JPH01284853A - Silver halide color photographic sensitive material and its color image forming method - Google Patents

Abstract

PURPOSE:To improve the coloring property of a coupler and the durability of a colored image by providing a layer contg. a specified yellow coupler and a specified phosphorus contg. compd. on the title material. CONSTITUTION:The layer contg. one or more kinds of the yellow couplers shown by formula I and one or more kinds of the compds. shown by formula IV is provided on the photosensitive material. In the formula, R<1> is an (unsubstd.)substd. N-phenylcarbamoyl group, R<2> is akyl or aryl group, X<1> is a group shown by formula II or III, etc., R<3> and R<4> are each hydrogen or halogen atom, etc., W<1> is an atomic group necessary for forming a prescribed ring, R is -(Y)n-R' group, Y is oxygen or sulfur atom, etc., (n) is 0 or 1, R' is a residual group of phosphoric acid, Q is a group shown by formula V, A is an atomic group capable of forming a benzene ring, X is a single bond or methylene group, etc. The replenishing amount of a replenisher in a washing and/or a stabilizing steps is preferably 0.5-50 times of an amount carried over from a prebath.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a photographic light-sensitive material, and more particularly to a silver halide color photographic light-sensitive material with improved color development and image stability. The present invention also relates to a color image forming method using this photosensitive material.

(Prior art) After exposing a silver halide photographic light-sensitive material to light, color development 1
By processing, the aromatic primary amine developing agent oxidized by silver halide reacts with the color-forming coupler.
One colored image is formed.

The yellow color group-forming coupler is ≠ equivalent coupler or % 1987-17630, British Patent No. 3,34.
No. 9,495, same J, IILol, 15P Hiro No., same J, lI-/! , 4! λ No. 3. α-acylacetanilides are known in which one hydrogen atom of the active methylene group described in Hirohiro 7゜ri2 is substituted with an aryloxy group, a halogen element, a sulfoxy group, an acyloxy group, etc. However, these couplers had drawbacks such as insufficient coupling reaction activity and poor image fastness.

If the color development is insufficient, there will be a large change in photographic properties due to fluctuations in developer components, which poses a problem in that stable quality cannot be obtained.Also, improvement in image fastness is due to the fact that quality deteriorates over time during storage. Since it causes deterioration, it is a performance that is strongly desired to be improved.

(Problem to be Solved by the Invention) A highly active yellow coupler which overcomes these drawbacks is obtained by replacing seven hydrogen atoms with a nitrogen atom in the active methylene group described in Tokikai Akihiro 7-co 6733. Couplers directly substituted by a heterocycle containing are known.

However, when using these couplers,
Although color development was improved, the fastness of the produced yellow image under light and wet heat conditions was insufficient, although slight improvements had been made.

On the other hand, when reducing the amount of washing water or stabilizing liquid, which is desirable for environmental conservation (for example, JP-A-Sho 7-
4!4LJ), such image fastness deteriorated significantly, and in this sense as well, the emergence of a yellow image fastening technique was desired.

On the other hand, as yellow image stabilizers, hindered aminos and hindered phenols are listed under British Patent No. 132tr.
It is known as the t-go, the same/Jj'AJIJ, and the same/≠ior hiro 6, etc.

However, although these compounds do improve the fastness of yellow color images, the effect was small and not sufficient.

Therefore, an object of the present invention is to provide a silver halide color photographic light-sensitive material which has excellent color development and improved yellow image fastness.

(Means for Solving the Problems) As a result of various studies to achieve the above object of the present invention, at least seven types of yellow couplers represented by the following general formula ('I) and the following general formula (A-1) were found. It has been found that the objects of the present invention can be achieved by a silver halide color photographic light-sensitive material containing at least one compound represented by the following.

General formula (I) In the formula, R1 represents a substituted or unsubstituted N-phenylcarbamoyl group, R represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, and Xl represents the following formula (a) , (b) or (C).

(a) (b) In formulas (a) and (b), R3 and R4 may be the same or different, and each represents a hydrogen atom, a hydrogen atom, a carboxylic acid ester group, an amine group, an alkyl group, or an alkylthio group. ,
It represents an alkoxy group, an alkylsulfonyl group, an alkylsulfinyl group, a carboxylic acid group, a sulfonic acid group, an unsubstituted or substituted phenyl group, or a heterocycle.

Together with Hiroseikan! Represents a nonmetallic atom required to form a membered ring or a 6-membered ring.

General formula [A-I:] R'' represents -S-1-NH-1 and -N-, n represents O or l. R' and R'' may be the same or different from each other, and each represents phosphoric acid represents the residue of Q is the general formula (
Represents a covalent group represented by A-I-/).

General formula (A-I-/) In the formula, A represents a group of atoms forming a substituted or unsubstituted benzene ring, and X is a single bond, a substituted or unsubstituted methylene group, -5-1-〇-1- NH-1 represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, a heterocyclic group, an acyl group, and a sulfonyl group.

Moreover, the free bond in the formula indicates the bonding position with O in Q of the general formula (A-I).

The two-power coupler used in the present invention is represented by the general formula (1), and will be described in detail below.

In formula (1), R represents a substituted or unsubstituted N-phenylcarbamoyl group, and substituents for the N-phenylcarbamoyl group include well-known substituents for yellow couplers,
For example, alkyl groups, alkenyl groups, alkoxy groups, alkoxycarbonyl groups, halogen atoms, alkoxycarbamoyl groups, aliphatic amide groups, alkylsulfamoyl groups, alkylsulfoneabado groups, alkylureido groups, alkyl-substituted succinimide groups, aryloxy group, aryloxycarbonyl group, arylcarbamoyl group, arylamide group, arylsulfamoyl group, arylsulfonamide group, arylureido group, carboxy group, sulfo group, nitro group, cyan group, thiocyano group, etc. There may be two or more substituents, and in that case, they may be the same or different from each other.

When R2 represents an alkyl group, it is preferably a tertiary alkyl group having 4 to 20 carbon atoms, such as a t-butyl group, a t-butyl group, or a t-butyl group.
-amyl group, t-octyl group, 1゜1-diethylpropyl group, 1,1-dimethylhexy) Lt5.1,1,5.
A typical example is 5-tetramethylhexyl group. As the substituents for the substituted alkyl group and the 1liF-substituted aryl group for R1, the substituents shown for R1 are representative.

The coupling-off group of Xl is a coupling-off group forming a 2-equivalent yellow coupler, that is, the following general formula (a),
Represents a group represented by (b) or (c).

(a) (b) R3 and R4 are each a hydrogen atom, a halogen atom, a carboxylic acid ester group, an amino group, an alkyl group, an alkylthio group,
It represents an alkoxy group, an alkylsulfonyl group, an alkylsulfinyl group, a carboxylic acid group, a sulfonic acid group, an unsubstituted or substituted phenyl group, or a heterocycle, and these groups may be the same or different.

(c)1 0 N.

〜／＼／ ゛Pa・11. W.

Represents a nonmetallic atom required to form a ring or a 6-membered ring.

A more preferred yellow coupler used in the present invention is represented by the following general formula (I').

General formula (I′) XI′ H′′
In the formula, R9 represents a tertiary alkyl group having 4 to 12 carbon atoms, or a phenyl group substituted with a halogen atom, an alkyl group, or an alkoxy group, or an unsubstituted phenyl group. RIG represents a halogen atom or an alkoxy group. , R' represents a hydrogen atom, a halogen atom, or an alkoxy group that may have a substituent. R" represents an acylamino group, an alkoxycarbonyl group, an alkylsulfamoyl group, an aryl The group represents a sulfamoyl group, an alkylsulfonamide group, an alkylsulfonamide group, an alkylureido group, an arylureido group, a succinimide group, an alkoxy group, or an aryloxy group.

X2 represents the following general formula (d), (e) or (f).

"In the R formula, R13 and R" each represent a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or a hydroxy group. Representing an aralkyl group or an acyl group, W'' represents an oxygen or ioca atom.

A particularly preferred yellow coupler used in the present invention is represented by the following general formula (1'').

General formula (1'') CI! In the formula, R11' represents an alkyl group or a phenyl group which may have a substituent.

These yellow couplers are, for example,
No. 83, No. 51-33410, No. 51-33410, JP-A No. 47-26133, No. 48-73147,
No. 51-102636, No. 52-82424, No. 5
It can be synthesized according to the method described in No. 2-115219, British Patent No. 1425020, and West German Patent No. 1547868.

Next, specific examples of the yellow coupler represented by the general formula (1) will be shown, but the present invention is not limited thereto.

(Y-1) 1 (Y-2) (Y-4) (Y-5) CHzCIhQC! Hs (Y-6) (Y-7> (Y-8) (Y-9) (Y-10) 1 (Y-11) H3 (Y-12) ; CH co (Y-13) (Y-14) OCJi CJs (Y-16) I (Y-17) (Y-18) NH-C-C4H9(n) ■ CM.

(Y-19) (Y-20) o-C-CHz ■ L (Y-21) I -CH (Y-22) (Y-23) I (Y-24> I (Y-'25) (Y -26> (Y-27) I (Y-28) I The group represented by the general formula CA-I) will be explained in more detail.

The phosphoric acid residues R' and R'' refer to the residues of phosphoric esters constituting the compound of the general formula CA-■, such as alkyl groups, alkenyl groups, cycloalkyl groups, aryl groups, and heterocycles. represents a group.

Among the compounds represented by the general formula (A-I), the case where n is / and Y is -O- is preferred from the viewpoint of the effects of the present invention.

Next, the group represented by the general formula (AI-/) will be explained in more detail.

The group represented by the general formula CA-I-/] is preferably a group represented by the general formula (A-1-2).

General formula [A-1-2] In the formula, the free bond and represents a group.

Next, R5, R6, R7 in general formula (A-T-2)
, R%X will be explained in detail.

In the general formula (A-I-, 2), R5, R6, R7 and R each represent a hydrogen atom or a substituent, and preferred substituents include an aliphatic group and an aromatic group (e.g. phenyl, naphthyl). , heterocycle (e.g. 2-pyridyl,
2-tetrahydropyranyl), halogen atoms (e.g.
fluorine, chlorine, bromine), uh aliphatic oxy groups (e.g. methoxy, butoxy), acyloxy groups (e.g. acetoxy, benzoyloxy), sulfonyloxy (e.g. ti
f, benzenesulfonyloxy), acylamino groups (e.g. acetylamino, benzoylamino), sulfonamido groups (e.g. methanesulfo/amide), amino groups, aliphatic and aromatic oxycarbonyl groups (e.g. phenoxycarbonyl, butoxycarbonyl) , a carbamoyl group (eg, eva, dimethylcarbamoyl, phenylcarbamoyl), a hydroxy group, and the like.

Preferably, X includes a substituted or unsubstituted methylene group (eg, methylene, impropylidene), an acyl bond, an oxygen atom, a sulfur atom, a sulfonyl bond, and an abano group.

In the present specification, 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 group, ethyl group, butyl group, dodecyl group, octadecyl group, alkynyl group, iS〇-propyl group, tert-butyl group, te
Examples include r t -octyl group, tert-dodecyl group, cyclohexyl group, cyclopentyl group, allyl group, vinyl group, λ-hexatecenyl group, and propargyl group.

Among the substituents mentioned above, substitutable groups include alkyl groups, aryl groups, heterocyclic groups, and alkoxy groups (
For example, methoxy group, λ-methoxyethoxy group, etc.),
Aryloxy groups (e.g., co-, Hiro-di-tert-amylphenoxy, -monochlorophenoxy, Hiro-cyanophenoxy, etc.), alkenyloxy groups (e.g.,
coufrobenyloxy group, etc.), acyl group (e.g., acetyl group, benzoyl group, etc.), ester group (e.g.,
butoxycarbonyl group, phenoxycarbonyl group, acetoxy group, benzoyloxy group, butoxysulfonyl group, toluenesulfonyloxy group, etc.), amide group (e.g. acetylamine group, ethercarbamoyl group, dimethylcarbamoyl group, methanesulfo/amide group, budelsulfonyl group), 7 amoyl group, etc.), sulfamide group (e.g., dipropylsulfamoylamino group, etc.), imide group (e.g., long cinimide group, hydantoinyl group, etc.), ureido group (e.g., phenylureido group, dimethylureido group, etc.), fatty group or aromatic sulfonyl group (e.g., methanesulfonyl group, 7-enylsulfonyl group, etc.),
aliphatic or aromatic thio groups (e.g. ethylthio group,
It may be substituted with a group selected from a phenylthio group, a hydroxy group, a cyan group, a carboxy group, a nitro group, a sulfo group, a halogen atom, and the like.

Specific examples of compounds represented by the general formula CA-1) are shown below, but the present invention is not limited thereto.

The compound represented by the general formula CA-1 of the present invention is described in US Pat. No. 2,735,765, US Pat. No. 3,7oo, Hiroj! They can be obtained by the method described in JP-A-62-2620μ7 or a method similar thereto.
Phosphorus Compounds J, Jo
hn Wiley & 5oz.

Inc., New York, / YjO, p. 226
.

It can be easily synthesized by reacting with phosphorus oxychloride, phosphoric acid or phosphorous dichloride according to the method described in US Pat. I can do it.

The coupler represented by the general formula (I) is preferably added to the emulsion layer at a ratio of 1xlO mol - 1 mol per mol of silver halide present in the same layer, and more preferably! ×10
Mol~! ×IO mole ratio.

The compound of general formula (A-I) may be added to the general formula (I) or the coupler represented by 1 molar to 20 mol, particularly preferably in the range of λ to 30 molar.

In carrying out the present invention, the lipophilic coupler represented by general formula (I) and the compound represented by general formula (A-1) are preferably dissolved or impregnated in lipophilic fine particles.

In addition to the above-mentioned compounds, the substances constituting the lipophilic fine particles include, if desired, additives such as couplers, oil-based solvents (including those fixed in a greenhouse such as wax), polymers, couplers, color mixture prevention agents, etc. Additives such as UV absorbers and UV absorbers are substances that also serve as oily solvents.

Here, the lipophilic fine particles mean fine particles that are not substantially dissolved in the gelatin aqueous solution and exist as a separate phase in the gelatin aqueous solution.

The lipophilic fine particles according to the present invention are usually prepared by combining a coupler of general formula 2N) and a compound of general formula Solvent alone (if no oil is required as mentioned above),
or dissolved in a mixed solvent of the oil and a low boiling point solvent,
Emulsify and disperse this solution in a hydrophilic colloid aqueous solution such as gelatin! Manufactured by Jii. There is no particular restriction on the particle size of the lipophilic fine particles, but it is preferably 0.05μ to 0.5μ, particularly 0.05μ to 0.5μ.
．． 1μ to 0.3μ is preferable.

Furthermore, the oil/coupler ratio is 0.0 by weight.
01 to Q and O are preferred.

Specific examples of the oil include phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, diisodecyl phthalate, dimethoxyethyl phthalate, etc.), phosphoric acid esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl). phosphate, monophenyl-p-t-butylphenyl phosphate, trioctyl phosphate, trinonyl phosphate), citric acid esters (e.g. acetyl tributyl citrate)
, benzoic acid esters (e.g. octyl benzoate), alkylamides (e.g. diethyl laurylamide, dibutyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate, diethyl azelate), trimesic acid esters (e.g. trimesic acid). tributyl), etc.

Examples of polymers include acrylic acid and methacrylic acid and their esters (e.g., methyl acrylate, ethyl acrylate, butyl methacrylate, etc.), acrylamide, methacrylamide, vinyl esters (e.g., vinyl acetate, vinyl propionate, etc.), acrylonitrile, styrene, divinylbenzene, vinyl alkyl ethers (e.g. vinyl ethyl ether), maleic acid esters (e.g. hamaeric acid methyl ester),
N-vinyl-2-pyrrolidone, N-vinylpyridine, 2
Latex polymers or water-insoluble and 8g solvent-soluble polymers produced using one or more of hexamers such as - and 4-beer pyridine are used.

Further, as the low boiling point solvent used to prepare the lipophilic fine particles according to the present invention, organic solvents having a boiling point of about 30° C. to 150° C. at atmospheric pressure, such as lower alkyl acetate such as ethyl acetate, isopropyl acetate, and butyl acetate; Ethyl propionate, methanol, ethanol, secondary butyl alcohol, cyclohexanol, fluorinated alcohol,
Examples include methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, acetone, methyl acetone, acetonitrile, dioxane, dimethyl formamide, dimethyl sulfoxide, chloroform, and cyclohexane.

In addition, the compound of the present invention can be used with various other known materials for forming photosensitive materials, such as silver halide, magenta, cyan couplers, etc.

Magenta couplers that can be used in the present invention include oil-protected indacylon or cyanoacetyl couplers, preferably pyrazoloazole couplers such as 5-pyrazolone and pyrazolotriazoles. The 5-pyrazolone 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 coloring dye, and typical examples thereof include U.S. Pat. Same No. 2゜3
No. 43.703, No. 2,600.788, No. 2,
No. 908.573, No. 3,062,653, No. 3
．． No. 152,896 and No. 3936.015, etc. As a leaving group for a two-equivalent 5-pyrazolone coupler, the nitrogen atom leaving group described in U.S. Pat. No. 4,310,619 or U.S. Pat.
．． The 5-pyrazolone coupler described in European Patent No. 73.636, which preferably has a ruthio group, and the 5-pyrazolone coupler described in European Patent No. 73.636, provides a high color density.

As a pyrazoloazole coupler, US Patent No. 3.
369,879, preferably the pyrazolo(5,1-c)(1,2,4)) liazoles described in U.S. Pat. (
Pyrazolotetrazoles and Research Disclosure 24230 (June 1984) and Research Disclosure 24230 (June 1984)
Imidazo (1) described in European Patent No. 119,741 in terms of low yellow side absorption and light fastness of color-forming dyes.
, 2-b) pyrazoles are preferred, as described in European Patent No. 119
．． Pyrazolo [1°5-b) (1,
2,4) Triazoles are particularly preferred.

Cyan couplers that can be used in the present invention include oil-protected naphthol-based and phenolic couplers, such as the naphthol-based couplers described in U.S. Pat. No. 2,474°293, and preferably U.S. Pat.
．． No. 212, No. 4゜146.396, No. 4,22
Typical examples include two-equivalent naphthol couplers of the oxygen atom elimination type described in No. 8.233 and No. 4.296.200. Specific examples of phenolic couplers include U.S. Patent Nos. 2.369.929 and 2.8.
No. 01,171, No. 2. 772. No. 162, No. 2,895,826, etc. Temperature and temperature robust cyan couplers are preferably used in the present invention, exemplified by U.S. Pat. No. 3.7.
72,002, a phenolic cyan coupler having an alkyl group equal to or higher than ethyl group at the meta-position of the phenol nucleus; US Pat. No. 2,772,162;
No. 758,308, No. 4,126.396, No. 4
．． No. 334,011, No. 4,327゜173, West German Patent Publication No. 3,329,729 and Japanese Patent Application No. 1983-4
2,5-diacylamino substituted phenolic couplers such as those described in US Pat.
No. 622, No. 4,333,999, No. 4. 45
1. No. 559 and No. 4,427,767, etc., which have a phenylureido group at the 2-position and have a 5-
These include phenolic couplers having an acylamino group in the position.

In addition, antioxidants, color forming N1 strong agents, ultraviolet absorbers, cyan, magenta and/or yellow pigments, anti-fading agents for images, color mixing inhibitors, anti-staining agents, anti-fogging agents, spectral sensitizers, dyes, and hardening films. Agents, surfactants, antistatic agents, development accelerators, desilvering accelerators, and the like can be added.

The color developer of the present invention will be explained below.

The color developer used in the present invention contains a known aromatic primary amine color developing agent.

Preferred examples are p-phenylenediamine derivatives, representative examples of which are shown below, but are not limited thereto.

D-IN, N-diethyl-p-phenylenediamine D-22-amino-5-diethylaminotoluene D-32-amino-5-(N-ethyl-N-laurylamino)toluene D-44-(N-ethyl- N-(β-hydroxyethyl)aminocoaniline D-52-methyl-4-[N-ethyl-N-(β-hydroxyethyl)aminocoaniline D-64-amino-3-methyl-N-ethyl-N −(β
-(methanesulfonamido)ethyl]-aniline D-7N-(2-amino-5-diethylaminophenylethyl)methanesulfonamide D-8N, N-dimethyl-p-phenylenediamine D-94-amino-3-methyl- N-ethyl-N-methoxyethylaniline D-104-amino-3-methyl-N-ethyl-N-β
-Ethoxyethylaniline D-114-amino-3-methyl-N-ethyl-N-β
-Butoxyethyl 7niline Among the above p-phenylenediamine derivatives, 4-amino-3-methyl-N-ethyl-N-(β-(
methanesulfonamido)ethyltoaniline (exemplified compound D-6).

Furthermore, these p-phenylenediamine derivatives may be salts such as sulfates, hydrochlorides, sulfites, and tri-toluenesulfonates.The amount of the aromatic-grade amine developing agent used is per developer solution Preferably about 0.1 g to about 20 g,
More preferred is a concentration of about 0.5 g to about 10 g.

In addition, sulfites such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite, potassium metasulfite, and carbonyl sulfite adducts are added to the color developer as preservatives as necessary. be able to.

In addition, as compounds that directly preserve the color developing agent, various hydroxylamines, Japanese Patent Application No. 61-18655
Hydroxamic acids described in No. 9, hydrazines and hydrazides described in No. 61-170756, and hydrazides described in No. 61-188
Phenols described in No. 742 and No. 61-203253, α-hydroxyketones and α-aminoketones described in No. 61-188741, and/or No. 61-18
It is preferable to add various saccharides described in No. 0616, and in combination with the above compounds, Japanese Patent Application Nos. 61-147823, 61-166674, 61-165621,
Monoamines described in No. 61-164515, No. 61-170789, No. 61-168159, etc., No. 61-173595, No. 61-164515, No. 6
Diamines described in No. 1-186560, etc., No. 61-1
65621 and polyamines described in 61-169789, polyamines described in 61-188619, nitroxy radicals described in 61-197760, alcohols described in 61-186561 and 61-197419. It is preferable to use the oximes described in Japanese Patent No. 61-198987, and the tertiary amines described in Japanese Patent No. 61-265149.

Other preservatives include various metals described in JP-A-57-44148 and JP-A-57-53749;
Salicylic acids described in No. 180588, JP-A-54-35
Alkanolamines described in No. 32, JP-A-56-94
Polyethyleneimines described in US Pat. No. 349, US Pat.
The aromatic polyhydroxy compound described in No. 746.544 may be contained if necessary, and addition of the aromatic polyhydroxy compound and triethanolamine is particularly preferable.

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

In order to maintain the above pH, it is preferable to use various buffering agents. Specific examples of buffering agents include sodium carbonate,
Potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (borax), tetraboron 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)
etc. can be mentioned. However, the present invention is not limited to these compounds.

The amount of the buffer added to the color developer is 0.1 mol/1
It is preferable that it is more than 0. 1 mol/l-0
, 4 mol/1 or more is particularly preferred.

In addition, various chelating agents can be used in the color developer as an anti-settling agent for calcium or magnesium or to improve the stability of the color developer.

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

Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N,N,N-4rimethylenephosphonic acid, ethylenediamine-N,N,N'.

N"-tetramethylenephosphonic acid, transcyclohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1- Hydroxyethylidene-1,1-diphosphonic acid, N,N'-bis(2-hydroxybenzyl)ethylenediamine-N,N'-diacetic acid Two or more of these chelating agents may be used in combination as necessary.

The amount of these chelating agents added may be sufficient as long as the amount is sufficient to sequester metal ions in the color developer. For example, 11
It is about 0.1g to Log per unit.

Any development accelerator can be added to the color developer if necessary.

The above-mentioned compounds used in the present invention have a particularly remarkable effect on Cζ in the case of color developers that are substantially free of benzyl alcohol. The amount of benzyl alcohol is 0. ．． 5mj! /j! The following are preferable, and the most preferable case is that it does not contain it at all.

Other development accelerators include Japanese Patent Publications No. 37-16088, No. 37-5987, No. 38-7826, No. 44-
No. 12380, No. 45-9019 and U.S. Patent No. 3.
813,247, etc., p-phenylenediamine compounds shown in JP-A-52-49829 and JP-A-50-15554, JP-A-50-137726, JP-B-Sho 44-30074, JP-A-56-156826 and JP-A No. 52-43429,
Quaternary ammonium salts represented by U.S. Patent No. 2.
No. 494,903, No. 3,128゜182, No. 4.2
No. 30,796, No. 3,253.919, Special Publication No. 1977
-11431, U.S. Patent No. 2,482,546, 2. 596. Amine compounds described in Japanese Patent Publication No. 37-16088, Japanese Patent Publication No. 42-25201, U.S. Patent No. 3,128,18, etc.
No. 3, Special Publication No. 41-11431, No. 42-23883
and U.S. Pat. No. 3,532,501, etc., and other 1-phenyl-3-
Pyrazolidones, imidazoles, etc. can be added as necessary.

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

The color developer used in the present invention preferably contains a fluorescent whitening agent.
Diamino-2,21-disulfostilbene compounds are preferred, the amount added is 0 to 5 g/l, preferably 0.1 g to
It is 4g/l.

Furthermore, various surfactants such as alkylsulfonic acids, alkylsulfonic acids, aliphatic carboxylic acids, and aromatic carboxylic acids may be added as necessary.

The processing temperature of the color developer of the present invention is 20 to 50°C, preferably 30 to 40°C. Processing time is 20 seconds to 5 minutes.
Preferably it is 30 seconds to 2 minutes.

It is preferable that the amount of replenishment is small, but 20
~600mA, preferably 50-300m1. More preferably 100mj! ~200m1.

Next, the desilvering step in the present invention will be explained.

The desilvering step of the present invention uses a bleach-fix solution.In the present invention, the effects of the present invention will be more pronounced if the process time of the desilvering step is shortened. That is, it is 6 minutes or less, more preferably 30 seconds to 4 minutes. More preferably, the time is 30 seconds to 60 seconds.

The bleach-fix solution used in the present invention will be explained below.

As the bleaching agent used in the bleach-fix solution used in the present invention, organic complex salts of iron, cobalt, nickel, manganese, and chromium can be used, but especially iron CI [[
Organic acid complex salts of
Organic acids such as malic acid are preferred.

Among these, aminopolycarboxylic acid complex salts of iron (I [[) are particularly preferred from the viewpoint of rapid processing and prevention of environmental pollution.
Aminopolycarboxylic acids useful for forming organic complex salts include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,3-diaminopropanetetraacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, Examples include methyliminodiacetic acid, iminodiacetic acid, glycol ether diamine tetraacetic acid, and the like.

These compounds may be sodium, potassium, lithium or ammonium salts. Among these compounds, iron (I [[)
Complex salts are preferred because they have a high bleaching edge.

These ferric ion complex salts may be used in the form of complex salts, or ferric salts such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, and ferric phosphate. etc. and an aminopolycarboxylic acid chelating agent in a solution.
An iron ion complex salt may be formed. Also, the chelating agent may be used in excess of the amount needed to form a ferric ion complex salt, and the amount added is 0.01 to 1.0 mol/! , preferably from 0.05 to 1,50 mol/l. Various compounds can be used as bleach accelerators in the bleach-fix solutions and/or their prebaths. For example, U.S. Pat. 8
93.858, German Patent No. 1,290,81
2 specification, JP-A-53-95630, Research Disclosure No. 17129 (July 1978 issue), compounds having a mercapto group or disulfide bond, and JP-A-45-8506, JP-A-Sho. 52~
No. 20832, No. 53-32735, U.S. Patent No. 3,7
Thiourea compounds described in No. 06,561, etc., or halides such as iodine and bromide ions are preferred because they have excellent bleaching blades.

In addition, the bleach-fix solution used in the present invention contains bromide (
Rehalogenating agents such as potassium bromide, sodium bromide, ammonium bromide) or chlorides (e.g. potassium chloride, sodium chloride, ammonium chloride) or iodides (e.g. ammonium iodide) may be included. . If necessary, one or more inorganic acids having a pH-adsorbing capacity such as boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, sulfite, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, etc. , organic acids and their alkali metal or ammonium salts, or corrosion inhibitors such as ammonium nitrate and guanidine.

The fixing agent used in the bleach-fixing solution according to the present invention may be a known fixing agent, such as sodium thiosulfate or ammonium thiosulfate. It is preferable to use salt, and also
A special bleach-fixing solution consisting of a combination of a fixing agent described in JP-A-55-155354 and a large amount of a halide such as potassium iodide can also be used. 11
The amount of fixing agent per mol is preferably from 0.3 to 2 mol, more preferably from 0.5 to 1.0 mol.

The pH of the bleach-fix solution of the present invention is 3.5 to 6.5, more preferably 4 to 6. To adjust these pH, various organic and inorganic acids, bases and! ! A street agent can be used. For example, acids include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, propionic acid, phenic acid, etc., and alkalis include sodium hydroxide, potassium hydroxide, aqueous ammonia, various amines, etc., but are not limited to these.

If the pH is higher than the present invention, the desilvering property and image stability will be poor, and if it is lower, the liquid stability will deteriorate and the leucoization of the cyan dye will become noticeable.

Further, the bleach-fix solution may contain various other fluorescent brighteners, antifoaming agents, surfactants, and organic solvents such as polyvinylpyrrolidone and methanol.

The bleach-fix solution and fixing agent used in the present invention contain sulfites (e.g., sodium sulfite, potassium sulfite,
ammonium sulfite, etc.), bisulfites (e.g. ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.), metabisulfites (e.g. potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.) ) These compounds contain sulfite ion-releasing compounds such as sulfite ions.
The content is preferably from 0.02 to 0.50 mol/l, more preferably from 0.04 to 0.40 mol/l.

Sulfites are commonly added as preservatives, but other preservatives include ascorbic acid, carbonyl bisulfite adducts,
Alternatively, a carbonyl compound or the like may be added.

Furthermore, buffering agents, fluorescent brighteners, chelating agents, antifoaming agents, antifungal agents, and the like may be added as necessary.

Next, the water washing step and/or stabilization step used in the present invention will be explained in detail below.

The amount of replenishment in the water washing and/or stabilization step in the present invention is approximately 50 g faster than the amount of O, S4' brought in from the previous bath.
More preferably, it is set to 5 times to 30 times.

The amount brought in from the pre-bath differs depending on the film properties of the photosensitive material, squeegee strength, processing speed, etc., but is practically about 20 ml to 100 ml per bath. 6 Water washing and/or stabilization of the present invention For the processing method of the process, it is preferable to adopt a multiple countercurrent method for the purpose of reducing the amount of replenishment, especially in 2-stage to 6-stage processing.
A multi-stage countercurrent system is preferred. In this case, the particularly preferred replenishment amount is 50 mj per 1 d of photosensitive material! ~500ml.

According to the multistage countercurrent method, the effect of the present invention is remarkable, but
Due to the increased sound leakage time of water in the tank, problems such as bacteria propagation and floating matter adhering to the photosensitive material occur.The present invention provides a solution to such problems in the processing of color photosensitive materials. As such, the method for reducing calcium and magnesium described in Japanese Patent Application No. 131632/1988 can be used very effectively. In addition, JP-A-57
Isothiazolone compounds and thiabendazoles described in No.-8542, chlorine-based disinfectants such as chlorinated sodium isocyanurate described in No. 61-120145, benzotriazole and copper ions described in Japanese Patent Application No. 1983-1 OSAS 7 Others include Hiroshi Horiguchi's ``Chemistry of anti-fungal agents'', Hygiene Technology Gold Wire ``Sterilization of microorganisms, surface absorption, and anti-mildew technology'', and ``Encyclopedia of anti-bacterial and anti-fungal agents'' edited by the Japanese Society of Antibacterial and Antifungal Research. Bactericides can also be used.

Further, in the washing water, a surfactant as a draining agent and a chelating agent typified by EDTA as a water softener can be used.

The above-mentioned water washing step can be followed or the stabilizing solution can be directly treated without going through the water washing step. Compounds that foster image stabilization functions are added to the stabilizing solution, such as aldehyde compounds such as formalin, and membranes suitable for dye stabilization.
Examples include buffering agents and ammonium compounds for adjusting to H. Further, in order to prevent the proliferation of bacteria in the liquid and to apply a fungicide to the photographic material after processing, the various fungicides and fungicides described above can be used.

Furthermore, a surfactant, a fluorescent brightener, and a hardening agent may also be added. In the processing of the photosensitive material of the present invention, when stabilization is performed directly without going through a water washing step, JP-A-57-
No. 8543, No. 58-14834, No. 60-2203
All known methods described in No. 45 and the like can be used.

In addition, it is also a preferable embodiment to use chelating agents such as 1-hydroxyethylidene-1,1-diphosphonic acid and ethylenediaminetemethylenephosphonic acid, and magnesium and bismuth compounds.

The pH of the water washing step or stabilization step of the present invention is 4 to 10, preferably 5 to 8. Temperature depends on the use of photosensitive materials.
Although it can be set variously depending on the characteristics, etc., the temperature is generally 15 to 45°C, preferably 20 to 40°C. The zero time can be set arbitrarily, but the effect of the present invention is more pronounced as it is shorter, and is preferably 30 seconds. ~4 minutes, more preferably 30 seconds ~ 2 minutes.

The smaller the amount of replenishment, the better in terms of running costs and reduction in emissions.

If the method of the present invention uses a color developer,
Applicable to any processing process, such as color paper, color reversal paper, color direct positive optical material, color positive film, color negative film, color reversal film, etc., but especially color paper, color reversal paper Application to is preferred.

The silver halide emulsion of the light-sensitive material used in the present invention can be of any halogen composition such as silver iodobromide, silver bromide, silver chlorobromide, silver chloride, etc. When performing replenishment treatment, add 60% silver chloride.
A silver chlorobromide emulsion or a silver chloride emulsion containing mol% or more is preferable, and a silver chloride content of 80 or more is more preferable,
90 to 100 mol% is particularly preferable, and when high sensitivity is required and fog during production, storage, and/or processing needs to be kept particularly low, 50 mol of silver bromide may be used. Silver chlorobromide emulsions containing % or more (may contain silver iodide of 3 mol % or less) are preferable, and more preferably 70 mol % or more of silver iodide.
It is preferably mol% or more.

Silver iodobromide and silver chloroiodobromide are preferable for color light-sensitive materials for photography, and the silver iodide content is preferably 0.1 to 15 mol %.

The silver halide grains used in the present invention may have different phases inside and on the surface, may have a multiphase structure such as a bonded structure, or may consist of a uniform sum of the entire grain, or may have They may be mixed.

The average grain size distribution of the silver halide grains used in the present invention can be narrow or wide (or wide), but it is determined by dividing the standard deviation value of the grain size distribution curve of the silver halide emulsion by the average grain size (variation). ratio) is within 20%, particularly preferably 1
It is preferable to use a so-called monodispersed silver halide emulsion of 5% or less in the present invention, and in order to satisfy the target gradation of the light-sensitive material, grains in the emulsion layer having substantially the same color sensitivity are preferably used. Two or more types of monodisperse silver halide emulsions with different sizes (preferably those having the above-mentioned fluctuation rate as monodispersity) are mixed in the same layer or mixed in separate layers.
Can be cloth. Furthermore, two or more types of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion may be mixed or layered for use.

The shape of the silver halide grains used in the present invention is regular (cubic, octahedral, rhombidodecahedral, dodecahedral, etc.).
r ) crystals or coexistence of these crystals, or irregular (ir) crystals such as spherical ones.
It may have a regular) crystal form,
They may also have a composite form of these crystal forms, or they may be tabular grains, especially those with a length/thickness ratio of 5 to 8.
or 8 or more tabular grains account for 50% of the total projected area of the grains.
An emulsion comprising a mixture of these various crystal forms may be used.

These various emulsions may be either a surface latent image type in which a latent image is mainly formed on the surface or an internal latent image type in which a latent image is formed inside the grains.

The photographic emulsion used in the present invention is Re5earchDi
Closure vol, 170 Item
N117643 (1, n, III) term (197
It can be adjusted using the method described in August, December).

The emulsion used in the present invention is usually one that has been subjected to physical ripening, chemical ripening, and spectral sensitization.

Additives used in such processes are described in Research Disclosure Vol. 176, No. 17643 (1978, 1).
February) and volume 187 of the same, 18716 (197
(September, November), and the relevant parts are summarized in the table below.

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

Additive type RRD 17643 RD 187161
Chemical sensitizers Page 23 Page 648 Right column 2 Anger increasing agents Same as above 3 Spectral sensitizers Pages 23-24 Page 648 Right column ~ Super sensitizers Page 649 Right column 4 Brightening agents Page 24 5 Anti-fog agent Pages 24-25 Page 649 right column and stabilizer 6 Kabra - Page 25 7 Organic solvent Page 25 8 Light absorber, fu Page 25-26 Page 649 right column ~
Ilter dye page 650 left column ultraviolet absorber 9 stain inhibitor page 25 right a page 650 left to right column 10 dye image stabilizer page 25 11 hard
Membrane agent Page 26 Page 651 Left column Additive type RD 17643 RD 18716
12 Binder page 26 Same as above 13
Plasticizer, lubricant Page 27 Page 650 Right column 14
Coating aid, pages 26-27 Same as above Surfactant 15 Static page 27 Same as above
Stopper Example 1 A multilayer silver halide photosensitive material A having the layer structure shown below was prepared on a paper support laminated on both sides with polyethylene. The coating solution was prepared as follows.

(First layer coating solution adjustment) Yellow coupler (ExY-1) and (ExY-2)
10.2g and 9.1g, respectively, 27.2cc of ethyl acetate and 7°7cc (8.0g of high boiling point solvent (Solv-1)
) was added and dissolved, and this solution was emulsified and dispersed in 185 cc of a 10% gelatin aqueous solution containing 10% sodium dodecylbenzenesulfonate gee. This emulsified dispersion and emulsions EMI and EM2 were mixed and dissolved, and the gelatin concentration was adjusted to have the following composition to prepare a first layer coating solution. The coating solutions for the second to seventh layers were also prepared in the same manner as the coating solution for the first layer. 1-oxy-3,5-dichloro-3-) riazine sodium salt was used as the gelatin hardening agent for each layer.

Moreover, (Cpd-2) was used as a thickener.

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

Support polyethylene laminated paper (white pigment (contains Ti(h) and bluish dye in the polyethylene on the first layer side) -th layer (blue color layer) Spectral sensitization with sensitizing dye (ExS-1) Monodispersed silver chlorobromide emulsion (EMI) ...0.13 multiplying dye (E
A monodisperse silver chlorobromide emulsion (EM
2) ...0.13 gelatin
...1.86 Yellow Cabler (ExY-1)・
...0.44 yellow coupler (ExY-2) ...0
．． 39 Solvent (So Iv-1)...0.
35 Second N (color mixture prevention FJ) Gelatin...0.99 Color mixture prevention agent (Cpd-3)...0.08 Third layer (green layer) Spectroscopy with sensitizing dye (ExS-2,3) Sensitized monodispersed silver chlorobromide emulsion (EM3) ...0.05 enhancing dye (E
Monodisperse silver chlorobromide emulsion spectrally sensitized with xS-2,3) (
EM4) ...0.11 gelatin
...1.80 magenta coupler (ExM-1)
...0.39 color image stabilizer (Cpd-4) ...
0.20 Solvent (Solv-2)...0.1
2 Solvent (Solv-3) -0,25 quaternary N (
Ultraviolet absorption N) Gelatin...1.60 Ultraviolet absorber (Cpd-7/Cpd-8/Cpd-9-3/2/
67 weight ratio)...0.70 Color mixing prevention agent (Cpd-
10) ...0.05 solvent (Solv-4)
...0.27 Fifth layer (red sensitive layer) Monodisperse silver chlorobromide emulsion (EMU) spectrally sensitized with a sensitizing dye (Ex S -4,5) ...0.07 Enhancing dye Monodisperse silver chlorobromide emulsion spectrally enhanced with (ExS-4,5), 0.16 gelatin
...0.92 cyan coupler (ExC-1)
...0.32 color image stabilizer (Cpd-8/Cpd-9
/Cpd-12-3/4/2: weight ratio)...0.1
7 Polymer for dispersion (Cp d-11)...0.
28 Solvent (Solv-2)...0.20
Sixth layer (ultraviolet absorption N) Gelatin...0.54 ultraviolet absorption (Cpd-7/Cpd-9/Cpd-12-115
/3: weight ratio)...0.21 solvent (So 1v-2
)...0. 08 Seventh layer (protective layer) Gelatin...Acrylic modified copolymer of 1.33 polyvinyl alcohol (denaturation degree 17%)
...0.17 liquid paraffin
...0.03 Also, at this time, Cpd-13 and Cpd-14 were used as the anti-irradiation dyes. Furthermore, each layer contains Alkanol
c F 120 (manufactured by Dainippon Ink Co., Ltd.) was used.

As a stabilizer for silver halide, cpa-t5, Cpd
-16 was used.

Details of the emulsion used are as follows.

Emulsion name Shape Laser diameter Br content Coefficient of variation (+
*o1%) EMI Cube 1.0 80 0.08EM
2 Cube 0.75 80 0.07EM3
Cube 0.5 83 0.09EM4 Cube 0.4 83 0.1OEM5 Cube 0.5 73 0.09EM6 Cube 0
．． 4 73 0.10 The structural formula of the compound used is as follows.

xY-1 I xY-2 Cj! ExM"I ExC-1 H Shini xS-1 Strive 5OJN(CtHs).

6X10-' mol/A g mol x S-2 5OJH(CJs)i 4X10"' mol/Ag mol 5OJN(CJs)s 8X10-' mol/Ag mol 1.8X10-' mol/Ag mol x S-5 pd-2 pd-3 H pa-4 c4n, (t) CJs(t) Cpd-10 0H JH Cpd-11 1← CHi CH-1 CON HC4Hq (t) (n = 100 to 1000) Solv-1 dibutyl phthalate 5olv- 2) Lyclesyl phosphate 5olv-3 Trioctylphosphate 5olv-4) Linonylphosphate pd-13 CI) d-14 H Cpd-16 N:N Next, in the first layer of the above photosensitive material, a yellow coupler, etc. Except for replacing the coupler of the present invention in Table 1 in mol (total of ExY 1 and EXY-2) amount, or adding an additional 50+no1% of the compound represented by the general formula (7Q-1) to the coupler. A similar photosensitive material BR was prepared.

After imagewise exposure of the above photosensitive material, Fujicolor vapor treatment 1
Continuous processing (running test) was performed using PP600 until twice the color development tank capacity was replenished in the following processing steps.

*Yindan Zhan Giant 2 rJffi 31”S;
Dragon 1 draw L no 3 second fierce [ta? 3-f mo king L
Color development 38℃ 1 minute 40 seconds 290mj! 17
A Bleach fixing 33℃ 60 seconds 150ml
9 II Rinse ■ 30-34℃ 20 seconds −
41 Rinse■ 30~34℃ 20 seconds -4β Rinse■ 30~'34℃ 20 seconds 364m j!
47! Drying: 70 to 80° C., 50 seconds *per 1.7 mL of photosensitive material (3-tank countercurrent force type for rinsing ① to ②) The composition of each processing solution is as follows.

Left standing Nizu Eketsu Mataemata direct catch dog Emizu
800mj! 800
ml diethylenetriaminepentavinegar M 1. Og 1.
0g Nitrilotriacetic acid 2.0g 2.0
g1-hydroxyethylidene-1,1-diphosphonic acid 2.0g 2.0g benzyl alcohol 16mj! 22mf diethylene glycol 10 ca12 10 ml
Sodium sulfite 2.0 g 2.5 g Bromide IJum 0.5 g - Potassium carbonate 30 g 30 gN
-Ethyl-N-(β-methanesulfone midoethyl) -3-methyl-4-aminoaniline sulfate 5.5 g 7.5 g Hydroxylamine sulfate 2-0 g 2.5 g Fluorescent agent (WHITEX4B, manufactured by Sumitomo Chemical) 1.5g 2.0g Add water and 1000m! ! 1000
m 1pH (25℃) 10.20
10.60 Star Emperor I Wataru Tank Liquid
Violet and phlegm water 400
ml 400 ml ammonium thiosulfate (70χ
) 200 ll1 l 300 ml Sodium sulfite 20 g 40 g Ethylenediaminetetraacetate iron (I[[) Ammonium 60 g 120
g Add ethylenediaminetetraacetic acid dihydrate to 1000m j! 100
k 1pH (25°C) 6.70 6.
30% ion-exchanged water (3 pp each of calcium and magnesium)
m or less) Photographic properties include the minimum density CD+ain), the maximum density (D w
It was expressed as two points: ax).

Next, as an image fastness test, 1. Light resistance test and
2. A thermal stability test was conducted. For the light resistance test, use a xenon fade meter (9,0000 Lux) to
The coloring density was 2.0 before the test and expressed as a percentage of the density reached after the lightfastness test.

In addition, the thermal stability test was conducted using IS at 80°C and 70% pH.
After being left for days, the color density +-5O before the test was expressed as a percentage of the density reached after the test.

The results are shown in Table 1.

As is clear from Table 1, it can be seen that the light-sensitive materials containing the yellow coupler of the present invention and the compound of the present invention maintain high color development and at the same time have significantly improved image fastness.

(R-1) I Example 2 A multilayer silver halide window optical material A having the layer structure shown below was prepared on a paper support laminated on both sides with polyethylene. The coating solution was prepared as follows.

(Preparation of first layer coating solution) 19.1 g each of yellow coupler (ExY-1), 21.2 cc of ethyl acetate and high boiling point solvent (Solv-1)
7.7cc (8.0g) was added and dissolved, and this solution was
The mixture was emulsified and dispersed in 185 cc of a 10% gelatin aqueous solution containing 8 cc of 0% sodium dodecylbenzenesulfonate.

This emulsified dispersion and emulsions EM7 and EM8 were mixed and dissolved, and the gelatin concentration was adjusted to have the following composition to prepare a first layer coating solution. The coating liquid from the second layer to the seventh layer is also
It was prepared in the same manner as the layer coating solution. 1-oxy-3,5-dichloro-3-triazine sodium salt was used as the gelatin hardening agent for each layer.

Moreover, (Cpd-2) was used as a thickener.

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

Support polyethylene laminate paper (the polyethylene on the first layer side contains a white pigment (TiOz) and a bluish dye) -th layer (blue sensitivity N) Monodispersed salt spectrally sensitized with an aggravating dye (ExS-1) Silver bromide emulsion (EM7): Monodisperse silver chlorobromide emulsion (EM7) spectrally enhanced with a 0.15 sensitizing dye (ExS-1)
EM8) ...0.15 gelatin
...1.86 Yellow Cabler (ExY -
1) ...0. 82 solvent (Solv-1)
...0.35 Second layer (color mixing prevention N) Gelatin ...0.99 Color mixing prevention agent (Cpd-3) ...0.08 Third layer (green sensitive layer) Exacerbating dye (ExS-2, 3) Monodisperse silver chlorobromide emulsion (EM9) spectrally enhanced with 0.12 enhancement dye (E
Monodisperse silver chlorobromide emulsion spectrally sensitized with xS-2,3) (
EMIO) ...0.24 gelatin
...1.24 magenta coupler (ExM-1)
...0.39 color image stabilizer (Cpd-4) ...
・0.25 color image stabilizer (Cpd-5)...0
．． 12 Solvent (Solv-2) -...0.25
Fourth layer (ultraviolet absorption N) Gelatin...1.60 ultraviolet absorber (Cp d-6/Cp d-7/Cpd-8-3/
2/6: Weight ratio) ...0.70 Color mixing prevention agent (C
pd-9) ...0.05? Container (So
Iv-3) ・ ・ ・ 0. 4
2 Fifth layer (red-sensitive layer) Monodisperse silver chlorobromide emulsion (EMII) spectrally sensitized with sensitizing dye (ExS-4,5)...0.07 sensitizing dye (
Monodisperse silver chlorobromide emulsion (EM12) spectrally sensitized with ExS-4,5)...0.16 gelatin
...0.92 cyan coupler (ExC-1)
...0.15 cyan coupler (ExC-2)
...0.18 color image stabilizer (Cpd-7/Cpd-8/
Cpd-10=3/4/2: weight ratio)...0.17
Dispersion polymer (Cp d -11) ...0.1
4 solvent (So 1v-1)...0.20
Sixth layer (ultraviolet absorbing layer) Gelatin...0.54 ultraviolet absorber (Cp d-6/Cp d-8/Cpd-10=1
15/3: Weight ratio)...0.21? Container (So
Iv-4) ・ ・ ・ 0.
08 Seventh layer (protective layer) Gelatin...1.33 Acrylic modified copolymer of polyvinyl alcohol - (degree of modification 17%)...0.17 Liquid paraffin...0.03 Also, at this time, As anti-gelation dyes, Cpd-12, Cp
d-13 was used. Further, in each layer, Alkanol XC (Dupont), sodium alkylbenzenesulfonate, succinic acid ester, and Magefacx F-120 (manufactured by Dainippon Ink) were used as emulsifying and dispersing agent coating aids. As a stabilizer for silver halide, cp
d-14 and Cpd-15 were used.

Details of the emulsion used are as follows.

2M7 Cube 1.0 1.00.1OEM8
Cube 0.8 1.00.1 OEM9
Cube 0.45 1.5 0.09EMIO Cube
0.34 1.5 0.09EMII Cube 0.
45 1.5 0.09EM12 Cube 0.34
1.6 0.10 Coefficient of variation = Standard deviation/Average size xY-1 xM-1 ExC-1 Cpd-2 cpa-3 H H Cpd-4 Cpd-5 H3 xS-1 5OaHN(CJs)s 6 X 10-' mol/A g mol 5OJN(Cz)Is) -e Cpd-7 H Cpd-8 Cpd-9 H Cpd-10 Cpd-11 -CH, -CH-←-7 (n = 100 ~ 1000
)■ C0N) ICaHq(t) Molecular weight lO million pd-
12 Cpd-13 SOYK So, Kpd-14 H Cpd-15 N ==-N Solv-1 Dibutyl phthalate 5olv-2) Lioctyl phosphate 5olv-3)
Linonyl phosphate 5olv-4) Lycresyl phosphate Next, in the first layer of the above light-sensitive material, yellow coupler was added in equal mol.
ft., or by replacing the coupler with the compound represented by the general formula (A) of the present invention,
Furthermore, the same photosensitive material B except that 50 mo1% was added.
- Created J.

After exposing the above photosensitive material through an optical wedge, it was processed in the following steps.

Color development on one skin, bleaching and fixing at 35℃ for 45 seconds
30~36℃ Stable for 45 seconds ■ 30~3
Stable for 20 seconds at 7℃ ■ 30-37℃ 2
Stable for 0 seconds ■ Stable for 20 seconds at 30-37℃ ■ Dry for 30 seconds at 30-37℃
70~85℃ 60 seconds (4 to stable ■-■
A tank countercurrent system was adopted. ) The composition of each treatment liquid is as follows.

Left: 11 Nagamizu 800
mj! Ethylenediaminetetraacetic acid 2.0g Triethanolamine 8.0g Sodium chloride 1.4g Potassium carbonate
25 gN-ethyl-N-(
β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate 5.0 g N,N-diethylhydroxylamine 4.2 g 5.6-cyhydroxybenzene-1゜2.4-trisulfonic acid 0.3 g Add 2.0g of fluorescent brightener (4,4'-diaminostilbene type) water to 1000n+1pH (25
℃) 10.10 Retirement 400I
I+j! Ammonium thiosulfate (70%) 100
ml Sodium sulfite 18g Ethylenediaminetetraacetic acid Iron acetate [l] Ammonium, 55g Disodium ethylenediaminetetraacetate 3g Add water
10100O! pH (25°C) 5.5 Genjoki formalin (37%) O, 1g formalin-sulfite adduct 0. Lg5-chloro-2-methyl-4-isothiazolin-3-one 0.02g2-methyl-4-isothiazolin-3-one 0.01gSulfuric acid steel
Add 0.005g water
1000mJp1000°C) 4.0 After the treatment, the photographic properties were evaluated in the same manner as in Example 1. The results are shown in Table 1.

As is clear from Table 2-1, the photosensitive material of the present invention has both high color development and image fastness.

Further, after exposure of photosensitive material A, continuous processing (running test) was carried out using a paper processing machine until the tank capacity for color development was replenished by one time in the following processing steps.

Processing process Temperature Time Replenishment amount Tank capacity Color development 3 to 0C seconds / & / wd
, / 7 l Deep white fixation 30~36°C≠! Seconds It/Resistance/71 Rinse■ 30~37°C2
0 seconds 101 rinse■ 30-37
°C 20 seconds 101 rinse ■ 30
~37°C 20 seconds 101 rinse■
30 to 37°C for 30 seconds 22od 101 drying 70 to ro0c to seconds Photosensitive material 1 m Heat (Rinse ■≠tank countercurrent method.) The composition of each processing solution is as follows.

Color developer 2ヱ2ri replenisher water
rootnl l
00d Ethylenediamine-N,N.

N, N-tetramethylenephosphonic acid /#f /#p triethanolamine j, Of Yo, Oy Sodium chloride 1. ≠1 □Potassium carbonate
λzy λ5yN-ethyl-N-(β-methanesulfonamidoethyl)-3 monomethyl-≠-abanoaniline sulfate yo, oy 'y, opN
, N-bis(carboxymethyl)hydrazine Hiro, λy t, oy optical brightener (≠, Hiro'-cya ξ nostilpene type) 2.0 Tako,! 2 Add water to 10100O1000m100Oλ
t'() io, or io, ≠5 bleach-fix solution (tank solution and replenisher are the same) water
Hiroooynl Ammonium thiosulfate (70%) 100ytl Sodium sulfite /7 Iron (In) ethylenediaminetetraacetate Ammonium 117 Disodium ethylenediaminetetraacetate! Ammonium dibromide Glacial acetic acid
yy add water
1000w100Oko! 0C)
Rinse solution (tank solution and refill solution are the same) Ion exchange water (calcium, magnesium each jppm
(Below) Next, the photosensitive materials A-J were exposed to light through an optical wedge and then processed using the processing solution used in the running test.

After the treatment, the photographic properties were evaluated in the same manner as in Example. The results are shown in Table 2-2.

As is clear from Table λ-λ, it can be seen that it is an effective image forming method that achieves both high color development and image fastness even when the amount of washing water replenisher is reduced.

Example 3 A photosensitive material was prepared by sequentially coating layers 17i (lowest layer) to 7th layer (top layer) on double-sided polyethylene laminated paper treated with corona discharge processing. The coating liquid for each layer was prepared as follows. The details of the structural formulas of the couplers, color image stabilizers, etc. used in the coating solution will be described later.

The coating liquid for the first layer was prepared as follows. i.e. 200 g of yellow coupler, 93.3 g of anti-fading agent.
g, 10 g of high boiling point solvent (p) and 5 g of solvent (q),
After heating and dissolving the mixture to which 600 ml of ethyl acetate was added as a co-solvent at 60°C, 3,300 mj of a 5% aqueous gelatin solution containing 330 ml of a 5% aqueous solution of Alkanol B (trade name, alkylnaphthalene sulfonate, manufactured by DuPont) was added.
! mixed with. Next, this liquid was emulsified using a colloid mill to prepare a coupler dispersion. Ethyl acetate was distilled off under reduced pressure from this dispersion, and the enhancing dye for the blue-sensitive emulsion layer and 1
-methyl-2-mercapto-5-acetylamino-1,
1.400 g of emulsion containing 3,4-) lyazole (A
96.7 g (containing 170 g of gelatin), and further added 2,600 g of a 10% aqueous gelatin solution to prepare a coating solution.

Support Paper laminated on both sides with polyethylene Support 1st layer (Blue feeling N) Silver chlorobromide emulsion (Silver bromide 8 (1+O1%)... 290 Yellow coupler... 600 Anti-fading agent (r)...・280 solvent (
p) ... 30 solvent (q)
... 15 gelatin
...1800 second layer (color mixing prevention layer) Silver bromide emulsion (unheated grain size 0.05 micron) Silver...
10 Color mixing inhibitor (s)...55 Solvent
(p) ... 30 solvent (
q) ... 15 gelatin
... 800 3rd layer (green feel N) Silver chlorobromide emulsion (silver bromide 7Qmo1%) ... 305 Magenta coupler ... 670 Anti-fading agent (1) ... 150 Anti-fading agent (
u) ... 10 solvent (p)
... 200 solvent (q)
... 10 gelatin
... 1400 4th layer (color mixing prevention layer) Color mixing prevention agent (S) ... 65 Ultraviolet absorber (n) ... 450 Ultraviolet absorber (0) ... 230 Solvent (
p) ... 50 solvent (q)
... 50 gelatin
... 1700 5th layer (red feeling N) Silver chlorobromide emulsion (silver bromide 70 mo1%) ... 210 Cyan coupler anti-fading agent (r) ... 250 Solvent (p) ... 160 Solvent
(q) ... 100 gelatin
...1800 6th layer (ultraviolet absorption layer) Ultraviolet absorber (n) ...260 Ultraviolet absorber (0) ...70 Melting medium
(p) ... 300 solvent (q
) ... 100 gelatin
... 700 7th layer (protective layer) Gelatin ... 620n:2-
(2-hydroxy-3,5-di-tert-amylphenyl)benzotriazole o: 2-(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: l,4-di-tert-amyl-2,5-dioctyloxybenzene u: 2,2'-methylenebis-(4-methyl -5-te
rt-Butylphenol Also, the following were used as aggravating dyes for each emulsion layer.

Front window emulsion N: anhydro-5-methoxy-5'-methyl-3,3'-disulfoprobyl selenacyanine hydroxide green-sensitive emulsion layer: anhydro-9-ethyl-5,5°-diphenyl-3, 31-Disulfoethyloxacarpocyanine hydroxide red-sensitive emulsion layer: 3.3'-diethyl-5-methoxy-9
,9'-(2,2-dimethyl-1,3-propano)thiadicarpocyanine iodide.The following substances were also used as stabilizers for each emulsion layer.

1-Methyl-2-mercapto-5-acetylamino-1
, 3,4-1-riazole The following dyes were also used as irradiation preventing 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-cissulfonatoanthracene-1,5-diyl)bis(aminomethanesulfonate)-tetrasodium salt Also, 1,2-bis(vinylsulfonyl) as a hardening agent
Ita for Etanwo.

The couplers used are as follows.

Yellow coupler Magenta coupler Cyan coupler 260■/Bo 120■/d (molar ratio 1:1) The compound of the present invention (A-7), C
A-9), (A-29), and (A-53) are each added in an additional 30 mol to the coupler! When four kinds of light-sensitive materials were prepared and the same treatments and operations as in Example 2 were carried out, the same effects as in Example 2 were obtained.

(Effects of the Invention) The combination of the yellow coupler of general formula (1) and the compound of general formula Ch-11 according to the present invention improves the coloring properties of the coupler and the fastness of the colored image to light, moist heat, etc. Furthermore, high color development and image fastness can be achieved even in a process in which the amount of washing water replenisher is reduced.

Patent applicant: Fuji Photo Film Co., Ltd. February 7, 1999

Claims (2)

[Claims] (1) It is characterized by having a layer containing at least one kind of yellow coupler represented by the following general formula (I) and at least one kind of compound represented by the following general formula [A-I] Silver halide color photographic material. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R^1 represents a substituted or unsubstituted N-phenylcarbamoyl group, R^2 represents an alkyl group or an aryl group, and X^ 1 represents a group represented by the following formula (a), (b) or (c). (a) (b) ▲There are mathematical formulas, chemical formulas, tables, etc.▼▲There are mathematical formulas, chemical formulas, tables, etc.▼ In formulas (a) and (b), R^3 and R^4 are the same but different. Each may be a hydrogen atom, a halogen atom, a carboxylic acid ester group, an amino group, an alkyl group, an alkylthio group, an alkoxy group, an alkylsulfonyl group, an alkylsulfinyl group, a carboxylic acid group, a sulfonic acid group, or an unsubstituted or substituted phenyl group. Or represents a heterocycle. (c) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In formula (c), W^1 is in formula (c). Represents nonmetallic atoms required to form a ring. General formula [A-I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R represents -(Y)_n-R'. Y is -O-,
-S-, -NH-, and ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and n represents 0 or 1. R′, R″
may be the same or different, and each represents a phosphoric acid residue. Q represents a divalent group represented by the general formula [A-I-1]. General formula [A-I-1] ▲ Numerical formulas, chemical formulas, tables, etc. are included▼ In the formula, A represents a group of atoms forming a substituted or unsubstituted benzene ring, and X is a single bond, a substituted or unsubstituted methylene group , -S-, -O-, -NH-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, -S
Represents O_2- and -SO-. R″′ is a hydrogen atom,
It represents an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, a heterocyclic group, an acyl group, and a sulfonyl group. In addition, the free bond in the formula indicates the bonding position with O in Q of the general formula [A-I]. (2) A silver halide photographic photosensitive material having a layer containing at least one kind of yellow coupler represented by the above general formula (I) and at least one kind of compound represented by the above general formula [A-I] The material is processed in a development process including a final water washing process in which the amount of replenisher in that process is 0.5 to 50 times the amount of processing liquid components brought in from the previous bath per unit area of the photosensitive material. A color image forming method characterized by: