JPS6035730A - Color photographic sensitive silver halide material - Google Patents

Abstract

PURPOSE:To improve the graininess and developed color state of a color image by incorporating a two-equiv. coupler having a specified group at the coupling position into a color photographic sensitive silver halide material. CONSTITUTION:A two-equiv. coupler having a group represented by formula I (where R is an aliphatic group, an aromatic group or a heterocyclic group, X is an ester bond, an amido bond, an ether bond, a thioether bond, a sulfonamide bond, a urethane bond or a ureido bond, and w is 2-3) at the coupling position is incorporated to obtain the desired color photographic sensitive silver halide material. Said coupler is synthesized by reacting a coupler halogenated at the coupling position with a compound represented by formula II. Suitable examples of the two-equiv. coupler are compounds represented by formulae III, IV.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to photographic couplers, particularly to color photographic materials containing novel two-equivalent couplers.

By color-developing the silver halide color photographic material, the oxidized aromatic-amine color developing agent reacts with the coupler to produce indophenol, indoaniline, immethane, azomethine, fenoxacin, imine, phenazine, and the like. It is known that similar pigments are produced and color images are formed (e.g. T, H, Jam
esi'The Theory of the Photo
graphicProcess,” Jr ed.
, the MacmillanCo, , New York
k,/? 7/, ppJlrJ-j 91! I).

In this system, a subtractive color method is usually used for color reproduction, with a silver halide emulsion that is selectively sensitive to back, green, and red, and yellow, magenta, and cyan color image forming agents that are complementary colors, respectively. is used. To form a yellow image, for example, acylacetanilide, malondianilide, or dibenzoylmethane couplers are used, and to form a magenta image, pyrazolone, pyrazolobenzimidazole, 77 noacetophenone, pyrazolo Triazole or indacylon couplers are used, and phenolic couplers such as phenols and naphthols are used to form cyan images.

Normally, color photographic materials are roughly divided into two types: an external method in which couplers are placed in a developing solution, and an internal method in which couplers are incorporated in each photosensitive layer of the material so as to maintain their independent functions. Ru. In the latter, the dye image-forming coupler is added to the silver halide emulsion.

The coupler added to the emulsion must be non-diffusible (diffusible) in the emulsion binder matrix.

Heretofore, two-equivalent couplers have been known in which a group capable of leaving the coupler is substituted at the coupling position of the coupler after the coupler undergoes a coupling reaction with an oxidized developing agent. Hiroequivalent couplers require a minimum equivalent amount of silver to produce one equivalent of dye, whereas lambda equivalent couplers allow one equivalent of silver to produce one equivalent of dye. That is, when a 2-equivalent coupler is used, the amount of coated silver in the photosensitive material can be reduced, making it possible to reduce the cost and make the layer thinner.

Although the known two-equivalent couplers have somewhat different performance, it has been desired to further improve the performance. In particular, for use in photographic materials such as color negatives and color reversals that require high sensitivity, λ-equivalent couplers with high color development are desired. However, the known two-equivalent couplers with high coloring properties have the disadvantage of poor graininess, and their coloring properties are still unsatisfactory.

Accordingly, an object of the present invention is to provide a color photographic material containing a highly color-forming two-equivalent coupler that forms color images with excellent graininess.

The object of the present invention has been achieved by a silver halide color photographic light-sensitive material containing a coupler having a group represented by the following general formula (I) at the coupling position.

General formula (I) In the formula, 几 represents an aliphatic group, an aromatic group or a heterocyclic group, and X represents an ester bond, amide bond, ether bond, thioether bond, sulfonamide bond, urethane bond or ureido bond, W represents an integer of 0 or 3.

Here, the definition of turnip 2- includes the known compounds described below. Cyan coupler residues include phenol and 7-tole; magenta coupler residues include pyrazolone, pyrazolo, triazole, pyrazolobenziminazole, and indane.

Examples of the yellow coupler residues include alpha acylacetamide, beta ketoacetate, malon diester, beta diketone, and himalon diamide. In addition to these, resorcinol, 3-aminophenol, and the like can be produced as coupler residues that form black or gray pigments by reaction with the oxidized product of the color-forming developer. In addition, examples of coupler residues that react with the oxidized product of the coloring agent to form a colorless compound include indanone, acetophuninone, and the like. The coupler residue has the general formula (I
) has a group of

Specifically, the aliphatic group represented by B in the general formula (1) has a carbon number of 1 to 0, and may be 1y-substituted or unsubstituted, linear, branched or cyclic, saturated or unsaturated. Preferred substituents are an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a halogen atom,
Acylamino group, sulfonamide group, carboquine group, phenyl group, 7, /l/ho group s ureido group, carbonyl group, heterocyclic group (contains a y atom, an oxygen atom, or a yellow atom as a hetero atom) or a 6-membered ring) or an alkylsulfonyl group.

Specifically, the aromatic group represented by R in the general formula (I) has 6 to 10 carbon atoms and may be substituted or unsubstituted. Preferred examples of the Okiyanagi group include an alkyl group, a halogen atom, an alkoxy group, an acylamino group, a sulfonamide group, an alkoxycarbonyl group, an N-alkylcarbamoyl group, a Heer'J Ay group, an imide group, a carboxyl group, and a hydroxy group. group, cyan group, aryl group, sulfamoyl group, ureido group, alkylthio group, or alkanoyl group.

In general formula (I), the heterocyclic group represented by 几 is specifically a 7-membered ring containing a hetero atom, nitrogen atom, oxygen atom or sulfur atom.

Specifically, they include an imidazolyl group, a triazolyl group, a pyridyl group, a pyrazolyl group, a furyl group, an azepinyl group, and a benzotriazolyl group.

These heterocycles may have substituents at substitutable positions. Substituents include alkyl groups, halogen atoms,
Alcoquine group, acylamino group, sulfonamide group, alkoxycarbonyl group, aryl group, sulfamoyl group, aryloki7 group, ureido group If 7〈 is preferably an alkylthio group〇 In general formula (1), the number of carbon atoms contained in 几 is a substitution Including the group, /-≠O, preferably 20.

Furthermore, the present invention is particularly effective in the general formula (1)
A coupler residue having a group represented by the following general formula (n), (II
I), (IV), (Vl, (Vl), (■).

This is when it is expressed as (■), (IX), (X), (XI) or (朋). These couplers are preferred because of their fast coupling speed.

General formula (II) General formula (I[l) L5 General formula (Vl) l'1I6 General formula (■) General formula (X) General formula (XI) General formula (Xu) 几. -CH-几11 In the above formula, the free bond derived from the coupling position represents the bonding position of the coupling-off group.

In the formula, R1 represents an aliphatic group, an aromatic group, an alkoxy group, or a heterocyclic group, and R2 and R3 each represent an aromatic group or a heterocyclic group.

In the formula, the aliphatic group represented by R1 preferably has 1 carbon atoms.
~r may be substituted or unsubstituted, linear or cyclic. Preferred substituents for the alkyl group include an alkoxy group, an aryloxy group, an amino group, an acylamino group, and a halogen atom, which may themselves have further substituents. Specific examples of aliphatic groups useful as 几1 are as follows: inpropyl, isodityl, tert-butyl, inamyl, tert.
t-7 mil group, /, /-dimethylbutyl group, /, /-dimethylbexyl group, nclohexyl group, comethoxyisopropyl group, cophenoxyisopropyl group, α-aminoisopropyl group, α-(diethylamino)isopropyl group, α-(succinimido)inopropyl group, α-
(phthalimido)isopropyl group, α-(benzenesulfonamido)isopropyl group, etc.

When R1, R2 or R3 represents an aromatic group (particularly a phenyl group), the aromatic group may be substituted. Aromatic groups such as phenyl groups have the following carbon atoms: alkyl groups, alkenyl groups, alkoxy groups, alkoxycarbonyl groups,
It may be substituted with an alkoxycarbonylamino group, an aliphatic amide group, an alkylsulfamoyl group, an alkylsulfonamide group, an alkylureido group, an alkyl-substituted succinimide group, etc. In this case, the alkyl group has an aromatic group such as phenylene in the chain. May intervene. The phenyl group may also be substituted with an aryloxy group, an aryloxycarbonyl group, an arylcarbamoyl group, an arylamido group, an arylsulfamoyl group, an arylsulfonamide group, an arylureido group, and the like.

几1. The phenyl group represented by 几2 or 几3 further includes an amino group, a hydroxy group, a carboxy group, a sulfo group, a nitro group, a cyano group, a thiocyano group, including those substituted with a lower alkyl group having carbon number/-4. It may be substituted with a group or a halogen atom.

In addition, R1, 几2 or I (a may represent a substituent 1 in which a phenyl group is fused with another ring, such as a naphthyl group, a quinolyl group, an isoquinolyl group, a chromanyl group, a chromanyl group, a tetrahydronaphthyl group, etc.). The substituents may themselves have further substituents.

When 几1 represents an alkoxy group, the alkyl moiety is a linear or branched alkyl group having 1 to t carbon atoms,
It represents an alknyl group, a cyclic alkyl group, or a cyclic alkenyl group, which may be substituted with a halogen atom, an aryl group, an alkoxy group, or the like.

When 几り%几2 or 几3 represents a heterocyclic group, the heterocyclic group is connected to the carbon atom of the carbonyl group of the acyl group in alpha acylacetamide or the amide group, respectively, through one of the carbon atoms forming the ring. It combines with the nitrogen atom of

Such heterocycles include thiophene, furan, pyran, pyrrole, pyrasol, pyridine, pyrazine, parimidine, pyridazine, indolizine, imidanyl,
Examples include thiazole, oxazole, triazine, thiadiazine, and oxazine. These may further have a cyclic substituent.

In the formula, R5 represents an aryl group (eg, phenyl group, α- or β-naphthyl group, etc.) or a heterocyclic group.

The aryl group may have one or more substituents, such as an alkyl group, an alkenyl group, a cyclic alkyl group, an aralkyl group, a cyclic alkenyl group, a halogen atom, a nitro group, a cyano group, an aryl group, and an alkoxy group. base, 7
11-ruoxy group, carboxy group, alkoxycarbonyl group, aryloxycarbonyl group, sulfo group, sulfamoyl group, carbamoyl group, acylamino group, diacylamino group, ureido group, urethane group, sulfonamide group, heterocyclic group, arylsulfonyl group , alkylsulfonyl group, arylthio group, alkylthio group, alkylamino group, dialkylamino group, anilino group, N-alkylanilino group, N-arylanilino group, N-acylanilino group, hydroxy group, mercapto group, etc. It's fine.

More preferred as R5 is phenyl in which at least one ortho position is substituted with an alkyl group, an alkoxy group, a halogen atom, etc. This is because the coupler remaining in the film is less likely to change color due to light or heat. It is useful.

Furthermore, 几5 is a heterocyclic group (for example, a j- or t-membered heterocyclic ring containing a nitrogen atom, an oxygen atom, or an ioc atom as a hetero atom, a fused heterocyclic group, a pyridyl group, a quinolyl group, a furyl group, a benzothiazolyl group) , oxasilyl group, imidazolyl group, naphthoxacylyl group, etc.), and may also represent a heterocyclic group substituted with the substituents listed for the above-mentioned aryl group.

In the formula, ratio 4 is a hydrogen atom, a linear or branched alkyl, alkenyl, cyclic alkyl, aralkyl, or cyclic alkenyl group having a carbon number of l (these groups may have the substituents listed for R5 above) ), aryl groups and heterocyclic groups (which may have substituents listed for ratio 5 above), alkylcarbonyl groups (e.g. methoxycarbonyl group, ethoxycarbonyl group, stearyloxycarbonyl group, etc.), Ryloxycarbonyl group (e.g., phenoxycarbonyl group, naphthoxycarbonyl group, etc.), aralkyloxycarbonyl group (e.g., evabenzyloxycarbonyl group, etc.), alkoxy group (e.g., methoxy group, ethoxy group, heptadecyloxy group, etc.) ), aryloxy groups (e.g., phenoxy, tolyloxy, etc.), alkylthio groups (e.g., ethylthio, dodecylthio, etc.), arylthio groups (e.g., phenylthio, α-naphthylthio, etc.), carboxyne groups, acylamino groups (e.g., acetylthio, etc.) Amino group, butanamide group, diacylamino group, ureido group (e.g. ureido, N-arylureido, N-alkylureido group, etc.), urethane group, thiourethane group, arylamine group (e.g. phenylamino, N-methylanilino group, λ −
Chloroanilino group, diphenylamino M, N-acetylanilino group, alkylamino group (e.g. n-bunalamino group, methylamino group, cyclohexylamino group, etc.)
, cycloamino group ε (e.g., piperidino group, pyrrolidino group, etc.), heterocyclic amino group (e.g., goupyridylamide group, cobenzoxazinolamino group, etc.), alkylcarbonyl group (e.g., methylcarbonyl group), arylsulfonyl groups (such as phenylcarbonyl groups),
Sulfonamide groups (e.g. alkylsulfonamide groups,
arylsulfonamide group, etc.), carbamoyl group C, ethylcarbamoyl group, dimethylcarbamoyl M, N-methyl-phenylcarbamoyl, N-phenylcarbamoyl n, etc.), sulfamoyl group (e.g., N-
Alkylsulfamoyl% N IN-dialkylsulfamoyl &, N-arylsulfamoyl group, N-alkyl-N-arylsulfamoyl i, N, N-diarylsulfamoyl group, etc.), cyano group, hydroxy represents any one of a group, a halogen atom, and a sulfo group.

In the formula, R6 represents a hydrogen atom or any linear or branched alkyl group, alkenyl group, cyclic alkyl group, aralkyl group, or cyclic alkenyl group with a carbon number of 1, and these have the substituents listed for R5 above. You may.

Further, R6 may represent an aryl group or a heterocyclic group, and may have the substituents listed for Ratio 5 above.

R s is a cyano group, an alkoxy group, an aryloxy group, a halogen atom, a carboxy group, an alkylcarbonyl group, an aryloxycarbonyl group, an aralkyl group, a sulfo group, a sulfazoyl group, a carbamoyl group, an acylamino group, a diacylamino group. , ureido group, urethane group,
Sulfonamide group, arylsulfonyl group, alkylsulfonyl group, arylthio group, alkylthio group, alkylamino group, dialkylamino group, anilino group, N-arylanilino group, N-alkylanilino group, N-acylanilino group, hydroxy group Alternatively, it may represent a mercapto group.

R7, R+3 and R9 each represent a group used in a typical i-equivalent type phenol or α-naphthol coupler. Specifically, R7 represents a hydrogen atom, a halogen atom, an alkoxycarbonylamino group, an aliphatic hydrocarbon residue. group, an N-arylureido group, and an acylamino group, and when two or more R7s exist in the same molecule, the two or more R7s may be different groups. Hydrogen residues include those having substituents.

When these substituents include an aryl group, the aryl group may have the substituents listed above for Rs.

Examples of R8 and R9 include groups selected from aliphatic hydrocarbon residues, aryl groups, and heterocyclic residues, or one of these groups may be a hydrogen atom, and these groups may be substituted with Including those with groups. Moreover, 几8 and 几9 may cooperate to form a nitrogen-containing heterocyclic nucleus. t is an integer of /~Hiroshi, m is an integer of /~3, and n is an integer of /-3. The aliphatic hydrocarbon residues may be either saturated or unsaturated, and may be straight chain ones,
It may be either branched or cyclic.

and preferably an alkyl group (e.g. methyl, ethyl,
propyl, isopropyl, butyl, t-butyl, isobutyl, dodecyl, octadecyl, lebutyl, cyclohexyl, etc.), and alkenyl groups (for example, allyl, octenyl, etc.). Aryl groups include phenyl and naphthyl groups, and representative heterocyclic residues include pyridinyl', quinolyl, chenyl, piperidyl, imidazolyl and the like. Substituents introduced into these aliphatic hydrocarbon residues, aryl groups, and heterocyclic residues include halogen atoms, nitro, hydroxy, carboxyl, amino, and substituted amino.

Sulfo, alkyl, alkenyl, aryl, heterocycle,
Examples include groups such as alkoxy, aryloxy, arylthio, arylazo, acylamino, carbamoyl, ester, acyl, acyloxy, sulfonamide, sulfamoyl, sulfonyl, and morpholino.

R10 is an arylcarbonyl group, an alkanoyl group having λ to 10 carbon atoms, an arylcarbamoyl group, and a carbon number 2 to 10
represents an alkanecarbamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group having carbon number/g, which may have a substituent, such as an alkoxy group, an alkoxycarbonyl group, an acylamino group,
Examples include an alkylsulfamoyl group, an alkylsulfonamide group, an alkylsacuniimide group, a halogen atom, a nitro group, a carboxyl group, a nitrile group, an alkyl group, or an aryl group.

``11 is an arylcarbonyl group, having 2 to 1 carbon atoms.

Alkanoyl group, arylcarbamoyl group, carbon number 2
~IO1 preferably! An alkanecarbamoyl group with ~/θ, an alkoxycarbonyl group or an aryloxycarbonyl group with carbon number/-g, an alkanesulfonyl group with carbon number/-g, a 71J-rusulfonyl group, an aryl group,! Negative or t-membered heterocyclic group (the hetero atom is selected from one elemental atom, oxygen atom, and iodine atom, such as triazolyl group, imidazolyl group, phthalimide group, succinimide group, furyl group, pyridyl group, or benzotriazolyl group) ), and these are the above-mentioned 几□.

It may have the substituents mentioned above.

The coupler of the present invention has a silver mole total of 2×10 in the emulsion layer.
That's 3 moles! ×10 1 mol preferably /×10-2
There is no mole! xio imol is added.

Furthermore, the present invention is effective against Kinuta by the following general formula (X
A coupler represented by I[l), (XIV) or (XV).

General formula (X[II) General formula (XIV) (R15)s General formula (XV) 1 Y means -0-C-, -S-.

Or it represents a divalent group represented by -〇-.

① and □2 represent a chain, branched or cyclic alkyl group having 3 or more carbon atoms (such as a propyl group or t-butyl group) or a substituted or unsubstituted phenyl group. The 1w substituent of the phenyl group is selected from a chloro atom, an alkoxy group, an alkanamide group, an alkanesulfonyl group, an alkanesulfonamide group, and < is a hydroxy group. When these substituents include an alkyl moiety, the number of carbon atoms is preferably from / to j.

R1s represents a halogen atom, an alkoxy group, an alkanamide group, an alkanesulfonyl group, an alkoxycarbonyl group, an alkanesulfonamide group, a complex compound, a hydroxy group, a carboxy group, or an alkyl group. When these substituents contain an alkyl moiety, the number of carbon atoms is preferably from 1 to 1, and it may be replaced by a hydroxy group or a carboxy group.

When 几13 represents a heterocyclic amide group, the heterocyclic ring contains a nitrogen atom, an oxygen atom or a sulfur atom as a hetero atom≠
It is a seven-negative ring. For example, l, 2. ≠-1・riazolyl group, imidazolyl group, furyl group, etc.

几14 represents a chain, branched or cyclic alkyl group having from 2 to 2 carbon atoms (e.g. propyl group, t-butyl group, etc.) and is substituted with a chloro atom, an alkoxy group, an alkanamide group, an alkanesulfonamide group or a hydroxyl group. may have been done. When these substituents contain an alkyl moiety, the number of carbon atoms is preferably from / to 3.

几15 represents a chloro atom, a methoxy group or a methanesulfonamide group.

sit: Represents an integer from 0 to 3.

R16 represents an acylamino group, an alkylureido group, or an arylureido group.

When the alkyl group part 16 is contained, it may be linear, cyclic or branched, and it may have the following substituent.

For example, halogen atoms, alkoxy groups, alkylthio groups,
Alkanamide group, carboxyl group, hydroxyl group,
Examples include an aryloxy group or an alkanesulfonamide group. When R16 contains a 71J-l moiety, it is preferably a phenyl group, which may have the following substituents. Examples thereof include a norogen atom, an alkoxy group, an alkanamide group, a hydroxyl group, an alkanesulfonamide group, an alkanesulfonyl group, a cyano group, a sulfamoyl group, a carbamoyl group, an alkoxycarbonyl group, and an alkanoyl group. The number of carbon atoms contained in R16, including substituents, is from / to male.

1 (17 represents an alkanamide group, a halogen atom, an alkyl group, or a hydrogen atom. When R17 contains an alkyl group moiety, it may be chain, cyclic, or branched, and it represents the following tll group. For example, a rogen atom, an alkoxy group, an alkylthio group, an alkanamide group, a carboxyl group, a hydroxyl group, an aryloxy group, or an alkanesulfinamide group.

The number of carbon atoms contained in R17 is from O to K including substituents.

IL18 represents a hydrogen atom or a hydrogen atom.

Next, the compounds of the present invention will be specifically shown, but the invention is not limited thereto.

(22) OH (23) C00)1 (24) (25) () 00H (26) (27) The coupler of the present invention can generally be synthesized by the following two synthetic routes.

In the formula, A represents a coupler residue, 2 represents a halogen atom (a bromine atom spanning a chloro atom), and W.

X and 几 have the same meanings as defined in general formula (I).

In the synthesis route (1), the reaction between the couplers whose coupling position is halogenated and the pyrazole serving as the leaving group can be carried out in a temperature range of 00 to 200°C in various solvents or by a solvent-free melting method. . The preferred temperature range is from 200 to /j00c, and in the solvent-free melting method, it is not necessary to raise the temperature above the melting temperature as long as both are dissolved. Preferred solvents include alcoholic solvents (ethanol, propatool, etc.), aromatic solvents (benzene, toluene, cyclene, etc.), aprotic polar solvents (dimethylformamide, sulfolane, etc.), and the like.

Since the pyrazole present in excess can be used as a dehydrohalogenating agent, a base is not particularly required, but may be used. The pyrazole used is, for example, ≠-hydroxyalkyl pyrazole, and after reaction with A-Z, the hydroxy group is /
A method of replacing it with -X-H through one step or several steps can also be used. The synthesis route (11) is an application of the known synthesis route for pyrazoles substituted at the hiro-position. This synthesis method is Jo
Urnal of American Chemica
lSociety Volume 7j page aoti-r (1913
year).

Next, a typical synthesis example of the coupler of the present invention will be described.

Synthesis Example (1) Synthesis of Exemplary Coupler (1) Goobromo/
-(λ, lI, 6-1lichlorophenyl)-J-hybaloylamino-j-pyrazoloyA♂, /f/oyohigu(
3-hydroxypropyl) virazolta r, 32 N,
N-dimethylformamide 100 THE, mixed with tθ
Stirred at 0C for 7 hours. After cooling to room temperature, ethyl acetate 2
00■ was added, and the mixture was transferred to a separating funnel and washed with N hydrochloric acid water.

After washing with water until neutral, the oil layer was separated and concentrated under reduced pressure. Acetonitrile was added to the residue, and the precipitated crystals were collected. After drying≠Hiroshi, j9/-(2,F.

A-) Lichlorophenyl)-gu(≠-(3-hydroxypropyl)pyrazolyl)-3-piparoylamino-!
- Obtained pyrazolone. That crystal! 2 and J' if
2,7-di-t-amylphenoxyacetic acid was mixed with N,N-dimethylformamide 60 relative. A solution of N,N-dicyclohexylcarbodiimide t,4tf dissolved in acetonitrile on a lj needle was dropped. The oily coupler (1) was post-treated in a conventional manner to form 22. I got /9.

Synthesis example (2) Synthesis example fi of exemplary coupler (12)
/-(2,≠,6-dolichlorophenyl)-1-(44-(J-hydroxypropyl)pyrazolyl)-3-piparoylamino-! of the intermediate obtained in l. -Pyrazolone 20
11b and 10 mL of thionyl chloride in chloroform tor.
The mixture was mixed in a 100-mL medium and left at room temperature (approximately 2J"C) overnight.

Water was gradually added to the reaction solution to separate the oil layer, which was washed with water until it became neutral. Remove the oil layer and reduce the pressure to give a yellow solid of -2g·t2, /-(,2,4t,7-1lichlorophenyl)-≠-(4'-(J-chloropropyl)pyrazolyl)-3-piparoylamino. -yo-pyrazolone (hereinafter referred to as compound/, 2A) was obtained.

Sodium hydride 3. 2 was added to 100 ml of tetrahydrofuran, and to this solution was added 21.monomercaptomyristate ethyl ester under water cooling. /f was added. The entire amount of compound/2A was added to this, and the mixture was stirred at room temperature for 3 days. The target coupler (12) in the form of an oil was obtained by post-treatment using a conventional method and purification by column chromatography.
．． I got ≠2.

The coupler of the present invention may be dissolved and emulsified in a high-boiling solvent as described later, or may be dissolved in a low-boiling organic solvent and emulsified and dispersed without using a high-boiling solvent.

As the above-mentioned high boiling point solvent, especially an organic solvent having a boiling point of 1 tO0C or higher, any known solvent can be used.

For example, phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.) and phosphoric acid esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate) described in US Patent λ, 322,027. ,
Citrate esters (e.g. acetyl tributyl citrate), benzoate esters (e.g. octyl benzoate)
, alkylamides (e.g. diethyl laurylamide)
, fatty acid esters (for example, dibutoxyethyl succinate, dioctyl acelate), trimesic acid esters (for example, tributyl trimesate), and the like are preferred. Particularly preferred are alkyl phosphates (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctylbutyl phosphate, etc.).

The coupler is introduced into the hydrophilic colloid layer using the high-boiling organic solvent described above, as described in U.S. Patent No. 3.2.2,02.
7, or using an organic solvent with a boiling point of about 3o0C to /j00c, such as lower alkyl acetate such as ethyl acetate, butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β- Ethoxyethyl acetate, methyl. After dissolving in cellosolve acetate etc., it is dispersed in hydrophilic colloid. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be mixed and used.

Also, special public Shoj/-jri ryu 3, tokukai Shoyu l-tata tag 3
It is also possible to use the polymer dispersion method described in .

When the coupler has an acid group such as carboxylic acid or sulfonic acid, it is introduced into the hydrophilic colloid as an alkaline aqueous solution.

The couplers of the present invention may be used in combination with other known couplers. For example:

As the magenta coupler, a pyrazolone, pyrazolotriazole, or imidazopyrazole coupler is used.

As yellow couplers, compounds of the benzoylacetanilide and pivaloylacetanilide series are advantageous.

7. As the uncoupler, a phenol compound, a naphthol compound, or the like is used.

Other compounds that release a development inhibitor upon development of DIR CUPRA or DIR CUB 2-1 may also be used.

Two or more types of couplers listed in ``2'' may be contained in the same layer. The same compound may be contained in λ or more different layers.

The undercoat layer of the photographic light-sensitive material of the present invention is a hydrophilic colloid layer consisting of a hydrophilic polymer such as gelatin (a bonded weight-bearing colloid of a photographic emulsion, which will be described later, or a mechanical colloid is also used), and is usually formed on a support. It is applied by coating on top of. in general,
By providing an undercoat layer, it is possible to improve adhesion with the photographic emulsion layer and prevent halation.

The color photographic material used in the present invention is suitable as long as it is a color photographic material that requires color development processing, such as color one-permanent film, color negative film, color reversal film, etc., but it is particularly suitable for print-sensitive materials (e.g., color paper, etc.). ) is preferred.

The photographic emulsion used in the present invention is P, GIafkides.
Author CI+1m1e et Physique Plio
tographique (Paul Monte 1, 1967), G, F'.

Written by Duffin Photographic Emul
sionChemistry(The Focal P
ress, /ri J&), V, L, Zelikman
et al. making and coatin
g Pbotographic Emulsion (Th
Mh'd adjustment can be carried out using the method described in e.g. That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt and soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. .

It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method).

As one type of simultaneous mixing method, a method in which pAg in the liquid phase in which silver halide is produced is kept constant, that is, a so-called Chondrald double jet method can also be used.

According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

Also, tabular particles (for example, the particle diameter/thickness value is r
An emulsion in which the above) occupies 50% of the total projected area can be used.

Two or more types of silver halide emulsions formed separately may be mixed and used.

In the photographic emulsion layer of the photographic light-sensitive material of the present invention, any of silver bromide, silver iodobromide, silver chlorobromide, silver chlorobromide, and silver chloride may be used as silver halide.

In the process of silver halide grain formation or physical ripening, cadmium salt, @lead salt, lead salt, thallium salt, iridium salt or its complex salt, rhodium salt or its complex salt, iron salt or iron complex salt, etc. are allowed to coexist. Good too.

The photographic emulsions used in this invention may be spectrally sensitized with methi/dyes and others. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, shungo merocyanine dyes, holoboraanine dyes, and hemi-7.
Included are anine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex melonanine dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, pyrroline nucleus, oxazinone nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenanol nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; nuclei in which an alicyclic hydrocarbon ring is fused to these nuclei; and these A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus of
That is, an indole nucleus, a benzindolenine nucleus, an indole nucleus, a penzoxazole nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a penzimitazole nucleus, a gynoline nucleus, etc. are applicable. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or composite merocyanine dyes contain pyrazoline-! as a core having a ketomethylene structure. -on nucleus, thiohydantoin nucleus, 2-thioxasolysine-λ, ≠-dione nucleus, thiazolisi/-λ, ≠-dione nucleus,
Five or more member heterocyclic nuclei such as rhodanine nuclei and thiobarbic acid nuclei can also be applied.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. Typical examples are U.S. patents Ko, t♂♂, J Hiroj, 2゜ri77.2 Kota, 3,
327,01rO No. 3,! , 2.2.0 Octopus No. 3, ! 27, 44t/issue, 3,1. /7,22
No. 3, same J, +4λg, rit≠ No., same 3.66 O, +t
No. o, 3,672. rri♂ No. 3, 1, 79.17
No. 21, 3, 703.

No. 377, No. 3, 76, No. 301, No. 3. ♂lII,
No. 609, 3,137. tAa No. 41. T02t
, No. 707, British Patent/ , 3'lll, No. 21/,
same/,! 07. IO, No. 3, I! 11! F Kosho 1/-3
-Geta No. 36, No. 13-/2!71, Tokukai Sho! λ-/
In addition to the sensitizing dyes described in IOT/R No. 71-/09 F, 2'j, dyes that do not themselves have a spectral sensitizing effect or substances that do not substantially absorb visible light. hand,
A substance exhibiting supersensitization may also be included in the emulsion. For example, aminostilbene compounds substituted with nitrogen-containing heterocyclic groups (for example, U.S. Pat.
35,7 Co. No. 1), aromatic organic acid formaldehyde condensates (for example, those described in U.S. Pat. No. 3.74'3.
0), cadmium salts, azaindene compounds, etc. US special%3. t,ls.

1.13, 3. AI! , l, II-/No. 3. t
/7.2 Geta issue, same 3. t3! , No. 72/ is particularly useful.

Gelatin is advantageously used as the admixture or protective colloid for photographic emulsions, but other parent, aqueous colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, albumin, casein s; cellulose derivatives such as hydroxyethyl cellulose, carboquine methyl cellulose, cellulose sulfates, etc., sugar derivatives such as sodium alginate, starch derivatives, etc. ; Polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid.

A wide variety of synthetic hydrophilic polymeric materials can be used, such as single or copolymers of polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, and the like.

Gelatin includes lime-processed gelatin, acid-processed gelatin, Bull, Soc, Sci, Phot, Ja
Oxygen-treated gelatin such as that described in Panban/l, page 30 (/A4) may also be used.

The invention is also applicable to multicolor, multicolor photographic dyes having at least two different spectral sensitivities on the support.

Multilayer natural color photographic materials usually have a red-sensitive emulsion layer on a support,
and at least one sensitive emulsion layer. The order of these layers can be arbitrarily selected as necessary. Usually, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the back-sensitive emulsion layer contains a yellow-forming coupler, but different combinations may be used depending on the case. .

The photosensitive material produced using the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes, and azo dyes. Among them, oxynol dyes; hemioxonol dyes and merocyanine dyes are useful.

In carrying out the present invention, the following known antifading agents may be used in combination, and the color image stabilizers used in the present invention may be used alone or in combination of two or more. Known anti-fading agents include hydroquinone derivatives, gallic acid derivatives, p-alkoxyphenols, p-oxyphenols, hisphenols, and the like.

The photosensitive material produced using the present invention contains hydroquinone derivatives, aminophenol derivatives,
It may also contain gallic acid derivatives, ascorbic acid conductors, and the like.

The photosensitive material produced using the present invention preferably contains an ultraviolet absorber in the hydrophilic colloid layer.

For example, benzotriazole compounds substituted with aryl groups (e.g., those described in U.S. Pat.
, 3/41.7ri≠ issue, same 3゜3! J, No. 41/), benzophenone compounds (for example, those described in JP-A-Sho≠6
-27♂≠), cinnamate ester compounds (for example, U.S. Pat. No. 3,705.tos, U.S. Pat. No. 3,70
7゜37), getadiene compounds (such as those described in U.S. Pat.
,700. 'I-Yu! ) can be used. Zarani US Patent 3. ≠No. 22.762, Tokukai Sho!
Those described in I-Ko 163 evening issue can also be used.

An ultraviolet absorbing coupler (for example, an α-naphthol cyan dye-forming coupler) or an ultraviolet absorbing polymer may be used. These UV absorbers may be mordanted into certain layers.

In the photographic material produced using the present invention, the photographic emulsion layer and other hydrophilic colloid layers may contain a stilbene-based, triazine-based, oxazole-based, or Shoe+1F-based brightener. These brighteners may be water-soluble, or water-insoluble brighteners may be used in the form of a dispersion.

Any known method can be used for the photographic processing of the light-sensitive material of the present invention. A known treatment liquid can be used. Processing temperature starts from normal/r0C! Temperature selected between O0C but below /Z00 or ROOC
The temperature may exceed . Any color development process that forms a dye image depending on the purpose can be applied.

Color developers generally consist of an alkaline aqueous solution containing a color developing agent. The color developing agent is a known primary aromatic amine developer 1 such as phenylene dianiline, 3-methyl-
Guamino-N, N-diethylaniline, l-amino-
N-ethyl-N-β-hydroxyethylaniline,! −
1+Rugu 7mi/-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-guamino-N-ethyl-N-β-methanesulfamide ethylaniline, ≠-amino-3-methyl-N-ethyl-N- β-methoxyethylaniline, etc.) can be used.

In addition, Photograph by F. A. Mason
icProcessing Chemistry (Fo
Cal Press, / 1966), 226~λλ
Page, U.S. Patent 2, No. 3, 0/j, same,! octopus,
36≠No., JP-A-Sho pg-+≠233, etc. may be used.

Color developers may also contain pH buffering agents such as alkali metal sulfites, carbonates, borates and phosphates, development inhibitors or antifoggants such as bromides, iodides and organic antifoggants. can. Also, if necessary, water softeners, preservatives such as hydroxylamine, etc.
Benzyl alcohol, diethylene glycol, etc.
jAIeJ agent.

Phenomenon promoters such as polyethylene glycols, quaternary ammonium salts, amines, etc. 1 Dye-forming couplers.

competitive couplers, fogging agents such as sodium borohydride, viscosity-imparting agents, polycarboxylic acid chelating agents as described in U.S. Pat.
S ) -2, l -2-2, 5' j No. K may contain the antioxidant described.

The photographic emulsion layer after color development is usually treated with nickel silver. Bleaching treatment may be performed simultaneously with fixing treatment, or may be performed separately.

Example 1 A magenta coupler of the present invention and a magenta coupler for comparison were dissolved in tricresyl phosphate ethyl acetate, mixed with an aqueous gelatin solution and emulsified with a homogenizer, and the emulsion was prepared as follows. Coating samples 1 to 7 as described below were prepared by adding the above-mentioned components to a silver germide emulsion. The luminescence amount of each compound is shown in parentheses.

(1) Emulsion layer Negative silver iodobromide emulsion (grain size 1.jμ iodine content 1/Ox/0-2mol 7m") Couplers listed in Table 1 (j, Ox/Omor/m2) Tricresyl phosphate (/ , / ? 7m2) gelatin
(,2,397m2) (2) Hoki layer λ, t-dichloro-6-hydroxy-5-sodium triazine (0,0397m2) Cellar Pn (2,0'i 7m2) These films are ≠o0C1 relative humidity After being left under 70% light for 1 hour, light was applied for sensitometry and light for graininess (RMS) measurement, and the next color development process was carried out.

Color development process Time Temperature 1 Color development @ 3' / t” 310C2 bleaching
White t '30 " 3 Washing 2' 4 Fixing ≠' 5 Washing ≠' 6 Stable /' Here, the compositions of each processing solution in the color development process are as follows.

Color developer water 100 inches Gu (N-ethyl-N-hydroxyethyl)amino-λ-methylaniline sulfate! 2 The value of acid is 1.11 um! 2 Hydroxylamine value acid salt 2g Potassium carbonate 309 Potassium hydrogen carbonate /, 29 Potassium bromide /, 29 Sodium chloride 0,. 29 Trisodium nitrilotriacetate i, 2y Add water
/7 (1)H/(7,/) Bleach solution water 100m9 Ferric ammonium base of ethylenediaminetetraacetic acid 100? Ethylenediaminetetraacetic acid disodium 11um 10f Potassium bromide /jθ? Acetic acid ioy Add water /1 (pHA, 7) Fixer water 100m0 Ammonium thiovalent acid 1 sot Sodium nitrous acid ioy Sodium hydrogen nitrite λ, evening? Add water /1 (pHA, 0) Stabilized liquid water to 00 mD formalin (37 cm) TamQ Drywell j+nl+ Add water /l The photographic properties and graininess results obtained are shown in Table 1.

2. From Table 1, it is clear that the coupler of the present invention has better graininess than the comparative coupler C-/, which shows similar sensitivity. Comparative coupler C-2 also showed almost the same graininess.
, has significantly higher sensitivity than C-3.

Couplers C-/ to C-J used for comparison here are as follows.

α Example 2 Multilayer color photosensitive paper sample 2 consisting of each layer having the composition shown below on a cellulose triacetate film support.
0/ was created.

(Sample) Q/) 1st layer: Antihalation layer (AHL) Gelatin layer containing black colloidal silver 2nd layer: Intermediate layer (ML) Co,! - Gelatin layer 3 containing an emulsified dispersion of di-t-octylhydroquinone: 1st red-sensitive emulsion (■ (ILl)... Silver coating amount /, 209 / m2 Sensitizing dye I...・＃
1x10' moles of sensitizing dye for 7 moles ■......For 1 mole of Senshi/,! x10
'Molar coupler C-≠... O, Oa per mole of silver Molar coupler C-4... 0.003 mole per mole of silver Coupler C-1... (j1 O,000 per mole
4 mol 1st layer: 2nd red-sensitive emulsion layer (RL2)... Button coating /, 1.0ri 7m2 Sensitization 1! !
Elementary I...for 1 mole of ω! , jx10 'mol sensitizing dye 11...... per mole of forceps/, 0x1
0'Mole coupler C-7...0.02 mole per mole of trowel Coupler C-t...0.0θ72 mole per mole of trowel No. Jl#: Middle layer (ML) Same as second layer J 1m: First green-sensitive emulsion layer (GLI)...
Coated silver amount / , A 9 /m2 Sensitizing dye ■...
...3 x 10 mol sensitizing dye per 1 mol of silver■.../x10' per mol of silver
Molar coupler C-g... 0005 moles per 1 mole of button Coupler C-ta... 0.00 g per 1 mole of button Coupler C-J... 0.00/! Mol 7th layer: 2nd green-sensitive emulsion layer (GL2) ゛°°°°° coated silver mound / , ! ? ? /m2 sensitizing dye 1.11...2.3x per mole of silver
10 mole sensitizing dye ■...0 per mole of silver, Ixlo
Mol coupler C-ta... 0.003 molar ratio per mol of trowel Cereal coupler coupler C-//...# per 1 mol θ, o/7 mole r1st: Yellow filter 2. Yellow colloidal silver in single layer (YFL) gelatin aqueous solution. a turn-1-off molar hydroquinone emulsified dispersion.

2nd layer: 7'# emulsion layer (BLI) ... Coated silver π is changed to coupler C-10...91 mol [to 0.25 mol coupler 〇-t... 1 mol of silver] 70th layer: 2nd W-sensitive emulsion layer (BL2) 19001. Coated steel amount / , / f 7m2 Coupler C-10... O0O0 mol per 1 mol of silver 1st/layer: Protective layer (PL) Trimethylmethanoacrylate particles (diameter/.

Apply a gelatin layer containing 5 μg.

In addition to the above composition, gelatin hardener H-7 and a surfactant were added to each layer.

The sample prepared as described above was designated as sample 20/.

(Samples, 20.Z to 207) Except that double the mole of comparison couplers C-/2 and C-/3 and equal mole U of the coupler of the present invention were used instead of coupler C-/ of GL2 in sample 20/. is sample λ similarly to sample 20/
θλ~207 were created, respectively.

Samples 207 to λ07 were exposed to white light for sensitometry and graininess measurement, and then subjected to the same color development process as in Example 1. The processed sample was subjected to density measurement and 8MS value measurement using red light. The results are shown in Table 2.

Table 2 1) 2) Sample Coupler Relative sensitivity RMS value λ0/(Comparative example) C-// 100 0,0.3j202 (Comparative example)
C-/2A≠ o, oil 203 (comparative example) C-/J
Otsu/0.0/Ir, 20≠(present invention) (11/10
o, o3/20J' (this invention) (611070,0
2, 2OA (present invention) (9110/0.0/1.
207 (Invention) IJ J'/ 0,0.2゜1) Reciprocal of the exposure amount that gives a fog of 100.2, relative value with sample 2θl as 1002) Density measured with an aperture of Hiro rμ diameter From the table MS value λ at the exposure dose giving 0.7, the sample made with the coupler of the present invention +11, (61), 2 (7 Hiroshi, 2Q!) is the sample made with the coupler for comparison. /
The sensitivity is higher and the graininess is better than that of the sample 20t of the coupler of the present invention +91t11, and 207 is the sample 20λ of the coupler for comparison.

, 203, although the sensitivity is considerably higher, the graininess is almost the same.

From the above results, the effectiveness of the coupler of the present invention is clear.

The compounds and comparative couplers used to prepare Samples 20/- and 207 are as follows.

Sensitizing dye I near/hydro-! ,! '-dichloro-3,3
'-di(r-sulfopropyl)-turconityl-thiacarbocyani/hydroxide viridinium salt sensitized color 'AE II: Anhydroterethyl-3.
3'-G(r-sulfopropyl)-≠,! ,≠′−!
'-Dibenzothiacarbocyanine hydroquinide triethylamine salt sensitizing dye Ill: Anthrotorethyl-j,!
'-cyclorho3.3'-di(γ-sulfofurovir)
Oxacarbocyanine sodium salt sensitizing dye ■: Anhydro, (,, r' , x' -tetrachloro-7
,/'-diethyl-3,3'-c(β-[β-(r-
Sulfopropoxy) ethoxy]ethylimidazolocarbocyanine hydroside sodium salt procedure □Continued amendment document Showa Tata Hirotsuki Nra Day 1, Incident indication Showa N year patent application No. 1 v-z, 332 No. 2
, Title of the invention: Silver halogenide color photographic light-sensitive material 3.
Relationship with the case of the person making the amendment Patent applicant Address 210-4 Nakanuma, Minamiashigara City, Kanagawa Prefecture Subject of amendment R% of the specification Column “Claims” and Column 5 of “Detailed Description of the Invention” Amend n's own listing in the "Claims" section of the description of contents as per the %11 paper.

The % self-inclusion in the "Detailed Description of the Invention" section of the specification is amended as follows.

1) Page 5, line 3 Before "sulfonamide" "Carbonic ester bond" Insert.

2) Page 6/, 2nd line "Alkoxycarbonyl group" [Alkoxycarbonyl group] and correct it.

3) Add compound (25) on page 36, line V to (l)
Compound on page V line (correct with α after 2'D).

5) No. 0 page 1 1200■ 「、zoorni」 and correct it.

What is claimed is a silver halide color photographic material containing a coupler characterized by having a group represented by the following general formula at the coupling position.

In the formula, R represents an aliphatic group, an aromatic group, or a heterocyclic group, and X represents an ester bond, amide bond, ether bond, thioether bond, Minku 322 Σ class% sulfonamide bond, urethane bond or ureido bond. , and W represents an integer of 0 or 3.

Claims (1)

[Scope of Claims] A silver halide color photographic light-sensitive material containing a coupler having a group represented by the following general formula at the coupling position. In the formula, 几 represents an aliphatic group, an aromatic group, or a heterocyclic group, X represents an ester bond, an amide bond, an ether bond, a thioether bond, a sulfonamide bond, a urethane bond, or a ureido bond, and W represents λ or 3 represents an integer.