JP2665667B2 - Silver halide color photographic light-sensitive material and processing method thereof - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a silver halide color photographic light-sensitive material, and particularly to a silver halide color photographic material having excellent color reproducibility and sharpness and having a wide exposure latitude. It relates to a photosensitive material.

Further, the present invention relates to a processing method using the above-mentioned photosensitive material. In particular, it is possible to improve a bleaching action, shorten a processing time, and perform a sufficient bleaching action to form a color image having good image quality. And a development processing method.

(Prior art) In recent years, silver halide light-sensitive materials, especially for photographic light-sensitive materials, are suitable for ultra-high-sensitivity light-sensitive materials typified by ISO1600 films and cameras in small format such as 110 and discs. There has been a demand for a photosensitive material having high image quality (color reproducibility and sharpness) that can be satisfied even with a print having a large enlargement magnification.

U.S. Patent for technology to improve color reproduction and sharpness
DIR compounds as described in 3,227,554 and the like, more preferably using a diffusible DIR compound described in JP-A-58-7150, to improve the color reproducibility by utilizing the layering effect,
A method for improving sharpness by using an edge effect is known.

On the other hand, non-photosensitive silver halide fine grain emulsions have been used in recent years to prevent the contamination of the developing solution from the photosensitive material during development or the incorporation of desensitizing substances from the developing solution into the photosensitive material. Has increased.

However, it has been found that the combined use of a DIR compound and a silver halide fine grain emulsion significantly reduces the layering effect. Until now, a combination of a DIR compound and a non-photosensitive silver halide fine grain as disclosed in JP-A-53-99938, a combination of a diffusible DIR compound and a non-photosensitive silver halide fine grain added to an emulsion layer, A combination of a diffusible DIR compound and a non-light-sensitive silver halide fine particle added to a non-light-sensitive layer as disclosed in JP-A-61-42656 is known. In order to combine them, a large amount of a DIR compound needs to be added, thereby increasing the film thickness and causing various side effects.

In addition, the demand for obtaining high-quality photographs under various exposure conditions has made it necessary to broaden the exposure latitude. For this reason, the use of photosensitive silver halide fine grain emulsions has been increasing further in recent years, and the above-mentioned problems have become more remarkable.

Furthermore, in recent years, there has been a strong demand in the art for faster processing, that is, a reduction in the time required for processing, and in particular, a reduction in the desilvering step, which accounts for nearly half of the conventional processing time, has become a major issue. For this reason, the desilvering process is improved in each of the case where the bleaching bath and the fixing bath are performed in two steps, and in the case where the bleaching bath and the fixing agent are performed in a single step using a bleach-fixing bath in which a bleaching agent and a fixing agent coexist. I have.

As the bleaching agent, a bleaching treatment method mainly using a ferric ion complex salt (for example, a ferric ion complex salt of aminopolycarboxylic acid, particularly, an iron (III) complex salt of ethylenediaminetetraacetate) is used.

However, since ferric ion complex salts have relatively low oxidizing power and insufficient bleaching power, those using this as a bleaching agent are, for example, low-sensitivity silver halide color photographic light-sensitive materials mainly composed of silver chlorobromide emulsions. When the material is subjected to bleaching or bleach-fixing, the desired purpose can be achieved for the time being, but it is mainly composed of silver chlorobromoiodide or silver iodobromide emulsion,
In addition, when processing high-sensitivity silver halide color photographic materials with color sensitization, especially color reversal photographic materials and photographic color negative photographic materials using high silver content emulsions, the bleaching action is insufficient and the It has the disadvantage that silver becomes poor and it takes a long time to bleach.

In color photographic materials, sensitizing dyes are generally used for the purpose of color sensitization. In particular, when tabular grains having a high silver content or a high aspect ratio are used for the purpose of increasing the sensitivity, there is a problem that the sensitizing dye adsorbed on the surface of the silver halide inhibits the bleaching of the silver generated by the development of the silver halide. Occurs.

As a bleaching agent other than the ferric ion complex salt, a persulfate is known, and usually a persulfate containing chloride is used as a bleaching solution. However, a disadvantage of bleaching solutions using persulfates is that they have a weaker bleaching power than ferric ion complex salts and have a significantly longer time to bleach.

Generally, bleaching agents having no pollution or corrosiveness to equipment have a weak bleaching power, and therefore, bleaching agents or bleach-fixing solutions using weak bleaching powers, especially ferric ion complex salts or persulfates. There is a desire to increase the bleaching capacity of corn.

In contrast, Research Disclosure 24023 (1
(April 984), JP-A-60-230653, etc., describe processing methods in which two or more ferric aminopolycarboxylic acid complex salts are used in combination, and these methods are also sufficiently bleached. It has not yet been able to exhibit the promoting effect.

(Problems to be Solved by the Invention) An object of the present invention is to provide a silver halide photographic light-sensitive material which is excellent in color reproducibility and sharpness and has a wide exposure latitude.

It is a further object of the present invention to provide a processing method for rapidly desilvering a silver halide color photographic light-sensitive material.

(Means for Solving the Problems) An object of the present invention is to provide a silver halide color photographic material having at least one silver halide emulsion layer provided on a support, wherein at least one of the silver halide emulsion layers is provided. The silver halide emulsion contained therein has a maximum particle size of up to 30% by number counted from the smallest one of the grains, and the equivalent particle diameter is 0.3 μm or less. A silver halide color photographic light-sensitive material characterized in that the compound cleaved after the reaction with the oxidized base material contains a compound that cleaves the development inhibitor by reacting with the oxidized form of another developing agent. I found that.

The emulsion according to the present invention has a maximum particle size of up to 30% by number counted from small particles having a sphere equivalent diameter of 0.3 μm.
An emulsion having the following distribution.

The term "individual grain size" as used in the present invention means that the silver halide emulsion is prepared by using "The Theory of the Photographic Process" by THJames et al.
(The Theory of the Photographic Process) Third Edition
Equivalent to the projected area corresponding to the area projected when micro-photographed by a method well known in the art (usually electron microscopy) as described in pages 36 to 43, published by McLamine Company (1966) Is the diameter. Here, the projected equivalent diameter of the silver halide grain is defined by the diameter of a circle equal to the projected area of the silver halide grain as described in the above-mentioned book.
Therefore, the shape of silver halide grains is not spherical (for example, cubic, octahedral, tetrahedral, tabular, potato-like, etc.)
In the case of the above, it can be obtained as described above.

Among all the particles determined here, the maximum particle diameter in the particle group counted from the smallest one to 30% is 0.3 μ or less in sphere equivalent diameter, preferably 0.25 μ or less, more preferably 0.2 μ or less , More preferably 0.17 μm or less.

The maximum particle diameter in the particle group is up to 30%, preferably up to 40%, more preferably up to 50%, counting from the smallest one, and it is desirable that the equivalent spherical diameter is 0.3 μm or less.

The silver halide grains may have a regular crystal form (normal crystal grains) such as a hexahedron, octahedron, dodecahedron, or tetradecahedron, or may be spherical, potato-shaped, or flat. It may have an irregular crystal form such as a shape. Although it is preferred that the amount of the emulsion is 0.1 g / m ² or more metallic silver terms, the increase of the silver amount for deterioration etc various bill harm desilvering occurs in 0.15~5.0g / m ² preferably there, more preferably 0.2~4.0g / m ^2, more preferably 0.3 to 3.0 g /
a m ^2.

The above emulsion may or may not have photosensitivity, but the addition position is between the layer containing the compound for applying the interimage effect and the layer receiving the interimage effect. It is preferably added to the layers or to these layers.

The halogen composition of the silver halide grains preferably contains silver bromide in an amount of 60 mol% or more and silver chloride in an amount of 10 mol% or less. More preferably, the grains contain 0 to 10 mol% of silver iodide, and particularly preferably 0 to 4 mol% of silver iodide.

The emulsion grains used in the present invention are produced by various production methods such as a neutral method, a semi-ammonia method and an ammonia method, and are produced by various production methods such as a simultaneous mixing method and a conversion method.

These emulsion grains may or may not be chemically sensitized. Further, spectral sensitization may be performed or spectral sensitization may not be performed.

The silver halide emulsions described above and other silver halide emulsions that can be used in the present invention are described, for example, in Research Disclosure (RD), No. 17643 (December 1978), pp. 22-23,
“I. Emulsion preparation and types”,
No. 18716 (November 1979), p. 648, Grafkid, "Physics and Chemistry of Photography", published by Paul Montell (P. Glaf)
kides, Chemic et Phisique Photographique Paul Monte
l, 1967), "Photographic Emulsion Chemistry" by Daffin, published by Focal Press (GFDuffin, Photographio Emulsion Chemist)
ry (Focal Press, 1966)), "Manufacture and coating of photographic emulsions" by Zelikman et al., published by Focal Press (VLZelikman)
et al, Making and Coating Photographic Emulsion, Fo
cal Press, 1964).

Monodispersed emulsions described in U.S. Pat. Nos. 3,574,628 and 3,655,394 and British Patent No. 1.413,748 can also be used.

Tabular grains having an aspect ratio of about 5 or more can also be used in the present invention. Tabular grains are described by Gaft, Gutoff, Photographic Science and Engineerin.
g), 14, 248-257 (1970); U.S. Pat.
4,226, 4,414,310, 4,433,048, 4,439,520
And British Patent No. 2,112,157.

The crystal structure may be uniform, the inside and the outside may be composed of different halogen compositions, or may have a layered structure.Also, silver halides having different compositions are joined by epitaxial bonding. And it may be bonded to a compound other than silver halide such as, for example, silver rhodan or lead oxide.

 Also, a mixture of particles of various crystal forms may be used.

As the silver halide emulsion, those subjected to physical ripening, chemical ripening and spectral sensitization can be used. The additive used in such a process is Research Disclosure No. 17643
And No. 18716, and the relevant portions are summarized in the table below.

Known photographic additives which can be used in the present invention are also described in the above two Research Disclosures, and the relevant portions are shown in the following table.

The compound which cleaves the development inhibitor by reacting the compound cleaved after the reaction with the oxidized developing agent of the present invention with another molecule of the oxidized developing agent is represented by the general formula [I].

Formula (I) A-PDI In the formula, A represents a group that reacts with an oxidized developing agent to release PDI, and PDI is cleaved from A and then forms a development inhibitor through a reaction with the oxidized developing agent. Represents a group.

Among the compounds represented by the general formula (I), preferred compounds are represented by the following general formula (II).

Formula _{(II) A- (L 1)} v -B- (L 2) w -DI wherein, A is by reaction with an oxidized product of a developing agent (L _{1) v} -
B represents a group that cleaves B- (L ₂ ) _w -DI; L ₁ represents a group that cleaves B- (L ₂ ) _w -DI after cleavage from A;
After cleavage from (L ₁ ) _v , it reacts with an oxidized developing agent to represent a group that cleaves (L ₂ ) _w- DI, L ₂ represents a group that cleaves DI after cleavage from B, and DI represents Represents a development inhibitor. v and w represent 0 or 1.

The reaction process in which the compound represented by the general formula (II) releases DI upon development is represented by the following reaction.

 Where A, L₁, B, L_Two, DI, v and w are in the general formula (II)
Represents the same meaning as described above, Is the developing agent oxidation
Represents the body.

 In the above reaction formula, B- (L_Two)_wFrom -DI (L_Two)_w
-Reaction producing DI characterizes the excellent effect of the present invention
You. That is, the reaction is T And B- (L_Two)_w-With DI
This is the next reaction. In other words, the reaction speed depends on each concentration.
Dependent. Therefore T Where a large amount of
Then B- (L_Two)_w-DI is (L_Two)_wGenerate DI immediately
You. In contrast, T That only a small amount is generated
R-B- (L_Two)_w-DI is (L_Two)_w-Slowly generate DI
You. This kind of reaction process is similar to the above-mentioned reaction process.
Effectively manifests its action.

Next, the compound represented by formula (II) will be described in detail.

In the general formula (II), A specifically represents a coupler residue or a redox group.

When A represents a coupler residue, known compounds can be used. For example, a yellow coupler residue (for example, a closed ketomethylene-type coupler residue), a magenta coupler residue (for example, a 5-pyrazolone-type, pyrazoloimidazole-type, or pyrazolotriazole-type coupler residue), a cyan coupler residue (for example, a phenol-type residue) , Naphthol-type coupler residues) and non-color-forming coupler residues (e.g., indanone-type, acetophenone-type coupler residues) or U.S. Patent Nos. 4,315,070, 4,183,752, and 4,171,223.
No. 4,226,934 and the like.

When A represents a redox group, it is specifically a group represented by the following general formula (III).

Formula (III) A ₁ -P- (X = Y) _n -QA _{2 In the} formula, P and Q each independently represent an oxygen atom or a substituted or unsubstituted imino group, and n X and Y At least one represents a methine group having-(L ₁ ) _v -BL ₂ ) _w -DI as a substituent, the other X and Y represent a substituted or unsubstituted methine group or a nitrogen atom, and n represents 1 And X represents an integer of 3 (n X and n Y represent the same or different), and A ₁ and A ₂ each represent a hydrogen atom or a group which can be removed by an alkali. Here P, X, Y, Q, are also included when any two substituents of A ₁ and A ₂ form a bivalent group and linked cyclic structure Te summer. For example, (X = Y) _n forms a benzene ring, a pyridine ring, and the like.

The groups represented by L ₁ and L ₂ in the general formula (II) may or may not be used in the present invention. It is appropriately selected according to the purpose. Groups represented by L ₁ and L ₂ and the like known linking groups described below, for example.

(1) A group that utilizes the cleavage reaction of hemiacetal.

For example, U.S. Pat.No. 4,146,396, JP-A-60-249148
And the groups represented by the following general formula. Here, the symbol * represents a position bonding to the left side in the general formula (I), and the symbol ** represents a position bonding to the right side in the general formula (I).

Wherein W is an oxygen atom, a sulfur atom, or A group (R ₃ represents an organic substituent), R ₁ and R ₂ represent a hydrogen atom or a substituent, t represents 1 or 2, and when t is ₂ , each of _two R ₁ and R ₂ represents May be the same or different, and also includes a case where any _{two of} R ₁ , R ₂ and R ₃ are connected to form a cyclic structure.
Specific examples include the following groups.

(2) A group that causes a cleavage reaction using an intramolecular nucleophilic substitution reaction.

For example, certain timing groups described in U.S. Pat. No. 4,248,962 can be mentioned. It can be represented by the following general formula.

* -Nu-Link-E-** (T-2) In the formula, an asterisk (*) indicates a position bonding to the left side in the general formula (I), and ** a position bonding to the right side in the general formula (I). Nu represents a nucleophilic group, an oxygen atom or a sulfur atom is an example, and E represents an electrophilic group.
Link is a group that can cleave the bond with ** by nucleophilic attack from Nu, and Link represents a linking group that links Nu and E sterically so that they can undergo an intramolecular nucleophilic substitution reaction. (T
Specific examples of the group represented by -2) are as follows.

(3) A group that causes a cleavage reaction by utilizing an electron transfer reaction along a conjugated system.

For example, they are described in U.S. Pat. No. 4,409,323 or 4,421,845 and are groups represented by the following general formula.

In the formulas, *, **, R ₁ , R ₂ and t have the same meanings as described for (T-1). Specific examples include the following groups.

(4) A group utilizing a cleavage reaction due to hydrolysis of an ester.

For example, the linking group described in West German Patent Publication No. 2,626,315 includes the following groups. In the formulas, * and ** have the same meaning as described for (T-1).

The group represented by B in the general formula (II) is specifically A
-(L ₁ ) a group which becomes a coupler after cleavage from _v or A-
(L ₁ ) a group that becomes an oxidation-reduction group after being cleaved from _v . Examples of the group serving as a coupler include, for example, in the case of a phenol type coupler, A
— (L ₁ ) is bonded to _v . Further, in the case of a 5-pyrazolone type coupler, the coupler is bonded to A- (L ₁ ) _{v at} an oxygen atom obtained by removing a hydrogen atom from a hydroxyl group of a tautomer type of 5-hydroxypyrazole. In each of these examples A- and (L _{1) v} released from the first phenol type coupler or 5-pyrazolone type couplers. (L ₂ ) _w −
It has DI. When B represents a group to be a redox group, it is preferably represented by the general formula (B-1).

In the general formula (B-1) * -P- (X '= Y') _n -QA _{2 In the} formula, an asterisk (*) indicates a position bonding to A- (L ₁ ) _v ;
A ₂ , P, Q and n have the same meanings as described in the formula (III), and at least one of n X ′ and Y ′ has methine having (L ₂ ) _w -DI as a substituent. X 'and Y' represent a substituted or unsubstituted methine group or a nitrogen atom. Where A ₂ , P,
The case where any two substituents of Q, X 'and Y' form a divalent group to form a cyclic structure is also included.

In the general formula (II), DI is a tetrazolylthio group, benzimidazolylthio group, benzothiadiazolylthio group, benzoxazolylthio group, benzotriazolyl group, benzoindazolyl group, triazolylthio group, imidazolylthio group, thiadia It is a zolylthio group, a thioether-substituted triazolyl group (for example, a development inhibitor described in US Pat. No. 4,579,816), or an oxadiazolyl group, which may have a substituent as appropriate. Representative examples include the following examples. In the following examples, the total carbon number is preferably 20 or less. Halogen atom, aliphatic group, nitro group, acylamino group, aliphatic oxycarbonyl group, aromatic oxycarbonyl group, imide group, sulfonamide group, aliphatic oxy group, aromatic oxy group, amino group, imino group, cyano group , Aromatic group, acyloxy group, sulfonyloxy group, aliphatic thio group, aromatic thio group, aromatic oxysulfonyl group, aliphatic oxysulfonyl group, aliphatic oxycarbonylamino group, aromatic oxycarbonylamino group, aliphatic Examples include an oxycarbonyloxy group, a heterocyclic oxycarbonyl group, a heterocyclic oxy group, a sulfonyl group, an acyl group, a ureido group, a heterocyclic group, a hydroxyl group, and the like.

In the general formula (II), when any two of the groups represented by A, L ₁ , B, L ₂ and DI have a bond other than the bond represented by the general formula (II) and are linked, Include. The effect of the present invention can be obtained even if the second bond is not cut during development. Examples of such couplings are for example:

The compound represented by the general formula (II) of the present invention includes a case where it is a polymer. That is, the following general formula (PI)
Derived from the monomer compound represented by the general formula (P-
A polymer having a repeating unit represented by I) or a non-color-forming monomer having at least one ethylene group and having no ability to couple with an oxidized form of an aromatic primary amine developing agent; It is a copolymer with more than one species.
Here, two or more monomers may be simultaneously polymerized.

General formula (PI) General formula (P-2) In the formula, R represents a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, or a chlorine atom, and A ₁ represents -CONH-, -NHCONH
-, - NHCOO -, - COO -, - SO 2 -, - CO -, - NHCO
_{-, - SO 2 NH -,} - NHSO 2 -, - OCO -, - OCONH -, - S
-, -NH- or -O-, wherein A ₂ is -CONH- or -CO
A ₃ represents an unsubstituted or substituted alkylene group having 1 to 10 carbon atoms, an aralkylene group or an unsubstituted or substituted arylene group, and the alkylene group may be linear or branched.

(Examples of the alkylene group include methylene, methylmethylene, dimethylmethylene, dimethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, decylmethylene, aralkylene groups such as benzylidene, and arylene groups such as phenylene and naphthylene.) Represents a compound residue represented by the general formula (II), and may be bonded at any site of A, L ₁ , B and L ₂ .

i, j, and k represent 0 or 1;
j and k are never 0 at the same time.

Here, as a substituent of the alkylene group, aralkylene group or arylene group represented by A ₃ , an aryl group (for example, phenyl group), a nitro group, a hydroxyl group, a cyano group, a sulfo group, an alkoxy group (for example, methoxy group), an aryloxy group (Eg, phenoxy group), acyloxy group (eg, acetoxy group), acylamino group (eg, acetylamino group), sulfonamide group (eg, methanesulfonamide group), sulfamoyl group (eg, methylsulfamoyl group), halogen atom (eg, Hydrogen, chlorine, bromine, etc.), carboxy group, carbamoyl group (eg, methylcarbamoyl group), alkoxycarbonyl group (eg, methoxycarbonyl group), and sulfonyl group (eg, methylsulfonyl group). When two or more substituents are present, they may be the same or different.

Next, non-color-forming ethylene-like monomers that do not couple with the oxidation product of the aromatic primary amine developer are derived from acrylic acid, α-chloroacrylic acid, α-alkylacrylic acid and these acrylic acids. Examples include esters or amides, methylenebisacrylamide, vinyl esters, acrylonitrile, aromatic vinyl compounds, maleic acid derivatives, and vinylpyridines. As the non-color-forming ethylenically unsaturated monomer used here, two kinds of abnormalities can be used simultaneously.

Next, more preferable ranges among the compounds of the present invention will be described.

Preferred examples of A in the general formula (I) or (II) include the following general formulas (Cp-1), (Cp-2), (Cp-3), and (Cp
-4), (Cp-5), (Cp-6), (Cp-7), (Cp-
8) or (Cp-9). These couplers are preferred because of their high coupling speed.

General formula (Cp-1) General formula (Cp-2) General formula (Cp-3) General formula (Cp-4) General formula (Cp-5) General formula (Cp-6) General formula (Cp-7) General formula (Cp-8) General formula (Cp-9) In the above formula, the free bond derived from the coupling position indicates the bonding position of the coupling-off group.

In the above formula, R ₅₁ , R ₅₂ , R ₅₃ , R ₅₄ , R ₅₅ , R ₅₆ , R ₅₇ , R
_58, when _{R 59, R 60, R 61} , R 62 or R ₆₃ contains a diffusion-resistant group, it has from 8 total carbon number 40, is preferably selected to be from 10 30, otherwise The total number of carbon atoms is preferably 15 or less. In the case of bis-type, telomer-type or polymer-type couplers, any of the above substituents represents a divalent group, and connects repeating units and the like. In this case, the range of the carbon number may be out of the range.

It will be described in detail R ₅₁ ~R _63, d and e below. Hereinafter, R ₄₁ represents an aliphatic group, an aromatic group or a heterocyclic group, R ₄₂ represents an aromatic group or a heterocyclic group, R ₄₃ ,
R ₄₄ and R ₄₅ represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group.

R ₅₁ has the same meaning as R ₄₁ . R ₅₂ and R ₅₃ are each R
And ₄₂ have the same meaning. R ₅₄ is a group having the same meaning as R ₄₁ , R ₄₁ S-group, R ₄₃ O-group, R ₄₁ OOC-group, Or an N≡C- group. R ₅₅ represents a group having the same meaning as R ₄₁ . R ₅₆ and R ₅₇ each have the same meaning as the R ₄₃ group, R ₄₁
S-group, R ₄₃ O-group, Represents R ₃₈ represents a group having the same meaning as R ₄₁ . R ₅₉ is R ₄₁
A group with the same meaning as R ₄₁ O-group, R ₄₁ S-group, halogen atom or Represents d represents 0 to 3. When d is plural, plural R _59s represent the same substituent or different substituents.
Further, each R ₅₉ may be linked to form a divalent group to form a cyclic structure. Examples of divalent groups for forming a cyclic structure include Is mentioned. Here, f represents an integer of 0 to 4, and g represents an integer of 0 to 2. R ₆₀ represents a group having the same meaning as ₄₁ . R ₆₁ represents a group having the same meaning as R ₄₁ . R ₆₂ is R ₄₁
A group having the same meaning as R ₄₁ CONH- group, R ₄₁ COCNH- group, R ₄₁ SO ₂ N
H-group, R ₄₁ S-group, halogen atom or Represents R ₆₃ is a group having the same meaning as R ₄₁ , R ₄₁ SO ₂ —, R ₄₃ OCO—, R ₄₃ O—SO ₂ —, halogen, nitro, cyano or R ₄₃ CO—. e
Represents an integer of 0 to 4. Each represent the same or different when there are a plurality of R ₆₂ or R _63.

In the above description, the aliphatic group is a saturated or unsaturated, linear or cyclic, linear or branched, substituted or unsubstituted aliphatic hydrocarbon group having 1 to 32, preferably 1 to 22 carbon atoms.
Representative examples include methyl, ethyl, propyl, isopropyl, butyl, (t) -butyl,
(I) -butyl group, (t) -amyl group, hexyl group, cyclohexyl group, 2-ethylhexyl group, octyl group,
Examples thereof include a 1,1,3,3-tetramethylbutyl group, a decyl group, a dodecyl group, a hexadecyl group, and an octadecyl group.

The aromatic group is a substituted or unsubstituted phenyl group having 6 to 20 carbon atoms, or a substituted or unsubstituted naphthyl group.

The heterocyclic group is a substituted or unsubstituted, preferably 3- to 8-membered, heterocyclic group having 1 to 20 carbon atoms, preferably 1 to 7 carbon atoms, wherein the heteroatom is selected from a nitrogen atom, an oxygen atom or a sulfur atom. It is. Representative examples of the heterocyclic group include 2-pyridyl, 4-pyridyl, 2-thienyl, 2-furyl, 2-imidazolyl, pyrazinyl, 2-pyrimidinyl, 1-imidazolyl, 1- Indolyl group, phthalimide group, 1,3,4-thiadiazol-2-yl group, benzoxazol-2-yl group, 2-
Quinolyl group, 2,4-dioxo-1,3-imidazolidine-5
-Yl group, 2,4-dioxo-1,3-imidazolidine-3-
Yl group, succinimide group, phthalimide group, 1,2,4-
Examples thereof include a triazol-2-yl group and a 1-pyrazolyl group.

When the aliphatic hydrocarbon group, the aromatic group and the heterocyclic group have a substituent, typical substituents include a halogen atom, an R ₄₇ O-group, an R ₄₆ S- group, R ₄₆ SO ₂ -group, R ₄₇ OCO-group, A group having the same meaning as R ₄₆ , R ₄₆ COO—, R ₄₇ OSO ₂ —, cyano or nitro. Here, R ₄₆ represents an aliphatic group, an aromatic group or a heterocyclic group, and R ₄₇ , R ₄₈ and R ₄₉ each represent an aliphatic group,
Represents an aromatic group, a heterocyclic group or a hydrogen atom. The meaning of the aliphatic group, the aromatic group or the heterocyclic group is the same as defined above.

Next, preferred ranges of R _{51 to} R ₆₃ , d and e will be described.

R ₅₁ is preferably an aliphatic group or an aromatic group. R ₅₂ , R ₅₃
And R ₅₅ is preferably an aromatic group. R ₅₄ is an R ₄₁ CONH- group,
Or Is preferred. R ₅₆ and R ₅₇ are preferably an aliphatic group, an R ₄₁ O-group, or an R ₄₁ S-group. R ₅₈ is preferably an aliphatic group or an aromatic group. In the general formula (Cp-6), R ₅₉ is preferably a chlor atom, an aliphatic group or an R ₄₁ CONH- group. d is 1
Or 2 is preferred. R ₆₀ is preferably an aromatic group. In the general formula (Cp-7), R ₅₉ is preferably an R ₄₁ CONH- group. In the general formula (Cp-7), d is preferably 1. R ₆₁ is preferably an aliphatic group or an aromatic group. . In the general formula (Cp-8), e is preferably 0 or 1. R ₄₁ for R ₆₂ OCON
An H-group, R ₄₁ CONH-group, or R ₄₁ SO ₂ NH- group is preferred, and the substitution position thereof is preferably the 5-position of the naphthol ring. R ₆₃
As R ₄₁ CONH- group, R ₄₁ SO ₂ NH- group, Nitro or cyano groups are preferred.

Next, typical examples of R _{51 to} R ₆₃ will be described.

R ₅₁ represents a (t) -butyl group, a 4-methoxyphenyl group, a phenyl group, a 3- {2- (2,4-di-t-amylphenoxy) butanamido} phenyl group, a 4-octadecyloxyphenyl group or Examples include a methyl group. R
₅₂ and R ₅₃ are 2-chloro-5-dodecyloxycarbonylphenyl, 2-chloro-5-hexadecylsulfonamidophenyl, 2-chloro-5-tetradecanamidophenyl, 2-chloro-5 − ｛4- (2,4
-Di-t-amylphenoxy) butanamidophenyl group, 2-chloro-5- {2- (2,4-di-t-amylphenoxy) butanamide} phenyl group, 2-methoxyphenyl group, 2-methoxy-5 Tetradecyloxycarbonylphenyl group, 2-chloro-5- (1-ethoxycarbonylethoxycarbonyl) phenyl group, 2-pyridyl group, 2-chloro-5-octyloxycarbonylphenyl group, 2,4-dichlorophenyl Group, 2-chloro-5-
(1-dodecyloxycarbonylethoxycarbonyl)
A phenyl group, a 2-chlorophenyl group or a 2-ethoxyphenyl group is exemplified. As R ₅₄ , 3- ｛2-
(2,4-di-t-amylphenoxy) butanamide @ benzamide group, 3- {4- (2,4-di-t-amylphenoxy) butanamide} benzamide group, 2-chloro-
5-tetradecanamidoanilino group, 5- (2,4-di-
t-amylphenoxyacetamide) benzamide group,
2-chloro-5-dodecenylsuccinimidoanilino group, 2-chloro-5- {2- (3-t-butyl-4-hydroxyphenoxy) tetradecanamido} anilino group, 2,2-dimethylpropane Examples include an imide group, a 2- (3-pentadecylphenoxy) butanamide group, a pyrrolidino group, and an N, N-dibutylamino group. As R ₅₅ , 2,4,6-trichlorophenyl group, 2-chlorophenyl group, 2,5-dichlorophenyl group, 2,3-dichlorophenyl group, 2,6-dichloro-4-methoxyphenyl Group, 4-
{2- (2,4-Di-t-amylphenoxy) butanamide} phenyl or 2,6-dichloro-4-methanesulfonylphenyl is a preferred example. R ₅₆ represents a methyl group, an ethyl group, an isopropyl group, a methoxy group, an ethoxy group, a methylthio group, an ethylthio group, a 3-phenylureido group, a 3-butylureido group, or a 3- (2,4
-Di-t-amylphenoxy) propyl group. R ₅₇ represents a 3- (2,4-di-t-amylphenoxy) propyl group, a 3- [4- {2- [4- (4-hydroxyphenylsulfonyl) phenoxy] tetradecanamido} phenyl] propyl group, a methoxy group; Group, ethoxy group, methylthio group, ethylthio group, methyl group, 1-methyl-2- {2-octyloxy-5- [2-octyloxy-5- (1,1,3,3-tetramethylbutyl) phenyl Enylsulfonamido) phenylsulfonamidoethyl group,
3- {4- (4-dodecyloxyphenylsulfonamido) phenyl} propyl group, 1,1-dimethyl-2- {2
-Octyloxy-5- (1,1,3,3-tetramethylbutyl) phenylsulfonamidoethyl group, or a dodecylthio group. R ₅₈ is 2-chlorophenyl, pentafluorophenyl, heptafluoropropyl, 1- (2,4-di-t-amylphenoxy) propyl, 3- (2,4-di-t-amylphenoxy) propyl Group, a 2,4-di-t-amylmethyl group, or a furyl group. R ₅₉ is a chloro atom, a methyl group,
Ethyl group, propyl group, butyl group, isopropyl group, 2
-(2,4-di-t-amylphenoxy) butanamide group, 2- (2,4-di-t-amylphenoxy) hexaneamide group, 2- (2,4-di-t-octylphenoxy)
Octane amide group, 2- (2-chlorophenoxy) tetradecaneamide group, 2,2-dimethylpropanamide group,
2- {4- (4-hydroxyphenylsulfonyl) phenoxy} tetradecaneamide group, or 2- {2- (2,
4-di-t-amylphenoxyacetamido) phenoxydibutanamide group. R ₆₀ is 4-cyanophenyl, 2-cyanophenyl, 4-butylsulfonylphenyl, 4-propylsulfonylphenyl, 4-ethoxycarbonylphenyl, 4-N, N-diethylsulfamoylphenyl Group, a 3,4-dichlorophenyl group or a 3-methoxycarbonylphenyl group. R ₆₁ is a dodecyl group, hexadecyl group, cyclohexyl group, butyl group, 3- (2,4-di-t-amylphenoxy) propyl group, 4- (2,4-di-t-amylphenoxy) butyl group, 3- Dodecyloxypropyl group, 2-tetradecyloxyphenyl group, t-butyl group, 2- (2-hexyldecyloxy) phenyl group, 2
-Methoxy-5-dodecyloxycarbonylphenyl group, 2-butoxyphenyl group or 1-naphthyl group. R ₆₂ is isobutyloxycarbonylamino group, ethoxycarbonylamino group, phenylsulfonylamino group, methanesulfonamide group, butanesulfonamide group, 4-methylbenzenesulfonamide group, benzamide group, trifluoroacetamide group, 3-phenylureido Group, butoxycarbonylamino group, or acetamido group. As R ₆₃ , 2,4-di-
t-amylphenoxyacetamide group, 2- (2,4-di-t-amylphenoxy) butanamide group, hexadecylsulfonamide group, N-methyl-N-octadecylsulfamoyl group, N, N-dioctylsulfur A moyl group, a dodecyloxycarbonyl group, a chlor atom, a fluorine atom, a nitro group, a cyano group, an N-3- (2,4-di-t-amylphenoxy) propylsulfamoyl group, a methanesulfonyl group or a hexadecylsulfonyl group; No.

A preferred range when A is represented by the general formula (III) in the general formula (II) will be described below.

When P and Q represent a substituted or unsubstituted imino group, it is preferably a sulfonyl group or an imino group substituted with an acyl group.

 At this time, P and Q are represented as follows.

General formula (N-1) General formula (N-2) Here, * indicates the position where A ₁ or A ₂ is bonded, and **
The mark represents the position _where the free bond of-(X = Yn) is bonded.

In the formula, the group represented by G is a linear or branched, chain or cyclic, saturated or unsaturated, substituted or unsubstituted aliphatic group having 1 to 32, preferably 1 to 22 carbon atoms (eg, methyl group, ethyl group) Group, benzyl group, phenoxybutyl group, isopropyl group, etc.), substituted or unsubstituted aromatic group having 6 to 10 carbon atoms (for example, phenyl group, 4-methylphenyl group,
A 1-naphthyl group, a 4-dodecyloxyphenyl group, etc.) or a 4- to 7-membered heterocyclic group selected from a nitrogen atom, a sulfur atom or an oxygen atom as a hetero atom (for example, a 2-pyridyl group, a 1-phenyl group) -4-imidazolyl group, 2-furyl group, benzothienyl group, etc.) are preferable examples.

A group from which A ₁ and A ₂ can be removed by an alkali (hereinafter, referred to as
When referred to as a precursor group), preferably a hydrolyzable group such as an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an imidoyl group, an oxazolyl group, a sulfonyl group, and the like, the reverse described in US Pat. No. 4,009,029. A precursor group of the type utilizing the Michael reaction, a precursor group of the type utilizing the anion generated after the ring cleavage reaction described in U.S. Pat.No. 4,310,612 as an intramolecular nucleophilic group, U.S. Pat.
No. 3,932,480 or 3,993,661, a precursor group in which an anion is electron-transferred through a conjugated system and thereby causes a cleavage reaction, and a cleavage reaction is caused by electron transfer of an anion reacted after ring opening described in U.S. Pat.No.4,335,200. Precursor groups or U.S. Pat.No. 4,363,865,
No. 4,410,618, a precursor group utilizing an imidomethyl group.

Preferably in formula (III) P represents an oxygen atom, is when A ₂ represents a hydrogen atom.

More preferably, in the general formula (III), X and Y are substituted or unsubstituted methine groups except that X and Y are each a methine group having — (L _{1 v} BL _{2 w} DI) as a substituent. It is when.

Among the groups represented by the general formula (III), particularly preferred groups are represented by the following general formulas (IV) or (V).

General formula (IV) General formula (V) In the formula, * represents the position at which L _{1 v} BL _2w -DI binds, P, Q, A ₁ and A ₂ have the same meanings as described in formula (III), and R represents a substituent. And q
Represents an integer of 0, 1 to 3. 2 when q is 2 or more
Two or more Rs may be the same or different, and when two Rs are substituents on adjacent carbons,
It also includes a case where the compound is linked to a valent group to represent a cyclic structure.
In that case, it becomes a benzene condensed ring, for example, naphthalenes,
Benzonorbornenes, chromans, indoles, benzothiophenes, quinolines, benzofurans, 2,3
-A ring structure such as dihydrobenzofurans, indans or indenes, which may further have one or more substituents; Preferred examples of the substituent when these condensed rings have a substituent and preferable examples of R when R does not form a condensed ring are as follows. That is, an aliphatic group (for example, a methyl group, an ethyl group,
Allyl group, benzyl group, dodecyl group), aromatic group (eg, phenyl group, naphthyl group, 4-phenoxycarbonylphenyl group), halogen atom (eg, chloro atom, bromo atom), alkoxy group (eg, methoxy group, A hexadecyloxy group), an alkylthio group (eg, a methylthio group, a dodecylthio group, a benzylthio group), an aryloxy group (eg, a phenoxy group, a 4-tert-octylphenoxy group, a 2,4-di-t-amylphenoxy group), Arylthio group (for example, phenylthio group, 4-dodecyloxyphenylthio group), carbamoyl group (for example, N-ethylcarbamoyl group, N-propylcarbamoyl group, N-hexadecylcarbamoyl group, Nt-butylcarbamoyl group, N- 3- (2,4-di-t-amylphenoxy) propylcarbamoyl group, N Methyl -N- octadecylcarbamoyl group), an alkoxycarbonyl group (e.g. methoxycarbonyl group, 2-cyano ethoxycarbonyl group,
Ethoxycarbonyl group, dodecyloxycarbonyl group,
3- (2,4-di-t-amylphenoxy) propoxycarbonyl group), aryloxycarbonyl group (for example, phenoxycarbonyl group, 4-nonylphenoxycarbonyl group), sulfonyl group (for example, methanesulfonyl group, benzenesulfonyl) Group, p-toluenesulfonyl group), sulfamoyl group (for example, N-propylsulfamoyl group, N-methyl-N-octadecylsulfamoyl group,
N-phenylsulfamoyl group, N-dodecylsulfamoyl group), acylamino group (for example, acetamido group,
Benzamide group, tetradecaneamide group, 4- (2,4-
Di-t-amylphenoxy) butanamide group, 2- (2,
4-di-t-amylphenoxy) butanamide group, 2-
(2,4-di-t-amylphenoxy) tetradecaneamide group), sulfonamide group (for example, methanesulfonamide group, benzenesulfonamide group, hexadecylsulfonamide group), acyl group (for example, acetyl group, benzoyl group, myristoyl group) , Palmitoyl group), nitroso group, acyloxy group (eg, acetoxy group, benzoyloxy group, lauryloxy group), ureido group (eg, 3
A phenylureido group, a 3- (4-cyanophenylureido group), a nitro group, a cyano group, or a heterocyclic group (a 4- to 6-membered heterocyclic group selected from a nitrogen atom, an oxygen atom or a sulfur atom as a hetero atom) For example, a 2-furyl group,
2-pyridyl group, 1-imidazolyl group, 1-morpholino group), hydroxyl group, carboxyl group, alkoxycarbonylamino group (for example, methoxycarbonylamino group,
Phenoxycarbonylamino group, dodecyloxycarbonylamino group), sulfo group, amino group, arylamino group (for example, anilino group, 4-methoxycarbonylanilino group, aliphatic amino group (for example, N, N-diethylamino group, dodecyl) Amino group), sulfinyl group (for example, benzenesulfinyl group, propylsulfinyl group), sulfamoylamino group (for example, 3-phenylsulfamoylamino group), thioacyl group (for example, thiobenzoyl group), thioureido group (For example, a 3-phenylthioureido group), a heterocyclic thio group (for example, a thiadiazolylthio group), an imide group (for example, a succinimide group, a phthalimide group, or an octadecenylimide group) or a heterocyclic amino group (for example, 4- Imidazolylamino group, 4-pyridylamino group) and the like.

When there is an aliphatic group moiety in the partial structure of the above substituent,
It has 1 to 32 carbon atoms, preferably 1 to 20 carbon atoms, and is a linear or cyclic, linear or branched, saturated or unsaturated, substituted or unsubstituted aliphatic group.

When an aromatic group is present in the partial structure of the substituent listed above, it has 6 to 10 carbon atoms, and is preferably a substituted or unsubstituted phenyl group.

The group represented by B in the general formula (II) is preferably a group represented by the general formula (B-1).

In the general formula (B-1), P preferably represents an oxygen atom, and Q is preferably an oxygen atom or the following. Here mark * represents a bond that binds to an _{(X '= Y') n} , ** mark represents a bond that binds to an A _2.

In the formula, G has the same meaning as described in formulas (N-1) and (N-2).

Further, when the group represented by B in the general formula (II) is represented by the following general formula (B-2) or (B-3), it is particularly preferable in the effects of the present invention.

General formula (B-2) General formula (B-3) Wherein * marks the A- (L _{1) v} - represents a bond that binds to, the mark ** - (L ₂₎ represents a bond that binds to an _w -DI, R, q, Q and A ₂ Has the same meaning as described in formula (IV) or (V).

Preferred examples of R in formulas (B-2) and (B-3) include the following. In the following examples, the total carbon number is preferably 15 or less. Aliphatic group (eg, methyl group, ethyl group), alkoxy group (eg, methoxy group, ethoxy group), alkylthio group (eg, methylthio group, ethylthio group), alkoxycarbonyl group (eg, methoxycarbonyl group, propoxycarbonyl group), aryloxy Carbonyl group such as phenoxycarbonyl group, carbamoyl group (for example, N-propylcarbamoyl group, Nt-butylcarbamoyl group, N-ethylcarbamoyl group), sulfonamide group (for example, methanesulfonamide group), acylamino group (for example, An acetamide group), a heterocyclic thio group (for example, a tetrazolylthio group), a hydroxyl group or an aromatic group.

In the general formula (II), the case where both v and w are 0 is a preferable example.

The group represented by A in the general formula (II) is particularly preferably a coupler residue.

Further preferred embodiments of the present invention will be described below.

Particularly preferred DI in the general formula (II) is a compound which has a development inhibiting property when cleaved as DI, but is a compound which does not substantially affect photographic properties after flowing out during color development. It is a development inhibitor having the property of being decomposed (or changed).

For example, U.S. Pat.No.4,477,563, JP-A-60-218,644
No. 60-221,750, No. 60-233,650, or No. 61-
The development inhibitors described in JP-A No. 11,743 are mentioned, and the following general formulas (D-1), (D-2), (D-3) and
(D-4), (D-5), (D-6), (D-7),
(D-8), (D-9), (D-10) or (D-11)
It is represented by

In the formula, an asterisk indicates AL ₁ ) _v -B- in the general formula (II).
(L ₂₎ w _- and represents the position of bond, X represents a hydrogen atom or a substituent, d represents 1 or 2, L ₃ represents a group containing a chemical bond which is cleaved in a developing solution, Y Is a substituent that exerts a development inhibiting action and represents an aliphatic group, an aromatic group, or a heterocyclic group.

The development inhibitor _{A- (L 1) v -B- (} L 2) w - to spread the photographic layers while showing a development inhibiting effect after cleavage from,
Part of the color developing solution flows out. Development inhibitor flowing out in the processing solution is rapidly degraded (e.g. hydrolysis of the ester bond) in the chemical linking moiety contained in such a reaction a hydroxyl ion or hydroxylamine generally included in L ₃ in the processing solution That is, the group represented by Y is cleaved, resulting in a compound having a high water solubility and a small development inhibiting property,
Eventually, the development suppressing effect is substantially eliminated.

X is preferably a hydrogen atom, but may represent a substituent, and the substituent may be an aliphatic group (eg, a methyl group or an ethyl group), an acylamino group (eg, an acetamido group, a propionamido group), or an alkoxy group (eg, Methoxy group, ethoxy group), halogen atom (for example, chloro atom,
Representative examples include a bromo atom), a nitro group, and a sulfonamide group (eg, a methanesulfonamide group).

The linking group represented by L _3, include chemical bonds to cleave in the developer. Examples of such chemical bonds include the examples given in the table below. Each of these is cleaved by a nucleophilic reagent such as hydroxy ion or hydroxylamine which is a component in the color developing solution.

The chemical bonding modes shown in the above table are linked directly or via an alkylene group and / or a phenylene group to the heterocyclic moiety constituting the development inhibitor, and directly linked to Y. When connecting via an alkylene group or a phenylene group, the intervening divalent group may contain an ether bond, an amide bond, a carbonyl group, a thioether bond, a sulfone group, a sulfonamide bond, and a urea bond.

When Y represents an aliphatic group, it is a saturated or unsaturated, linear or branched, chain or cyclic, substituted or unsubstituted hydrocarbon group having 1 to 20, preferably 1 to 10 carbon atoms, particularly preferably It is a hydrocarbon group having a substituent.

When Y represents an aromatic group, it is a substituted or unsubstituted phenyl group or a substituted or unsubstituted naphthyl group.

When Y represents a heterocyclic group, it is a 4- to 8-membered heterocyclic group containing a sulfur atom, an oxygen atom or a nitrogen atom as a hetero atom.

As the heterocyclic ring, for example, a pyridyl group, an imidazolyl group,
Examples include a furyl group, a pyrazolyl group, an oxazolyl group, a thiazolyl group, a thiadiazolyl group, a triazolyl group, a diazolidinyl group, and a diazinyl group.

When the aliphatic hydrocarbon group, the aromatic group, and the heterocyclic group have a substituent, the substituent is a halogen atom, a nitro group, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, Alkanesulfonyl group having 1 to 10 carbon atoms, arylsulfonyl group having 6 to 10 carbon atoms, 1 to 1 carbon atoms
10, alkanamide group, anilino group, benzamide group,
Alkylcarbamoyl group having 1 to 10 carbon atoms, carbamoyl group, arylcarbamoyl group having 6 to 10 carbon atoms, 1 carbon atom
-10 alkylsulfonamide group, C6-C10 arylsulfonamide group, C1-C10 alkylthio group, C6-C10 arylthio group, phthalimide group, succinimide group, imidazolyl group, 1,2, 4-triazolyl group, pyrazolyl group, benzotriazolyl group, furyl group, benzothiazolyl group, alkylamino group having 1 to 10 carbon atoms, alkanoyl group having 1 to 10 carbon atoms, benzoyl group, alkanoyloxy having 1 to 10 carbon atoms Group, benzoyloxy group, C1-C5 perfluoroalkyl group, cyano group, tetrazolyl group, hydroxy group, mercapto group, amino group, C1-C10 sulfamoyl group, C6-C10 arylsulfur Moyl group, morpholino group,
C6-C10 aryl group, pyrrolidinyl group, ureido group, urethane group, C1-C10 alkoxycarbonyl group, C6-C10 aryloxycarbonyl group, imidazolidinyl group or C1-C10 alkylideneamino And the like.

(Examples of Compound) Specific examples of the compound of the present invention will be shown below, but the invention is not limited thereto.

The compound represented by the general formula [I] of the present invention can be synthesized, for example, by the synthesis methods described in JP-A-60-185950, JP-A-61-233741 and JP-A-61-238047.

A typical synthesis example is shown below, but other compounds can be synthesized in the same manner.

Synthesis Example (1) Synthesis of Exemplified Compound (1) The compound was synthesized by the following synthesis route.

First Step (Synthesis of Compound 3 ) 62 g of Compound 2 , 18 g of potassium hydroxide, and 10 ml of water were added to 700 ml of toluene, and the mixture was heated under reflux for 1 hour under a nitrogen atmosphere, and then water was distilled off azeotropically with toluene. N, N-
200 ml of dimethylformamide was added, the mixture was heated to 100 ° C., and 57 g of Compound 1 was added. After reacting at 100 ° C. for 1 hour, the mixture was cooled to room temperature, ethyl acetate was added, and the mixture was transferred to a separating funnel and washed with water. The ethyl acetate layer was removed, and the solvent was distilled off under reduced pressure to obtain 53 g of an oily residue containing 3 as a main component.

Second Step (Synthesis of Compound 4 ) 53 g of 3 obtained above was dissolved in a mixed solvent of 400 ml of ethanol and 120 ml of water, and 40 g of potassium hydroxide was added. The mixture was heated under reflux for 4 hours, neutralized with hydrochloric acid, separated and extracted with ethyl acetate and water, the ethyl acetate layer was separated, and the solvent was distilled off to obtain 43 g of an oily residue containing 4 as a main component.

Third Step (Synthesis of Compound 5 ) 43 g of 4 obtained above was dissolved in 300 ml of ethyl acetate, and 69 g of heptafluorobutanoic anhydride was added dropwise at room temperature. After reaction for 30 minutes, water was added, and the mixture was washed with a separating funnel. After removing the oil layer and distilling off the solvent, column chromatography was performed to isolate and produce the desired product from the residue. Silica gel was used as a filler, and chloroform containing 2.5% ethanol was used as an eluent. 47 g of an oil 5 were obtained.

Fourth Step (Synthesis of Compound 6 ) 5 , 47 g, iron powder, 36.3 g and 10 ml of acetic acid were added to a mixed solvent of 40 ml of water and 400 ml of isopropanol, and the mixture was heated under reflux for 1 hour. The solution was concentrated while heating, and the solution was concentrated to about half. The precipitated crystals were collected by filtration to obtain 44 g of 6 .

Step 5 (Synthesis of Compound 7 ) 44 g of 6 was added to 400 ml of acetonitrile, and the mixture was heated under reflux.
28 g of 2- (2,4-di-t-amylphenoxy) butanoyl chloride was added dropwise. After refluxing for 30 minutes, the mixture was cooled to room temperature, ethyl acetate was added, and the mixture was washed with water using a separating funnel. The oil layer was removed, the solvent was distilled off under reduced pressure, and the residue was recrystallized from acetonitrile to obtain 60 g of 7 .

Sixth step (synthesis of compound 8 ) 7 , 60 g were added to 500 ml of dichloromethane. After cooling to −10 ° C., 34.5 g of boron tribromide was added dropwise. -5 ° C
After reaction for 20 minutes as described below, an aqueous solution of sodium carbonate was added until the aqueous layer became neutral. It was transferred to a separating funnel and washed with water.
The oil layer was removed and the solvent was distilled off under reduced pressure. The residue was recrystallized from acetonitrile to obtain 45.2 g of 8 .

Step 7 (Synthesis of Exemplified Compound (1)) 8 and 45.2 g were added to 600 ml of acetonitrile, and room temperature (25 ° C.)
Then, 100 ml of a chloroform solution containing 20.2 g of 1-phenyltetrazolyl-5-sulfenyl chloride was added dropwise. Ethyl acetate was added and the mixture was transferred to a separating funnel and washed with water. The oil layer was removed and the solvent was distilled off. Recrystallization from a mixed solvent of hexane and ethyl acetate gave 45.3 g of the exemplary compound (1).

Synthesis Example (2) Synthesis of Exemplified Compound (16) In Step 7 of Synthesis Example (1), 1-phenyltetrazolyl-5-sulfenyl chloride was replaced with 1-ethoxycarbonylmethoxycarbonylmethyl- instead of 20.2 g. 5
-Sulfenyl chloride was synthesized in the same manner as in Synthesis Example (1) except that 26.7 g was used. However, a mixed solvent of hexane and chloroform was used as a recrystallization solvent.

Synthesis Example (3) Synthesis of Exemplified Compound (8) The compound was synthesized by the following synthesis route.

First Step (Synthesis of Compound 10 ) 9 (Synthesized by the method described in J. Am Chem Soc., 81 , 4606 (1959)), 147.7 g, potassium hydroxide, 24.6 g and water 15 ml were added to toluene 1. The mixture was refluxed for 1 hour.
Water and toluene were distilled off azeotropically. To the residue, N, N-dimethylformamide (500 ml, 1 , 70 g) and cuprous chloride (0.5 g) were added and reacted at 120 ° C. for 4 hours. After cooling to room temperature, hydrochloric acid 12m
l, 150 ml of water and 500 ml of methanol were added. The precipitated crystals were collected by filtration to obtain 120 g of 10 .

Second Step (Synthesis of Compound 11 ) 55.9 g of 10 was added to a mixed solvent of 300 ml of ethanol and 100 ml of water, and nitrogen gas was passed therethrough. Add 3 parts of potassium hydroxide to this solution.
1.4 g was added and the mixture was heated under reflux for 6 hours. After cooling to room temperature, hydrochloric acid was added for neutralization. 500 ml of ethyl acetate was added, and the mixture was transferred to a separating funnel and washed with water. The oil layer was separated and the solvent was distilled off under reduced pressure. The entire residue (46.2 g) was used in the next step.

Third Step (Synthesis of Compound 12 ) 46.2 g of Compound 11 obtained in the step was dissolved in 500 ml of ethyl acetate. At room temperature, 47.3 g of heptafluorobutanoic anhydride was added dropwise. After reacting at that temperature for 40 minutes, aqueous sodium carbonate was added to neutralize. The oil layer was taken with a separating funnel and washed with water. The oil layer was separated, the solvent was distilled off under reduced pressure, and chloroform was added to the residue to precipitate crystals. This was removed and the filtrate was concentrated to obtain 52.5 g of compound 12 . All of this was used in the next step.

Fourth Step (Synthesis of Compound 13 ) 52.5 g of Compound 12 obtained above, 53 g of reduced iron, 3 g of ammonium chloride and 3 ml of acid acid were added to a mixed solvent of 280 ml of isopropanol and 40 ml of water, and the mixture was heated under reflux for 1 hour. The solution was filtered while hot, and the solution was concentrated under reduced pressure. When the crystals precipitated, concentration was stopped and the mixture was cooled. 45.2
g of compound 13 was obtained.

Fifth Step (Synthesis of Compound 14 ) 45.2 g of compound 13 was added to 500 ml of acetonitrile, and 28.3 g of 2- (2,4-di-t-acylphenoxy) butanoyl chloride was added dropwise under reflux with heating. The mixture was reacted under reflux for 30 minutes, cooled to room temperature, added with 500 ml of ethyl acetate, and washed with water. The oil layer was separated and the solvent was distilled off under reduced pressure. The residue was recrystallized from ethyl acetate and n-hexane to obtain 14 (56.7 g).

Sixth Step (Synthesis of Compound 15 ) 56.7 g of 14 was added to a mixed solvent of 250 ml of tetrahydrofuran, 250 ml of acetonitrile and 10 ml of N, N-dimethylformamide, and 42.4 g of thionyl chloride was added dropwise at room temperature. After reacting for 30 minutes, the mixture was cooled to -10 ° C. To this solution, 67.7 g of propylamine was added dropwise while maintaining the temperature at 0 ° C. or lower. After reacting at that temperature for 30 minutes, ethyl acetate was added and washed with water.
The oil layer was separated and the solvent was distilled off under reduced pressure. 45.2 g by recrystallizing the residue from a mixed solvent of ethyl acetate and hexane
I got 15 .

Seventh Step (Synthesis of Compound 16 ) 45.2 g of 15 was added to a mixed solvent of 300 ml of methanol and 15 ml of hydrochloric acid, and the mixture was heated under reflux for 1 hour. After cooling to room temperature, 200 ml of water was added, and the precipitated crystals were collected by filtration to obtain 28.6 g of 16 .

Eighth Step (Synthesis of Exemplified Compound (8)) 28.6 g of 16 was added to 600 ml of tetrahydrofuran, cooled to -10 ° C, and 4.6 g of aluminum chloride was added. 1-
Phenyltetrazolyl-5-sulfenyl chloride 8.8 g
60 ml of a dichloromethane solution containing was added dropwise. After reacting at -10 ° C for 30 minutes, ethyl acetate and water were added. The oil layer was separated with a separating funnel and washed with water. The oil layer is taken, the solvent is distilled off under reduced pressure, and the residue is recrystallized from a mixed solvent of hexane and ethanol to obtain 24.9 g of the desired exemplified compound (8).
I got

Synthesis Example (4) Synthesis of Exemplified Compound (17) In the eighth step of Synthesis Example (3), 16.8 was used instead of 8.8 g of 1-phenyltetrazolyl-5-sulfenyl chloride.
Synthesis was performed in the same manner as in Synthesis Example (3) except that g of 5- (4-methoxycarbonylphenoxycarbonylmethylthio) -1,3,4-thiadiazolyl-2-sulfenyl chloride was used.

Synthesis Example (5) Synthesis of Exemplified Compound (18) I've had it. After drying, 19.6 g of compound 5 was obtained as white crystals.

(Synthesis of Compound 17 ) Compound 13 (19.6 g) was iron powder (15 g), ammonium chloride (1 g), water
To a mixture of 10 ml and 80 ml of isopropyl alcohol, 1 ml of acetic acid was added, and the mixture was refluxed for 20 minutes. After the reaction solution was passed to remove iron powder, the solution was concentrated under reduced pressure.
Further, 100 ml of acetonitrile was added thereto, and 2,4-di-te
9.0 g of rt-amylphenoxyacetyl chloride was added dropwise at 40 ° C. After stirring for 1 hour, the precipitated crystals were collected to obtain 21.2 g of Compound 17 .

(Synthesis of Compound 18 ) 21.2 g of Compound 17 was dissolved in 100 ml of dimethylacetamide, and 5.4 g of thionyl chloride was added dropwise at 0 ° C. After stirring for 30 minutes, the reaction solution was cooled to −10 ° C., and 50 ml of a dimethylacetamide solution of 8.1 g of propylamine was added dropwise so as not to exceed 0 ° C. After stirring for 2 hours, the reaction product was extracted with ethyl acetate, and after washing with water, the solvent was distilled off.

60 ml of acetic acid and 2 ml of hydrochloric acid were added to the obtained crude crystals, and the mixture was refluxed for 1 hour. After cooling, 120 ml of water was slowly dropped into the reaction solution to precipitate crystals. After passing through the crystals, the crystals were washed with acetonitrile to obtain 12.9 g of compound 18 as white crystals.

(Synthesis of Exemplified Compound (18)) Compound 18 , 12.9 g, and 2- (2-methoxycarbonyl)
Ethylthio-5-chlorothio-1,3,4-thiadiazole, 17.4 g and 4.2 g of triphenylphosphine were dissolved in 130 ml of tetrahydrofuran and refluxed for 2 hours.

The reaction product was extracted with ethyl acetate, washed with water and the solvent was distilled off. Further, crystallization was performed with chloroform and hexane to obtain 10.0 g of the exemplified compound (18). (Mp218.0 ~
In 219.0 ° C.) Synthesis of Synthesis Example (6) Synthesis Example Compound of Exemplified Compound (19) (18), the Compound 13 2,4
Exemplified compound (19) was synthesized in exactly the same manner except that α- {2,4-di-tert-amylphenoxy} butanoyl chloride was used in place of di-tert-amylphenoxyacetyl chloride (mp207. 0-212.0 ° C).

Synthesis Example (7) Synthesis of Exemplified Compound (34) In the synthesis method of Exemplified Compound (18), 2- (2-methoxycarbonyl) ethylthio-5-chlorothio-1,3,4
Exemplified compound (19) was synthesized in exactly the same manner except that 2-methoxycarbonylthio-5-chlorothio-1,3,4-thiadiazole was used in place of -thiadiazole (mp 208.0-209.0 ° C). .

Synthesis Example (8) Synthesis of Exemplary Compound (26) In the synthesis method of Exemplary Compound (18), 2- (2-methoxycarbonyl) ethylthio-5-chlorothio-1,3,4
-Instead of thiadiazole, 2- (1-methoxycarbonylthio-1-methyl) methylthio-5-chlorothio-
Exemplified compound (26) was synthesized in exactly the same manner except that 1,3,4-thiadiazole was used (mp 136.0 to 138.0).
° C).

The compound represented by the general formula [I] of the present invention is preferably added to a light-sensitive silver halide emulsion layer or a layer adjacent thereto in a light-sensitive material.
⁻⁶ to 1 × 10 ⁻³ mol / m ² , preferably 3 × 10 ^{−6 to} 5 ×
Preferably from 10 ^-4 mol / m ² is ^{1 × 10 -5 ~2 × 10 -4} mol / m 2.

As for the method of adding the compound represented by the general formula [I] of the present invention, the compound can be added in the same manner as in a usual coupler as described later.

Various color couplers can be used in the present invention, and specific examples thereof are described in the above-mentioned patents described in Research Disclosure (RD) No. 17643, VII-CG.

As a yellow coupler, for example, U.S. Pat.
No. 501, No. 4,022,620, No. 4,326,024, No. 4,40
No. 1,752, JP-B-58-10739, UK Patent No. 1,425,020
And Nos. 1,476,760 and the like.

As the magenta coupler, 5-pyrazolone-based and pyrazoloazole-based compounds are preferable, and US Patent No. 4,310,
No. 619, No. 4,351,897, European Patent No. 73,636, U.S. Pat. No. 3,061,432, No. 3,725,067, Research Disclosure No. 24220 (June 1984) JP-A-60-33552
No., Research Disclosure No. 24230 (June 1984)
), JP-A-60-43659, U.S. Pat. Nos. 4,500,630 and 4,540,654 are particularly preferred.

Cyan couplers include phenolic and naphthol couplers, U.S. Pat.Nos. 4,052,212, 4,146,396, 4,228,233, 4,296,200,
No. 2,369,929, No. 2,801,171, No. 2,772,162, No. 2,895,826, No. 3,772,002, No. 3,758,308,
No. 4,334,011, No. 4,327,173, West German Patent Publication No. 3,
No. 329,729, European Patent No. 121,365A, U.S. Patent No. 3,446,6
No. 22, No. 4,333,999, No. 4,451,559, No. 4,427,
No. 767, EP 161,626A and the like are preferred.

Colored couplers for correcting unwanted absorption of coloring dyes are described in Research Disclosure No.17643 VII.
Section G, U.S. Pat.No. 4,163,670, JP-B-57-39413,
U.S. Pat.Nos. 4,004,929 and 4,138,258; British Patent No.
Those described in 1,146,368 are preferred.

As a coupler in which the coloring dye has an appropriate diffusivity,
Preferred are those described in U.S. Pat. No. 4,336,237, British Patent No. 2,125,570, European Patent No. 96,570, and West German Patent (Published) No. 3,234,533.

Typical examples of polymerized dye-forming couplers include U.S. Patent Nos. 3,451,820, 4,080,211 and 4,367,282.
And British Patent No. 2,102,173.

Couplers that release a photographically useful residue upon coupling may be used simultaneously in the present invention. DIR couplers releasing a development inhibitor are described in the above-mentioned RD17643, Patents described in VII to F, JP-A-57-151944 and JP-A-57-154234.
And Nos. 60-184248 and U.S. Pat. No. 4,248,962 are preferred.

Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include UK Patent Nos. 2,097,140 and 2,1
No. 31,188, JP-A Nos. 59-157638 and 59-170840 are preferred.

In addition, as couplers that can be used in the light-sensitive material of the present invention, competitive couplers described in U.S. Pat.No. 4,130,427, U.S. Pat.Nos. 4,283,472 and 4,338,393,
Examples thereof include a multi-equivalent coupler described in JP-A-4,310,618 and a coupler that releases a dye that recolors after release described in EP-A-173,302A.

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

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

The steps and effects of the latex dispersion method, and specific examples of the latex for impregnation are described in U.S. Pat. No. 4,199,363 and West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.

Suitable supports that can be used in the present invention include, for example, those described above.
No. 17643, page 28, and No. 18716, page 647, right column to page 648, left column.

The color photographic light-sensitive material according to the present invention is described in RD.No.
Developing can be carried out by a conventional method described in 17643, pp. 28-29, and No. 18716, 651, left column to right column.

The color photographic light-sensitive material of the present invention is usually subjected to washing or stabilization after development, bleach-fixing or fixing.

In the water washing step, two or more tanks are generally countercurrently washed to save water. As a stabilizing treatment, a multi-stage countercurrent stabilizing treatment as described in JP-A-57-8543 is exemplified as a representative example instead of the washing step.

 Next, preferred processing steps of the present invention will be described.

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

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

The processing bath having bleaching ability generally refers to a bleaching solution and a bleach-fixing solution, but in the present invention, a bleaching solution is preferred in terms of excellent bleaching power. The desilvering step of the present invention includes, for example, the following steps, but is not limited thereto.

Bleaching-Fixing Bleaching-Bleaching-Fixing Bleaching-Fixing Bleaching-Fixing-Bleaching-Fixing Bleaching-Washing-Fixing In particular, the steps and steps are preferred in order to exert the effects of the present invention.

The bleaching agent of the present invention comprises at least one ferric complex salt of a compound selected from the above-mentioned compound (A) and 1,3-diaminopropanetetraacetic acid ferric complex salt in a molar ratio of the former to the latter of 3 or less. (Including 0). The preferred molar ratio is 1.8 to 0.5. If the molar ratio exceeds 3, the bleaching power decreases, resulting in poor desilvering. When the ratio of ferric salt of 1,3-diaminopropanetetraacetic acid is extremely high, bleaching fog may be slightly generated.

The amount of the bleaching agent of the present invention is 0.05 mol to 1 mol, preferably 0.1 mol to 0.5 mol, per 1 bath having bleaching ability.

Other than the above-mentioned iron (III) complex with aminopolycarboxylic acid, an aminopolycarboxylic acid group can be added to the processing solution having the bleaching ability of the present invention. It is particularly preferable to add a compound of the compound group (A). A preferable addition amount is from 0.0001 mol to 0.1 mol /, more preferably from 0.003 mol to 0.05 mol /.

The aminopolycarboxylic acid and its ferric complex salt are usually preferably used in the form of an alkali metal salt or an ammonium salt, and an ammonium salt is particularly preferable in terms of excellent solubility and bleaching power.

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

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

For such bleaching accelerators, for example, U.S. Patent No. 3,893,858, German Patent No. 1,290,812, British Patent No. 1,138,842, JP-A-53-95630, Research Disclosure No. 17129 (1978
A compound having a mercapto group or a disulfide group, a thiazolidine derivative described in JP-A-50-140129, a thiourea derivative described in U.S. Pat. No. 3,706,561; The iodides described in 16235, the polyethylene oxides described in German Patent No. 2,748,430, the polyamine compounds described in JP-B-45-8836, and the like can be used. Particularly preferred are mercapto compounds as described in GB 1,138,842.

In particular, in the present invention, the following general formulas (IA) to (VI
The bleaching accelerator represented by A) can be preferably used because of its excellent bleaching ability and low bleaching fog.

Formula (IA) R ^1A -SM ^{1A In the} formula, M ^1A represents a hydrogen atom, an alkali metal atom, or ammonium. R ^1A represents an alkyl group, an alkylene group, an aryl group, or a heterocyclic residue. The number of carbon atoms of the alkyl group is preferably 1 to 5, and most preferably 1 to 3. The preferred carbon number of the alkylene group is 2 to 5. Examples of the aryl group include a phenyl group and a naphthyl group, and a phenyl group is particularly preferable. As the heterocyclic residue, a nitrogen-containing 6-membered ring such as pyridine and triazine and a nitrogen-containing 5-membered ring such as azole, pyrazole, triazole and thiadiazole are preferable. Particularly preferred is an atom. R ^1A may be further substituted with a substituent.
Examples of the substituent include an alkyl group, an alkylene group, an alkoxy group, an aryl group, a carboxy group, a sulfo group, an amino group, an alkylamino group, a dialkylamino group, a hydroxy group, a carbamoyl group, a sulfamoyl group, and a sulfonamide group. Can be.

Of the general formula (IA), preferred are those represented by the general formula (IA
-1) to (IA-4).

General formula (IA-1) In the formula, R ^2A , R ^3A and R ^4A may be the same or different, and represent a hydrogen atom, a substituted or unsubstituted lower alkyl group (preferably having 1 to 5 carbon atoms, particularly preferably a methyl group, an ethyl group, and a propyl group. ) Or an acyl group (preferably having 1 carbon atom)
To 3, for example, an acetyl group and a propionyl group), and kA is an integer of 1 to 3. ^Z1A is an anion (chlorine ion, bromine ion, nitrate ion, sulfate ion, p-
Toluenesulfonate, oxalate, etc.).
kA represents 0 or 1, and iA represents 0 or 1.

R ^2A and R ^3A may be linked together to form a ring.
R ^2A , R ^3A and R ^4A are preferably a hydrogen atom or a substituted or unsubstituted lower alkyl group.

Here, the substituents of R ^2A , R ^3A , and R ^4A are preferably a hydroxy group, a carboxy group, a sulfo group, an amino group, and the like.

General formula (IA-2) General formula (IA-3) General formula (IA-4) In the formula, R ^5A represents a hydrogen atom, a halogen atom (eg, a chlorine atom or a bromine atom), an amino group, a substituted or unsubstituted lower alkyl group (preferably having 1 to 5 carbon atoms, particularly a methyl group, an ethyl group, a propyl group) Are preferred), an amino group having an alkyl group (a methylamino group, an ethylamino group,
Dimethylamino group, diethylamino group, etc.) represents a substituted or unsubstituted alkylthio group.

Here, as the substituent that R ^5A has, a hydroxy group,
Examples include a carboxy group, a sulfo group, an amino group, and an amino group having an alkyl group.

Formula (II A) R ^1A -S—S—R ^{6A In the} formula, R ^1A is the same as R ^{1A in} Formula (IA), and R ^6A is
Synonymous with R ^1A . R ^1A and R ^6A may be the same or different.

Among the general formula (II A), preferred are those represented by the general formula (II
A-1).

General formula (II A-1) In the formula, R ^7A , R ^8A and R ^9A have the same ^meanings as R ^2A , R ^3A and R ^4A .
hA and kA and Z ^1A is hA and kA the general formula (IA-1), is the same as Z ^1A. iB represents 0, 1 or 2.

General formula (III) In the formula, R ^10A and R ^11A may be the same or different, and each is a hydrogen atom, an alkyl group which may have a substituent (preferably a lower alkyl group, for example, a methyl group, an ethyl group, a propyl group), A phenyl group which may have a substituent, or a heterocyclic residue which may have a substituent (more specifically, a compound containing at least one hetero atom such as a nitrogen atom, an oxygen atom, and a sulfur atom) And a heterocyclic group, for example, a pyridine ring, a thiophene ring, a thiazolidine ring, a benzoxazole ring, a benzotriazole ring, a thiazole ring, an imidazole ring and the like. R ^12A represents a hydrogen atom or a lower alkyl group which may have a substituent (eg, a methyl group, an ethyl group, etc., preferably having 1 to 3 carbon atoms).

Here, the substituents of R ^10A to R ^12A include a hydroxy group, a carboxy group, a sulfo group, an amino group, a lower alkyl group and the like.

R ^13A represents a hydrogen atom, an alkyl group, or a carboxy group.

General formula (IV A) In the formula, R ^14A , R ^15A , R ^16A may be the same or different,
Each represents a hydrogen atom or a lower alkyl group (for example, a methyl group, an ethyl group, etc., preferably having 1 to 3 carbon atoms). kB represents an integer of 1 to 5.

X ^1A represents an amino group, a sulfo group, a hydroxy group, a carboxy group, or a hydrogen atom which may have a substituent. The substituent represents a substituted or unsubstituted alkyl group (for example, a methyl group, an ethyl group, a hydroxyalkyl group, an alkoxyalkyl group, a carboxyalkyl group, etc.), and the two alkyl groups may form a ring.

R ^14A , R ^15A and R ^16A may be linked to each other to form a ring. R ^{14A to} R ^16A are particularly preferably a hydrogen atom, a methyl group or an ethyl group, and X ^1A is preferably an amino group or a dialkylamino group.

General formula (VA) Here, A ^1A is an n-valent aliphatic linking group, aromatic linking group, or heterocyclic linking group. (When n = 1, A ^1A represents a mere aliphatic group, aromatic group, or heterocyclic group. ) The aliphatic coupler group represented by A ^1A has 3 carbon atoms.
To 12 alkylene groups (for example, trimethylene, hexamethylene, cyclohexylene, etc.).

Examples of the aromatic linking group include an arylene group having 6 to 18 carbon atoms (eg, phenylene, naphthylene, etc.).

Examples of the heterocyclic linking group include a heterocyclic group (for example, thiophene, furantriazine, pyridine, piperidine, etc.) comprising one or more heteroatoms (for example, oxygen atom, sulfur atom, nitrogen atom).

Here, the number of the aliphatic linking group, the aromatic linking group, and the heterocyclic linking group is usually one, but two or more linking groups may be linked, and the linking type may be directly or divalent linking group (for example,- O
-, -S-, It may be —SO ₂ —, —CO— or a linking group formed from these linking groups, and R ^20A represents a lower alkyl group. ).

The aliphatic linking group, aromatic linking group, and heterocyclic linking group may have a substituent.

Examples of the substituent include an alkoxy group, a halogen atom, an alkyl group, a hydroxy group, a carboxy group, a sulfo group, a sulfonamide group, and a sulfamoyl group.

X ^2A is -O-, -S-, Wherein R ^21A represents a lower alkyl group (eg, a methyl group, an ethyl group, etc.), and R ^17A and R ^18A represent a substituted or unsubstituted lower alkyl group (eg, a methyl group, an ethyl group, a propyl group, an isopropyl group) Group, a pentyl group, etc.), and the substituent includes a hydroxy group, a lower alkoxy group (for example, methoxy group, methoxyethoxy group, hydroxyethoxy group, etc.), an amino group (for example, unsubstituted amino group, dimethylamino group, An N-hydroxyethyl-N-methylamino group) is preferred. Here, when there are two or more substituents, they may be the same or different.

R ^19A is a lower alkylene group having 1 to 5 carbon atoms (methylene,
Ethylene, represents trimethylene, methyl methylene, etc.), Z ^2A is an anion (halide ions (chlorine ion, bromine ion), represents a nitrate ion, sulfate ion, p- toluenesulfonate, and oxalate etc.).

R ^17A and R ^18A are linked via a carbon atom or a hetero atom (eg, an oxygen atom, a nitrogen atom, a sulfur atom) to form a 5- or 6-membered hetero ring (eg, a pyrrolidine ring, a piperidine ring, a morpholine ring, a triazine ring). Or an imidazolidine ring).

R ^17A (or R ^18A ) and A are linked via a carbon atom or a hetero atom (eg, an oxygen atom, a nitrogen atom, a sulfur atom) to form a 5- or 6-membered hetero ring (eg, a hydroxyquinoline ring, a hydroxyindole ring, An isoindoline ring).

Further, R ^17A (or R ^18A ) and R ^19A are carbon atoms or hetero atoms (eg, oxygen, nitrogen, sulfur atoms)
And may form a 5- or 6-membered heterocyclic ring (eg, a piperidine ring, a pyrrolidine ring, a morpholine ring, etc.). lA is 0 or 1, mA is 0 or 1, nA is 1, 2
Or 3, pA is 0 or 1, and qA is 0, 1, 2, or 3.
Represents

General formula (VI A) Wherein, X ^1A, kB is X ^1A of the general formula (VI A), the same as kB.

M ^2A is a hydrogen atom, an alkali metal atom, ammonium,
Or Represents R ^22A represents a hydrogen atom or a lower alkyl group (having 1 to 5 carbon atoms and optionally having a substituent).

Specific examples of the compounds represented by formulas (IA) to (VI A) are shown below.

Among the above-mentioned bleaching accelerators, particularly preferred compounds are IA-
2, IA-5, IA-13, IA-14, IA-15, IA-16, I
A-19, IIA-1, IIA-11, VA-1, VIA-1, and VIA-2.

The amount of the bleaching accelerator added is 0.
01 g to 20 g, preferably 0.1 g to 10 g.

The bleaching solution constituting the present invention contains, in addition to the bleaching agent and the above compound, a bromide such as potassium bromide, sodium bromide, ammonium bromide or a chloride such as potassium chloride, sodium chloride or ammonium chloride. An agent can be included. The concentration of the rehalogenating agent is 0.1 to 5 mol, preferably 0.5 to 3 mol, per bleaching solution. In addition, sodium nitrate, nitrates such as ammonium nitrate, boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate,
It is possible to add one or more kinds of inorganic acids, organic acids, and salts thereof having a pH buffering ability, such as tartaric acid, which are known to be generally used in a bleaching solution.

The pH of the bath having the bleaching ability of the present invention is generally from 6 to 1, preferably from 5.8 to 1.5, most preferably from 5.3 to 2. In a preferred pH range, there is little bleaching fog,
Also, desilvering performance is excellent.

The replenishment rate of the bath having bleaching ability of the present invention the photosensitive material 1 m ² per 50Ml～2000ml, preferably 100Ml～1000ml.

In the present invention, after processing in a bath having bleaching ability, processing is generally performed in a bath having fixing ability. However, this does not apply when the bath having bleaching ability is a bleach-fixing solution.

The bath having the fixing ability of the present invention refers to a bleach-fix bath or a fixing bath.

As fixing agents for these baths having fixing ability, thiosulfates such as sodium thiosulfate, ammonium thiosulfate, sodium ammonium thiosulfate and potassium thiosulfate;
Sodium thiocyanate, ammonium thiocyanate,
Thiocyanates such as potassium thiocyanate, thiourea, thioether and the like can be used. The amount of these fixing agents is 0.3 mol to 3 mol per processing solution, preferably
0.5 mol to 2 mol.

The bath having a fixing ability should contain a sulfite as a preservative, such as sodium sulfite, potassium sulfite, ammonium sulfite, and a bisulfite adduct of hydroxylamine, hydrazine, and an aldehyde compound, such as sodium acetaldehyde bisulfite. Can be. Further, various fluorescent whitening agents, defoaming agents or surfactants, and organic solvents such as polyvinylpyrrolidone and methanol can be contained.
It is preferable to use the sulfinic acid compound described in 3831.

Preferably 3000ml from the photosensitive material 1 m ² per 300ml as replenishing amount of the bath having fixing ability but, more preferably 300ml
From 1000ml.

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

The shorter the total time of the desilvering step of the present invention, the more remarkable the effect of the present invention can be obtained. The preferred time is 1 minute to 4 minutes, more preferably 1 minute 30 seconds to 3 minutes. The processing temperature is from 25 ° C to 50 ° C, preferably from 35 ° C to 45 ° C. In a preferable temperature range, the desilvering speed is improved, and generation of stain after processing is effectively prevented.

In the desilvering step of the present invention, it is preferable that stirring is strengthened as much as possible in order to more effectively exert the effects of the present invention.

As a specific method of strengthening stirring, JP-A-62-183460,
JP-A-62-183461 describes a method of impinging a jet of a processing solution on an emulsion surface of a light-sensitive material, a method of increasing a stirring effect by using a rotating means disclosed in JP-A-62-183461, and further, a method of immersion in a liquid. There are a method of improving the stirring effect by moving the photosensitive material while bringing the emulsion surface into contact with the wiper blade to make the emulsion surface turbulent, and a method of increasing the circulation flow rate of the entire processing solution. Such a stirring improving means is effective in any of the bleaching solution, the bleach-fixing solution and the fixing solution. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film, thereby increasing the desilvering speed.

Further, the means for improving the stirring is more effective when a bleaching accelerator is used, and can significantly increase the accelerating effect or eliminate the fixing inhibition effect of the bleaching accelerator.

The automatic developing machine used in the present invention is disclosed in JP-A-60-191257.
It is preferable to have the photosensitive material conveying means described in JP-A Nos. 191258 and 191259. As described in Japanese Patent Laid-Open No. 191257/1985, such a conveying means can significantly reduce the carry-in of the processing solution from the pre-bath to the post-bath, and is highly effective in preventing the performance price of the processing solution. Such an effect is particularly effective for reducing the processing time in each step and reducing the replenishing amount of the processing solution.

The color developer used in the present invention contains a known aromatic primary amine color developing agent. A preferred example is a p-phenylenediamine derivative, representative examples of which are shown below, but are not limited thereto.

D-1 N, N-diethyl-p-phenylenediamine D-2 2-amino-5-diethylaminotoluene D-3 2-amino-5- (N-ethyl-N-laurylamino) toluene D-4 4- [ N-ethyl-N- (β-hydroxyethyl) amino] aniline D-5 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline D-6 4-amino-3-methyl -N-ethyl-N-
[Β- (methanesulfonamido) ethyl] -anion D-7 N- (2-amino-5-diethylaminophenylethyl) methanesulfonamide D-8 N, N-dimethyl-p-phenylenediamine D-9 4-amino -3-Methyl-N-ethyl-N-methoxyethylaniline D-10 4-Amino-3-methyl-N-ethyl-N-β
-Ethoxyethylaniline D-11 4-amino-3-methyl-N-ethyl-N-β
-Butoxyethylaniline Among the above p-phenylenediamine derivatives, particularly preferred is Exemplified Compound D-5.

Further, these p-phenylenediamine derivatives may be salts such as sulfate, hydrochloride, sulfite, and p-toluenesulfonate. The amount of the aromatic primary amine developing agent to be used is preferably about 0.1 g to about 20 g, more preferably about 0.5 g to about 10 g, per developer.

Further, as a preservative, a sulfite such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite, potassium metasulfite, or a carbonyl sulfite adduct is added to the color developer as necessary. be able to.

The preferred addition amount is 0.5 g to 10 g per color developer.
More preferably, it is 1 g to 5 g.

Examples of compounds which directly preserve the color developing agent include various hydroxylamines, hydroxamic acids described in Japanese Patent Application No. 61-186559, hydrazines described in JP-A-61-170756, hydrazides, and hydrazides described in JP-A-61-188742. No. 61-2032
Phenols described in No. 53, α-hydroxyketones and α-aminoketones described in No. 61-188741, and / or
It is preferable to add various sugars described in JP-A-61-180616. Also, in combination with the above compound, Japanese Patent Application No. 61-147823,
Nos. 61-166674, 61-165621, 61-164515,
Monoamines described in 61-170789, 61-168159, etc., 61-173595, 61-164515, 61-186560
No. 61-165621 and No. 61-165621.
Polyamines described in 169789, polyamines described in 61-1888619, nitroxy radicals described in 61-197760, alcohols described in 61-186561 and 61-197419, 61-198987 The oximes described therein, and 61-26 of the same.
It is preferable to use tertiary amines described in No. 5149.

Other preservatives include JP-A Nos. 57-44148 and 57-5.
Various metals described in 3749, salicylic acids described in JP-A-59-180588, alkanolamines described in JP-A-54-3532, polyethyleneimines described in JP-A-56-94349, U.S. Pat. An aromatic polyhydroxy compound described in 3,746,544 may be contained as necessary. Particularly, addition of an aromatic polyhydroxy compound is preferred.

The color developer used in the book is preferably pH 9-1.
2, more preferably 9 to 11.0, and the color developer may further contain a compound of a known developer component.

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

Specific examples of the buffer include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate,
Sodium tetraborate (borax), potassium tetraborate, o
-Sodium hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, 5-sulfo-
Examples thereof include sodium 2-hydroxybenzoate (sodium 5-sulfosalicylate) and potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate). However, the invention is not limited to these compounds.

The amount of the buffer added to the color developer was 0.1 mol / mol.
It is preferably at least 0.1 mol / -0.4 mol / m.

In addition, various chelating agents can be used in the color developer as a precipitation inhibitor for calcium or magnesium, or for improving the stability of the color developer.

As the chelating agent, an organic acid compound is preferable, and examples thereof include aminopolycarboxylic acids, organic phosphonic acids, and phosphonocarboxylic acids. Specific examples are shown below, but the present invention is not limited thereto.

Nitrilotriacetic acid, diethyltriaminepentaacetic acid, ethylenediaminetetraacetic acid, N, N, N-trimethylenephosphonic acid,
Ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid, transcyclohexanediaminetetraacetic acid, 1,2
-Diaminopropanetetraacetic acid, hydroxyethyliminodiacetic acid, glycol ether diaminetetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N , N'-bis (2-hydroxybenzyl) ethylenediamine-N, N'-diacetic acid, and two or more of these chelating agents may be used in combination, if necessary.

These chelating agents may be added in an amount sufficient to block the metal ions in the color developer. For example, 1
It is about 0.1g to 10g per unit.

An optional development accelerator can be added to the color developer as needed. However, it is preferred that the color developer of the present invention does not substantially contain benzyl alcohol from the viewpoints of pollution, liquid preparation and prevention of color contamination. Here, "substantially" means that the developer contains no more than 2 ml, preferably no developer.

Other development accelerators include JP-B-37-16088,
7-5987, 38-7826, 44-12380, 45-9919
Thioether compounds disclosed in U.S. Pat. No. 3,813,247 and US Pat. No. 3,813,247; p-phenylenediamine compounds disclosed in JP-A-52-49829 and JP-A-50-15554;
-137726, JP-B-44-30074, JP-A-56-156826 and JP-A-52-43429, etc., quaternary ammonium salts, U.S. Pat.Nos. 2,494,903, 3,128,182, 4,23
Nos. 0,796, 3,253,919, JP-B-41-11431, U.S. Patent Nos. 2,482,546, 2,596,926 and 3,582,346, etc., and the amine compounds described in JP-B-37-16088, 42-2.
No. 5201, U.S. Pat.No. 3,128,183, JP-B-41-11431,
No. 42-23883 and U.S. Pat.No. 3,532,501, polyalkylene oxides and other 1-phenyl-3
-Pyrazolidones, imidazoles and the like can be added as needed.

In the present invention, an optional antifoggant can be added as required. As the antifoggant, alkali metal halides such as sodium chloride, potassium bromide and potassium iodide and organic antifoggants can be used. Examples of organic antifoggants include benzotriazole, 6-
Nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-
Representative examples include nitrogen-containing heterocyclic compounds such as thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine.

The color developer used in the present invention may contain a fluorescent whitening agent. As the fluorescent brightening agent, a 4,4'-diamino-2,2'-disulfonestilbene compound is preferable. The addition amount is 0 to 5 g / preferably 0.1 g to 4 g /.

If necessary, various surfactants such as alkylsulfonic acid, arylphosphonic acid, aliphatic carboxylic acid and aromatic carboxylic acid may be added.

The processing temperature of the color developer of the present invention is from 20 to 50C, preferably from 30 to 45C. Processing time is 20 seconds to 5 minutes, preferably 30
Seconds to 3 minutes. The replenishment amount is preferably smaller, but is preferably 100 to 1500 ml, preferably 100 to 800 ml, per m ^{2 of} the light-sensitive material.
More preferably, it is 100 ml to 400 ml.

Also, the color developing bath is divided into two or more baths as necessary,
Replenish the color developer replenisher from the last bath or the last bath,
The development time and the replenishment amount may be reduced.

The processing method of the present invention can also be used for color reversal processing. In the present invention, a so-called black-and-white first developing solution used for reversal processing of a color photographic light-sensitive material which is generally known as a black-and-white developing solution used at this time, or a solution used for processing a black-and-white photosensitive material can be used. In addition, various well-known additives generally added to a black-and-white developer can be contained.

Typical additives include developing agents such as 1-phenyl-3-pyrazolidone, methol and hydroquinone, preservatives such as sulfites, and accelerators composed of alkalis such as sodium hydroxide, sodium carbonate and potassium carbonate. , Potassium bromide, 2-methylbenzimitazole,
Examples thereof include inorganic or organic inhibitors such as methylbenzthiazole, water softeners such as polyphosphate, and a development inhibitor comprising a small amount of iodide or a mercapto compound.

The processing method of the present invention comprises the above-described processing steps such as color development, bleaching, bleach-fixing and fixing. here,
After the bleach-fixing or fixing step, processing steps such as washing and stabilization are generally performed. However, after a bath having a fixing ability, a simple stabilization treatment without substantial washing is performed. Processing methods can also be used.

Known additives can be added to the washing water used in the washing step, if necessary. For example, water softeners such as inorganic phosphoric acid, aminopolycarboxylic acid, and organic phosphoric acid, fungicides that prevent the growth of various bacteria and algae, and deterrents (eg, isothiazolone, organochlorine fungicides, benzotriazole, etc.) , A drying load, and a surfactant for preventing unevenness can be used. Or LE
West, “Water Quality Criteria”, Phot.Sci.and.Eng., V
ol. 9, No. 6, pages 344 to 359 (1965) and the like can also be used.

As the stabilizing solution used in the stabilizing step, a processing solution that stabilizes the dye image is used. For example, a liquid having a buffer capacity of pH 3 to 6, a liquid containing an aldehyde (for example, formalin), or the like can be used. The stabilizing solution may contain, as necessary, a metal compound such as an ammonium compound, Bi, or Al, a fluorescent brightener, a chelating agent (eg, 1-hydroxyethylidene-1,1-diphosphonic acid), a bactericide, and a deodorant. , A hardener, a surfactant and the like can be used.

In the washing step and the stabilizing step, a multi-stage countercurrent system is preferable, and the number of stages is preferably two to four. The replenishing amount is 1 to 50 times, preferably 2 to 30 times, more preferably 2 to 15 times the amount brought in from the previous bath per unit area.

Water used in these washing or stabilizing steps is not limited to tap water, and may be C
a, It is preferable to use water deionized to an Mg concentration of 5 mg / or less, water that has been sterilized by halogen, an ultraviolet germicidal lamp, or the like.

In the above-described processing steps of the photosensitive material, when the continuous processing is performed by the automatic developing machine, the processing solution may be concentrated due to evaporation, particularly when the processing amount is small or the opening area of the processing solution is large. Becomes In order to correct such concentration of the processing solution, it is preferable to replenish an appropriate amount of water or a correction solution.

In addition, the amount of waste liquid can also be reduced by using a method in which the overflow solution in the washing step or the stabilization step is flowed into a bath having a fixing ability, which is a pre-bath.

(Examples) Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto.

Example 1 On a cellulose triacetate film support having an undercoat, a multilayer color photographic light-sensitive material sample 101 comprising the following tanks was prepared.

The amount coated amount (Composition of photosensitive layer) is represented in units of g / m ² of silver for silver halide and colloidal silver, also couplers, the amount for the additives and gelatin, expressed in units of g / m ^2, The sensitizing dyes are shown in terms of moles per mole of silver halide in the same layer.

First layer: Anti-halation layer Black colloidal silver Silver 0.37 U-1 0.027 U-2 0.055 U-3 0.064 HBS-3 0.076 Gelatin 2.81 Second layer: Intermediate layer U-1 0.027 U-2 0.054 U-3 0.063 HBS- 3 0.076 Gelatin 1.52 Third layer: First red-sensitive emulsion layer Silver iodobromide emulsion 0.43 AgI 10% mol%, equivalent sphere diameter 0.9μ Variation coefficient 28.8% Diameter / thickness ratio 5.1 Silver iodobromide emulsion Silver 0.11 AgI4 mol% Sphere equivalent diameter 0.6μ Variation coefficient 36.6% Diameter / thickness ratio 3.4 Silver iodobromide emulsion 0.55 AgI 2 mol%, sphere equivalent diameter 0.45μ Variation coefficient 28% Diameter / thickness ratio 2.7 Sensitizing dye I 4.7 × 10 ^-3 C -1 0.14 C-2 0.15 C-3 0.08 C-5 0.08 HBS-1 0.06 HBS-2 0.13 C-10 0.14 Gelatin 1.66 Fourth layer: Second red-sensitive emulsion layer Silver iodobromide emulsion (AgI 3.5 mol%) , Ball equivalent diameter 0.35μ diameter /
Thickness ratio 1.0 Coefficient of variation 10.6%) Silver 0.73 Sensitizing dye I 4.0 × 10 ^-3 C-1 0.27 C-2 0.28 C-3 0.07 C-4 0.11 HBS-1 0.12 HBS-2 0.24 C-10 0.007 Gelatin 2.34 Fifth layer: Intermediate layer Gelatin 0.92 Cpd-5 0.10 HBS-1 0.053 Dye I 0.075 U-4 0.023 U-5 0.036 HBS-4 7.7 × 10 ^-3 Sixth layer: First green-sensitive emulsion layer Silver iodobromide emulsion Silver 0.48 Sensitizing dye II 3.6 × 10 ^-3 Sensitizing dye III 1.7 × 10 ^-3 C-6 0.33 C-7 0.077 HBS-1 0.29 Gelatin 1.13 7th layer: Second green-sensitive emulsion layer Silver iodobromide emulsion Silver 0.21 AgI10 Mol% equivalent sphere diameter 0.9μ coefficient of variation 28.8% diameter / thickness ratio 5.1 silver iodobromide emulsion silver 0.09 AgI4 mol% equivalent sphere diameter 0.6μ variation coefficient 36.6% diameter / thickness ratio 3.4 silver iodobromide emulsion silver 0.24 AgI2 mol% Spherical equivalent diameter 0.45μ Coefficient of variation 28% Diameter / thickness ratio 2.7 Sensitizing dye II 2.2 × 10 ^-3 Sensitizing dye III 1.0 × 10 ^-3 C-6 0.20 C-8 0.071 C-4 0.079 C-5 0.038 HBS- 1 0.18 Gelatin 0.79 Eighth layer: Third green-sensitive emulsion layer Silver iodobromide emulsion Silver 0.44 AgI 10 mol% Equivalent sphere diameter 1.2 μ Variation coefficient 29.4% Diameter / thickness ratio 6.3 Sensitizing dye II 5.6 × 10 ^-4 Sensitizing dye III 2.1 × 10 ^-4 Sensitizing dye IV 3.6 × 10 ^-5 C-6 0.036 C-5 0.020 HBS-1 0.032 Gelatin 0.34 Ninth layer: Yellow filter layer Yellow colloidal silver Silver 0.11 Cpd-5 0.28 HBS-1 0.15 Gelatin 1.19 10th layer: 1st blue-sensitive emulsion layer Silver iodobromide emulsion 0.33 AgI 1 mol% sphere equivalent diameter 0.45 μ Variation coefficient 20.1% Diameter / thickness ratio 1.8 Sensitizing dye-V 1.7 × 10 ^-3 C-9 0.65 C- 4 0.10 HBS-1 0.22 Gelatin 0.85 11th layer: 2nd blue-sensitive emulsion layer Silver iodobromide emulsion Silver 0.17 AgI 4.1 mol% Sphere equivalent diameter 0.43μ Variation coefficient 25% Diameter / thickness ratio 3.6 Silver iodobromide emulsion Silver 0.21 AgI 7 mol% Sphere equivalent diameter 0.9 μ Variation coefficient 49% Diameter / thickness ratio 4.6 Sensitizing dye V 3.0 × 10 ^-3 C-9 0.28 C-4 0.044 HBS-1 0.10 Gelatin 0.75 12th layer: 1st protective layer Gelatin 0.60 U-4 0.10 U-5 0.15 HBS-4 0.033 Dye II 0.15 13th layer: 2nd protective layer Polymethyl methacrylate particles 0.14 Diameter about 1.5 μm Gelatin 0.87 In each layer, in addition to the above composition, gelatin effect agent H-1 And a surfactant were added.

Preparation of Sample 102 Except for the coupler C-4 in the 10th layer of Sample 101, except that C-11 was added by correcting the amount so that the inter-image effect from the blue light-sensitive layer to the green light-sensitive layer was adjusted, and the gradation was adjusted. Is sample 101
It was produced in the same manner as described above.

Preparation of Samples 103 and 104 The emulsions of the 10th layer of Samples 101 and 102 were prepared by adding 0.1 mol% of AgI sphere equivalent diameter of 0.1%.
The emulsions were prepared in the same manner as in Samples 101 and 102 except that the emulsion was replaced with an emulsion having 35 μ, a coefficient of variation of 19.5%, and a diameter / thickness ratio of 1.0, and the amount of sensitizing dye was optimized and the gradation was adjusted.

Preparation of Samples 105 and 106 Emulsion of the 10th layer of Samples 101 and 102 was prepared using AgI1 mol%
The emulsions were prepared in the same manner as Samples 101 and 102, except that the emulsions were changed to 0.31 μm, the coefficient of variation was 24.8%, and the diameter / thickness ratio was 1.0, and the amount of sensitizing dye was optimized and the gradation was adjusted.

Preparation of Samples 107 and 108 Emulsion of the 10th layer of Samples 101 and 102 was 1 mol% of AgI, equivalent sphere diameter
The emulsions were prepared in the same manner as in Samples 101 and 102, except that the emulsion was replaced with an emulsion having 0.19μ, a coefficient of variation of 15.2%, and a diameter / thickness ratio of 1.0, the amount of sensitizing dye was optimized, and the gradation was adjusted.

The samples 101 to 108 thus obtained were subjected to imagewise exposure with white light, and were subjected to development processing as described below to obtain characteristic curves of cyan, magenta and yellow images. Among them, a straight line is drawn on the characteristic curve of the yellow color image so that the main gradation part has the smallest value by the least squares method, and an area between the straight lines shifted by 0.1 from the straight line in density is created. Find the point where the characteristic curve deviates,
Exposure latitude △ logE, difference between high and low exposure side
Was L _B.

The main gradation portion is a characteristic curve portion between a point at which the density is 0.2 higher than Dmin on the characteristic curve (S _0.2 ) and a point at which the density is higher than Dmin by 1.0 (S _1.0 ).

Further, after giving uniform green light to the samples 101 to 108 and further performing the development processing as shown below after imagewise exposure with blue light, the characteristic curve 1 of the yellow color image as shown in FIG. A magenta color image density of 2 was obtained. Here △
_DG indicates that the blue-sensitive emulsion layer was changed from an unexposed portion (point A) to an exposed portion (B
This indicates the degree of suppression that a uniformly fogged green photosensitive emulsion layer suffers when developed in (dot). That is, in FIG. 1, curve 1 represents a characteristic curve relating to the yellow color image of the blue-sensitive emulsion, and curve 2 represents a uniform magenta image density of the green-sensitive layer by green exposure. Point A represents a fog portion of the yellow image, and point B represents an exposure amount portion which gives a yellow density of 2.5.

Measure of the concentration left於Ru magenta density in the unexposed area point A (a) and於Ru magenta density in the point B (b) (a-b) △ expressed in D _G, color reproducibility (color turbidity) And

MTF measurement is based on The Theory of Photographic Process
The method described in 3rd edd (published by Matsuku Miran Co., Ltd. by Mies) was followed.

The color development processing was performed at 38 ° C. according to the following processing steps.

Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Rinse 2 minutes 10 seconds Fixed 4 minutes 20 seconds Rinse 3 minutes 15 seconds Stable 1 minute 05 seconds The processing solutions used in each process are as follows. Was.

Color developer Diethylenetriaminepentaacetic acid 1.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 2.0 g Sodium sulfite 4.0 g Potassium carbonate 30.0 g Potassium bromide 1.4 g Potassium iodide 1.3 mg Hydroxylamine sulfate 2.4 g 4- (N- Ethyl-N-β-hydroxyethylamino)
-2-Methylaniline sulfate 4.5g Add water 1.0 pH10.0 Bleach solution Ferric ammonium ethylenediaminetetraacetate 100.0g Disodium ethylenediaminetetraacetate 10.0g Ammonium bromide 150.0g Ammonium nitrate 10.0g Add water 1.0 pH6.0 Fixer Ethylenediaminetetraacetic acid disodium salt 1.0g Sodium sulfite 4.0g Ammonium thiosulfate aqueous solution (70%) 175.0ml Sodium bisulfite 4.6g Add water 1.0 pH6.6 Stabilizer Formalin (40%) 2.0ml Polyoxy Ethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 g HBS-1 Tricresyl phosphate HBS-2 Dioctyl phthalate HBS-3 Dibutyl phthalate HBS-4 Bis (2-ethylhexyl) phthalate Table 1 shows that the samples (104, 106, 108) of the present invention are very excellent in the MTF value (sharpness) and ΔD _G (color turbidity) of the magenta image as compared with the samples (101, 103, 105, 107) using the compounds other than the present invention. . Further, it can be seen that the exposure latitude is wider than that of the sample 102, the MTF value (sharpness) of the magenta image is improved, and ΔD _G (color turbidity) is hardly deteriorated.

Example 2 In place of compound C-11 (exemplified compound (26)) added to the tenth layer of samples 102, 104, 106, and 108 of Example 1, exemplified compounds (18), (19), and (27) , (34), and (35), the same effect as in the first embodiment can be obtained.

Example 3 A sample 201 which was a multilayer color photographic material comprising the following layers was prepared on an undercoated cellulose triacetate film support.

The amount coated amount (Composition of photosensitive layer) is represented in units of g / m ² of silver for silver halide and colloidal silver, also couplers, the amount for the additives and gelatin, expressed in units of g / m ^2, The sensitizing dyes are shown in terms of moles per mole of silver halide in the same layer.

First layer (anti-halation layer) Black colloidal silver 0.2 Gelatin 1.3 C-13 0.06 U-4 0.1 U-5 0.2 HBS-1 0.01 HBS-3 0.01 Layer (intermediate layer) Gelatin 1.5 U-4 0.06 U-5 0.03 C-10 0.02 Dye III 0.004 HBS-1 0.1 HBS-3 0.09 Third layer (first) Red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 2 mol%, internal high AgI type, equivalent sphere diameter 0.3)
8μ, coefficient of variation of sphere equivalent diameter 20%, irregular particles, diameter / thickness ratio 2.5) Coating amount of silver ...... 0.4 gelatin ...... 0.6 sensitizing dye-VI ...... 1.0 x 10 ^-4 sensitizing dye-VII ...... 3.0 × 10 ^-4 sensitizing dye-I 1 × 10 ^-5 C-1 ...... 0.06 C-2 ...... 0.06 C-12 ...... 0.04 C-10 ...... 0.03 HBS-1 ...... 0.03 HBS-3 0.014 Fourth layer (second red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 5 mol%, high internal AgI type, equivalent sphere diameter 0.7)
mu, 25% coefficient of variation of the sphere-equivalent diameter, irregular particles, diameter / thickness ratio 4) coating silver amount ...... 0.7 Sensitizing dye -VI ...... 1 × 10 ^-4 Sensitizing dye -VII ...... 3 × 10 ^{- 4} Sensitizing dye-I 1 × 10 ^-5 C-1 0.24 C-2 0.24 C-12 0.04 C-10 0.04 HBS-1 0.15 HBS-3 0.02 Fifth layer (third red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 10 mol%, internal high AgI type, equivalent sphere diameter 0.
8μ, coefficient of variation of equivalent sphere diameter 16%, irregular shaped particles, diameter / thickness ratio 1.3) Silver coating amount 1.0 gelatin 1.0 sensitizing dye-VI 1 × 10 ^-4 sensitizing dye-VII 3 × 10 ^-4 sensitizing dye-I 1 × 10 ^-5 C-14… 0.05 C-15… 0.1 HBS-1… 0.01 HBS-3… 0.05 0.05 6th layer (intermediate layer) Gelatin: 1.0 Cpd-11: 0.03 HBS-1: 0.05 Seventh layer (first green-sensitive emulsion layer) Silver iodobromide emulsion (AgI 2 mol%, internal high AgI type, equivalent sphere diameter 0.5)
μ, Coefficient of variation of equivalent sphere diameter 20%, amorphous particles, diameter / thickness ratio 2.0) Coating silver amount …… 0.30 Sensitizing dye-II… 5 × 10 ^-4 Sensitizing dye-IV …… 0.3 × 10 ^{− 4} Sensitizing dye-III ... 2 x ^10-4 gelatin ... 1.0 C-6 ... 0.2 C-4 ... 0.03 C-13 ... 0.03 HBS-1 ... 0.5 Eighth layer (second green sensitive emulsion) Layer) Silver iodobromide emulsion (AgI 4 mol%, internal high AgI type, equivalent sphere diameter 0.6)
μ, Coefficient of variation of sphere equivalent diameter 38%, irregular shaped particles, diameter / thickness ratio 4) Silver coating amount: 0.4 sensitizing dye-II 5 × 10 ^-4 sensitizing dye-III 2 × 10 ^{− 4} Sensitizing dye-IV 0.3 × 10 ^-4 C-6 0.25 C-13 0.03 C-7 0.015 C-4 0.01 HBS-1 0.2 Ninth layer (third green sensitive emulsion) Layer) Silver iodobromide emulsion (AgI 6 mol%, internal high AgI type, equivalent sphere diameter 1.0
μ, Coefficient of variation of equivalent sphere diameter 80%, amorphous particles, diameter / thickness ratio 1.2) Silver coating amount …… 0.85 Gelatin …… 1.0 Sensitizing dye-VIII …… 3.5 × 10 ^-4 Sensitizing dye-IX …… 1.4 × 10 ^-4 C-16 ... 0.01 C-17 ... 0.03 C-18 ... 0.20 C-13 ... 0.02 C-5 ... 0.02 HBS-1 ... 0.20 HBS-3 ... 0.05 Layer 10 (Yellow filter layer) Gelatin: 1.2 Yellow colloidal silver: 0.08 Cpd-2: 0.1 HBS-1: 0.3 Eleventh layer (first blue-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, high AgI) Mold, ball equivalent diameter 0.5μ,
Coefficient of variation of sphere equivalent diameter: 15%, octahedral grains, diameter /) Silver coating amount: 0.4 Gelatin: 1.0 Sensitizing dye-V: 2 × 10 ^-4 C-9: 0.9 C-4: 0.07 HBS-1 0.2 Layer 12 (second blue-sensitive emulsion layer) Silver iodobromide emulsion (AgI 10 mol%, internal high AgI type, equivalent sphere diameter 1.
3 μ, coefficient of variation of equivalent sphere diameter 25%, irregular particles, diameter / thickness ratio 4.5) Coating silver amount: 0.50 Gelatin: 0.6 Sensitizing dye-V: 1 × 10 ^-4 C-9: 0.25 HBS -1 ... 0.07 13th layer (first protective layer) Gelatin ... 0.8 U-4 ... 0.1 U-5 ... 0.2 HBS-1 ... 0.01 HBS-3 ... 0.01 14th layer (second protective layer) ) Gelatin: 0.45 polymethyl methacrylate particles (1.5μ diameter): 0.2
H-1... 0.4 Cpd-3... 0.5 Cpd-4... 0.5 In addition to the above components, a surfactant was added to each layer as a coating aid. The sample prepared as described above was used for sample 20.
It was set to 1.

Preparation of Sample 202 Except for coupler C-12 in the third layer of Sample 201, except that C-11 was added in an amount corrected so that the inter-image effect from the red-sensitive layer to the blue-sensitive layer was adjusted, and gradation was adjusted. Is sample 101
Created in the same way as

Preparation of Samples 203 and 204 The emulsion of the seventh layer of Samples 201 and 202 was replaced with an emulsion having an equivalent sphere diameter of 0.43 μm, a coefficient of variation of 33%, and a diameter / thickness ratio of 2.1, and the sensitizing dye was optimized to adjust the gradation. Other than sample 20
Created in the same way as 1, 202.

Preparation of Samples 205 and 206 The emulsions of the seventh layer of Samples 201 and 202 were replaced with emulsions having an equivalent sphere diameter of 0.3 μm, a coefficient of variation of 28%, and a diameter / thickness ratio of 2.5, respectively, and optimized sensitizing dyes and adjusted gradation. Sample 20 except
Created in the same way as 1, 202.

Preparation of Samples 207 and 208 The emulsion of the seventh layer of Samples 201 and 202 was replaced with an emulsion having an equivalent sphere diameter of 0.25μ, a coefficient of variation of 32%, and a diameter / thickness ratio of 1.9 to optimize the sensitizing dye and adjust the gradation. Sample 20 except
Created in the same way as 1, 202.

The samples 201 to 208 thus obtained were subjected to imagewise exposure with white light, and were subjected to a developing process as described below to obtain characteristic curves of cyan, magenta and yellow images. Of these, for the characteristic curve of the magenta color image, a straight line is drawn so that the main gradation part has the smallest value by the least squares method, and an area between straight lines shifted by 0.1 in density from the straight line is created. Find the point where the characteristic curve deviates,
Exposure latitude △ logE, difference between high and low exposure side
L _G.

The main gradation portion is a characteristic curve portion between a point at which the density is 0.2 higher than Dmin on the characteristic curve (S _0.2 ) and a point at which the density is higher than Dmin by 1.0 (S _1.0 ).

Further, after giving uniform blue light to the samples 201 to 208 and further performing the development processing as shown below after imagewise exposure with red light, the characteristic curve 1 of the cyan image as shown in FIG. A yellow image density of 2 was obtained. Where △ D _B
Indicates that the red-sensitive emulsion layer is from the unexposed portion (point A) to the exposed portion (B
This indicates the degree of suppression that the uniformly fogged blue-sensitive emulsion layer undergoes when developed in (dot). That is, in FIG. 2, curve 1 represents a characteristic curve for the cyan image of the red-sensitive emulsion, and curve 2 represents the yellow image density of the blue-sensitive layer by uniform blue exposure. Point A is the fog portion of the cyan image,
Point B represents an exposure amount portion that gives a cyan density of 1.0.

The density left (ab) of the yellow density (a) at the unexposed area point A and the yellow density (b) at the same point _B is represented by ΔDB, and is a measure of color reproducibility (color turbidity). And

Example 1 for MTF measurement and color development processing
And done in exactly the same way. Table 2 shows the results obtained from these.

Next, the chemical structural formulas or chemical names of the compounds used in this example other than Example 1 are shown below.

As in Example 1, the samples of the present invention (204, 2
06, 208) are samples (201, 203, 205, 207, 20) outside the present invention.
Compared to 2), it can be seen that it is improved in that sharpness and color turbidity are not deteriorated while widening the latitude.

Example 4 Compound C-11 used in the third layer of Samples 202, 204, 206, and 208 of Example 3 (instead of Exemplified Compound (26), Exemplified Compounds (18), (19), (27), In the case of using (34) and (35), the same result as in the third embodiment can be obtained.

Example 5 Using Samples 101 to 108 and Examples 201 to 208 of Example 1,
After the imagewise exposure, a continuous process (running test) was performed in the following processing step until the color developing solution was replenished twice the tank capacity. However, the composition of the fixing solution was changed as shown in Table 3, and each of them was performed.

The automatic developing machine used was a belt transport system described in JP-A-60-191257, and each processing bath was disclosed in JP-A-62-183460.
The jet stirring method described in the item No. is used.

 The processing steps are described below.

The composition of each processing solution used is shown below.

(Stabilizing solution) Common to mother liquor and replenisher Formalin (37%) 1.2 ml 5-Chloro-2-methyl-4-isothiazolin-3-one 6.0 mg 2-Methyl-4-isothiazolin-3-one 3.0 mg Surfactant [ C ₁₀ H ₂₁ -O-CH ₂ CH ₂ O ₁₀ ] 0.4 Ethylene glycol 1.0 Water 1.0 pH 5.0-7.0 The sample was exposed to 20 CMS, treated with each running equilibrium solution, and the residual silver It was determined by the X-ray method.

As a result, the difference between the bleaching solutions A to I was remarkable.
The difference between 1-108, the difference between samples 201-208 was relatively small.

Bleaching solution A followed by B had the largest amount of residual silver, and samples treated with bleaching solutions D, E, and H had the least amount of residual silver, indicating the effect of the present invention.

[Brief description of the drawings]

FIG. 1 shows a characteristic curve. 1 represents the characteristic curve of the yellow image of the blue-sensitive layer, 2 represents the magenta image density of the green-sensitive layer by uniform green exposure, and 3 represents the theoretical magenta density line of the green-sensitive layer by uniform green exposure. FIG. 2 shows a characteristic curve. 1 represents the characteristic curve of the cyan image of the red-sensitive layer, 2 represents the yellow image density of the blue-sensitive layer by uniform blue exposure, and 3 represents the theoretical yellow density line of the blue-sensitive layer by uniform blue exposure.

Continuation of the front page (72) Inventor Hideki Naito 210 Nakanakanuma, Minamiashigara-shi, Kanagawa Prefecture Fujisha Shin Film Co., Ltd. Examiner Isao Fujii (56) References JP-A-60-185950 (JP, A) JP-A-62 -62358 (JP, A) JP-A-63-226648 (JP, A) JP-A-62-262859 (JP, A)

Claims (2)

(57) [Claims] 1. A silver halide color photographic material comprising at least one silver halide emulsion layer provided on a support, wherein the silver halide emulsion contained in at least one of the silver halide emulsion layers is The largest particle size in the particle group up to 30% by counting from the smallest particle is the equivalent spherical diameter.
0.3 μm or less, in the light-sensitive material, the compound cleaved after reaction with the oxidized developing agent contains a compound that cleaves the development inhibitor by reacting with another oxidized developing agent. Characteristic silver halide color photographic material. 2. A method of subjecting a silver halide color light-sensitive material of claim (1) to color development processing and thereafter processing with a processing solution having bleaching ability, wherein said processing solution having bleaching ability is used as a bleaching agent. The second of the compounds selected from the following compound group (A)
A silver halide comprising at least one iron complex salt and a ferric complex of 1,3-diaminopropanetetraacetic acid in a molar ratio of the former to the latter of 3 or less (including 0). Processing method for color photographic light-sensitive materials. Compound A A-1 Ethylenediaminetetraacetic acid A-2 Diethylenetriaminepentaacetic acid A-3 Cyclohexanediaminetetraacetic acid A-4 1,2-Propylenediaminetetraacetic acid