JP2520643B2 - Image forming method - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to an image forming method for a silver halide color photographic light-sensitive material, and more particularly to an image forming method which is not significantly affected by process variations during continuous processing. Is.

(Prior Art) A color developing solution containing an aromatic primary amine color developing agent has been used for a long time in the formation of color development, and now plays a central role in the image forming method of color photography. Is playing. However, the above color developer has a problem that it is very easily oxidized by air or metal, and when a color image is formed using the oxidized developer, fog increases, sensitivity and gradation change. It is well known that desired photographic characteristics cannot be obtained due to the

Therefore, various means for improving the preservative property of color developing solutions have been studied, and among them, the method of using hydroxylamine and sulfite ion in combination is the most general.
However, when hydroxylamine is decomposed, ammonia is generated to cause fog, and the color developing property is lowered by reacting with the oxidant of the main agent, while sulfite ion acts as a competing compound of the developing agent to develop the color developing property. It is difficult to say that any of them is preferable as a compound (preservative) for improving the preservative property of the color developing solution, because they have drawbacks such as inhibiting the above.

In particular, sulfite ion has long been used as a compound for improving the preservative property of various developing agents or preventing the decomposition of hydroxylamine, but it greatly inhibits the coloring property, and is particularly harmful to pollution and liquid preparation. When it is used in a system containing no alcohol, the color density is remarkably reduced.

(Problems to be Solved by the Invention) However, when sulfite ions are removed, the concentration fluctuations of hydroxylamines and color developing agents in the developer become large, which also adversely affects the photographic properties.

Therefore, it is necessary to use a preservative instead of sulfite ion, but it is possible to add an aromatic primary amine preservative by adding triethanolacin described in US Pat. No. 4,170,48, polyethyleneimine described in US Pat. It was not possible to obtain a sufficient effect on sex. In particular, the change in photographic property due to the variation in the concentration of hydroxylamine and the like due to the removal of sulfite ion is generally the largest in the yellow image forming layer, and therefore its improvement has been particularly desired.

On the other hand, conventional yellow couplers are 4-equivalent couplers or JP-A-50-87650, U.S. Pat.
Α-acyl acetanilides in which one hydrogen atom of an active methylene group described in 408, 194, 3,415,652 and 3,447,928 is substituted with an aryloxy group, a halogen element, a sulfoxy group, an acyloxy group, etc. are known. However, these couplers have drawbacks such as insufficient coupling reaction activity and giving remarkable color fog.

As a yellow coupler which overcomes these drawbacks and has higher activity, one active hydrogen atom of a methylene group described in JP-A-47-26133 and JP-A-56-44420 is prepared by a heterocycle containing a nitrogen atom directly. Substituted couplers are known,
The improvement was recognized as compared with the conventional coupler, but the effect was insufficient.

Further, in Japanese Patent Application No. 61-295002, an attempt is made to suppress changes in photographic properties due to concentration fluctuations of hydroxylamine and aromatic primary amines due to the removal of sulfite ion in a developer by using these active couplers. However, the degree of improvement is still insufficient, and the color development obtained is not satisfactory.

Therefore, the present invention does not adversely affect the obtained photographic performance, particularly photographic performance relating to yellow image formation, in a developer system which does not substantially contain sulfite ion, and contains an aromatic primary amine. An object of the present invention is to provide an image forming method for a silver halide photographic light-sensitive material in which a developer does not change with time.

Another object of the present invention is to provide an image forming method of a silver halide photographic light-sensitive material, which does not impair the color forming property even when treated with a developer which does not substantially contain benzyl alcohol, which is harmful to pollution and preparation. To do.

(Means for Solving the Problems) The above object of the present invention is to provide a silver halide color photographic light-sensitive material having a layer containing at least one 2-equivalent yellow coupler represented by the following general formula (I), with a sulfite ion. It was found to be achieved by a method for forming an image of a silver halide color photographic light-sensitive material, which is characterized in that it is treated with a color developing solution which is substantially free of .

General formula (I) (In the formula, R ¹ represents a substituted or unsubstituted tertiary alkyl group or a substituted or unsubstituted aryl group.

R ² represents a halogen atom or an alkoxy group.

R ³ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.

Y ¹ represents a divalent linking group.

X is Represents W ¹ represents a non-metal atom necessary to form a 4- to 6-membered ring with the nitrogen atom in the formula. ) As described above, since hydroxylamines generally reduce the color developability by reacting with the oxidation product of the main agent, the present inventor has predicted that the use of a more highly active coupler will result in less variation in photographic performance. In the present invention, the sulfite ion is substantially eliminated for the first time by using the 2-equivalent yellow coupler of the above formula (I) of the present invention among various known high activity couplers as mentioned above. It has been found that the above-mentioned object of the present invention can be effectively achieved in a system that does not contain the same.

As described above, a coupler in which one hydrogen atom of an active methylene group is directly substituted with a heterocycle containing a nitrogen atom is known as a highly active yellow coupler. The substituent contained in the phenylcarbamoyl group in the coupler is the present invention. By specifying the --NHCOY ₁ --SO _z R ³ group as in the coupler of formula (I), the stability of the developer containing no sulfite ion with time is improved, and the fluctuation of the obtained photographic performance is reduced and It was found that the color developability was improved.

Further, since the color developing solution can maintain a good color developing property even if it does not substantially contain benzyl alcohol, it is useful in terms of pollution and preparation.

Next, the 2-equivalent yellow coupler represented by formula (I) will be described in detail.

In the general formula (I), the tertiary alkyl group represented by R ¹ includes an unsubstituted (eg t-butyl group) and a substituted alkyl group. The substituent introduced into the alkyl group may be a halogen atom (eg, fluorine, chlorine, bromine, etc.), an alkoxy group (eg, methoxy, ethoxy group, etc.)
Aryloxy group (eg, phenoxy group, 4-chlorophenoxy group, etc.) alkylthio group (eg, methylthio,
n-butylthio group, etc.) arylthio group (eg, phenylthio group, etc.), alkylsulfonyl group (eg, methanesulfonyl group, n-butanesulfonyl group, etc.), arylsulfonyl group (eg, benzenesulfonyl group, 4-methoxybenzenesulfonyl group, etc.), Examples thereof include an acylamino group (eg, acetylamino group) and an amino group (eg, diethylamino group) cyano group. The aryl group represented by R ¹ is preferably a phenyl group and may have a substituent. As the substituent of the aryl group,
Examples thereof include the same groups as the alkyl group, but also include an alkyl group (eg, methyl, ethyl, t-butyl group, etc.) and the like.

R ² represents a chlorine atom or an alkoxy group (eg, methoxy, ethoxy, etc.).

The alkyl group represented by R ³ includes an unsubstituted (eg, n-octyl group, n-dodecyl group, n-heptadecyl group etc.) and a substituted alkyl group.

Examples of the substituent introduced into the above alkyl group include the substituent represented by R ¹ .

An aryl group represented by R ³ is preferably a phenyl group,
Includes unsubstituted and substituted phenyl groups.

Examples of the substituent introduced into the phenyl group include the same groups as the alkyl group, but also include an alkyl group (eg, methyl, ethyl group, etc.) and the like.

Y ₁ represents a divalent linking group and represents an alkylene group, an arylene group, an aralkylene group or a divalent organic group represented by the following general formula (Ia).

General formula (Ia) -A-V-B- (In formula, A and B are respectively the alkylene groups which may have a substituent, the arylene group, or the aralkylene group,
V represents two bridging groups. ) As the substituents of A and B, the same groups as in the case of R ¹ can be mentioned.

Examples of V include oxy, thio, carboxide and sulfonamide groups.

The coupling-off group of X has the following structure.

W ¹ in the formula Together with a non-metallic atom required to form a 4-, 5- or 6-membered ring.

 It is more preferably represented by the following (d) to (f).

In the formula, R ⁹ and R ¹⁰ each represent a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group or a hydroxy group. R ¹¹ , R ¹² and R ¹³ each represent a hydrogen atom, an alkyl group, an aryl group, an aralkyl group or an acyl group. W ² represents an oxygen or sulfur atom.

Next, specific examples of the coupler used in the present invention will be given, but the coupler of the present invention is not limited thereto.

Other examples of the yellow coupler represented by formula (I) of the present invention include those described in JP-B-56-44420.

These couplers are generally used in an amount of 2 × 10 ^-3 mol to 5 × 10 ^-1 mol, preferably ¹ × 10 ^-1 mol, per mol of silver in the emulsion layer.
^-2 mol to 5 × 10 ^-1 mol is added.

The above couplers and the like can be used in combination in two or more kinds in the same layer in order to satisfy the characteristics required for the light-sensitive material, and it is of course possible to add the same compound in two or more different layers.

To introduce the coupler into the silver halide emulsion layer, known methods such as the method described in US Pat. No. 2,322,027 are used. For example, alkyl phthalates (such as dibutyl phthalate and dioctyl phthalate), phosphates (such as diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, and dioctyl butyl phosphate), citrates (such as tributyl acetyl citrate), Benzoic acid esters (eg, octyl benzoate), alkyl amides (eg, diethyl lauryl amide), fatty acid esters (eg, dibutoxyethyl succinate, diethyl azelate), trimesic acid esters (eg, tributyl trimesate), and the like, or a compound having a boiling point of about Organic solvent at 30 ° C to 150 ° C, for example, lower alkyl acetate such as ethyl acetate and butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxy After being dissolved in ethyl acetate, methyl cellosolve acetate, etc., it is dispersed in a hydrophilic colloid. The high boiling point organic solvent and the low boiling point organic solvent may be mixed and used.

The coupler developer used in the present invention will be described below.

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

(D-1) N, N-diethyl-p-phenylenediamine (D-2) 4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline (D-3) 2-methyl-4- [ N-ethyl-N- (β-
Hydroxyethyl) amino] aniline (D-4) 4-amino-3-methyl-N-ethyl-N-
(Β Methanesulfonamidoethyl) aniline Further, these p-phenylenediamine derivatives may be salts such as sulfates, hydrochlorides, sulfites and p-toluenesulfonates. 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 developing solution.

In particular, the use of the color developing agent (D-4) in the presence of the compound of the general formula (I) is preferable in that the fog increase is small and good photographic characteristics are obtained.

The color developer of the present invention contains substantially no sulfite ion, but it is preferable to contain various organic preservatives instead.

Organic preservatives include monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, ethers, oximes, amides and sulfonamides and nitrogen-containing heterocycles (eg DABC
O group) is preferable. These will be described.

Monoamines that can be used in the present invention are represented by the following general formula (I
It is a compound represented by I).

General formula (II) In the formula, R ²¹ and R ²² each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group or a heterocyclic group, and R ²³ is an alkyl group, an alkenyl group,
It represents an aryl group, an aralkyl group or a heterocyclic group. Here, R ²¹ and R ²² , R ²¹ and R ^23, or R ²² and R ²³ may be linked to form a nitrogen-containing heterocycle. However, R ²¹ has 2 to 2 carbon atoms
In the case of a hydroxyalkyl group having 6 carbon atoms, R ²² and R ²³ do not simultaneously represent an unsubstituted alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 2 to 6 carbon atoms, or a benzyl group.

The alkyl group represented by R ²¹ , R ²² and R ²³ preferably has 1 to 12 carbon atoms, and may be linear, branched, or cyclic (specifically, methyl group, ethyl group, n-propyl group). Group, iso-propyl group, n-butyl group, t-butyl group, t-amyl group, n-hexyl group, cyclohexyl group); an alkenyl group having 2 to 6 carbon atoms is preferable, It may be branched or cyclic (specifically, allyl group, isopropenyl group, cyclohexenyl group, etc.); aryl group having 6 to 12 carbon atoms is preferable (specifically, phenyl group, tolyl group, naphthyl group). A group); an aralkyl group having preferably 7 to 12 carbon atoms (specifically, a benzyl group, a phenethyl group, etc.); a heterocyclic group containing a nitrogen atom, an oxygen atom and / or a sulfur atom as a hetero atom Charcoal Preferably those having 1 to 12 (specifically, an imidazolyl group, a pyrazolyl group, triazolyl group, pyridyl group and the like).

R ²¹ , R ²² , and R ²³ may have a substituent when other than a hydrogen atom, and specific examples of the substituent include a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), alkyl Group (methyl group, ethyl group, butyl group, t-butyl group, methoxyethyl group, carboxymethyl group, hydroxyethyl group, etc.) aryl group (phenyl group, tolyl group,
Naphthyl group), alkoxy group (methoxy group, ethoxy group, methoxyethoxy group, hydroxyethoxy group, etc.), aryloxy group (phenoxy group, p-nitrophenoxy group, etc.), sulfonyl group (methanesulfonyl group, benzenesulfonyl group, etc.) ), Sulfonamide group (methanesulfonamide group, benzenesulfonamide group, etc.), sulfamoyl group (unsubstituted sulfamoyl group,
Dimethylsulfamoyl group, ethylsulfamoyl group, etc.), carbamoyl group (unsubstituted carbamoyl group, methylcarbamoyl group, dimethylcarbamoyl group, ethylcarbamoyl group, etc.), amide group (acetamide group, benzamide group, etc.), ureido group ( Methylureido group, ethylureido group, phenylureido group, etc.), alkoxycarbonylamino group (methoxycarbonylamino group, methoxyethoxycarbonylamino group, etc.), acyl group (acetyl group, benzoyl group, etc.), formyl group, cyano group, carboxy Group, sulfo group, hydroxy group, nitro group, alkylthio group (methylthio group, hydroxyethylthio group, carboxymethylthio group, etc.), arylthio group (phenylthio group, etc.), and the like, and there are two or more substituents. Huang may also Tsu different the same.

The nitrogen-containing heterocyclic group formed by linking R ²¹ and R ²² , R ²¹ and R ^23, or R ²² and R ²³ is a saturated or unsaturated 3- to 8-membered ring and is an oxygen atom in addition to the carbon atom and the nitrogen atom. , May contain a sulfur atom, and may be condensed with a benzene ring or a heterocycle. Specifically, an aziridine ring, an azetidine ring,
Pyrrolidine ring, piperidine ring, piperazine ring, pyrroline ring, imidazolidine ring, pyrazolidine ring, indoline ring, morpholine ring, pyrrole ring, imidazole ring, pyrazole ring, indole ring, indazole ring, triazole ring, tetrazole ring, phenoxylidine ring, Examples thereof include a tetrahydrothiazine ring, and more preferably a saturated or unsaturated 5- or 6-membered ring. Further, these nitrogen-containing heterocycles may have a substituent, and specific examples of the substituent include the same substituents as the above R ²¹ , R ²² and R ²³ .

When any one of R ²¹ , R ²² and R ²³ has a carboxy group, the compound of the general formula (II) preferably has 3 or more carbon atoms, and when any one of R ²¹ , R ²² and R ²³ is a carboxyphenyl group. The substitution position of the amino group is preferably the meta position or para position of the carboxy group.

A hydrogen atom and an alkyl group are particularly preferable as R ²¹ and R ²² . As R ²³ , an alkyl group is particularly preferable.

Specific examples of the compound represented by formula (II) are shown below, but the invention is not limited thereto.

II-6 (HOCH ₂ CH _{2 2} NCH ₂ CH ₂ SO ₂ CH ₃ II-7 HNCH ₂ COOH) ₂ II-9 H ₂ NCH ₂ CH ₂ SO ₂ NH ₂ Specific examples other than the above include the compound examples A-1 to A-12 described in Japanese Patent Application No. 61-147823, pages 9 to 10; 61-166.
Compound Example I- (1) -described on pages 10-14 of the specification of No. 674
Compound Examples I- (1) to I- (21); I- (22); No. 61-165621, pages 11 to 14; Compound Examples I- (1) to I- (4
2); Compound Examples I- (1) to I- (II) described on pages 9 to 11 of the specification, 61-170789; Compound example I described on pages 11 to 16 of the specification of 61-168159. -(1) to I (24); ibid. 61-
169789 Compound Example I- (1) described on pages 9-12
-I- (20); No. 61-186561 specification, compound examples I- (1) to I- (15) described on pages 8 to 10; No. 61-197420, page 10, line 4 to 13 Compound Example I-described on page 2, line
(1) to I- (35); and the like.

The compounds represented by the general formula (II) are disclosed in Japanese Patent Application No.
-147823, 61-166674, 61-165621, 61-
164515, 61-170789, 61-168159, 61-16
It can be obtained by the method described in the specifications of 9789, 61-186561 and 61-197420.

The diamines that can be used in the present invention are represented by the following general formula (II
It is a compound represented by I).

General formula (III) In the formula, R ³¹ , R ³² , R ³³ , and R ³⁴ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a heterocyclic group, and specifically, the above general formula (II) Is synonymous with R ²¹ and R ²² . However, when R ³¹ is a hydroxyalkyl group having 2 to 6 carbon atoms, R ³² , R ³³ , R
³⁴ does not simultaneously take a hydrogen atom, an unsubstituted alkyl group having 1 to 6 carbon atoms, and a hydroxyalkyl group having 2 to 6 carbon atoms.

Here, R ³¹ and R ³² , R ³³ and R ³⁴ may be combined to form a nitrogen-containing heterocycle, and specific nitrogen-containing heterocycles include R ²¹ and R ²² in the general formula (II), It has the same meaning as a nitrogen-containing heterocycle formed by connecting R ²¹ and R ²³ or R ²² and R ²³ .

R ³⁵ represents a divalent organic group, specifically an alkylene group, an arylene group, an aralkylene group, an alkenylene group or a heterocyclic group. Here, the alkylene group and alkenylene group may be linear, branched, or cyclic and preferably have 1 to 6 carbon atoms, and specifically, methylene group, dimethylene group, trimethylene group, methyldimethylene group. , Dimethyltrimethylene group, hexamethylene group, ethylene group, butenylene group, And the like. The arylene group preferably has 6 to 10 carbon atoms, and specifically, And the like. The aralkylene group preferably has 7 to 12 carbon atoms, and specifically, And the like. The heterocyclic group preferably has 1 to 8 carbon atoms, and specifically, And the like. These alkylene group, alkenylene group, arylene group, aralkylene group, and heterocyclic group may have a substituent, and specific substituents are represented by the general formula (I
It has the same meaning as the substituent of R ²¹ , R ²² and R ²³ of I), and when there are two or more substituents, they may be the same or different.

In the general formula (III), the total carbon number of R ³¹ , R ³² , R ³³ , R ³⁴ and R ³⁵ is at least 2.

As R ³¹ , R ³² , R ³³ and R ³⁴ , a hydrogen atom and an alkyl group are particularly preferable, and as R ³⁵ , an alkylene group is particularly preferable.

Specific examples of the compound represented by formula (III) are shown below, but the invention is not limited thereto.

III-8 HO ₂ CCH ₂ NHCH ₂ CH ₂ NHCH ₂ COOH Specific examples other than the above include Japanese Patent Application No. 61-173595
Compound Examples I- (1) to I- (20) described on pages 10 to 13;
No. 61-164515, compound examples I-described on pages 10 to 16
(1) to I- (42); Compound Examples I- (1) to I- (24);
Compound Examples I- (1) to I described on pages 9 to 12 of 89 specification
-(20); No. 61-186560, compound examples I- (1) to I- (13), I- (1) described on page 10, line 4 to page 13, line 5.
5) and I- (19) to I- (25); and the like.

The compound represented by the general formula (III) is disclosed in Japanese Patent Application No. 61-1.
73595, 61-164515, 61-168159, 61-169
It can be obtained by the method described in No. 789 and No. 61-186560.

The polyamines that can be used in the present invention are compounds represented by the following general formula (IV).

General formula (IV) In the formula, R ⁴¹ , R ⁴² , R ⁴³ and R ⁴⁴ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group or a heterocyclic group, and specifically, in the general formula (II), Synonymous with R ²¹ and R ²² .

R ⁴¹ and R ⁴² , R ⁴³ and R ⁴⁴ may be combined to form a nitrogen-containing heterocycle, and specifically, R ²¹ and R ²² in the above general formula (II), R ^22
It has the same meaning as a nitrogen-containing heterocycle formed by linking ²¹ and R ²³ or R ²² and R ²³ .

R ⁴⁵ , R ⁴⁶ , and R ⁴⁷ each independently represent a divalent organic group, and specifically have the same meaning as R ^{35 in} formula (III).

X ⁴¹ and X ⁴² are independent R represents a linking group composed of —O—, —S—, —CO—, —SO ₂ —, —SO— or a combination of these linking groups;
⁴⁸ is synonymous with R ⁴¹ , R ⁴² , R ⁴³ , and R ⁴⁴ .

m represents 0 or an integer of 1 or more. The upper limit of m is not particularly limited and may be a high molecular weight as long as the compound is water-soluble, but usually m is preferably in the range of 1 to 3.

However, when m = 0 and R ⁴⁸ is a hydroxyalkyl group having 2 to 6 carbon atoms, R ⁴¹ , R ⁴² , R ⁴³ , and R ⁴⁴ are simultaneously a hydrogen atom, an unsubstituted alkyl group having 1 to 6 carbon atoms, 2 to 2 carbon atoms
It does not take the hydroxyalkyl group of 6.

Specific examples of the compound represented by formula (IV) are shown below, but the invention is not limited thereto.

IV-2 (HOCH ₂ CH _{2 2} NCH ₂ CH ₂ OCH ₂ CH ₂ NCH ₂ CH ₂ OH) ₂ IV-6 H ₂ NCH ₂ CH ₂ NH _n H (n = 500 to 20,000) Specific examples other than the above include Japanese Patent Application No. 61-165621
Compound Examples I- (1) to I- (21) described on pages 11 to 14;
No. 61-169789, compound examples I-described on pages 9 to 12
(1) to I- (20); and the like.

The compound represented by the above general formula (IV) is disclosed in Japanese Patent Application No. 61-16.
It can be obtained by the method described in 5621 and 61-169789.

The quaternary ammonium salts that can be used in the present invention are compounds represented by the following general formula (V).

General formula (V)(Where R⁵¹Represents an n-valent organic group, R⁵², R⁵³And R⁵⁴Is
Each independently represents a monovalent organic group. R⁵², R⁵³And R⁵⁴
Of at least two of these groups are combined to form a quaternary ammonium
It may form a heterocycle containing a sulfur atom. n is 1 or more
Is an integer and X Represents a counter anion. ) R in the general formula (V)⁵¹Is monovalent or higher, preferably
It is a monovalent to trivalent organic group. R⁵¹As an example of monovalent group of
Is a substituted or unsubstituted alkyl group (having 1 to 20 carbon atoms).
Alkyl groups of, for example, methyl group, ethyl group, 2-hydr
Roxyethyl group, 2-ethoxyethyl group, Carboxyme
Cyl group, 3-hydroxypropyl group, 3-sulfopropyi group
Group, benzyl group, cyclohexyl group, cyclohexyl
Methyl group, isobutyl group, etc.), aryl group (6 carbon atoms)
~ 20 aryl groups such as phenyl, 4-methoxy
Phenyl group, 2,4-dichlorophenyl group, etc.), heterocycle
Group (heterocyclic group having 1 to 20 carbon atoms, for example, pyridine-4-
Ile group, etc.) and the like. These groups have
As the substituent that may be present, a halogen atom, a hydroxyl group, a sulfo group
Groups, carboxyl groups, and optionally substituted alkyl groups
Group, aryl group, heterocyclic group, alkoxy group, arylo
Xy, sulfonyl, acyl, amino, etc. are preferred.
New

Examples of the divalent group of R ⁵¹ include substituted or unsubstituted,
Alkylene group (alkylene group having 1 to 20 carbon atoms, for example,
Ethylene group, tetramethylene group, propylene group, etc.),
An arylene group (an arylene group having 6 to 20 carbon atoms, for example,
p-phenylene group, m-phenylene group, o-phenylene group, etc.), heterocyclic group (heterocyclic group having 1 to 20 carbon atoms, such as 2,3-pyridylene group), or two or more of them linked together Examples of the divalent group include a halogen atom, a hydroxyl group, a sulfo group, a carboxyl group, and an optionally substituted alkyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, sulfonyl group. ,
An acyl group and an amino group are preferred.

R ⁵² , R ⁵³ and R ⁵⁴ are monovalent organic groups, and among them, preferred are the specific examples of the monovalent group mentioned for R ⁵¹ . A particularly preferred monovalent group among R ⁵² , R ⁵³ and R ⁵⁴ is a substituted or unsubstituted alkyl group, and at least one of R ⁵² , R ⁵³ and R ⁵⁴ is a hydroxyalkyl group, an alkoxyalkyl group or a carboxyalkyl group. Is most preferable.

At least two groups out of R ⁵² , R ⁵³ and R ⁵⁴ may combine to form a heterocycle containing a quaternary ammonium atom (eg, a pyrrolidinium ring, a pyridinium ring, etc.).

n is an integer of 1 or more, and the present invention includes the case where the compound of the general formula (V) is an oligomer, but n is preferably an integer of 1 to 3, more preferably 1 or 2.

 X Represents any counter anion. X As an example of
Halogen ions (eg Cl , Br , F , I What
Th), various acids (sulfuric acid, nitric acid, phosphoric acid, p-toluenesulfur)
Acid radicals of organic or inorganic acids such as phosphonic acid and acetic acid
Can be given.

The compound represented by the general formula (V) may be contained as a side chain group of a polymer added to the color developing solution.

Specific examples of the compound represented by formula (V) are shown below, but the invention is not limited thereto.

V-2 C₂H_Five-N CH₂H_FourOH)₃ 1 / 2SO_Four V-3 N CH₂H_FourOH)_Four NO₃  V-4 (C₂H_{Five 2}N C₂H_FourOH)₂ Cl   V-8 (HOC₂H_{Four 3}N -C₂H_Four-N C₂H_FourOH)₃2NO₃    As a specific example other than the above, Japanese Patent Application No. 61-188619
Compound Examples I- (1) to I- (25) etc. described on pages 12 to 16
Can be mentioned.

The compound represented by the general formula (V) is disclosed in Japanese Patent Application No. 61-18.
It can be obtained based on the method described in 8619.

The nitroxy radicals that can be used in the present invention are compounds represented by the following general formula (VI).

General formula (VI) R ⁶¹ and R ⁶² each independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. R ⁶¹ and R ⁶² may be the same as or different from each other, and R ⁶¹ and R ⁶² may be linked to each other to form a ring structure. However, R ⁶¹ and R ⁶² are not hydrogen atoms at the same time. Further, these alkyl group, aryl group or heterocyclic group may have a substituent.
Examples of such a substituent include a hydroxy group, an oxo group, a carbamoyl group, an alkoxy group, a sulfamoyl group, a carboxy group, and a sulfo group. Examples of the heterocyclic group include a pyridyl group and a piperidyl group.

Preferably, R ⁶¹ and R ⁶² are a substituted or unsubstituted aryl group or a tertiary alkyl group (eg t-butyl group).

Specific examples of the compound represented by formula (VI) are shown below, but the invention is not limited thereto.

In addition to the above, specific examples include Japanese Patent Application No. 61-197760
Examples thereof include compound examples I- (1) to I- (36) described on pages 10 to 13.

The compound represented by the general formula (VI) is disclosed in Japanese Patent Application No. 61-19.
It can be obtained based on the method described in 7760.

Alcohols used in the present invention are represented by the following general formula (VI
It is a compound represented by I).

General formula (VII) In the formula, R ⁷¹ represents a hydroxy-substituted alkyl group (preferably having 1 to 10 carbon atoms, for example, a hydroxymethyl group, a hydroxyethyl group, etc.), and R ⁷² is an unsubstituted alkyl group (preferably having 1 to 10 carbon atoms, such as , Methyl group, ethyl group, etc.) or a group similar to R ⁷¹ . R ⁷³ represents a hydrogen atom or a group similar to R ⁷² . X ⁷¹ is a hydroxy group, a carboxyl group, a sulfo group, a nitro group, an unsubstituted or hydroxy-substituted alkyl group (preferably having a carbon number of 1 to 10, for example, methyl group, hydroxymethyl group, ethyl group, etc.),
Unsubstituted or substituted amide group (preferably having 2 to 2 carbon atoms)
10, for example, acetamido group, 2-hydroxybenzamide group, etc.), or an unsubstituted or substituted sulfonamide group (preferably having 1 to 10 carbon atoms, for example, methanesulfonamide group, 4-methylbenzenesulfonamide group, etc.) Represent.

In the general formula (VII), X ⁷¹ is preferably a hydroxy group, a carboxyl group or a hydroxyalkyl group.

Specific examples of the compound represented by formula (VII) are shown below, but the invention is not limited thereto.

VII-4 HO-CHCH ₂ OH) ₂ VII-5 (HOCH _{2 3} C-COOH VII-6 CCH ₂ OH) ₄ VII-7 (HOCH _{2 3} C-CH ₃ VII-8 (HOCH _{2 3} C-NHCOCH ₃ Specific examples other than the above include compound examples I- (1) to I- (15) described on pages 8 to 10 of Japanese Patent Application No. 61-186561;
No. 61-197419, compound examples I-described on pages 8 to 9
(1) to I- (9); and the like.

The compound represented by the general formula (VII) is disclosed in Japanese Patent Application No. 61-1.
It can be obtained based on the method described in 86561 and 61-197419.

The ethers that can be used in the present invention are represented by the following general formula (VI
It is a compound represented by I).

General formula (VIII) In the formula, R ⁸¹ , R ⁸² , and R ⁸³ each independently represent a hydrogen atom or an alkyl group (preferably having 1 to 10 carbon atoms, such as a methyl group or an ethyl group), and n is a positive integer up to 500. Represent.

The alkyl group represented by R ⁸¹ , R ⁸² , and R ⁸³ preferably has 5 or less carbon atoms, and more preferably 2 or less carbon atoms. R ⁸¹ , R ⁸² , and R ⁸³ are very preferably hydrogen atoms or methyl groups, and most preferably hydrogen atoms.

n is preferably a positive integer of 3 or more and 100 or less, and more preferably 3 or more and 30 or less.

Specific examples of the compound represented by formula (VIII) are shown below, but the invention is not limited thereto.

VIII-1 HOCH ₂ CH ₂ O ₄ OH VIII−2 CH ₃ OCH ₂ CH ₂ O ₃ OH VIII−3 CH ₃ OCH ₂ CH ₂ O ₂ OCH ₃ VIII-5 HOCH ₂ CH ₂ OCH ₃ VIII-6 C ₂ H ₅ OCH ₂ CH ₂ O ₂ OH VIII-7 HOCH ₂ CH ₂ O _n H Average molecular weight Approx. 300 VIII-8 HOCH ₂ CH ₂ O _n H Average molecular weight Approx. 800 VIII-9 HOCH ₂ CH ₂ O _n H average molecular weight about 3,000 VIII-10 HOCH ₂ CH ₂ O _n H average molecular weight about 8,000 The compound represented by the general formula (VIII) can be easily obtained as a commercial product.

The oximes that can be used in the present invention are represented by the following general formula (IX)
Is a compound represented by.

General formula (IX) In the formula, R ⁹¹ and R ⁹² each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. R ⁹¹ and R ⁹² may be the same or different, and these groups may be linked together.

As the substituent of the alkyl group and the aryl group, a halogen atom, an alkyl group, an aryl group, a hydroxyl group, an alkoxyl group, an aryloxy group, an amino group,
Carboxyl group, sulfo group, phosphonic acid group, carbamoyl group, sulfamoyl group, sulfonyl group, ureido group,
Examples thereof include an acyl group, an acylamino group, a sulfonamide group, an alkylthio group, an arylthio group, a nitro group and a cyano group, which may be substituted with two or more alkyl groups and two or more aryl groups. Moreover, the hydroxyl group, the carboxyl group, and the sulfo group may be salts of alkali metals (for example, sodium, potassium, etc.).

Preferred as R ⁹¹ and R ⁹² is a halogen atom,
An alkyl group substituted with a hydroxyl group, an alkoxyl group, an amino group, a carboxyl group, a sulfo group, a phosphonic acid group, a nitro group, and the like, and an unsubstituted alkyl group.

The total number of carbon atoms in the general formula (IX) is preferably 30 or less, more preferably 20 or less.

Specific examples of the compound represented by formula (IX) are shown below, but the invention is not limited thereto.

Specific examples other than the above include Japanese Patent Application No. 61-198987
Examples thereof include compound examples I- (1) to I (20) described on pages 11 to 14.

The compound represented by the above general formula (IX) is disclosed in Japanese Patent Application No. 61-
It can be obtained based on the method described in 198987.

The amide and sulfonamide compounds that can be used in the present invention are compounds represented by the following general formula (X).

General formula (X) In the formula, X ¹⁰¹ and X ¹⁰² each independently represent -CO- or -SO _2- , and R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ , R ¹⁰⁵ and R ^105
106 each independently represents a hydrogen atom or an unsubstituted or substituted alkyl group, and R ¹⁰⁷ represents an unsubstituted or substituted alkylene group, an unsubstituted or substituted arylene group or an unsubstituted or substituted aralkylene group. l, m and n each independently represent 0 or 1.

The alkyl group represented by R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ , R ¹⁰⁵ and R ¹⁰⁶ may be linear, branched or cyclic, and preferably has 1 to 12 carbon atoms. As a substituent,
Halogen atom (fluorine atom, chlorine atom, bromine atom), alkoxy group (methoxy group, ethoxy group, etc.), aryloxy group (phenoxy group, etc.), sulfonyl group (methylsulfonyl group, ethylsulfonyl group, phenylsulfonyl group, etc.), Sulfonamide group (methylsulfonamide group, benzenesulfonamide group, etc.), sulfamoyl group (unsubstituted sulfamoyl group, methylsulfamoyl group, dimethylsulfamoyl group, phenylsulfamoyl group, etc.), carbamoyl group (unsubstituted carbamoyl group) , Methylcarbamoyl group, phenylcarbamoyl group, etc.),
Amido group (acetylamide group, phenylamide group, etc.), ureido group (methylureido group, phenylureido group, etc.), alkoxycarbonylamino group (methoxycarbonylamino group, ethoxycarbonylamino group, etc.), cyano group, acyl group (acetyl group) Group, benzoyl group, etc.), nitro group, alkylthio group (methylthio group etc.), arylthio group (phenylthio group etc.), hydroxy group, sulfo group and carboxy group.

The alkylene group represented by R ¹⁰⁷ may be linear, branched, or cyclic, and preferably has 1 to 6 carbon atoms, and specifically includes methylene group, dimethylene group, trimethylene group, methyldimethylene group, Dimethyl trimethylene group,
Hexamethylene group, And the like. The arylene group preferably has 6 to 10 carbon atoms, and specifically, And the like. The alkylene group preferably has 7 to 12 carbon atoms, and specifically, And the like. These alkylene group, arylene group, the substituent of the aralkylene group, R ¹⁰¹ ,
The same substituents as R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ , R ¹⁰⁵ and R ¹⁰⁶ can be mentioned. When there are two or more substituents, they may be the same or different.

As R ¹⁰⁷ , an alkylene group is particularly preferable.

Specific examples of the compound represented by formula (X) are shown below, but the invention is not limited thereto.

X-6 H ₂ NSO ₂ NHSO ₂ NH ₂ Specific examples other than the above are Japanese Patent Application No. 61-201861.
Examples thereof include compound examples I- (1) to I- (27) described on pages 11 to 16.

The compound represented by the above general formula (X) is disclosed in Japanese Patent Application No. 61-20.
It can be obtained based on the method described in 1861.

The nitrogen-containing heterocycle that can be used in the present invention has the following general formula (X
It is a compound represented by I).

General formula (XI) In the formula, X ¹¹¹ represents a trivalent atom group necessary for completing the condensed ring, and R ¹¹¹ and R ¹¹² represent an alkylene group, an arylene group, an alkenylene group, and an aralkylene group. here
R ¹¹¹ and R ¹¹² may be the same or different.

In general formula (XI), the number of carbon atoms of X ¹¹¹ is preferably 20 or less, more preferably 10 or less, still more preferably 6 or less. R ¹¹¹ may contain atoms such as nitrogen, oxygen and sulfur.

In general formula (XI), R ¹¹¹ and R ¹¹² may each be substituted with a ground group. The carbon number of R ¹¹¹ and R ¹¹² is preferably 10 or less, more preferably 6 or less, and further preferably 3 or less. R ¹¹¹ and R ¹¹² are preferably an alkylene group or an arylene group, and more preferably an alkylene group.

The compound of general formula (XI) may be a bis form, a tris form, etc. linked by X ¹¹¹ .

Specific examples of X ^{111 in} the general formula (XI) include C═N−, —CH ₂ CH ₂ N, And so on.

Specific examples of R ¹¹¹ and R ^{112 in} the general formula (XI) include methylene group, ethylene group, propylene group, butylene group, pentylene group, 1,2-cyclohexylene group, 1-methylethylene group, 1,2- Dimethylethylene group, 1-carboxyethylene group, 1,2-phenylene group, 1,2-vinylene group, 1,3-
Examples thereof include a propenylene group, and these include an alkyl group, a halogen atom, a carboxyl group, a sulfo group, a hydroxyl group, an alkoxy group, an alkylthio group, an amino group, an amide group, an acyl group, a carbamoyl group, a sulfamoyl group, and a heterocyclic group. May be further replaced.

Among the general formula (XI), the particularly preferable one is the general formula (XI
-A) and compounds represented by (XI-b).

In the formula, X ¹¹¹ represents N or CH. R ¹¹¹ and R ¹¹² are defined as in formula (XI), and R ¹¹³ is R ¹¹¹ and R ¹¹² .
A group similar to ¹¹² or Represents

In general formula (XI-a), X ¹¹² is preferably N. The carbon number of R ¹¹¹ , R ¹¹² , and R ¹¹³ is preferably 6 or less, more preferably 3 or less, and most preferably 2. R ¹¹¹ , R ¹¹² and R ¹¹³ are alkylene groups,
An arylene group is preferred, and an alkylene group is most preferred.

In the formula, R ¹¹¹ and R ¹¹² are defined as in the general formula (XI).

In general formula (XI-b), it is preferable that R ¹¹¹ and R ¹¹² have 6 or less carbon atoms. R ¹¹¹ and R ¹¹² are preferably an alkylene group or an arylene group, and most preferably an alkylene group.

Among the compounds represented by formulas (XI-a) and (XI-b), the compound represented by formula (XI-a) is particularly preferable.

Specific examples of the compound represented by formula (XI) according to the present invention are shown below, but the present invention is not limited thereto.

Many compounds of general formula (XI) according to the present invention can be easily obtained as commercial products.

The addition amount of the compounds represented by the general formulas (II) to (XI) is preferably 0.01 g to 100 g, and more preferably 0.1 g to 20 g, per color developing solution.

Further, the compounds of the general formulas (II) to (XI) of the present invention, in a system using an aromatic primary amine color developing agent, in combination with a compound which directly stabilizes the developing agent,
Particularly remarkable preservative performance. As the "compound which directly stabilizes the developing agent", water-soluble antioxidants are generally known, and examples thereof include hydroxylamines, hydroxamic acids, hydrazines, hydrazides, phenols and α-hydroxyketones. , Α-aminoketones,
And sugars.

The details of the compounds that are preferably used in combination are described below.
Hydroxylamines are represented by the following general formula (XII).

General formula (XII) In the formula, R ¹²¹ and R ¹²² represent a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkenyl group, or an unsubstituted or substituted aryl group.

It is preferable that R ¹²¹ and R ¹²² are an alkyl group or an alkenyl group, and it is more preferable that at least one of them has a substituent. R ¹²¹ and R ¹²² may be linked to form a hetero ring together with the nitrogen atom.

The alkyl group and the alkenyl group may be linear, branched, or cyclic, and the substituent is a halogen atom, an aryl group, an alkoxy group, an aryloxy group, a sulfonyl group,
Sulfonamide group, sulfamoyl group, carbamoyl group, amide group, ureido group, alkoxycarbonylamino group, allyloxycarbonylamino group, alkoxycarbonyl group, aryloxycarbonyl group, cyano group, hydroxy group, carboxy group, sulfo group, nitro group , Amino groups, alkylthio groups, arylthio groups, and heterocyclic groups. Here, R ¹²¹ and R ¹²² may be the same or different, and the substituents of R ¹²¹ and R ¹²² may be the same or different.

The carbon number of R ¹²¹ and R ¹²² is preferably 1-10, and particularly 1
-5 are preferable. The nitrogen-containing heterocycle formed by linking R ¹²¹ and R ¹²² , a piperidyl group, a pyrrolidyl group,
Examples thereof include N-alkylpiperazyl group, morpholyl group, indolinyl group and benztriazolyl group.

Preferred substituents for R ¹²¹ and R ¹²² are a hydroxy group, an alkoxy group, a sulfonyl group, an amido group, a carboxy group, a cyano group, a sulfo group, a nitro group and an amino group.

Specific examples of the compound represented by formula (XII) used in the present invention are shown below, but the scope of the present invention is not limited to this compound.

Absent.

XII-19 NH ₂ OH The compound represented by the general formula (XII) can be synthesized by the known method shown below. U.S. Patent No.
3,661,996, 3,362,961, 3,293,034, Japanese Patent Publication No. 4
2-2794, U.S. Patent Nos. 3,491,151 and 3,655,764,
3,467,711, 3,455,916, 3,287,125, 3,2
87,124.

These compounds may form salts with various acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, oxalic acid and acetic acid.

Hydroxamic acids are represented by the following general formula (XIII).

General formula (XIII) In the formula, A ¹³¹ is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkoxy group, a substituted Alternatively, it represents an unsubstituted aryloxy group, a substituted or unsubstituted carbamoyl group, a substituted or unsubstituted sulfamoyl group, an acyl group, a carboxy group, a hydroxyamino group, or a hydroxyaminocarbonyl group. As the substituent, a halogen atom, an aryl group, an alkyl group, an alkoxy group, an aryloxy group, a hydroxy group, a sulfonyl group, a sulfonamide group, a sulfamoyl group, a sulfo group, an amide group, a ureido group, a cyano group, a hydroxyaminocarbonyl group,
Examples thereof include a carboxy group, a nitro group, an amino group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylthio group, an arylthio group, and a heterocyclic group (pyridyl group, morpholino group, etc.).

Preferably A ¹³¹ is a substituted or unsubstituted alkyl group,
An aryl group, an amino group, an alkoxy group, and an aryloxy group. Particularly preferred examples are a substituted or unsubstituted amino group, an alkoxy group, and an aryloxy group. The number of carbon atoms is preferably 1-10.

X ¹³¹ -SO ₂ -, or represents a -SO-. Preferably X ¹³¹ is Is.

R ¹³¹ is a hydrogen atom, a substituted or unsubstituted alkyl group,
It represents a substituted or unsubstituted aryl group. At this time,
A ¹³¹ and R ¹³¹ may combine to form a ring structure. The substituent is the same as the substituent mentioned in A ¹³¹ . Preferably
R ¹³¹ is a hydrogen atom.

Y ¹³¹ represents a hydrogen atom or a group capable of becoming a hydrogen atom by a hydrolysis reaction.

Specific examples of the case where Y ¹³¹ represents a group capable of becoming a hydrogen atom by a hydrolysis reaction include the following.

1) Method of protecting with ester bond or urethane bond, that is, Y ¹³¹ is Represents Here, examples of R ¹³² include a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted amino group.

2) A method of protecting with an imidomethyl blocking group described in JP-A-57-158638, that is, Y ¹³¹ is Represents Where J is And Z represents a plurality of atoms necessary for completing a heterocycle having at least one 5-membered ring or 6-membered ring.

Specific compounds are shown below, but the invention is not limited thereto.

Compound example The above compounds can be obtained based on the description in JP-A-61-186559.

Hydrazines and hydrazides are represented by the following general formula (XIV)
Is a compound represented by.

General formula (XIV) In the formula, R ¹⁴¹ , R ¹⁴² and R ^{143 each} represent a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group or a heterocyclic group, and R ¹⁴⁴ represents a hydroxy group, a hydroxyamino group, a substituted or unsubstituted alkyl group. Group, aryl group, heterocyclic group, alkoxy group, aryloxy group, carbamoyl group, ammono group.

X ¹⁴¹ is --CO--, --SO _2-, or Represents a divalent group selected from, and n is 0 or 1. Particularly, when n = 0, R ¹⁴⁴ represents a group selected from an alkyl group, an aryl group and a heterocyclic group, and R ¹⁴³ and R ¹⁴⁴ may together form a heterocycle.

In formula (XIV), R ¹⁴¹ , R ¹⁴² , and R ¹⁴³ are preferably hydrogen atoms or alkyl groups, and most preferably R ¹⁴¹ and R ¹⁴² are hydrogen atoms.

In formula (XIV), R ¹⁴⁴ represents an alkyl group, an aryl group,
It is preferably an alkoxy group, a carbamoyl group or an amino group. X ¹⁴¹ is preferably —CO— or —SO ₂ —, and most preferably —CO—.

XIV−2 NH ₂ NHCH _{2 2} OH XIV-4 NH ₂ NHCOOC ₂ H ₅ XIV-6 NH ₂ NHCONH ₂ XIV-7 NH ₂ NHSO ₃ H XIV-8 NH ₂ NHCOCONHNH _{2 The} above compounds can be obtained based on the description in Japanese Patent Application No. 61-170756.

 Phenols are represented by the following general formula (XV).

General formula (XV) In the formula, R ¹⁴¹ represents a hydrogen atom, a halogen atom, an alkyl group,
Aryl group, alkoxy group, aryloxy group, carboxyl group, sulfo group, carbamoyl group, sulfamoyl group, amide group, sulfonamide group, ureido group, alkylthio group, arylthio group, nitro group, cyano group, amino group, formyl group, acyl Represents a group, a sulfonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkoxysulfonyl group and an aryloxysulfonyl group.

When R ¹⁵¹ is further substituted, the substituent is a halogen atom, an alkyl group, an aryl group, a hydroxyl group,
Alkoxy group, aryloxy group, carboxyl group, sulfo group, carbamoyl group, sulfamoyl group, amide group,
Sulfonamide group, ureido group, alkylthio group, arylthio group, nitro group, cyano group, amino group, formyl group, acyl group, sulfonyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkoxysulfonyl group, aryloxysulfonyl group, and Heterocyclic groups (morpholyl group, pyridyl group, etc.) and the like,
Further, these substituents may substitute two or more and two or more kinds for R ¹⁵¹ . When there are two or more R ^151, they may be the same or different, and when they are adjacent to each other, they may be bonded to each other to form a ring. The ring structure is a 5- to 6-membered ring and is constituted by a carbon atom, a hydrogen atom, a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom and the like, and may be saturated or unsaturated. In addition,
In R ¹⁵¹ and its substituent, the carboxyl group and the sulfo group are an alkali metal (Na, K, etc.),
The amino group may form a salt with various acids such as hydrochloric acid.

R ¹⁵² represents a hydrogen atom or a hydrolyzable group. The hydrolyzable group is a group that can be converted into a hydrogen atom by hydrolysis, and as a specific example thereof, (Here, R ¹⁵³ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted amino group.). That is, it is a method of protecting with an ester bond or a urethane bond.
Another example is the protection with imidomethyl blocking groups described in JP-A-57-158638. That is, (Where R ¹⁵⁴ is Or And R ¹⁵⁵ represents a plurality of atoms necessary for completing a heterocycle having at least one 5-membered ring or 6-membered ring. ). Further, m and n are integers from 1 to 5, respectively.

In formula (XV), preferred R ¹⁵¹ is alkyl group, halogen atom, alkoxy group, alkylthio group, carboxyl group, sulfo group, carbamoyl group, sulfamoyl group, amino group, amide group, sulfonamide group, nitro group and cyano group. It is a base. Of these, an alkoxy group, an alkylthio group, an amino group, and a nitro group are particularly preferable, and these are more preferably at the ortho position or para position of the (OR ¹⁵² ) group. The carbon number of R ¹⁵¹ is preferably from 1 to 10, and particularly preferably from 1 to 6.

Preferred R ¹⁵² is a hydrogen atom or a hydrolyzable group having 1 to 5 carbon atoms. Also (OR ¹⁵² )
When there are two or more groups, it is more preferable that they are located in the ortho position or the para position relative to each other.

Specific examples are shown below, but the present invention is not limited to these.

The above compounds can be obtained based on Japanese Patent Application Nos. 61-188742 and 61-203253.

The α-hydroxyketones and α-aminoketones are represented by the following general formula (XVI).

General formula (XVI) In the formula, R ¹⁶¹ represents a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, an alkoxy group, an aryloxy group or an amino group, and R ¹⁶² represents a hydrogen atom, a substituted or unsubstituted alkyl group or an aryl group. , R ¹⁶¹ and R ¹⁶² may together form a carbocycle or a heterocycle.

X ¹⁶¹ represents a hydroxyl group or a substituted or unsubstituted amino group.

In formula (XVI), R ¹⁶¹ is preferably a hydrogen atom, an alkyl group, an aryl group or an alkoxy group, and R ^161
162 is preferably a hydrogen atom or an alkyl group.

The above compound can be obtained based on Japanese Patent Application No. 61-188741.

 The "sugar" used in the present invention will be described in detail.

(Also referred to as carbohydrate) saccharide comprises monosaccharide and polysaccharide, many have the general formula C _n H _2m O _m. The monosaccharides are generally referred to as aldehydes or ketones of polyhydric alcohols (referred to as aldose and ketose, respectively) and their reduced derivatives, oxidized derivatives, dehydrated derivatives, and a wider range of derivatives such as amino sugars and thio sugars. The polysaccharide refers to a product obtained by dehydrating and condensing two or more of the aforementioned monosaccharides.

Among these sugars, more preferable ones are aldoses having a reducing aldehyde group, and derivatives thereof, and particularly preferable ones are those corresponding to monosaccharides.

Specific examples of saccharides that can be used in the present invention are shown below, but the present invention is not limited thereto.
(These optical isomers can be used as well.) The above compounds can be easily obtained as commercial products.

The amount of the compounds represented by the general formulas (XII) to (XVII) added is 0.01 g to 50 g, preferably 0.5 g to 20 g, per 1 color developing solution.

Other sulfite ions known as preservatives are not substantially contained in the present invention. Substantially, it may be added in a range that does not affect the photographic characteristics, specifically 0 to 0.005 mol / l, preferably 0 to 0.002 mol / l, more preferably 0 to 0.0005 mol / l. Is.

As other preservatives, hydroxyacetones described in U.S. Pat.No. 3,615,503 and British Patent 1,306,176, α-aminoarbonyl compounds described in JP-A-52-143020 and 53-89425, JP-A-57-44148 And various metals described in JP-A-57-53749, various sugars described in JP-A-52-102727, α, α'-dicarbonyl compounds described in 59-160141, and 59-180588. Salicylic acids, the same 56-7564
The gluconic acid derivative described in No. 7 may be contained as necessary, and two or more kinds of these preservatives may be used in combination as required. It is particularly preferable to add an aromatic polyhydroxy compound.

It is preferable that the color developer of the present invention does not substantially contain benzyl alcohol in terms of fog and increase in stain after processing. That is, it does not contain substantially,
5.0 ml or less, preferably 2 ml or less, per color developer,
More preferably, it is not contained at all.

The color developer used in the present invention preferably has a pH of 9
-12, more preferably 9-11.0, and the color developing solution may contain other known developer component compounds.

In order to maintain the above pH, it is preferable to use various buffers. As the buffer, carbonate, phosphate, borate, tetraborate, hydroxybenzoate, glycine salt,
N, N-dimethylglycine salt, leucine salt, norleucine salt, guanine salt, 3,4-dihydroxyphenylalanine salt, alanine salt, aminobutyrate, 2-amino-2-methyl-1,3-propanediol salt, valine salt , Proline salt, trishydroxyaminomethane salt, lysine salt and the like can be used. In particular, carbonates, phosphates, tetraborate and hydroxybenzoates are highly soluble and have a high pH of 9.0 or above.
It is particularly preferable to use these buffers because they have excellent buffering ability in the H region, have no adverse effect on photographic performance (fog, etc.) even when added to a color developing solution, and are inexpensive.

Specific examples of these buffers include sodium carbonate,
Potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (borax), tetraborate Potassium acid, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, 5-
Sodium sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate)
And so on. However, the invention is not limited to these compounds.

The amount of the buffer added to the color developing solution is preferably 0.1 mol / l or more, and particularly preferably 0.1 mol / l to 0.4 mol / l.

In addition, various chelating agents can be used in the color developing solution as a precipitation preventing agent for calcium and magnesium, or for improving the stability of the color developing solution.

As the chelating agent, an organic acid compound is preferable, for example, aminopolycarboxylic acids described in JP-B-48-30496 and JP-B-44-30232, JP-A-56-97347, JP-B-56-39359 and West German Patent No. 2,227,639. Organic phosphonic acids described,
JP-A-52-102726, JP-A-53-42730, JP-A-54-121127
Nos. 55-126241 and 55-6559506, and phosphonocarboxylic acids described in JP-A-58-195845 and JP-A-58-195845.
The compounds described in 203440 and JP-A-53-40900 can be mentioned. Specific examples are shown below, but the present invention is not limited thereto.

-Nitrilotriacetic acid-Diethylenetriaminepentaacetic acid-Ethylenediaminetetraacetic acid-Triethylenetetraminehexaacetic acid-N, N, N-trimethylenephosphonic acid-Ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid-1,3 -Diamino-2-propanoltetraacetic acid-Transcyclohexanediaminetetraacetic acid-Nitrilotripropionic acid-1,2-diaminopropanetetraacetic acid-Hydroxyethyliminodiacetic acid-Glycol ether diaminetetraacetic acid-Hydroxyethylenediaminetriacetic acid-Ethylenediamineorthohydroxyphenyl Acetic acid 2-phosphonobutane-1,2,4-tricarboxylic acid 1-hydroxyethylidene-1,1-diphosphonic acid N, N'-bis (2-hydroxybenzyl) ethylenediamine-N, N'-diacetic acid If necessary, use two or more chelating agents in combination. Is also good.

The amount of these chelating agents added may be an amount sufficient to block the metal ions in the color developing solution. Eg 1
It is about 0.1g to 10g per unit.

If necessary, any development accelerator can be added to the color developing solution.

As a development accelerator, Japanese Patent Publication Nos. 37-16088 and 37-598.
No. 7, No. 38-7826, No. 44-12380, No. 45-9019, and thioether compounds represented by U.S. Pat.No. 3,813,247, etc., and are represented by JP-A Nos. 52-49829 and 50-15554. p-Phenylenediamine compound, JP-A-50-1377
No. 26, Japanese Patent Publication No. 44-30074, JP-A No. 56-156826 and 5
2-43429, particularly quaternary ammonium salts represented, p-aminophenols described in U.S. Pat. Nos. 2,610,122 and 4,119,462, U.S. Pat. Nos. 4,494,903, 3,128,182.
No. 4,230,796, 3,253,919, Japanese Patent Publication No. 41-11431
U.S. Pat.Nos. 2,482,546, 2,596,926 and 3,58.
Amine compounds described in 2,346, etc., JP-B-37-16088
No. 42-25201, U.S. Pat.No. 3,128,183, Japanese Patent Publication No. 41
-11431, 42-23883 and U.S. Pat.
Phenyl-3-pyrazolidones, hydrazines, mesoionic compounds, ionic compounds, imidazoles, and the like can be added as necessary.

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

The color developer used in the present invention preferably contains a fluorescent whitening agent. 4,4'-
Diamino-2,2'-disulfostilbene compounds are preferred. The addition amount is 0 g to 5 / l, preferably 0.1 g to 4 g / l.

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

The processing temperature of the color developer of the present invention is from 20 to 50 ° C, preferably from 30 to 40 ° C. Processing time is 20 seconds to 5 minutes, preferably 30
Seconds to 2 minutes. The replenishment amount is preferably smaller, but is preferably ^{20 to} 600 ml, and more preferably 50 to 300 ml, per m ^{2 of} the light-sensitive material. More preferably, it is 100 ml to 200 ml.

Next, the bleaching solution, the bleach-fixing solution and the fixing solution used in the present invention will be described.

As the bleaching agent used in the bleaching solution or the bleach-fixing solution used in the present invention, any bleaching agent can be used, but especially organic complex salts of iron (III) (for example, aminopolyamines such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid). Carboxylic acids, complex salts of aminopolyphosphonic acid, phosphonocarboxylic acid and organic phosphonic acid) or organic acids such as citric acid, tartaric acid and malic acid; persulfates; hydrogen peroxide and the like are preferable.

Of these, organic complex salts of iron (III) are particularly preferable from the viewpoint of rapid processing and prevention of environmental pollution. Examples of aminopolycarboxylic acids, aminopolyphosphonic acids, or organic phosphonic acids or salts thereof useful for forming organic complex salts of iron (III) include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediamine-N- ( β-oxyethyl) -N, N ′,
N'-triacetic acid, 1,3-diaminopropanetetraacetic acid, triethylenetetraminehexaacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, nitrilotripropionic acid, cyclohexanediaminetetraacetic acid, 1,3-diamino-2-propanoltetraacetic acid , Methyliminodiacetic acid, iminodiacetic acid, hydroxyliminodiacetic acid, dihydroxyethylglycine ethyletherdiaminetetraacetic acid, glycoletherdiaminetetraacetic acid, ethylenediaminetetrapropionic acid, ethylenediaminedipropionacetic acid, phenylenediaminetetraacetic acid, 2-phosphonobutane-1, 2,4-triacetic acid, 1,3-diaminopropanol-N, N, N ', N'-tetramethylenephosphonic acid, ethylenediamine-N, N, N', N'-tetramethylenephosphonic acid, 1,3- Propylenediamine-N, N, N ', N'-tetramethylenephospho Acid, 1-hydroxyethylidene-1,1-diphosphonic acid, and the like.

These compounds may be sodium, potassium, lithium or ammonium salts. Among these compounds, the iron (III) complex salts of ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid and methyliminodiacetic acid are preferred because of their high bleaching power.

These ferric ion complex salts may be used in the form of complex salts, and ferric salts such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, ferric phosphate. And a chelating agent such as aminopolycarboxylic acid, aminopolyphosphonic acid or phosphonocarboxylic acid may be used to form a ferric ion complex salt in a solution. When used in the form of a complex salt, one type of complex salt may be used, or two or more types of granular salt may be used. On the other hand, when a complex salt is formed in a solution using a ferric salt and a chelating agent, one or more ferric salts may be used. Further, one or more chelating agents may be used. In any case, the chelating agent may be used in excess of the amount of forming the ferric ion complex salt. Among the iron complexes, aminopolycarboxylic acid iron complexes are preferable, and the addition amount is 0.01 to 1.0 mol / l.
It is preferably 0.05 to 0.50 mol / l.

Further, a bleaching accelerator can be used in the bleaching solution or the bleach-fixing solution, if necessary. Specific examples of useful bleaching accelerators include U.S. Patent No. 3,893,858 and West German Patent No. 1,29.
0,812, 2,059,988, JP-A-53-32736, 53-5
7831, 53-37418, 53-65732, 53-72623
No. 53-95630, No. 53-95631, No. 53-104232,
No. 53-124424, No. 53-141623, No. 53-28426, Research Disclosure No. 17129 (July 1978), compounds having a mercapto group or a disulphide group; JP-A-50-140129. Thiazolidine derivatives as described; JP-B-45-8506, JP-A-52-20832,
No. 53-32735, thiourea derivatives described in U.S. Pat. Polyamine compounds described in JP-B-45-8836; Other JP-A-49-42434,
49-59644, 53-94927, 54-35727, 55
-26506 and 58-163940, and iodine, bromine ion and the like can be mentioned. Among them, a compound having a mercapto group or a disulphide group is preferable in that accelerated curing is large, and particularly, U.S. Pat. No. 3,893,858.
The compounds described in No. 1, West German Patent 1,290,812 and JP-A-53-95630 are preferred.

In addition, the bleaching solution or bleach-fixing solution used in the present invention contains a bromide (for example, potassium bromide, sodium bromide,
Rehalogenating agents such as ammonium bromide) or chlorides (eg potassium chloride, sodium chloride, ammonium chloride) or iodides (eg ammonium iodide) can be included. One or more inorganic acids having a pH buffering capacity, such as boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, if necessary, Organic acids and their alkali metal or ammonium salts, or corrosion inhibitors such as ammonium nitrate and guanidine can be added.

The bleach-fixing solution or the fixing agent used in the fixing solution according to the present invention includes known fixing agents, that is, thiosulfates such as sodium thiosulfate and ammonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate; ethylene. Bisthioglycolic acid, 3,6-dithia-1,8
A thioether compound such as octanediol and a water-soluble silver halide solubilizer such as thioureas, and these may be used alone or in admixture of two or more. Further, a special bleach-fixing solution containing a combination of a fixing agent described in JP-A-55-155354 and a large amount of a halide such as potassium iodide can be used.
In the present invention, the use of thiosulfates, particularly ammonium thiosulfates, is preferred.

The amount of the fixing agent per 1 is preferably 0.3 to 2 mol, more preferably 0.5 to 1.0 mol.

The pH range of the bleach-fixing solution or the fixing solution in the present invention is from 3 to
10 is preferable, and 5 to 9 is particularly preferable. When the pH is lower than this, desilvering property is improved, but deterioration of the liquid and leuco conversion of the cyan dye are promoted. Conversely, if the pH is higher than this, desilvering will be delayed and stain will easily occur.

To adjust the pH, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, bicarbonate, ammonia, caustic potash, caustic soda, sodium carbonate, potassium carbonate and the like can be added as necessary.

Further, the bleach-fixing solution may contain various other fluorescent whitening agents, defoaming agents or surfactants, polyvinylpyrrolidone, organic solvents such as methanol and the like.

The bleach-fixing solution or the fixing solution according to the present invention may be a sulfite (for example, sodium sulfite, potassium sulfite,
Ammonium bisulfite, etc.), bisulfite (eg, ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.), metabisulfite (eg, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.) ) And the like. These compounds have a sulfite ion equivalent of about 0.02.
The content is preferably 0.5 to 0.50 mol / l, more preferably 0.04 to 0.40 mol / l.

As a preservative, it is common to add sulfite,
In addition, ascorbic acid, a carbonyl bisulfite addition product, a carbonyl compound, or the like may be added.

Further, a buffer, an optical brightener, a chelating agent, an antifoaming agent, a fungicide, and the like may be added as necessary.

Next, the water washing step in the present invention will be described. Here, the “rinsing process” includes rinsing treatment, rinsing acceleration treatment, and other alternative rinsing treatments.

In the present invention, it is possible to use a treatment method in which a so-called "stabilization treatment" is performed without providing a substantial water washing step instead of the usual "water washing treatment".

The amount of rinsing water or the stabilizing solution in the present invention is difficult to define because it depends on the number of baths in multi-stage countercurrent processing and the amount of the pre-bath component of the light-sensitive material brought in, but in the present invention, the final The bleaching or fixing solution component in the bath or the bath after the bath having the fixing ability may be 1 × 10 ^-4 or less. For example, in the case of washing with countercurrent flow in 3 tanks, about 1000 ml per 1 m ² of light-sensitive material
It is preferably used above, more preferably 5000 ml or more. In the case of water-saving processing, 100 to 1m ² of light-sensitive material
It is recommended to use 1000 ml.

The washing or stabilizing treatment temperature is 15 ° C to 45 ° C, more preferably 20 ° C to 35 ° C.

In the washing step, various known compounds may be added for the purpose of preventing precipitation and stabilizing the washing water. For example, chelating agents such as inorganic phosphoric acid, aminopolycarboxylic acid, and organic phosphonic acid, bactericides and antifungal agents that prevent the generation of various bacteria, algae, and molds (for example, "Journal of Antibacterial・ Anti-Fungal Ages "(J.Antibact.Antifung.Agents), Vo1.11, No.
5, p207 to 223 (1983) and compounds described in Hiroshi Horiguchi's "Chemistry of Antibacterial and Antifungal", metal salts represented by magnesium salts and aluminum salts, alkali metal and ammonium salts, or dry load. If necessary, a surfactant or the like for preventing unevenness can be added. Or West, “Photographic Science and Engineering Linearing Magazine (Phot.Sci.En
g.), Vol. 6, pp. 344-359 (1965), etc., may be added.

Further, the present invention is particularly effective in the case of adding a chelating agent, a bactericidal agent and an antibacterial agent to the washing water to greatly reduce the amount of washing water by multi-stage countercurrent washing with two or more tanks. It is also particularly effective when a multi-stage countercurrent stabilization treatment step (so-called stabilization treatment) as described in JP-A-57-8543 is carried out instead of the usual water washing step. In these cases, the bleaching and fixing components in the final bath should be 5 × 10 ^-2 or less, preferably 1 × 10 ^-2.
The following is acceptable. Further, a method of significantly reducing the amount of water by using only water such as distilled water or ion-exchanged water from which calcium ions and magnesium ions in the water are significantly removed is also effective.

Various compounds are added to the stabilizing bath for the purpose of stabilizing an image. For example, adjust the membrane pH (eg pH 3 ~
8) various buffering agents (for example, borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acid, dicarboxylic acid, polycarboxylic acid, etc. Are used in combination) and aldehydes such as formalin. Other chelating agents (inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphonic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), bactericidal agents (thiazole-based, isothiazole-based, halogenated phenol, sulfanilamide, benzotriazole, etc.) ), Various additives such as surfactants, optical brighteners and hardeners may be used, and two or more kinds of the same or different target compounds may be used in combination.

Also, ammonium chloride as a membrane pH adjuster for the processor,
It is preferable to add various ammonium salts such as ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate in order to improve the image storability.

When the amount of wash water or stabilizing solution as described above is significantly reduced, a part or all of the overflow solution of wash water may flow into the bleach-fixing bath or fixing bath which is the pre-bath. It is preferable for the purpose of reduction.

In the present processing step, a constant finish can be obtained by using a replenisher of each processing liquid to prevent fluctuations in the liquid composition during continuous processing. The replenishment amount can be reduced to half or less than the standard replenishment amount for cost reduction.

In each treatment bath, a heater, a temperature sensor, a liquid level sensor, a circulation pump, a filter, various floating pigs, various squeegees, nitrogen stirring, air stirring, and the like may be provided as necessary.

In the method of the present invention, any processing step can be applied as long as the processing uses a color developing solution. For example, it can be applied to the processing of color paper, color reversal paper, color positive film, color negative film, color reversal film and the like, but it is particularly preferably applied to color paper and color reversal paper.

The silver halide emulsion of the light-sensitive material used in the present invention is
Any halogen composition having silver iodobromide, silver bromide, silver chlorobromide, silver chloride or the like can be used. For example, when performing rapid processing or low replenishment processing of a color paper or the like, a silver chlorobromide emulsion or a silver chloride emulsion containing 60 mol% or more of silver chloride is preferable, and furthermore, a silver chloride content of 80 to 100 is preferable. Molar% is particularly preferred. In addition, high sensitivity is required, and at the time of manufacturing,
When it is necessary to suppress the fog during storage and / or processing to a particularly low level, a silver chlorobromide emulsion or a silver bromide emulsion containing 50 mol% or more of silver bromide (3 mol% or less of silver iodide) May be contained), and more preferably 70 mol% or more. Silver bromoiodide and silver chloroiodobromide are preferable for the color light-sensitive material for photography, and the silver iodide content is preferably 3 to 15 mol%.

The silver halide grains used in the present invention may have different phases in the inside and the surface layer, may have a multi-phase structure having a junction structure, or may have a uniform phase as a whole. Moreover, they may be mixed.

The average grain size of the silver halide grains used in the present invention is represented by the grain diameter (in the case of spherical grains or grains close to spheres) and the ridge length in the case of cubic grains, which is the average based on the projected area. Is expressed in terms of yen) is preferably 2 μm or less and 0.1 μm or more, and particularly preferably 1.5 μm or less and 0.15 μm or more. The grain size distribution may be narrow or wide, but the value (variation rate) obtained by dividing the standard deviation value in the grain size distribution curve of the silver halide emulsion by the average grain size is within 20%, particularly preferably 15 It is preferred to use so-called monodisperse silver halide emulsions within the range of% in the present invention. Further, in order to satisfy the target gradation of the light-sensitive material, two or more kinds of monodisperse silver halide emulsions having different grain sizes in the emulsion layers having substantially the same color sensitivity (the above-mentioned monodispersity is the same). Those having a variation rate are preferable) can be mixed in the same layer or multilayer-coated in different layers. Further, two or more kinds of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion may be used as a mixture or as a mixture.

The silver halide grains used in the present invention have a regular shape such as a cube, an octahedron, a rhodohedron and a tetradecahedron.
It may be a compound having different crystal forms or a coexisting form thereof, may have an irregular crystal form such as a sphere, or may have a composite form of these crystal forms. Further, tabular grains may be used, and in particular, an emulsion in which tabular grains having a length / thickness ratio value of 5 to 8 or 8 or more account for 50% or more of the total projected area of grains may be used. It may be an emulsion composed of a mixture of these various crystal forms. These various emulsions may be either a surface latent image type which forms a latent image mainly on the surface or an internal latent image type which is formed inside the grain.

The photographic emulsion used in the present invention is Research Disclosure (RD) vol.170 Item No.17643 (I, II, III).
It can be prepared using the method described in section (December 1978).

The emulsion used in the present invention is usually one that has been physically ripened, chemically ripened and spectrally sensitized. Additives used in such processes are Research Disclosure Vol. 176, No. 17643 (December 1978) and Vol. 187,
No. 18716 (November 1979), and the relevant locations are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the locations described in the table below are shown.

Various color couplers can be used in the present invention. Here, the color coupler means a compound capable of forming a dye by a coupling reaction with an oxidized product of an aromatic primary amine developing agent. Typical examples of useful color couplers in addition to the 2-equivalent yellow couplers of this invention are naphthol or phenolic compounds and pyrazolone or pyrazoloazole compounds. Further, an open-chain or heterocyclic ketomethylene compound may be used in combination as a yellow coupler other than the present invention. Specific examples of these cyan, magenta and yellow couplers that can be used in the present invention are described in Research Disclosure (RD) 17643 (1978, 1
(Feb.) Section VII-D and the patent cited in 18717 (November 1979).

The color coupler incorporated in the light-sensitive material preferably has a ballast group or is polymerized to be diffusion resistant. The amount of coated silver can be reduced in the case of a two-equivalent color coupler in which a coupling active position is substituted by a leaving group, rather than a four-equivalent color coupler in which a hydrogen atom is present. A coupler in which the color-forming dye has a suitable diffusibility, a colorless coupler, or a DIR coupler which releases a development inhibitor upon coupling reaction or a coupler which releases a development accelerator can also be used.

Examples of the magenta coupler which can be used in the present invention include oil-protection type indazolone type or cyanoacetyl type, preferably 5-pyrazolone type and pyrazoloazole type couplers such as pyrazolotriazoles. The 5-pyrazolone-based coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamino group, from the viewpoint of the hue and color density of the color forming dye, and typical examples thereof are U.S. Pat.Nos. 2,311,082 and 2,343,703. ,
No. 2,600,788, No. 2,908,573, No. 3,062,653
No. 3,152,896 and No. 3,936,015. As the leaving group of the 2-equivalent 5-pyrazolone-based coupler, the nitrogen atom leaving group described in US Pat. No. 4,310,619 or the arylthio group described in US Pat. No. 4,351,897 is preferable. Further, the 5-pyrazolone-based coupler having a ballast group described in EP 73,636 provides a high color density.

As the pyrazoloazole-based coupler, US Pat.
369,879 pyrazolobenzimidazoles, preferably pyrazolo [5,1-c] [1,2,4] triazoles described in US Pat. No. 3,725,067, Research Disclosure 24220 (June 1984). Pyrazolotetrazoles and Research Disclosure 24 described
The pyrazolopyrazoles described in 230 (June 1984) can be mentioned. The imidazo [1,2-b] pyrazoles described in European Patent No. 119,741 are preferable in view of less yellow sub-absorption of the color forming dye and light fastness, and European Patent No. 119,8
The pyrazolo [1,5-b] [1,2,4] triazole described in No. 60 is particularly preferable.

The image forming method of the present invention is particularly performed by the following general formula (XVIII).
It is preferable to use magenta couplers represented by (XIX) and (XIX).

General formula (XVIII) General formula (XIX) In formula (XVIII), R ¹⁸¹ and R ¹⁸² represent a substituted or unsubstituted phenyl group, R ¹⁸³ represents a hydrogen atom, an aliphatic or aromatic acyl group, an aliphatic or aromatic sulfonyl group, and Y ¹⁸¹ represents Represents a hydrogen atom or a group capable of splitting off upon coupling reaction with an oxidant with a developing agent (hereinafter abbreviated as splitting group), and in the formula (XIX), R ¹⁹¹ represents a hydrogen atom or a substituent, and Za and Zb Represents methine, substituted methine, or ═N—, and Y ¹⁹¹ represents a halogen atom or a leaving group. Furthermore, R ¹⁸¹ , R ¹⁸² , R ¹⁸³ or Y ¹ ; R ¹⁹¹ , Za, Zb or Y ¹⁹¹ may form a dimer or higher multimer.

The aliphatic group mentioned here represents a linear, branched or cyclic alkyl group, alkenyl or alkynyl group.

R ^{181 to} R ¹⁸³ , R in the general formulas (XVIII) and (XIX)
¹⁹¹ , Y ¹⁸¹ , Y ¹⁹¹ , Za and Zb will be described in detail.

In the general formulas (XVIII) and (XIX), Y ¹⁸¹ or Y ¹⁹¹
Represents a coupling-off group (hereinafter referred to as a leaving group), the leaving group is a coupling activated carbon via an oxygen, nitrogen, sulfur or carbon atom, an aliphatic group, an aromatic group, a heterocyclic group, An aliphatic / aromatic or heterocyclic sulfonyl group, a group that bonds with an aliphatic / aromatic or heterocyclic carbonyl group, a halogen atom, an aromatic azo group, etc., and an aliphatic group contained in these leaving groups, The aromatic or heterocyclic group may be substituted with a substituent permissible in R ¹⁸¹ (described later), and when two or more of these substituents are present, they may be the same or different. The group is further R
¹⁸¹ may have a permissible substituent.

As used herein, the term "aliphatic group" refers to a linear, branched or cyclic aliphatic hydrocarbon group, and includes saturated and unsaturated groups such as alkyl, alkenyl, and alkynyl groups. Representative examples include methyl, ethyl, butyl, dodecyl, octadecyl, eicosenyl, iso-propyl, tert-butyl, tert-octyl, tert-dodecyl, cyclohexyl, cyclopentyl, Examples include an allyl group, a vinyl group, a 2-hexadecenyl group, and a propargyl group.

Specific examples of the coupling-off group include a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, an aliphatic or aromatic sulfonyloxy group, an acylamino group, an aliphatic or aromatic sulfonamide group, an alkoxycarbonyloxy group, There are aryloxycarbonyloxy groups, aliphatic / aromatic or heterocyclic thio groups, carbamoylamino groups, 5- or 6-membered nitrogen-containing heterocyclic groups, imide groups, aromatic azo groups, etc. ^It may be substituted with a group allowed as a substituent of ¹⁸¹ . Further, there is a bis-type coupler obtained by condensing a 4-equivalent coupler with an aldehyde or a ketone as a leaving group bonded via a carbon atom. The leaving group of the present invention may contain a photographically useful group such as a development inhibitor and a development accelerator. A preferred combination of leaving groups in each general formula will be described later.

The magenta coupler represented by the general formula (XVIII) is R
It is known in the art that when ¹⁸² is a hydrogen atom, it has the following keto-enol tautomerism. Therefore, the structure on the left side is equivalent to the structure on the right side.

In the general formula (XVIII), R ¹⁸³ and R ¹⁸¹ are each an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkenyloxy group, an acyl group, an ester group, an amide group, a sulfamide group, an imide group. An ureido group, an aliphatic or aromatic sulfonyl group,
It may be substituted with a group selected from an aliphatic or aromatic thio group, a hydroxy group, a cyano group, a carboxy group, a nitro group, a sulfo group, a halogen atom and the like. When there are two or more substituents, they may be the same or different.

Preferred R ¹⁸² in formula (XVIII) is a hydrogen atom,
It is an aliphatic acyl group or an aliphatic sulfonyl group, and particularly preferred R ¹⁸² is a hydrogen atom. Preferred Y ¹⁸¹ is of the type that leaves at a sulfur, oxygen or nitrogen atom, with sulfur atom leaving groups being especially preferred.

The compound represented by the general formula (XIX) is a 5-membered-5-membered condensed nitrogen hetero coupler (hereinafter referred to as a 5,5N heterocyclic coupler), and its color-developing nucleus has isoelectronic aromaticity with naphthalene. It has a chemical structure commonly referred to as azapentalene. Among the couplers represented by formula (XIX), a preferred compound is 1H-imidazo [1,2-b].
Pyrazoles, 1H-pyrazolo [5,1-d] [1,2,4] triazoles, 1H pyrazolo [1,5-b] [1,2,4] triazoles and 1H-pyrazolo [1,5- d] tetrazoles, each having the general formula (XIX-1), (XIX-2), (XI
It is represented by X-3) and 9 (XIX-4).

The substituents in the general formulas (XIX-I) to (XIX-4) will be described in detail. R ¹⁹² , R ¹⁹³ and R ¹⁹⁴ are a hydrogen atom, a halogen atom, a cyano group, an aliphatic group, an aromatic group,
Heterocycle, aromatic amino group, heterocycle amino group, R ¹⁹⁵ O
-, R ¹⁹⁵ SO−, R ¹⁹⁵ SO ₂ −, R ¹⁹⁵ SO ₂ NH−, R ¹⁹⁵ NH-, R ¹⁹⁵ S-, (Wherein R ¹⁹⁵ represents an aliphatic group, an aromatic group, a heterocyclic group, an aromatic amino group or a heterocyclic amino group), a silyl group, a silyloxy group, a silylamino group or an imide group. R
¹⁹² , R ¹⁹³ and R ¹⁹⁴ may be, in addition to the groups described above, a carbamoyl group, a sulfamoyl group, a ureido group and a sulfamoylamino group, and the nitrogen atom of these groups is permissible for R ¹⁸¹ . It may be substituted with the substituent. X ¹⁹¹ is synonymous with Y ¹⁹¹ . Also R ¹⁹² , R ¹⁹³ , R ¹⁹⁴
Alternatively, X ¹⁹¹ may be a divalent group to form a dimer, or may be a group connecting the polymer chain and the coupler mother nucleus.

Preferred R ¹⁹² , R ¹⁹³ and R ¹⁹⁴ are a hydrogen atom, a halogen atom, an aliphatic group having 1 to 36 carbon atoms, an aromatic group having 6 to 36 carbon atoms, a heterocyclic group or an aromatic or heterocyclic amino group, R ¹⁹⁵ O−, R ¹⁹⁵ CONH−, R ¹⁹⁵ SO ₂ NH−, R ¹⁹⁵ NH−, R
¹⁹⁵ S, R ¹⁹⁵ NHCONH-, Alternatively, it is a R ¹⁹⁵ OCONH group. Preferred X ¹⁹¹ is a halogen atom, an acylamino group, an imide group, an aliphatic or aromatic sulfonamide group, a 5- or 6-membered nitrogen-containing heterocyclic group bonded to the coupling active position with a nitrogen atom, an aryloxy group, an alkoxy. A group, an arylthio group and an alkylthio group.

The magenta coupler represented by the general formula (XVIII) is
JP-A-49-74027, JP-A-49-74028, JP-B-48-27930
No. 53-33846 and US Pat. No. 3,519,429. General formula (XIX-1), (XIX-
The magenta couplers represented by 2), (XIX-3) and (XIX-4) are described in JP-A-59-162548, US Pat. No. 3,725,067, JP-A-59-171,956 and JP-A-60, respectively. −
It is synthesized by the method described in 33,552 or the like.

The image forming method of the present invention is particularly performed by the following general formula (M-1).
And the magenta couplers represented by (M-II) are preferably used.

General formula (MI) (In the formula, Ar represents an aryl group, R ²⁰¹ represents a hydrogen atom, an acyl group or an aliphatic or aromatic sulfonyl group, R ²⁰² represents a halogen atom or an alkoxy group,
R ²⁰³ represents an alkyl group, an aryl group, a halogen atom, an alkoxy group, an aryloxy group, an acylamino group, an imide group, a sulfonamide group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, an alkylthio group or a sulfonyl group, and m is 0. Represents an integer from 4 to
Z ²⁰¹ represents a hydrogen atom or a group capable of splitting off during a coupling reaction with an oxidized product of a developing agent. ) Examples of the coupling-off group represented by Z ²⁰¹ are a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, a sulfonyloxy group, an amino group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an aliphatic or aromatic group. Group thio groups, imide groups, N-heterocycles, aromatic azo groups and the like. These leaving groups may include photographically useful groups.

General formula (M-II) (In the formula, R ²¹¹ represents a hydrogen atom, an acyl group or an aliphatic or aromatic sulfonyl group, and R ²¹⁴ represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, or an arylthio group. ,
Z ²¹² and Z ²¹³ are Alternatively, -N = is represented, and Z ²¹² and Z ²¹³ are both Or it cannot be -N =. Y ²¹¹ represents an alkylene group or an arylene group, represents an R ²¹⁵ alkyl group or an aryl group, and n represents an integer of 0 or 1.

Z ²¹¹ represents a hydrogen atom or a group capable of splitting off during a coupling reaction with an oxidized product of a developing agent. In the formula (M-II), Y ²¹¹ represents an alkylene group or an arylene group, for example, a group shown below.

_{-CH 2 CH 2 -, - CH} 2 -, Such.

Z ²¹¹ represents a hydrogen atom or a coupling-off group, and examples thereof include a halogen atom, an alkoxy group,
Examples include an aryloxy group, an acyloxy group, a sulfonyloxy group, an amide group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an aliphatic or aromatic thio group, an imide group, an N-heterocycle and an aromatic azo group. These leaving groups may include photographically useful groups.

Specific examples of the magenta couplers represented by the general formula (M-I) and the general formula (M-II) are shown below, but the present invention is not limited thereto.

Cyan couplers that can be used in the present invention include oil-protection type naphthol-based and phenol-based couplers, naphthol-based couplers described in U.S. Pat.No. 2,474,293, preferably U.S. Pat.Nos. 4,052,212, 4,146,396, and No. 4,228,233 and No. 4,296,200
As a representative example, the oxygen atom-releasing two-equivalent naphthol-based couplers described in JP-A No. 1994-242242 can be mentioned. Further, specific examples of the phenol-based coupler are described in U.S. Patents 2,369,929 and 2,80.
1,171, 2,772,162, 2,895,826 and the like. Cyan couplers that are fast against humidity and temperature are preferably used in the present invention, and typical examples thereof include a phenol having an alkyl group of ethyl group or higher at the meta-position of the phenol nucleus described in U.S. Pat.No. 3,772,002. Cyan couplers, U.S. Pat.Nos. 2,772,162, 3,758,308, 4,126,396, 4,334,011,
No. 4,327,173, West German Patent Publication No. 3,329,729 and JP-A-59-166956, and 2,5-diacylamino-substituted phenolic couplers described in U.S. Pat.
No. 2, No. 4,333,999, No. 4,451,559 and No. 4,4
Nos. 27,767 and the like include phenolic couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position.

Particularly, in the image forming method of the present invention, at least one of the cyan couplers represented by the following general formula (CI) is used.
By using the seed, it is possible to obtain good photographic properties with less fog. Such an effect is remarkable.

 The general formula (CI) will be described in detail below.

General formula (C-I) (In the formula, R ²²¹ represents an alkyl group, a cycloalkyl group, an aryl group, an amino group or a heterocyclic group. R ²²² represents an acylamino group or an alkyl group having 1 or more carbon atoms. R ²²³ represents a hydrogen atom or a halogen atom. Represents an alkyl group or an alkoxy group, R ²²³ may combine with R ²²² to form a ring, Z ²²¹ represents a hydrogen atom, a halogen atom or an oxidized product of an aromatic primary amine color developing agent. In the general formula (C-I), examples of the alkyl group having 1 to 32 carbon atoms of R ²²¹ include a methyl group, a butyl group, a tridecyl group, a cyclohexyl group and an allyl group. Examples of the aryl group include phenyl group and naphthyl group, and examples of the heterocyclic group include 2-pyridyl group and
A 2-furyl group and the like.

When R ²²¹ is an amino group, a phenyl-substituted amino group which may have a substituent is particularly preferable.

R ²²¹ is further an alkyl group, aryl group, alkyl or aryloxy group, carboxy group, alkyl or arylcarbonyl group, alkyl or aryloxycarbonyl group, acyloxy group, sulfamoyl group, carbamoyl group, sulfonamide group, acylamino group, sulfonyl group. It may be substituted with a substituent selected from a group, a hydroxy group, a cyano group, a nitro group and a halogen atom.

In formula (CI), Z ²²¹ represents a hydrogen atom or a coupling-off group, and examples thereof include a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, a sulfonyloxy group, an amide group, and an alkoxycarbonyl. Examples thereof include an oxy group, an aryloxycarbonyloxy group, an aliphatic or aromatic thio group, an imide group, an N-heterocycle and an aromatic azo group. These leaving groups may include photographically useful groups.

R ²²¹ or R ²²² of the general formula (C-I) may form a dimer or a multimer of more than that.

Specific examples of the cyan coupler represented by the general formula (CI) are shown below, but the present invention is not limited thereto.

The cyan coupler represented by the above general formula (CI) can be synthesized based on the description of Japanese Patent Application No. 59-166956 and Japanese Patent Publication No. 49-11572.

The graininess can be improved by using a coupler in which the color forming dye has an appropriate diffusibility. Such dye-diffusing couplers are described in U.S. Patent No. 4,366,237 and British Patent No.
Specific examples of magenta couplers are described in 2,125,570, and specific examples of magenta or cyan couplers are described in EP 96,570 and West German Patent Application Publication No. 3,234,533.

The dye-forming coupler and the above-mentioned special coupler may form a dimer or higher polymer. Typical examples of polymerized dye forming couplers are described in US Pat. Nos. 3,451,820 and 4,080,211. Specific examples of polymerized magenta couplers are described in British Patent No. 2,102,173 and U.S. Patent No. 4,367,282.

The various couplers used in the present invention can be used in combination of two or more kinds in the same layer of the light-sensitive layer in order to satisfy the properties required for the light-sensitive material, and the same compound can be used in two or more different layers. Can also be introduced.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods. Examples of the high boiling point organic solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027. Further, the steps of the latex dispersion method, effects, specific examples of latex for impregnation are described in U.S. Pat.
363, West German Patent Application (OLS) Nos. 2,541,274 and
No. 2,541,230.

The standard amount of the color coupler used is in the range of 0.001 to 1 mol per mol of the photosensitive silver halide,
Preferably in magenta couplers 0.003 to 0.3 moles,
In the case of a cyan coupler, the amount is 0.002 to 0.3 mol.

The photographic light-sensitive material used in the present invention is applied to a commonly used plastic film (cellulose nitrate, cellulose acetate, polyethylene terephthalate, etc.), a flexible support such as paper or a rigid support such as glass. For details on the support and coating method, see Research Disclosure Vol. 176 Item 17643 XV (P.27)
X VII (P.28) (December 1978 issue).

In the present invention, a reflective support is preferably used. The "reflective support" is one which enhances the reflectivity and makes the dye image formed on the silver halide emulsion layer clear, and such a reflective support includes titanium oxide, zinc oxide, Examples include those coated with a hydrophobic resin containing a light reflecting substance such as calcium carbonate and calcium sulfate dispersed therein, and those using a hydrophobic resin containing a light reflecting substance dispersed therein as a support.

(Examples) Hereinafter, the present invention will be described in more detail by showing specific examples of the present invention. However, the present invention is not limited to the following examples.

Example 1 As shown in Table A, the first layer (bottom layer) to the seventh layer of the double-sided polyethylene laminated paper treated by corona discharge machining
Layers (uppermost layer) were sequentially applied to form a photographic paper sample. Preparation of the coating solution for each layer is as follows. The details of the structural formulas, such as the coupler and the color image stabilizer, used in the coating solution will be described later.

The coating liquid for the first layer was prepared as follows. That is, yellow coupler (Y-1) 200 g, anti-fading agent 9
A mixture of 3.3 g, 10 g of high boiling point solvent (p) and 5 g of solvent (q) and 600 ml of ethyl acetate as an auxiliary solvent was dissolved by heating at 60 ° C., and then alkanol B (trade name, alkylnaphthalene sulfonate, manufactured by DuPont). Was mixed with 3,300 ml of 5% gelatin aqueous solution containing 330 ml of 5% aqueous solution of. Next, this liquid was emulsified using a colloid mill to prepare a coupler dispersion. Ethyl acetate was distilled off from this dispersion under reduced pressure,
Emulsion 1,400 g containing sensitizing dye for blue-sensitive emulsion layer and 1-methyl-2-mercapto-5-acetylamino-1,3,4-triazole (including 96.7 g as Ag and 170 g of gelatin)
The coating solutions of the second to seventh layers prepared by adding 2,600 g of a 10% aqueous gelatin solution were further prepared according to the composition of Table A according to the first layer.

However, each yellow coupler shown in Table 3 below was used as the first layer yellow coupler to produce a printing paper.

n2- (2-Hydroxy-3,5-di-tert-aluminiumphenyl) benzotriazole o2- (2-Hydroxy-3,5-di-tert-butylphenyl) benzotriazole p Di (2-ethylhexyl) phthalate q dibutyl phthalate r 2,5-di-tert-amylphenyl-3,5-di-tert-butylhydroxybenzoate s 2,5-di-tert-octylhydroquinone t 1,4-di-tert-amyl-2, 5-Dioctyloxybenzene u 2,2'-methylenebis- (4-methyl-6-tert-butylphenol) The following substances were used as sensitizing dyes in each emulsion layer.

Blue-sensitive emulsion layer; Anhydro-5-methoxy-5'-methyl-3,3'-disulfopropylselenacyanine hydroxide Green sensitive emulsion layer; Anhydro-9-ethyl-5,5'-diphenyl-3,3 ' -Disulfoethyloxacarbocyanine hydroxide red-sensitive emulsion layer; 3,3'-diethyl-5-methoxy-9,9 '
-(2,2-Dimethyl-1,3-propano) thiadicarbocyaniodide The following compounds were used as stabilizers for each emulsion layer.

1-methyl-2-mercapto-5-acetylamino-
1,3,4-Triazole The following substances were used as anti-irradiation dyes.

4- (3-carboxy-5-hydroxy-4- (3-
(3-carboxy-5-oxo-1- (4-sulfonatophenyl) -2-pyrazolin-4-ylidene) -1-propenyl) -1-pyrazolyl) benzenesulfonate-
Dipotassium salt N, N '-(4,8-dihydroxy-9,10-dioxo-3,7
-Disulfonatoanthracene-1,5-diyl) bis (aminomethanesulfonate) -tetrasodium salt Also, 1,2-bis (vinylsulfonyl) ethane was used as a hardening agent.

 The couplers used are as follows.

Yellow coupler See table 1 The multilayer color photographic paper obtained as described above was imagewise exposed and then continuously processed in the following processing steps. Treatment process Temperature Time Replenishment amount Color development 38 ℃ 3 minutes 30 seconds 160ml / m ² Bleach-fix 30 ℃ 1 minute 30 seconds 100ml / m ² Rinse 30 ℃ 40 seconds Rinse 30 ℃ 40 seconds Rinse 30 ℃ 40 seconds 200ml / m ² Dry 60-70 ° C 50 seconds Rinsing was a three-tank countercurrent system from the rinse to the rinse.

 The composition of each treatment liquid used is as follows.

Bleach-fixing solution (tank solution and replenisher are the _{same) EDTA Fe (III) NH 4} · 2H 2 O 60g EDTA · 2Na · 2H 2 O 4g Ammonium thiosulfate (70%) 1000 ml by addition of 120ml Sodium sulfite 16g glacial acetic acid 7g water pH 5.5 Rinse solution (same as tank solution and replenisher solution) 5-chloro-2-methyl-4-isothiazolin-3-one 40 mg 2-methyl-4-isothiazolin-3-one 10 mg 2-octyl-4-isothiazolin-30 -ON 10 mg Bismuth electrified (40%) 0.5 g Nitrilo-N, N, N-trimethylenephosphonic acid (40%) 1.0
g 1-hydroxyethylidene-1,1-diphosphonic acid (60
%) 2.5g Optical brightener (4,4'-diaminostilbene type) 1.0g Ammonia water (26%) 2.0ml Add water to 1000ml KOH pH 7.5 Meanwhile, add a part of the above color developer to 1% The beaker was left in an open system at 33 ° C. for 20 days, and then treated with the aged solution in the above treatment step.

The treatment using the color developing solution (aging solution) left for 20 days was referred to as the aging solution test, and the treatment using the color developing solution (fresh solution) before standing was referred to as the fresh solution test.

Photographic properties obtained by the fresh liquid test and the aged liquid test are shown in Table 1.

The photographic property is represented by two points, that is, D _min at yellow density and gradation.

D _min represents the minimum density, and gradation represents the density change from the point where the density is 0.5 to the density point on the high exposure side of 0.3 at log E.

Comparative yellow coupler The yellow couplers of the present invention represent those corresponding to the above exemplified compound numbers.

According to Table 1, in the comparative examples using color developers other than the present invention (Nos. 1 to 7 and 9 to 12), highly active yellow couplers (Y-ha) and (Y-ni) were used. If (N
o.4 and 5) Although it is improved to some extent, the increase of D _min and the change of gradation are large in the aged liquid. Furthermore, when a coupler other than the present invention is used, the change in D _min is large even when the color developer of the present invention is used (No. 8).

Only in accordance with the present invention, fluctuations in the photographic characteristics with the passage of time described above become small, and the effect is more remarkable in the absence of benzyl alcohol. Example 2 As a magenta coupler in the third layer of Example 1,
(M-5), (M-6), (M-7), (M-8),
(M-9), as a cyan coupler in the fifth layer,
Similar effects were obtained using (C-1), (C-2) and (C-8).

Example 3 A light-sensitive material was prepared in the same manner as in Example 1 except that silver chlorobromide emulsion (0.1 mol% of silver bromide) was used as the silver chlorobromide emulsion in each layer of the light-sensitive material prepared in Example 1. When the following processing was performed, the same effect as that of Example 1 was obtained. Further, for the development processing at this time, the same processing solution as in Example 1 was used except that 1.5 g / l of sodium chloride was used in place of potassium bromide in the color developing solution. Processing process Temperature Time Color development *) 35 ° C 45 seconds Bleach fixing 35 ° C 45 seconds Stable 1 35 ° C 20 seconds Stable 2 35 ° C 20 seconds Stable 3 35 ° C 20 seconds Example 4 On a paper support laminated on both sides with polyethylene. A multilayer color photographic paper having the layer constitution shown in Table B was prepared. The coating liquid was prepared as follows.

Preparation of coating solution for the first layer: 19.1 g of yellow coupler (Y-1) and 4.4 g of color image stabilizer (b), 27.2 cc of ethyl acetate and 7.7 cc of solvent (c).
Was added and dissolved, and this solution was emulsified and dispersed in 185 cc of a 10% aqueous gelatin solution containing 8 cc of 10% sodium dodecylbenzenesulfonate. On the other hand, silver chlorobromide emulsion (90.0 mol% of silver bromide,
(Ag 70 g / kg) was added with the following blue-sensitive sensitizing dye in an amount of 5.0 × 10 ^-4 mol per mol of silver. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a coating solution for the first layer so as to have the composition shown in Table 2. The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. As the gelatin hardening agent for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used.

 The following were used as the spectral sensitizing dye for each layer.

The following compounds were added to the red-sensitive emulsion layer in an amount of 2.6 × 10 ^-3 mol per mol of silver halide.

Further, 1- (5-methylureidophenyl) -5-mercaptotetrazole was added to each of the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer per mol of silver halide.
8.5 × 10 ^-5 mol, 7.7 × 10 ^-4 mol and 2.5 × 10 ^-4 mol were added.

Further, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer in an amount of 1.2 × 10 ^-2 mol, 1.1 × 10 ^-2
Mole was added.

The following dyes were added to the emulsion layer to prevent irradiation.

(A) Yellow coupler See Table 2 (K) the solvent _{O = PO-C 9 H 19} (iso)) 3 As shown in Table 2, color photographic papers were prepared, each containing a different yellow coupler.

The above photosensitive material was exposed through an optical wedge and processed in the following steps. Processing temperature Time Color development 38 ° C 1 minute 40 seconds Bleaching and fixing 30-34 ° C 1 minute 00 seconds Rinse 30-34 ° C 20 seconds Rinse 30-34 ° C 20 seconds Rinse 30-34 ° C 20 seconds Drying 70-80 ℃ 50 seconds (Rinse → 3 tank countercurrent method) The composition of each processing solution is as follows.

Color developer Water 800 ml Compound A of the present invention See Table 2 〃 B 〃 Diethylenetriaminepentaacetic acid 1.0 g 1-Hydroxyethylidene-1,1-diphosphonic acid (60
%) 2.0 g Nitrilotriacetic acid 2.0 g Benzyl alcohol 15 ml Diethylene glycol 10 ml Sodium sulfite See Table 2 Potassium bromide 0.5 g Potassium carbonate 30 g N-ethyl-N- (β-methanesulfonamidoethyl)
-3-Methyl-4-aminoaniline sulfate 5.5g Optical brightener (WHITEX 4B, Sumitomo Chemical Co., Ltd.) 1.5g Add water 1000ml pH 10.25 Bleach-fix solution Water 400ml Ammonium thiosulfate (70%) 200ml Sodium phosphite 20g Ethylenediaminetetraacetic acid Iron (III) ammonium 60g Ethylenediaminetetraacetic acid disodium 10g Water is added 1000ml pH (25 ℃) 7.00 Rinse solution Benzotriazole 1.0g Ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid 0.3g 1000 ml pH (25 ° C.) 7.50 continuous treatment (running test) by adding water was carried out under each condition until replenishing with a volume three times the tank capacity (20 l) of the color developing solution. Then, changes in the B concentration in the stain and the gradation portion at the start of the running process and at the end of the running process were measured by a Fuji type densitometer. Furthermore, after the sample at the end of the running treatment was left at 80 ° C. (5 to 10 RH) for 1 month, the change in B concentration in the stain part was measured again.

 The results of changes in photographic properties obtained are shown in Table 2.

According to the present invention, the change in photographic characteristics due to running is small, and the increase in yellow stain with the lapse of processing is small.

At this time, as the third layer magenta coupler (M-1
The same effect was obtained using 6), (M-7) and (M-31).

Example 5 A multilayer color photographic paper having the layer constitution shown in Table C was prepared on a paper support laminated on both sides with polyethylene. The coating liquid was prepared as follows.

Preparation of first layer coating solution 29.1 cc of ethyl acetate and 7.7 cc of solvent (c) in 19.1 g of yellow coupler (a) and 4.4 g of color image stabilizer (b)
Was added and dissolved, and this solution was emulsified and dispersed in 185 cc of a 10% aqueous gelatin solution containing 8 cc of 10% sodium dodecylbenzenesulfonate. On the other hand, silver chlorobromide emulsion (silver bromide 1.0 mol%, A
g70 g / kg) was added with the following blue-sensitive sensitizing dye in an amount of 5.0 × 10 ⁻⁴ mol per mol of silver. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a coating solution for the first layer so as to have the composition shown in Table C. The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. As the gelatin hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used.

 The following were used as the spectral sensitizing dye for each layer.

The following compounds were added to the red-sensitive emulsion layer in an amount of 2.6 × 10 ^-3 mol per mol of silver halide.

Further, 1- (5-methylureidophenyl) -5-mercaptotetrazole was added to each of the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer per mol of silver halide.
8.5 × 10 ⁻⁵ mol, 7.7 × 10 ⁻⁴ mol, 7.5 × 10 ⁻⁴ mol were added.

The following dyes were added to the emulsion layer to prevent irradiation.

and (A) Yellow coupler Y-11 or Y-12 (K) the solvent _{O = PO-C 9 H 19} (iso)) 3 The obtained color photographic paper was processed in the following processing steps in which the composition of the color developing solution was changed. Processing process Temperature Time Color development 35 ℃ 45 seconds Bleach fixing 35 ℃ 45 seconds Stable 1 35 ℃ 20 seconds Stable 2 35 ℃ 20 seconds Stable 3 35 ℃ 20 seconds Dry 70-80 ℃ 60 seconds Stabilizer 3 to 1 3 tank countercurrent water washing was performed.
The treatment liquids used are as follows.

Color developer N, N-Diethylhydroxylamine 0.03mol DABCO 0.04mol Sodium sulfite 0.2g Potassium carbonate 0.2g Nitrilotriacetic acid 1g Sodium chloride 1.5g N-ethyl N- (β-methanesulfonamidoethyl)-
3-methyl-4-amino aniline sulfate 5.5g brightener (4,4'-diaminostilbene type) was added to 3.0g water 1000 ml pH 10.05 Bleach-fixing solution _{EDTA Fe (III) NH 4 ·} 2H 2 O 60g EDTA・ 2Na ・ 2H ₂ O 4g Ammonium thiosulfate (70%) 120ml Sodium sulfite 16g Glacial acetic acid 7g Water added 1000ml pH 5.5 Stabilizer Formalin (37%) 0.1ml 1-Hydroxyethylidene-1,1-diphosphonic acid (60
%) 1.6 ml Bismuth chloride 0.35 g Ammonia water (26%) 2.5 ml Nitrilotriacetic acid / 3Na 1.0 g EDTA / 4H 0.5 g Sodium sulfite 1.0 g 5-Chloro-2-methyl-4-isothiazolin-3-one 50 mg Water In addition, when a treatment of 1000 ml or more was performed, the same effect as in Example 4 was obtained.

Example 6 Instead of the compound XI-8 used in No. 13 of Example 4, the following compounds II-1, II-5, II-8, II-11, III-
6, III-9, IV-I, IV-6, IV-8, V-1, V-
5, VI-1, VI-5, VII-2, VII-5, VIII-3, VI
When the afterimage processing was similarly performed using II-7, IX-2, IX-4, X-1, and X-6, the Δ gradation and the value of ΔD _min after the lapse of time were both favorable results as compared with the comparative example. was gotten.

Example 7 A running test was conducted in the same manner as in Example 4 and No. 8 except that the composition of the rinse liquid was only ion-exchanged water (calcium and magnesium were each 3 ppm or less). It was possible to obtain favorable photographic characteristics.

(Effects of the Invention) The present invention significantly improves the stability and color developability of a color developing solution, and as a result, even in a processing method using a color developing solution after a lapse of time, a fog increase and a gradation change are significantly suppressed. To give a color image with excellent photographic properties.

Such effects of the present invention were particularly remarkable in a color developer which does not substantially contain benzyl alcohol, which has a high pollution load.

Further, even in the continuous processing, the increase in fog was remarkably reduced, and the stability of the obtained color image with time was excellent.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Takatoshi Ishikawa 210 Nakanuma, Minamiashigara City, Fuji Photo Film Co., Ltd. (56) References JP 54-3532 (JP, A) JP 58-153934 (JP) , A) JP 62-206549 (JP, A) JP 63-188136 (JP, A) JP 63-81425 (JP, A) JP 63-141054 (JP, A) JP 63-148258 (JP, A)

Claims (1)

(57) [Claims] 1. A silver halide color photographic light-sensitive material having a layer containing at least one 2-equivalent yellow coupler represented by the following general formula (I), which contains substantially no sulfite ion and is aromatic. An image forming method for a silver halide color photographic light-sensitive material, which comprises processing with a color developing solution containing a primary amine. General formula (I) (In the formula, R ¹ represents a tertiary alkyl group or an aryl group. R ² represents a halogen atom or an alkoxy group. R ³ represents an alkyl group or an aryl group. Y ¹ represents a divalent linking group. X is Represents W ¹ represents a non-metal atom necessary to form a 4- to 6-membered ring with the nitrogen atom in the formula. )