JPS61249052A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a color photographic sensitive material superior in sharpness and the like by incorporating a diffusion-resistant coupler to be allowed to release an alkali-soluble dye or a colorless compd. by development processing and further to be allowed to release a development inhibitor oxidation reaction. CONSTITUTION:A silver halide emulsion layer or a hydrophilic colloidal layer contains a compd. represented by formula I in which A is a coupler residue to be cleft at the bond A-RED by the reaction with the oxidation product of a color developing agent to form an alkali-soluble dye or a colorless compd.; RED is a group, after the cleavage from A, being oxidized to release the development inhibitor DI; and Ballast is an org. group for giving diffusion resistance. It is preferred for the group A to have a substituent having COOH, SO3H, or OH, and this compd. is embodied by formula II, thus permitting a sharp image small in color turbidity to be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Tumor Application) The present invention relates to a color photographic material containing a novel compound whose development inhibitor can be cleaved by development processing.

(Prior Art) Many studies have been conducted on color photographic materials with the aim of improving graininess, sharpness and color reproducibility. One such technology is couplers that release development inhibitors. It is commonly referred to as a DIR coupler.

Among DIR couplers, a group of couplers is known that does not substantially form a dye upon coupling reaction with an oxidized developing agent. For example, U.S. Patent No. 3.632,3'
l! No. r, 3.95g, No. 993, 3. Ri &/, de! ; De No., 3.9-g.

olIIi No. 3,931,994, sameg, ob, 3
．． 9! ;0 No., same gu, Ohiro 9. Gu Ss, same Gu.

/, ltri, No. 916, same da, /za 7.110, same 1
, λ-A, ? The coupler described in JII issue etc. is known. These compounds have favorable properties as well as drawbacks. The biggest drawback is the low reactivity with oxidized color developing agents. Furthermore, U.S. Pat. are doing. This type of DIR coupler does not care about the hue of the dye produced, and color reproducibility is unlikely to be impaired even when used in various color image forming layers.

Among the couplers disclosed herein, those having a diffusion-resistant group in the timing group and a water-soluble group in the coupler residue have preferable properties as they can be incorporated into photographic layers as internal couplers. However, it has been known for the purpose of improving photographic properties such as improving sharpness (DIR couplers without timing groups: for example, U.S. Pat.
-273SII No. J, 933. ! ;No. 00, same da,
ogt,.

It has been found that this is not much different from the DIR coupler (coupler described in No. 09'1, same, y, tiz, s; ot, etc.).

(Object of the Invention) Therefore, an object of the present invention is to provide a color photographic material with less color turbidity and excellent sharpness by using a novel IR coupler.

(Structure of the Invention) The above object has been achieved by a color photographic material containing a coupler represented by the following general formula (I).

General formula (1) % formula % In the formula, A represents a coupler residue that cleaves the bond between A and RED by reaction with an oxidized developing agent and produces an alkali-soluble dye or a colorless compound, and RED
Represents a group that cleaves DI through a reaction process in which it is oxidized after being cleaved by GiA, DI represents a development inhibitor, and Ba1l
ast represents an organic atomic group for making the compound represented by the above general formula diffusion resistant.

In the general formula (1), A means a coupler residue that reacts with an oxidized developing agent to form an alkali-soluble reaction product. That is, those having at least seven carboxyl groups, sulfo groups, or hydroxyl groups as substituents are preferred.

The coupler residues used in the present invention are preferably the following. Yellow coupler residues include open chain ketomethylenes, magenta coupler residues include S-pyrazolones, pyrazolotriazoles, pyrazoloimidazoles, or cyanoacetophenones, and cyan coupler residues include phenols or naphthols. I can do it. In the present invention, it is preferred that these coupler residues have at least one carboxyl group, sulfo group or hydroxyl group at a substitutable position.

In general, the present invention is particularly effective for the general formula (I
), A or the following general formula (CI)-/), (Cp-λ
), (Cp-j), (Cp-1I), (Cp-r), (
Cp-+), (Cp-7), (Cp-t), (Cp-9
), (Cp-10/) or (Cp-//). These couplers are preferred because of their high coupling speed.

General formula (Cp-/) General formula (Cp-2) General formula (Cp-,?) Summer general formula (Cp-II) General formula (Cp-r) General formula (Cp-6) General formula (Cp-7 ) General formula (Cp-za) General formula (Cp-9) General formula (Cp-10) General formula (Cp-//) R60CHR61 In the above formula ζ, the free bond derived from the coupling position is: Represents the bonding position of the coupling-off group. In the above formula, R51%R52, R53, R54%R55,
R56s R57s R5as R59s The total number of carbon atoms contained in R60 or R61 is preferably 73 or less.

Next, R51 of the general formula (Cp-/) to (Cp-//)
~R61t%m and p will be explained.

In the formula, R51 represents an aliphatic group, an aromatic group, an alkoxy group, or a heterocyclic group, and R52 and R53 each represent an aromatic group or a heterocyclic group.

In the formula, the aliphatic group represented by R51 preferably has carbon atoms t, is, substituted or unsubstituted, linear or cyclic,
It may be either. Preferred substituents for the alkyl group include an alkoxy group, an aryloxy group, an amino group, an acylamino group, a halogen atom, a carboxyl group, a hydroxyl group, and a sulfo group, which may themselves have further substituents. Specific examples of aliphatic groups useful as R51 are as follows. : Isoprobyl group, isobutyl group, tert-butyl group, isoamyl group, ter
t-amyl group, /,/-dimethylbutyl group, 1. /-dimethylhexyl group, /, I-diethylhexyl group, cyclohexyl group, comethoxyisopropyl group, cophenoxyisopropyl group, α-aminoisopropyl group, α
-(diethylamino)isopropyl group, α-(succinimido)isopropyl group, α-(phthalimido)isopropyl group, α-(benzenesulfonamido)isopropyl group, and the like.

When R51, R52 or R53 represents an aromatic group (% phenyl group), the aromatic group may be substituted. Aromatic groups such as phenyl groups include alkyl groups, alkenyl groups, alkoxy groups, alkoxycarbonyl groups, alkoxycarbonylamino groups, aliphatic amide groups, alkylsulfamoyl groups, alkylsulfonamide groups, and alkylureido groups having a carbon number of IO or less. , an alkyl-substituted succinimide group, etc., and in this case, the alkyl group may have an aromatic group such as phenylene interposed in the chain. 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, etc., and the aryl group of these substituents The moiety may be further substituted with one or more alkyl groups having a total of 10 or less carbon atoms.

The phenyl group represented by R51, R52 or R53 further includes an amine 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 1 to 2 carbon atoms. Alternatively, it may be substituted with a halogen atom.

R51, R52 or Rsa is a substituent in which a phenyl group is fused with another ring, such as a naphthyl group, a quinolyl group,
It may also represent an isoquinolyl group, a chromanyl group, a chromanyl group, a tetrahydronaphthyl group, etc. These substituents may themselves have further substituents.

When R51 is an alkoxy group, the alkyl portion has a carbon number of / to /! F preferably represents a linear or branched alkyl group, alkenyl group, cyclic alkyl group, or cyclic alkenyl group of / to B, which may be substituted with a halogen atom, an aryl group, an alkoxy group, or the like.

When R51, R52 or Rsa 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 nitrogen atom of the amide group, respectively, through one of the carbon atoms forming the ring. Combine with. Such multiple rings include thiophene, furan,
Pyran, pyronyl, pyrazole, pyridine, pyrazine,
Examples include pyrimidine, pyrimidine, indolizine, imidazole, thiazole, oxazole, triazine, thiadiazine, oxazine, and the like. These may further have a substituent on the ring.

In the general formula (Cp-3), Ras represents carbon number l to l
! Preferably 1 to 10 linear or branched alkyl groups (e.g. methyl, isopropyl, tert-butyl,
hexyl group, etc.), alkenyl group (e.g. allyl group, etc.), cyclic alkyl group (e.g. cyclopentyl group, cyclohexyl group, norbornyl group, etc.), aralkyl group (e.g. benzyl, β-phenylethyl group, etc.), cyclic alkenyl group (e.g. cyclo pentenyl, cyclohexenyl group, etc.), and these represent halogen atoms, nitro groups,
Cyano group, aryl group, alkoxy group, aryloxy group, carboxy group, alkylthiocarbonyl group, arylthiocarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, sulfo group, sulfamoyl group,
Carbamoyl group, acylamino group, diacylamino group,
ureido group, urethane group, thiourethane group, sulfonamide group, heterocyclic group, arylsulfonyl group, alkylsulfonyl group, arylthio group, alkylthio group, alkylamino group, dialkylamino group, anilino group, N-arylanilino group, N-a/Izkylanilino group, N-
It may be substituted with an acylanilino group, hydroxyl group, mercapto group, etc.

Furthermore, R55 may represent an aryl group (eg, phenyl group, α- or β-naphthyl group, etc.). The aryl group may have seven or more substituents, such as an alkyl group, an alkenyl group, a cyclic alkyl group,
Aralkyl group, cyclic alkenyl group, halogen atom, nitro group, cyan group, aryl group, alkoxy group, aryloxy group, carboxyl 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, alkyl It may have an amino group, dialkylamino group, anilino group, N-alkylanilino group, N-arylanilino group, N-acylanilino group, hydroxyl group, etc.

Furthermore, Rss is a heterocyclic group (for example, a 3- or 6-membered heterocyclic ring containing a nitrogen atom, an oxygen atom, or a sulfur atom as a heteroatom, a fused heterocyclic group, a pyridyl group, a quinolyl group,
furyl group, benzothiazolyl group, oxasilyl group, imidazolyl group, naphthoxacylyl group, etc.), heterocyclic group substituted with the substituents listed for the above aryl group, aliphatic or aromatic acyl group, alkylsulfonyl group, arylsulfonyl group may represent an alkylcarbamoyl group, an arylcarbamoyl group, an alkylthiocarbamoyl group or an arylthiocarbamoyl group.

In the formula, R54 is a hydrogen atom, a linear or branched alkyl, alkenyl, cyclic alkyl, aralkyl, or cyclic alkenyl group having 1 to 10 carbon atoms (these groups have the substituents listed above for R55). ), aryl groups and heterocyclic groups (these are the above R
may have the substituents listed for ss), alkoxycarbonyl 4: (e.g. methoxycarbonyl group, ethoxycarbonyl group, etc.), aryloxycarbonyl group (e.g. phenoxycarbonyl group, naphthoxycarbonyl group, etc.), aralkyloxycarbonyl group groups (e.g., benzyloxycarbonyl group, etc.), alkoxy groups (e.g., methoxy group, ethoxy group, etc.), aryloxy groups (e.g., phenoxy group, tolyloxy group, etc.), alkylthio groups (e.g., ethylthio group, octylthio group, etc.)
, arylthio group (e.g., phenylthio group, α-naphthylthio group, etc.), carboxy group, acylamino group (e.g., acetylamino group, pivaloylamino group, etc.), diacylamino group, N-alkylacylamino group (e.g., N
-methylpropionamide group, etc.), N-arylacylamino group (e.g., N-phenylacetamide group, etc.)
, ureido groups (e.g. ureido, N-arylureido, N-alkylureido groups, etc.), urethane groups, thiourethane groups, arylamine groups (e.g. phenylamino,
N-methylanilino group, diphenylamino group, N-acetylanilino group, cochloroanilino group, etc.), alkylamino group (e.g. n-butylamino group, methylamine group, cyclohexylamino group, etc.), cycloamino group (
(e.g., piperidino group, pyrrolidino group, etc.), heterocyclic amide group (e.g., coubiridylamino group, cobenzoxazolylamino group, etc.), alkylcarbonyl S (e.g., methylcarbonyl group, etc.), arylcarbonyl group (
(e.g., phenylcarbonyl group), sulfonamide group (e.g., alkylsulfonamide group, arylsulfonamide group, etc.), carbamoyl group (e.g., ethylcarbamoyl group, dimethylcarbamoyl group, N-methyl-phenylcarbamoyl, N-phenylcarbamoylnato),
Sulfamoyl group (e.g. N-alkylsulfamoyl, N,N-dialkylsulfamoyl group, N-arylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, N,N-diarylsulfamoyl group) ), cyan group, hydroxyl group, or sulfo group.

In the formula, R56 represents a hydrogen atom or a linear or branched alkyl group, alkenyl group, cyclic alkyl group, aralkyl group, or cyclic alkenyl group having 1 to 73 carbon atoms, preferably 1 to io carbon atoms, and these represent the above-mentioned R55. It may have the listed substituents.

Further, R56 may represent an aryl group or a heterocyclic group, and these may have the substituents listed for R55 above.

R56 is a cyano group, an alkoxy group, an aryloxy group, a halogen atom, a carboxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, a sulfo group, a sulfamoyl group, a carbamoyl group, an acylamino group, a diacylamino group, or a 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-
It may also represent an acylanilino group or a hydroxyl group.

R57, R58 and R59 each represent a group used in a normal da equivalent type phenol or α-naphthol coupler, specifically, R57 is a hydrogen atom,
Examples include halogen atom, alkoxycarbonylamino group, aliphatic hydrocarbon residue, N-arylureido group, acylamino group, -〇-R62 or -8-Rs2 (where R62 is an aliphatic hydrocarbon residue), and the same molecule When one or more R7 exists in the group, one or more R57 may be different groups, and the aliphatic hydrocarbon residues include those having a substituent.

In addition, when these substituents include an aryl group, the aryl group may have the substituents listed for R55 above.

R58 and R59 (!: is an aliphatic hydrocarbon residue,
Examples include groups selected from aryl groups and heterocyclic residues, or one of these groups may be a hydrogen atom, and these groups include those having substituents. Further, R5O and R59 may jointly form a nitrogen-containing heterocyclic nucleus.

The aliphatic hydrocarbon residues may be either saturated or unsaturated, and may be straight-chain, branched, or
Any ring-shaped one may be used. Preferred are alkyl groups (eg, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, isobutyl, cyclobutyl, cyclohexyl, etc.) and alkenyl groups (eg, allyl, octenyl, etc.). Typical aryl groups include phenyl and naphthyl groups, and typical heterocyclic residues include pyridinyl, quinolyl, chenyl, piperidyl, and imidazolyl. Substituents introduced into these aliphatic hydrocarbon residues, aryl groups and heterocyclic residues include halogen atoms, nitro, hydroxy, carboxyl, amino, substituted amino, sulfo, alkyl,
Examples include groups such as alkenyl, aryl, heterocycle, alkoxy, aryloxy, arylthio, arylazo, acylamino, carbamoyl, ester, acyl, acyloxy, sulfonamide, sulfamoyl, sulfonyl, and morpholino.

t represents an integer of l-da, m represents an integer of 1 to 3, and p represents an integer of / to 3.

R2O is an arylcarbonyl group, an alkanoyl group having co to is preferably co to 10 carbon atoms, an arylcarbamoyl group, an alkanecarbamoyl group having 2 to 13 carbon atoms, preferably 2 to IO, and preferably 1 to 3 carbon atoms. The alkoxycarbonyl group in ~10 also represents an aryloxycarbonyl group, and these may have a substituent, such as an alkoxy group, an alkoxycarbonyl group, an acylamino group, an alkylsulfamoyl group, an alkylsulfone group. These include an amide group, an alkylsuccinimide group, a halogen atom, a nitro group, a carboxyl group, a nitrile group, an alkyl group, or an aryl group.

R61 is an arylcarbonyl group, ° carbon number λ ~/! Preferably an alkanoyl group or arylcarbamoyl group having - to 10 carbon atoms, an alkanecarbamoyl group having λ to /3 carbon atoms, preferably 2 to IO, an alkoxycarbonyl group or aryloxycarbonyl group having 1 to 13 carbon atoms, preferably / to 10 carbon atoms. Alkylsulfonyl group, arylsulfonyl group, aryl group of several l to lj, preferably 1 to IO,! or 6-membered heterocyclic group (the hetero atom is selected from nitrogen atom, oxygen atom, sulfur atom, such as triazolyl group, imidazolyl group, phthalimide group, succinimide group, furyl group, pyridyl group or benzotriazolyl group) ), which may have the substituents mentioned above for Rao.

Among the above coupler residues, yellow coupler residues include those in the general formula (Cp-/) in which R51 represents a t-butyl group or a substituted or unsubstituted aryl group, and R52 represents a substituted or unsubstituted aryl group. and in the general formula (Cp-, 2), it is preferable that R52 and R53 represent a substituted or unsubstituted aryl group.

Preferred magenta coupler residues are of the general formula (C
When R54 in p-j) represents an acylamino group, ureido group, or arylamino group, and R55 represents a substituted aryl group, R54 in general formula (Cp-ta) or
Acylamino group, ureido group and arylamino group,
When R56 represents a hydrogen atom, and the general formula (Cp
-s) and (Cp-6) R54 and R56
This is a case in which it represents a straight-chain or branched-chain alkyl group, alkenyl group, cyclic alkyl group, aralkyl group, or cyclic alkenyl group.

Preferred cyan coupler residues have the general formula (Cp
In -7), when R57 represents an acylamino group or ureido group at the 2-position, an acylamino group or an alkyl group at the 5-position, and a hydrogen atom or a chlorine atom at the 6-position, and Rsy in the general formula (Cp-9), a hydrogen atom at the 3-position, an acylamino group, a sulfonamide group, an alkoxycarbonyl group, R58 is a hydrogen atom, and R59
represents a phenyl group, an alkyl group, an alkenyl group, a cyclic alkyl group, an aralkyl group, and a cyclic alkenyl group.

Preferred colorless coupler residues have the general formula (Cp
-10), when R57 represents an acylamino group, a sulfonamide group, or a sulfamoyl group, the general formula (
This is the case where R60 and Rsl in Cp-//) represent an alkoxycarbonyl group.

In the general formula (I), RED is a group having a reducing action after being cleaved from A. That is, after cleavage from A, RED reduces the oxidized developing agent and is itself oxidized. Only when RED is oxidized does it have an electrophilic reactive side and can be attacked by nucleophiles (such as hydroxyl ions, hydroxylamine or sulfite ions) in the developer solution. This reaction triggers the development inhibitor to be released from (the oxidized form of) RED. Compounds that release development inhibitors upon oxidation are described, for example, in U.S. Patent No. J, ? ,30,
No. 843, same? ,,77? , A; No. 29, etc. are known.

In general formula (1), RED is preferably hydroquinones, catechols, pyrogallols, naphthohydroquinones, phenols substituted with an amine group at the ortho or para position (the amino group is a sulfonyl group, an aliphatic group, (including cases in which the benzene ring (or benzene-fused f ring, pyrimidine ring, pyrimidine ring, quinoline ring, isoquinoline ring, etc.). These REDs are preferably bonded to A via an oxygen atom obtained by removing a hydrogen atom from the hydroxyl group of the aromatic alcohol. Furthermore, l) I is preferably bonded to a ring-constituting atom of the aromatic ring.

The diffusion-resistant group represented by Bal 1 as t in the general formula (I) means an organic atomic group for enlarging the molecule so that the compound does not move from the layer to which it is added. Ba1last preferably has a total carbon number of 1
Represents an aliphatic group of 0 or more or an aromatic group in which the total number of carbon atoms of all substituents is 10 or more, and these atomic groups include ether bonds, amide bonds, ureido bonds, thioether bonds, ester bonds, and sulfonamide bonds. , a carbonyl group, a sulfonyl group, an imide group, a thioureido bond, etc. are also included.

In general formula (I), I is preferably a tetrazolylthio group substituted at the 1-position with an aliphatic group or an aromatic group, /
or a cobenzotriazole group, l-penzoindazolyl group, benzimidazolylthio group, benzoxazolylthio group, imidazolylthio group, oxazolylthio group, triazolylthio group, oxadiazolylthio group or thiadiazolylthio group, These include cases in which the following substituents are present at substitutable positions. Preferred substituents include aliphatic groups (e.g., methyl group, ethyl group, etc.), aromatic groups (e.g., phenyl group, cochlorophenyl group, etc.), halogen atoms (e.g., fluorine atom, chloro atom, etc.), alkoxy groups (e.g., methoxy group, benzyloxy group), alkylthio group (e.g. ethylthio group, butylthio group), aryloxy group (e.g. phenylthio group),
Arylthio group (e.g. phenylthio group), carbamoyl group (e.g. N-ethylcarbamoyl group), alkoxycarbonyl group (e.g. methoxycarbonyl group), aryloxycarbonyl group (e.g. phenoxycarbonyl group), sulfonyl group (e.g. benzenesulfonyl group, methanesulfonyl group), sulfamoyl group (N-ethylsulfamoyl fi), acylamino group (e.g. acetamido group, benzamide group), sulfonamide group (e.g. methanesulfonamide group, benzenesulfonamide group), acyl group ( For example, acetyl group, benzoyl group),
nitroso group, acyloxy group (e.g. ayatoxy group),
Ureido group (e.g. J-phenylureido group, 3-ethylureido group), imide group (e.g. succinimide group)
, nitro group, cyano group, heterocyclic group (a 1- to 6-membered heterocyclic ring selected from a nitrogen atom, an oxygen atom, or a sulfur atom as a hetero atom, such as a caufuryl group, a cobiridyl group, a / -imidazolyl group, an l-morpholino group) ), hydroxyl group, carboxyl group, alkoxycarbonylamino group (e.g. methoxycarbonylamino group, phenoxycarbonylamino group), sulfo group, amino group, anilino group (e.g. coumethoxyanilino group), aliphatic amino group (e.g. diethylamino group) group), sulfinyl group (e.g. ethylsulfinyl group), sulfamoylamino group (
For example, ethylsulfamoylamide 7), a thioacyl group (eg, phenylthiocarbonyl group), a thioureido group (eg, 3-phenylthioureido group), or a heterocyclic amino group (eg, imidazolylamino group).

When there is an aliphatic group in the partial structure of the above substituent, the number of carbon atoms is /~, preferably /-10, chain or cyclic, straight chain or branched, saturated or unsaturated, substituted or unsubstituted. is an aliphatic group. When the partial structure of the substituent listed above contains an aromatic group, the number of carbon atoms is 6 to 10,
Preferred is a substituted or unsubstituted phenyl group. Particularly preferred compounds of the present invention are those represented by the following general formulas (n) and (2).

General formula (II) (R)n In the general formula, A and DI represent the same meanings as explained in general formula (1), X represents a hydroxyl group or a sulfonamide group, and R represents a substituent. n represents an integer from 1 to 3, and at least one of the n R's represents a Ba1last group defined in general formula (I). When n is 2 or more, R represents the same substituent or different substituents. When λ R's represent adjacent substituents, the case where they are connected as covalent groups to represent a cyclic structure is also included.

Such benzene condensed rings are preferably benzonorbornenes, chromans, indoles, benzothiophenes, quinolines, benzofurans: 1. 'J
-dihydrobenzofurans, indanes, indenes, naphthalenes, etc. The case where these condensed rings are substituted with a substituent R is also included.

When the benzene ring or benzene condensed ring has a substituent R, preferred substituents include the substituents listed for DI above. However, when R represents a Ba1last group, the total number of carbon atoms contained in R is 10 to 3.

In the compound of the present invention, a compound separated by a coupling reaction with an oxidized developing agent (in general formula (I), RED
The following groups) are oxidized, and the development inhibitor is further cleaved through nucleophilic addition and elimination reactions.

A series of such reactions together characterize the effects of the present invention. That is, the rate of the oxidation reaction depends on the concentration of the oxidized developing agent. The reaction is fast where a large amount of oxidized developing agent is generated, and the reaction is slow where only a small amount of oxidized developing agent is generated. As a result, the development inhibitor is released at different rates. At this time, the development inhibiting effect becomes effective, and it is considered that the effects of the present invention can be obtained.

From the above explanation, it is clear that the compounds of the present invention react by a completely different mechanism from conventionally known couplers having a timing group, and therefore have different functions.

The compound of the present invention can be used in various light-sensitive materials (for example, color negative films, color reversal films, color positive films) by various known methods. It is generally used as a mixture with the main coupler, but may also be used as the main coupler.

Any layer such as a high-sensitivity layer or a low-sensitivity layer can be selected depending on the purpose.

The layer to which the compound of the present invention is added is the photosensitive silver halide-containing layer or a layer adjacent thereto.

The amount of the compound of the present invention added varies depending on the structure and use of the compound, but is preferably lx/θ-6 to 1 mol, particularly preferably 1x/θ-3 to 1 mol per mol of silver in the layer containing the compound or the adjacent layer. x10-1 mol.

The compounds of the present invention may be used alone or in combination with known couplers in a certain layer. When used in conjunction with other color image-forming couplers, the ratio of the invention metallurgy to the other color image-forming couplers (inventive coupler/other color image-forming couplers) is O8//9. 9-90/10. Preferably 3/9! ~go/se.

Examples of the compounds used in the present invention include, but are not limited to, the following compounds.

(G) OH C2H5 Next, a synthesis example of the present invention will be specifically described.

Synthesis Example 1 (Synthesis of Exemplary Compound (2)) α-pivaloyl-α-chloro-2t-chloro-3'-succinimide acetanilide, lde,32, l-pivaloyloxy-,
y-(/-phenyltetrazolylthio)-codedecylcarbamoylphenol, 22. 'It and triethylamine.

The mixture was added to acetonitrile Jθθ and heated to reflux for an hour. Cool to room temperature! f- ammonia water C, 1 t
%) and stirred at room temperature for 1 hour. Dityl acetate Sθθ-
was added and transferred to a separatory funnel and washed with water. After washing with dilute hydrochloric acid, further washing with water was performed. The oil layer was taken and the solvent was distilled off under reduced pressure. The desired coupler (2) was obtained by recrystallizing the residue from ethyl acetate and n-hexane.

Synthesis Example 2 (Synthesis of Exemplary Compound (7)) S-Fluoro-
6-methyl-coffenyl-7゜3-benzoxazole/! ;, kf1J-pentadecyluda-methoxyphenol 22.79 and t-butoxypotassium 7.6f N
, N-dimethylformamide 100- plus 1000C
The mixture was stirred for g hours. After cooling to room temperature, 500 g of ethyl acetate was added and the mixture was washed with water using a separating funnel. The oil layer was taken and the solvent was distilled off under reduced pressure. Co/crystal by crystallization using a mixed solvent of Impropatool and hexane.

3? I got it. This is referred to as intermediate l.

Potassium hydroxide io, stt with ethanol 70ml and 7
It was dissolved in a mixed solvent of z and io-, and nitrogen gas was passed through it.

2/, A;f of the intermediate 1 obtained above was added to this and heated under reflux for 2 hours. After cooling to room temperature, it was poured into dilute hydrochloric acid 500-, and the precipitated crystals were taken out. Weight after drying is /gt
Met. This is called an intermediate.

The intermediate /gfi/ was added to acetonitrile θ0- and heated to reflux. 6. l-methoxycarbonylbenzoyl chloride was added to this. rif was added in three portions. After reacting for one hour, the mixture was cooled, 1 nt of ethyl acetate was added, and the mixture was transferred to a separatory funnel and washed with water. The oil layer was concentrated and hexane was added to the residue to obtain crystals of St. This will be referred to as Intermediate 3.

Intermediate 3 79. ! ; f was added to dichloromethane 200°C and cooled to OoC. This includes boron tribromide,
S- was added dropwise. After reacting for 3 hours, the temperature was gradually returned to room temperature. A saturated aqueous sodium hydrogen carbonate solution was gradually added to this solution to neutralize the reaction solution. The mixture was transferred to a separatory funnel, washed with dilute hydrochloric acid, washed with water, and the oil layer was taken, and the solvent was distilled off under reduced pressure. Next, add 100% of acetonitrile to the residue and stir at room temperature for 6. 7-phenyltetrazolylsulfinyl chloride (A2) was added and reacted for 1 hour at room temperature. Dityl acetate 3oθ- was added to the reaction mixture and treated in the same manner as above to obtain crystals of 6f/l. The crystals were added to 200 bottles of 10% aqueous methanol in which lIr potassium hydroxide was dissolved and reacted for 3 hours. The desired coupler (7) was post-treated using a conventional method to obtain 73. I got 2 coins.

The silver halide photographic material used in the present invention may be a monochromatic color photographic material having one light-sensitive silver halide emulsion layer on a support, or a multilayer color photographic material having at least one light-sensitive silver halide emulsion layer on a support. It can also be applied to materials.

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

The same or other photographic emulsion layer or non-light-sensitive layer of the photographic light-sensitive material prepared using the present invention may be represented by the general formula (I) as described above.
Together with the compound represented by, color couplers, i.e. aromatic primary amine developers (e.g.
A compound that develops color by oxidative coupling with a phenylenediamine derivative, an aminophenol derivative, etc.) may also be used.

The silver halide multilayer color photographic light-sensitive material using the present invention usually uses yellow, magenta, and cyan color-forming couplers, or the couplers of the present invention can be used for all three colors, and if necessary, Some of the couplers of the present invention can also be replaced with conventionally known color couplers.

Useful color couplers are cyan, magenta and yellow colored couplers, typical examples of which are naphthol or phenolic non-compounds, pyrazolone or pyrazoloazole compounds and open chain or heterocyclic ketomethylene compounds. Specific examples of these cyan, magenta and yellow couplers used in the present invention can be found in Research Fist Disclosure (Re5search 1).
isclosure ) / 7AI1.3 ( / differential /
- Month) ■ - D and the patent cited in Section 71 (No. 7979).

The color coupler incorporated in the light-sensitive material is preferably diffusion-resistant by having a ballast group or being polymerized. A two-pixel color coupler substituted with a leaving group can reduce the amount of coated silver and provide higher sensitivity than a four-equivalent color coupler in which the coupling active position is a hydrogen atom. Couplers in which the color-forming dye has adequate diffusivity, non-color-forming couplers, or DIR couplers that release a development inhibitor or couplers that release a development accelerator upon coupling reaction can also be used.

A representative example of the yellow coupler that can be used in the present invention is an oil-protected acylacetamide coupler. A specific example is U.S. Patent No. 1, '1
07. -7O, same No.-, ff7s, ozq and same No.3. It is written in Ko A, SOt, issue, etc. As a two-pixel yellow coupler, US Pat.
OIr, 1. '! Da No. 3.1-992g, No. 3.933,507 and Hiromu No. 0.2, l, 2
The oxygen atom dissociative yellow coupler described in No. 0-, etc. or Tokko Sho! ;g-107.39, U.S. Patent No. Da, GuO/, 7! ;λ issue, same issue, 31t, 02
Da issue, RD/gO! ;3 (D/979), U.S. Patent No. 1゜412k, No. 020, West German Published Application No. CO, CO.
De.

No. 77, No. λ, lA/, 31. ．． / issue, same issue.

32, 3g No. 7 and the same No. 3, Da 33. A typical example is the nitrogen atom separation type yellow coupler described in GL Co. α-pivaloylacetanilide couplers have excellent color fastness, especially light fastness, while α-benzoylacetanilide couplers provide high color density.

Magenta couplers that can be used in the present invention include oil-protected indacylon or cyanoacetyl couplers, preferably pyrazoloazole couplers such as 3-pyrazolone and pyrazolotriazoles. Among the S-pyrazolone couplers, couplers in which the 3-position is substituted with an arylamino group or an acylamino group are preferable from the viewpoint of the hue and color density of the coloring dye. − No., same No. λ.

J'lJ, No. 703, No. 1,00,7gg,
Same No. 90g, No. 573, No. 3.062,633, No. 3. /! ;2,194 and the same No. 3°de 3t,
It is written in the OIS issue etc. As a leaving group for two-equivalent S-pyrazolone couplers, U.S. Patent No. d, 310.
The nitrogen atom leaving group described in AI9 or U.S. Patent No. DA, 3! ;/, the arylthio group described in No. g9'1 is particularly preferred.

Also European Patent No. 73, A31. It has a ballast group as described in the issue! - Pyrazolone couplers provide high color density.

As pyrazoloazole couplers, US Pat.
Pyrazolobenzimidazoles described in JOtsu No. 9.179, preferably pyrazolo(,t,/-C)[i,s,lI]triazoles described in U.S. Pat. , Research Disclosure: llIco2
Pyrazolotetrazoles and Research Disclosure, 21! , 23
Examples include pyrazolopyrazoles described in 0 (June 2019). European Patent No. 1/? in terms of low yellow side absorption of the coloring dye and light fastness. The imidazo(/,2-b)pyrazoles described in European Patent No. 1/Te1gAO ζ are preferred, and the pyrazolo[/, described in European Patent No. 1/Te1gAO ζ].

s-b:] [:/, 2. [g]Triazole is particularly preferred.

Cyan couplers that can be used in the present invention include oil-protected naphthol-based and phenol-based couplers, and are disclosed in U.S. Pat.

No. 293, preferably the naphthol couplers described in U.S. Patent No. DA, 0! ;2.272, same No.G.

Typical examples include the two-equivalent naphthol couplers of the oxygen atom separation type described in Japanese Patent Application No. 16,396, No. 22g, 233, and No. 1,294,200. Further, specific examples of phenolic couplers include U.S. Pat.
No. 1, No.-, 772, 16, No. 2, No. 1, ffj
, No. 114, etc. Cyan couplers that are robust to humidity and temperature are preferably used in the present invention, exemplified by U.S. Pat. No. 3.7 Cuco, 00
A phenolic cyan coupler having an alkyl group greater than or equal to an ethyl group at the meta-position of the phenol nucleus described in No. 2;
U.S. Patent No. 2,77, /A:4, U.S. Patent No. 3.7! ;za,, No. 30, No. 17. /2A, No. 391゜, No. D, 33'l, No. 0//, No. G, 3 cores.

No. 173, West German Patent Publication No. 3.32, No. 729, and % Gansho J4-1721, 7/, etc.
-Diacylamino-substituted phenolic couplers and U.S. Patent No. 3. 'I'lA, ls2, 4th and 3rd JJ,
Phenolic couplers having a phenylureido group at the co-position and an acylamino group at the 1-position, etc., as described in No. 999, Nos. TT, 1Isi, Ssd, and No. It is.

In order to correct unnecessary absorption in the short wavelength range of dyes generated from magenta and cyan couplers, it is preferable to use colored couplers in combination with color sensitive materials for photographing. U.S. Patent No. 'I,/A3. Yellow-colored magenta couplers described in ARI No. 0 and Japanese Patent Publication Sho S.C. No. 39DA No. 13, or US Pat. /DaA,,
A typical example is the magenta-colored cyan coupler described in No. 31, No. 1.

The granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Such blur couplers are described in US Pat. ;、! Specific examples of magenta couplers are given in No. 70, and European Patent No. Zorro.

Specific examples of yellow, magenta or cyan couplers are described in No. 370 and in German Published Application No. 3.13'l, No. 333.

The dye-forming couplers and the above-mentioned special couplers may form polymers that are more than duplexes. Typical examples of polymerized dye-forming couplers are described in U.S. Patent No. 3. Dasi, gkoogo and doshida,ogo.

, No. 211. Examples of polymerized magenta couplers are described in British Patent No. 2,10.2,173 and US Pat. No. 347,2g.

These couplers may be either da-equivalent or mono-equivalent to silver ions. It may also be a colored coupler that has a color correction effect or a coupler that releases a development inhibitor during development (so-called DI'R coupler).

In addition to DIR couplers, there are also colorless DIs in which the coupling-reactive product is colorless and releases a development inhibitor.
It may also contain an R coupling compound. In addition to the DIR coupler, the light-sensitive material may contain a compound that releases a development inhibitor during development.

In order to satisfy the characteristics required for a photosensitive material, two or more of the above-mentioned couplers can be used together in the same photographic layer, or the same compound can be introduced into two or more different layers. You can also do that.

In order to introduce the coupler of the present invention and the coupler which can be used in combination into the silver halide emulsion layer, known methods such as the method described in US Pat. No. 2,3.22,0 can be used. For example, phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric esters (
diphenyl phosphate, triphenyl phosphate, tric, resyl phosphate, dioctyl butyl phosphate), citric acid esters (e.g. acetyl tributyl citrate), benzoic acid esters (e.g. octyl benzoate), alkyl amides (e.g. diethyl lauryl). amides), fatty acid esters (e.g. dibutoxyethylsuccinate, diethyl azelate), trimesic acid esters (e.g. tributyl trimesate), etc.
Or boiling point 30°C or l! fO0C is dissolved in an organic solvent such as lower alkyl acetate such as ethyl acetate or butyl acetate, ethyl propionate, -butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, etc., and then dispersed in a hydrophilic colloid. be done. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be used in combination.

Also, Tokko Akira! ;/-,? Deza! r3, JP-A-5i-1
The polymer dispersion method described in No. 994# can also be used.

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.

As the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used alone or together with gelatin.

In the present invention, the gelatin may be either lime-treated or acid-treated. For details on how to make gelatin, see Arthur Guais.
Weiss), Macromolecular Chemistry of Gelatin
cular Chemistry of Qelati
nχ (Academic Press)
ess ), published in /9A'7).

Any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used as silver halide in the photographic emulsion layer of the photographic light-sensitive material used in the present invention. A preferred silver halide is silver iodobromide containing 13 moles of silver iodide or less. ! Preferred for f is silver iodobromide containing silver iodide from λ molti to 12 molti.

The average grain size of silver halide grains in a photographic emulsion (the grain size is the grain diameter for spherical or approximately spherical grains, and the edge length for cubic grains, expressed as an average based on the projected area) is Although not particularly limited, it is preferably 3μ or less.

The particle size may be narrow, wide, or porous.

Silver halide grains in photographic emulsions may have regular crystal bodies such as cubic or octahedral, or may have spherical,
It may have an irregular crystalline shape such as a plate shape, or it may have a composite shape of these crystalline shapes. It may also consist of a mixture of particles of various crystalline forms.

Further, an emulsion may be used in which ultratabular silver halide grains having a grain diameter of three times or more the grain thickness occupy SO% or more of the total projected area.

The silver halide grains may have different phases inside and on the surface. Further, the particles may be particles in which a latent image is mainly formed on the surface, or may be particles in which a latent image is mainly formed inside the particles.

The photographic emulsion used in the present invention is B. gracchide (p
-Glafkides), 1 Chimie etc.
sique photography )'
(Paul Montel/I/
) Publishing, 1946), V. L. Zelikman et al., "Making and Coating Photographic Emulsions"
photographic emulsion)”
('l'he Focal Press)
It can be adjusted using the method described in, for example, published by Press) Sha, /fAII). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. good.

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 form of the simultaneous mixing method, a method of keeping I) Ag in the layer phase in which silver halide is produced, ie, 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.

Silver halide emulsions of λ or higher types formed separately may be mixed and used.

In the process of silver halide grain formation or physical ripening, a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be allowed to coexist.

Silver halide emulsions are usually chemically sensitized.

For chemical sensitization, for example, an etch fuser (H
, Fieser) ed.
Silver Halogen Niden(, [)ieQrundla
gender photography p
rozessemit 5ilber Halogen
iden)” (Akademischeverlagschaft)
esellschaft), 194g), No. 673
Page 34! You can use the method described in Tei.

Namely, sulfur sensitization using compounds containing sulfur that react with active gelatin and silver (e.g., thiosulfates, thioureas, mercapto compounds, rhodanines); reducing substances (e.g., stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds); noble metal compounds (e.g. total complex salts, pt, I
A noble metal sensitization method using complex salts of metals of group 1 of the periodic table such as r, pd, etc. can be used alone or in combination.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. Namely, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. such as benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially l-phenyl-!-mercaptotetrazole); mercaptopyrimidines; mercaptotriazines; Zaindenes, tetraazaindenes (%1cp-hydroxy-substituted (/, 3.3a, ri) tetraazaindenes), pentaazaindene nato; henzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid Many compounds known as antifoggants or stabilizers can be added, such as amides and the like.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared using the present invention may contain coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and photographic property improvement (e.g.
Various surfactants may be included for various purposes such as development acceleration, high contrast, and sensitization.

The photographic emulsion layer of the photographic light-sensitive material of the present invention contains, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholines, quaternary ammonium salt compounds, urethane derivatives,
It may also contain urea derivatives, imidazole derivatives, 3-pyrazolidones, and the like.

The photographic material used in the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer in the photographic emulsion layer or other hydrophilic colloid layer for the purpose of improving dimensional stability. For example, alkyl acrylate, alkyl methacrylate, alkoxyalkyl acrylate, alkoxyalkyl methacrylate, glycidyl acrylate, glycidyl methacrylate, acrylamide, methacrylamide, vinyl ester (e.g. vinyl acetate), acrylonitrile, olefin, styrene, etc. alone or in combination, or Acrylic acid, methacrylic acid, α
, β-unsaturated dicarboxylic acid, hydroxyalkyl acrylate, hydroxyalkyl methacrylate, sulfoal, 5-kyl acrylate, sulfoalkyl methacrylate, styrene sulfonic acid, and the like can be used.

The photographic emulsions used in the present invention may be spectrally sensitized with methine dyes and others. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, viroline nucleus, oxazoline nucleus, thiazoline nucleus, virol nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus,
Pyridine nuclei, etc.; Nuclei in which an alicyclic hydrocarbon ring is fused to these nuclei; and nuclei in which aromatic hydrocarbon rings are fused to these nuclei, i.e., indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxane nucleus, etc. Dole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus, etc. are applicable. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or composite merocyanine dyes have a ketomethylene structure-containing nucleus, such as a pyrazolin-3-one nucleus, a thiohydantoin nucleus, a cortioxazolidine nucleus, a terdione nucleus, a thiazolidine nucleus, a terdione nucleus, a rhodanine nucleus, and a thiobarbyl acid nucleus. A-membered heteroartic ring nuclei can 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.

Along with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
A substance exhibiting supersensitization may also be included in the emulsion. for example,
Aminostyl compounds substituted with nitrogen-containing heterocyclic groups (for example, U.S. Patent No. 933.390, J, 4,7j
, 7co/issue), aromatic organic acid formaldehyde condensates (for example, those described in U.S. Patent A, q'q3.rio
(described in the above issue), cadmium salts, azaindene compounds, etc.

The photographic material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer or other hydrophilic colloid layer.

For example, chromium salts (chromium alum, chromium acetate, etc.)
, aldehydes, (formaldehyde, cryoxal, geltaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (co, 3-dihydroxy dioxane, etc.), activated vinyl compounds (t, 3.s -Triacryloyl-hexahydro-8-)riazine, 1.3-
(vinylsulfonyl-coprobanol, etc.), active halogen compounds (co-, 6-hydroxy-s-
triazines, etc.), mucohalogen acids (mucochloric acid,
mucophenoxychloric acid, etc.), etc. can be used alone or in combination.

In the photosensitive material produced using the present invention, when dyes, ultraviolet absorbers, etc. are contained in the hydrophilic colloid layer, they may be mordanted with a cationic polymer or the like.

The photosensitive material produced using the present invention may contain a hydroquinone derivative, an aminephenol derivative, or the like as a color antifoggant.

The photosensitive material produced using the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, benzotriazole compounds substituted with aryl groups (e.g. those described in U.S. Pat.
Hirogo, same 3.3S.

6g1), benzophenone compounds (e.g., those described in JP-A-27GlI), cinnamic acid ester compounds (e.g., U.S. Pat.
No. 3. RiOri, 37! (as described in US Pat. No. 1), butadiene compounds (e.g., US Pat.

0'l! ! , No. 2 Cobb), or benzoxazole compounds (e.g., those described in U.S. Pat.
4t! ! It is also possible to use the r number ζ (described here).

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

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, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful.

In carrying out the present invention, the following known anti-fading 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 antifading agents include hydroquinone derivatives, gallic acid derivatives, p-alkoxyphenols, p-oxyphenol derivatives, and bisphenols.

Photographic processing of layers comprising photographic emulsions made using the present invention includes, for example, Research Disclosure No. 74 No. 2
Any of the known methods and known treatment liquids as described on pages g to 30 can be applied. The processing temperature is usually chosen between 7g0c and zo0c, but t
The temperature may be lower than t 0c or higher than Sθ0C.

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, such as phenylene diamines (e.g., guamino-N, N-diethylaniline, 3-methyl-guamino-N, N-') ethylaniline, guamino-N
-Ethyl-N-β-hydroxyethylaniline 1.7-
Methylder-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-guamino-N-dithyl-N-β-methanesulfamide ethylaniline, guamino-3-methyl-N-ethyl-N-β- This can be done by using methoxyethylaniline, etc.).

In addition, F.N. Mason (F, A.

"Photographic Processing - I Misunderstood" by David Mason,
essingChemistry)” (Focalpress, 7766), pages 6 to λ29, U.S. Patent Co., /9J, 0/
! I, same, j? 2.36 Hiro issue, JP-A Show 1lt-A'
Those described in 1fJJ issue 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 include. Also, if necessary, water softeners, preservatives such as hydroxylamine,
Organic solvents such as benzyl alcohol, diethylene glycol, polyethylene glycol, quaternary ammonium salts,
Development accelerators such as amines, dye-forming couplers, competitive couplers, fogging agents such as sodium boron hydride, auxiliary developers such as /-phenyl-3-pyrazolidone, viscosity-imparting agents, polycarboxylic acid chelating agents, antioxidants. It may also contain agents.

After color development, the photographic emulsion is usually bleached.

The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. Examples of bleaching agents include polyvalent golds such as Tetsumen, Kobal HID, Chromium (Corporate), and Copper (II).

Compounds of the genus, peracids, quinones, nitroso compounds, etc. are used.

For example, ferricyanide, dichromate, organic complex salts of iron(2) or cobalt(IB), aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, 1,3-diamino-propanol-hydroacetic acid, or Complex salts of organic acids such as citric acid, tartaric acid, and malic acid; persulfates, permanganates, and nitrosophenols can be used. Among these, potassium ferricyanide, iron sodium ethylenediaminetetraacetate, and iron [phase] ammonium ethylenediaminetetraacetate are particularly useful.

Ethylenediaminetetraacetic acid iron complex salts are useful in both stand-alone bleach solutions and -bath bleach-fix solutions.

As the fixer, one having a commonly used composition can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as fixing agents can be used. The fixing solution may contain a water-soluble aluminum salt as a hardening agent.

Here, after the fixing step or bleach-fixing step, washing with water,
Although it is common practice to perform a treatment process such as stabilization, it is also possible to perform only a water washing process or, conversely, to perform only a stabilization process without providing a substantial water washing process (%
-g! It is also possible to use a simple processing method such as Publication No. 4#).

The washing water used in the washing step may contain known additives, if necessary. For example, chelating agents such as inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid,
Bactericidal agents and antifungal agents to prevent the growth of various bacteria and algae, hardening agents such as magnesium salts and aluminum salts, surfactants to prevent drying load and unevenness, etc. can be used. Or L.E. West (L, E.

West), “Water Quality Criteria
)” Photographic Science and Engineering (photo+Sci, and, [ng,
), vOl, DeNllApagN11Apa ~3!
;De(/?lt) etc. can also be used.

Further, the water washing step may be carried out using a cypress tank or more if necessary, and multistage countercurrent water washing (for example, 2 to 9 stages) (l!
- The amount of water used for rinsing may be reduced.

As the stabilizing liquid used in the stabilizing step, a processing liquid that can stabilize a dye image is used. For example, a solution having a buffering capacity of pH 3 to O, a solution containing an aldehyde (for example, formalin), etc. can be used. Optical brighteners, chelating agents, bactericidal agents, antibacterial agents, hardeners, surfactants, and the like can be used in the stabilizing liquid as necessary.

・Also, the stabilization process may be carried out using more than one tank if necessary, and multi-stage countercurrent stabilization (e.g. co-stage)
As a result, the amount of stabilizing liquid can be reduced, and the water washing step can also be omitted.

(Examples) The present invention will be described in detail below using Examples, but the present invention is not limited to these Examples.

Example 1 A multilayer color photosensitive material sample was prepared on a polyethylene terephthalate film support, each layer having the composition shown below.

First layer; antihalation layer; gelatin layer containing black colloidal silver; first layer; middle layer! - Third layer of gelatin layer containing an emulsified dispersion of D-t-octylhydroquinone; First red-sensitive emulsion layer Silver iodobromide emulsion (silver iodide; jmolti)...Silver coating amount
/, A f/m2 Sensitizing dye I--Da for 1 mole of fist silver! ;X10 mole sensitizing dye ■.../ per mole of silver/! ;×10 mole coupler EX-/・0 per mole of silver, OJ! i mole coupler EX-3・0.00J per 7 moles of silver Mol 2nd layer; 2nd red-sensitive emulsion layer Silver iodobromide emulsion (silver iodide;/θ mole)...Silver coating amount i, lIy /m2 Sensitizing dye ■...Jx/θ mole per 1 mole of silver Sensitizing dye ■...For 7 moles of silver /×IO mole coupler EX-/・0 for 1 mole of silver 600 Comol coupler EX-λ・O for 1 mole of silver, O comol coupler EX-,?・0,00/for 1 mole of silver
6 mole S layer; same as the second intermediate layer 6th layer: first green-sensitive emulsion layer Silver iodobromide emulsion (silver iodide: 6 moles)...Silver coating amount
/, try/m2 Sensitizing dye ■...zxio mole per mole of silver Sensitizing dye ■...φ・CoX10 mole coupler EX-! per mole of silver・O, OS per mol of silver Molar coupler EX-j ・0.00 g per mol of silver Molar coupler EX-TA ・O, oois per mol of silver 7th layer; 1st positive emulsion layer Silver iodobromide emulsion (silver iodide; t mole)...silver coating amount
/ , J t / m 2 Sensitizing dye ■...3 x 10 mol per 1 mol of silver Sensitizing dye IV-.../, Co x 10 mol Coupler EX-7, silver O per mole. 0/7 molar coupler EX-A - 0.00 J molar per mole of silver 3rd layer: yellow filter layer Yellow colloidal silver in gelatin aqueous solution, 2. ．． 11--
Gelatin layer containing an emulsified dispersion of di-t-octylhydroquinone Second layer: First positive emulsion layer Silver iodobromide emulsion (silver iodide; 6 mol %)...Silver coating amount
0.7 fif/m2 Coupler EX-Z Φ O per mole of silver, λ S mole Coupler EX-9 @ 0.0/ per mole of silver! k mole io layer; blue-sensitive emulsion layer silver iodobromide (silver iodide; 6 mol%)...Silver coating amount θ,
&f/m2 Coupler EX-fφ 0.06 mol per 1 mol of silver 11th layer; First protective layer silver iodobromide (1 mol of silver iodide, average grain size θ, 0 μ)
... Silver coating amount o, st/m2 Ultraviolet absorber UV
Gelatin layer 7th λ layer containing an emulsified dispersion of -/; 7th protective layer A gelatin layer containing polymethylmethanoacrylate particles (diameter approximately Sμ) is coated.

In addition to the above composition, gelatin hardening agent H-7 and a surfactant were added to each layer. The sample prepared as described above was designated as sample 10/.

Preparation of Samples 10 to 10 Samples were prepared in the same manner as Sample 10/, except that coupler EX-9 in the low green-sensitive emulsion layer of Sample 10/ was changed as shown in Table 7.

Sample 10/~/θ samples were wedge exposed to sunlight,
When the processing described below was carried out, almost the same sensitivity and 151f tone were obtained. The sharpness of the green sensitive layer of these samples was evaluated using a conventional MTE value.

The structural formula of the compound used is as follows.

Compound used to prepare the sample EX-CoEX-,7 x-p EX-j EX-4 (?j EX-7 where (t)Cs H17 is (CHa)30CH2C
(CH3) represents 2-.

EX-Z EX-9 (Conventional DIR Coupler) EX-,10 (EX-// (U.S. Pat. No. j, A/!r,!) as described in U.S. Pat. No. 1112,6λ9
06) H-/CH2=CH-802-CH2-CONH-CH3I CH2=CH-802-CH2-CONH-CH2 coupler) UV-/x/y=7/s (weight ratio ) Sensitizing dye■ Sensitizing dye■ (CH2)ssO3H@N(CzHs) 3 Sensitizing dye■ Sensitizing dye■ 2H5 Na5O3(CH2)3(OCHzCH2)zDeveloped at 3g 0C according to the following processing steps .

Color development 2 minutes 73 seconds Bleach White 6 minutes 30 seconds Washing with water Washing 2 minutes 10 seconds Fixed arrival time: 20 seconds Water Washing 3 minutes 75 seconds Stable Fixed 1 minute OS seconds The composition of the treatment liquid used in each step was as follows.

Color developer diethylenetriaminepentaacetic acid/, 0fl-hydroxyethylidene-/.

l-diphosphonic acid 2.02 Sodium sulfite a, or potassium carbonate
30. Ofpotassium bromide
1. Potassium iodide / ,
, 711v hydroxylamine sulfate J, lI
s' goo (N-ethyl-N-β-hydroxyethylamine)-1-methylaniline sulfate 9. Add JP water
1. θt9H10,0 Bleach solution ethylenediaminetetraacetic acid ferric ammonium salt ioθ, Of ethylenediaminetetraacetic acid disodium salt 10. Of ammonium bromide /kO, Of ammonium nitrate
10.0F Add water
/,01pHA,.

Fixer Ethylenediaminetetraacetic acid disodium salt 1. θ2 Sodium sulfite tt, or ammonium thiosulfate water bath solution (70%) 173.0ml Sodium bisulfite da, Af Add water
/, 01 pHb, b Stabilized formalin (4tO), Otd Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization: 10) o, 3 by adding water /, OL Regarding the obtained sample / m The MTF values of 3 m3 lida and 90 green sensitive layers were measured. The results are shown in Table-7.

Table 7 *Represents a compound added in place of coupler EX-9 in the first green-sensitive layer.

**Displayed as a molar ratio when the number of moles of EX-9 added is 1.

It is clear from the table that the couplers of the present invention significantly improve sharpness compared to conventional DIR couplers.

Claims (1)

[Scope of Claims] A color photographic material characterized by containing a coupler represented by the following general formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, A represents a coupler residue that cleaves the bond between A and RED by reaction with an oxidized developing agent and produces an alkali-soluble dye or colorless compound itself. ,RED
represents a group that cleaves DI through a reaction process in which it is oxidized after cleavage from A, DI represents a development inhibitor, and Balla
st represents an organic atomic group for making the compound represented by the above general formula diffusion resistant.