkylamides,
Boiling point of fatty acid ester, trimesic acid ester, etc. 150
An organic solvent having a temperature of ℃ or higher is used.

Preferably, it is a high boiling point organic solvent with a dielectric constant of 6.0 or less and 1.9 or more and a vapor pressure of 0.5 mml-(g or less) at 100°C.

Anionic surfactants, nonionic surfactants, Cationic surfactants can be used.

Between the emulsion layers of the color photographic light-sensitive material of the present invention (between the same color-sensitive layers and/or between different color-sensitive layers), the oxidized form of the developing agent or the electron transfer agent may migrate, causing color turbidity or sharpness. An antifoggant is used to prevent deterioration and graininess from becoming noticeable.

The color antifoggant may be used in the emulsion layer itself, or in an intermediate layer provided between adjacent emulsion layers.

In the color light-sensitive material using the silver halide emulsion of the present invention, an image stabilizer can be used to prevent deterioration of the dye image.

A UV absorber is added to the hydrophilic colloid layers such as the protective layer and intermediate layer of the photosensitive material of the present invention in order to prevent fogging due to discharge caused by charging of the photosensitive material due to friction, etc., and to prevent image deterioration due to UV light. It may be included.

A color light-sensitive material using the silver halide emulsion of the present invention can be provided with auxiliary layers such as a filter layer, an antihalation layer and/or an antiirradiation layer. These layers and/or the emulsion layer may contain dyes that flow out of the color light-sensitive material or are bleached during development.

The silver halide emulsion layer and/or other hydrophilic colloid layer of a silver halide photosensitive material using the silver halide emulsion of the present invention reduces the gloss of the photosensitive material, improves the ease of writing, and provides a layer between the photosensitive materials. A matting agent can be added to prevent sticking.

A lubricant can be added to reduce the sliding friction of the light-sensitive material using the silver halide emulsion of the present invention.

An antistatic agent for the purpose of preventing static electricity can be added to a light-sensitive material using the silver halide emulsion of the present invention.

Antistatic agents are sometimes used in the antistatic layer on the side of the support on which the emulsion is not laminated, or they are used to protect the emulsion layer and/or the side other than the emulsion layer on which the emulsion layer is laminated with respect to the support. It may also be used in a colloid layer.

The photographic emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material using the silver halide emulsion of the present invention may include improved coatability,
Various surfactants are used for the purposes of preventing static electricity, improving slipperiness, emulsifying and dispersing, preventing adhesion, and improving photographic properties (promotion of development, Ii! film formation, sensitization, etc.).

The light-sensitive material using the silver halide emulsion of the present invention includes a photographic emulsion layer, other layers are a baryta layer or an α-olefin polymer, etc., a flexible reflective support such as paper or synthetic paper laminated with cellulose acetate, cellulose acetate, It can be applied to films made of semi-synthetic or synthetic polymers such as cellulose nitrate, polystyrene, polyvinyl chloride, boreethylene terephthalate, polycarbonate, and polyamide, as well as rigid bodies such as glass, metal, and ceramics.

The silver halide material of the present invention can be used directly or (adhesiveness of the support surface, antistatic property, dimensional stability) after corona discharge, ultraviolet irradiation, flame treatment, etc. , to improve wear resistance, hardness, antihalation, friction properties, and/or other properties) 1 or 2 g
, may be applied through an overlying subbing layer.

When coating a photographic light-sensitive material using the silver halide emulsion of the present invention, a thickener may be used to improve coating properties. Particularly useful coating methods are extrusion coating and curtain coating, which allow two or more layers to be applied simultaneously.

The light-sensitive material of the present invention can be exposed using electromagnetic waves in a spectral region to which the emulsion layer constituting the light-sensitive material of the present invention is sensitive. Light sources include natural light (sunlight), tungsten electric lamps, fluorescent lamps, mercury lamps, xenon arc lamps, carbon arc lamps, xenon flash lamps, cathode ray tube flying spots, various laser lights, light emitting diode lights, electron beams,
Any known light source can be used, such as light emitted from a phosphor excited by X-rays, γ-rays, α-rays, etc.

Exposure times include not only exposure times of 1 millisecond to 1 second commonly used in cameras, but also exposure times shorter than 1 microsecond, such as exposure times of 100 microseconds to 1 microsecond using cathode ray tubes and xenon flash lamps.
Microsecond exposures can be used, and exposures longer than 1 second are also possible. The exposure may be performed continuously or intermittently.

In the treatment method of the present invention, treatment baths known in the art may be combined as necessary for the treatment step.
Any processing step can be used. Examples of treatment steps preferably used in the present invention are listed below.

1. Color development - bleach fixing - washing with water 2. Color development - bleach fixing - stabilization 3. Color development - constant bleaching, washing with water 4. Color development - constant bleaching - stabilization Note that the water washing step, which may be performed between each treatment bath, was omitted.

Among the treatment steps 1 to 4 above, 1 to 2 are preferred from the viewpoint of speeding up and reducing pollution.

The aromatic primary amine color developing agents used in the color developing solution of the present invention include known ones that are widely used in various color photographic processes. These developers include p-phenylenediamine derivatives. These compounds are generally used in the form of salts, such as hydrochloride or 'flL salts, as they are more stable than in the free state. Additionally, these compounds are generally used in concentrations of from about 0.1 g to about 300 g per ton of color developer, preferably from about 1 g to about 15 g per 1 ton of color developer.

For rapid development, the amount is more preferably 4 g or more, and 69 to 15 degrees is particularly preferable.

Particularly useful primary aromatic amino color developers are N, N'
-Dialkyl-p-phenylenediamine compound, and the alkyl group and phenyl group may be substituted with any substituent. Among them, examples of particularly useful compounds include N,N'-diethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, N,
N'-dimethyl-〇-phenylenediamine hydrochloride, 2
-amino-5-(N-ethyl-N-dodecylamino)-
Toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, N-
Ethyl-N-β-hydroxyethylaminoaniline, 4
-amino-3-methyl-N.

N'-diethylaniline, 4-amino-N-(2-methoxyethyl)-N-ethyl-3-methylaniline-p-
Examples include toluene sulfonate.

In addition to the above-mentioned primary aromatic amine color developer, the color developer used in the process of the present invention further contains various components that are normally added to color developers, such as sodium hydroxide and sodium carbonate. , alkali agents such as potassium carbonate, alkali metal sulfites, hydroxyamines, alkali metal bisulfites, alkali metal thiocyanates, alkali metal halides, benzyl alcohol, water softeners, thickeners, etc. may be optionally contained. You can also do it.

The pH of the color developing solution is usually 7 or more, and generally in the range of 10 to 13. For quick development p)-
110.5 or more is preferable.

Color development temperature is usually 15°C or higher, generally 20°C.
It is in the range of °C to 50 °C. For rapid development, the temperature is preferably 30°C or higher, more preferably 35°C or higher.

In the present invention, after color development processing, processing is performed with a processing liquid having a fixing ability, but if the processing liquid having a fixing ability is a fixing liquid, a bleaching treatment is performed before that. As the bleaching agent used in the bleaching step, a gold R complex salt of an organic acid is used, and the metal complex oxidizes the metallic silver produced by development to convert it into silver halide, and at the same time, it colors the uncolored part of the coloring agent. It has a composition in which metal ions such as iron, cobalt, copper, etc. are coordinated with aminopolycarboxylic acid or organic acids such as oxalic acid and citric acid. The most preferred organic acids used to form such metal complexes of organic acids include polycarboxylic acids or aminopolycarboxylic acids. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts.

Specific representative examples of these include the following.

[1] Ethylenediaminetetraacetic acid [2] Nitrilotriacetic acid [3] Iminodiacetic acid [4] Ethylenediaminetetraacetic acid disodium salt [5] Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt [6] Ethylenediaminetetraacetic acid tetrasodium salt [7] Nitrilotriacetic acid The bleaching agent used in the sodium acetate salt contains a metal complex salt of an organic acid as described above as a bleaching agent, and may also contain various additives. As additives, it is particularly desirable to include rehalogenating agents, metal salts, and chelating agents such as alkali halides or ammonium halides, such as potassium bromide, sodium bromide, sodium chloride, and ammonium bromide.

Also, borates, oxalates, acetates, carbonates, phosphates, etc.
H! Buffers, alkylamines, polyethylene oxides, and other substances known to be commonly added to bleaching solutions can be added as appropriate.

Furthermore, the fixer and bleach-fixer contain ammonium sulfite,
VA salts such as potassium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, sodium metabisulfite, boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate , pHl1!, which consists of various salts such as potassium carbonate, sodium binitite, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide, etc. ! The i-agent may be used alone or may contain two or more types. Further, a bleaching accelerator may be included.

When carrying out the process of the present invention while replenishing the bleach-fix solution (bath) with a bleach-fix replenisher, the bleach-fix solution (bath) may contain thiosulfate, thiocyanate, sulfite, etc. These salts may be added to the bleach-fixing replenisher to replenish the processing bath.

In the present invention, in order to increase the activity of the bleach-fix solution, air or oxygen may be blown into the bleach-fix bath and the bleach-fix replenisher storage tank as desired (or a suitable oxidizing agent may be added). For example, hydrogen peroxide, bromate, persulfate, etc. can be used as appropriate.

The humidity of bleaching, fixing and bleach-fixing baths is also usually above 15°C, generally in the range of 20°C to 50°C, but preferably above 30°C for rapid processing. In this case, the processing time is generally within 2 minutes, but it can be changed depending on the temperature, bleaching ability and fixing ability. For rapid processing, it is preferably used within 90 seconds.

Although the stabilization treatment can be added after the water washing step, from the viewpoint of speeding up, a water washing substitute stabilizing solution is preferable. The water-washing alternative stabilizer may contain an anti-bacterial agent, an ammonium compound, a chelating agent, and the like. For these specific conditions, reference may be made to JP-A-58-134636, etc., but the treatment temperature is preferably 20"C to 45C.

The water used in the washing step may be either so-called "reserved water" or "running water", but efficient upstream water is preferable. Furthermore, it is also possible to use the method for reducing the amount of washing water and the multistage countercurrent treatment method described in JP-A-57-8543 and JP-A-58-134,636.

Next, the present invention will be explained in detail with reference to examples.

Example 1 A multilayer color photosensitive material was prepared by sequentially applying the following layers to a paper support coated on both sides with polyethylene.

Layer (1): Blue-sensitive silver halide emulsion layer Gelatin is 16+no/df 1 Blue-sensitive silver chlorobromide emulsion is 3II1 g/d12 in terms of silver, yellow coupler Y-2 is 8QI
It was coated to have the same amount of silver as Mdf.

Layer (2): Gelatin was coated at a coating amount of 4 m/di'.

Layer (3): Green-sensitive silver halide emulsion layer The magenta coupler shown in Table 1 is slQ/d1x, and the green-sensitive silver chlorobromide emulsion is 1 in terms of silver.
mM (If, dimethyl phthalate at 4HJ/di' and gelatin at 16 m
It was applied so that it became coating material 1 of v/dv'.

Layer (4): Intermediate layer ultraviolet absorber 2-(2'-hydroxy-3', 5
6B/df of '-di-t-amylphenol)-benzotriazole and 14 m of gelatin (coating material m of 1/df) were applied.

Layer (5): Red-sensitive silver halide emulsion layer Cyan coupler (C-7): 4 m9/df, dioctyl phthalate: 2ff1 g/d12, and red-sensitive silver chlorobromide emulsion: 3+11 in terms of silver! The coating was applied so that the coating amount was J/(112).

Layer (6): Intermediate layer ultraviolet absorber 2-(2'-hydroxy-3', 5
'-di-t-amylphenol)-benzotriazole at 2111 g/dv' and gelatin at 6111 g/dv'! J/
dvz7) The coating was applied to a coating weight of 6ma/df.

Layer 7): Protective layer Apply gelatin with a coating amount of 9ma/df. I painted it to look like this.

The sample thus prepared is referred to as tit material 1.

Next, Samples 2 to 21 were prepared which were the same as Sample 1 except that a magenta coupler and an antioxidant were added to the third layer of Sample 1 in the combinations shown in Table 1.

These samples 1 to 21 were exposed to blue light using a photosensitive needle (model KS-7, manufactured by Konishiroku Photo Industry Co., Ltd.), and then subjected to the following treatments.

Standard processing steps (processing temperature and processing time) [1] Color development 38°C 1 minute, 3 minutes 30 seconds [2] Bleach fixing 33°C 1 minute 30 seconds [3] Washing process
25-30℃ 3 minutes [4] Drying 75-80℃
Approximately 2 minutes Processing solution composition (color developer [A1 composition) Benzyl alcohol 151g Ethylene glycol 151g Potassium sulfite 2.0g Potassium bromide
0.7g sodium chloride
0.2g potassium carbonate
30. Oa human O xylamine sulfate 3,
0g polyphosphoric acid (TPPS) 2.59
3-Methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl)-aniline@acid f1 5.5g Fluorescent brightener (4,4'-diaminostilbenzsulfonic acid derivative) 1.0 g Potassium hydroxide 2.0 g Add water to bring the total volume to 12 and adjust to IIH 10.20.

Color developer [8] Composition Color developer [A] except that it does not contain benzyl alcohol
] The composition was the same as that of

Color developer [C] Composition The composition was the same as color developer B except that 100111M ffi of auxiliary developer ■-1 was added.

(Bleach-fix solution) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60 Q Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% solution) 100. Q Ammonium sulfite (40% solution) 27.5 [adjust to pi-17.1 with potassium carbonate or glacial acetic acid, add water to bring the total amount to 1 t
shall be.

Next, the maximum density of each yellow reflection was measured.

In addition, in order to evaluate the degree of magenta treatment stain, the sample was left in the air for 30 seconds after color development, bleach-fixed, and washed with water, and the magenta reflection density of the white portion of each sample was measured, which was determined as magenta treatment stain.

These results are shown in Table 1.

As is clear from Table 1 below, the color density of processed samples 5 to 8 that were processed with developer B, which does not use benzyl alcohol, has decreased, but they were processed with developer C that added an auxiliary developer. In treated samples 9 to 21, recovery of color density was observed. However, Samples 9 to 11 show an increase in magenta processing stains.

Samples 12-21 treated according to the method of the present invention have reduced occurrence of magenta processing stains. The reduction in magenta processing stain caused by the combination of the magenta coupler and antioxidant of the present invention was completely unexpected with other processing solutions.

Therefore, according to the method of the present invention, it is possible to perform good processing with good color development even in a low-pollution processing solution and without an increase in magenta processing stain.

Example 2 Samples were prepared in which each auxiliary developer was added to Layer 1 of a silver halide photographic light-sensitive material having the same structure as in Example 1, and treated with Processing Solution B. Further, samples were prepared in which the type of high boiling point organic solvent in layer 3 was changed, and the samples were treated in the same manner as in Example 1, and the maximum reflection density and magenta treatment stain density were measured.

The results are shown in Table 2.

As is clear from Table 2 below, even when the auxiliary mulberry is incorporated into the photosensitive material R1, the method of the present invention can be used, even if the process without benzyl alcohol is used, and even if J3 is used in the processing solution. It shows good color development and does not increase magenta stain.

[Example 3] 3- in the color developer [C] used in Example 1
Instead of methyl-4-amino-N-edyl-N-(β-methanesulfonamidoethyl)-aniline sulfate, 3
-Methyl-4-amino-N-edyru-N-hydroxyedyru-aniline sulfate, 3-methyl-4-amino-N-
Ethyl-N-(2-methoxyethyl)-aniline-p-
Color developing solutions [D] and [E] were prepared with the same composition except that t-fluorene sulfonate was used in equimolar amounts.
child .

Example 1 except that the above color developing solutions [D] and [E] were used.
When tested in the same manner as in Example 1, almost the same results as in Example 1 were obtained.

procedure'? Hoshosho (Method) 2. Name of the invention Processing method for silver halide photographic light-sensitive materials 3. Relationship with the person making the amendment Patent applicant address 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name
(127) Representative Director of Konishiroku Photo Industry Co., Ltd.
Keio Benko 4, Agent 102 Address 4-1-1-6 Kudankita, Chiyoda-ku, Tokyo Subject to amendment

Claims (1)

[Claims] A method for processing a silver halide photographic material, which comprises at least the steps of imagewise exposing and color developing a silver halide photographic material having at least one silver halide emulsion layer on a support. , at least one of the silver halide emulsion layers includes at least one magenta coupler represented by the following general formula [I] and a magenta coupler represented by the following general formula [I].
A halogen compound containing at least one compound selected from compounds represented by I], [III], [IV] and [V], and wherein the color developing step is carried out in the presence of an auxiliary developer. Processing method for silver chemical photographic materials. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. You may. X represents a hydrogen atom or a substituent that can be separated by reaction with an oxidized product of a color developing agent. Further, R represents a hydrogen atom or a substituent. ] General formula [I
I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group, R_2, R_3,
R_5 and R_6 are each a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group, an alkenyl group, an aryl group,
Represents an alkoxy group or an acylamino group, R_4
represents an alkyl group, a hydroxy group, an aryl group or an alkoxy group. Further, R_1 and R_2 may be ring-closed with each other to form a 5- or 6-membered ring, in which case R_4 represents a hydroxy group or an alkoxy group. Also, R_3 and R_4 are ring-closed,
A 5-membered hydrocarbon ring may be formed, in which case R_1
represents an alkyl group, an aryl group, or a heterocyclic group. However, the case where R_1 is a hydrogen atom and R_4 is a hydroxy group is excluded. ) General formula [III] ▲ Numerical formulas, chemical formulas, tables, etc. Represents an oxy group, acyl group, acylamino group, acyloxy group, sulfonamide group, cycloalkyl or alkoxycarbonyl group, and R_2 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an acyl group, a cycloalkyl group or a heterocyclic group. Description, R_3 is a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, an aryloxy group, an acyl group, an acyloxy group,
Represents a sulfonamide group, cycloalkyl group, or alkoxycarbonyl group. ) Y represents an atomic group necessary to form a chroman or coumaran ring. General formula [IV] ▲ Numerical formulas, chemical formulas, tables, etc. Represents an oxy group, an acyl group, an acylamino group, an acyloxy group, a sulfonamide group, a cycloalkyl group, or an alkoxycarbonyl group. R^2 is a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, a hydroxy group, an aryl group, an acyl group. , represents an acylamino group, an acyloxy group, a sulfonamide group, a cycloalkyl group, or an alkoxycarbonyl group.) General formula [V] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, R^1 is an aliphatic group, cyclo It represents an alkyl group or an aryl group, and Y represents a group of nonmetallic atoms necessary to form a 5- to 7-membered heterocycle together with the nitrogen atom. However, when there are two or more heteroatoms among the nonmetallic atoms containing nitrogen atoms forming the heterocycle, at least two heteroatoms are not adjacent to each other. ]