JPS61240240A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a color photographic sensitive material superior in sharpness, graininess, and color reproductivity, and high in sensitivity by using a coupler to be allowed to release a compd. by the coupling reaction with the oxidation product of a color developing agent, and allowing said compd. to be oxidized and to release the precursor of a photographic useful group. CONSTITUTION:The coupler is represented by the formula: A-RED-B in which A is a coupler residue to be allowed to release RED-B by the coupling reaction with the oxidation product of a color developing agent; RED-B is a group to be allowed to release B again by the oxidation reduction reaction with the oxidation product of a color developing agent; A is a residue of yellow coupler (open-chain ketomethylene, etc.), a residue of non-coloring coupler (indanon, acetophenone, etc.) or the like, and B is a precursor capable of producing a photographic useful group, such as a development inhibitor, development accelerator, foggant, dye, or competitive reaction compd. It is preferred for the group RED to combine with the coupler residue A through the O atom of the OH group of an aromatic alcohol by replacing H of the OH group.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a color photographic light-sensitive material containing a novel compound capable of making photographically useful groups available during development processing. .

(Prior Art) Many studies have been carried out on subtractive color photographic materials with the aim of improving sharpness, graininess, color reproducibility, and increasing sensitivity.

One such technology is couplers that release photographically useful groups. In addition to couplers that release a photographically useful group from the coupling position of the coupler, couplers that release a photographically useful group from the coupling position via a timing group have recently been disclosed. For example, U.S. Patent No. G, 24tr,
Ribu No. 2, same <1. <10? , No. 323, etc. On the other hand, in another attempt, an example of releasing a coupler that releases a photographically useful group from the coupler was presented in US Patent No. Q, 4tJ? , No. 93 discloses.

Although these known couplers have a certain degree of performance, they are still insufficient, and further improvements have been desired.

That is, recent high-sensitivity photosensitive materials, such as SO/600
In color negative films, the size of silver halide is increased to increase sensitivity, so it is an undeniable fact that graininess becomes noticeable, and improvements have been desired.

Furthermore, since the film size of disc cameras, which are convenient to carry, is small, the enlargement magnification during printing is large, and it is necessary to further improve the sharpness of images.

(Object of the Invention) Accordingly, an object of the present invention is to provide a color photographic material with excellent sharpness, graininess, or color reproducibility, or with high sensitivity.

(Structure of the Invention) The above object is to provide at least one compound characterized in that, after a coupling reaction with an oxidized developing agent, the cleaved compound is oxidized to produce a precursor of a photographically useful group. This was achieved by a silver halide color photographic light-sensitive material containing:

Preferred couplers used in the present invention have the following general formula (I
).

General formula (1) % formula % In the formula, the compound reacts with the oxidized developing agent to produce RE.
Represents a coupler residue that releases D-B, and R[D represents a group that releases B after the bond with A is cleaved and undergoes a redox reaction with the oxidized developing agent; Represents a group that produces a photographically useful group after cleavage.

In general formula (I), A specifically refers to yellow coupler residues (open-chain ketomethylene couplers, etc.), magenta coupler residues (!-pyrazolone, pyrazolotriazole, pyrazoloimidazole, etc.), cyan coupler residues (phenol, naphthol, etc.) ), colorless coupler residues (indanone, acetophenone, etc.).

As the yellow coupler core, for example, U.S. Patent Nos. 3 and 2
6j, jO6, same, r7j, θ! No. 2, 3.4t
Or, /94, JP-A-4TR-294T32, q♂-44/j4, same! Goo/33 Kota, 1O
-r7tjO, etc., and as magenta coupler cores, U.S. Pat.
042. Otsu! No. 3, same 3, /λ72.2≦No. 3, same 3,
4t/ri, 3ri No. 7, same 3. ! /ri, 4t Kota, same j
, Ill, No. 670, JP-A-Sho Geter No. 111631, same! Tar/7/rij6, same! Those described in U.S. Pat. ≦, No. 543, same a, 009.0
Issue 3j, same evening! ! ! , Tade 9, Tokukai Sho! θ−／／
Ko03r, Koko10-//741 Koko, jj-32
No. 077, j3-10ri No. 630, Research Disclosure
), 4/j741/, JP-A-Shoj7-204t!
Examples include those described in No. 4tj.

Furthermore, U.S. Pat. Wow! ! , Tade No. 3, same 3. Ri6/, Ri! Examples include those listed in the No.

Furthermore, the present invention is particularly effective because the general formula (1
), a person has the following general formula (Cp −/), (Cp-2
), (Cp-J), (Cp-4'), (Cp-j), (
Cp-≦), (Cp-7), (Cp-#), (Cp-?
), (Cp-10) or (Cp-//). These couplers are preferred because of their high coupling speed.

General formula (Cp −/) General formula (Cp-co) General formula (Cp-j) General formula (Cp-4t) General formula (Cp-j) General formula (Cp-a) General formula (Cp-y) General Formula (Cp-♂) General formula (Cp-ta) General formula (Cp-10) General formula (Cp-//) In the above formula, the free bond derived from the coupling position is the bond of the coupling-off group Indicates the position @ in the above formula・R61・R62・R'ss・R54%fL65
s R56s R67s R158% ”69%BJ
If R60 or R61 contains a diffusion-resistant group, it is selected such that the total number of carbons is /~3.2, preferably 10-22 - otherwise the total number of carbons is /!
The following are preferred.

Next, the formulas (CI)-/) to (Cp-//) [
11 to RatjL, m and p will be explained.

In the formula, R'st represents an aliphatic group, an aromatic group, an alkoxy group, or a heterocyclic group, and R52 and RIS3 each represent an aromatic group or a heterocyclic group.

In the formula, the aliphatic group represented by R51 preferably has 4 to 2-2 carbon atoms and may be substituted or unsubstituted, chain-like 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 R'at are: isopropyl, isobutyl, tart-butyl, isoamyl, tert-amyl, /, /-dimethyl. Butyl group, /, /-dimethylhexyl group, /, /-diethylhexyl group, dodecyl group, hexadecyl group, octadecyl group, cyclohexyl group, -1methoxyisozolopyl group, cophenoxyisopropyl group, 2-p- tert-butylphenoxyisopropyl group, α-aminoisopropyl group, α-(diethylamino)isopropyl group, α-(succinimide)isopropyl group, α-(phthalimide)
Examples include isopropyl group and α-(benzenesulfonamido)isopropyl group.

When "51", "62" or "53" contains an aromatic group (% phenyl group), the aromatic group may be substituted. Aromatic groups such as phenyl groups include alkyl groups having 3 or less carbon atoms, alkenyl groups, alkoxy groups, alkoxycarbonyl groups, alkoxycarbonylamino groups, aliphatic amide groups, alkylsulfamoyl groups, alkylsulfonamide groups, and alkylureido groups. The alkyl group may be substituted with a group, 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. The aryl group may be further substituted with one or more alkyl groups having a total number of carbon atoms of / to -2-2.

The phenyl group represented by "51", "52" or R63 further includes an amino group, including one substituted with a lower alkyl group having a carbon number/~, hydroxyl group, carboxy group, sulfo group, nitro group, cyano group, It may be substituted with a thiocyano group or a halogen atom.

R'st%R52 or R'ss may also represent a substituent 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. These substituents may themselves have further substituents.

When R51 represents an alkoxy group, the alkyl moiety represents a linear or branched alkyl group, alkenyl group, cyclic alkyl group, or cyclic alkenyl group having 7 to 32 carbon atoms, preferably 7 to -2-2 carbon atoms. , these may be substituted with a halogen atom, an aryl group, an alkoxy group, or the like.

When R51, R52 or R'ss represents a heterocyclic group, the heterocyclic group connects the carbon atom of the carbonyl group of the acyl group in alpha acylacetamide or the amide group through one of the carbon atoms forming the ring, respectively. Combines with nitrogen atoms. Examples of such heterocycles include thiophene, furan, pyran, pyrrole, pyrazole, pyridine, pyrazine, pyrimidine, biritazine, indolizine, imidazole, thiazole, oxazole, triazine, thiadiazine, and oxazine. These may further have a substituent on the ring.

In the general formula (Cp-s), R55 is a linear or branched alkyl group having from 3.2 to 22 carbon atoms (for example, methyl, isopropyl, tert-butyl, hexyl, dodecyl, etc.); Alkenyl groups (e.g. allyl group, etc.), cyclic alkyl groups (e.g. cycloanthenyl group, cyclohexyl group, norbornyl group, etc.), aralkyl groups (e.g. benzyl, β-phenylethyl group, etc.), cyclic alkenyl groups (e.g. cycloanthenyl group, cyclohexenyl group, etc.), and these represent halogen atoms, nitro groups, cyano groups, aryl groups, alkoxy groups,
Aryloxy group, carboxy group, alkylthiocarbonyl group, arylthiocarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, sulfo group, sulfamoyl group, carbamoyl group, acylamino group, diacylamino group, urei subgroup, 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-alkylanilino group, N - May be substituted with an acylanilino group, a hydroxyl group, a mercapto group, etc.

Furthermore, R5g may represent an aryl group (eg, phenyl group, α- or β-naphthyl group). 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, cyano 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, R'ss is a heterocyclic group (for example, a !- or e-membered heterocyclic group 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 groups substituted with the substituents listed for the above aryl group, aliphatic! ? , : may represent an acyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkylcarbamoyl group, an arylcarbamoyl group, an alkylthiocarbamoyl group, or an arylthiocarbamoyl group.

In the formula, R54 is a hydrogen atom, carbon number / to 3-1, preferably / to J, 2 straight chain or branched alkyl, alkenyl, cyclic alkyl, aralkyl, cyclic alkenyl group (
These groups may have the substituents listed for R'ss above), aryl groups and heterocyclic groups (which may have the substituents listed for R'ss above),
Alkoxycarbonyl group (e.g., methoxycarbonyl group, ethoxycarbonyl group, stearyloxycarbonyl group, etc.), Roxycarbonyl group (e.g., phenoxycarbonyl group, naphthoxycarbonyl group, etc.) 1,
Aralkyloxycarbonyl groups (e.g. indyloxycarbonyl group, etc.), alkoxy groups (e.g. methoxy group, ethoxy group, heptadecyloxy group, etc.), aryloxy groups (e.g. phenoxy group, tolyloxy group, etc.), alkylthio groups (e.g. ethylthio group) ,
dodecylthio group, etc.), arylthio group (e.g. phenylthio group, α-naphthylthio group, etc.), carboxy group,
Acylamino group (e.g. acetylamino group, 3 ((2
t”-G ter t-amylphenoxy)acetamide] benzamide group, etc.), diacylamino group, N
-Alkylacyl amino groups (e.g. N-methylzolopionamide group, etc.), N-arylacylamide groups (e.g. N-phenylacetamide group, etc.), ureido groups (e.g. ureido, N-arylureido, N-alkylureido groups) ), urethane group, thiourethane group, arylamino group (e.g. phenylamino, N-methylanilino group, diphenylamino group, N-acetylanilino group,
- One Roro! -tetradecanamide anilino group, etc.)
, alkylamino groups (e.g. n-butylamino group, methylamino group, cyclohexylamino group, etc.), cycloamino groups (e.g. lydino group, pyrrolidino group, etc.), heterocyclic amino groups (e.g. goupyridylamino group, -1 benzoxazorylamino group, etc.), alkylcarbonyl group (e.g., methylcarbonyl group, etc.), carbonyl group (e.g., phenylcarbonyl group, etc.), sulfonamide group (e.g., alkylsulfonamide group, arylsulfonamide group, etc.) , carbamoyl group (e.g. ethylcarbamoyl group, dimethylcarbamoyl group, N-phenylcarbamoyl, N-phenylcarbamoyl, etc.), sulfamoyl group (looking forward: N-alkylsulfamoyl, N,N-dialkylsulfamoyl group) , N-arylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, N,N-diarylsulfamoyl group, etc.), cyano group, hydroxy group, and sulfo group.

In the formula, R56 is a hydrogen atom or a linear or branched alkyl group having 1 to 32 carbon atoms, preferably / to 22 carbon atoms,
It represents an alkenyl group, a cyclic alkyl group, an aralkyl group, or a cyclic alkenyl group, which may have the substituents listed for R'ss above.

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

R'sa also represents 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, ureido group, urethane group, sulfonamide group, arylsulfonyl group, alkylsulfonyl group, arylthio group, alkylthio group,
alkylamino group, dialkylamino group, anilino group,
N-acetylanilino group, N-alkylanilino group, N
It may also represent a -7 sylanilino group or a hydroxyl group.

R57, 几58 and R59 each represent a group used in a conventional Buddha-equivalent type phenol or α-naphthol coupler, specifically R5? is a hydrogen atom,
Examples include halogen atom, alkoxycarbonylamino group, aliphatic hydrocarbon residue, N-aryl ureido group, acylamino group s 0-R62 or -8-R62 (however, 几62 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.

Further, when these substituents include an aryl group, the aryl group may have the substituents listed for R6 above.

Examples of R6B and R+ss 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 have substituents. Including those with. Further, R5g and R'se may cooperate to form a nitrogen-containing heterocyclic nucleus.

The aliphatic hydrocarbon residues may be either saturated or unsaturated, and may be linear, linear, or
Any ring-shaped one may be used. Preferred are alkyl groups (e.g., methyl, ethyl, propyl, isopropyl, butyl, t-butyl, isobutyl, dodecyl, octadecyl, cyclobutyl, cyclohexyl, etc.) and alkenyl groups (e.g., allyl, octenyl, etc.). .

Aryl groups include phenyl groups, naphthyl groups, etc.
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, substituted amino, sulfo, alkyl, alkenyl, aryl, peterocycle, alkoxy, Ori-ruoxy, arylthio, arylazo, acylamino, carbamoyl, ester, acyl, acyloxy, sulfonamide, sulfamoyl,
Examples include groups such as sulfonyl and morpholino.

L is an integer of /~g, m is an integer of /~3, and p is an integer of /~! represents an integer.

1Rao is an arylcarbonyl group, an alkanoyl group having λ to 3-2 carbon atoms, preferably 2 to 22 carbon atoms, an arylcarbamoyl group, an alkanecarbamoyl group having 2 to 3-2 carbon atoms, preferably Co-Yuko alkanecarbamoyl group, preferably 3-2 carbon atoms; Precisely/~2
2 represents an alkoxycarbonyl group or an aryloxycarbonyl group, which may have a substituent, and examples of the substituent include an alkoxy group, an alkoxycarbonyl group, an acylamino group, an alkylsulfamoyl group, an alkylsulfonamide group, and an alkyl group. Succinimide group, No.1
0gen atom, nitro group, carboxyl group, nitrile group,
Such as an alkyl group or an aryl group.

R61 is an arylcarbonyl group, an alkanoyl group having 2 to 32 carbon atoms, preferably -2.2 carbon atoms, an arylcarbamoyl group, and an arylcarbamoyl group having 2 to 32 carbon atoms, preferably 2 to 2! , 2 alkanecarbamoyl groups, carbon numbers/~3λ, preferably /~-1 alkoxycarbonyl groups or aryloxycarbonyl groups, carbon numbers/~3.2, preferably /~2 alkylsulfonyl groups, arylsulfonyl groups, aryl group,
j-membered or 4-membered heterocyclic group (the hetero atom is selected from a nitrogen atom, an oxygen atom, a sulfur atom, such as a triazolyl group, an imidazolyl group, a phthalimide group, a succinimide group, a furyl group, a pyridyl group, or an incitriazolyl group) ), which may have the substituent described above for R+go.

Among the above coupler residues, yellow coupler residues include general formula (Cp-/) in which R51 is a t-butyl group or a substituted or unsubstituted aryl group, and the 8th ring is a substituted or unsubstituted aryl group. It is preferred that R52 and R53 represent a substituted or unsubstituted aryl group in the general formula (Cp--2).

Preferred magenta coupler residues are of the general formula (C
When R54 in general formula (Cp-4t) represents an acylamino group, a ureido group, or an arylamino group, and R'ss represents a substituted aryl group, R54 in general formula (Cp-4t)
is an acylamino group, a ureido group, or an arylamino group, and when R56 represents a hydrogen atom, and the general formula (
R54 and R in Cp-j) and (Cp-f)
'ss represents a linear or branched alkyl group, alkenyl group, cyclic alkyl group, aralkyl group, or cyclic alkenyl group.

Preferred cyan coupler residues have the general formula (Cp
When R57 in -7) represents an acylamino group or ureido group at the 2nd position, an acylamino group or an alkyl group at the 5th position, and a hydrogen atom or a chlorine atom at the 5th position, and R57 in the general formula (Cp-9), a hydrogen atom at position 5, an acylamino group, a sulfonamide group, an alkoxycarbonyl group, R58 is a hydrogen atom, and R51
This is the case where 1 represents a phenyl group, an alkyl group, an alkenyl group, a cyclic alkyl group, an aralkyl group, or a cyclic alkenyl group.

Preferred as colorless coupler residues are General 1
In formula (Cp-/θ), R'sy represents an acylamino group, sulfonamide group or sulfamoyl group, and in general formula (Cp-//), R'ao and R61 represent an alkoxycarbonyl group.

Further, any part of R51 to R61 may form a bis-form or higher polymer, and a heptad polymer or a non-bis polymer having an ethylenically unsaturated group in any part of these groups may be formed. It may also be a copolymer with a color-forming monomer.

When the coupler residue of the present invention represents a polymer, it is a polymer derived from a monomeric coupler represented by the following general formula (Cp-/, 2) and having a repeating unit represented by the general formula (Cp-/j). , or a non-chromogenic monomer containing at least 7 ethylene groups that does not have the ability to couple with the oxidized form of an aromatic primary amine developing agent.
It means a copolymer with more than one species. Here, two or more types of monomer couplers may be simultaneously polymerized.

General formula (Cp-72) CH2-C+A 27TtA s +TeA s fH
Q General formula (Cp-/J) 1←CH2-C→- Person 2 sho HA 3 Length 6 A 1 piece Q J In the formula, R is a hydrogen atom, number of carbon atoms / ~ lower alkyl group on the French side,
or represents a chlorine atom, A1 is 100NR'-1-N
R' C0NB, '-1-NR' COO-1-CO
O-1-SO2-1-〇〇-1-N㇠C0-1-8O2
NR'-1-NR' 802-1-OCO-1-0CO
NR'-1-NR' - or -〇-, A2 is -
CONR'- or -C00-, R' represents a hydrogen atom, an aliphatic group or an aryl group, and when there are two or more R's in the molecule, they may be the same or different. A
3 represents an unsubstituted or substituted alkylene group, an aralkylene group, or an unsubstituted or substituted arylene group having 7 to 70 carbon atoms, and the alkylene group may be linear or branched.

(Alkylene groups include methylene, methylmethylene, dimethylmethylene, dimethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, decylmethylene, aralkylene groups include benzylidene, arylene groups include phenylene, naphthylene, etc.) Q is In any part of 几1 to R11 of the general formulas (Cp-/) to (Cp-//), the general formulas (Cp-7,
2) or a group bonded to (Cp-/j).

'sJs and k represent 0 or /.

Examples of substituents for the alkylene group, aralkylene group, or arylene group represented by A3 include aryl group (e.g. phenyl group), nitro group, hydroxyl group, cyano group, sulfo group, alkoxy group (e.g. methoxy group), aryloxy group ( (e.g., phenoxy group), acyloxy group (e.g., acetoxy group), acylamino group (e.g., acetylamino group), sulfonamide group (e.g., methanesulfonamide group), sulfamoyl group (e.g., methylsulfamoyl group), halogen atom (e.g., fluorine, (chlorine, bromine, etc.), carboxy groups, carbamoyl groups (eg, methylcarbamoyl groups), alkoxycarbonyl groups (eg, methoxycarbonyl groups, etc.),% sulfonyl groups (eg, methylsulfonyl groups). When there are two or more of these substituents, they may be the same or different.

Next, non-color-forming ethylene-like monomers that do not couple with the oxidation products of aromatic-grade amine developers include acrylic acid, α-chloroacrylic acid, α-alkyl acrylic acid, and derivatives of these acrylic acids. Examples include esters or amides, methylenebisacrylamide, vinyl esters, azirylonitrile, aromatic vinyl compounds, maleic acid derivatives, vinylpyridines, and the like. Two or more kinds of the non-color-forming ethylenically unsaturated monomers used here can also be used at the same time.

In the general formula (I), RED is preferably a λ hydroquinone, catechol, pyrogallol, naphthohydroquinone, ortho- or nocera-position amine group-substituted phenol (the amino group is a sulfonyl group, an aliphatic group, an aromatic group or may be substituted with a heterocyclic group, etc.),
Examples include bisphenols or compounds in which the benzene ring portion of the above compounds is replaced with a nitrogen-containing aromatic group (eg, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, quinoline ring, isoquinoline ring, etc.).

Preferably, the precursor of the photographically useful group represented by B in the general formula (1) is a group that is converted into a photographically useful group after being cleaved from RED, or is further cleaved after being cleaved from RED. Represents a group that causes a reaction and releases a photographically useful group.

As an example of a group which changes into a photographically useful group after being cleaved from RED, West German Published Patent Application (OL8) No. J, 307
, the development inhibitor precursor described in J-Otk. The development inhibitor precursor described in this patent is! -anilino/, l, J, 4t-thiatriazole. This compound itself does not have a development inhibiting effect, and exhibits a development inhibiting effect only when it reacts with an alkali during development to cause a rearrangement reaction to produce j-mercapto-/-phenyltetrazole.

Preferred examples of the group which, after being cleaved by RED, further undergoes a cleavage reaction to release a photographically useful group include the following.

(1) A group that utilizes the cleavage reaction of hemiacetal, such as U.S. Pat. Tar 106 Co No. 23, same! Day 706224 and! A group described in Turf No. 54ttj and represented by the following general formula.

几l In the formula, the * mark represents the bonding position to RED=, R1 and 'FL2 represent a hydrogen atom or a substituent, n represents/or -, and when n is -, each of R1 and B2 is the same or different. Any two of R1 and R2 may be connected to form a cyclic structure. PUG represents a photographically useful group.

(2) A group that causes a cleavage reaction using an intramolecular nucleophilic substitution reaction. For example, U.S. Patent No. g, 24tr, 262
The timing group described in the issue.

(8) A group that causes a cleavage reaction using an electron transfer reaction along a conjugated system. For example, U.S. Patent No. g, 4t0, 3.
No. 23 or a group represented by the following general formula (British Patent No. 2,09≦).

Groups described in No. 2♂3A).

In the formula, the * mark represents a bonding position to RED, R3 and R4 represent a hydrogen atom or a substituent, and PUG represents a photographically useful group.

In detail, the photographically useful groups formed from the group represented by B in general formula (1) include development inhibitors, development accelerators, fogging agents, dyes, and competing compounds (developing agent oxidized product capture agents).
, etc.

In general formula (I), RED is preferably bonded to a human via an oxygen atom obtained by removing a hydrogen atom from the hydroxyl group of the aromatic alcohol.

The compound represented by the general formula (I) releases R and ED-B by reaction with an oxidized developing agent during development. R11!
1D-B has a reducing effect and reacts with oxidation products (for example, oxidized developing agent) generated during development. Now, RED-
Let B be an oxidized compound, 0X-B. OX-B reacts with nucleophiles such as hydroxyl ions, hydroxylamine, and sulfite ions present in the developer to cleave B. For example, the reaction that releases B from RED is described in US Patent No. 3?
This is the same reaction as the compound described in 3θ♂≦3. In the course of these reactions, the rate at which OX-B is produced from RED-B depends on the concentration of oxidation products generated during development. In other words, in areas where a large amount of oxidized developing agent is generated, the R generated by the coupling reaction is
BD-B immediately generates 0X-B. In contrast, where only a small amount of oxidized developing agent is generated, RBD-B produced by the coupling reaction slowly produces OX-B. This is because the reaction between RED-B and the oxidized developing agent is a secondary reaction and depends on the respective concentrations. The compound of the present invention undergoes a series of reaction processes in which the compound cleaved from the coupler undergoes the redox reaction described above, followed by a reaction to produce B, and finally a reaction to produce a photographically useful group from B. produces photographically useful groups.

It is clear from the above explanation that the compounds of the present invention react by a completely different mechanism from conventional couplers having a timing group, and therefore have different functions. Furthermore, the compounds of the present invention are resistant to air oxidation.
It is also clear that it is stable against hydrolysis. This is because RED has a structure that is oxidized only after it is separated from A, and only when it is oxidized to OX does it generate an electrophilic reaction side and is attacked by nucleophiles such as hydroxy ions. be.

In the compound of the present invention, A, RED, and B can be selected from a wide range, and depending on the selection, it can be used in various sensitive materials (for example, color negative film, color reversal film, color positive film) by various known methods. . Generally, DIR coupler is mixed with the main coupler,
It can be used as a colored coupler, a competitive coupler, a development accelerating coupler, etc., and may also be used as a main coupler. Any layer such as a high-sensitivity layer or a low-sensitivity layer can be selected depending on the purpose. Thus, the present invention encompasses two groups of compounds that can be used in various ways in various sensitive materials for various purposes. This means that the properties of the reaction product with the oxidized developing agent can be selected by the coupling component (e.g. selection of the dye to be formed, selection of a colorless product), and R from A to RED by the arbitrary selection of the RED. This compound has the characteristics that the release rate of ED-B or the range of action of RED-B can be easily adjusted, and the type of photographic action can be selected depending on the purpose by arbitrarily selecting B. Because there is.

ED compound (reducing agent) in JP-A No. 67-73763
Examples of couplers that emit . This compound has the sole purpose of reducing the oxidized developing agent and is completely different from the present invention. The present invention is significant in that it releases photographically useful groups, and has the excellent function of controlling the release depending on the concentration of the oxidized developing agent and at the same time adjusting the diffusion range.

The amount of the compound of the present invention added varies depending on the structure and use of the compound, but is preferably from /x/θ to 1 mol, particularly preferably from /x70 per mol of silver in the layer containing the compound or the adjacent layer! ×70−1 mole. Any layer such as a high-sensitivity layer or a low-sensitivity layer can be selected depending on the purpose.

The group represented by RI13D in general formula (1) is preferably represented by the following general formula.

In the formula, the * mark represents the position where it is bonded to a person, and the * mark represents the position where it is bonded to B.

(w)n In the formula, D is a hydroxyl group, an aromatic sulfonamide group,
Represents an aliphatic sulfonamide group or a heterocyclic sulfonamide group, W is an aliphatic group, an aromatic group, a halogen atom, an alkoxy group, an alkylthio group, an aryloxy group, an arylthio group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group. group, sulfonyl group, sulfamoyl group, acylamino group, sulfonamide group, carbamoyl group, acyl group, nitroso group, acyloxy group,
ureido group, imide group, nitro group, cyan group, heterocyclic group, heterocyclic thio group, hydroxyl group, carboxyl group, alkoxycarbonylamino group, sulfo group, amino group, anilino group, sulfinyl group, sulfamoylamino group,
Represents a thioacyl group, thioureido group or heterocyclic amino group. n is 0. represents an integer from / to 3, and when n is 2 or more, W represents the same thing or different things, and λ W
When these are adjacent, it also includes the case where they become a monovalent group and connect to form a condensed ring to a benzene ring. Such examples include benzonorbornenes, chromans, indoles, benzothiophenes or indazoles. When there is an aliphatic group in the partial structure of W and D, the number of carbon atoms is 7 to 2, preferably / to 10, and is chain or cyclic, straight chain or branched, saturated or unsaturated, substituted or unsaturated. It is an unsubstituted aliphatic group. When the partial structure of W and D contains an aromatic group, the number of carbon atoms is 6 to 10,
Preferred is a substituted or unsubstituted phenyl group.

In the general formula (1), the photographically useful group generated from B after B is cleaved is disclosed in US Patent Nos. a, z4tr.

Photographically useful groups described in Patent No. 6- (general formula P in said patent)
(represented by UG) and Tokukaisho! Tar/for4
A fogging agent (the part of the leaving group released from the puller in the patent) described in No. 1 is a preferred example.

Tokukai Akira here! ? The fogging agent described in No. -/Ror4to is represented by the following general formula.

Here, the * mark represents the position where it is bonded to RED.

In the formula, 2 represents a monocyclic or condensed heterocyclic ring consisting of carbon atoms and nitrogen atoms, L represents a divalent linking group, 5 represents a hydrogen atom or an alkoxycarbonyl group, and "6" represents a hydrogen atom, an acyl group, a sulfonyl group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, a thioacyl group, a thiocarbamoyl group, an alkyl group, or an aryl group.

Among these, particularly preferred is the j-aryltetrazolylthio group! -A development inhibitor such as an aliphatic substituted tetrazolylthio group or a benzotriazolyl group.

The above-mentioned inhibitors also include cases where they have the substituents listed for W above at substitutable positions.

Specific examples of the compounds of the present invention are listed below, but the compounds are not limited thereto.

NHCOC? Hts H CH3 Synthesis Example/ (Synthesis of Exemplary Coupler (1)) α-Chloro-
α-piparoyl-2'-ri-o-ro! ′-(gu(,2s
”-di-t-amylphenoxy)butanamido)acetanilide JOf% core-co-3-(z,th-
209 ml of dimethylbenzotriazol-/-ylmethoxy)-terpivaloyloxyphenol and 1/1 liter of triethylamine were added to 200 ml of acetonitrile and heated under reflux. After reacting for several hours, the mixture was cooled to room temperature, 200% of ethyl acetate was added thereto, and the mixture was transferred to a separatory funnel and washed with water. After neutralization with dilute hydrochloric acid, the mixture was washed with water until neutral.

The oil layer was separated and the solvent was distilled off under reduced pressure. To this was added 300 d of a methanol solution in which potassium hydroxide rP was dissolved, and the mixture was allowed to react at room temperature for 3 hours. To this was added 100 d of ethyl acetate, and the mixture was transferred to a separating funnel and treated in the same manner as above. The resulting concentrated residue was purified by column chromatography filled with silica gel. By collecting the fractions containing the compound of interest, the 6y exemplary coupler (
1) was obtained.

The silver halide photographic material used in the present invention may be a monochromatic color photographic material having one light-sensitive copper halide emulsion layer on a support, or a multilayer color photographic material having at least one light-sensitive copper 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-photosensitive layer of the photographic light-sensitive material produced using the present invention has the general formula (1) described above.
Along with the compound represented by
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, but the couplers of the present invention can also 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 coloring couplers, typical examples of which are naphthol or phenolic 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 are provided in Research Disclosure.
sclosure)/7t4tJ (December 1977)
Section V[-D is described in the patent cited in 7/7/97.

The color coupler incorporated in the light-sensitive material is preferably diffusion-resistant by having a pallast group or being polymerized. A divalent color coupler substituted with a leaving group can reduce the amount of coated silver and provide higher sensitivity than a nominal color coupler whose 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. 4t.
o2. Ko/θ issue, same issue, tri! , No. 0!7 and No. 3, 26j, and 304 of the same. As a two-wheel yellow coupler, US Patent No. 3, 4tOr, 1
No. 941, same number, j, 4t4t7. Ri2
R, No. 3,933,307, No. 9,02, 6λθ, etc., or Japanese Patent Publication No. Shoj-R-/θ73, U.S. Patent No. 4t0/, ri No. 31, same No. 3, 32≦, 024
No., RD/♂0! J (/7 years ago), British Patent No. 1゜4t2Jr, No.
Colli.

No. 77, No. 2. Typical examples thereof include the nitrogen atom dissociative yellow couplers described in No. 347, No. 2,32, No. 527, No. 2,41jJ, No. 114, and the like. The α-piparoylacetanilide-based cazolers have excellent color fastness, particularly light fastness, while the α-benzoylacetanilide-based couplers provide high color density.

The magenta coupler that can be used in the present invention is preferably an oil-protected indacylon or cyanoacetyl coupler! - Pyrazoloazole couplers such as pyrazolone and pyrazolotriazoles are mentioned. ! - As for the 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. 2゜J
4tJ, No. 703, No. 00.7/r, No. λ, No. 573, No. 3, 0≦λ, No. 663, No. 3. /! It is described in Ko, tri No. 4 and tri No. 3゜934.01, etc. As a leaving group for divalent pyrazolone couplers, U.S. Patent No. 4T, JLO, 6/
The nitrogen atom leaving group described in US Patent No. 'I
The arylthio group described in -, 3j/, rri No. 7 is particularly preferred.

Further, the pyrazolone coupler having a ballast group described in European Patent No. 73,336 provides high color density.

As pyrazoloazole couplers, US Patent JL,
3t, pyrazolobenzimidazoles as described in US Pat. No. 272, preferably US Pat. No. 3,7λ! Pyrazolo(j,/-c) [/, 2,4t] triazoles described in , No. 057, Research Disclosure 2μ220 (/
the law of nature? Pyrazolotetrazoles and Research Disclosure = 4t23θ (/9t4
Examples include the pyrazolopyrazoles described in June 2013). European Patent No. 1/? in terms of low yellow side absorption of the coloring dye and light fastness. , imidazo (
'/, 2-b) Pyrazoles are preferred, such as pyrazolo [/] as described in European Patent No. 1/DE, 260.

jb)(/, z, gettriazole is particularly preferred.

Cyan couplers that can be used in the present invention include oil-protected naphthol-based and phenol-based couplers, and US Patent No. J, 4t? 4t.

Naphthol couplers described in US Pat. No. 273, preferably US Pat.

Typical examples include the oxygen atom dissociating type dicarium naphthol couplers described in No. 22F, No. 233, and No. J, 29≦, Koθ0. Specific examples of phenolic couplers include U.S. Patent No. 2,349,92, U.S. Pat. , 12
It is written in No. 4 etc. Humidity and temperature robust cyan couplers are preferably used in the present invention, exemplified by U.S. Pat. ,772.002
A phenolic cyan coupler having an alkyl group equal to or higher than ethyl group at the meta-position of the phenol nucleus described in US Pat.
C# issue, same issue, /2bu, 396 issue, same issue, 3J4t
, 0// issue, same issue, 3 cores.

773, West German Patent Publication No. 3,322,7 Kota, and Japanese Patent Application No. 1987-4t-2t77, etc.
'-Diacylamino substituted phenolic couplers and U.S. Pat.
33. It has a phenylureido group at the 11th position and is described in Wata No. 9, Watashi No. These include phenolic couplers having an acylamino group at the - position.

In order to correct unnecessary absorption in the short wavelength range of dyes generated from magenta and cyan couplers, it is a good idea to use colored couplers in combination with color sensitive materials for photography. U.S. Patent No. g/<j, 470 and Japanese Patent Publication No. 7
Yellow colored magenta coupler described in -3ri4t73 etc. or U.S. Pat. r and British Patent No. 1, /
Typical examples include the magenta-colored cyan coupler described in No. 4t4.347.

Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Such blur couplers are described in U.S. Patent No. G, 344. Specific examples of magenta couplers are given in British Patent No. 37 and British Patent No. 70,
Also European patent number 26°! No. 70 and West German Application Publication No. 3
．． No. 2341,333 describes specific examples of yellow, magenta or cyan couplers.

The dye-forming couplers and the special couplers described above may form dimers or more polymers. Typical examples of polymerized dye-forming couplers are described in U.S. Patent No. 3. tri, 22
No. 0 and No. 1, oio.

It is described in issue 2//. Examples of polymerized magenta couplers are described in British Patent No. 2,10,773 and US Patent No. 4t, 31a7,27.

These couplers may be either monoequivalent or monoequivalent to silver ions. It may be a color coupler having a color correction effect, or a coupler that releases a development inhibitor upon development (so-called DIR 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.

The couplers of the present invention and couplers that can be used in combination can be introduced into the silver halide emulsion layer by known methods, such as the method described in US Pat. No. 2,322,027.

For example, phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.) - phosphoric acid esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (e.g. acetyl tributyl citrate), Benzoic acid esters (e.g. octyl benzoate), alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate, diethyl azelate), trimesic acid esters (e.g. tributyl trimesate), etc., or boiling point Organic solvents at 30°C to /ro0c, such as lower alkyl acetates such as ethyl acetate and butyl acetate,
After being dissolved in ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, etc., it is dispersed in a hydrophilic colloid. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be used in combination.

Also, Tokko Akira! /-3ri/jj issue, Tokukai Showi-! cotton 4
The dispersion method using polymers described in No. t3 can also be used.

When the kazolar 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 Vuis.
Weiss), The-7 Chromolecular Chemistry Oz Gelatin (The Macromolecule
lar Chemistry of Gelatin
), (Academic P
ress ), published in 2013).

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. Preferred silver halide is silver iodobromide containing silver iodide in a molar ratio of /j or less. Particularly preferred is silver iodide containing from λ to /2 mole of silver iodide.

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

The particle size may be narrow or wide.

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 consist of a mixture of particles of various crystalline forms -1° and the diameter of the particle is its thickness! Ultra-tabular silver halide grains more than double the total projected area! An emulsion that accounts for θ% or more may be used.

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

The photographic emulsion used in the present invention is P.
, Glafkides), 'Chfmje etPh
ysique Photographique )'
(Bo) L/-Montel (Paul Montel)
) Publishing, / 36 years), V-0 El Celikman (
V.L.

Zelikman), 1 Making and Coating Photographic Emulsion (Ma
King and Coating Photogra
phicEmulsion)” (published by The Focal Press, /
It can be adjusted using the method described in, for example, 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 type of simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called Chondral 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.

211 or more silver halide emulsions formed separately may be mixed and used.

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

Silver halide emulsions are usually chemically sensitized.

For chemical sensitization, for example, an etch fuser (H
, Fieser), ed.
enderPhotographischenPr
ozesse mit 5ilber Halo
Geniden) (Akademische Verl.
agsgesellschaft), /Riotsu? ), Gogori! The method described on pages 734 to 734 can be used.

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 such as 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 /-phenyl-mercaptotetrazole); mercaptopyrimidines; mercaptotriazines; Danes, tetraazaindenes (tetraazaindenes substituted with hydroxyl (/, J, JR, 7) on #), hantaazaindenes, etc.; benzenethiosulfonic acid, benzenesulfonic acid, benzenesulfonic acid amide, etc. A number of compounds known as antifoggants or stabilizers can be added, such as.

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 light-sensitive 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. Eva, vinyl acetate), acrylonitrile, olefin, styrene, etc. alone or in combination, or these. and acrylic acid, methacrylic acid, α
, β-unsaturated dicarboxylic acid, hydroxyalkyl acrylate, hydroxyalkyl methacrylate, sulfoalkyl acrylate, sulfoalkyl methacrylate,
Polymers containing combinations of styrene sulfonic acid and the like as monomer components could 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, pyrroline 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 contain pyrazoline-! as a core having a ketomethylene structure. -on nucleus, thiohydantoin nucleus, corchioxazolidine-,
2,4t-dione nucleus, thiazolidine-,2,4t-dione nucleus, rhodanine nucleus, thiobarbic acid nucleus, etc.! ~
It can be applied to all members.

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. Pat.
λ/), aromatic organic acid formaldehyde condensates (eg, those described in US Pat. No. 7,413.610), cadmium salts, azaindene compounds, and the like.

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, glyoxal, geltaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (λ, 3-dihydroxydioxane, etc.), activated vinyl compounds (/, J, j-Triacryloyl-hexahydro-3-triazine, /, 3-
vinylsulfonyl-coprono-q-nol), active halogen compounds (2m''-dichloro-bu-hydroxy-s-1 riazine, etc.), mucohalogen I (mucochloric acid, mucophenoxychloric acid, etc.), etc. alone or Can be used 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 light-sensitive material produced using the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, etc. as a color anti-capri agent.

The photosensitive material produced using the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, benzotriazole compounds substituted with an oryl group (e.g., those described in U.S. Patent No. 3.
Same 3,3! λ.

61/), benzophenone compounds (e.g. those described in JP-A No. 4-27/4),
Cinnamate ester compounds (e.g., U.S. Pat. No. 3,701.
No. 101, 3,707. J7j), butadiene compounds (eg, those described in US Pat.

04tj, Co., Ltd.) or benzoxazole compounds (for example, those described in U.S. Pat. No. 3,700.4t).
(described in No. jj) can be used. 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 I 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 combination1, 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 hibisphenols.

Photographic processing of layers comprising photographic emulsions made using the present invention includes, for example, Research Disclosure No. 776 No. 2.
Any of the known methods and known treatment liquids as described in pages 1 to 30 can be applied. Processing temperature is usually from /♂0C! It is chosen between θ0C, /1
The temperature may be lower than 0C or higher than 500C.

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. 9-
Amino-N, N-diethylaniline, 3-methyl-guamino-N, N-diethylaniline, teramino-N-
Ethyl-N-β-hydroxyethylaniline, 3-methyl-guamino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-guamino-N-ethyl-N
-β-methanesulfamide ethylaniline, guamino-3-methyl-N-ethyl-N-β-methoxyethylaniline, etc.) can be used.

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

Mason), “Photographic Processing Chemistry”
ssing Chemistry)' (focal
Published by Focal Press, /rijj), pp. 2-22, U.S. Patent Co., /rij, 0/
No. J, same! Octopus, Jta, Tokukai Showa 4t, r-6
You may use the thing described in 4t233 etc.

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. etc. can be included. 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, l-7enyl-3-virasoliton. It may also contain auxiliary developing agents, viscosity imparting agents, polycarboxylic acid chelating agents, antioxidants and the like.

After color development, the photographic emulsion layer is usually bleached.

The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. Examples of bleaching agents include iron (1),
Compounds of polyvalent metals such as cobalt (1), chromium (VI), and copper (It), peracids, quinones, nitroso compounds, and the like are used.

For example, ferricyanide, dichromate, organic complex salts of iron(1) or copal 1-(1), such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, /.

Aminopolycarboxylic acids such as 3-diamino-11propanoltetraacetic acid; complex salts of organic acids such as citric acid, tartaric acid, and malic acid; persulfates, permanganates; nitrosophenols, and the like can be used. Among these, potassium ferricyanide, iron ethylenediaminetetraacetate (1)
Sodium and iron(I) ammonium ethylenediaminetetraacetate are particularly useful. Iron ethylenediaminetetraacetate (
I) Complex salts are useful both in stand-alone bleach solutions and in -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 (Japanese Patent Laid-Open No. 57
It is also possible to use a simple processing method such as JP-A-rJr4tJ).

The rinsing water used in the rinsing step can contain known additives, if necessary. For example, chelating agents such as inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid,
Bactericides and anti-fungal agents to prevent the growth of rice bacteria and algae, hardeners such as magnesium salts and aluminum salts, and surfactants to prevent drying load and unevenness can be used. Or L.E. West (L, E.

Water Quality Cr1te
ria)'Photographic Science and Engineering (Photo, 8ci, and En
g, ), Vol, ta 44 page j 4t4
It is also possible to use compounds described in t to J j ri (/rit tS) and the like.

Further, the washing step may be performed using two or more tanks according to the required C, and the washing water may be saved by performing multi-stage countercurrent washing (for example, - to ? stages).

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, antifouling agents, hardeners, surfactants, and the like can be used in the stabilizing liquid as necessary.

In addition, the stabilization process may be performed using a tank on a λ tank plate if necessary, and the stabilizing liquid can be saved by performing multi-stage countercurrent stabilization (for example, 1 to 9 stages), and furthermore, the water washing process can be omitted. You can also do it.

(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.

1st layer; antihalation layer; gelatin layer containing black colloidal silver; 1st layer; intermediate layer; 3rd gelatin layer containing an emulsified dispersion of λ, j-di-t-octylhydroquinone; 7th red-sensitive emulsion layer; iodobromide layer; Silver emulsion (silver iodide; ! mole qb)...silver coating amount /, buy / m! Sensitizing dye I...G, j x / θ per mole of silver Sensitizing dye ■...Ha j x 10 per mole of silver Coupler EX-/-G per mole of silver 0.03 mole coupler EX-3 - 3 moles of o, oo per 7 moles of silver 2nd layer; 3rd red-sensitive emulsion layer Silver iodobromide emulsion (silver iodide; 70 mol%) Silver coating amount 7 .4t 7m ” Sensitizing dye ■... 3 x / θ per mole of silver Sensitizing dye ■ ... / x 70 per mole of silver Coupler EX - / - per mole of silver 0.001 mole coupler EX-j 0 for 1 mole of silver, 0.02 mole coupler EX-j for 1 mole of silver
40, θ θ / 2nd mole! Layer: 6th layer same as the 2nd intermediate layer; 1st green-sensitive emulsion layer Silver iodobromide emulsion (silver iodide; 6 mol%)...Silver coating amount
/, ♂y / m 2 Sensitizing dye I...for 1 mole of silver! ×/θ molar sensitizing dye ■...λ×10 molar per mole of silver Coupler EX-a・0,0 per mole of silver! Molar coupler EX-r・O1 θO♂ molar coupler EX-r・O,0011 mol per mol of silver 7th layer; First blue-sensitive emulsion layer Silver iodobromide emulsion (silver iodide; )・・・Amount of silver coating
/, 37/m" Sensitizing dye ■...3 x 10 mol per mol of silver Sensitizing dye ■.../ 2 x 10 mol coupler E per mol of silver
X-7・0.077 mol per mol of silver Coupler EX-6・0.003 mol per mol of silver 2nd layer; Yellow filter layer Yellow colloidal silver and λ in gelatin aqueous solution! -G-t-
Emulsified dispersion of octylhydroquinone, Gelatin layer 2nd layer; 1st blue-sensitive emulsion layer Silver iodobromide emulsion (silver iodide; 6 molt)...Silver coating amount
0.717m" Coupler EX-, r・0.21 mol per mol of silver Coupler EX-?・0.0/j mol per mol of silver 70th layer; 2nd blue-sensitive emulsion layer Silver iodobromide (Silver iodide; g morch)...Silver coating amount 0
, 6 f 7m" Coupler EX-r - 0,0 mol per mol of silver 11th layer; First protective layer silver iodobromide (1 mol of silver iodide, average grain size 0.07μ)
...Silver coating amount 0.317m" Ultraviolet absorber UV
A first layer of gelatin containing an emulsified dispersion of -/; a second protective layer of polymethylmethanoacrylate particles (diameter approx./);

Apply a gelatin layer containing jμ).

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

Preparation of Samples 702 to θ Coupler EX sample 10 of low green-sensitive emulsion layer of Sample 10/
When a sample of /~/θ9 was wedge-exposed to sunlight and processed as described below, a sample with almost the same sensitivity and gradation was obtained. The sharpness of the green sensitive layer of these samples was evaluated using a conventional MTF value.

The structural formula of the compound used is as follows.

Compound (t) used to prepare the sample Cs H1l EX-5 a EX-t EX-7 Here (tl C8H1? is (CH3)s CCH2
Represents C(CH3)2-.

EX-/EX-ta (conventional DI coupler) EX-10 (coupler described in U.S. Pat. Couplers listed in the issue) UV-/ Sensitizing dye ■ Sensitizing dye ■ Sensitizing dye I Na so 3 (CH2) 3 (OCH2CH2)
2 Development processing was carried out at 3?0C according to the following processing steps.

Color development　　λ minutes 4tj seconds Bleach White 4 minutes 30 seconds Water Washing - Minutes 70 seconds Fixed arrival time: 10 seconds Wash with water for 3 minutes/! seconds Safe, stable, 7 minutes 01 seconds The composition of the treatment liquid used in each step was as follows.

Color developer diethylenetriaminepentaacetic acid 7.0P/-hydroxyethylidene-/.

/-diphosphonic acid 2,0-sodium sulfite ta,OF potassium carbonate
3o,oy potassium bromide
i, 4ty potassium iodide /,
JIIF hydroxylamine sulfate, 2.4t
Tag-(N-ethyl-N-β-hydroxyethylamine)-comethylaniline sulfate 4t, jpAdd water /・'2pH10,θ Bleach solution Ethylenediaminetetraacetic acid ferric ammonium salt 100,θtaethylenediaminetetraacetic acid Disodium salt /θ,oy ammonium bromide /60,09 ammonium nitrate
10. Add water
/, θ2pHd, θ' fixer ethylenediaminetetraacetic acid disodium salt /, θ1 sodium sulfite g, O ammonium sulfate aqueous solution (70%) iyj, owt sodium bisulfite g, otsu 1 add water
/ , 01°pa, g, a Stabilizing liquid formalin (tochi) 2.014 Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization +10) 0. j1p water was added /, OA obtained sample / parrot Yumoto and g.

The MTF value of the green sensitive layer of the book was 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 /.

It can be seen from the table that the MTF value is significantly higher in the case using the coupler of the present invention than in the case using the conventional DIR coupler.

Patent Applicant: Fuji Photo Film Co., Ltd. Procedural Amendment 1, Showa t No. 1, Month, Day 1, Case Indication: Showa t No. 7J04cO
No. 2, Title of the invention Silver halide color photographic light-sensitive material 3. Relationship with the case of the person making the amendment Patent applicant 4. Subject of the amendment Column 5, "Detailed explanation of the invention" of the specification, Contents of the amendment Note 11t in the "Detailed Description of the Invention" column is amended as follows.

l) First page, first line "R7" RtyJ and correct it.

2) First page line "R5" R55J and correct it.

3) Page 22, line 10 and correct it.

≠) Represents the bonding position to rRED on page 2//line "W is an oxygen atom, a sulfur atom, or a -N- group (Ra represents an organic substituent. For example, an aliphatic group, an acyl group. , a sulfonyl group, a carbamoyl group, a sulfamoyl group, or an aromatic group).

! ) [Hydrogen atom or substituent] in the -th line of page 1 is defined as "a hydrogen atom or an organic substituent (for example, an aliphatic group, an acyl group, a sulfonyl group, a carbamoyl group, a sulfamoyl group, or an aromatic group)" to correct.

6) Kota page/3rd line After rR11R2J "and W" Insert.

7) No. 1 page! row [After any R1, R2J [and RaJ Insert.

r) Insert the description in Attachment A after "Represents the Photographic Useful Fund" on page 22, line 16.

ri) Page 30, line 2 [Timing group with description. ], insert the description in Attachment B.

IO) Insert "(for example, an aliphatic group, aromatic group, acyl group, sulfonyl group, carbamoyl group, or alkoxycarbonyl group)" after "hydrogen atom or substituent" on page 30, line IO.

//) rPUG on page 30, line 11 represents a photographically useful group. '', insert the description in Attachment C.

t2) Third! page/line "of " and correct it.

/J) Page 34, line λ “Integer J7F of O1/~3!- "Integer from O to 3" and correct it.

/4c) 3rd page / line (represented by rPUG)” after “U.S. Pat. No. μ, ≠77.163, ibid.

! Insert the "development inhibitor described in No. 0043μ".

Specific examples of the group represented by the above general formula include the following. Here, the mark * represents the position where it binds to RED, and the mark ** represents the position where it binds to PUG.

l (p )
The mark ** represents the position where it bonds with PUG. represent.

Specifically, the following examples are given. In the formula, the * mark represents the position where RED is bonded, and the ** mark represents the position where PUG is bonded.

Claims (1)

[Claims] A silver halide color photographic light-sensitive material containing at least one compound characterized in that, after a coupling reaction with an oxidized developing agent, the cleaved compound is oxidized to produce a precursor of a photographically useful group.