DE69031679T2 - Silver halide color photographic material containing a yellow colored cyan coupler - Google Patents

Description

FIELD OF INVENTION:

This invention relates to a silver halide color photographic material. More particularly, it relates to a silver halide color photographic material containing a yellow-colored cyan coupler and a development inhibitor-releasing compound and having excellent color reproducibility and sharpness over the entire exposure range, and whose color reproducibility and sharpness are hardly affected by changes in processing.

DESCRIPTION OF THE STATE OF THE ART:

In recent years, particularly in the field of silver halide photographic materials for photography, attempts have been made to provide silver halide photographic materials that have excellent color reproducibility, sharpness and high sensitivity, such as ISO 400 type photographic materials (e.g. Super HG-400 sold by Fuji Photo Film Co.) that have high image quality comparable to ISO 100.

As agents for improving color reproducibility and sharpness, the compounds of the formula (I) of the present invention have been proposed in JP-A-60-185950 (the term "JP-A" herein means an "unexamined published Japanese patent application"), JP-A-61-233741 (corresponding to U.S. Patent No. 4,618,571), JP-A-62-151850, JP-A-63-163454 (corresponding to U.S. Patent No. 4,824,772) and JP-A-63-281160. By these compounds, the interlayer and edge effects are improved, and the color reproducibility and sharpness are also improved to some extent. However, there are problems in that if the amount of the development inhibitor released by these compounds is insufficient for development inhibition, sufficient interlayer and edge effects cannot be obtained; and that if the sensitive layers to be inhibited are not properly developed, the desired interlayer effect cannot be obtained. In addition, these compounds do not provide a sufficient effect over the entire exposure range and the use of these compounds somewhat reduces the sensitivity of the photographic material. In addition, when the layer arrangement is used in conventional photographic materials for photography, that is, when the arrangement is made in the order of a red-sensitive layer with a cyan coupler, a green-sensitive layer with a magenta coupler and a blue-sensitive layer with a yellow coupler, with the red-sensitive layer being closest to the carrier, the red-sensitive layer and blue-sensitive layer are far apart from each other, so that problems arise in that a sufficient interlayer effect between these layers cannot be achieved by Use of these compounds cannot be obtained and causes a reduction in the sensitivity of the green-sensitive layer.

On the other hand, it is disclosed in JP-A-61-221748 and DE-A-3 815 469 that similar effects (in terms of photographic properties) as an interlayer effect from the red-sensitive emulsion layer to the blue-sensitive emulsion layer can be obtained by using a yellow-colored cyan coupler in the red-sensitive emulsion layer. However, by the methods described in the above patents, i.e. by using these compounds alone, it is difficult to obtain sufficient effects over the entire exposure range. Conventional yellow-colored cyan couplers have problems in that the molecular extinction coefficients of their yellow dyes are low and their coupling activity is also low.

EP-A-0 423 727 is prior art according to Article 54(3) EPC and discloses a photographic material comprising yellow-coloured cyan couplers.

SUMMARY OF THE INVENTION:

A first object of the present invention is to provide a photographic material which has excellent color reproducibility and particularly red reproducibility over the entire exposure range.

A second object of the present invention is to provide a photographic material having excellent sharpness.

A third object of the present invention is to provide a photographic material which is less dependent on processing.

A fourth object of the present invention is to provide a photographic material which is highly sensitive.

These objects of the present invention have been achieved by providing a silver halide color photographic material comprising a support and thereon at least one red-sensitive silver halide emulsion layer containing a cyan coupler, at least one green-sensitive silver halide emulsion layer containing a magenta coupler and at least one blue-sensitive silver halide emulsion layer containing a yellow coupler, which photographic material contains at least one compound having the following general formula (I) in an amount of 1 x 10⁻⁶ to 1 x 10⁻³ mol/m²:

A-(L₁)v-B-(L₂)w-DI (I)

wherein A represents a group which is split off from (L₁)vB-(L₂)w-DI by a reaction of the compound of formula (I) with an oxidation product of a developing agent; L₁ represents a linking group which is split off from B after cleavage of the bond between A and L₁; B represents a group which reacts with an oxidation product of a developing agent under Release of (L₂)w-DI; L₂ represents a group which is split off from DI after cleavage of the bond between L₂ and B; DI represents a development inhibitor; v and w each represent an integer from 0 to 2 and when v or w is 2, the two L₁ groups or the two L₂ groups may be the same or different, and which contains at least one yellow-coloured cyan coupler having an absorption maximum at 400 to 500 nm which forms a cyan dye having an absorption maximum at 630 to 750 nm by coupling with the oxidation product of an aromatic primary amine developing agent, with the proviso that the compound of formula (I) is not

is.

DETAILED DESCRIPTION OF THE INVENTION:

The compounds with the general formula (I) are discussed in more detail below.

The term "aliphatic group" means an aliphatic hydrocarbon group which may be a saturated or unsaturated hydrocarbon group or a linear, branched or cyclic hydrocarbon group such as an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group or an alkynyl group. The term "aryl group" means at least one substituted or unsubstituted phenyl and naphthyl group. An acyl moiety (e.g. in the acyl group or acylamino group) means aliphatic and aromatic acyl moieties. A sulfonyl moiety (in a sulfonyl group or sulfonamido group) means aliphatic and aromatic sulfonyl moieties. A carbamoyl group, sulfamoyl group, amino group and ureido group include unsubstituted and substituted representatives. A heterocyclic group is a 3- to 8-membered group with at least one of N, O and S atoms as a heteroatom.

The compounds of general formula (I) are cleaved by the following reaction pathway during the development to release DI:

wherein A, L₁, v, B, L₂, w and DI have the same meanings as in formula (I); and QDI represents an oxidation product of a developing agent.

More specifically, A in formula (I) represents a coupler unit for color development or a unit which is split off during development and which can reduce the oxidation product of a developing agent which occurs during development.

Conventional groups can be used as the coupler unit represented by A, including yellow coupler units (e.g., open-chain ketomethylene coupler units), magenta coupler units (e.g., 5-pyrazolone, pyrazobimidazole, and pyrazolotriazole coupler units), cyan coupler units (e.g., phenol and naphthol coupler units), and non-color forming coupler units (e.g., indanone and acetophenone coupler units). Heterocyclic coupler units described in U.S. Patent Nos. 4,315,070, 4,183,752, 3,961,959, or 4,171,223 can be used.

Preferred examples of A include coupler units having the formulas (Cp-1), (Cp-2), (Cp-3), (Cp-4), (Cp-5), (Cp-6), (Cp-7), (Cp-8), (Cp-9) and (Cp-10).

These coupler units are preferred because they have a high coupling speed.

In the above formulas, the free bonds at the coupling positions represent the bonding positions of the groups that are split off by the coupling.

When R₅₁, R₅₂, R₅₃, R₅₄, R₅₃, R₅₆, R₅₆, R₅₇, R₅₄, R₅₃, R₅₆, R₅₄, R₅₆, R₅₇, R₅₆, R₅₃, R₅₆, R₅₆, R₅₁, R₅₆, R₅₁, R₅₆, or R₅₃ in the above formulas contains a non-diffusible group, the total number of carbon atoms in the group is 8 to 40, preferably 10 to 30. In other cases, the total number of carbon atoms is preferably not more than 15. When the couplers are of the bis-type, telomer type or polymer type, one of the above substituent groups is a divalent group linked to a repeating unit. In this case, the total number of carbon atoms may be outside the above range.

R₅₁₁ to R₆₃, b, d and e will now be explained in more detail.

Hereinafter, R₄₁ represents an aliphatic group, an aromatic group or a heterocyclic group; R₄₂ represents an aromatic group or a heterocyclic group; and R₄₃, R₄₄ and R₄₅, which may be the same or different, each represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group.

R₅₁₁ has the same meaning as R₄₁; b is 0 or 1; R₅₂ and R₅₃ each have the same meaning as R₄₂; R₅₄ means

R₅₅ has the same meaning as R₄₁;

R₅₆ and R₅₆ each represent

R₅₋₀ has the same meaning as R₄₁; R₅₋₀ means

a halogen atom or

d is 0 or an integer of 1 to 3, and when d is 2 or 3, plural R₅₇ groups may be the same or different, or each R₅₇ is a divalent group and these divalent groups may be bonded to each other to form a new structure. Typical examples of divalent groups forming a ring structure include the following groups:

and

where f is 0 or an integer from 1 to 4 and g is 0, 1 or 2.

R₆₀₁ has the same meaning as R₄₁; R₆₁ has the same meaning as R₄₁; R₆₂ means

a halogen atom or

means

a halogen atom, a nitro group, a cyano group or R₄₃CO-; and e is 0 or an integer from j to 4. When two or more R₆₂ or R₆₃ groups are present, they may be the same or different.

In the present invention, the groups are defined as follows unless otherwise stated.

The aliphatic group is a saturated or unsaturated, linear or cyclic, straight-chain or branched, substituted or unsubstituted aliphatic hydrocarbon group having preferably 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms. Typical examples thereof include methyl groups, ethyl groups, propyl groups, isopropyl groups, butyl groups, t-butyl groups, i-butyl groups, t-amyl groups, hexyl groups, cyclohexyl groups, 2-ethylhexyl groups, octyl groups, 1,1,3,3-tetramethylbutyl groups, decyl groups, dodecyl groups, hexadecyl groups and octadecyl groups. The aromatic group is a substituted or unsubstituted phenyl or naphthyl group having preferably 6 to 20 carbon atoms. The heterocyclic group is preferably a 3- to 8-membered substituted or unsubstituted heterocyclic group having 1 to 20 carbon atoms, preferably 1 to 7 carbon atoms, wherein the heteroatoms are selected from a nitrogen, oxygen and sulfur atom. Typical examples of heterocyclic groups include a 2-pyridyl group, 2-thienyl group, 2-furyl group, 1-imidazolyl group, 1-indolyl group, phthalimido group, 1,3,4-thiadiazol-2-yl group, 2-quinolyl group, 2, 4-dioxo-1,3-imidazolidin-5-yl- group, 2,4-dioxo-1,3-imidazolidin-3-yl group, succinimido group, 1,2,4-triazol-2-yl group and 1-pyrazolyl group.

The above-described aliphatic hydrocarbon group, aromatic group and heterocyclic group may optionally contain one or more substituent groups. Typical examples of such substituent groups include a halogen atom,

a cyano group and a nitro group, wherein R₄₆ represents an aliphatic group, an aromatic group or a heterocyclic group, and R₄₇, R₄₈ and R₄₇ each represent an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom. The aliphatic group, the aromatic group and the heterocyclic group have the same meanings as described above.

Preferred examples of R₅₁₁ to R₆₃ and d and e are as follows:

preferably R₅₁ is an aliphatic or aromatic group. preferably R₅₂, R₅₃ and R₅₅ are each an aromatic group. R₅₄ is preferably R₅₁CONH- or

R 56 and R 57 are preferably an aliphatic group, an aromatic group, R 41 O- or R 41 S-; and R 58 is preferably an aliphatic group or an aromatic group. In formula (Cp-6), R 59 is preferably a chlorine atom, an aliphatic group or R 41 CONH-; d is preferably 1 or 2; and R 60 is preferably an aromatic group. In formula (Cp-7), R 59 is preferably R 41 CONH-; d is preferably 1; and R 61 is preferably an aliphatic group or an aromatic group. In formula (Cp-8), e is preferably 0 or 1; R 62 is preferably 0 or 1. is preferably R₄₁OCONH-, R₄₁CONH- or R₄₁SO₂NH- and these groups are preferably located at the 5-position of the naphthol ring. In formula (Cp-9), R₆₃ is preferably

a nitro group or a cyano group. In formula (Cp-10), R₆₃ is preferably

or R₄₃CO-.

If A in formula (I) represents a unit capable of reduction, the compounds of formula (I) can be represented by formula (II) according to the Kendall-Pelz rule.

A1-P-(X=Y)n-Q-A2 (II)

In formula (II), P and Q independently represent an oxygen atom or a substituted or unsubstituted imino group; at least one of the n X groups and the n Y groups represents a methine group having a group -(L₁)vB-(L₂)w-DI as a substituent group, and the other X and Y groups independently represent a substituted or unsubstituted methine group or a nitrogen atom; n represents an integer of 1 to 3 (when n is 2 or more, the n X groups or n Y groups may be the same or different); and A₁ and A₂ each represents a hydrogen atom or a group capable of being split off by an alkali. Any two substituents of P, X, Y, Q, A₁ and A₂ may be divalent groups and may be combined with each other to form a ring structure. All such ring structures are within the scope of the present invention. For example, (X=Y)n may form a benzene ring or pyridine ring and other rings such as the following:

When P and Q are each a substituted or unsubstituted imino group, a sulfonyl or acyl group-substituted imino group is preferred, and P and Q can be represented by the following formulas:

In formulas (N-1) and (N-2), the symbol * represents a position where A₁ or A₂ is bonded, and the symbol ** indicates the position where one of the dangling bonds of (X=Y)n- is bonded.

In the formulas (N-1) and (N-2), the group represented by G is preferably a straight-chain or branched, linear or cyclic, saturated or unsaturated, substituted or unsubstituted, aliphatic hydrocarbon group having 1 to 32 carbon atoms (including the carbon atoms of the substituent), preferably 1 to 22 carbon atoms (e.g. methyl, ethyl, benzyl, phenoxybutyl, isopropyl), a substituted or unsubstituted aromatic group having 6 to 10 carbon atoms (e.g. phenyl, 4-methylphenyl, 1-naphthyl, 4-dodecyloxyphenyl), a 4- to 7-membered substituted or unsubstituted heterocyclic group having at least one nitrogen atom, sulfur atom or oxygen atom as a heteroatom, wherein the group with a benzene ring (e.g. 1-phenyl-4- imidazolyl, 2-furyl, benzothienyl, 1-benzoxalyl, pyrazolyl, 1-methyl-3-pyrazolyl and pyridyl) or a group -O-G' (where Gt has the same meaning as G). Examples of substituents for G or G' include a halogen atom, a hydroxy group, a carboxy group, a sulfo group, a phosphono group, a phosphino group, a cyano group, an alkoxy group, an aryl group, an aryloxy group, an alkoxycarbonyl group, an amino group, an ammonium group, an acyl group, a carbonamido group, a sulfonamido group, a carbamoyl group, a sulfamoyl group and a sulfonyl group.

In the general formula (II), P and Q are preferably independently an oxygen atom or a group having the formula (N-1).

When A1 and A2 are each a group capable of being split off by an alkali (hereinafter referred to as a precursor group), preferred examples of such a group include a hydrolyzable group such as an acyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, imidoyl, oxalyl and sulfonyl group (preferably having 1 to 6 carbon atoms and optionally substituted with a substituent such as those mentioned in the definition of G); a precursor group which undergoes a retro-Michael reaction as described in U.S. Patent No. 4,009,029; a precursor group which uses as an intramolecular nucleophilic group an anion formed after a ring cleavage reaction as described in U.S. Patent No. 4,310,612; a precursor group that causes a cleavage reaction by electron transfer of an anion through a conjugated system, as described in U.S. Patents 3,674,478, 3,932,480 and 3,993,681; a precursor group that causes a cleavage reaction by electron transfer of an anion that reacts after ring cleavage, as described in U.S. Patent 4,335,200; and a precursor group that utilizes an imidomethyl group, as described in U.S. Patents 4,363,865 and 4,410,618.

In the formula (II), the cases where P is an oxygen atom and A2 is a hydrogen atom are preferred.

In formula (II), the X and Y groups which do not contain a methine group with a group -(L₁)vB-(L₂)w-DI as Substituents, preferably substituted or unsubstituted methine groups.

Among the compounds of formula (II), those having the following general formulas (III) or (IV) are particularly preferred:

In formulas (III) and (IV), the mark * represents the position where the group -(L₁)vB-(L₂)w-DI is bonded; P, Q, A₁ and A₂ have the same meanings as in formula (II); R₆₄ is a substituent group; and q is or an integer of 1 to 3. When q is 2 or more, two or more R₆₄ groups may be the same or different. When two R₆₄ groups are substituent groups bonded to adjacent carbon atoms, they may each be a divalent group and may be bonded to each other to form a ring structure. All such ring structures are within the scope of the present invention. invention. For example, they can form fused benzene rings which include ring structures such as naphthanes, benzonorbornenes, chromans, benzothiophenes, benzofurans, 2,3-dihydrobenzofurans or indenes. These fused rings can contain one or more substituent groups. Preferred examples of substituent groups for these condensed rings when two R₆₄ groups form a condensed ring, and preferred examples of R₆₄ when the R₆₄ groups do not form a condensed ring include: an R₄₁ group, a halogen atom, R₄₃O-, R₄₃S-, R₄₃(R₄₄)NCO-, R₄₃OOC-, R₄₃SO₂, R₄₃(R₄₄)NSO₂-, R₄₃CON(R₄₄)-, R₄₁SO₂(R₄₃)-, R₄₃CO-, R₄₁COO-, R₄₁SO-, a nitro group, R₄₃(R₄₄)NCON-(R₄₅)-, a cyano group, R₄₁OCON(R₄₃)-, R₄₃OSO₂-, R₄₃(R₄₄)N-, R₄₃(R₄₄)NSO₂N(R₄₅)-, and

wherein R₄₁, R₄₃, R₄₄ and R₄₅ are as defined above.

In formulas (III) and (IV), A₁ and A₂ are preferably a hydrogen atom.

In formula (I), the cases in which A is a coupler unit for color development are preferred.

The groups L₁ and L₂ in formula (I) may be used or omitted depending on the intended purpose. Examples of groups having the formula L₁ and L₂, when used, include the following linking groups. In the following formulas, either the character * means the position where A is bound and the character ** means the position where B is bound, or the character * means the position where B is bound and the character ** means the position where DI is bound.

In the above formulas, R₁₀ is a group which may be substituted on a benzair ring (typical substituents for this have already been described above in the definition of R₆₄); R₁₁ has the same meaning as R₄₁; R₁₂ is a hydrogen atom or one of the groups already described above in the definition of R₆₄; and t is an integer from 0 to 4.

The group B in formula (I) is preferably a group which can be oxidized and is capable of reducing an oxidation product of a developing agent, or is a group which forms a substantially colorless compound by a coupling reaction with an oxidation product of a developing agent. When the group represented by B is a group capable of reducing an oxidation product of a developing agent, B is preferably a group represented by the following general formula (V)

*-P'-(X'=Y')n'-Q'-A₂' (V)

wherein the mark * represents the position at which the group of formula (V) is connected to the left side in formula (I); A₂', P', Q' and n' have the same meanings as A₂, P, Q and n in formula (II), respectively, with the proviso that at least one of the n'X' groups and the n'Y' groups is a methine group having a (L₂)w-DI group as a substituent group, and the other X'andY' groups represent substituted (examples of substituents include the same groups as defined for R₆₄ and a hydroxy group) or unsubstituted methine groups or a nitrogen atom. When any two of A₂', P', Q', X' and Y' are divalent groups, they may be combined with each other to form a ring structure. All such ring structures are within the scope of the present invention. Examples of such ring structures include a benzene ring, an imidazole ring and a pyridine ring.

In formula (V), P' is preferably an oxygen atom and Q' is preferably an oxygen atom or a group having one of the following formulas. In the following formulas, the mark * represents a bond linked to (X'=Y')n' and the mark ** represents a bond linked to A₂':

In the above formulas, G is defined as in formulas (N-1) and (N-2).

Particularly preferably, Q' is an oxygen atom or a

Group.

Typical examples of the group B in formula (I) include the following groups, where the symbol * indicates a position where each group is reacted with A-(L₁)n in formula (I), and the symbol ** represents a position at which each group is linked to (L₂)w-DI in formula (I).

In formulas (B-1) to (B-10), R₁₃ has the same meaning as R₆₄, R₁₄ and R₁₅ each have the same meaning as R₄₁, l is an integer of 0 to 2, m is an integer of 0 to 3, and a is an integer of 0 or 1.

Specific examples of B which is split off to form a compound exhibiting a reducing action include the reducing agents described in U.S. Patent Nos. 4,741,994 and 4,477,560, JP-A-61-102646, JP-A-61-107245, JP-A-61-113060, JP-A-64-13547, JP-A-64-13548 and JP-A-64-73346.

When the group represented by B in formula (I) is a group which forms a substantially colorless compound by a coupling reaction with an oxidation product of a developing agent, examples of these groups include phenol and naphthol coupler units, pyrazolone coupler units and indanone coupler units. These units are linked to A-(L₁)v through an oxygen atom. These coupler units become couplers after splitting off A-(L₁)v and coupling with the oxidation products of the developing agents. Usually, colored dyes are formed, but if the diffusibility is suitably increased without a non-diffusible group,

the dyes into the processing solutions during development, and therefore substantially no dyes remain in the photographic material. Alternatively, when the dyes formed are diffusible dyes, they react with alkaline components (e.g. hydroxyl ions, sulfite ions) in the developing solutions during development; the dyes decompose and become colorless; and therefore substantially no dyes remain in the photographic material even if colored dyes are formed. Preferred examples of B include the following groups in which the mark * indicates the position at which each group is connected to A-(L₁)v and the mark ** indicates the position at which each group is connected to (L₂)w-DI.

In formulas (B-21), (B-22) and (B-23), R₁₃, R₁₄ and m are as defined above and R₁₆ has the same meaning as R₄₃.

The group represented by B in formula (I) is preferably a group which reduces an oxidation product of a developing agent after elimination of A-(L₁)v.

The compounds of the formula (I) of the present invention may be in the form of a polymer. All such polymers are within the scope of the present invention. Namely, these polymers are derived from a monomer compound represented by the following general formula (PI) and repeating units represented by the following general formula (P-II), or are copolymers of the monomer compound with at least one non-color-forming monomer which has at least one ethylene group and is incapable of coupling with oxidation products of aromatic primary amine developing agents. Two or more of the above monomer compounds may be polymerized simultaneously.

In formulas (P-I) and (P-II), RR represents a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms or a chlorine atom; A₁₁ represents -CONH-, -NHCONH-, -NHCOO-, -COO-, -SO₂-, -CO-, -NHCO-, -SO₂NH-, -NHSO₂-, -OCO-, -OCONH-, -NH- or -O-; A₁₂ represents -CONH- or -COO-; A₁₃ represents a substituted or unsubstituted alkylene or aralkylene group having preferably 1 to 10 carbon atoms or an unsubstituted or substituted arylene group. The alkylene group or alkylene moiety in the aralkylene moiety may be straight chain or branched.

QQ represents a unit of a compound having the formula (I) and may be linked to any of A, L₁, B and L₂.

i, j and k each mean 0 or 1, but in no case are i, j and k simultaneously 0.

Examples of substituent groups for the alkylene group, the aralkylene group or the arylene group represented by R₁₃ include: aryl (e.g. phenyl, naphthyl), nitro, hydroxyl, cyano, sulfo, alkoxy (e.g. methoxy), aryloxy (e.g. phenoxy), acyloxy (e.g. acetoxy), acylamino (e.g. acetylamino), sulfonamido (e.g. methanesulfonamido), sulfamoyl (e.g. methylsulfamoyl), halogen (e.g. fluorine, chlorine, bromine), carboxy, carbamoyl (e.g. methylcarbamoyl), alkoxycarbonyl (e.g. Methoxycarbonyl) and sulfonyl (e.g. methylsulfonyl, phenylsulfonyl). If these groups have two or more substituent groups, the substituent groups may be the same or different.

Examples of non-color-forming ethylenic monomers that do not couple with oxidation products of aromatic primary amine developing agents include acrylic acid, α-chloroacrylic acid, α-alkylacrylic acids, esters and amides of these acrylic acids, methylenebisacrylamide, vinyl esters, acrylonitrile, aromatic vinyl compounds, maleic acid derivatives and vinylpyridines. These non-color-forming ethylenically unsaturated monomers can be used either alone or as a mixture of two or more.

As the group represented by DI in formula (I), units of conventional development inhibitors can be used. For example, a heterocyclic mercapto group, a 1-indazolyl group and a triazolyl group can be preferably used. Specifically, examples thereof include tetrazolylthio groups, thiadiazolylthio groups, oxadiazolylthio groups, triazolylthio groups, benzoxazolylthio groups, benzothiazolylthio groups, benzimidazolylthio groups, 1-(or 2-)benzotriazolyl groups, 1,2,4-triazolyl-1-(or 4-)yl groups and 1-indazolyl groups. These groups may be substituted. Examples of substituent groups include aliphatic groups, aromatic groups, heterocyclic groups and those groups already described above in the definition of substituent groups for the aromatic group.

The compounds of formula (I) according to the invention can be synthesized according to the methods given in US Patents 4,618,571 and 4,770,982, JP-A-63-284159, JP-A-60-203943 and JP-A-63-23152.

Specific examples of compounds used in the photographic materials of the present invention include, but are not limited to, the following compounds.

Preferably, the compounds of formula (I) according to the invention are added to the light-sensitive silver halide emulsion layers or layers adjacent thereto in the photographic materials. Particularly preferably, the compounds are added to the red-sensitive silver halide emulsion layer. The compounds are used in an amount of 1 x 10⁻⁶ to 1 x 10⁻³ mol/m²₁, preferably 3 x 10⁻⁶ to 5 x 10⁻⁴ mol/m², more preferably 1 x 10⁻⁴ to 2 x 10⁻⁴ mol/m².

The compounds of formula (I) can be added to the photographic material according to the invention in the same manner as the addition of conventional couplers, which is described below.

The yellow-colored cyan couplers of the photographic material according to the invention are described in more detail below.

The yellow-colored cyan couplers in the photographic material according to the invention refer to cyan couplers which have an absorption maximum at 400 to 500 nm in the visible absorption range of the couplers and which form cyan dyes with an absorption maximum at 630 to 750 nm in the visible absorption range by their coupling with the oxidation product of an aromatic primary amine color developing agent.

The amount of the yellow-colored cyan coupler in the silver halide color photographic material of the invention is preferably from 0.05 to 0.30 g/m².

Among the yellow-colored cyan couplers, preferred are cyan couplers which release a unit of a water-soluble compound. Examples of such units include a 6-hydroxy-2-pyridone-5-ylazo group, a pyrazolone-4-ylazo group, a 2-acylaminophenylazo group or a 2-sulfonamidophenylazo group, and a 5-aminopyrazol-4-ylazo group through a coupling reaction with the oxidation product of an aromatic primary amine color developing agent.

The water-soluble compound should be dissolved out of the photographic material during development processing. The compound is preferably soluble in a developing solution having pH 9 to 12 in an amount of at least 1 g/l, more preferably at least 3 g/l at 25°C.

Preferably, the colored cyan couplers in the photographic material of the present invention can be represented by the following general formulas (CI) to (CIV).

In formulas (CI) to (CIV), Cp represents a cyan coupler unit (T is connected to its coupling site); T represents a timing group, k represents an integer of 0 or 1; X represents an N, O or S-containing divalent group which is connected to (T)k via the N, O or S atom and which is also connected to Q; and Q represents an arylene group or a divalent heterocyclic group (preferably having 6 to 12 carbon atoms, e.g. phenylene, naphthylene).

In formula (CI), R₁ and R₂ are independently a hydrogen atom, a carboxyl group, a sulfo group, a cyano group, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aryl group, a heterocyclic group, a carbamoyl group, a sulfamoyl group, a carbonamido group, a sulfonamido group or an alkylsulfonyl group; R₃ is a hydrogen atom, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aryl group or a heterocyclic group; and at least one of T, X, Q, R₁, R₂ and R₃ contains a water-soluble group (e.g., hydroxyl, carboxyl, sulfo, amino, ammonium, phosphono, phosphino, hydroxylsulfonyloxy).

It is understood that the group

in

Formula (CI) can exist in tautomeric forms as follows. All such tautomeric structures lie in the range of compounds of formula (I). (where R₃ is hydrogen) etc.

In the formula (CII), R₄ is an acyl group or sulfonyl group; R₅ is a group which may be bonded to the benzene ring; j is an integer of 0 to 4, when j is 2 or more, two or more R₅ groups may be the same or different; and at least one of T, X, Q, R₄ and R₅ contains a water-soluble group (e.g., hydroxyl, carboxyl, sulfo, phosphono, phosphino, hydroxysulfonyloxy, amino, ammonium).

In formulas (CIII) and (CIV), R�9 is a hydrogen atom, a carboxyl group, a sulfo group, a cyano group, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aryl group, an alkoxy group, a cycloalkoxy group, an aryloxy group, a heterocyclic group, a carbamoyl group, a sulfamoyl group, a carbonamido group, a sulfonamido group, an alkylsulfonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group or a sulfonyl group; R₁₀ is a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group; and at least one group from T, X, Q, R�9 and R₁₀ contains a water-soluble group (e.g. hydroxyl, carboxyl, sulfo, phosphono, phosphino, hydroxysulfonyloxy, amino, ammonium).

In addition, the compounds with the following group exist in tautomeric forms:

The compounds with the general formulas (CI) to (CIV) are discussed in more detail below.

Examples of coupler moieties represented by Cp include conventional cyan coupler moieties (e.g., phenol and naphthol couplers).

Preferred examples of Cp, among the compounds listed in the description of compounds of formula (I) are coupler units having the general formulae (Cp-6), (Cp-7) and (Cp-8).

The timing group represented by T in formulas (CI) to (CIV) is a group which is released from X after cleavage of the bond between Cp and T by the coupling reaction of the coupler with an oxidation product of an aromatic primary amine color developing agent. The timing group is used for various purposes, e.g., stabilizing the coupler, controlling the release time of X, etc. Examples of timing groups include conventional timing groups which have been exemplified by formulas (T-1) to (T-7) in describing compounds of formula (I).

Although k can be an integer of 0 or 1, the case that k is 0 is more preferred, i.e. that Cp is directly connected to X.

X is a divalent group linked to (T)k through an N, O or S atom. Preferably X is

or a divalent group linked to (T)k via N, such as a heterocyclic group (e.g. a group derived from pyrrolidine, piperidine, morpholine, piperazine, pyrrole, pyrazole, imidazole, 1,2,4-triazole, benzotriazole, succinimide, phthalimide, oxazolidine-2,4-dione, imidazolidine-2,4-dione, 1,2,4-triazolidine-3,5-dione) or a composite group derived from these groups and an alkylene group (e.g. methylene, ethylene, propylene), a cycloalkylene group (e.g. 1,4-cyclohexylene), an arylene group (e.g. o-phenylene, p-phenylene), a divalent heterocyclic group (e.g. a group derived from pyridine or thiophene), -CO-, -SO₂-, -COO-, -CONH-, -SO₂NH-, -SO₂O-, -NHCO-, -NHSO₂-, -NHCONH-, -NHSO₂NH- or -NHCOO-. More preferably, X is a group having the following general formula (II):

*-X₁-(L-X₂)m-** (II)

In formula (II), the symbol * represents the position where the group is bonded to (T)k; the symbol ** represents the position where the group is bonded to Q; X₁ represents -O- or -S-; L represents an alkylene group; X₂ represents a single bond,

or NHSO₂O-; and m represents an integer

Number of 0 to 3. The total number of carbon atoms (hereinafter referred to as carbon number) in X is preferably 0 to 12, more preferably 0 to 8. More preferably X is -OCH₂CH₂O-.

Q is an arylene group or a divalent heterocyclic group. When Q is an arylene group, the arylene group may be a condensed ring and may contain one or more substituent groups (examples of substituent groups include halogen atoms, hydroxyl, carboxyl, sulfo, nitro, cyano, amino, ammonium, phosphono, phosphino, alkyl, cycloalkyl, aryl, carbonamido, sulfonamido, alkoxy, aryloxy, acyl, sulfonyl, carboxyl, carbamoyl and sulfamoyl). The arylene group preferably has 6 to 15 carbon atoms, more preferably 6 to 10 carbon atoms. When Q is a divalent heterocyclic group, the heterocyclic group is a 3- to 8-membered, preferably 5- to 7-membered, monocyclic or condensed heterocyclic group having at least one heteroatom selected from the group consisting of N, O, S, P, Se and Te as a member of the heterocyclic ring (e.g., a group derived from pyridine, thiophene, furan, pyrrole, pyrazole, imidazole, thiazole, oxazole, benzothiazole, benzoxazole, benzofuran, benzothiophene, 1,3,4-thiodiazole, indole and quinoline) and may contain one or more substituent groups (examples of substituent groups are the same as for the arylene group in Q). The carbon number is preferably 2 to 15, more preferably 2 to 10. Preferably, Q is

Accordingly, the most preferred -(T)kXQ group

The aliphatic hydrocarbon group represented by R₁, R₂ or R₃ may be a straight-chain or branched group (e.g., alkyl) and may contain unsaturated bonds and one or more substituent groups (examples of substituent groups include halogen atoms, hydroxyl, carboxyl, sulfo, phosphono, phosphino, cyano, alkoxy, aryl, alkoxycarbonyl, amino, ammonium, acyl, carbonamido, sulfonamido, carbamoyl, sulfamoyl and sulfonyl).

When R₁, R₂ or R₃ is an alicyclic hydrocarbon group, the group is a 3- to 8-membered group which may contain cross-linking groups, unsaturated bonds or substituent groups (examples of substituent groups are the same as those described above in the definition of substituent groups for the aliphatic hydrocarbon group R₁, R₂ or R₃).

When R₁, R₂ or R₃ is an aryl group, the aryl group may be a condensed ring and may contain one or more substituent groups (examples of substituent groups are alkyl groups, cycloalkyl groups and the groups described above in the definition of the substituent groups for the aliphatic hydrocarbon group R₁, R₂ or R₃).

When R₁, R₂ or R₃ is a heterocyclic group, the heterocyclic group is a 3- to 8-membered, preferably a 5- to 7-membered monocyclic or condensed heterocyclic group having at least one heteroatom selected from the group consisting of N, S, O, P, Se and Te as a member of the heterocyclic ring (e.g. imidazolyl, thienyl, pyrazolyl, thiazolyl, pyridyl, quinolinyl) and may contain one or more substituent groups (examples of substituent groups are the same as those described above in the definition of the substituent groups for the aryl group R₁, R₂ or R₃).

In this specification, a carboxyl group may include a carboxylate group, a sulfo group may include a sulfonate group, a phosphono group may include a phosphinate group, and a phosphono group may include a phosphonate group.

Counterions include Li+, Na+, K+ and ammonium.

Preferably, R1 is a hydrogen atom, a carboxyl group, an alkyl group having 1 to 10 carbon atoms (e.g. methyl, t-butyl, sulfomethyl, 2-sulfomethyl, carboxymethyl, 2-carboxymethyl, 2-hydroxymethyl, benzyl, ethyl, isopropyl) or an aryl group having 6 to 12 carbon atoms (e.g. phenyl, 4-methoxyphenyl, 4-sulfophenyl), with a hydrogen atom, a methyl group or a carboxyl group being particularly preferred.

Preferably, R₂ is a cyano group, a carboxyl group, a carbamoyl group having 1 to 10 carbon atoms, a sulfamoyl group having 0 to 10 carbon atoms, a Sulfo group, an alkyl group having 1 to 10 carbon atoms (eg methyl, sulfomethyl), a sulfonyl group having 1 to 10 carbon atoms (eg methylsulfonyl, phenylsulfonyl), a carbonamido group having 1 to 10 carbon atoms (eg acetamido, benzamido) or a sulfonamido group having 1 to 10 carbon atoms (eg methanesulfonamido, toluenesulfonamido), with a cyano group, a carbamoyl group or a carboxyl group being particularly preferred.

Preferably, R3 is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms (e.g., methyl, sulfomethyl, carboxymethyl, ethyl, n-butyl, benzyl, 4-sulfobenzyl) or an aryl group having 6 to 15 carbon atoms (e.g., phenyl, 4-carboxyphenyl, 3-carboxyphenyl, 4-methoxyphenyl, 2,4-dicarboxyphenyl, 2-sulfophenyl, 3-sulfophenyl, 4-sulfophenyl, 2,4-disulfophenyl, 2,5-disulfophenyl), with an alkyl group having 1 to 7 carbon atoms or an aryl group having 6 to 10 carbon atoms being more preferred.

R₄ is preferably an acyl group having the following general formula (III) or a sulfonyl group having the following general formula (IV):

When R₁₁ is an aliphatic hydrocarbon group, the group includes both straight-chain and branched groups (preferably with 1 to 6 carbon atoms) and may contain unsaturated bonds and one or more substituent groups (examples of substituent groups include halogen atoms, hydroxyl, carboxyl, sulfo, phosphono₁, phosphino, cyano, alkoxy, aryl, alkoxycarbonyl, amino, ammonium, acyl, carbonamido, sulfonamido, carbamoyl, sulfamoyl and sulfonyl).

When R₁₁ is an alicyclic hydrocarbon group, the group is a 3- to 8-membered group which may contain crosslinking groups and unsaturated bonds and one or more substituent groups (examples of substituent groups are those described above in the definition of substituent groups for the aliphatic hydrocarbon group R₁₁).

When R₁₁ is an aryl group, the aryl group may be a fused ring and may contain one or more substituent groups (examples of substituent groups include an alkyl group, a cycloalkyl group, and those groups as described above in the definition of substituent groups for the aliphatic hydrocarbon group R₁₁).

When R₁₁ is a heterocyclic group, the heterocyclic group is a 3- to 8-membered (preferably 5- to 7-membered) monocyclic or condensed heterocyclic group containing at least one heteroatom selected from the group consisting of N, S, O, P, Se and Te as a member of the heterocyclic ring (e.g. imidazolyl, thienyl, pyrazolyl, thiazolyl, pyridyl, quinolyl) and may contain one or more substituent groups (examples of substituent groups are those described above in the definition of substituent groups for the aryl group R₁₁).

In this specification, a carboxyl group may include a carboxylate group, a sulfo group may include a sulfonate group, a phosphino group may include a phosphinate group, and a phosphono group may include a phosphonate group. Counterions include Li+, Na+, K+ and ammonium.

Preferably, R₁₁ is an alkyl group having 1 to 10 carbon atoms (e.g. methyl, carboxymethyl, sulfoethyl, cyanoethyl), a cycloalkyl group having 5 to 8 carbon atoms (e.g. cyclohexyl, 2-carboxycyclohexyl) or an aryl group having 6 to 10 carbon atoms (e.g. phenyl, 1-naphthyl, 4-sulfophenyl), with an alkyl group having 1 to 3 carbon atoms and an aryl group having 6 carbon atoms being particularly preferred.

R₅ is a group which may be bonded to the benzene ring, and preferably an electron-donating group. Particularly preferably, R₅ is a -NR₁₂R₁₃ or -OR₁₄- group, which is preferably bonded to the 4-position of the ring. R₁₂, R₁₃ and R₁₄ are each a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group, and each of these groups has the same meaning as R₁₁. R₁₂ and R₁₃ may be bonded to each other to form a ring. Regarding the ring formed, a nitrogen-containing heterocyclic ring in which the Nitrogen other atoms are all carbon atoms, preferred.

j is an integer from 0 to 41, preferably 1 to 2, particularly preferably 1.

When R�9 or R₁₀ is an aliphatic hydrocarbon group, the group may be a straight chain or branched group, may contain unsaturated bonds and may contain one or more substituent groups (e.g., halogen atoms, hydroxyl, carboxyl, sulfo, phosphono, phosphino, cyano, alkoxy, aryl, alkoxycarbonyl, amino, ammonium, acyl, carbonamido, sulfonamido, carbamoyl, sulfamoyl, sulfonyl).

When R₉ or R₁₀ is an alicyclic hydrocarbon group, the group is a 3- to 8-membered group which may contain cross-linking groups, unsaturated bonds or substituent groups (examples of substituent groups are those described above in the definition of substituent groups for the aliphatic hydrocarbon group R₉ or R₁₀).

When R₉ or R₁₀ is an aryl group, the aryl group may be a condensed ring and may have one or more substituent groups (examples of substituent groups are an alkyl group, a cycloalkyl group, and those groups as described above in the definition of substituent groups for the aliphatic hydrocarbon groups R₉ and R₁₀).

When R₉ or R₁₀ is a heterocyclic group, the heterocyclic group is a 3- to 8-membered (preferably 5- to 7-membered) monocyclic or condensed heterocyclic group containing at least one heteroatom selected from the group consisting of N, S, O, P, Se and Te as a member of the heterocyclic ring (e.g. imidazolyl, thienyl, pyrazolyl, thiazolyl, pyridyl, quinolinyl) and may contain one or more substituent groups (examples of the substituent groups are those described above in the definition of the substituent groups for the aryl group R₉ or R₁).

In this specification, a carboxyl group may include a carboxylate group, a sulfo group may include a sulfonate group, a phosphino group may include a phosphinate group, and a phosphono group may include a phosphonate group. Counterions include Li+, Na+, K+ and ammonium.

Preferably, R�9 is a cyano group, a carboxyl group, a carbamoyl group having 1 to 10 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, an aryloxycarbonyl group having 7 to 11 carbon atoms, a sulfamoyl group having 0 to 10 carbon atoms, a sulfo group, an alkyl group having 1 to 10 carbon atoms (e.g. methyl, carboxymethyl, sulfomethyl), a sulfonyl group having 1 to 10 carbon atoms (e.g. methylsulfonyl, phenylsulfonyl), a carbonamido group having 1 to 10 carbon atoms (e.g. acetamido, benzamido), a sulfonamido group having 1 to 10 carbon atoms (e.g. methanesulfonamido, toluenesulfonamido), an alkyloxy group (e.g. methoxy, ethoxy) or an aryloxy group (e.g. phenoxy), with a cyano group, a carbamoyl group, an alkoxycarbonyl group and a carboxyl group being particularly preferred.

Preferably, R₁₀ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms (e.g., methyl, sulfomethyl, carboxymethyl, ethyl, 2-sulfoethyl, 2-carboxyethyl, 3-sulfopropyl, 3-carboxypropyl, 5-sulfopentyl, 5-carboxypentyl, 4-sulfobenzyl) or an aryl group having 6 to 15 carbon atoms (e.g., phenyl, 4-carboxyphenyl, 3-carboxyphenyl, 2,4-dicarboxyphenyl, 4-sulfophenyl, 3-sulfophenyl, 2,5-disulfophenyl, 2,4-disulfophenyl), with an alkyl group having 1 to 7 carbon atoms or an aryl group having 6 to 10 carbon atoms being more preferred.

Special examples of Cp, X, Q,

and

in the formulas (CI) to (CIV) include the following groups.

Examples of Cp: (Examples of X) (Examples of Q)

Examples of

Examples of

Examples of

Examples of colored couplers according to the invention

In the silver halide color photographic material according to the invention, the compound having the formula (I) and the yellow-colored cyan coupler are preferably each incorporated into at least one of the silver halide emulsion layers and an adjacent light-insensitive intermediate layer.

In a further advantageous embodiment of the present invention, the compound of formula (I) is incorporated into the layer having the same color sensitivity as the layer containing the yellow-colored cyan coupler.

Preferably, the compounds with the general formula (I) and the yellow-colored cyan coupler are contained in the same red-sensitive silver halide emulsion layer.

The color couplers having the formula (CI) can generally be synthesized by a diazo coupling reaction of a 6-hydroxy-2-pyridone compound with an aromatic diazonium salt or heterocyclic diazonium salt having a coupler structure.

The former 6-hydroxy-2-pyridone compounds can be synthesized by methods described in Klinsberg, Heterocyclic Compound - Pyridine and its Derivatives, Part 3 (Interscience 1962); J. Am. Chem. Soc., Vol. 65, page 449 (1943); J. Chem. Tech. Biotechnol., Vol. 36, page 410 (1986); Tetrahedron, Vol. 22, page 445 (1966); JP-B-61-52827 (the term "JP-B" as used herein means a "tested Japanese Patent Publication"); DE-PS 2 162 612, 2 349 709 and 2 902 486; and US-PS 3 763 170.

The latter diazonium salts can be synthesized by methods described in U.S. Patents 4,004,929 and 4,138,258, JP-A-61-72244 and JP-A-61-273543. The diazo coupling reaction of the 6-hydroxy-2-pyridone compounds with the diazonium salts can be carried out in a solvent such as methanol, ethanol, methyl cellosolve, acetic acid, N,N-dimethylformamide, N,N-dimethylacetamide, tetrahydrofuran, dioxane, water or a mixture thereof. In this reaction, sodium acetate, potassium acetate, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, sodium hydroxide, potassium hydroxide, pyridine, triethylamine, tetramethylurea or tetramethylguanidine can be used as a base. The reaction temperature is generally from -78 to +60°C, preferably from -20 to +30°C.

Synthesis examples of color couplers according to the invention are given below. SYNTHESIS EXAMPLE 1 - Synthesis of Coupler (YC-1): Coupler

Synthesis of compound (a):

125.2 g of taurine and 66 g of potassium hydroxide were added to 500 mL of methanol. The mixture was stirred under reflux. 110 g of methyl cyanoacetate was added dropwise over a period of about 1 hour. The mixture was heated under reflux for 5 hours and then left overnight. The precipitated crystals were collected by filtration, washed with ethanol and dried to give 202.6 g of compound (a) as crystals.

Synthesis of compound (b):

11.5 g of compound (a) and 3.5 g of potassium carbonate were added to 11.5 ml of water. While heating the mixture on a steam bath with stirring, 7.8 g of ethyl acetoacetate was added dropwise. The mixture was stirred for 7 hours and then left to cool. 9.2 ml of concentrated hydrochloric acid was added to precipitate crystals. The crystals were collected by filtration, washed with methanol and dried to give 10.4 g of compound (b) as crystals.

Synthesis of coupler (YC-1):

10.1 g of compound (c) synthesized by the method described in U.S. Patent No. 4,138,258 was dissolved in 60 ml of N,N-dimethylformamide and 60 ml of methyl cellosolve. While cooling the resulting solution with ice, 4.3 ml of concentrated hydrochloric acid was added and a solution of 1.84 g of sodium nitrite in 5 ml of water was added dropwise to prepare a diazonium solution. 60 ml of methyl cellosolve and 20 ml of water were added to 7.8 g of compound (b) and 8.2 g of sodium acetate. While stirring the resulting solution under ice-cooling, the above diazonium solution was added dropwise. After the dropwise addition, the mixture was stirred for 1 hour and then stirred at room temperature for 2 hours. The precipitated crystals were collected by filtration, washed with water, dried and dispersed in 500 ml of methanol. The dispersion was heated to reflux for 1 hour and then allowed to cool. The crystals were collected by filtration, washed with methanol and dried to give 13.6 g of the desired coupler (YC-1) in The compound was obtained in the form of red crystals with a melting point of 269 to 272°C (decomposition). The structure of the compound was confirmed by 1H-NMR spectrum, mass spectrum and elemental analysis. The compound exhibited a wavelength absorption maximum in methanol at 457.7 nm and had a molecular extinction coefficient of 41,300. The compound was found to have good spectral absorption characteristics as a yellow-colored coupler. SYNTHESIS EXAMPLE 2 - Synthesis of Coupler (YC-3) Coupler

75 ml of N,N-dimethylformamide and 75 ml of methyl cellosolve were added to 19.2 g of compound (d) synthesized by the method of JP-A-62-85242 (US Pat. No. 4,837,136) to dissolve it. While stirring the resulting solution under ice-cooling, 5.6 ml of concentrated hydrochloric acid was added and a solution of 2.5 g of sodium nitrite and 5 ml of water was then added dropwise. After the dropwise addition, the mixture was stirred for 1 hour and then at room temperature for 1 hour to prepare a diazonium solution.

75 ml of methyl cellosolve and 26 ml of water were added to 10.1 g of compound (b) and 10.7 g of sodium acetate. While stirring the resulting solution under ice-cooling, the above diazonium solution was added dropwise. After the dropwise addition, the mixture was stirred for 1 hour and then at room temperature for 2 hours. The precipitated crystals were collected by filtration and dispersed in 200 ml of methanol. A solution of 2.2 g of sodium hydroxide in 10 ml of water was added dropwise. The mixture was stirred for 3 hours and neutralized with concentrated hydrochloric acid. The precipitated crystals were washed with water and then with methanol and dried. The resulting crude crystals were purified from hot methanol in the same manner as in Synthesis Example 1 to obtain 14.8 g of the desired coupler (YC-3) having a melting point of 246 to 251 °C (decomposition). The structure of the compound was confirmed by ¹H-NMR spectrum, mass spectrum and elemental analysis. The compound showed a wavelength absorption maximum in methanol at 457.6 nm and had a molecular extinction coefficient of 42,700. The compound was found to have good spectral absorption characteristics as a yellow-colored coupler. SYNTHESIS EXAMPLE 3 - Synthesis of Coupler (YC-30) Diketene Coupler

Synthesis of compound (s):

137.1 g of anthranilic acid was added to 600 ml of acetonitrile. The mixture was refluxed with stirring. 92.5 g of diketene was added dropwise over a period of about 1 hour. The mixture was refluxed for 1 hour and cooled to room temperature. The precipitated crystals were collected by filtration, washed with acetonitrile and dried to obtain 200.5 g of compound (e) in the form of crystals.

Synthesis of compound (f):

199.1 g of compound (e), 89.2 g of ethyl cyanoacetate and 344 g of 28% sodium methoxide were added to 0.9 L of methanol. The mixture was reacted at 120°C in an autoclave for 8 hours. After the reaction mixture was allowed to stand overnight, the reaction mixture was concentrated under reduced pressure. 700 ml of water was added and the mixture was acidified with 230 ml of concentrated hydrochloric acid. The precipitated crystals were recovered by filtration. The resulting crude crystals were washed with a mixed solvent of ethyl acetate and acetonitrile under heating to obtain 152 g of compound (f).

Synthesis of coupler (YC-30):

13.0 g of compound (g), synthesized according to the method of US-PS 4,138,258, was dissolved in 40 ml of N,N-dimethylformamide. While cooling the resulting solution with ice, 4.5 ml of concentrated hydrochloric acid was added and a solution of 1.48 g of sodium nitrite and 5 ml of water was added dropwise to prepare a diazonium solution. 20 ml of N,N-dimethylfortamide and 15 ml of water were added to 6.0 g of compound (f) and 8 g of sodium acetate. While stirring the mixture under ice-cooling, the above diazonium solution was added dropwise. After the addition, the mixture was stirred at room temperature for 30 minutes and acidified with hydrochloric acid. The product was extracted with ethyl acetate, washed with water and concentrated under reduced pressure. The concentrate was recrystallized from a mixed solvent of ethyl acetate and methanol to give 13 g of coupler (YC-30) as yellow crystals.

The coupler (YC-30) had a melting point of 154 to 156ºC. Its structure was confirmed by ¹H-NMR spectrum, mass spectrum and elemental analysis. The compound showed a wavelength absorption maximum in methanol at 458.2 nm and had a molecular extinction coefficient of 42,800. The compound was found to have good spectral absorption characteristics as a yellow-colored coupler. SYNTHESIS EXAMPLE 4 - Synthesis of Coupler (YC-86) Matchmaker

(1) Synthesis of compound (3):

445.5 g of phenyl ether compound (1) and 90.1 g of isopropanolamine (2) were added to 600 ml of acetonitrile and the mixture was heated to reflux for 2 hours. After being allowed to cool with water, the precipitated crystals were collected by filtration. The crystals were dried to give 342 g of compound (3) with a melting point of 162 to 165°C.

(2) Synthesis of compound (5):

341 g of hydroxyl compound (3) and 231 g of 2-hexyldecanoyl chloride were added to 880 ml of acetonitrile. The mixture was heated to reflux for 2 hours. After being allowed to cool with ice, the precipitated crystals were collected by filtration. The crystals were dried to give 437 g of compound (5) with a melting point of 97 to 100 °C.

(3) Synthesis of compound (6):

370 g of nitro compound (5), 6 g of 10% Pd-C catalyst and 1 L of ethyl acetate were placed in an autoclave and hydrogenated at 50°C for 3 hours. After completion of the reduction reaction, the catalyst was removed by filtration and the filtrate was concentrated under reduced pressure. The residue obtained was recrystallized with n-hexane. The precipitated crystals were collected by filtration and dried to give 327 g of amine compound (7) having a melting point of 95 to 97°C.

(4) Synthesis of coupler (YC-86):

20 g of amine compound (7) were dissolved in 60 ml of dimethylformamide. While cooling the solution with ice, 7.6 ml of concentrated hydrochloric acid were added. In addition, a solution of 2.7 g of sodium nitrite in 10 ml of water was added dropwise over a period of 20 minutes and the solution was stirred for a further 30 minutes to form a diazo solution.

9.7 g of pyridone (7) and 13 g of sodium acetate were added to a mixture of 30 ml of water and 30 ml of dimethylformamide and dissolved. After cooling the resulting solution with water, the diazo solution was gradually added with stirring at a temperature of not higher than 10°C. After further stirring for 15 minutes, the product was extracted with ethyl acetate, washed three times with water, and the organic layer was concentrated under reduced pressure. The residue was crystallized with a methanol-ethyl acetate mixture, the precipitated crystals were collected by filtration and dried, thus obtaining 21.2 g of coupler (YC-86) having a melting point of 117 to 119°C.

The yellow-colored cyan couplers represented by the formulas (CII) to (CIV) can be synthesized by the methods described in JP-B-58-6939 (the term "JP-B" here means an "examined Japanese patent application") and JP-A-1-197563. The couplers represented by the general formula (CI) can be synthesized by the methods described in the above-mentioned patent documents.

Among the yellow-colored cyan couplers, the couplers having the formulas (CI) and (CII) are more preferred, and the couplers having the formula (CI) are particularly preferred.

Preferably, the yellow-colored cyan couplers of the present invention are added to light-sensitive silver halide emulsion layers or adjacent light-insensitive interlayers in the photographic materials. More preferably, the yellow-colored cyan couplers are added to the red-sensitive emulsion layer. The total amount of the couplers added to the photographic material is preferably 0.005 to 0.30 g/m², more preferably 0.02 to 0.20 g/m², particularly preferably 0.03 to 0.15 g/m².

The yellow-colored couplers in the photographic material of the present invention can be added in the same manner as in the addition of conventional couplers described below. From the viewpoint of increasing the interlayer effect between the red-sensitive layer and the blue-sensitive layer and improving sharpness, it is preferred that a polymer coupler obtained from at least one monomer represented by the following general formula (F) is used in the green-sensitive layer of the silver halide color photographic material of the present invention (specifically, the layer order from the support is red-, green- and blue-sensitive layers, and the yellow-colored coupler and the compound represented by the formula (I) are incorporated in the red-sensitive layer):

In formula (P), R₁₂₁ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a chlorine atom; -D- represents -COO-, -CONR₁₂₂- or a substituted or unsubstituted phenylene group; -E- represents a substituted or unsubstituted alkylene, phenylene or aralkylene group; -F- means -CONR₁₂₂₀-, -NR₁₂₂₂CONR₁₂₂₀-, -NR₁₂₂COO-, -NR₁₂₂CO-, -OCONR₁₂₂-, -NR₁₂₂-, -COO-, -OCO-, -CO-, -O-, -S-, -SO₂-, -NR₁₂₂SO₂ or -SO₂NR₁₂₂-; R₁₂₂₂ represents a hydrogen atom or a substituted or unsubstituted, saturated or unsaturated aliphatic group or a substituted or unsubstituted aryl group, and when two or more R₁₂₂ groups are present per molecule, they may be the same or different; and p, q and r each represent 0 or 1, with the proviso that p, q and r cannot be 0 at the same time.

Examples of substituents for the groups D, E and R₁₂₂ include a halogen atom, a hydroxy group, a carboxy group, a sulfo group, a phosphono group, a phosphino group, a cyano group, an alkoxy group, an aryl group, an aryloxy group, an alkoxycarbonyl group, an amino group, an ammonium group, an acyl group, a carbonamido group, a sulfonamido group, a carbamoyl group, a sulfamoyl group and a sulfonyl group.

T in formula (P) represents a magenta coupler unit (which is linked to -(F)r- at a position of Ar, Z and R₁₃₃) having the following general formula (Q)

In formula (Q), Ar represents known substituent groups for the 1-position of 2-pyrazolin-5-one couplers, such as alkyl groups, substituted alkyl groups (e.g. haloalkyl such as fluoroalkyl, cyanoalkyl, benzylalkyl), substituted or unsubstituted heterocyclic groups (e.g. 4-pyridyl groups, 2-thiazolyl groups), substituted or unsubstituted aryl groups (examples of substituent groups for the heterocyclic group and the aryl group include alkyl groups such as methyl and ethyl), an alkoxy group (e.g. methoxy, ethoxy), an aryloxy group (e.g. phenyloxy), an alkoxycarbonyl group (e.g. methoxycarbonyl), an acylamino group (e.g. acetylamino), a carbamoyl group, an alkylcarbamoyl group (e.g. methylcarbamoyl, ethylcarbamoyl), a dialkylcarbamoyl group (e.g. Dimethylcarbamoyl), an arylcarbamoyl group (eg phenylcarbamoyl), an alkylsulfonyl group (eg methylsulfonyl), an arylsulfonyl group (eg phenylsulfonyl), an alkylsulfonamido group (eg methanesulfonamido), an arylsulfonamido group (eg phenylsulfonamido), a sulfamoyl group, an alkylsulfamoyl group (eg ethylsulfamoyl), a dialkylsulfamoyl group (eg dimethylsulfamoyl), an alkylthio group (eg methylthio), an arylthio group (eg phenylthio), a cyano group, a nitro group and a halogen atom (eg fluorine, chlorine, bromine). If two or more of these substituent groups are present, they may be the same or different.

Particularly preferred substituent groups are a halogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group and a cyano group.

R₁₃₃ represents a substituted or unsubstituted anilino group, an acylamino group (eg alkylcarbonamido, phenylcarbonamido, alkoxycarbonamido, phenyloxycarbonamido), a ureido group (eg alkylureido, phenylureido) or a sulfonamido group. These groups may be substituted. Examples of substituent groups include a halogen atom (e.g. fluorine, chlorine, bromine), a straight chain or branched alkyl group (e.g. methyl, t-butyl, octyl, tetradecyl), an alkoxy group (e.g. methoxy, ethoxy, 2-ethylhexyloxy, tetradecyloxy), an acylamino group (e.g. acetamido, benzamido, butanamido, octanamido, tetradecanamido, α-(2,4-di-tert-amylphenoxy)acetamido, α-(2,4-di-tert-amylphenoxy)butylamido, α-(3-pentadecylphenoxy)hexanamido, α-(4-hydroxy-3-tert-butylphenoxy)tetradecanamido, 2-oxo-pyrrolidin-1-yl, 2-oxo-5-tetradecylpyrrolidin-1-yl, N-methyltetradecanamido), a sulfonamido group (e.g. methanesulfonamido, benzenesulfonamido, ethylsulfonamido, p-toluenesulfonamido, octanesulfonamido, p-dodecylbenzenesulfonamido, N-methyl-N-tetradecanesulfonamido), a sulfamoyl group (e.g. sulfamoyl, N-methylsulfamoyl, n-ethylsulfamoyl, N, N-dimethylsulfamoyl, N, N-dihexylsulfamoyl, N-hexadecylsulfamoyl, N-[3-(dodecyloxy)-propyl]sulfamoyl, N-[4-(2,4-di-tert-amylphenoxy)butyl]-sulfamoyl, N-methyl- N-tetradecylsulfamoyl), a carbamoyl group (e.g. N-methylcarbamoyl, N-butylcarbamoyl, N-octadecylcarbamoyl, N-[4-(2,4-di-tert-amylphenoxy)butyl]-carbamoyl, N-methyl- N-tetradecylcarbamoyl), a diacylamino group (e.g. N-succinimido, N-phthalimido, 2,5-dioxo-1-oxazolidinyl, 3-dodecyl-2,5-dioxo-1-hydantoinyl, 3-(N-acetyl-N- dodecylamino)succinimido), an alkoxycarbonyl group (e.g. methacryloxycarbonyl, tetradecyloxycarbonyl, benzyloxycarbonyl), a an alkoxysulfonyl group (e.g. methoxysulfonyl, butoxysulfonyl, octyloxysulfonyl, tetradecyloxysulfonyl), an aryloxysulfonyl group (e.g. phenoxysulfonyl, p-methylphenoxysulfonyl, 2,4-di-tert-amylphenoxysulfonyl), an alkanesulfonyl group (e.g. methanesulfonyl, ethanesulfonyl, octanesulfonyl, 2-ethylhexylsulfonyl, hexadecanesulfonyl), an arylsulfonyl group (e.g. benzenesulfonyl, 4-nonylbenzenesulfonyl), an alkylthio group (e.g. methylthio, ethylthio, hexylthio, benzylthio, tetradeaylthio, 2-(2,4-di-tert-amylphenoxy)-ethylthio), an arylthio group (e.g. phenylthio, p-tolylthio), an alkyloxycarbonylamino group (e.g. Methoxycarbonylamino, ethyloxycarbonylamino, benzyloxycarbonylamino, hexadecyloxycarbonylamino), an alkylureido group (e.g. N-methylureido, N,N-dimethylureido, N-methyl-N- dodecylureido, N-hexadecylureido, N,N-dioctadecylureido), an acyl group (e.g. acetyl, benzoyl, octadecanoyl, p-dodecanamidobenzoyl), a nitro group, a carboxyl group, a sulfo group, a hydroxyl group and a trichloromethyl group.

In the substituent groups described above, the alkyl group and alkyl moiety preferably have 1 to 36 carbon atoms and the aryl group preferably has 6 to 38 carbon atoms.

Z represents a halogen atom (e.g. a chlorine atom or bromataine), a group linked through an oxygen atom and split off by a coupling reaction (e.g. acetoxy, propanoyloxy, benzoyloxy, ethoxyoxaloyloxy, pyruvinyloxy, cinnamoyloxy, phenoxy, 4-cyanophenoxy, 4-titaniumsulfonamidophenoxy, α-naphthoxy, 4-cyanoxy, 4-methanesulfonamidophenoxy, p-naphthoxy, 3-pentadecylphenoxy, benzyloxycarbonyloxy, ethoxy, 2-cyanoethoxy, benzyloxy, 2-phenethyloxy, 2-phenoxyethoxy, 5-phenyltetradecyloxy and 2-benzothiazolyloxy), a coupling leaving group linked through a nitrogen atom (e.g. as disclosed in JP-A-59-99437, e.g. benzenesulfonamido, N-ethyltoluenesulfonamido, heptafluorobutanamido, 2,3,4,5,6-pentafluorobenzamido, octanesulfonamido, p-cyanophenylureido, N,N- diethylsulfamoylamino, 1-piperidyl, 5,5-dimethyl-2,4- dioxo-3-oxazolidinyl, 1-benzyl-5-ethoxy-3-hydantoinyl, 2-oxo-1,2-dihydro-1-pyridinyl, imidazolyl, pyrazolyl, 3,5- diethyl-1,2,4-triazol-1-yl, 5- or 6-bromobenzotriazol-1-yl, 5-methyl-1,2,4-triazol-l-yl and benzimidazolyl), a coupling leaving group linked via a sulfur atom (e.g. phenylthio, 2-carboxyphenylthio, 2-methoxy-5-octylphenylthio, 4-methanesulfonylthio, 4-octanesulfonamidophenylthio, benzylthio, 2-cyanoethylthio, 5-phenyl-2,3,4,5-tetrazolylthio and 2-benzothiazolyl).

Preferred coupling leaving groups are those which are linked via a nitrogen atom and a particularly The preferred coupling leaving group is a pyrazolyl group.

E represents a substituted or unsubstituted alkylene, aralkylene or phenylene group having preferably 1 to 10 carbon atoms. The alkylene group may be straight chain or branched. Examples of alkylene groups include a methylene group, a methylmethylene group, a dimethylmethylene group, a dimethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group and a decylmethylene group. An example of an aralkylene group includes a benzylidene group. An example of a phenylene group includes a p-phenylene group, an m-phenylene group and a methylphenylene group.

Examples of substituents for the alkylene group, the aralkylene group or the phenylene group represented by E include: an aryl group (e.g. phenyl), a nitro group, a hydroxyl group, a cyano group, a sulfo group, an alkoxy group (e.g. methoxy), an aryloxy group (e.g. phenoxy), an acyloxy group (e.g. acetoxy), an acylamino group (e.g. acetylamino), a sulfonamido group (e.g. methanesulfonamido), a sulfamoyl group (e.g. methylsulfamoyl), a halogen atom (e.g. fluorine, chlorine and bromine), a carboxy group, a carbamoyl group (e.g. methylcarbamoyl), an alkoxycarbonyl group (e.g. methoxycarbonyl), a sulfonyl group (e.g. methylsulfonyl). If E has two or more substituents, they may be the same or different.

Examples of non-color-forming ethylene monomers which can copolymerize with a coupler monomer represented by the formula (P) and cannot couple with an oxidized product of an aromatic primary amine developing agent include an acrylic acid ester, a methacrylic acid ester, a crotonic acid ester, a vinyl ester, a maleic acid diester, a fumaric acid diester, an itaconic acid diester, an acrylamide, a methacrylamide, a vinyl ether and a styrene.

Specific examples of such monomers are given below.

Examples of acrylic acid esters include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, acetoxyethyl acrylate, phenyl acrylate, 2-methoxyacrylate, 2-ethoxyacrylate and 2-(2-methoxyethoxy)ethyl acrylate. Examples of methacrylic esters include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, 2-hydroxyethyl methacrylate and 2-ethoxyethyl methacrylate. Examples of crotonic acid esters include butyl crotonate and hexyl crotonate. Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate and vinyl benzoate.

Examples of maleic acid diesters include diethyl maleate, dimethyl maleate and dibutyl maleate. Examples of fumaric acid diesters include diethyl fumarate, dimethyl fumarate and dibutyl fumarate. Examples of itaconic acid diesters include diethyl itaconate, Dimethyl itaconate and dibutyl itaconate. Examples of acrylamides include acrylamide, methylacrylamide, ethylacrylamide, propylacrylamide, n-butylacrylamide, tert-butylacrylamide, cyclohexylacrylamide, 2-methoxyethylacrylamide, dimethylacrylamide, diethylacrylamide and phenylacrylamide. Examples of methaarylamides include methylmethacrylamide, ethylmethacrylamide, n-butylmethacrylamide, tert-butylmethacrylamide, 2-methoxymethacrylamide, dimethylmethacrylamide and diethylmethacrylamide.

Examples of vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether and dimethylaminoethyl vinyl ether. Examples of styrenes include styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, chloromethylstyrene, methoxystyrene, butoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, methyl vinyl benzoate and 2-methylstyrene.

Examples of other monomers include allyl compounds (e.g. allyl acetate), vinyl ketones (e.g. methyl vinyl ketone), heterocyclic vinyl compounds (e.g. vinyl pyridine), glycidyl esters (e.g. glycidyl acrylate), unsaturated nitriles (e.g. acrylonitrile), acrylic acid, methacrylic acid, itaconic acid, maleic acid, monoalkyl itaconates (e.g. monomethyl itaconate), monoalkyl maleates (e.g. monomethyl maleate), citraconic acid, vinyl sulfonic acid, acryloyloxyalkyl sulfonic acids (e.g. acryloyloxymethyl sulfonic acid) and acrylamidoalkyl sulfonic acids (e.g. 2-acrylamido-2-methylethane sulfonic acid). These acids can be in the form of a salt. such as an alkali metal salt (e.g. Na, K) or a salt of an ammonium ion.

Among these monomers, acrylic esters, methacrylic esters, styrenes, maleic acid esters, acrylamides and methacrylamides are preferred comonomers.

These monomers can be used either alone or in combination of two or more. For example, a combination of n-butyl acrylate and styrene, a combination of n-butyl acrylate and butyl styrene, and a combination of t-butyl methacrylamide and n-butyl acrylamide can be used.

In general, the coupler-forming unit represented by the formula (P) preferably accounts for 5 to 80% by weight of the above magenta coupler. However, from the viewpoint of color reproducibility, color formation and stabilization, it is preferred that the proportion of the color-forming unit in the coupler is 30 to 70% by weight. In this case, the equimolar weight (gram of polymer containing 1 mole of monomer coupler) is 250 to 4,000, but is not limited thereto.

The above polymeric couplers are preferably added to silver halide emulsion layers or light-insensitive layers adjacent thereto. A polymeric magenta coupler is preferably contained in the green-sensitive silver halide emulsion layer or in a light-insensitive layer adjacent thereto.

The magenta polymer couplers, when used in the green-sensitive silver halide emulsion layers, are used in an amount of 0.005 to 0.5 mol, preferably 0.03 to 0.25 mol (based on coupler monomers) per mole of silver used in the same layer.

When the magenta polymer couplers are used in the light-insensitive layers, the polymer couplers are used at a coating weight of 0.01 to 1.0 g/m², preferably 0.1 to 0.5 g/m².

The polymer couplers can be prepared by emulsifying and dispersing a solution of a lipophilic polymer coupler in the form of a latex in an organic solvent in an aqueous gelatin solution, the polymer coupler being obtained by polymerizing a monomer coupler in the manner given above. Alternatively, the polymer coupler can be prepared directly by an emulsion polymerization process.

A process for emulsifying and dispersing the lipophilic polymeric coupler in the form of a latex in an aqueous gelatin solution is described in U.S. Patent No. 3,451,820. The emulsion polymerization can be carried out using the methods described in U.S. Patent Nos. 4,080,211 and 3,370,952.

The syntheses of the above polymeric magenta couplers are carried out using the compounds described in JP-A-56-5543, JP-A-57-94752, JP-A-57-176038, JP-A-57-204038, JP-A-58-28745, JP-A-58-10738, JP-A-58-42044 and JP-A-58-145944, polymerization initiators and solvents.

The polymerization temperature depends on the molecular weight of the polymers to be synthesized, the Types of initiators etc. Polymerization can be carried out at a temperature of below 0ºC to more than 100ºC, but usually polymerization is carried out at a temperature of 30 to 100ºC.

Examples of polymeric magenta couplers which can be used in the present invention include, but are not limited to, the following compounds (the subscript after the parentheses indicates the molar proportion).

The photographic material of the present invention has a support and thereon at least one blue-sensitive silver halide emulsion layer, green-sensitive silver halide emulsion layer and red-sensitive silver halide emulsion layer. There is no particular limitation on the number of silver halide emulsion layers and non-sensitive layers and the order of the layers. A typical example is a silver halide photographic material having at least one sensitive layer from a plurality of silver halide emulsion layers having substantially the same color sensitivity but different light sensitivities, the sensitive layer being a unit sensitive layer having color sensitivity to one of blue light, green light and red light. In a multilayer silver halide color photographic material, the sensitive layer units are generally arranged in the order of a red-sensitive layer, a green-sensitive layer and a blue-sensitive layer from the support. However, the order may be reversed from the above order depending on the purpose of use. In addition, the arrangement may be such that a differently light-sensitive layer is inserted into layers having the same color sensitivity.

Non-sensitive layers such as various interlayers may be provided between the sensitive silver halide layers or as the top or bottom layer. The interlayers may contain couplers or DIR compounds described in JF-A-61-43748, JF-A-59-113438, JP-A-59-113440, JP-A-61-20037 and JP-A-61-20038. The intermediate layers may also contain color mixing inhibitors as commonly used.

A plurality of silver halide emulsion layers constituting each sensitive layer unit preferably includes a two-layer structure of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer as described in DE-PS 1 121 470 and GB-PS 923 045. Preferably, the layers are arranged so that the light sensitivity decreases toward the support. A light-insensitive layer may be provided between the silver halide emulsion layers. The low-sensitivity emulsion layer may be provided on the side farther from the support and the high-sensitivity emulsion layer may be provided closer to the support as described in JP-A-57-112751, JP-A-62-200350, JP-A-62-206541 and JP-A-62-206543.

In specific embodiments, the layer may be arranged in the order of low sensitivity blue sensitive layer (BL) / high sensitivity blue sensitive layer (EH) / high sensitivity green sensitive layer (GH) / low sensitivity green sensitive layer (GL) / high sensitivity red sensitive layer (RH) / low sensitivity red sensitive layer (RL) from the outermost layer, or in the order of BH/BL/GL/GH/RH/RL, or in the order of BH/BL/GH/GL/RL/RH.

The order can also be a blue-sensitive layer/GH/RH/GL/RL from the outermost layer, as described in JP-B-55-34932. In addition, the arrangement may be in the order of blue-sensitive layer/GL/RL/GH/RH from the outermost layer as described in JP-A-56-25738 and JF-A-62-63936.

In another embodiment, the layer structure contains three layers having different photosensitivities in such an arrangement that the uppermost layer is a silver halide emulsion layer having the highest photosensitivity, the middle layer is a silver halide emulsion layer having a lower photosensitivity than that of the upper layer, and the lower layer is a silver halide emulsion layer having a lower photosensitivity than that of the middle layer, so that the photosensitivity becomes lower toward the support, as described in JP-B-49-15495. Even if the layer structure consists of three layers having different photosensitivities, the order may also be a medium-sensitive emulsion layer, high-sensitive emulsion layer, low-sensitive emulsion layer from the outermost support layer, as described in JF-A-59-202464.

In yet another embodiment, the arrangement may be in the order of high-sensitivity emulsion layer, low-sensitivity emulsion layer, medium-sensitivity emulsion layer or the order of low-sensitivity emulsion layer, medium-sensitivity emulsion layer, high-sensitivity emulsion layer.

If the layered structure consists of four or more layers, the various arrangements described above can also be made.

Preferably, a donor layer (CL) having a multilayer effect and a different spectral sensitivity distribution from the light-sensitive main layers such as BL, GL and RL is provided immediately adjacent to or close to the sensitive main layers to improve color reproducibility, such a donor layer being described in US Pat. Nos. 4,663,271, 4,705,744 and 4,707,436, JP-A-62-160448 and JP-A-63-89850.

As stated above, different layer structures and arrangements can be selected depending on the intended use.

The preferred silver halide contained in the photographic emulsions of the photographic material according to the invention is silver iodobromide, silver iodochloride or silver iodochlorobromide, each with a silver iodide content of not more than about 30 mol%. Particularly preferred is silver iodobromide or silver iodochlorobromide, each with a silver iodide content of 2 to 25 mol%.

The silver halide grains in the photographic emulsions may have a regular crystal form such as a cubic, octahedral or tetradecahedral form, an irregular crystal form such as a spherical or tabular form, crystal defects such as twin planes, or a composite form thereof.

The size of the silver halide grains may range from fine grains having a grain size of not more than 0.2 µm to coarse grains having a grain size of about 10 µm in terms of the diameter of the projected area. A polydisperse emulsion or a monodisperse emulsion may be used as desired.

The silver halide photographic emulsions of the present invention can be prepared by the methods described in Research Disclosure (RD) No. 17643 (December 1978), pages 22 to 23, 1. Emulsion Preparation and Types; ibid. No. 18716 (November 1979), page 648; ibid. No. 307105 (November 1989), pages 863 to 865; P. Glafkides, Chimie et Phisique Photographique (Paul Montel, 1967), G.F. Duffin, Photographic Emulsion Chemistry (Focal Press, 1966) and V.L. Zelikman et al, Making and Coating Photographic Emulsion (Focal Press, 1964).

Monodisperse emulsions described in U.S. Patents 3,574,628 and 3,655,394 and British Patent 1,413,748 are also preferred.

Tabular grains having an aspect ratio of not less than about 5 can be used in the present invention. The tabular grains can be readily prepared by the methods described in Gutoff, Photographic Science and Engineering, Vol. 14, pages 248 to 257 (1970), U.S. Patent Nos. 4,434,226, 4,414,310, 4,433,048 and 4,439,520 and British Patent No. 2,112,157.

Grains having a uniform crystal structure or a crystal structure with different halogen composition between the inner part and the surface region may be used. Grains having a laminar crystal structure may be used. A silver halide with a different composition may be bonded to the grains by epitaxial growth. A compound such as silver rhodanide or lead oxide, which is different from a silver halide, may be bonded to the grains. A mixture of grains with different crystal forms may be used.

Silver halide emulsions are usually subjected to physical ripening, chemical ripening and spectral sensitization and then used. Additives used for these steps are described in Research Disclosure No. 17643, ibid. No. 18716 and ibid. No. 307105 and listed in a table below.

Preferably, non-light-sensitive finely divided silver halide grains are used in the present invention. The term "non-light-sensitive finely divided silver halide grains" as used herein means finely divided silver halide grains that are non-light-sensitive during imagewise exposure to obtain a dye image and are not substantially developed in the processing step. Non-prefogged grains are preferred.

Finely divided silver halide grains have a silver bromide content of 0 to 100 mol% and can optionally contain silver chloride and/or silver iodide. Grains containing 0.5 to 10 mol% silver iodide are preferred.

Finely divided silver halide grains have an average grain size (average of the diameters of circles with areas corresponding to the projected areas) of preferably 0.01 to 0.5 µm, more preferably 0.02 to 0.2 µm.

Finely divided silver halide grains can be prepared in the same manner as in the preparation of ordinary light-sensitive silver halides. In the preparation of finely divided silver halide grains, it is not necessary that the surfaces of the silver halide grains be optically or spectrally sensitized. However, it is preferable to add a conventional stabilizer such as triazole, azaindene, benzthiazolium, a mercapto compound or a zinc compound before adding the finely divided silver halide grains to the coating solutions. Colloidal silver is preferably incorporated into layers containing the finely divided silver halide grains.

Conventional photographic additives that can be used in the present invention are described in the three Research Disclosures listed in the following table.

Preferably, compounds are added that can react with formaldehyde and fix it, such as described in U.S. Patent Nos. 4,411,987 and 4,435,503 to prevent deterioration of photographic properties due to formaldehyde gas.

Various color couplers can be used in the present invention. Examples are described in the patents listed in the above-described Research Disclosure No. 17643, VII-C to G, and ibid. No. 307105, VII-C to G.

Preferred examples of yellow couplers include those described in U.S. Patent Nos. 3,933,501, 4,022,620, 4,326,024, 4,401,752 and 4,248,961, JP-B-58-10739, British Patent Nos. 1,425,020 and 1,476,760, U.S. Patent Nos. 3,973,968, 4,314,023 and 4,511,649 and EP-A-249,473.

5-pyrazolone compounds and pyrazoloazole compounds are preferred as magenta couplers. Particularly preferred are magenta couplers described in U.S. Patents 4,310,619 and 4,351,897, BP-PS 73,636, U.S. Patents 3,061,432 and 3,725,067, Research Disclosure No. 24220 (June 1984), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, JP-A-61-72238, JP-A-60-35730, JP-A-55-118034, JP-A-60-185951, U.S. Patents 4,500,630, 4,540,654 and 4,556 630 and W088/04795.

Phenol couplers and naphthol couplers can be used as cyan couplers. Preferred cyan couplers include those described in U.S. Patents 4,052,212, 4,146,396, 4,228,233, 4,296,200, 2,369,929, 2,801,171, 2,772,162, 2,895,826, 3,772,002, 3,758,308, 4,334,011 and 4,327,173, DE-OS 3,329,729, EP-A-121,365 and EP-A-249,453, U.S. Patents 3,446,622, 4,333,999, 4,775,616, 4 451 559, 4 427 767, 4 690 889, 4 254 212 and 4 296 199 and JP-A-61-42658.

Preferred couplers which form developed dyes with controlled diffusion are those described in US-PS 4,366,237, GB-PS 2,125,570, EP-PS 96,570 and DE-OS 3,234,533.

In addition to the color couplers, compounds described in Research Disclosure No. 17643, VII-G, ibid. No. 307105, VII-G, US Patent No. 4,163,670, JP-B-57-39413, US Patent Nos. 4,004,929 and 4,138,258 and GB Patent No. 1,146,368 are also preferred in the photographic material according to the invention, namely as color couplers for correcting the unnecessary absorption of developed dyes. Preferably, couplers are used to correct the undesirable absorption of developed dyes by fluorescent dyes which are split off during coupling, as described in U.S. Patent No. 4,774,181, or couplers which have as a leaving group a dye precursor group which can react with developing agents to form a dye, as described in U.S. Patent No. 4,777,120.

Compounds which release a photographically useful group upon coupling can be preferably used in the present invention. Preferred DIR couplers which release retarders are described in the patents cited in the above-described RD No. 17643, VII-F. ibid. No. 307105, VII-F, as well as JP-A-57-151944, JP-A-57-154234, JP-A-60-184248, JP-A-63-37346, JP-A-63-37350 and U.S. Patent Nos. 4,248,962 and 4,782,012.

As couplers which imagewise release nucleating agents or development accelerators during development, those compounds described in British Patents 2,097,140 and 2,131,188, JP-A-59-157638 and JPA-59-170840 are preferred.

Other examples of compounds that can be used in the present invention include competing couplers described in U.S. Patent No. 4,130,427, polyequivalent couplers described in U.S. Patent Nos. 4,283,472, 4,338,393 and 4,310,618, couplers that release dyes that form color again after release described in EP-A-173,302 and EP-A-313,308, couplers that release bleaching accelerators described in RD No. 11449, RD No. 24241 and JP-A-61-201247, couplers that release ligands described in U.S. Patent No. 4,555,477, couplers that release leuco dyes described in JP-A-63-75747, and couplers which release fluorescent dyes, described in US-PS 4,774,181.

Couplers used in the present invention can be introduced into the photographic materials by various known dispersion methods.

Examples of high boiling solvents used for an oil-in-water dispersion process are described in U.S. Patent No. 2,322,027.

Examples of high boiling organic solvents having a boiling point of not less than 175ºC at normal pressure, which can be used in the oil-in-water dispersion process used include phthalic acid esters (e.g. dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis(2,4-di-t-amylphenyl)phthalate, bis(2,4-di-t-amylphenyl)isophthalate, bis(1,1-diethylpropyl)phthalate), phosphoric or phosphonic acid esters (e.g. triphenyl phosphate, tricresyl phosphate, 2-ethylhexyldiphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenyl phosphate), benzoic acid esters (e.g. 2-ethylhexyl benzoate, dodecyl benzoate, 2-ethylhexyl-p-hydroxybenzoate), amides (e.g. N,N-diethyldodecanamide, N,N-diethyllaurylamide, N-tetradecylpyrrolidone), alcohols or phenols (eg isostearyl alcohol, 2,4-di-tert-amylphenol), aliphatic carboxylic acid esters (eg bis(2-ethylhexyl)sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate), aniline derivatives (eg N,N-dibutyl-2-butoxy-5-t-octylaniline) and hydrocarbons (eg paraffin, dodecylbenzene, diisopropylnaphthalene). Organic solvents having a boiling point of not less than about 30°C, preferably not less than about 50°C but not more than about 160°C, can be used as co-solvents. Examples of co-solvents include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-hydroxyethyl acetate and dimethylformamide.

Examples of steps for latex dispersion methods, its effects and impregnating latexes are described in US-PS 4,199,363 and German Offenlegungsschriften 2,541,274 and 2,541,230.

Preferably, antiseptic and anti-mold agents, such as 1,2-benzoisothiazolin-3-one, n-butyl p- hydraxybenzaate, phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol and 2-(4-thiazolyl)benzimidazole, described in JP-A-63-257747, JP-A-62-272248 and JP-A-1-80941 and phenethyl alcohol are added to the color photographic materials of the present invention.

The present invention can be applied to various color photographic materials. Typical examples of color photographic materials according to the present invention include color negative films for general purposes and motion picture films, color reversal films for slides or TV, color papers, color positive films and color reversal papers.

Examples of supports that can be used in the present invention include those described in the above-described RD No. 17643 (page 28), RD No. 18716 (page 647, right column to page 648, left column) and RD No. 307105 (page 879).

In the photographic material of the present invention, the total thickness of the entire hydrophilic colloid layers on the emulsion side is preferably not more than 28 µm, more preferably not more than 23 µm, even more preferably not more than 18 µm, and particularly preferably not more than 16 µm. The layer swelling rate T1/2 is preferably not longer than 30 seconds, more preferably not longer than 20 seconds. The layer thickness refers to a layer thickness obtained by measuring the thickness of a layer at 25°C and 55% RH under air conditioning. (2 days). The film swelling rate T1/2 can be measured by methods known in the field of photography, for example, using a swelling meter described in A. Green et al, Fhotogr. Sci. Eng., Vol. 19, No. 2, pages 124 to 129. T1/2 is defined as the time required for the film thickness to reach 1/2 of the saturated film thickness when processing with a color developer solution is carried out at 30ºC for 3 minutes and 15 seconds, and 90% of the attainable maximum swollen film thickness is referred to as the saturated film thickness.

The layer swelling rate T1/2 can be controlled by adding a hardener to gelatin as a binder or by changing the time conditions after coating. A swelling ratio of 150 to 400% is preferred. The swelling ratio can be obtained from the maximum swollen layer thickness under the above conditions using the formula (maximum swollen layer thickness - layer thickness)/layer thickness.

The color photographic materials of the invention can be developed by conventional methods described in RD No. 17643 (pages 28 to 29), RD No. 18716 (page 651, left to right columns) and RD No. 307105 (pages 880 to 881).

Colour developing solutions which can be used in the processing of the photographic materials according to the invention are preferably aqueous alkali solutions which consist mainly of aromatic primary amine Color developing agents. Aminophenol compounds are usable as color developing agents and p-phenylenediamine compounds are preferred as color developers. Typical examples include 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline and salts thereof such as the sulfates, hydrochlorides and p-toluenesulfonates. Among them, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline sulfate is particularly preferred. These compounds can be used either alone or in combination of two or more, depending on the purpose.

In general, the color developing solutions contain pH buffers such as alkali metal carbonates, borates and phosphates; development retarders such as chlorides, bromides, iodides, benzimidazoles, benzothiazoles and mercapto compounds; and antifogging agents. If desired, the color developing solutions may optionally contain preservatives such as hydroxylamine, diethylhydroxylamine, sulfites; hydrazines such as N,N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine, catecholsulfonic acids; organic solvents such as ethylene glycol and diethylene glycol; development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts and amines; color forming couplers; competing couplers; auxiliary developing agents such as 1-phenyl-3-pyrazolidone; adhesives; and chelating agents such as aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids and phosphonocarboxylic acids, e.g. Ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid and ethylenediamine-di(o-hydroxyphenylacetic acid) and their salts.

When reversal processing is to be carried out, generally, black and white development is carried out first and then color development. Black and white developer solutions may contain conventional developing agents, such as dihydroxybenzenes (e.g. hydroquinone), 3-pyrazolidones (e.g. 1-phenyl-3-pyrazolidone) and aminophenols (e.g. N-methyl-p-aminophenol). These developing agents may be used either alone or in combination of two or more.

The pH of the color developing solutions and the black and white developing solutions is generally in the range of 9 to 12. The replenishment rate of these developing solutions varies depending on the type of color photographic materials, but is usually not more than 3 l/m² of photographic material. The replenishment rate can be reduced to 500 ml or less if the concentration of bromide ions in the replenisher is reduced. When the amount of replenisher is reduced, it is advantageous that the contact area of the developing solution with air is reduced to prevent evaporation or air oxidation of the solution. The contact area of the photographic Process solution with air in the process tank is represented by an opening ratio given below:

Opening ratio = contact area (cm²) of the process solution with air/volume (cm³) of the process solution

The aperture ratio is preferably not larger than 0.1, preferably 0.001 to 0.05. Methods for reducing the aperture ratio include a method in which a cover such as a floating lid is provided on the surface of the photographic processing solution in the processing tank; a method in which a movable cover is used as described in JP-A-1-82033, and a slit development method as described in JP-A-63-216050. Preferably, the aperture ratio is reduced not only for the color development and black/white development steps, but also for all subsequent steps such as bleaching, bleach-fixing, fixing, washing and stabilizing steps. The replenishment rate can be reduced by inhibiting the accumulation of bromide ions in the developing solution.

Color development usually takes 2 to 5 minutes. However, if a higher temperature and pH are used and the color developing agents are used in higher concentrations, the process time can be shortened.

After color development, the photographic emulsion layer is generally bleached. Bleaching can be carried out simultaneously with fixation (bleach-fixing treatment) or separately. Bleach-fixing treatment can be carried out after bleaching to speed up processing. Processing can be carried out with a bleach-fixing bath consisting of two consecutive baths. Fixing can be carried out before bleach-fixing treatment. Bleaching can be carried out after bleach-fixing treatment, depending on the purpose. Examples of bleaching agents include compounds of polyvalent metals such as iron (III), peracids, quinones and nitro compounds. Typical examples of bleaching agents include organic complex salts of iron (III), such as complex salts of aminopolycarboxylic acids (e.g. ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminepropanetetraacetic acid, glycol ether diaminetetraacetic acid), citric acid, tartaric acid and malic acid. Among them, iron(III) complex salts of aminopolycarboxylic acids such as (ethylenediaminetetraacetato) iron(III) complex and (1,3-diaminopropanetetraacetato) iron(III) complex are preferred for rapid processing and prevention of environmental pollution. In addition, iron(III) complex salts of aminopolycarboxylic acids are usable as bleaching solutions and bleach-fixing solutions. The pH of the bleaching solutions containing the iron(III) complex salts of aminopolycarboxylic acids and bleach-fixing solutions containing the iron(III) complex salts is usually in the range of 4.0 to 8. A lower pH may be used to accelerate processing. If desired, the bleaching solution, the bleach-fixing solution and their pre-baths may contain bleaching accelerators. Examples of bleaching accelerators include compounds having a mercapto group or disulfide group described in U.S. Patent No. 3,893,858, German Patent Nos. 1,290,812 and 2,059,988, JP-A-53-32736, JP-A-53-57831, JP-A-53-37418, JP-A-53-72623, JP-A-53-95630, JP-A-53-95631, JP-A-53-104232, JP-A-53-124424, JP-A-53-141623, JP-A-53-28426 and Research Disclosure No. 17129 (July 1978); and thiazolidine derivatives described in JP-A-50-140219; thiourea derivatives described in JP-B-45-8506, JP-A-52-20832, JP-A-53-32735 and US-PS 3 706 561; iodides described in DE-PS 1 127 715 and JP-A-58-16235; polyoxyethylene compounds described in DE-PS 996 410 and 2 748 430; polyamine compounds described in JP-B-45-8836; Compounds described in JP-A-49-40943, JP-A-49-59644, JP-A-53-94927, JP-A-54-35727, JP-A-55-26506 and JP-A-58-163940; and bromide ions. Among them, compounds having a mercapto group or disulfide group are preferred because of their high accelerating effect. In particular, the compounds described in U.S. Patent No. 3,893,858, German Patent No. 1,290,812 and JP-A-53-95630 are preferred. In addition, the compounds described in U.S. Patent No. 4,552,834 are preferred. These bleaching accelerators can be incorporated into the photographic materials. They are particularly effective in carrying out bleach-fixing of the color photographic materials for photography.

In addition to the compounds described above, the bleaching and bleach-fixing solutions preferably contain organic acids to prevent stains are produced by bleaching. Particularly preferred organic acids are compounds with an acid dissociation constant (pKa) of 2 to 5. Examples of organic acids include acetic acid and propionic acid.

Examples of fixing agents used in the fixing solution and bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas and a large amount of iodide. As the fixing agent, thiosulfates are widely used. In particular, ammonium thiosulfate is particularly widely used. A combination of a thiosulfate with a thiocyanate, a thioether compound or a thiourea is also preferred. Sulfites, bisulfites, carbonyl bisulfite adducts and sulfinic acid compounds described in EP-A-294 769 are preferred as preservatives for the fixing solution and bleach-fixing solution. In addition, aminopolycarboxylic acids or organic phosphonic acids are preferably added to the fixing solution or bleach-fixing solution to stabilize the solution.

Preferably, compounds having a pka of 6.0 to 9.0, especially imidazoles such as imidazole, 1-methylimidazole, 1-ethylimidazole and 2-methylimidazole, are added in an amount of 0.1 to 10 mol/l to the fixing solution or bleach-fixing solution to adjust the pH.

Shorter desilvering times (overall) are preferred as long as no desilvering defects occur. The desilvering time is preferably 1 to 3 minutes, more preferably 1 to 2 minutes. The process temperature is 25 to 50ºC, preferably 35 to 45ºC. If desilvering is carried out at a temperature within the preferred range, the desilvering speed increases and the formation of stains after processing is effectively prevented.

In the desilvering step, it is preferable to intensify convection as much as possible. Methods for intensifying convection include a method in which a jet of the processing solution is impinged on the surfaces of the emulsions of the photographic materials as described in JP-A-62-183460; a method in which stirring is enhanced by a rotating device as described in JP-A-62-183461; a method in which a wiper blade mounted in the solution is brought into contact with the emulsion surfaces and the photographic material is transferred to thereby cause turbulent flow, thereby improving the stirring effect; and a method in which the total amount of the circulating processing solution is increased. Such means for improving convection are effectively applicable to any of the bleaching solution, bleach-fixing solution and fixing solution. It is considered that the improvement of convection increases the supply of the bleaching solution and fixing solution to the emulsion layers and, as a result, increases the desilvering rate. The means for improving convection described above are more effective when bleaching accelerators are used. The accelerating effect can be greatly increased and the problem of inhibition of fixation caused by the bleaching accelerators can be solved.

Preferably, automatic developing machines for use in processing the photographic materials of the present invention are equipped with transfer devices for photographic materials described in JP-A-60-191257, JF-A-60-191258 and JP-A-60-191259. As stated in JP-A-60-191257, the transfer devices can greatly reduce the amount of the processing solution transferred from one bath to the subsequent bath, so that the properties of the processing solution can be preserved very well. This is particularly effective for shortening the processing time at each step or for reducing the replenishment rate of the processing solution.

Usually, the color photographic materials of the present invention are subjected to washing and/or stabilization after desilvering. The amount of washing water in the washing step varies greatly depending on the characteristics of the photographic material (e.g., depending on the substances used such as couplers), their use, the temperature of the washing water, the number of washing tanks (the number of stages), the regenerator system (countercurrent, cocurrent) or other conditions. The relationship between the amount of water and the number of washing tanks in a multi-stage countercurrent system can be determined by the method described in the Journal of the Society of Motion Picture and Television Engineers, Vol. 64, pages 248 to 253 (May 1955).

According to the multi-stage countercurrent system described in the above article, the amount of washing water can be greatly However, the residence time of the water in the tanks is prolonged and, as a result, bacteria grow and resulting suspended matter is deposited on the photographic material. A method for reducing calcium and magnesium ion concentrations described in JF-A-62-288838 can be effectively used for the color photographic materials of the present invention to solve this problem. In addition, isothiazolone compounds, thiabendazole compounds, chlorine-containing germicides such as sodium chloroisocyanurate and benzotriazole compounds described in JP-A-57-8542, and germicides described in Chemistry of Germicidal Antifungal Agent, (1986) by Hiroshi Horiguchi (Sankyo Shuppan), Sterilization Disinfection, Antifungal Technique, published by Sanitary Technique Society, and Antibacterial and Antifungal Cyclopedie (1986) published by Nippon Antibacterial Antifungal Society can be used.

The pH of the washing water in the treatment of the photographic materials of the present invention is in the range of 4 to 9, preferably 5 to 8. The temperature of the washing water and the washing time vary depending on the characteristics of the photographic materials and the use, but the temperature and the time of washing are generally 15 to 45°C for 20 seconds to 10 minutes, preferably 25 to 40°C for 30 seconds to 5 minutes. The photographic materials of the present invention can be processed directly with stabilizing solutions instead of washing water. Such a stabilizing treatment can be carried out by conventional methods. described in JP-A-57-8543, JP-A-58-14834 and JP-A-60-220345.

A stabilizing treatment following washing may be carried out. The stabilizing treatment may be used as a final bath for the color photographic materials for photography. An example includes a stabilizing bath containing a dye stabilizer and a surfactant. Examples of dye stabilizers include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde-sulfite adducts.

The stabilizing bath may contain various chelating agents and anti-mold agents. Overflow solutions from the regeneration of the washing water and/or the stabilizing solution may be reused in other steps, such as the desilvering step. When the freezing solutions are concentrated by evaporation during processing with automatic developing machines, water is preferably added again to compensate for the amount of evaporated water.

Color developing agents can be added to the silver halide color photographic materials of the present invention to simplify and speed up processing. Preferably, color developing agent precursors are used for incorporation into the photographic materials. Examples of precursors include indoaniline compounds described in U.S. Patent No. 3,342,597; Schiff base compounds described in U.S. Patent No. 3,342,599, Research Disclosure No. 14858 and ibid. No. 15159; aldol compounds described in

Research Disalosure No. 13924; metal complex salts described in U.S. Patent No. 3,719,492; and urethane compounds described in JP-A-53-135628.

If desired, 1-phenyl-3-pyrazolidones can be incorporated into the silver halide color photographic materials of the present invention for the purpose of accelerating color development. Typical examples of such compounds include those described in JP-A-56-64339, JP-A-57-144547 and JP-A-58-115438.

In the present invention, the various processing solutions are used at a temperature of 10 to 50°C. Generally, a temperature of 33 to 38°C is used. However, a higher temperature may be used to speed up processing and shorten the processing time, while a lower temperature is used to improve image quality and improve the stability of the processing solutions.

The silver halide photographic materials of the present invention include heat-developable light-sensitive materials described in U.S. Patent No. 4,500,626, JP-A-60-133449, JP-A-59-218443, JP-A-61-238056 and EP-A2-210 660.

The present invention will now be explained in more detail with reference to the following examples, which, however, are not to be construed as limiting the inventions in any way.

Unless otherwise indicated, all parts, percentages and ratios are by weight.

EXAMPLE 1

The surface of a cellulose triacetate film support having an undercoat layer was coated with the following layers having the following compositions to provide a multilayer color photographic material as Sample 101.

Compositions of the photographic layers:

The coating weights of silver halide and colloidal silver are given in g/m² of silver. The coating weights of couplers, additives and gelatin are given in g/m². The amount of sensitizing dyes is given in moles per mole of silver halide in the same layer.

In addition, the following compounds Cpd-3, Cpd-5, Cpd-6, Cpd-7, Cpd-8, P-1, P-2, W-1, W-2, W-3 were added to improve durability, processability, pressure resistance, mildew resistance and anti- mold properties, antistatic properties and applicability, and the upper layer, the fourteenth layer, was applied at the same time. The track film thickness was 16.5 µm as measured by a contact film thickness gauge.

The chemical structural formulas and chemical names of the compounds used in the present invention are as follows:

Solv-1: Triaresyl phosphate

Solv-2; dibutyl phthalate

Solv-3: Tri(2-ethylhexyl)phosphat

W-3 C₈F₁₇₆SO₂N(C₃H₇) CH₂COOK

P-1 Copolymer of vinylpyrrolidone and vinyl alcohol (copolymerization ratio 70:30 parts by weight)

P-2 Polyethylacrylate

Samples 102 to 106:

Each of Samples 102 and 103 was prepared in the same manner as Sample 101, except that ExY-16 in an amount of twice the molar amount of ExC-4 or ExM-17 in an amount of 1.4 times the molar amount of ExC-4 was used instead of ExC-4 in each of the third and fourth layers of Sample 101. Each of Samples 104, 105 and 106 was prepared in the same manner as Sample 101, except that Compound (5) in an amount of four times the molar amount of ExC-4, Compound (7) in an amount of three times the molar amount of ExC-4 or Compound (14) in an amount of four times the molar amount of ExC-4 was used instead of ExC-4 in the third and fourth layers of Sample 101.

Samples 107 to 124:

Each of Samples 107 to 124 was prepared by adding the yellow-colored coupler YC-26 in an amount of 0.025 and 0.008 g/m2 to the fourth and fifth layers of each of Samples 101 to 106. Similarly, YC-32 and YC-47 were added to prepare Samples 113 to 124.

Samples 125 to 131:

Each of samples 125 to 131 was prepared in the same manner as sample 101, except that YC-3, YC-24, YC-25, YC-1, YC-85, YC-86 and YC-89 were used instead of YC-26, respectively.

Samples 132 and 133:

Sample 132 was prepared in the same manner as Sample 110, except that ExM-9 in an amount of twice the weight of the preferred coupler P-13 was used instead of the coupler P-13 in the seventh and eighth layers of Sample 110, the amount of Solv-1 was changed to 1.8 times that used in Sample 110, and the amount of gelatin was increased to 1.5 times that of Sample 110. A Sample 133 was prepared in the same manner as Sample 132, except that an equimolar amount of ExM-11 was used instead of ExM-9.

The relative sensitivity of the green-sensitive layer of Samples 132 and 133 obtained by the color development described below was the same as that of Sample 110. The scratch resistance was using a 0.05 mm diameter sapphire pencil. There was little difference in scratch resistance between these samples. It was also confirmed that the film strength and photographic properties of these samples were almost the same.

The samples prepared above were subjected to imagewise red exposure and then to the following color development (Condition A). Separately, the samples were subjected to uniform blue exposure so that the yellow density of the red unexposed area of Sample 101 in the following color development became 1.2 after the imagewise red exposure, and the samples were then subjected to imagewise red exposure and developed (Condition B).

The relative sensitivity was determined from the logarithm of the reciprocal of the exposure amount that gave a density of (fog + 0.2) under condition A. The color haze was determined from a value obtained by subtracting the yellow density in the red unexposed area from the yellow density in an exposure amount that gave a cyan density of (fog + 0.3) and (fog + 0.1) under conditions A and B.

The sharpness of these samples was determined using the conventional MIF method.

Development was carried out at 38ºC under the following conditions.

Each of the processing solutions used in each stage had the following composition: TABLE 1 TABLE 1 CONTINUED TABLE 1 CONTINUED

It is apparent from Table 1 that the samples of the present invention gave better results in terms of color reproducibility, high MTF values and sharpness at any exposure amount under both conditions A and B than samples 104 to 106 obtained by using only the compounds of formula (I) of the present invention and no yellow-colored coupler with low color haze. In addition, it is apparent that the samples of the present invention are highly sensitive and have excellent color reproducibility in terms of color haze and sharpness in terms of MTF value, compared with samples 107 to 109, 113 to 115 and 119 to 121 obtained by using dicouplers described in German Patent 3,815,469 without using any compound of formula (I) according to the present invention. That is, Table 1 shows that when the present invention is applied to photographic materials, photographic materials having improved color reproducibility under various exposure conditions, being highly sensitive and having excellent sharpness can be obtained.

In addition, Sample 110 obtained by using the polymer coupler (P-13) is highly sensitive and has good sharpness and color reproducibility as compared with Samples 132 and 133 obtained by using ExM-9 and ExM-11, respectively. Therefore, it is clear that the use of the polymer coupler is preferred in the present invention.

EXAMPLE 2

Evaluation of color turbidity of Samples 101 to 128, 132 and 133 was made in the same manner as in Example 1 except that the following developing solution (spent model solution) was used instead of the color developing solution of Example 1, the developing solution being a spent model solution in which evaporation of the solution and deterioration by air oxidation occurred because the processing amount was small.

The difference in the development results between Examples 1 and 2 is shown in Table 2 (a minus sign means that the color turbidity of the photographic material developed with the used solution is high). TABLE 2

From Table 2, it is clear that even when the samples according to the invention are processed with a spent model solution, the change in color turbidity is small, while when samples outside the scope of the invention are processed with the spent model solution, the change in color turbidity is large. Therefore, it is clear that the color turbidity of samples according to the invention is only slightly process-dependent.

EXAMPLE 3

A yellow-colored coupler (YC-3) in an amount of 0.004 g/m², 0.013 g/m² and 0.008 g/m² was added to the third, fourth and fifth layers of Sample 105 of JP-A-1-214849, respectively, to prepare Sample 201 (Compound (26) is the same as Compound (4) and no yellow-colored cyan coupler is contained). Similarly, YC-26, YC-28 and YC-59 were added to prepare Samples 202, 203 and 204.

The color turbidity of these samples was evaluated in the same manner as in Example 1. The following color development was carried out and the MTF value was measured.

From Table 3, it is clear that Samples 201 to 204 of the present invention are highly sensitive, have low color turbidity under any exposure conditions, and have excellent sharpness compared with Sample 105 of JP-A-1-214849.

Color development was carried out at 38ºC with an automatic developing machine under the following conditions.

In the above processing, washes (1) and (2) were carried out by a countercurrent system from (2) to (1). The processing solutions had the following compositions.

The replenishment rate of each processing solution was such that the replenishment rate in color development was 1200 ml/m² of photographic material and that in each of the other steps, including washing, was 800 ml. The amount of processing solution transferred from a pre-bath to the washing step was 50 ml/m² of photographic material. TABLE 3

* Sample 105 of JP-A-1-214849

** (4) is the compound No. of the present invention

EXAMPLE 4

The yellow colored cyan coupler (YC31) in an amount of 0.012 g/m² and compound (12) of the formula (I) of the present invention in an amount of 0.010 g/m² were added to the fourth layer of sample (108) (containing no compound of the formula (I) and no yellow colored coupler of the present invention) of JP-A-61-51146. The sample was processed in the same manner as in Example 1 of JP-A-61-51146. The yellow color turbidity of the resulting sample was small compared with sample 108 of JP-A-51146.

Claims (16)

1. Color photographic silver halide material comprising a support and thereon at least one red-sensitive silver halide emulsion layer with a cyan coupler, at least one green-sensitive silver halide emulsion layer with a magenta coupler and at least one blue-sensitive silver halide emulsion layer with a yellow coupler, the photographic material containing at least one compound with the following general formula (I) in an amount of 1 x 10⁻⁶ to 1 x 10⁻³ mol/m²: A-(L₁)v-B-(L₂)w-DI (I) wherein A represents a group which is split off from (L₁)vB-(L₂)w-DI by a reaction of the compound of formula (I) with an oxidation product of a developing agent; L₁ represents a linking group which is split off from B after cleavage of the bond between L₁ and A; B represents a group which reacts with an oxidation product of a developing agent to split off (L₂)w-DI; L₂ represents a group which is split off from DI after cleavage of the bond between B and L₂; DI represents a development inhibitor; v and w each represent a integer from 0 to 2 and when v or w is 2, the two L₁ groups or the two L₂ groups may be the same or different, and contains at least one yellow-coloured cyan coupler having an absorption maximum at 400 to 500 nm which forms a cyan dye having an absorption maximum at 630 to 750 nm by coupling with the oxidation product of an aromatic primary amine developing agent, with the proviso that the compound of formula (I) is not is. 2. A silver halide color photographic material according to claim 1, wherein the compound of formula (I) and the yellow-colored cyan coupler are each incorporated into at least one of the silver halide emulsion layers and a light-insensitive intermediate layer adjacent thereto. 3. Color photographic silver halide material according to claim 1, wherein the compound of formula (I) is incorporated into the layer having the same color sensitivity as the layer containing the yellow-colored cyan coupler 4. The silver halide color photographic material according to claim 1, wherein the layer containing the compound of the formula (I) is a red-sensitive layer. 5. The silver halide color photographic material according to claim 1, wherein the yellow-colored cyan coupler is contained in the red-sensitive layer. 6. The silver halide color photographic material according to claim 1, wherein the compound having the general formula (I) and the yellow-colored cyan coupler are contained in the same red-sensitive silver halide emulsion layer. 7. Color photographic silver halide material according to claim 1, wherein a polymeric magenta coupler is contained in the green-sensitive silver halide emulsion layer or a light-insensitive layer adjacent thereto. 8. A silver halide color photographic material according to claim 1, wherein the order of the layers from the support is red-, green- and blue-sensitive silver halide layers and a polymeric magenta coupler is contained in the green-sensitive silver halide emulsion layer. 9. The silver halide color photographic material according to claim 1, wherein the amount of the yellow-colored cyan coupler is 0.05 to 0.30 g/m². 10. The silver halide color photographic material according to claim 1, wherein the yellow-colored cyan coupler can release a water-soluble dye unit having a group selected from the group consisting of a 6-hydroxy-2-pyridone-5-ylazo group, a pyrazolone-4-ylazo group, a 2-acylaminophenylazo group, a 2-sulfonamidophenylazo group, a 5-aminopyrazol-4-ylazo group by a coupling reaction with an oxidation product of an aromatic primary amine developing agent. 11. A silver halide color photographic material according to claim 11, wherein the yellow-colored cyan coupler is selected from the group consisting of couplers having the formulas (CI) to (CIV): wherein Cp represents a cyan coupler moiety (T is connected to its coupling site); T represents a timing group; k represents 0 or 1; X represents a N, O or S-containing divalent group which is connected to (T)k through the N, O or S atom and which is also connected to Q; Q represents an arylene group or a divalent heterocyclic group; R₁ and R₂ each represent a hydrogen atom, a carboxyl group, a sulfo group, a cyano group, a linear or branched hydrocarbon group which may contain unsaturated bonds and one or more substituent groups, a 3- to 8-membered ring which may contain crosslinking groups, unsaturated bonds or substituent groups, a substituted or unsubstituted phenyl or naphthyl group, a 3- to 8-membered ring having at least one heteroatom selected from N, O and S atoms, a substituted or unsubstituted carbamoyl group, a substituted or unsubstituted sulfamoyl group, a substituted or unsubstituted carbonamido group, an aliphatic or aromatic sulfonamido group or an alkylsulfonyl group; R₃ is a hydrogen atom, a linear or branched hydrocarbon group which may contain unsaturated bonds and one or more substituent groups, a 3- to 8-membered ring which may contain crosslinking groups, unsaturated bonds or substituent groups, a substituted or unsubstituted phenyl or naphthyl group, a 3- to 8-membered ring having at least one heteroatom selected from N, O and S atoms; wherein the group wherein the group may exist in the form of at least one of its other tautomeric forms; R₄ is an aliphatic or aromatic acyl group or an aliphatic or aromatic sulfonyl group; R₅ is a group which may be bonded to the benzene ring; j is an integer of 0 to 4; when j is 2 or more, two or more R₅ groups may be the same or different; R�9 is a hydrogen atom, a carboxyl group, a sulfo group, a cyano group, a straight-chain or branched hydrocarbon group, the unsaturated bonds and one or more substituent groups, a 3- to 8-membered ring which may contain crosslinking groups, unsaturated bonds or substituent groups, a substituted or unsubstituted phenyl or naphthyl group, an alkoxy group, a cycloalkoxy group, an aryloxy group, a 3- to 8-membered ring having at least one heteroatom selected from N, O and S atoms, a substituted or unsubstituted carbamoyl group, a substituted or unsubstituted sulfamoyl group, a carbonamido group, an aliphatic or aromatic sulfonamido group, an alkylsulfonyl group, an arylsulfonyl group, an alkoxycarbonyl group or an aryloxycarbonyl group; R₁₀ is a hydrogen atom, a straight-chain or branched hydrocarbon group which may contain unsaturated bonds and one or more substituent groups; a 3- to 8-membered ring which may contain crosslinking groups, unsaturated bonds or substituent groups, a substituted or unsubstituted phenyl or naphthyl group or a 3- to 8-membered ring having at least one heteroatom selected from N, O and S atoms; wherein the group may be in any of its tautomeric forms; and wherein the coupler is T, X, Q, R₁, R₂, R₃, R₄, R₅, R₆ and R₁₀ contains at least one water-solubilizing group. 12. The silver halide color photographic material according to claim 1, wherein the yellow-colored cyan coupler is added to a silver halide emulsion layer or a light-insensitive interlayer adjacent thereto. 13. A silver halide color photographic material according to claim 7, wherein the polymeric magenta coupler is a polymer derived from at least one monomer selected from the group consisting of monomers having the formula (P) wherein R₁₂₁ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a chlorine atom; -D- represents - COO-, -CONR₁₂₂- or a 1 substituted or unsubstituted phenylene group; -E- represents a substituted or unsubstituted alkylene, phenylene or aralkylene group; -F- means -CONR₁₂₂₀-, -NR₁₂₂CONR₁₂₂₀-, -NR122COO-, -NR122CO-, -OCONR₁₂₂₀-, -NR₁₂₂₀-, -COO-, -OCO-, -CO-, -O-, -S-, -SO₂-, -NR₁₂₂SO₂- or -SO₂NR₁₂₂-; R₁₂₂₂ represents a hydrogen atom or a substituted or unsubstituted saturated or unsaturated aliphatic group or a substituted or unsubstituted aryl group, and when two or more R₁₂₂ groups are present per molecule, they may be the same or different; and p, q and r each represent 0 or 1, provided that p, q and r are not simultaneously 0; T represents a unit (which is linked to -(F)r- at any position of Ar, Z and R₁₃₃) of a magenta coupler having the formula (Q) wherein Ar represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an acylamino group, a carbamoyl group, an alkylcarbamoyl group, a dialkylcarbamoyl group, an arylcarbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkylsulfonamido group, an arylsulfonamido group, a sulfamoyl group, an alkylsulfamoyl group, a dialkylsulfamoyl group, an alkylthio group, an arylthio group, a cyano group, a nitro group and a halogen atom; R₁₃₃ represents an anilino group, an acylamino group, a ureido group or a sulfonamido group, which groups may be substituted; Z represents a halogen atom and a group which is bonded via an oxygen atom, a nitrogen atom or a sulphur atom and is split off by a coupling reaction; 14. The silver halide color photographic material according to claim 13, wherein the polymer is a copolymer with a non-color-forming ethylenic monomer. 15. The silver halide color photographic material according to claim 71, wherein the polymeric magenta coupler is used in the green-sensitive silver halide emulsion layer in an amount of 0.005 to 0.5 mol/mol of the silver used in the same layer. 16. The silver halide color photographic material according to claim 7, wherein the polymeric magenta coupler is used in the light-insensitive layer in an amount of 0.01 to 1.0 g/m².