JP3526060B2 - Nitrogen-containing heterocyclic compound, color developing agent, processing composition and color image forming method - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel silver halide color photographic developing agent, a processing solution composition containing the developing agent and a color image forming method using the processing solution. The present invention relates to a color photographic developing agent that gives a low and high maximum image density, a processing composition containing the developing agent, and a color image forming method using the processing solution.

[0002]

2. Description of the Related Art It has been proposed in the past to use a paraphenylenediamine type compound, particularly an N, N-dialkyl-substituted paraphenylenediamine type compound, as a color developing agent (color developing agent) added to a color developing solution. For example, proposals have been made on a devised alkyl group substituted at the N-position, and devised devised substituents on the benzene nucleus.

Regarding the use of analogs of para-phenylenediamine as a color developing agent, US Pat. Nos. 2,196,739 and 2,566,259, N, relating to tetrahydroquinoline type / dihydroindole type compounds have been used.
There are descriptions in U.S. Pat. No. 2,612,500 regarding the-(p-aminophenyl) hexamethyleneimine system, and U.S. Pat. No. 2,707,681 regarding the 9-aminojulolidine system and the like.

Regarding the use of compounds other than the para-phenylenediamine derivative as color developing agents, US Pat. No. 3,04,04 relates to 3-indazolinone compounds.
3,694, British Patent No. 7 for hydrazone derivative systems
90,327, 4-amino-5-pyrazolone system are described in French Patent 1,124,967, and triaminopyrimidine system is described in West German Patent 2,549,161.

By the way, the color developing agent plays two roles at the same time, that is, developing a silver halide, and its oxidant forming a color photographic coupler and a dye. Therefore, the required photographic performance has a great many items such as the developing activity, the hue of the dye formed by the color reaction with the coupler, and the stability of the dye against heat and light. On the other hand, the recent global environmental problems have strongly demanded the promotion of resource saving and energy saving. This situation is not an exception for color developing agents, of course, and there has been a demand for the development of a color developing agent capable of more efficient image formation in addition to the above-mentioned required performance.

[0006]

The present invention has been made in view of the above circumstances, and its object is to:
To provide a color developing agent that enables efficient color image formation by giving a high maximum image density while being small in fog, and a silver halide color photographic light-sensitive material using the developing agent. It is an object of the present invention to provide a processing liquid for materials and a color image forming method.

[0007]

Means for Solving the Problems The above problems include a nitrogen-containing heterocyclic compound represented by the following general formula (I), a color developing agent, and a halogen containing at least one of the developing agents. This is solved by a color image forming method characterized by developing a silver halide color photographic light-sensitive material with a processing solution containing a silver halide color photographic light-sensitive material and at least one developing agent. General formula (I)

[0008]

[Chemical 2]

In the formula, R ₁ and R ₂ are each a carbon atom having 1 to 6 carbon atoms.
Substituted alkyl group or hydroxyl having 1 to 6 total carbon atoms
Group, carboxyl group, alkoxy group, alkylamino
Group, ureido group, sulfonamide group, carbamoyl group,
Alkoxycarbonylamino group, sulfamoyl group
Represents an alkyl group substituted with a sulfonyl group . A represents a nonmetallic atom group necessary for forming a 5-membered unsaturated heterocycle represented by the following general formulas A-1 to A-17. R ₁ and R ₂ , R ₁ and A and R ₂ and A cooperate with each other to obtain nitrogen-containing heterothene.
It may form a ring.

[Chemical 51]

[Chemical 52] In the formula, R ₁₁ and R ₁₂ may be the same or different,
Hydrogen atom, halogen atom, alkyl group, aryl group,
Telocyclic group, cyano group, nitro group, hydroxyl group, cal
Voxyl group, alkoxy group, aryloxy group, acyl
Amino group, amino group, alkylamino group, anilino group,
Ureido group, sulfamoylamino group, alkylthio
Group, arylthio group, alkoxycarbonylamino group,
Sulfonamide group, carbamoyl group, sulfamoyl
Group, a sulfonyl group, an alkoxycarbonyl group, a heterocyclic
Oxy group, azo group, acyloxy group, carbamoyloxy group
Si group, silyl group, silyloxy group, aryloxycal
Bonylamino group, imide group, heterocyclic thio group, sulfi
A nyl group, a phosphonyl group, an aryloxycarbonyl group,
Represents an acyl group. R ₁₃ is a hydrogen atom, an alkyl group, or an ant
Group, heterocyclic group, hydroxyl group, alkoxy group,
Aryloxy, acylamino, amino, alk
Luamino group, anilino group, ureido group, sulfamoyl
Amino group, alkylthio group, arylthio group, alkoxy
Cycarbonylamino group, sulfonamide group, sulfamo
Group , sulfonyl group, heterocyclic oxy group, acyloxy group
Si group, carbamoyloxy group, aryloxycarboni
It represents a ruamino group, an imide group or a heterocyclic thio group.

In the present invention, R ₁ , R ₂ and A in the compound represented by the general formula (I) will be described in detail below. R ₁ and R ₂ may be the same or different and each represents an alkyl group, an aryl group or a heterocyclic group. These are alkyl groups, alkenyl groups, alkynyl groups, hydroxyl groups, nitro groups, carboxyl groups, cyano groups, halogen atoms, aryl groups, heterocyclic groups, alkoxy groups,
Aryloxy group, acylamino group, alkylamino group, anilino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamide group, carbamoyl group,
Sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyl group, silyloxy group, aryloxycarbonylamino group, imide group, heterocyclic thio group, sulfinyl group, phosphonyl group , An aryloxycarbonyl group or an acyl group may be further substituted.

More specifically, examples of R ₁ and R ₂ will be shown. The alkyl group is a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms , such as methyl, ethyl or propyl.
L, isopropyl, t-butyl, 2-hydroxyethyl
L, 3-hydroxypropyl, 2-methanesulfonami
Doethyl, 3-methanesulfonamidopropyl, 2-me
Tansulphonylethyl, 2-methoxyethyl, cyclope
Ethyl, 2-carboxylethyl, 3-carbamoylp
Ropil, hexyl, 2-hydroxypropyl, 4-hydr
Roxybutyl, 2-carbamoylaminoethyl, 4-carb
Lubamoylaminobutyl, 4-carpamoylbutyl, 2
-Carbamoyl-1-methylethyl .

[0012]

R ₁ and R ₂ may form a ring in cooperation with each other. The ring formed is not particularly limited,
Among them, 5-member, 6-member, and 7-member composed of an element selected from the group consisting of carbon atom, oxygen atom, nitrogen atom, and sulfur atom.
It is preferably a membered saturated ring, and examples of the ring include pyrrolidino, piperazino and morpholino. These rings may have a substituent allowed by R ₁ .

[0014]

A in the general formula (I) is the general formula A-1.
~ Forms a 5-membered unsaturated heterocycle represented by A-17
Represents a group of non-metal atoms required for.

[0016]

[Chemical 3]

[0017]

[Chemical 4]

[0018]

[Chemical 5]

[0019]

[Chemical 6]

[0020] R ₁₁ and R ₁₂ and R ₁₃ are, A alkyl group,
It may be further substituted with an alkenyl group, an alkynyl group, an aryl group, a hydroxyl group, a nitro group, a cyano group, a halogen atom or other substituents formed by an oxygen atom, a nitrogen atom, a sulfur atom or a carbon atom. * Represents one of the —NH ₂ groups in formula (I),
The remaining one represents a —NR ₁ (R ₂ ) group. R ₁₁ , R ₁₂ , R
_{When 13} and * are groups capable of forming a ring, they may form a ring only in the case of being indicated by a dotted line in the general formulas A-1 to A-17. . General formula A
The case where R ₁₁ , R ₁₂ , R ₁₃ in -1 to A-17 and the ring-closed structure shown by the dotted line are present will be described in detail below.

[0021]

More specifically, examples of the substituents of R ₁₁ and R ₁₂ will be shown. The halogen atom is, for example, a fluorine atom or a chlorine atom. The alkyl group is a linear, branched or cyclic alkyl group having 1 to 16 carbon atoms, preferably 1 to 6 carbon atoms, and examples thereof include methyl, ethyl, propyl, isopropyl, t-butyl, 2-hydroxyethyl, 3 -Hydroxypropyl, benzyl, 2-methanesulfonamidoethyl, 3-methanesulfonamidopropyl, 2-methanesulfonylethyl, 2-methoxyethyl, cyclopentyl, 2-acetamidoethyl, 2-carboxyethyl, 2-carbamoylethyl, 3 -Carbamoylpropyl, hexyl, 2-hydroxypropyl, 4-hydroxybutyl, 2-carbamoylaminoethyl, 3-carbamoylaminopropyl, 4-carbamoylaminobutyl, 4-carbamoylbutyl, 2-carbamoyl1-methylethyl, 4-nitrobutyl so That.

The aryl group is an aryl group having 6 to 24 carbon atoms, and examples thereof include phenyl, naphthyl and p-methoxyphenyl. The heterocyclic group is a 5-membered or 6-membered saturated or unsaturated heterocyclic ring containing 1 or more oxygen atom, nitrogen atom, or sulfur atom having 1 to 5 carbon atoms, and the number of heteroatoms constituting the ring. The number of the elements may be one or more, and examples thereof include 2-furyl, 2-cenyl, 2-pyrimidinyl, 2-benzotriazolyl, imidazolyl and pyrazolyl. The alkoxy group is an alkoxy group having 1 to 16 carbon atoms, preferably 1 to 6 carbon atoms, and examples thereof include methoxy, ethoxy, 2-methoxyethoxy, and 2-methanesulfonylethoxy. The aryloxy group is an aryloxy group having 6 to 24 carbon atoms, and examples thereof include phenoxy, p-methoxyphenoxy and m- (3
-Hydroxypropionamido) phenoxy. The acylamino group is an acylamino group having 1 to 16 carbon atoms, preferably 1 to 6 carbon atoms, for example, acetamide, 2
-Methoxypropionamide, p-nitrobenzoylamide. Alkylamino group has 1 to 1 carbon atoms
6, preferably an alkylamino group having 1 to 6 carbon atoms, such as dimethylamino, diethylamino and 2-hydroxyethylamino. Anilino group has 6 to 2 carbon atoms
Anilino group 4 is, for example, anilino, m-nitroanilino, N-methylanilino. The ureido group is a ureido group having 1 to 16 carbon atoms, preferably 1 to 6 carbon atoms, and examples thereof include ureido, methylureido, N, N-diethylureido and 2-methanesulfonamidoethylureido.

The sulfamoylamino group has 0 carbon atoms.
To 16, preferably a sulfamoylamino group having 0 to 6 carbon atoms, such as dimethylsulfamoylamino, methylsulfamoylamino, and 2-methoxyethylsulfamoylamino. The alkylthio group has 1 to 1 carbon atoms.
16, preferably an alkylthio group having 1 to 6 carbon atoms, such as methylthio, ethylthio and 2-phenoxyethylthio. The arylthio group is an arylthio group having 6 to 24 carbon atoms, and examples thereof include phenylthio, 2-carboxyphenylthio, and 4-cyanophenylthio. The alkoxycarbonylamino group has 2 to 2 carbon atoms.
16, preferably an alkoxycarbonylamino group having 2 to 6 carbon atoms, such as methoxycarbonylamino, ethoxycarbonylamino, and 3-methanesulfonylpropoxycarbonylamino. The sulfonamide group is a sulfonamide group having 1 to 16 carbon atoms, preferably 1 to 6 carbon atoms, and examples thereof include methanesulfonamide, p-toluenesulfonamide, and 2-methoxyethanesulfonamide. The carbamoyl group is a carbamoyl group having 1 to 16 carbon atoms, preferably 1 to 6 carbon atoms, and examples thereof include carbamoyl, N, N-dimethylcarbamoyl and N-ethylcarbamoyl. The sulfamoyl group has 0 to 1 carbon atoms
6, preferably a sulfamoyl group having 0 to 6 carbon atoms, such as sulfamoyl, dimethylsulfamoyl and ethylsulfamoyl. C1 as a sulfonyl group
To 16, preferably an aliphatic or aromatic sulfonyl group having 1 to 6 carbon atoms, and examples thereof include methanesulfonyl, ethanesulfonyl, and 2-chloroethanesulfonyl. The alkoxycarbonyl group is an alkoxycarbonyl group having 1 to 16 carbon atoms, preferably 1 to 6 carbon atoms, and examples thereof include methoxycarbonyl, ethoxycarbonyl and t-butoxycarbonyl. The heterocyclic oxy group has 1 to 1 carbon atoms.
5 is a 5-membered or 6-membered saturated or unsaturated heterocyclic oxy group containing at least one oxygen atom, nitrogen atom, or sulfur atom, and the number of heteroatoms constituting the ring and the kind of element are 1 However, it may be plural, for example, 1-phenyltetrazolyl-5-oxy, 2-tetrahydropyranyloxy, and 2-pyridyloxy.

The azo group is an azo group having 1 to 16 carbon atoms, preferably 1 to 6 carbon atoms, for example, phenylazo, 2-
Hydroxy-4-propanoylphenylazo and 4-sulfophenylazo. The acyloxy group is an acyloxy group having 1 to 16 carbon atoms, preferably 1 to 6 carbon atoms, and examples thereof include acetoxy, benzoyloxy and 4-hydroxybutanoyloxy. The carbamoyloxy group is a carbamoyloxy group having 1 to 16 carbon atoms, preferably 1 to 6 carbon atoms, and examples thereof include N, N-dimethylcarbamoyloxy, N-methylcarbamoyloxy and N-phenylcarbamoyloxy. The silyl group is a silyl group having 3 to 16 carbon atoms, preferably 3 to 6 carbon atoms, such as trimethylsilyl, isopropyldiethylsilyl,
It is t-butyldimethylsilyl. The silyloxy group is a silyloxy group having 3 to 16 carbon atoms, preferably 3 to 6 carbon atoms, and examples thereof include trimethylsilyloxy, triethylsilyloxy and diisopropylethylsilyloxy. The aryloxycarbonylamino group is an aryloxycarbonylamino group having 7 to 24 carbon atoms, and examples thereof include phenoxycarbonylamino, 4-cyanophenoxycarbonylamino, and 2,6-dimethoxyphenoxycarbonylamino. The imide group has 4 to 1 carbon atoms
The imide group of 6 is, for example, N-succinimide or N-phthalimide. Heterocyclic thio group has 1 to 5 carbon atoms
A 5-membered or 6-membered saturated or unsaturated heterocyclic thio group containing at least one oxygen atom, nitrogen atom, or sulfur atom, and the number of heteroatoms constituting the ring and the kind of element are There may be a plurality, for example, 2-benzothiazolylthio and 2-pyridylthio.

The sulfinyl group has 1 to 16 carbon atoms,
Preferred is a sulfinyl group having 1 to 6 carbon atoms, and examples thereof include methanesulfinyl, benzenesulfinyl, and ethanesulfinyl. The phosphonyl group has 2 to 1 carbon atoms
6, preferably a phosphonyl group having 2 to 6 carbon atoms, for example,
Methoxyphosphonyl, ethoxyphosphonyl and phenoxyphosphonyl. The aryloxycarbonyl group is an aryloxycarbonyl group having 7 to 24 carbon atoms, and examples thereof include phenoxycarbonyl, 2-methylphenoxycarbonyl, and 4-acetamidophenoxycarbonyl. The acyl group is an acyl group having 1 to 16 carbon atoms, preferably 1 to 6 carbon atoms, such as acetyl, benzoyl,
It is 4-chlorobenzoyl. Incidentally, R ₁₁ and / or R
_{When 12} is a hydroxyl group, an amino group or an alkylamino group, the compounds represented by the general formulas A-1 to A-17 may have a tautomeric structure.
Needless to say, ~ A-17 includes such compounds.

Of these, R ₁₁ and R ₁₂ are preferably hydrogen atom, halogen atom, alkyl group having 1 to 6 carbon atoms,
Cyano group, hydroxyl group, alkoxy group having 1 to 6 carbon atoms, acylamino group having 1 to 6 carbon atoms, dialkylamino group having 2 to 12 carbon atoms, ureido group having 1 to 6 carbon atoms, sulfur group having 2 to 12 carbon atoms Famoylamino group, alkoxycarbonylamino group having 1 to 6 carbon atoms, sulfonamide group having 1 to 6 carbon atoms, carbamoyl group having 1 to 6 carbon atoms, 2 carbon atoms
To 12 sulfamoyl group, sulfonyl group having 1 to 6 carbon atoms, alkoxycarbonyl group having 2 to 6 carbon atoms, and 1 carbon atom
To 6 acyl groups, more preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, an alkoxy group having 1 to 6 carbon atoms, an acylamino group having 1 to 6 carbon atoms, and 2 carbon atoms.
~ 12 dialkylamino group, C1-6 ureido group, C2-12 sulfamoylamino group, C1-6 alkoxycarbonylamino group, C1-6
A sulfonamide group, a carbamoyl group having 1 to 6 carbon atoms,
A sulfamoyl group having 2 to 12 carbon atoms, a sulfonyl group having 1 to 6 carbon atoms, and an alkoxycarbonyl group having 2 to 6 carbon atoms.

R ₁₃ is a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a hydroxyl group, an alkoxy group, an aryloxy group, an acylamino group, an amino group, an alkylamino group, an anilino group, a ureido group, a sulfamoylamino group. , An alkylthio group, an arylthio group, an alkoxycarbonylamino group, a sulfonamide group, a sulfamoyl group, a sulfonyl group, a heterocyclic oxy group, an acyloxy group, a carbamoyloxy group, an aryloxycarbonylamino group, an imide group, and a heterocyclic thio group. These are further substituted with an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a hydroxyl group, a nitro group, a cyano group, a halogen atom or another substituent formed by an oxygen atom, a nitrogen atom, a sulfur atom or a carbon atom. The specific examples are the same as those in R ₁₁ and R ₁₂ . R ₁₃ is preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms,
Acylamino group having 1 to 6 carbon atoms, amino group, 2 to 2 carbon atoms
12 dialkylamino group, C1-6 ureido group, C1-6 sulfamoylamino group, C1
To an alkoxycarbonylamino group, a sulfonamide group having 1 to 6 carbon atoms, a sulfamoyl group having 2 to 12 carbon atoms, a sulfonyl group having 1 to 6 carbon atoms, and an imide group having 4 to 8 carbon atoms, and more preferably Hydrogen atom, carbon number 1-6
Is an alkyl group.

In the general formulas A-1 to A-17, in the case of having a closed ring structure represented by a dotted line, the number of ring members may be any number of members, but among them, it is a 5-membered, 6-membered or 7-membered ring. Preferably there is. Since the compound represented by the general formula (I) is extremely unstable when stored as a free amine, it is generally manufactured and stored as a salt of an inorganic acid or an organic acid, and it is necessary to add the compound to the treatment liquid only after the storage. It is preferable to use a free amine. Examples of the inorganic or organic acid for salt-forming the compound of the general formula (I) include hydrochloric acid, sulfuric acid, phosphoric acid, p-toluenesulfonic acid, methanesulfonic acid, naphthalene-1,5-
Examples thereof include disulfonic acid. Among these, sulfuric acid, p
-Toluenesulfonic acid salt is preferable, and salt formation with sulfuric acid is most preferable. Specific examples of typical developing agents represented by formula (I) in the invention are shown below, but the invention is not limited thereto.

[0030]

[Chemical 7]

[0031]

[Chemical 8]

[0032]

[Chemical 9]

[0033]

[Chemical 10]

[0034]

[Chemical 11]

[0035]

[Chemical 12]

[0036]

[Chemical 13]

[0037]

[Chemical 14]

[0038]

[Chemical 15]

[0039]

[Chemical 16]

[0040]

[Chemical 17]

[0041]

[Chemical 18]

[0042]

[0043]

The color developing agent of the present invention can be synthesized, for example, according to the following synthesis example. (Synthesis Example) The color developing agent (D
-2) was synthesized.

[0045]

[Chemical 21]

(Synthesis of Compound (3)) 24.4 g of (2) was added to 44.4 g of (1), and stirring was continued at 80 ° C. for 30 minutes and then at 120 ° C. for 7 hours. Next, ethyl acetate was added and the mixture was washed with saturated brine and the ethyl acetate was distilled off under reduced pressure to obtain 39.6 g of an oil containing the compound (3). (Synthesis of Compound (4)) (3) 37.1 g of N, N-dimethylformamide 14
8 ml, ethyl iodide 58.7 ml,
138 g of potassium carbonate was added, and stirring was continued at 60 ° C. for 3 hours. Next, ethyl acetate was added and the mixture was washed with saturated brine, ethyl acetate was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography to obtain 3.7 g of compound (4).
(Yield from (1) 4%). (Synthesis of Compound (5)) (2) To 2.65 g of water, 15.8 ml of water and 4.2 ml of concentrated hydrochloric acid were added, and a 2 ml aqueous solution of 1.09 g of sodium nitrite was added dropwise under stirring with ice cooling. Next, the reaction system was neutralized with sodium bicarbonate, extracted with ethyl acetate, and ethyl acetate was distilled off under reduced pressure to obtain 3.00 g of an oil containing the compound (5). (Synthesis of Exemplified Compound (D-2)) (5) 1.52 g was dissolved in ethanol, 10% palladium carbon was added thereto, and then hydrogen gas was contacted under normal pressure. After that, it was filtered using Celite as a filter aid, and the filtrate was mixed with 1,5
2.79 g of naphthalenedisulfonic acid tetrahydrate was added.
The exemplified compound (D-
2.34 g of 1,5-naphthalenedisulfonate of 2) was obtained (62% yield from (4)).

The amount of the color developing agent used in the present invention is 1
The concentration is preferably 0.1 g to 20 g, and more preferably 1 g to 15 g per liter. The processing temperature of the developer is 20 to 50 ° C, preferably 30 to 45 ° C. The color developing agent of the present invention is also preferably used alone or in combination with other known p-phenylenediamine derivatives. Representative examples of the compound to be combined are shown below, but the invention is not limited thereto. P-1 N, N-diethyl-p-phenylenediamine P-2 2-amino-5- (N, N-diethylamino) toluene P-3 2-amino-5- (N-ethyl-N-laurylamino) toluene P-4 4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline P-5 2-methyl-4- [N-ethyl-N- (β-
Hydroxyethyl) amino] aniline P-6 4-amino-3-methyl-N-ethyl-N-
[Β- (Methanesulfonamide) ethyl] aniline P-7 N- (2-amino-5-N, N-diethylaminophenylethyl) methanesulfonamide P-8 N, N-dimethyl-p-phenylenediamine P-9 4-amino-3-methyl-N-ethyl-N-
Methoxyethylaniline P-10 4-amino-3-methyl-N-ethyl-N-
β-ethoxyethylaniline P-11 4-amino-3-methyl-N-ethyl-N-
β-butoxyethylaniline

Among the above-mentioned p-phenylenediamine derivatives, the exemplified compound P is particularly preferable as the compound to be combined.
-5 or P-6. In addition, these p-phenylenediamine derivatives and sulfates, hydrochlorides, sulfites, p-
Toluenesulfonate, nitrate, naphthalene-1,5-
It is generally used in a salt such as a disulfonate. The amount of the aromatic primary amine developing agent used is the amount of developer 1
It is preferably about 0.1 g to about 20 g per liter. The amount of the main drug used in combination is 1/10 to 10 with respect to 1 mol of the main drug of the general formula of the present invention unless the effects of the present invention are impaired.
It is preferable to use mol. The color developing solution used in the present invention is generally alkaline, and is preferably an alkaline aqueous solution having a pH of 9 to 12.5.

The color developer contains a pH buffer such as an alkali metal carbonate, borate or phosphate, a chloride salt,
It generally contains a development inhibitor such as bromide salt, iodide salt, benzimidazole, benzothiazole or mercapto compound, or an antifoggant. If necessary, hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine, various preservatives such as catecholsulfonic acids, ethylene glycol, Organic solvents such as diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, 1-
Auxiliary developing agents such as phenyl-3-pyrazolidone, tackifiers, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, various chelating agents represented by phosphonocarboxylic acids, for example, ethylenediaminetetraacetic acid, Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, Representative examples are N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof.

When reversal processing is carried out, black and white development is usually carried out before color development. In this black-and-white developer, known black-and-white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone or aminophenols such as N-methyl-p-aminophenol are used alone. Alternatively, they can be used in combination. The color developing solution and the black and white developing solution generally have a pH of 9 to 12. The replenishing amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per 1 square meter of the light-sensitive material, and it is 500 ml or less by reducing the bromide ion concentration in the replenishing solution. You can also do it. When the replenishment amount is reduced, it is preferable to prevent the liquid evaporation and air oxidation by reducing the contact area of the treatment tank with the air. The contact area between the photographic processing liquid and air in the processing tank can be represented by the aperture ratio defined below. That is, aperture ratio = [contact area between treatment liquid and air (cm ² )] ÷ [volume of treatment liquid (cm ³ )] The above aperture ratio is preferably 0.1 or less, and more preferably 0.001 to 0.05. Is. As a method of reducing the aperture ratio in this way, in addition to providing a cover such as a floating lid on the photographic processing liquid surface of the processing tank, a method using a movable lid described in JP-A-1-82033 is disclosed. The slit development processing method described in 63-216050 can be mentioned. Reducing the aperture ratio is not limited to both the color development and black and white development steps, but also the subsequent steps such as bleaching, bleach-fixing,
It is preferably applied in all steps such as fixing, washing with water, and stabilization. Further, the amount of replenishment can be reduced by using a means for suppressing the accumulation of bromide ions in the developing solution. The color development processing time is usually set between 2 and 5 minutes, but the processing time can be further shortened by using a high temperature and high pH and using a color developing agent at a high concentration.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. Further, in order to speed up the processing, a processing method of bleach-fixing processing after bleaching processing may be used. Further, treatment with two continuous bleach-fixing baths, fixing treatment before the bleach-fixing treatment, or bleaching treatment after the bleach-fixing treatment can be optionally carried out according to the purpose. As the bleaching agent, compounds of polyvalent metals such as iron (III), peracids, quinones, nitro compounds and the like are used. As a typical bleaching agent, an organic complex salt of iron (III),
For example, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid, and other aminopolycarboxylic acids or complex salts of citric acid, tartaric acid, malic acid, etc. Etc. can be used. Of these, iron (III) aminopolycarboxylates including ethylenediaminetetraacetic acid iron (III) complex salts and 1,3-diaminopropanetetraacetic acid iron (III) complex salts
Complex salts are preferable from the viewpoint of rapid processing and prevention of environmental pollution. Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in both the bleaching solution and the bleach-fixing solution. The pH of a bleaching solution or a bleach-fixing solution using these iron (III) aminopolycarboxylic acid complex salts is usually 4.0 to 8, but a lower pH can be used for speeding up the processing.

These bleaching treatments are preferably carried out immediately after color development, but in the case of reversal treatments, they are generally carried out via an adjusting bath (which may be a bleaching promoting bath). These adjusting baths may contain an image stabilizer described later. If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and the bleaching accelerating bath which is a pre-bath thereof. Specific examples of useful bleach accelerators are described in the following specification: US Pat. No. 3,893,858,
West German Patent Nos. 1,290,812 and 2,059,988, JP-A-53-3
No. 2736, No. 53-57831, No. 53-37418, No. 53-72623,
53-95630, 53-95631, 53-104232, 53-1
24424, 53-141623, 53-28426, Research
Compounds having a mercapto group or a disulfide group described in Disclosure No. 17129 (July 1978), etc .; Thiazolidine derivatives described in JP-A No. 50-140129;
JP-B-45-8506, JP-A-52-20832, JP-A-53-32735,
Thiourea derivatives described in U.S. Pat. Polyamine compounds described in JP-B-45-8836; Other JP-A-49-40,943 and 49-5
No. 9,644, No. 53-94,927, No. 54-35,727, No. 55-26,
Compounds described in Nos. 506 and 58-163,940; bromide ion and the like can be used. Among them, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of a large accelerating effect, and particularly, U.S. Pat. No. 3,893,858 and West German Patent 1,290,81.
Compounds described in JP-A No. 2 and JP-A-53-95,630 are preferable.
Further, the compounds described in US Pat. No. 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color light-sensitive material for photography.

In addition to the above compounds, the bleaching solution and the bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach stain. A particularly preferred organic acid has an acid dissociation constant (p
Ka) is a compound of 2 to 5, and specifically, acetic acid, propionic acid, hydroxyacetic acid and the like are preferable. Examples of the fixing agent used in the fixing solution and the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas, and a large amount of iodide salts, but thiosulfates are generally used. In particular, ammonium thiosulfate can be used most widely. Further, the combined use of thiosulfate and thiocyanate, thioether compounds, thiourea and the like is also preferable.
Preservatives for fixers and bleach-fixers include sulfites, bisulfites, carbonyl bisulfite adducts or European patents.
The sulfinic acid compounds described in 294769A are preferred. Further, various aminopolycarboxylic acids and organic phosphonic acids are preferably added to the fixing solution and the bleach-fixing solution for the purpose of stabilizing the solution. In the present invention, the fixing solution or the bleach-fixing solution contains a compound having a pKa of 6.0 to 9.0 for pH adjustment, preferably an imidazole such as imidazole, 1-methylimidazole, 1-ethylimidazole or 2-methylimidazole. It is preferable to add 0.1 to 10 mol / liter.

The total time of the desilvering process is preferably as short as possible so long as no desilvering failure occurs. Preferred time is 1 to 3 minutes
Minutes, more preferably 1 minute to 2 minutes. The treatment temperature is 25 ° C to 50 ° C, preferably 35 ° C to 45 ° C. In the preferable temperature range, the desilvering rate is improved, and the stain generation after the processing is effectively prevented. In the desilvering process, it is preferable that the stirring is strengthened as much as possible.
As a specific method for strengthening stirring, a method of impinging a jet of a processing solution on the emulsion surface of the light-sensitive material described in JP-A-62-183460, or stirring using a rotating means of JP-A-62-183461 Method to increase the effect, further moving the photosensitive material while the emulsion surface is in contact with the wiper blade provided in the solution to further improve the stirring effect by making the emulsion surface turbulent, circulation of the entire processing solution There is a method of increasing the flow rate. Such a stirring improving means is effective in any of the bleaching solution, the bleach-fixing solution and the fixing solution. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film, and consequently the desilvering rate. Further, the above-mentioned stirring improving means is more effective when a bleaching accelerator is used, and it is possible to remarkably increase the accelerating effect and eliminate the fixing inhibiting action of the bleaching accelerator. The automatic processor used for the light-sensitive material of the present invention is disclosed in JP-A-60-191257.
No. 60-191258 and No. 60-191259. The above-mentioned JP-A-6
As described in No. 0-191257, such a conveying means can significantly reduce the carry-in of the treatment liquid from the front bath to the rear bath, and is highly effective in preventing the performance deterioration of the treatment liquid. Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.

The silver halide color photographic light-sensitive material of the present invention is generally washed with water and / or stabilized after desilvering. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), application, and further, the rinsing water temperature, the number of rinsing tanks (number of stages), replenishment method such as countercurrent, forward flow, and various other conditions. It can be set in a wide range.
Of these, the relationship between the number of washing tanks and the water volume in the multi-stage countercurrent system is as follows.
nd Tele-vision Engineers Volume 64, P. 248 ~ 253 (195
May, May issue). According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate, and the suspended matter produced adheres to the photosensitive material, etc. Problem arises. In the processing of the color light-sensitive material of the present invention, as a solution to this problem, the method of reducing calcium ion and magnesium ion described in JP-A-62-288838 can be very effectively used. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8,542, chlorine-based bactericides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., Hiroshi Horiguchi "Chemistry of antifungal agents" (1986)
Sankyo Publishing, Sanitary Technology Society, "Microbial sterilization, sterilization, antifungal technology" (1982), Industrial Technology Association, Japan Antibacterial and Antifungal Society edited, "Antibacterial and Antifungal Encyclopedia" (1986) Can also be used.

Rinsing water in the processing of the light-sensitive material of the present invention
The pH is 4-9, preferably 5-8. The washing water temperature and the washing time can be variously set depending on the characteristics of the light-sensitive material, the use, etc., but in general, it is 20 seconds to 10 minutes at 15 to 45 ° C., preferably
A range of 30 seconds to 5 minutes at 25-40 ° C is selected. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such stabilization treatment, all known methods described in JP-A-57-8543, JP-A-58-14834 and JP-A-60-220345 can be used. In addition, there is a case where further stabilization treatment is carried out after the water washing treatment, and an example thereof is a stabilizing bath containing a dye stabilizer and a surfactant, which is used as a final bath of a color light-sensitive material for photographing. be able to. Formaldehyde is generally used as a dye stabilizer, but N-methylolazole, hexamethylenetetramine, formaldehyde bisulfite adduct, dimethylolurea, azolylmethylamine derivative and the like are preferable from the viewpoint of work environment safety. Among them, N-methylol-1,2,4-triazole and N
-N-methylolazoles such as methylolpyrazole and 1,4-bis (1,2,4-triazole-1-
Azolylmethylamine and its derivatives such as ylmethyl) piperazine are preferable because of high image stability, and
Triazoles such as 2,4-triazole and 1,4-
Combined use of a derivative thereof such as bis (1,2,4-triazol-1-ylmethyl) piperazine (Japanese Patent Application No. 3-1599).
No. 18) is preferable because of high image stability and low formaldehyde vapor pressure. Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow solution accompanying the above washing with water and / or supplementation of the stabilizing solution can be reused in other steps such as the desilvering step. In the processing using an automatic processor, etc., when the above processing solutions are concentrated by evaporation,
It is preferable to correct the concentration by adding water. The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents. For example, indoaniline compounds described in U.S. Pat.No. 3,342,597, No. 3,342,599, Schiff base type compounds described in Research Disclosure Nos. 14,850 and No. 15,159, aldol compounds described in No. 13,924, U.S. Pat.No. 3,719,492. Metal salt complexes described, JP-A-53-135
The urethane compound described in No. 628 can be mentioned.
The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-3- (2-phenyl) -3- (phenyl) -3-phenyl-3-(-3-phenyl) -3-phenyl-3-(-3-phenyl) -3- (phenyl-3-phenyl) -3- (phenyl) -3-phenyl-3-(-3-phenyl) -3-(-3-phenyl-)-3- (phenyl) -3-phenyl-3- (3-phenyl) -3- (3-phenyl-3-phenyl) -3- (3-phenyl-3-phenyl-3-phenyl-3-phenyl-3- (3-phenyl-3-phenyl-3-phenyl-3-phenyl-3- (3-phenyl-3-phenyl-3-chloro-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-bromo-3-)-3-candidates, if necessary
You may incorporate pyrazolidones. Typical compounds are described in JP-A-56-64339, JP-A-57-144547, JP-A-58-115438 and the like. Various treatment liquids in the present invention are 10 ℃
Used at ~ 50 ° C. Normally, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature accelerates the processing to shorten the processing time, and a lower temperature lowers the image quality to improve the stability of the processing liquid. be able to.

In the color light-sensitive material used in the present invention, at least one of a blue-sensitive layer, a green-sensitive layer and a red-sensitive silver halide emulsion layer is provided on a support. Well, there is no particular limitation on the number and order of layers of the silver halide emulsion layer and the non-photosensitive layer. As a typical example, at least one photosensitive layer consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities is typically provided on a support.
And a light-sensitive layer is a unit light-sensitive layer having color sensitivity to any of blue light, green light, and red light. In general, the unit photosensitive layers are arranged in order of the red-sensitive layer, the green-sensitive layer and the blue-sensitive layer from the support side. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layers. Non-photosensitive layers such as various intermediate layers may be provided between the above-described silver halide photosensitive layers and as the uppermost layer and the lowermost layer. In the intermediate layer, JP-A-61-4
3748, 59-113438, 59-113440, 61-20037
No. 61-20038, a coupler as described in
A DIR compound or the like may be contained, and a color mixing inhibitor may be contained as is commonly used. A plurality of silver halide emulsion layers forming each unit photosensitive layer are described in West German Patent No.
A two-layer structure of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer can be preferably used as described in 1,121,470 or British Patent No. 923,045. In general, it is preferable that the layers are arranged so that the photosensitivity is gradually lowered toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. In addition, JP-A-57-112751, JP-A-62-200350, JP-A-57-112751
As described in 62-206541 and 62-206543, a low-sensitivity emulsion layer may be provided on the side farther from the support and a high-sensitivity emulsion layer may be provided on the side closer to the support. As a specific example, from the side farthest from the support, low-sensitivity blue photosensitive layer (BL) / high-sensitivity blue photosensitive layer (BH) / high-sensitivity green photosensitive layer (GH) / low-sensitivity green photosensitive layer (GL) / High-sensitivity red photosensitive layer (RH) / Low-sensitivity red photosensitive layer (RL), or BH / BL / GL / GH / RH / RL,
Or they can be installed in the order of BH / BL / GH / GL / RL / RH. Also, as described in JP-B-55-34932, from the side farthest from the support, the blue-sensitive layer / GH / RH
It can also be arranged in the order of / GL / RL. Also, JP-A-56-2
As described in the specifications of 5738 and 62-63936,
Blue photosensitive layer / GL / RL / GH / RH from the side farthest from the support
It can also be arranged in the order of. Further, as described in JP-B-49-15495, the upper layer is a silver halide emulsion layer having the highest sensitivity, the middle layer is a silver halide emulsion layer having a lower sensitivity, and the lower layer is more sensitive than the middle layer. An example is an arrangement in which a silver halide emulsion layer having a low degree of sensitivity is arranged, and the layer is composed of three layers having different sensitivities in which the sensitivities are gradually lowered toward the support. Even when it is composed of three layers having different sensitivities, as described in JP-A-59-202464, a medium-sensitivity emulsion from the side distant from the support in the same color-sensitive layer. Layers / high-speed emulsion layers / low-speed emulsion layers may be arranged in this order. In addition, they may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer.
Also, in the case of four or more layers, the arrangement may be changed as described above. U.S. Pat.No. 4,663,271 to improve color reproduction
No. 4,705,744, No. 4,707,436, JP-A-62-1
BL, GL, RL described in the specifications of 60448 and 63-89850
It is also preferable to dispose a donor layer (CL) having a multi-layer effect, which has a spectral sensitivity distribution different from that of the main photosensitive layer, such as adjacent to or adjacent to the main photosensitive layer. As described above, various layer configurations and arrangements can be selected according to the purpose of each light-sensitive material.

When the photographic light-sensitive material used in the present invention is a color negative film or a color reversal film, the preferable silver halide contained in the photographic emulsion layer is about 30.
It is silver iodobromide, silver iodochloride, or silver iodochlorobromide containing less than mol% of silver iodide. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 25 mol% silver iodide. When the photographic light-sensitive material used in the present invention is a direct positive color light-sensitive material, the preferred silver halide contained in the photographic emulsion layer is silver chlorobromide or silver bromide. When the photographic light-sensitive material used in the present invention is a color photographic paper, the silver halide contained in the photographic emulsion layer is composed of silver chlorobromide or silver chloride containing substantially no silver iodide. Those can be preferably used. Here, the term "substantially free of silver iodide" means that the silver iodide content is 1 mol% or less, preferably 0.
It means 2 mol% or less. Regarding the halogen composition of these silver chlorobromide emulsions, any silver bromide / silver chloride can be used. This ratio can take a wide range depending on the purpose, but a silver chloride ratio of 2 mol% or more can be preferably used. A so-called high silver chloride emulsion having a high silver chloride content is preferably used for a light-sensitive material suitable for rapid processing. The silver chloride content of these high silver chloride emulsions is preferably 90 mol% or more, more preferably 95 mol% or more. For the purpose of reducing the replenishment amount of the developing solution, an almost pure silver chloride chlorobromide emulsion having a silver chloride content of 98 to 99.9 mol% is also preferably used. Silver halide grains in photographic emulsions have regular crystals such as cubes, octahedra and tetradecahedrons, grains having irregular crystal forms such as spheres and plates, twin planes, etc. It may have a crystal defect of, or a composite form thereof. The grain size of silver halide is about 0.2 μm or less
It may be large-sized grains up to 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion. The silver halide photographic emulsion which can be used in the present invention includes, for example, Research Disclosure (RD) No. 17643 (December 1978), pp. 22-23, "I. Emulsion preparation and types", and
No.18716 (November, 1979), p.648, ibid., No.307105 (1989)
November), pp.863-865, and "Graphide's Physics and Chemistry", published by Paul Montel (P.Glafkides, Chemie).
et Phisique Photographique, PaulMontel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (G.
F. Duffin, Photographic Emulsion Chemistry (Focal P
ress, 1966)), "Production and coating of photographic emulsions" by Zelikman et al., published by Focal Press (VL Zelikman et al.,
Making and Coating Photographic Emulsion, Focal Pr
ess, 1964) and the like.

Monodisperse emulsions described in US Pat. Nos. 3,574,628 and 3,655,394 and British Patent 1,413,748 are also preferable. Further, tabular grains having an aspect ratio of about 3 or more can be used in the present invention. Tabular grains are described by Gatov, Photographic Science and Engineering (Gutoff, PhotographicScience
and Engineering), Vol. 14, pp. 248-257 (1970);
U.S. Pat.Nos. 4,434,226, 4,414,310, 4,433,0
It can be easily prepared by the method described in 48, 4,439,520 and British Patent 2,112,157. The crystal structure may be uniform, may have a different halogen composition between the inside and the outside, may have a layered structure, and may have a different composition by epitaxial bonding. Alternatively, it may be bonded to a compound other than silver halide such as silver rhodanide and lead oxide. Also, a mixture of particles having various crystal forms may be used. The above emulsion may be either a surface latent image type which forms a latent image mainly on the surface, an internal latent image type which is formed inside the grain or a type which has a latent image both on the surface and inside, but a negative type emulsion. It is necessary to be. Among the internal latent image type emulsions, core / shell type internal latent image type emulsions described in JP-A-63-264740 may be used. The method for preparing this core / shell type internal latent image type emulsion is described in JP-A-59-133542. The shell thickness of this emulsion varies depending on the development process and the like, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

The silver halide emulsion is usually used after physical ripening, chemical ripening and spectral sensitization. Additives used in such a process are described in Research Disclosure No. 17643, No. 18716 and No. 307105, and the relevant portions are summarized in the table below. In the light-sensitive material of the present invention, two or more kinds of emulsions having different characteristics of at least one of the grain size, grain size distribution, halogen composition, grain shape and sensitivity of the light-sensitive silver halide emulsion,
It can be used by mixing in the same layer. US Patent No.
No. 4,082,553, the surface of which is covered with a silver halide grain, U.S. Pat. It can be preferably used for the silver emulsion layer and / or the substantially light-insensitive hydrophilic colloid layer. The fogged silver halide grain inside or on the surface means a silver halide grain capable of developing uniformly (non-imagewise) regardless of the unexposed portion and exposed portion of the light-sensitive material. . A method for preparing a silver halide grain whose inside or surface is fogged is described in US Pat.
It is described in No. 9-214852. The silver halide forming the inner nucleus of a core / shell type silver halide grain having a fogged grain inside may have the same halogen composition or different halogen compositions. As the silver halide whose inside or surface is fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. There is no particular limitation on the grain size of these fogged silver halide grains, but as the average grain size,
0.01 to 0.75 μm, particularly 0.05 to 0.6 μm is preferable. Also,
The grain shape is not particularly limited, and may be regular grains or polydisperse emulsions, but monodisperse grains (at least 95% of the weight or number of silver halide grains are within ± 40% of the average grain size) (Having a particle size of 1).

In the present invention, it is preferable to use a non-photosensitive fine grain silver halide. The non-photosensitive fine grain silver halide is a fine grain of silver halide which is not exposed to light during imagewise exposure for obtaining a dye image and is not substantially developed in the developing treatment, and it is preferable that it is not fogged in advance. . The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may optionally contain silver chloride and / or silver iodide. Preferred is one containing 0.5 to 10 mol% of silver iodide. Fine grain silver halide has an average grain size (average value of circle equivalent diameter of projected area)
Is preferably 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm. The fine grain silver halide can be prepared by a method similar to that for ordinary photosensitive silver halide. In this case, the surface of the silver halide grain does not need to be chemically sensitized nor spectral sensitization. However, prior to adding this to the coating liquid, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, or mercapto-based compound or a zinc compound in advance. Colloidal silver can be preferably contained in this fine grain silver halide grain-containing layer. Coated silver amount of the light-sensitive material of the present invention is preferably 6.0 g / m ² or less, 4.5 g / m ² or less is most preferred.

Known photographic additives that can be used in the present invention are also described in the above three Research Disclosures, and the relevant portions are shown in the following table. Types of additives RD17643 RD18716 RD307105 1. Chemical sensitizer, page 23, page 648, right column, page 866 2. Sensitivity enhancer, page 648, right column 3. Spectral sensitizer, page 23 to 24, page 648, right column 866 to 868 Color sensitizer: page 649, right column 4. Whitening agent: page 24, page 647, right column 868, page 5, fogging prevention, page 24-25, page 649, right column, page 868-870, stabilizer, light absorber, 25- Page 26 Page 649 Right column Page 873 Filter ~ Page 650 Left column Dye, UV absorber 7. Stain 25 Page Right column 650 Page Left column 872 Inhibitor ~ Right column 8. Dye image Page 25 650 Page Left column 872 Stabilizer 9. Hardener 26 pages 651 left column 874-875 pages 10. Binder 26 pages 651 pages left column 873-874 pages 11. Plasticizer, page 27 650 pages right column 876 Lubricants 12. Coating aids , Pages 26 to 27, page 650, right column, pages 875 to 876, surfactant 13. static, page 27, page 650, right column, pages 876 to 877, inhibitor 14. matting agent, pages 878 to 879

Further, in order to prevent deterioration of photographic performance due to formaldehyde gas, it is preferable to add to the light-sensitive material a compound capable of reacting with formaldehyde described in US Pat. Nos. 4,411,987 and 4,435,503. . In the light-sensitive material of the present invention, U.S. Pat.
No. 4,788,132, JP-A-62-18539, JP-A 1-28
It is preferable to contain the mercapto compound described in No. 3551. The light-sensitive material used in the present invention is described in JP-A 1-1060.
It is preferable to include a compound described in No. 52, which releases a fogging agent, a development accelerator, a silver halide solvent or a precursor thereof regardless of the amount of developed silver produced by the development processing. International publication for the light-sensitive material used in the present invention
Dyes or EP 317,308A dispersed by the method described in WO88 / 04794 and JP-A-1-502912, U.S. Pat. No. 4,420,5
It is preferable to incorporate the dyes described in JP-A No. 55-59359 and JP-A No. 1-259358. Various color couplers can be used in the present invention, and specific examples thereof include Research Disclosure No. 17643, VII-CG, and No. 30710 mentioned above.
5, VII-C to G.
Yellow couplers include, for example, U.S. Pat.
No. 1, No. 4,022,620, No. 4,326,024, No. 4,4
01,752, 4,248,961, Japanese Patent Publication 58-10739, British Patents 1,425,020, 1,476,760, U.S. Patents
3,973,968, 4,314,023, 4,511,649,
Those described in European Patent No. 249,473A and the like are preferable.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat. Nos. 4,310,619, 4,351,897 and European Patent 73,63 are preferred.
6, U.S. Pat.Nos. 3,061,432 and 3,725,067,
Research Disclosure No. 24220 (June 1984
Month), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, JP-A 61-7.
No. 2238, No. 60-35730, No. 55-118034, No. 60-185951
U.S. Pat.Nos. 4,500,630, 4,540,654, and
Those described in 4,556,630 and International Publication WO88 / 04795 are particularly preferable. Examples of cyan couplers include phenol-based and naphthol-based couplers, and US Pat.
52,212, 4,146,396, 4,228,233, and
4,296,200, 2,369,929, 2,801,171,
No. 2,772,162, No. 2,895,826, No. 3,772,002
No. 3, No. 3,758,308, No. 4,334,011, No. 4,32
7,173, West German Patent Publication 3,329,729, European Patent 12
1,365A, 249,453A, U.S. Pat.No. 3,446,622
No. 4, No. 4,333,999, No. 4,775,616, No. 4,45
1,559, 4,427,767, 4,690,889, and
Those described in 4,254,212, 4,296,199 and JP-A-61-42658 are preferable. Furthermore, JP-A-64-553,
Pyrazoloazole couplers described in JP-A Nos. 64-554, 64-555 and 64-556 and imidazole couplers described in US Pat. No. 4,818,672 can also be used. Typical examples of polymerized dye-forming couplers are described in US Pat.
3,451,820, 4,080,211 and 4,367,282,
No. 4,409,320, No. 4,576,910, British patent 2,1
No. 02,137 and European Patent No. 341,188A.

Examples of couplers in which the color forming dye has an appropriate diffusibility include US Pat. No. 4,366,237 and British Patent No. 2,12.
5,570, European Patent 96,570, West German Patent (Publication)
Those described in 3,234,533 are preferable. Colored couplers for correcting unnecessary absorption of color forming dyes are described in Research Disclosure No. 17643, Item VII-G, No. 307.
105 VII-G, U.S. Pat. No. 4,163,670, Japanese Examined Patent Publication No. 57
-39413, U.S. Pat.Nos. 4,004,929, 4,138,258
And those described in British Patent No. 1,146,368 are preferred.
Further, a coupler that corrects unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in U.S. Pat.No. 4,774,181, and a dye capable of reacting with a developing agent described in U.S. Pat. It is also preferable to use a coupler having a precursor group as a leaving group.
Compounds releasing a photographically useful residue upon coupling are also preferably used in the present invention. DIR couplers that release development inhibitors are described in RD 17643, VII-F above.
And Patent Nos. 307105 and VII-F, JP-A-57-151944, 57-154234, 60-184248,
63-37346, 63-37350, U.S. Patent 4,248,962,
Those described in JP-A-4,782,012 are preferable. RD No.1
The bleaching accelerator releasing couplers described in 1449, 24241 and JP-A-61-201247 are effective for shortening the processing time having a bleaching ability, and in particular, the above-mentioned tabular silver halide grains. The effect is great when it is added to the photosensitive material using. Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent 2,097,140.
No. 2,131,188, JP-A-59-157638, and 59-170.
Those described in No. 840 are preferable. In addition, JP 60-1070
No. 29, No. 60-252340, JP-A No. 1-4940, No. 1-45687
By the redox reaction with the oxidant of the developing agent described in No.
Compounds that release a fogging agent, a development accelerator, a silver halide solvent and the like are also preferable.

Other compounds which can be used in the light-sensitive material used in the present invention include US Pat. No. 4,130,4
Competitive couplers described in US Pat. No. 4,283,472
Nos. 4,338,393, 4,310,618, etc., multiequivalent couplers, DIR redox compound releasing couplers, DI, as described in JP-A-60-185950, JP-A-62-24252, etc.
R coupler-releasing coupler, DIR coupler-releasing redox compound or DIR redox-releasing redox compound, couplers releasing a dye that undergoes color recovery after separation described in European Patents 173,302A and 313,308A, and US Pat.
Ligand releasing couplers described in JP 55,477 A, JP-A-63-7
Examples thereof include a coupler releasing a leuco dye described in 5747, and a coupler releasing a fluorescent dye described in US Pat. No. 4,774,181.

The coupler used in the present invention can be introduced into the photographic material by various known dispersion methods. Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027. Specific examples of the high-boiling organic solvent having a boiling point of 175 ° C. or higher at atmospheric pressure used in the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis phthalate. (2,4-di-t-amylphenyl) phthalate, bis (2,4-di-t-amylphenyl)
Isophthalate, bis (1,1-diethylpropyl) phthalate, etc.), phosphoric acid or phosphonic acid esters (triphenyl phosphate, tricresyl phosphate,
2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di
-2-Ethylhexylphenylphosphonate, etc., Benzoic acid esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), Amides (N, N-diethyldodecaneamide, N, N-diethyllauryl) Amides, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4-di-tert-amylphenol, etc.), aliphatic carboxylic acid esters (bis (2-ethylhexyl) sebacate, dioctylazese) Rate, glycerol tributyrate, isostearyl lactate,
Trioctyl citrate, etc., aniline derivatives (N, N-
Dibutyl-2-butoxy-5-tert-octylaniline, etc.), hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.) and the like. The auxiliary solvent has a boiling point of about 30 ° C or higher, preferably 50 ° C.
Organic solvents above 160 ° C can be used. Typical examples are ethyl acetate, butyl acetate, ethyl propionate,
Methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide and the like can be mentioned. The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in US Pat. No. 4,199,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.

In the color light-sensitive material relating to the present invention,
Phenethyl alcohol and JP-A Nos. 63-257747 and 62-27
No. 2248, and 1,2-benzisothiazolin-3-one described in JP-A-1-80941, n-butyl p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol, 2 It is preferable to add various preservatives or antifungal agents such as-(4-thiazolyl) benzimidazole. The present invention can be applied to various color light-sensitive materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers. Suitable supports that can be used in the present invention include, for example:
The RD. No. 17643, page 28, No. 18716, page 647, right column to page 648, left column, and No. 307105, page 879. In the light-sensitive material according to the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is preferably 28 μm or less, more preferably 23 μm or less, and 18 μm or less.
m or less is more preferable, and 16 μm or less is particularly preferable. The film swelling speed T _1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. The film thickness is 25 ° C and 55% relative humidity (2
The film swelling speed T _1/2 can be measured according to a method known in the art. For example, a swellometer (swelling meter) of the type described by A. Green et al. In Photographic Science and Engineering (Photogr.Sci.Eng.), No. 19, No. 2, pp. 124-129. ) Is used, T _1/2 is 90% of the maximum swollen film thickness reached when the film is processed with a color developer at 30 ° C. for 3 minutes and 15 seconds, and the saturated film thickness is defined as 1 / of the saturated film thickness. It is defined as the time to reach 2.
The film swelling speed T _1/2 can be adjusted by adding a film hardening agent to gelatin as a binder or changing aging conditions after coating. The swelling rate is 1
50 to 400% is preferable. The swelling rate is calculated from the maximum swollen film thickness under the conditions described above by the formula: (maximum swollen film thickness-film thickness)
/ Can be calculated according to the film thickness. The light-sensitive material of the present invention has a total dry film thickness of 2 μm to 20 μm on the side opposite to the side having the emulsion layer.
It is preferable to provide a hydrophilic colloid layer of m (referred to as a back layer). This back layer preferably contains the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, surface active agent and the like. The swelling ratio of this back layer is preferably 150 to 500%.

[0070]

【Example】

Example 1 On a subbed cellulose triacetate film support,
Each layer having the composition shown below was applied in multiple layers to prepare Sample 101, which is a multilayer color light-sensitive material. (Photosensitive layer composition) The main materials used for each layer are classified as follows; ExC: Cyan coupler UV: UV absorber ExM: Magenta coupler HBS: High boiling organic solvent ExY: Yellow coupler H: Gelatin Hardening agent ExS: Number corresponding to each component of the sensitizing dye indicates the coating amount expressed in g / m ² , and for silver halide, the coating amount in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown in mol unit per mol of silver halide in the same layer.

(Sample 101) First layer (antihalation layer) Black colloidal silver Silver 0.18 Gelatin 1.40 ExM-1 0.18 ExF-1 2.0 × 10 ^-3 HBS-1 0.20

[0072] Second layer (middle layer)       Emulsion G Silver 0.065       2,5-di-t-pentadecylhydroquinone 0.18       ExC-2 0.020       UV-1 0.060       UV-2 0.080       UV-3 0.10       HBS-1 0.10       HBS-2 0.020       Gelatin 1.04

Third Layer (Low Sensitivity Red Sensitive Emulsion Layer) Emulsion A Silver 0.25 Emulsion B Silver 0.25 ExS-1 6.9 × 10 ^-5 ExS-2 1.8 × 10 ^-5 ExS-3 3.1 × 10 ^-4 ExC-1 0.17 ExC-3 0.030 ExC-4 0.10 ExC-5 0.020 ExC-7 0.0050 ExC-8 0.010 Cpd-2 0.025 HBS-1 0.10 Gelatin 0.87

Fourth Layer (Medium Sensitivity Red Sensitive Emulsion Layer) Emulsion D Silver 0.70 ExS-1 3.5 × 10 ^-4 ExS-2 1.6 × 10 ^-5 ExS-3 5.1 × 10 ^-4 ExC-1 0.13 ExC-2 0.060 ExC-3 0.0070 ExC-4 0.090 ExC-5 0.025 ExC-7 0.0010 ExC-8 0.0070 Cpd-2 0.023 HBS-1 0.10 Gelatin 0.75

Fifth Layer (High Sensitivity Red Sensitive Emulsion Layer) Emulsion E Silver 1.40 ExS-1 2.4 × 10 ^-4 ExS-2 1.0 × 10 ^-4 ExS-3 3.4 × 10 ^-4 ExC-1 0.12 ExC-3 0.045 ExC-6 0.020 ExC-8 0.025 Cpd-2 0.050 HBS-1 0.22 HBS-2 0.10 Gelatin 1.20

Sixth layer (intermediate layer) Cpd-1 0.10 HBS-1 0.50 Gelatin 1.10

Seventh Layer (Low Sensitivity Green Sensitive Emulsion Layer) Emulsion C Silver 0.35 ExS-4 3.0 × 10 ^-5 ExS-5 2.1 × 10 ^-4 ExS-6 8.0 × 10 ^-4 ExM-1 0.010 ExM-2 0.33 ExM-3 0.086 ExY-1 0.015 HBS-1 0.30 HBS-3 0.010 Gelatin 0.73

Eighth Layer (Medium Sensitivity Green Sensitive Emulsion Layer) Emulsion D Silver 0.80 ExS-4 3.2 × 10 ⁻⁵ ExS-5 2.2 × 10 ⁻⁴ ExS-6 8.4 × 10 ⁻⁴ ExM-2 0.13 ExM-3 0.030 ExY-1 0.018 HBS-1 0.16 HBS-3 8.0 × 10 ^-3 Gelatin 0.90

Ninth Layer (High Sensitivity Green Sensitive Emulsion Layer) Emulsion E Silver 1.25 ExS-4 3.7 × 10 ^-5 ExS-5 8.1 × 10 ^-5 ExS-6 3.2 × 10 ^-4 ExC-1 0.010 ExM-1 0.030 ExM-4 0.040 ExM-5 0.019 Cpd-3 0.040 HBS-1 0.25 HBS-2 0.10 Gelatin 1.44

[0080] 10th layer (yellow filter layer)       Yellow colloidal silver 0.030       Cpd-1 0.16       HBS-1 0.60       Gelatin 0.60

Eleventh Layer (Low Sensitivity Blue Sensitive Emulsion Layer) Emulsion C Silver 0.18 ExS-7 8.6 × 10 ⁻⁴ ExY-1 0.020 ExY-2 0.22 ExY-3 0.50 ExY-4 0.020 HBS-1 0.28 Gelatin 1.10

Twelfth Layer (Medium Sensitivity Blue Sensitive Emulsion Layer) Emulsion D Silver 0.40 ExS-7 7.4 × 10 ^-4 ExC-7 7.0 × 10 ^-3 ExY-2 0.050 ExY-3 0.10 HBS-1 0.050 Gelatin 0.78

13th layer (high-sensitivity blue-sensitive emulsion layer) Emulsion F Silver 1.00 ExS-7 4.0 × 10 ⁻⁴ ExY-2 0.10 ExY-3 0.10 HBS-1 0.070 Gelatin 0.86

Fourteenth Layer (First Protective Layer) Emulsion G Silver 0.20 UV-4 0.11 UV-5 0.17 HBS-1 5.0 × 10 ^-2 Gelatin 1.00

Fifteenth layer (second protective layer) H-1 0.40 B-1 (diameter 1.7 μm) 5.0 × 10 ^-2 B-2 (diameter 1.7 μm) 0.10 B-3 0.10 S-1 0.20 Gelatin 1.20

Further, in order to improve the storability, processability, pressure resistance, antifungal / antibacterial property, antistatic property and coating property of each layer, W-1 to W-3, B-4 to B are appropriately added. -6, F
-1 to F-17 and iron salt, lead salt, gold salt, platinum salt,
It contains iridium salt and rhodium salt.

[0087]

[Table 1]

In Table 1, (1) Emulsions A to F were reduction-sensitized at the time of grain preparation using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-91938. (2) Emulsions A to F were subjected to gold sensitization, sulfur sensitization and selenium sensitization in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate according to the examples of JP-A-3-237450. Has been done. (3) Low molecular weight gelatin was used for the preparation of tabular grains according to the example of JP-A 1-158426. (4) Dislocation lines as described in JP-A-3-237450 have been observed in tabular grains and normal crystal grains having a grain structure using a high voltage electron microscope.

[0089]

[Chemical formula 22]

[0090]

[Chemical formula 23]

[0091]

[Chemical formula 24]

[0092]

[Chemical 25]

[0093]

[Chemical formula 26]

[0094]

[Chemical 27]

[0095]

[Chemical 28]

[0096]

[Chemical 29]

[0097]

[Chemical 30]

[0098]

[Chemical 31]

[0099]

[Chemical 32]

[0100]

[Chemical 33]

[0101]

[Chemical 34]

[0102]

[Chemical 35]

[0103]

[Chemical 36]

After exposing the color photographic light-sensitive material as described above, it was processed by an automatic developing machine by the method described below (until the cumulative replenishment amount of the developing solution became 3 times the tank capacity). (Processing method) Processing time Processing temperature Replenishment amount Tank capacity Color development 4 minutes 50 seconds 40 ℃ 22 ml 20 liters Bleaching 3 minutes 00 seconds 38 ℃ 25 ml 40 liters Water washing (1) 15 seconds 24 ℃ (2) ( 1 liter to 10 liters countercurrent piping water washing (2) 15 seconds 24 ℃ 15 ml 10 liters fixed 3 minutes 00 seconds 38 ℃ 15 ml 30 liters water rinse (3) 30 seconds 24 ℃ From (4) to (3) 10 liters Countercurrent piping system Washing with water (4) 30 seconds 24 ℃ 1200 ml 10 liters Stability 30 seconds 38 ℃ 20 ml 10 liters Dry 4 minutes 20 seconds 55 ℃ * Replenishment amount per 35 mm width 1 m length

Next, the composition of the treatment liquid will be described. (Color developer) Tank liquid (g) Replenisher (g)   Diethylenetriamine pentaacetic acid 1.0 1.2   1-hydroxyethylidene-1,1-     Diphosphonic acid 2.0 2.2   Sodium sulfite 4.0 4.8   Potassium carbonate 30.0 39.0   Potassium bromide 1.4 0.3   Potassium iodide 1.5 mg −   Hydroxylamine sulfate 2.4 3.1   Exemplified compound (D-2)     1,5-Dinaphthalene sulfonate 10.6 15.9   1.0 liter with water added 1.0 liter   pH (adjusted with potassium hydroxide and sulfuric acid) 10.20 10.30

[0106] (Bleaching solution) Tank solution (g) Replenisher solution (g)   Sodium ferric ethylenediaminetetraacetate     Trihydrate 100.0 120.0   Ethylenediaminetetraacetic acid disodium salt 10.0 11.0   3-mercapto-1,2,4-triazole 0.03 0.08   Ammonium bromide 140.0 160.0   Ammonium nitrate 30.0 35.0   Ammonia water (27%) 6.5 ml 4.0 ml   1.0 liter with water added 1.0 liter   pH (adjusted with ammonia water and nitric acid) 6.0 5.7

[0107] (Fixer) Tank solution (g) Replenisher (g)   Ethylenediaminetetraacetic acid disodium salt 0.5 0.7   Ammonium sulfite 20.0 22.0   Ammonium thiosulfate aqueous solution           (700 g / l) 295.0 ml 320.0 ml   Acetic acid (90%) 3.3 4.0   1.0 liter with water added 1.0 liter   pH (adjusted with aqueous ammonia and acetic acid) 6.7 6.8

[0108] (Stabilizer) Tank liquid / replenisher common (g)   Sodium p-toluenesulfinate 0.03   Polyoxyethylene-p-monononylphenyl     Ether (average degree of polymerization 10) 0.2   Ethylenediaminetetraacetic acid disodium salt 0.05   1,2,4-triazole 1.3   1,4-bis (1,2,4-triazole-1-     Ilmethyl) piperazine 0.75   1.0 liter with water   pH 8.5

The running treatment liquid thus obtained is referred to as treatment 152. Next, a similar color developing solution was prepared, except that the exemplary compound (D-2), which is a color developing agent in the color developing solution, is shown in Table 101, and an equimolar amount of the color developing agent of the present invention was used. The same continuous treatment was performed to obtain each running treatment liquid (treatments 152 to 159). Further, a running processing solution was obtained in the same manner as in Processing 152 except that only the exemplary compound (D-2) which was a color developing agent in the color developing solution was removed. This running treatment liquid is referred to as treatment 151. Next, after subjecting the sample 101 to wedge exposure, each running treatment liquid (treatment 151 to
159), and the optical density and the maximum image density in the fog portion of the yellow image of each of the obtained samples were measured. The color developing agent of the present invention was evaluated by subtracting the value obtained in treatment 151 from the value obtained in treatments 152-159. The results are shown in Table 101.

Table 101 Processing Color-developing agent Fog density Maximum image density Remarks 152 D-2 0.03 2.79 Invention 153 D-6 0.04 2.77 〃 154 D-9 0.01 2.81 〃 155 D-12 0.01 2.90 〃 156 D-19 0.03 2.78 〃 157 D-23 0.07 2.74 〃 158 D-27 0.05 2.77 〃 159 D-360 .02 2.78 From Table 101, it is clear that the color developing agent of the present invention has a high image forming efficiency while maintaining a low fog density and giving a high maximum image density.

Example 2 The surface of a paper support laminated on both sides with polyethylene was subjected to a corona discharge treatment, and then a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided, and various photographic constituent layers were further coated to prepare a A multilayer color photographic paper having the layer structure shown was produced. The coating liquid was prepared as follows.

Preparation of coating liquid for the first layer Yellow coupler (ExY) 19.1 g and color image stabilizer (Cpd-1) 4.4 g and color image stabilizer (Cpd-7) 0.
To 7 g, 27.2 cc of ethyl acetate and solvent (Solv--3)
And (Solv-7) 4.1 g each were added and dissolved,
This solution was emulsified and dispersed in 185 cc of a 10% gelatin aqueous solution containing 8 cc of 10% sodium dodecylbenzenesulfonate to prepare an emulsified dispersion A. On the other hand, silver chlorobromide emulsion A (cube, large size emulsion with average grain size 0.88 μm and 0.70 μm
3: 7 mixture with a small size emulsion of (silver molar ratio). (The coefficient of variation of the grain size distribution is 0.08 and 0.10, respectively. In each size emulsion, 0.3 mol% of silver bromide is locally contained in a part of the grain surface.)
Was prepared. In this emulsion, the blue sensitizing dyes A and B shown below were 2.0 × 10 ⁻⁴ moles per mole of silver for the large-sized emulsion A, and respectively for the small-sized emulsion A. 2.5 × 10 ⁻⁴ mol is added. The chemical ripening of this emulsion was performed by adding a sulfur sensitizer and a gold sensitizer. The above emulsified dispersion A and this silver chlorobromide emulsion A were mixed and dissolved to prepare a coating solution for the first layer having the following composition.

Coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. 1-Oxy-3,5-dichloro-s-triazine sodium salt was used as a gelatin hardening agent for each layer.

Further, Cpd-10 and Cpd-11 are provided in each layer.
Were added so that the total amount was 25.0 mg / m ² and 50.0 mg / m ² , respectively.

The following spectral sensitizing dyes were used in the silver chlorobromide emulsion of each photosensitive emulsion layer.

[0116]

[Chemical 37]

(2.0 × 10 ^-4 mol for large size emulsion A and 2.5 × 10 ^-4 mol for small size emulsion A per mol of silver halide)

[0118]

[Chemical 38]

(Per mol of silver halide, 4.0 × 10 ⁻⁴ mol for large size emulsion B and 5.6 × 10 ⁻⁴ mol for small size emulsion B), and

[0120]

[Chemical Formula 39]

(1 mol of silver halide: 7.0 × 10 ^-5 mol for large size emulsion B and 1.0 × 10 ^-5 mol for small size emulsion B)

[0122]

[Chemical 40]

(0.9 × 10 ⁻⁴ mol for large size emulsion C and 1.1 × 10 ⁻⁴ mol for small size emulsion C per mol of silver halide)

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.

[0125]

[Chemical 41]

For the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer, 1- (5-methylureidophenyl)-
5-Mercaptotetrazole to silver halide 1
8.5 x 10 ^-5 mol, 7.7 x 10 ^-4 mol, 2.5 x 10 per mol
^-4 mol was added.

For the blue-sensitive emulsion layer and the green-sensitive emulsion layer, 4-hydroxy-6-methyl-1,3,3a, 7-
Tetrazaindene was added in an amount of 1 × 10 ^-4 mol and 2 × 10 ^-4 mol per mol of silver halide, respectively.

Further, in order to prevent irradiation, the following dyes (in parentheses represent coating amount) were added to the emulsion layers.

[0129]

[Chemical 42]

(Layer Structure) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents the coating amount in terms of silver.

Support polyethylene laminated paper [polyethylene on the first layer side contains a white pigment (TiO ₂ ) and a bluish dye (ultraviolet)]

[0132] First layer (blue sensitive emulsion layer)   The above-mentioned silver chlorobromide emulsion A 0.30   Gelatin 1.22   Yellow coupler (ExY) 0.82   Color image stabilizer (Cpd-1) 0.19   Solvent (Solv-3) 0.18   Solvent (Solv-7) 0.18   Color image stabilizer (Cpd-7) 0.06

[0133] Second layer (color mixing prevention layer)   Gelatin 0.64   Color mixing inhibitor (Cpd-5) 0.10   Solvent (Solv-1) 0.16   Solvent (Solv-4) 0.08

[0134] Third layer (green sensitive emulsion layer)     Silver chlorobromide emulsion (cubic, large size emulsion with an average grain size of 0.55 μm;   ． 1: 3 mixture with 39 μm small size emulsion (Ag molar ratio). Particle size distribution   Coefficient of variation is 0.10 and 0.08, respectively, and each size emulsion is AgBr 0.8.   Molar% was locally contained in a part of the particle surface.) 0.12   Gelatin 1.28   Magenta coupler (ExM) 0.23   Color image stabilizer (Cpd-2) 0.03   Color image stabilizer (Cpd-3) 0.16   Color image stabilizer (Cpd-4) 0.02   Color image stabilizer (Cpd-9) 0.02   Solvent (Solv-2) 0.40

[0135] Fourth layer (UV absorption layer)   Gelatin 1.41   Ultraviolet absorber (UV-1) 0.47   Color mixing inhibitor (Cpd-5) 0.05   Solvent (Solv-5) 0.24

[0136] Fifth layer (red sensitive emulsion layer)     Silver chlorobromide emulsion (cubic, large size emulsion with average grain size 0.58 μm,   ． 1: 4 mixture with 45 μm small size emulsion (Ag molar ratio). Particle size distribution   Coefficient of variation of 0.09 and 0.11, AgBr 0.6 mol% for each size emulsion   0.23 localized in a part of the particle surface)   Gelatin 1.04   Cyan coupler (ExC) 0.32   Color image stabilizer (Cpd-2) 0.03   Color image stabilizer (Cpd-4) 0.02   Color image stabilizer (Cpd-6) 0.18   Color image stabilizer (Cpd-7) 0.40   Color image stabilizer (Cpd-8) 0.05   Solvent (Solv-6) 0.14

[0137] Sixth layer (UV absorption layer)   Gelatin 0.48   Ultraviolet absorber (UV-1) 0.16   Color mixing inhibitor (Cpd-5) 0.02   Solvent (Solv-5) 0.08

[0138] Seventh layer (protective layer)   Gelatin 1.10   Acrylic modified copolymer of polyvinyl alcohol 0.17       (Degree of denaturation 17%)   Liquid paraffin 0.03

[0139]

[Chemical 43]

[0140]

[Chemical 44]

[0141]

[Chemical formula 45]

[0142]

[Chemical formula 46]

[0143]

[Chemical 47]

[0144]

[Chemical 48]

First, a sensitometer (FWH type, manufactured by Fuji Photo Film Co., Ltd., color temperature of light source: 3200 ° K) manufactured by Fuji Photo Film Co., Ltd. was used for each sample, and gradation exposure of a three-color separation filter for sensitometry was performed. The exposure at this time is 2 with an exposure time of 0.1 seconds.
The exposure amount was 50 CMS.

The exposed sample was treated with a paper processor using a solution having the following processing steps and processing solution composition,
Continuous processing (running test) was carried out until the tank was replenished with twice the color developing tank capacity. Processing process Temperature Time Replenisher ^* Tank capacity Color development 39 ° C 1 minute 15 seconds 161 ml 17 liters Bleach fixing 30-35 ° C 45 seconds 215 ml 17 liters Rinse 1 30-35 ° C 20 seconds-10 liters Rinse 2 30- 35 ℃ 20 seconds -10 liters Rinse 3 30 to 35 ℃ 20 seconds 350 ml 10 liters Dry 70 to 80 ℃ 60 seconds * Replenishment amount per 1 m ² of light-sensitive material (3 tank countercurrent method from rinse 3 to 1) .)

The composition of each processing liquid is as follows. [Color developer] [Tank liquid] [Replenisher]   800 ml water 800 ml   Ethylenediamine-N, N, N, N-     Tetramethylenephosphonic acid 1.5 g 2.0 g   Potassium bromide 0.015 g −   Triethanolamine 8.0 g 12.0 g   Sodium chloride 1.4 g −   Potassium carbonate 25 g 25 g   Exemplified compound (D-2)     1,5-naphthalenedisulfonate 2.4 g 3.3 g   N, N-bis (carboxymethyl) hi     Drazine 4.0 g 5.0 g   N, N-di (sulfoethyl) hydroxy     Sylamine 1Na 4.0 g 5.0 g   Optical brightener (WHITEX 4B, Sumitomo Chemical) 1.0 g 2.0 g   Add water 1000 ml 1000 ml     pH (25 ℃) 10.20 10.60

[0148] [Bleaching fixer] (tank solution and replenisher are the same)   400 ml water   Ammonium thiosulfate (70%) 100 ml   Sodium sulfite 17 g   Ethylenediaminetetraacetic acid iron (III) ammonium 55 g   Ethylenediaminetetraacetic acid disodium 5 g   Ammonium bromide 40 g   1000 ml with water     pH (25 ° C) 6.0

[Rinse solution] (The same tank solution and replenisher solution) Ion-exchanged water (3 ppm each for calcium and magnesium)
Hereinafter, the running treatment liquid thus obtained is treated 252.
And Next, a similar color developing solution is prepared except that the exemplary compound (D-2) which is a color developing agent in the color developing solution is shown in Table 201 in an equimolar amount, except that the color developing agent of the present invention is used. Each running treatment liquid (treatments 252 to 259) was obtained by performing the same continuous treatment. In addition, processing 252
A running processing solution was obtained in exactly the same manner except that only the exemplified compound (D-2) which was a color developing agent in the color developing solution was removed. This running treatment liquid is treated 251
And Next, after subjecting the sample 201 to wedge exposure,
Processing was carried out using each of the running processing liquids (Processing 251-259), and the optical density and the maximum image density in the fog portion of the yellow image of each of the obtained samples were measured. The color developing agent of the present invention was evaluated by subtracting the value obtained in treatment 251 from the value obtained in treatments 252 to 259. The results are shown in Table 201.

Table 201 Processing Color developing agents Fog density Maximum image density Remark 252 D-2 0.01 2.31 Present invention 253 D-4 0.02 2.29 〃 254 D-8 0.04 2.33 〃 255 D-11 0.00 2.35 〃 256 D-20 0.03 2.32 〃 257 D-22 0.03 2.33 〃 258 D-30 0.06 2.32 〃 259 D-460 .00 2.34 From Table 201, it is clear that the color developing agent of the present invention has high image forming efficiency while giving a high maximum image density while maintaining a low fog density. Example 3 Example 3 and photosensitive material 9 described in JP-A-2-93641
In an equimolar amount of the color developing agent in the color developing solution described in the publication, the color developing agents (D-13) and (D-1) of the present invention.
7), (D-25) and (D-40) were replaced with exactly the same processing solutions, and the resulting images were exposed and developed, and the images obtained had a high maximum image density while maintaining a low fog density. It was preferable.

Example 4 Example 1 and sample 101 described in JP-A-2-854.
Is an equimolar amount of the color developing agent in the color developing solution described in the publication, the color developing agents (D-1), (D-5) of the present invention,
Except for substituting (D-42) and (D-47), an exactly the same processing solution was prepared, exposed and developed, and the obtained image is a preferable one which gives a high maximum image density while maintaining a low fog density. there were.

Example 5 The color photographic light-sensitive material of Example 1 described in JP-A-1-158431 was used, and an equimolar amount of the color developing agent in the color developing solution described therein was used to develop the color developing agent of the present invention ( D-7),
Except for substituting (D-10), (D-18), and (D-21), the same processing solutions were prepared, exposed and developed, and the obtained images had a high maximum image while maintaining a low fog density. It was preferable to give the concentration.

Example 6 The color photographic light-sensitive material of Example 1 and Sample No. 1 described in JP-A-2-90145 was used, and an equimolar amount of the color developing agent in the color developing solution described in the same publication was used. Color developing agents (D-26), (D-29), (D-34), (D-
When a completely the same processing liquid was prepared, exposed and developed except that it was replaced with 43), the obtained image was preferable because it gave a high maximum image density while maintaining a low fog density.

[0154]

The color developing agent of the present invention gives a high maximum image density while maintaining a low fog density, that is, has a high image forming efficiency.

Continuation of the front page (56) Reference JP-A-63-177136 (JP, A) JP-A-3-209371 (JP, A) JP-A-3-246282 (JP, A) JP-A-3-2185 (JP , A) JP 49-61338 (JP, A) JP 60-224679 (JP, A) JP 57-121056 (JP, A) JP 2-264772 (JP, A) JP 2-32069 (JP, A) JP-A-4-312581 (JP, A) JP-A-4-147137 (JP, A) JP-A-4-226452 (JP, A) JP-A-63-24254 (JP, A) A) JP-A-2-275446 (JP, A) JP-A-55-500381 (JP, A) European patent application publication 433854 (EP, A 1) European patent application publication 375977 (EP, A 1) Synthesis, 1985 , No. 8, p. 794-796 Heterocycles, 1984, Vol. 22, No. 11, p. 2513-2516 Gazz. Chim. Ital. , 1989, Vol. 119, No. 7, p. 411-413 J. Heterocycl. Chem. , 1973, Vol. 10, No. 2, p. 181-185 Khim. Geterosikl. Soedin. 1985, No. 8, p.1090-1094J. Heterocycl. Chem. , 1983, Vol. 20, No. 1, p. 17-21 Tetrahedron, 1970, Vol. 26, No. 6, p. 1393-1400 Farmaco, Ed. Sci. 1968, Vol. 23, No. 10, p. 919-944 Photogr. Sci. Eng. 1978, Vol. 22, No. 5, P. 263-267 (58) Fields investigated (Int.Cl. ⁷ , DB name) G03C 7/413 G03C 7/407 CA (STN) REGISTRY (STN)

Claims (3)

(57) [Claims] 1. A color developing agent for silver halide color photographic represented by the following general formula (I). General formula (I) In the formula, R ₁ and R ₂ are each an unsubstituted alkyl group having 1 to 6 carbon atoms or a hydroxyl group or carboxy having 1 to 6 carbon atoms.
Group, alkoxy group, alkylamino group, ureido group,
Sulfonamide group, carbamoyl group, alkoxycarbo
Nylamino group, sulfamoyl group or sulfonyl group
Represents an alkyl group substituted with . A is the following general formula A-1
~ A- 17 represents a group of non-metal atoms necessary for forming a 5-membered unsaturated heterocycle . R ₁ and R ₂ , R ₁ and A, and R ₂ and A may cooperate with each other to form a nitrogen-containing heterocycle. [Chemical 49] [Chemical 50] In the formula, R ₁₁ and R ₁₂ may be the same or different,
Hydrogen atom, halogen atom, alkyl group, aryl group,
Telocyclic group, cyano group, nitro group, hydroxyl group, cal
Voxyl group, alkoxy group, aryloxy group, acyl
Amino group, amino group, alkylamino group, anilino group,
Ureido group, sulfamoylamino group, alkylthio
Group, arylthio group, alkoxycarbonylamino group,
Sulfonamide group, carbamoyl group, sulfamoyl
Group, a sulfonyl group, an alkoxycarbonyl group, a heterocyclic
Oxy group, azo group, acyloxy group, carbamoyloxy group
Si group, silyl group, silyloxy group, aryloxycal
Bonylamino group, imide group, heterocyclic thio group, sulfi
A nyl group, a phosphonyl group, an aryloxycarbonyl group,
Represents an acyl group. R ₁₃ is a hydrogen atom, an alkyl group, or an ant
Group, heterocyclic group, hydroxyl group, alkoxy group,
Aryloxy, acylamino, amino, alk
Luamino group, anilino group, ureido group, sulfamoyl
Amino group, alkylthio group, arylthio group, alkoxy
Cycarbonylamino group, sulfonamide group, sulfamo
Group, sulfonyl group, heterocyclic oxy group, acyloxy group
Si group, carbamoyloxy group, aryloxycarboni
It represents a ruamino group, an imide group or a heterocyclic thio group. 2. A processing composition for a silver halide color light-sensitive material comprising at least one of the color developing agents. 3. A color image forming method, which comprises developing a silver halide color photographic light-sensitive material with a processing solution containing at least one of the color developing agents.