DE69027521T2 - Silver halide color photographic material containing a yellow-colored cyan coupler - Google Patents

Description

BACKGROUND OF THE INVENTION 1. FIELD OF THE INVENTION:

The invention relates to a silver halide color photographic material. More particularly, it relates to a photographic material having excellent color reproducibility and sharpness as well as copyability due to the incorporation of a yellow-colored cyan coupler and a diffusion development inhibitor-releasing coupler.

2. STATE OF THE ART:

In recent years, the provision of silver halide photographic materials having excellent color reproducibility, sharpness and high sensitivity, such as ISO 400 photographic materials (e.g., Super HG-400 from Fuji Photo Film Co.) having high image quality comparable to ISO 100 materials, has been demanded, particularly in the field of photographic materials for photography.

As a means for improving color reproducibility and sharpness, it is known to use DIR compounds described in JP-A-54-145135 (the term "JP-A" as used herein means an unexamined published Japanese patent application), JP-A-56-114946 and JP-A-57-151944 (corresponding to U.S. Patent Nos. 4,248,962, 4,409,323 and 4,477,563, respectively). Interlaminar and edge effects are improved, and color reproducibility and sharpness are also improved to some extent by these compounds. However, there are problems in that if the amount of retarder released from these compounds is insufficient to retard development, sufficient interlaminar and edge effects cannot be obtained; and if the sensitive layers to be retarded are not properly developed, the desired interlaminar effect cannot be obtained. In addition, these compounds do not provide a sufficient effect over the entire exposure range and their use lowers the sensitivity of the color-sensitive layers to which they are added as well as that of the adjacent color-sensitive layers.

On the other hand, JP-A-61-221748 and DE-A 3 815 469 disclose that corresponding effects (in terms of photographic quality) such as an interlaminar effect from a red-sensitive emulsion layer to a blue-sensitive emulsion layer can be obtained by using a yellow-colored cyan coupler in the red-sensitive emulsion layer. However, it is difficult to achieve the above-mentioned described methods, ie by using these compounds alone. Conventional yellow-colored cyan couplers have the problem that the molecular extinction coefficients of their yellow dyes are low and that their coupling activity is also low.

Furthermore, there are problems in that due to the low molecular extinction coefficients of the yellow couplers used in conjunction with them, the layers of photographic materials become comparatively thick and the interlaminar effects and sharpening become low. In addition, since the developed dyes of the yellow couplers are not adapted to the spectral absorption of the yellow-colored couplers, copyability with auto-printers used in local laboratories is inadequate.

EP-A-0 208 502 discloses that an interlaminar interim effect resulting in improved colour saturation together with increased sharpening due to the edge effect can be obtained by using diffusible inhibitors or their precursors. Suitable inhibitor groups and synchronisation groups are disclosed.

JP-A-63-304242 relates to thermally developable color photosensitive materials. A silver halide emulsion together with a reducing agent, a binder and a dye-providing substance are used as certain yellow colored cyan couplers used in the emulsion.

SUMMARY OF THE INVENTION:

A first object of the invention is the provision of a photographic material which has excellent color reproducibility.

A second object of the invention is the provision of a photographic material which has excellent sharpness.

A third object of the invention is to provide a photographic material which has excellent copying ability in auto-printers.

A fourth object of the invention is the provision of a photographic material which is highly sensitive.

These objects according to the invention have been achieved by providing a silver halide colour photographic material comprising a support on which there is at least one red-sensitive silver halide emulsion layer containing a cyan coupler, as well as 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, wherein the photographic material comprises at least one Compound of the following general formula (I) and at least one yellow colored cyan coupler:

A- (TIME)n-B (I)

wherein A represents a coupler moiety which is released from (TIMEn)-B by a coupling reaction with an oxidation product of an aromatic primary amine developing agent; TIME represents a synchronizing group which is bonded to the active coupling site of A and which releases B after A is released by the coupling reaction; B represents a group of the following general formulas (IIa), (IIb), (IIc), (IId), (IIe), (IIf), (IIg) (IIh), (IIi), (IIj), (IIk), (IIl), (IIm), (IIn), (IIo) or (IIp); n represents an integer of 0 or 1, and when n is 0, B is directly bonded to A.

In the above formulas, X₁ represents a substituted or unsubstituted aliphatic group having 1 to 4 carbon atoms (carbon atoms in the substituents are not included; hereinafter the same applies unless otherwise defined), or a substituted phenyl group, substituent groups are a hydroxyl group, an alkoxycarbonyl group, an acylamino group, a carbamoyl group, a sulfonyl group, a sulfonamido group, a sulfamoyl group, an acyloxy group, a ureido group, a carboxyl group, a cyano group, a nitro group, an amino group, an alkoxycarbonylamino group and an acyl group, the number of carbon atoms in these substituent groups is not more than 3, the phenyl group may have one or more substituents.

X₂ represents a hydrogen atom, an aliphatic group, a halogen atom, a hydroxyl group, an alkoxy group, an alkylthio group, an alkoxycarbonyl group, an acylamino group, a carbamoyl group, a sulfonyl group, a sulfonamido group, a sulfamoyl group, an acyloxy group, a ureido group, a cyano group, a nitro group, an amino group, an alkoxycarbonylamino group, an aryloxycarbonyl group or an acyl group; X₃ represents an oxygen atom, a sulfur atom or a amino group having 0 to 4 carbon atoms; m represents an integer of 1 or 2; the total number of carbon atoms in X₂ or (X₂)m groups is not more than 8; and when m = the two X₂ groups may be identical or different from each other, wherein the yellow colored cyan coupler is capable of coupling a unit of a water-soluble dye having a group selected from 6-hydroxy-2-pyridon-5-ylazo, 2-acylaminophenylazo and 2-sulfonamidophenylazo by a coupling reaction with an oxidation product of a aromatic primary amine developing agent. X₂ can be attached at any position of the nucleus.

More precisely, X�1; a substituted or unsubstituted aliphatic group having 1 to 4 carbon atoms (examples of substituent groups are an alkoxy group, an alkoxycarbonyl group, a hydroxyl group, an arylamino group, a carbamoyl group, a sulfonyl group, a sulfonamido group, a sulfamoyl group, an amino group, an acyloxy group, a cyano group, a ureido group, an acyl group, a halogen atom and an alkylthio group, the number of carbon atoms in these substituent groups is not more than 3; the aliphatic group may have one or more substituent groups; and these groups may be further substituted with these groups, an aliphatic group or an aromatic group) or a substituted phenyl group (substituent groups are a hydroxyl group, an alkoxycarbonyl group, an acylamino group, a carbamoyl group, a sulfonyl group, a sulfonamido group, a sulfamoyl group, an acyloxy group, a ureido group, a carboxyl group, a cyano group, a nitro group, an amino group, an alkoxycarbonylamino group and an acyl group, the number of carbon atoms in these substituent groups is not more than 3, the phenyl group may have one or more substituents); X₂ is an aliphatic group, a halogen atom, a hydroxyl group, an alkoxy group, an alkylthio group, an alkoxycarbonyl group, an acylamino group, a carbamoyl group, a sulfonyl group, a sulfonamido group, a sulfamoyl group, an acyloxy group, a ureido group, a cyano group, a nitro group, an amino group, an alkoxycarbonylamino group, an aryloxycarbonyl group or an acyl group (these groups may be further substituted with, for example, a hydroxy group, an alkoxycarbonyl group, a carboxyl group or an acyloxy group); X₃ is an oxygen atom, a sulfur atom or an imino group having 0 to 4 carbon atoms (the imino group may be substituted with an alkyl group); m is an integer of 1 or 2; the total number of carbon atoms in X₂ or (X₂)m groups is not more than 8; and when m = 2, the two X₂ groups may be identical or different from each other.

The terms for the groups in the present invention are defined as follows unless otherwise defined.

The term "aliphatic group" means an aliphatic hydrocarbon group which may be a saturated or unsaturated hydrocarbon group or a straight-chain, branched or cyclic hydrocarbon group such as an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, etc. The term "aryl group" means at least one substituted or unsubstituted phenyl and naphthyl group. An acyl moiety (in an acyl group, acylamino group, etc.) means an aliphatic and aromatic acyl moiety. A sulfonyl moiety (in a sulfonyl group, sulfonamido group) means a aliphatic and aromatic sulfonyl units. A carbamoyl group, sulfamoyl group, amino group and ureido group include unsubstituted and substituted groups thereof. A heterocyclic group is a 3- to 8-membered one having at least one N, O or S atom as a heteroatom therein.

In the present invention, it is preferred to use a synchronization type DIR coupler in which both A and B are bonded to each other through a TIME group, in which n = 1.

The compounds represented by formula (I) are discussed in more detail below.

The coupler unit represented by A in formula (I) includes a coupler unit which is coupled with an oxidation product of an aromatic primary amine developing agent to form a dye (e.g., yellow, magenta, cyan, etc.) and a coupler unit which forms a coupling reaction product having substantially no absorption in the visible light region.

Examples of a yellow dye image forming coupler unit represented by A include pivaloylacetanilide, benzoylacetanilide, malondiester, malondiamine, dibenzoylmethane, benzothiazolylacetamide, malonestermonoamide, benzothiazolylacetate, benzoxazolylacetamide, benzoxazolylacetate, malondiester, benzimidazolylacetamide and benzimidazolylacetate coupler units; and coupler units consisting of heterocyclic ring-substituted acetamides or heterocyclic ring-substituted acetates as described in US-PS 3,841,880; coupler units derived from acylacetamides as described in US-PS 3,770,446, GB-PS 1,459,171, DE-OS 2,503,099, JP-A-50-139738 and Research Disclosure 15737; and heterocyclic coupler units as described in US-PS 4,046,574.

Preferred examples of magenta dye image-forming coupler units represented by A include coupler units comprising a 5-oxo-2-pyrazoline nucleus, a pyrazolo[1,5-a]benzimidazole nucleus, a pyrazoloimidazole nucleus, a pyrazolotriazole nucleus, or a pyrazolotetrazole nucleus, and cyanoacetophenone coupler units.

Preferred examples of cyan dye image-forming coupler units represented by A include coupler units having a phenol nucleus or an α-naphthol nucleus.

In addition, there are couplers that have the same effect as DIR couplers, although these couplers largely do not form a dye after a retarder is released by coupling with an oxidation product of a developing agent. Examples of this type of coupler units represented by A include the coupler units described in U.S. Patents 4,052,213, 4,088,491, 3,632,345, 3,958,993, and 3,961,959.

Preferred examples of TIME in formula (I) include the following groups.

(1) Groups utilizing the cleavage reaction of hemiacetal as described in U.S. Patent No. 4,146,396 and JP-A-60-249148, JP-A-60-249149 and JP-A-60-218645. An example of this is a group represented by the following general formula:

In the above formula, the mark * represents the position at which the group is bonded to the coupling site of A; R₁ and R₂ each represent a hydrogen atom or a substituent group; n represents 1 or 2; when n = 2, the two R₁ groups or the two R₂ groups are identical or different from each other; R₁ and R₂ or any of the two R₁ groups and any of the two R₂ groups may be combined to form a ring structure; and B is as defined above in formula (I).

(2) Groups that cause a cleavage reaction by an intramolecular nucleophilic substitution reaction, such as the synchronization group described in U.S. Patent No. 4,248,962.

(3) Groups that undergo a cleavage reaction by an electron transfer reaction along a conjugated system, such as the group described in US-PS 4 409 323 and the group represented by the following general formula (described in GB-A 2 096 783):

In the above formula, the mark * represents a position at which the group is bonded to the coupling site of A; R₃ and R₄ each represent a hydrogen atom or a substituent group; and B is as defined above in formula (I). Examples of R₃ include an alkyl group having 1 to 24 carbon atoms (e.g. methyl, ethyl, benzyl, dodecyl) or an aryl group having 6 to 24 carbon atoms (e.g. phenyl, 4-tetradecyloxyphenyl, 4-methoxyphenyl, 2,4,6-trichlorophenyl, 4-nitrophenyl, 4-chlorophenyl, 2,5-dichlorophenyl, 4-carboxyphenyl, p-tolyl). Examples of R₄ include a hydrogen atom, an alkyl group with 1 to 24 carbon atoms (eg methyl, ethyl, undecyl, pentadecyl), an aryl group with 6 to 36 carbon atoms (eg phenyl, 4-methoxyphenyl), a cyano group, an alkoxy group with 1 to 24 carbon atoms (eg methoxy, ethoxy, dodecyloxy), an amino group with 0 to 36 carbon atoms (eg amino, dimethylamino, piperidino, dihexylamino, anilino), a carbonamido group with 1 to 24 carbon atoms (eg acetamido, benzamido, tetradecanamido), a Sulfonamido group with 1 to 24 carbon atoms (e.g. methylsulfonamido, phenylsulfonamido), a carboxyl group, an alkoxycarbonyl group with 2 to 24 carbon atoms (e.g. methoxycarbonyl, ethoxycarbonyl, dodecyloxycarbonyl) and a carbamoyl group with 1 to 24 carbon atoms (e.g. carbamoyl, dimethylcarbamoyl, pyrrolidinocarbonyl).

The substituent groups represented by X₁, X₂ and X₃ in the general formulas (IIa) to (IIp) are discussed in detail below.

Examples of X�1; close Methyl, Ethyl, Propyl, Butyl, Methoxyethyl, Ethoxyethyl, Tsobutyl, Allyl, Dimethylaminoethyl, Propargyl, Chloroethyl, Methoxycarbonylmethyl, Methylthioethyl, 4-Hydroxyphenyl, 3-Hydroxyphenyl, 4-Sulfamoylphenyl, 3-Sulfamoylphenyl, 4-Carbamoylphenyl, 3-Carbamoylphenyl , 4-Dimethylaminophenyl, 3-Acetamidophenyl, 4-Propanamidophenyl, 4-Methoxyphenyl, 2-Hydroxyphenyl, 2,5-Dihydroxyphenyl, 3-Methoxycarbonylaminophenyl, 3-(3- Methylureido)phenyl, 3-(3-Ethylureido)phenyl, 4 -Hydroxyethoxyphenyl and 3-acetamido-4-methoxyphenyl. Examples of X2 close Methyl, Ethyl, Benzyl, n-Propyl, i-Propyl, n-Butyl, i-Butyl, Cyclohexyl, Fluorine atom, Chlorine atom, Bromine atom, Toxic atom, Hydroxylmethyl, Hydroxyethyl, Hydroxy, Methoxy, Ethoxy, Butoxy, Allyloxy, Benzyloxy, Methylthio , Ethylthio, Methoxycarbonyl, Ethoxycarbonyl, Acetamido, Propanamido, Butanamido, Octanamido, Benzamido, Dimethylcarbamoyl, Methylsulfonyl, Methylsulfonamido, Phenylsulfonamido, Dimethylsulfamoyl, Acetoxy, Ureido, 3-Methylureido, Cyano, Nitro, Amino, Dimethylamino, Methoxycarbonylamino, Ethoxycarbonylamino, Phenoxycarbonyl, methoxycarbonyl, methoxyethyl and acetyl. Examples of X₃ include oxygen atom, sulfur atom, imino group, methylimino group, ethylimino group, propylimino group and allylimino group.

Among the groups represented by formulae (IIa) to (IIp), the groups represented by formulae (IIa), (IIb), (IIi), (IIj), (IIk) and (IIl) are preferred. Particularly preferred are the groups represented by formulae (IIa), (IIi), (IIj) and (IIk).

Examples of the groups represented by B in formula (I) include the following groups:

The compound of formula (I) is incorporated into at least one blue-, green- or red-sensitive layer and an adjacent light-insensitive intermediate layer, preferably into a red-sensitive layer.

In general, the couplers are used together as a mixture with main couplers. The ratio of the coupler of the general formula (I) to the main coupler is 0.1 to 100 mol%, preferably 1 to 50 mol%. The proportion of the coupler of the general formula (I) to the silver halide is 0.01 to 20 mol%, preferably 0.5 to 10 mol% per mole of silver halide in the same layer when the compound is incorporated in a silver halide emulsion layer, or to silver halide in the adjacent silver halide emulsion layer which has the higher silver halide content of the two adjacent silver halide emulsion layers when the compound is incorporated in a light-insensitive intermediate layer.

The effects achieved by the present invention are particularly remarkable when A in formula (I) is a coupler unit represented by the following general formulas (Cp-1), (Cp-2), (Cp-3), (Cp-4), (Cp-5), (Cp-6), (Cp-7), (Cp-8) (Cp-9), (Cp-10) or (Cp-11). These couplers are preferred because their coupling rate is high.

In the above formulas, the dangling bonds derived from the coupling sites represent the positions at which the coupling moiety is bonded to the group eliminated by the coupling. When R₅₁, R₅₂, R₅₃, R₅₄, R₅₃, R₅₄, R₅₆, R₅₇, R₅₄, R₅₃, R₅₆, R₅₆, R₅₇, or R₅₁ in the above formulas has a non-diffusing group, each substituent group is selected so that the total of carbon atoms is 8 to 32, preferably 10 to 22. Otherwise, the total of carbon atoms is preferably not more than 15.

R₅₁ to R₆₁, l, m and p in the above formulas (Cp-1) to (Cp-11) are discussed below.

R₅₁ is an aliphatic group, an aromatic group, an alkoxy group or a heterocyclic group, and R₅₂ and R₅₃ are each an aromatic group or a heterocyclic group.

The aliphatic group represented by R₅₁ is an aliphatic hydrocarbon group having preferably 1 to 22 carbon atoms which has a substituted or unsubstituted, straight-chain, branched or cyclic hydrocarbon group and may optionally have one or more substituent groups. Preferred examples of substituent groups for the aliphatic group include an alkoxy group, an aryloxy group, an amino group, an acylamino group and a halogen atom. If desired, these substituent groups may be further substituted with at least one substituent such as a hydroxy group, a nitro group, a cyano group, a group having 0 to 32 carbon atoms such as an amino group, a sulfo group, a carbonamido group, a sulfonamido group, a carbamoyl group, a sulfamoyl group, a ureido group, an alkoxycarbonyl group and an aryloxycarbonyl group.

Specific examples of suitable aliphatic groups for R₅₁ include isopropyl, isobutyl, tert-butyl, isoamyl, tert-amyl, 1,1-dimethylbutyl, 1,1-dimethylhexyl, 1,1-diethylhexyl, dodecyl, hexadecyl, octadecyl, cyclohexyl, 2-methoxyisopropyl, 2-phenoxyisopropyl, 2-p- tert-butylphenoxyisopropyl, α-aminoisopropyl, α-(diethylamino)isopropyl, α-(succinimido)isopropyl, α-(phthalimido)isopropyl and α-(benzenesulfonamido)isopropyl.

When R₅₁, R₅₂ or R₅₃ is an aromatic group (particularly a phenyl group), the aromatic group may be substituted. The aromatic group (such as a phenyl group) may be substituted by an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an alkoxycarbonylamino group, an aliphatic amido group, an alkylsulfamoyl group, an alkylsulfonamido group, an alkylureido group or an alkyl-substituted succinimido group, each group having not more than 32 carbon atoms. The alkyl moiety in these groups may be substituted with an aromatic group such as an alkyl-substituted phenylene group. In addition, the phenyl group represented by R₅₁, R₅₂ or R₅₃ may be substituted by an aryloxy group, an aryloxycarbonyl group, an arylcarbamoyl group, an arylamido group, an arylsulfamoyl group, an arylsulfonamido group or an arylureido group. The aryl portion of these substituent groups may be further substituted with one or more alkyl groups (the total of carbon atoms is 1 to 22).

Furthermore, the phenyl group represented by R₅₁, R₅₂ or R₅₃ may be substituted by an unsubstituted or C₁₋₆-lower alkyl-substituted amino group, hydroxy group, carboxy group, sulfo group, nitro group, cyano group, thiocyano group or a halogen atom.

R₅₁, R₅₂ or R₅₃ may be a condensed group in which a phenyl group is condensed with another ring, such as a naphthyl group, a quinolyl group, an isoquinolyl group, a chromanyl group, a coumaranyl group and a tetrahydronaphthyl group. These groups may themselves be further substituted.

When R₅₁ is an alkoxy group, the alkyl moiety of the alkoxy group is a straight-chain or branched alkyl or alkenyl group or a cyclic alkyl or Alkenyl group, each group has 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms. These groups may be substituted by a halogen atom, an aryl group or an alkoxy group.

When R₅₁, R₅₂ or R₅₃ is a heterocyclic group, the heterocyclic group is bonded through a carbon atom as a member of the ring to the carbon atom of the carbonyl group of the acyl group in α-acylacetamido or to the nitrogen atom of an amido group. Examples of such heterocyclic rings include thiophene, furan, pyran, pyrrole, pyrazole, pyridine, pyrazine, pyrimidine, pyridazine, indolizine, imidazole, thiazole, oxazole, triazine, thiadiazine and oxazine. These rings may have a substituent such as a hydroxy group, a nitro group, a cyano group, a group having 1 to 32 carbon atoms such as an amino group, a sulfo group, a carbonamido group, a sulfonamido group, a carbamoyl group, a sulfamoyl group, a ureido group, an alkoxycarbonyl group and an aryloxycarbonyl group.

In formula (Cp-3), R₅₅ has 1 to 32 carbon atoms (including the carbon atoms of the substituent, if any), preferably 1 to 22 carbon atoms, R₅₅ is a straight-chain or branched alkyl group (e.g. methyl, isopropyl, tert-butyl, hexyl, dodecyl), a straight-chain or branched alkenyl group (e.g. allyl), a cyclic alkyl group (e.g. cyclopentyl, cyclohexyl, norbornyl), an aralkyl group (e.g. benzyl, β-phenethyl) or a cyclic alkenyl group (e.g. cyclopentyl, cyclohexenyl), each of which may have one or more substituent groups. Examples of the substituent groups include a halogen atom, a nitro group, a cyano group, an aryl group, an alkoxy group, an aryloxy group, a carboxy group, an alkylthiocarbonyl group, an arylthiocarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfo group, a sulfamoyl group, a carbamoyl group, an acylamino group, a diacylamino group, a ureido group, a urethane group, a thiourethane group, a sulfonamido group, a heterocyclic group, an arylsulfonyl group, an alkylsulfonyl group, an arylthio group, an alkylthio group, an alkylamino group, a dialkylamino group, an anilino group, an N-arylanilino group, an N-alkylanilino group, an N-acylanilino group, a hydroxyl group and a mercapto group.

Further, R₅₅ may be an aryl group (e.g., phenyl, α- or β-naphthyl) which may have one or more substituent groups preferably having 1 to 18 carbon atoms. Examples of the substituent groups include an alkyl group, an alkenyl group, a cyclic alkyl group, an aralkyl group, a cyclic alkenyl group, a halogen atom, a nitro group, a cyano group, an aryl group, an alkoxy group, an aryloxy group, a carboxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfo group, a sulfamoyl group, a carbamoyl group, an acylamino group, a diacylamino group, a ureido group, an aminocarbonyloxy group, an alkoxycarbonylamino group, a aryloxycarbonylamino group, a sulfonamido group, a heterocyclic group, an arylsulfonyl group, an alkylsulfonyl group, an arylthio group, an alkylthio group, an alkylamino group, a dialkylamino group, an anilino group, an N-alkylanilino group, an N-arylanilino group, an N-acylanilino group and a hydroxyl group.

Furthermore, R₅₅ may be a heterocyclic group (for example, a 5- or 6-membered heterocyclic ring containing at least one heteroatom selected from nitrogen, oxygen and sulfur, and a condensed heterocyclic group such as pyridyl, quinolyl, furyl, benzothiazolyl, oxazolyl, imidazolyl and naphthoxazolyl), a substituted heterocyclic group (examples of substituent groups are those as given above in the description of the substituent groups for the aryl group), an aliphatic or aromatic acyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkylcarbamoyl group, an arylcarbamoyl group, an alkylthiocarbamoyl group or an arylthiocarbamoyl group.

R₅₄ is a hydrogen atom or a group having 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms, and is a straight-chain or branched alkyl, alkenyl, cyclic alkyl, aralkyl or cyclic alkenyl group (these groups may have one or more substituent groups; examples of the substituent groups are those as described above in the description of the substituent groups for R₅₅), an aryl group or a heterocyclic group (these groups may have one or more substituent groups; examples of the substituent groups are those as described above in the description of the substituent groups for R₅₅), an alkoxycarbonyl group (e.g. methoxycarbonyl, ethoxycarbonyl, stearyloxycarbonyl), an aryloxycarbonyl group (e.g. phenoxycarbonyl, naphthoxycarbonyl), an aralkyloxycarbonyl group (e.g. benzyloxycarbonyl), an alkoxy group (e.g. methoxy, ethoxy, heptadecyloxy), an aryloxy group (e.g. phenoxy, tolyloxy), an alkylthio group (e.g. ethylthio, dodecylthio), an arylthio group (e.g. phenylthio, α-naphthylthio), a carboxyl group, an acylamino group (e.g. acetylamino, 3-[(2,4-di-tert-amylphenoxy)acetamido]benzamido), a Diacylamino group, an N-alkylacylamino group (e.g. N-methylpropionamido), an N-arylacylamino group (e.g. N-phenylacetamido), a ureido group (e.g. ureido, N-arylureido, N-alkylureido), an aminocarbonyloxy group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, an aminocarbonylthio group, an alkylthiocarbonylamino group, an arylthiocarbonylamino group, an arylamino group (e.g. phenylamino, N-methylanilino, diphenylamino, N-acetylanilino, 2-chloro-5-tetradecanamidoanilino), an alkylamino group (e.g. n-butylamino, methylamino, cyclohexylamino), a cycloamino group (e.g. piperidino, pyrrolidino), a heterocyclic amino group (e.g. 4-pyridylamino, 1,2-benzoxazolylamino), an alkylcarbonyl group (e.g. methylcarbonyl), an arylcarbonyl group (e.g. phenylcarbonyl), a sulfonamido group (e.g. alkylsulfonamido, arylsulfonamido), a carbamoyl group (e.g. Ethylcarbamoyl, dimethylcarbamoyl, N-methylphenylcarbamoyl, N-phenylcarbamoyl), a sulfamoyl group (e.g. N-alkylsulfamoyl, N,N-dialkylsulfamoyl, N,N-arylsulfamoyl, N-alkyl-N-arylsulfamoyl, N-diarylsulfamoyl), a cyano group, a hydroxyl group or a sulfo group.

R₅₆ is a hydrogen atom, a straight-chain or branched alkyl group, an alkenyl group, a cyclic alkyl group, an aralkyl group or a cyclic alkenyl group, each having 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms. These groups may be substituted. Examples of the substituent groups are those described above in the description of the substituent groups for R₅₆.

Furthermore, R₅₆ may represent an aryl group or a heterocyclic group, each of which may have one or more substituent groups. Examples of the substituent groups are those as described above in the description of the substituent groups for R₅₆.

Further, R₅₆ may represent a cyano group, an alkoxy group, an aryloxy group, a halogen, a carboxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, a sulfo group, a sulfamoyl group, a carbamoyl group, an acylamino group, a diacylamino group, a ureido group, an aminocarbonyloxy group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonamido group, an arylsulfonyl group, an alkylsulfonyl group, a arylthio group, an alkylthio group, an alkylamino group, a dialkylamino group, an anilino group, an N-arylanilino group, an N-alkylanilino group, an N-acylanilino group or a hydroxyl group. These groups may be further substituted with a substituent as described above for R₅₅.

R₅₇, R₅₈ and R₅₇ each represents a group used in conventional four-equivalent type phenol or α-naphthol couplers. More specifically, R₅₇ represents a hydrogen atom, a halogen atom, an alkoxycarbonylamino group, an aliphatic hydrocarbon group, an N-arylureido group, an acylamino group, or an -O-R₆₂ or -S-R₆₂ group (wherein R₆₂ is an aliphatic hydrocarbon group). The number of carbon atoms of the group represented by R₅₇ is preferably from 1 to 32. When two or more R57 groups exist per molecule, the two or more R57 groups may be different from each other. The aliphatic hydrocarbon residue may contain one or more substituent groups as described above in the description of the substituents for the alkyl group. The number of carbon atoms of these substituents is preferably from 1 to 28. R57 may be substituted at any position of the nucleus.

When these substituent groups have an aryl group, the aryl group may have one or more substituent groups. Examples of the substituent groups are those given above in the description of the substituents for R₅₅.

R₅₈ and R₅₈ are each a group selected from an aliphatic hydrocarbon group, an aryl group and a heterocyclic group. The carbon number of these groups is preferably 1 to 32. Alternatively, one of them may be a hydrogen atom. These groups may have one or more substituent groups. If desired, R₅₈ and R₅₈ may be combined with each other to form a nitrogen-containing heterocyclic ring which may further contain at least one selected from N, O and S atoms.

The aliphatic hydrocarbon group may be a saturated or unsaturated hydrocarbon group or a straight-chain, branched or cyclic hydrocarbon group. Preferably, the hydrocarbon group is an alkyl group (eg, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, isobutyl, dodecyl, octadecyl, cyclopropyl, cyclohexyl) or an alkenyl group (eg, allyl, octenyl). Examples of the aryl group include a phenyl group and a naphthyl group. Typical examples of a heterocyclic group include pyridinyl, quinolyl, thienyl, piperidyl and imidazolyl. Examples of the substituent groups which may be introduced into the aliphatic hydrocarbon group, the aryl group and the heterocyclic group include a halogen atom, a nitro group, a hydroxy group, a carboxyl group, an amino group, a substituted amino group, a sulfo group, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an arylthio group, an arylazo group, an acylamino group, a carbamoyl group, an ester group (including an alkoxycarbonyl group and an aryloxycarbonyl group), an acyl group, an acyloxy group, a sulfonamido group, a sulfamoyl group. a sulfonyl group and a morpholino group.

l is an integer from 1 to 4, in is an integer from 1 to 3 and p is an integer from 1 to 5.

R₆₀ represents an arylcarbonyl group, an alkanoyl group having 2 to 32 carbon atoms, preferably 2 to 22 carbon atoms, an arylcarbamoyl group, an alkanecarbamoyl group having 2 to 32 carbon atoms, preferably 2 to 22 carbon atoms, an alkoxycarbonyl group having 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms, or an aryloxycarbonyl group, each of which may have one or more substituent groups. Examples of the substituent groups include an alkoxy group, an alkoxycarbonyl group, an acylamino group, an alkylsulfamoyl group, an alkylsulfonamido group, an alkylsuccinimido group, a halogen atom, a nitro group, a carboxyl group, a nitrile group, an alkyl group and an aryl group.

R₆₁ represents an arylcarbonyl group, an alkanoyl group having 2 to 32 carbon atoms, preferably 2 to 22 carbon atoms, an arylcarbamoyl group, an alkanecarbamoyl group having 2 to 32 carbon atoms, preferably 2 to 22 carbon atoms, an alkoxycarbonyl group having 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms, an aryloxycarbonyl group, a An alkylsulfonyl group having 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms, an arylsulfonyl group, an aryl group, or a 5- or 6-membered heterocyclic group (the heteroatom is selected from nitrogen, oxygen and sulfur) such as a triazolyl group, an imidazolyl group, a phthalimido group, a succinimido group, a furyl group, a pyridyl group or a benzotriazolyl group, each of which may have one or more substituent groups. Examples of the substituent groups are those as described above in the description of the substituent groups for R₆₀.

Among the yellow coupler units described above, preferred are those of the formula (Cp-1) wherein R51 is a t-butyl group or a substituted or unsubstituted aryl group and R52 is a substituted or unsubstituted aryl group, and those of the formula (Cp-2) wherein R52 and R53 are each a substituted or unsubstituted aryl group.

As magenta coupler units, preferred are those of the formula (Cp-3) wherein R₅₄ is an acylamino group, a ureido group or an arylamino group and R₅₅ is a substituted aryl group; those of the formula (Cp-4) wherein R₅₄ is an acylamino group, a ureido group or an arylamino group and R₅₆ is a hydrogen atom; and those of the formulas (Cp-5) and (Cp-6) wherein R₅₄ and R₅₆ are each a straight-chain or branched alkyl group, an alkenyl group, a cyclic alkyl group, an aralkyl group or a cyclic alkenyl group.

As the cyan coupler units, those represented by the formula (Cp-7) in which R57 is an acylamino group or a ureido group at the 2-position, an acylamino group or an alkyl group at the 5-position, and a hydrogen or a chlorine atom at the 6-position, and those represented by the formula (Cp-9) in which R57 is a hydrogen atom, an acylamino group, a sulfonamido group or an alkoxycarbonyl group at the 5-position, R58 is a hydrogen atom, and R59 is a phenyl group, an alkyl group, an alkenyl group, a cyclic alkyl group, an aralkyl group or a cyclic alkenyl group are preferred.

As non-color forming coupler units, preferred are those of the formula (Cp-10) wherein R57 is an acylamino group, a sulfonamido group or a sulfamoyl group, and those of the formula (Cp-11) wherein R60 and R61 are each an alkoxycarbonyl group.

A compound containing at least two coupler units such as a bis-, tris- or tetrakis compound or a polymer may be formed by any group of R51 to R61. The polymer may be a polymer of a monomer having an ethylenically unsaturated group on any of these groups or a copolymer thereof with a non-color forming monomer.

When the coupler is a polymer, the polymer is either (1) a polymer derived from a monomer coupler of the following general formula (Cp-12) and composed of repeating units of the following general formula (Cp-13); or (2) a copolymer of said monomer coupler with at least a non-color forming monomer having at least one ethylene group and incapable of coupling with an oxidation product of an aromatic primary amine developing agent. Two or more monomer couplers may be polymerized simultaneously.

In the above formulas, R is a hydrogen atom, a lower alkyl having 1 to 4 carbon atoms or a chlorine atom; A₁ is -CONR'-, -NR'CONR'-, -NR'COO-, -COO-, SO₂-, -CO-, -NRCO-, -SO₂NR'-, -NR'SO₂-, -OCO-, -OCONR', -NR'- or -O-; A₂ is -CONR'- or -COO-, R' is a hydrogen atom, an aliphatic group or an aryl group; when two or more R groups exist per molecule, the two or more R' groups may be identical or different from each other; A₃ is -CONR'- or -COO- is an unsubstituted or substituted alkylene group having 1 to 10 carbon atoms, an aralkylene group or an unsubstituted or substituted arylene group (the alkylene group may be a straight-chain or branched alkylene group such as methylene, methylmethylene, dimethylmethylene, dimethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, decylmethylene, and an aralkylene group such as phenylene and naphthylene); Q is a group which allows the groups of the formulas (Cp-1) to (Cp-11) can be bonded to the compound of formula (Cp-12) or (Cp-13) through any group selected from R₅₁₁ to R₆₁₁; i, j and k are each 0 or 1 and in no case are i, j and k simultaneously 0.

Examples of the substituent groups of the alkylene group, the aralkylene group or the arylene group represented by A₃ 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, bromine), a carboxyl group, a carbamoyl group (e.g. methylcarbamoyl), an alkoxycarbonyl group (e.g. methoxycarbonyl), a sulfonyl group (e.g. methylsulfonyl). When two or more substituent groups exist, they may be identical or different from each other.

Examples of the compounds of formula (I) are shown below. (A mixture of compounds substituted in the 5- and 6-positions; the same for (D-12), (D-14), (D-27), (D-29), (D-46), (D-47), (D-48), (D-49), (D-50), (D-52), (D-53) and (D-54))

The compounds described here can be synthesized by the methods described in JP-A-54-145135, JP-A-63-37346, JP-A-56-114946, JP-A-57-154234, JP-A-58-162949 (corresponding to U.S. Patents 4,248,962, 4,861,701, 4,409,323, 4,421,845 and 4,482,629, respectively), JP-A-63-37350, JP-A-57-151944 (corresponding to U.S. Patent 4,477,563), JP-A-58-205150, JP-A-60-218645, the literature and others. Patent specifications are described.

The yellow colored cyan couplers are described below.

The yellow colored cyan couplers refer to cyan couplers which have an absorption maximum at 400 to 500 nm in the visible absorption region of the couplers and form cyan dyes having an absorption maximum at 630 to 750 nm in the visible absorption region by coupling with the oxidation product of an aromatic primary amine developing agent.

Among the yellow-colored cyan couplers, preferred are those cyan couplers which release a unit of a water-soluble compound having a 6-hydroxy-2-pyridon-5-ylazo group, a water-soluble pyrazolone-4-ylazo group, a water-soluble 2-acylaminophenylazo group, a 2-sulfonamidophenylazo group, a 5-aminopyrazol-4-ylazo group by a coupling reaction with the oxidation product of an aromatic primary amine developing agent.

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

Preferably, the colored cyan couplers can be represented by the following general formulas (CI) and (CII):

In formulas (CI) and (CII), Cp represents a cyan coupler unit (T is bonded to the coupling site thereof); T represents a synchronizing group; k represents 0 or 1; x represents an N-, O- or S-containing divalent group which is bonded to (T)k through the N-, O- or S-atom and which is also bonded to Q; and Q represents an arylene group or a divalent heterocyclic group.

In the formula (CI), R₁ and R₂ are independently a hydrogen atom, a carboxyl group, a sulfo group, a cyano group, an alkyl group, a cycloalkyl 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 alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group; and at least one of T, X, Q, R₁, R₂ and R₃ has a water-soluble group (e.g. hydroxyl, carboxyl, sulfo, amino, ammonium, phosphono, phosphino, hydroxysulfonyloxy).

It is clear that the group

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

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

The compounds of the general formulas (CI) and (CII) are discussed in more detail below.

Examples of the coupler unit represented by Cp include conventional cyan coupler units (e.g. units of phenyl type and naphthol type couplers).

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

The synchronizing group represented by T in formulas (CI) and (CII) is a group which is released from X after the bond between Cp and T is cleaved by the coupling reaction of the couplers with an oxidation product of an aromatic primary amine developing agent. The synchronizing group is used for various purposes, such as controlling the coupling reactivity, stabilizing the couplers, controlling the release synchronization of X, etc. Examples of the synchronizing group close conventional synchronizing groups of formulas (T-1) to (T-7) as given in the description of the compounds of formula (I).

Although k can be an integer of 0 or 1, in general the case where k = 0 is preferred, i.e. that Cp is directly bonded to X.

X is a divalent group bonded to (T)k through an N, O or S atom. Preferably, X is -O-, -S-, -O-, O O-, -OS-, -CNH-, -OSO₂, -OSO₂NH- or a bivalent group bonded to (T)k through 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 the like) or a composite group of 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 bivalent heterocyclic group (e.g. a group derived from pyridine, thiophene or the like), -CO-, -SO₂-, -COO-, -CONH-, -SO₂NH-, -SO₂O-, -NHCO-, NHSO₂-, -NHCONH-, -NHSO₂NH- or -NHCOO-. More preferably, X is a group of the following general formula (II):

*-X₁-(L-X₂)m-** (II)

In formula (II), the mark * represents the position where the group is bonded to (T)k; the Mark ** represents the position where the group is attached to Q; X₁ represents -O- or -S-; L represents an alkylene group; X₂ represents a single bond, -O-, -S-, -CO-, -SO₂-, -OC-, -CO-, -NHC-, - NH-, -SO₂NH-, NHSO₂-, -SO₂O-, -OSO₂-, -O O-, -O NH-, -NH O-, -NH NH-, -NHSO₂NH-, -OS-, -SO₂NH- or NHSO₂O-; and m represents an integer of 0 to 3. The total of carbon atoms (hereinafter referred to as carbon number) in X is preferably 0 to 12, more preferably 0 to 8. Most preferably, X is -OCH₂CH₂O-.

Q in formula (I) is an arylene group or a divalent heterocyclic group. When Q is an arylene group, the arylene group may be a condensed ring, and the arylene group may have one or more substituent groups (e.g., halogen atom, hydroxyl, carboxyl, sulfo, nitro, cyano, amino, ammonium, phosphono, phosphino, alkyl, cycloalkyl, aryl, carbonamido, sulfonamido, alkoxy, aryloxy, acyl, sulfonyl, carboxyl, carbamoyl, sulfamoyl). The number of carbon atoms is preferably 6 to 15, more preferably 6 to 10.

When Q is a divalent heterocyclic group, it is a 3- to 8-membered (preferably 5- to 7-membered) monocyclic or fused heterocyclic ring group having at least one heteroatom selected from 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-thiadiazole, indole or quinoline). The heterocyclic group may have one or more substituent groups (examples of the substituent groups include those already described above in the definition of the substituent groups for the arylene group Q). The number of C is preferably 2 to 15, more preferably 2 to 10.

The most preferred Q is

Therefore, the most preferred -(T)kXQ--

When R₁, R₂ or R₃ in formula (I) is an alkyl group, the alkyl group includes both straight-chain and branched alkyl groups which may have unsaturated bonds and one or more substituent groups (e.g. halogen, hydroxyl, carboxyl, sulfo, phosphono, phosphino, cyano, alkoxy, aryl, alkoxycarbonyl, amino, ammonium, acyl, carbonamido, sulfonamido, carbamoyl, sulfamoyl or sulfonyl).

When R₁, R₂ or R₃ is a cycloalkyl group, the cycloalkyl group is a 3- to 8-membered cycloalkyl group, which may have crosslinking groups, unsaturated bonds or substituent groups (examples of the substituent groups include those already described above in the definition of the substituent groups for the alkyl group R₁, R₂ or R₃).

When R₁, R₂ or R₃ is an aryl group, the aryl group may be a condensed ring and may have substituent groups (examples of the substituent groups include alkyl, cycloalkyl and those already described above in the definition of the substituent groups for the alkyl group R₁, R₂ or R₃).

When R₁, R₂ or R₃ is a heterocyclic group, the heterocyclic group is a 3- to 8-membered (preferably 5- to 7-membered) monocyclic or condensed heterocyclic ring group containing at least one heteroatom selected from N, S, O, P, Se and Te as a member of the heterocyclic ring. Examples of the heterocyclic group include thiazolyl, thienyl, pyrazolyl, thiazolyl, pyridyl and quinolinyl. The heterocyclic group may have one or more substituent groups (examples of the substituent groups are the same as those of the aryl groups R₁, R₂ or R₃).

The carboxyl group includes a carboxylate group; the sulfo group includes a sulfonate group; the phosphine group includes a phosphinate group; and the phosphonic group includes a phosphonate group. These groups can include any counter ions, including Li+, Na+, K+, or 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-sulfoethyl, carboxymethyl, 2-carboxyethyl, 2-hydroxyethyl, 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 sulfoamyl group having 0 to 10 carbon atoms, a sulfo group, an alkyl group having 1 to 10 carbon atoms (e.g. methyl, 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) or a sulfonamido group having 1 to 10 carbon atoms (e.g. 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, carboxyethyl, 2-sulfoethyl, 2-carboxyethyl, 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, 2,4-disulfophenyl). More preferably, R₃ is an alkyl group having 1 to 7 carbon atoms or an aryl group having 6 to 10 carbon atoms.

Preferably, R₄ is an acyl group of the following general formula (III) or a sulfonyl group of the following general formula (IV):

When R₁₁ is an alkyl group, the alkyl group includes both straight chain and branched groups and may contain unsaturated bonds, and may have one or more substituent groups (examples of the substituent groups include halogen atom, hydroxyl, carboxyl, sulfo, phosphono, phosphino, cyano, alkoxy, aryl, alkoxycarbonyl, amino, ammonium, acyl, carbonamido, sulfonamido, carbamoyl, sulfamoyl, sulfonyl).

When R₁₁ is a cycloalkyl group, the cycloalkyl group is a 3- to 8-membered cycloalkyl group, which may contain crosslinking groups and unsaturated bonds, and which may have one or more substituent groups (examples of the substituent groups are those given above in the description of the substituent groups for the alkyl group R₁₁).

When R₁₁ is an aryl group, the aryl group may be a condensed ring or may have one or more substituent groups (examples of the substituent groups include an alkyl group, a cycloalkyl group and those as given above in the description of the substituent groups for the alkyl 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 ring group containing at least one heteroatom selected from N, S, O, P, Se and Te as a member of the heterocyclic ring (e.g., imidazolyl, thienyl, pyrazolyl, thiazolyl, pyridyl, quinolinyl) and may have one or more substituent groups (examples of the substituent groups are those as given above in the description for the substituent groups of the aryl group R₁₁).

Note that in this specification, the carboxyl group may include a carboxylate group, the sulfo group may include a sulfonate group, the phosphino group may include a phosphinate group, and the phosphonic group may include a phosphonate group. Counter ions are Li⁺, Na⁺, K⁺, ammonium, etc.

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), of which an alkyl group having 1 to 3 carbon atoms and an aryl group having 6 carbon atoms are particularly preferred.

R₅ is a group which may be substituted and is preferably an electron donor group. More preferably, R₅ is a group -NR₁₂R₁₃ or -OR₁₄, which is preferably bonded in the 4-position. R₁₂, R₁₃ and R₁₄ are each a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group, and thus each of them has the same meaning as R₁₁. R₁₂ and R₁₃ may be combined with each other to form a ring. As the ring to be formed, an alicyclic nitrogen-containing heterocyclic ring is preferred.

j is an integer from 0 to 4, preferably 1 to 2, particularly preferably 1.

Specific examples for Cp, X, Q,

in the formulas (CI) and (CII) include the following groups: (Examples of Cp)

(Examples of X)

-O-, -S-, -OCH₂-, -OCH₂CH₂-, -OCH₂CH₂O-, -OCH₂CH₂CH₂O-, -O(CH₂CH₂O)₂-, -OCH₂CH�2S-, -OCH₂CH�2NHCO-, -OCH₂CH�2NHSO₂-, -OCH₂CH�2SO₂-, -OCH₂CH�2OCO-, -OCH₂CH₂CO-, -SCH₂CONH-, -SCH₂COO-,

-OCH₂CH₂OSO₂-, -OCO-, (Examples of Q) Examples of Examples of Examples of color couplers

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

The above-mentioned 6-hydroxy-2-pyridone compounds can be prepared by processes as 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 here means an "examined Japanese patent publication"); German Patent Nos. 2,162,612, 2,349,709 and 2,902,486; and US Patent No. 3,763,170.

The diazonium salts can be prepared according to the methods described in U.S. Patent Nos. 4,004,929 and 4,138,258 and 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 the like 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 -78 to +60ºC, preferably -20 to +30ºC.

Synthesis examples of the color couplers of the present invention are described below. SYNTHESIS EXAMPLE 1 - Synthesis of coupler (YC-1) Matchmaker

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 heating and reflux. 110 g of methyl cyanoacetate was added dropwise over a period of 1 hour. The mixture was heated under reflux for 5 hours and then left overnight. The precipitated crystals were separated by filtration, washed with ethanol and dried to obtain 202.6 g of the compound (a) in crystalline form.

Synthesis of compound (b):

11.5 g of the compound (a) and 3.5 g of potassium carbonate were added to 11.5 ml of water. While the mixture was heated with stirring on a steam bath, 7.8 g of ethyl acetoacetate was added dropwise. The mixture was stirred for 7 hours and then cooled. 9.2 ml of concentrated saline salts were added to precipitate a crystalline precipitate. The crystals were separated by filtration, washed with methanol and dried to obtain 10.4 g of the compound (b) in crystalline form.

Synthesis of the coupler (YC-1):

10.1 g of compound (c), prepared according to the method described in U.S. Patent No. 4,138,258, were dissolved in 60 ml of N,N-dimethylformamide and 60 ml of methyl cellosolve.

While the resulting solution was cooled with ice, 4.3 ml of concentrated hydrochloric acid was added thereto, 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 separated by filtration, washed with water, dried and dispersed in 500 ml of methanol. The dispersion was heated under reflux for 1 hour and then allowed to stand to cool. The crystals were collected by filtration, washed with methanol and dried to obtain 13.6 g of the desired coupler (YC-1) as red crystals having a melting point of 269 to 272°C (decomposition). The structure of the compound was confirmed by 1H-NMR mass spectrum and elemental analysis. The compound showed a maximum absorption wavelength in methanol at 457.7 nm and had a molecular extinction coefficient of 41,300. The compound showed good spectral absorption characteristics as a yellow-colored coupler. SYNTHESIS EXAMPLE 2 - Synthesis of the coupler (YC-3) Matchmaker

75 ml of N,N-dimethylformamide and 75 ml of methyl cellosolve were added to 19.2 g of the compound (d) prepared by the method described in JP-A-62-85242 (US Patent No. 4,837,136) to dissolve it. While stirring the resulting solution under ice-cooling, 5.6 ml of concentrated hydrochloric acid was added thereto, and then a solution of 2.5 g of sodium nitrite in 5 ml of water was added dropwise. After the dropwise addition, the mixture was stirred for 1 hour and then for another 1 hour at room temperature, thereby preparing 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 the resulting solution was stirred under ice-cooling, the above diazonium solution was added dropwise. After the dropwise addition, the mixture was stirred for 1 hour and then for 2 hours at room temperature. The precipitated crystals were separated 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 maximum absorption wavelength in methanol of 457.6 nm and had a molecular extinction coefficient of 42,700. The compound showed good spectral absorption characteristics as a yellow-colored coupler. SYNTHESIS EXAMPLE 3 - Synthesis of Coupler (YC-30) Diketen Matchmaker

Synthesis of compound (e):

137.1 g of anthranilic acid was added to 600 ml of acetonitrile. The mixture was heated to reflux with stirring. 92.5 g of diketene was added dropwise over a period of 1 hour. The mixture was heated to reflux 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 crystalline form.

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 thereto and the mixture was acidified with 230 ml of concentrated hydrochloric acid. The precipitated crystals were separated by filtration. The resulting crude crystals were washed with a mixed solvent of ethyl acetate and acetonitrile under heating to obtain 152 g of the compound (f).

Synthesis of the coupler (YC-30):

13.0 g of the compound (g) prepared by the method described in U.S. Patent No. 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 thereto and a solution of 1.48 g of sodium nitrite in 5 ml of water was added dropwise to prepare a diazonium solution. 20 ml of N,N-dimethylformamide and 15 ml of water were added to 6.0 g of the compound (f) and 8 g of sodium acetate. With stirring and ice-cooling, the above diazonium solution was added dropwise to the mixture. After the addition, the mixture was stirred for 30 minutes at room temperature and acidified with hydrochloric acid. The product was extracted with ethyl acetate, washed with water and concentrated under reduced pressure. The concentrate was crystallized from a mixed solvent of ethyl acetate and methanol to obtain 13 g of the coupler (YC-30) as yellow crystals.

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

(1) Synthesis of compound (3):

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

(2) Synthesis of compound (5):

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

Synthesis of compound (6):

370 g of the nitro compound (5), 6 g of a 10% Pb-C catalyst and 1 l of ethyl acetate were placed in an autoclave and a hydrogenation reaction was carried out 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 from n-hexane. The precipitated crystals were purified by Filtration and dried to obtain 327 g of the amine compound (7) having a melting point of 95 to 97 °C.

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

20 g of the amine compound (7) was dissolved in 60 ml of dimethylformamide. While cooling the resulting solution with ice, 7.6 ml of concentrated hydrochloric acid was added thereto. Further, 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 an additional 30 minutes to obtain a diazo solution.

9.7 g of the 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 therein. After cooling the resulting solution with water, the diazo solution was gradually added with stirring at a temperature 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 recrystallized from a methanol-ethyl acetate mixture, the precipitated crystals were separated by filtration and dried to obtain 21.2 g of the coupler (YC-86) having a melting point of 117 to 119 °C.

The yellow-colored cyan couplers of formulas (CII) to (CIV) can be prepared by the methods described in JP-B-58-6939 (the term "JP-B-" as used herein used meant an "examined Japanese patent publication") and JP-A-1-197563. The couplers of the general formula (CI) can be prepared by the processes described in the patent specifications cited above.

Among the yellow-colored cyan couplers used in the present invention, the couplers represented by the formulas (CI) and (CII) are more preferred, and in particular, the couplers represented by the formula (CI) are particularly preferred.

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

The yellow-colored couplers used in the present invention can be added in the same manner as in the addition of conventional couplers, as described below.

It is particularly preferred that benzoylacetanilide type yellow couplers of the following general formula (A) are used in the silver halide color photographic materials of the present invention. The yellow couplers of the formula (A) have high ε (molar extinction coefficient) values, so that the thickness of the photographic layers can be reduced. As a result, not only the sharpness but also the color reproducibility is improved because the interlaminar effect is increased. Furthermore, the yellow-colored cyan couplers of formulas (CI) and (CII) and the developed dyes of these yellow couplers are similar in spectral absorption waveforms. Accordingly, the copyability in various auto printers using color filters with different spectral characteristics, different light sources and different light sensors and manufactured by different companies is good (because the stability can be maintained even if the shooting conditions and the amount of exposure are varied).

In formula (A), M and Q each represent a group or an atom that can be bonded to the benzene ring; L represents a hydrogen atom, a halogen atom or an aliphatic oxy group; m represents an integer of 0 to 5; n represents an integer of 1 to 4; X represents a group that can be eliminated by a coupling reaction with an oxidation product of an aromatic primary amine developing agent; when m = 2 or more, the two or more M groups may be identical or different from each other; when n = 2 or more, the two or more Q groups may be identical or different from each other. and M, Q, L or X may be a single bonding or a bivalent to tetravalent bonding group comprising a bis-, tris- or tetrakis compound with two to four units of the yellow coupler of formula (A).

Examples of M and Q include a halogen atom (e.g. fluorine, chlorine, bromine), an aliphatic group having 1 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, an aliphatic oxy group having 1 to 20 carbon atoms, an aromatic oxy group having 6 to 20 carbon atoms, a carbonamide group having 2 to 24 carbon atoms, a sulfonamide group having 0 to 20 carbon atoms, a carbamoyl group having 1 to 24 carbon atoms, a sulfamoyl group having 0 to 20 carbon atoms, an acyloxy group having 2 to 20 carbon atoms, an aliphatic oxycarbonyl group having 2 to 20 carbon atoms, a substituted amino group having 2 to 24 carbon atoms, an aliphatic thio group having 1 to 24 carbon atoms, a ureido group having 1 to 20 carbon atoms, a Sulfamoylamino group with 0 to 20 carbon atoms, a cyano group, an aliphatic oxycarbonylamino group with 2 to 20 carbon atoms, an imido group with 4 to 20 carbon atoms, an aliphatic sulfonyl group with 1 to 20 carbon atoms, an aromatic sulfonyl group with 6 to 20 carbon atoms, a heterocyclic group with 1 to 20 carbon atoms. These groups can be further substituted. L is a hydrogen atom, a halogen atom (fluorine, chlorine, bromine) or an aliphatic oxy group with 1 to 24 carbon atoms, which can be substituted. X is a group which can be formed by a coupling reaction with an oxidation product of an aromatic primary amine. developing agent. More specifically, X is a group of the following general formula (B), (C) or (D):

In formula (B), R' is an aromatic group having 2 to 30 carbon atoms, a heterocyclic group having 1 to 28 carbon atoms, an acyl group having 2 to 28 carbon atoms, an aliphatic sulfonyl group having 1 to 24 carbon atoms, or an aromatic sulfonyl group having 6 to 24 carbon atoms.

In formula (C), R" is an aliphatic group having 1 to 30 carbon atoms, an aromatic group having 6 to 30 carbon atoms, or a heterocyclic group having 1 to 28 carbon atoms.

In formula (D), Y is a non-metallic atom group required to form a monocyclic or condensed 5- to 7-membered heterocyclic ring together with N. Examples of the heterocyclic ring formed by Y together with N include pyrrole, pyrazole, imidazole, 1,2,4-triazole, tetrazole, indole, indazole, benzimidazole, benztriazole, tetraazaindene, succinimide, phthalimide, saccharin, oxazolidine-2,4-dione, imidazolidine-2,4-dione, thiazolidine-2,4-dione, urazole, parabenic acid, maleimide, 2-pyridone, 4-pyridone, 6-pyridazone, 6-pyrimidone, 2-pyrazolone, 1,3,5-triazin-2-one, 1,2,4-triazin-6-one, 1,3,4-triazin-6-one, 2-oxazolone, 2-thiazolone, 2-imidazolone, 3-isoxazolone, 5-tetrazolone and 1,2,4-triazolo-5-one. These heterocyclic rings can be substituted. Examples of substituent groups include a halogen atom, a hydroxy group, a nitro group, a cyano group, a carboxyl group, an aliphatic group, an aromatic group, a heterocyclic group, an aliphatic oxy group, an aromatic oxy group, an aliphatic thio group, an aromatic thio group, an aliphatic oxycarbonyl group, a carbonamido group, a sulfonamido group, a carbamoyl group, a sulfamoyl group, a ureido group, a sulfamoylamino group, an aliphatic oxycarbonylamino group, and a substituted amino group.

In formula (A), the aliphatic group includes straight-chain, branched and cyclic alkyl, alkenyl and alkynyl groups. These groups may be substituted, for example, with an aryl group, a halogen atom, an alkoxycarbonyl group, an alkoxy group or an aryloxy group. Examples of the aliphatic group include methyl, ethyl, isopropyl, n-butyl, t-butyl, t-amyl, n-hexyl, cyclohexyl, n-octyl, 2-ethylhexyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, 2-hexyldecyl, n-octadecyl, allyl, benzyl, phenethyl, undecenyl, octadecenyl, trifluoromethyl, chloromethyl, cyanoethyl, 1-(ethoxycarbonyl)ethyl, methoxyethyl, butoxyethyl, 3-dodecyloxypropyl and phenoxyethyl. The heterocyclic group includes substituted or unsubstituted monocyclic or fused heterocyclic rings. Examples of the heterocyclic group include 2-furyl, 2-thienyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-quinolyl, oxazol-2-yl, thiazol-2-yl, benzoxazol-2-yl, benzthiazol-2-yl, 1,3,4-thiadiazol-2-yl, 1,3,4-oxadiazol-2-yl and groups derived from the compounds of the formula

(wherein

the same as that in formula (D)). The aromatic group includes substituted or unsubstituted monocyclic or condensed aryl groups. Examples of substituents include an alkyl group, a halogen atom and an alkoxy group. Examples of the aromatic group include phenyl, tolyl, 4-chlorophenyl, 4-methoxyphenyl, 1-naphthyl, 2-naphthyl and 4-t-butylphenoxyphenyl.

Preferred examples of the groups of the couplers of the formula (A) which can be preferably used in the present invention are shown below.

Preferably, M is an aliphatic group (e.g. methyl, ethyl, n-propyl, t-butyl), an aliphatic oxy group (e.g. methoxy, ethoxy, n-butoxy, n-dodecyloxy), a halogen atom (e.g. fluorine, chlorine, bromine), a carbonamido group (e.g. acetamido, n-butanamido, n-tetradecanamido, benzamido) or a sulfonamido group (e.g. methylsulfonamido, n-butylsulfonamido, n-octylsulfonamido, n-dodecylsulfonamido, toluenesulfonamido). Preferably L is a chlorine atom or an aliphatic oxy group (methoxy, ethoxy, methoxyethoxy, n-octyloxy, 2-ethylhexyloxy, n-tetradecyloxy).

Preferably, Q is, in addition to the groups given above as preferred examples of M, an aliphatic oxycarbonyl group (e.g. methoxycarbonyl, ethoxycarbonyl, n-butoxycarbonyl, n-hexyloxycarbonyl, 2-thylhexyloxycarbonyl, 1-(ethoxycarbonyl)ethyloxycarbonyl, 3-dodecyloxypropyloxycarbonyl, n-decyloxycarbonyl, n-dodecyloxycarbonyl, phenethyloxycarbonyl) or a carbamoyl group (e.g. dimethylcarbamoyl, dibutylcarbamoyl, dihexylcarbamoyl, di-2-ethylhexylcarbamoyl, n-dodecylcarbamoyl). Preferably, m is an integer of 0 to 2 and n is an integer of 0 to 2. Preferably, X is the group of formula (B) wherein R' is an aromatic group (eg, 4-methoxycarbonylphenoxy, 4-methylsulfonylphenoxy, 4-cyanophenoxy, 4-dimethylsulfamoylphenoxy, 2-acetamido-4-ethoxycarbonylphenoxy, 4-ethoxycarbonyl-2-methylsulfonamidophenoxy) or a group of formula (D). Among the groups represented by formula (D), a group of the following general formula (E) is more preferred:

In formula (E), V is a substituted or unsubstituted methylene group or a substituted or unsubstituted imino group; W is an oxygen atom, a sulfur atom, a substituted or unsubstituted methylene group or an unsubstituted imino group; and when V is an imino group, W is neither an oxygen atom nor a sulfur atom. Examples of the group of formula (E) include succinimido, phthalimido, 1-methyl-imidazolidin-2,4-dion-3-yl, 1-benzyl-imidazolidin-2,4-dion-3-yl, 5-ethoxy-1-methylimidazolidin-2,4-dion-3-yl, 5-methoxy-1-methylimidazolidin-2,4-dion-3-yl, 5,5-dimethyl-oxazolidin-2,4-dion-3-yl, thiazolidin-2,4-dion-3-yl, 1-benzyl-2-phenyltriazolidin-3,5-dion-4-yl, 1-n-propyl-2-phenyltriazolidin-3,5-dion-4-yl and 5-Ethoxy-1- benzylimidazolidin-2,4-dion-3-yl.

Each of the groups M, Q, L and X of the yellow coupler represented by formula (A) may be a single bond or a bivalent to tetravalent bonding group forming a bis-, tris-, tetrakis compound of the yellow coupler. However, compounds having one or two yellow coupler units are preferred. When the yellow coupler of formula (A) is in the form of a bis- to tetrakis compound, the number of carbon atoms of M, Q, L or X may exceed the range described above.

Examples of the yellow couplers of the formula (A) which can be used in the present invention include, but are not limited to, the following compounds. (A mixture of compounds substituted in the 4- or 5-sterling)

The above-described yellow couplers which can be preferably used can be prepared by conventional methods, such as the preparation methods described in U.S. Patent Nos. 3,227,554, 3,408,194, 3,415,652, 3,447,928 and 4,401,752, British Patent No. 1,040,710, JP-A-47-26133, JP-A-47-37736, JP-A-48-733147, JP-A-48-94432, JP-A-48-68834, JP-A-48-68835, JP-A-48-68836, JP-A-50-34232, JP-A-51-50734, JP-A-51-102636, JP-A-55-598, JP-A-55-161239, JP-A-56-95237, JP-A-56-161543, JP-A-56-153343 JP-A-59-174839 and JP-A-60-35730.

The photographic material of the present invention has a support on which at least a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer are provided. There is no particular limitation on the number of layers of the 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 composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different light sensitivity, the sensitive layer being a uniformly sensitive layer having color sensitivity to each of blue light, green light and red light. In a multilayer silver halide color photographic material, the uniformly sensitive layers 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 arrangement may be in the reverse order to that described above depending on the purpose of use. Further, the arrangement may be such that another light-sensitive layer may be interposed in the same color-sensitive layers.

Non-sensitive layers, such as various interlayers, may be provided between sensitive silver halide layers or on the top or bottom layer thereof.

The interlayers may contain couplers or DIR compounds as described in JP-A-61-43748, JP-A-59-113438, JP-A-59-113440, JP-A-61-20037 and JP-A-61-20038. The interlayers may also contain color mixing inhibitors as conventionally used.

A plurality of silver halide emulsion layers constituting each uniformly sensitive layer preferably include a two-layer structure consisting 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. It is preferred that the layers are applied such that the photosensitivity decreases toward the support. A non-sensitive layer may be provided between 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 on the side 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 (BH) / high-sensitivity green-sensitive layer (GH) / low-sensitivity green-sensitive layer (GL) / high-sensitivity red-sensitive layer (RH) / low-sensitivity red-sensitive layer (RL), starting from the outermost Layer, or in the order BH/BL/GL/GH/RH/RL or in the order BH/BL/GH/GL/RL/RH.

The arrangement may be in the order of blue-sensitive layer/GH/RH/GL/RL from the outermost layer as described in JP-B-55-34932. Further, 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 JP-A-62-63936.

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

In yet another embodiment, the arrangement can be made in the order of highly sensitive Emulsion layer / low-sensitivity emulsion layer / medium-sensitivity emulsion layer, or in the order low-sensitivity emulsion layer / medium-sensitivity emulsion layer / high-sensitivity emulsion layer.

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

It is preferable that a donor layer (CL) having a multilayer effect and having a spectral sensitivity distribution different from that of the main sensitive layers such as BL, GL and RL is provided directly adjacent to or near the main sensitive layers, thereby improving color reproducibility. The above donor layer is described in U.S. Patents 4,663,271, 4,705,744 and 4,707,436, JP-A-62-160448 and JP-A-63-89850.

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

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

Silver halide grains in the photographic emulsions may have a regular crystal form such as cubic, octahedral or tetradecahedral, an irregular crystal form such as spherical or tabular, a crystal having a defect such as a twinned face, or a composite form thereof.

The size of the silver halide grains can range from fine grains having a grain size of not more than about 0.2 µm to large-size grains having a grain size of about 10 µm in terms of the diameter of the projected area. Any polydisperse and monodisperse emulsion can be used.

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

Monodisperse emulsions as described in US 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 processes 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 with a regular crystal structure or a crystal structure that differs in the halogen composition inside and on the surface can be used. Grains with a laminar crystal structure can be used. Silver halide with a different composition can be added to the grains by epitaxial growth. A compound such as silver rhodanide or lead oxide can be added to the grains in addition to silver halide. A mixture of grains with different crystal forms can 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. 30716 and are listed in a table below.

It is preferred in the present invention that non-sensitive finely divided silver halide grains are used. The term "non-sensitive finely divided silver halide grains" as used herein refers to finely divided silver halide grains which are not light-sensitive during exposure to obtain a color image and which are largely not developed. Grains that have not been previously veiled 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 (the average of the diameters of the circles whose area corresponds 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 the usual 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 preferred that a conventional stabilizer such as triazole, azaindene, benzothiazole, a mercapto compound or a zinc compound be added before the finely divided silver halide grains are added to the coating solutions. In layers containing the finely divided silver halide grains, colloidal silver is preferably incorporated.

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

It is preferred that compounds capable of reacting with formaldehyde to fix it, as described in U.S. Patent Nos. 4,411,987 and 4,435,503, be added to the photographic materials, thereby preventing the photographic quality from being impaired by formaldehyde gas.

Various color couplers can be used in the present invention. Examples thereof are described in the patent specifications cited 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 as described in US Patents 4,310,619 and 4,351,897, EP 73,636, US Patents 3,0el,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, US 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. Patent Nos. 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, EP-A-249 453, US-PSen 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.

Typical examples of dye-forming polymerized couplers are those described in U.S. Patent Nos. 3,451,820, 4,080,211, 4,367,282, 4,409,320 and 4,576,910, British Patent No. 2,102,137 and EP-A-341,188.

Preferred couplers which form developed dyes with controlled diffusion are those described in US Pat. No. 4,366,237, GB Pat. No. 2,125,570, EP 96,570 and DE-OS 3,234,533.

In addition to the colored couplers used in the present invention, preferred compounds are described in Research Disclosure No. 17643, Section VII-G, ibid No. 307105, Section VII-G, US Patent No. 4,163,670, JP-B-57-39413, US Patent Nos. 4,004,929 and 4,138,258 and British Patent No. 1,146,368, which serve as colored couplers for correcting the unnecessary absorption of the developed dyes. It is also preferred to use couplers for correcting unnecessary absorption of developed dyes in which fluorescent dyes are released during coupling, as described in U.S. Patent No. 4,774,181, or couplers having as an elimination group a dye precursor group capable of reacting 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 development inhibitors other than those in the present invention are described in the patent specifications cited in the above-mentioned RD No. 17643, Section VII-F, ibid. No. 307105, Section VII-F and JP-A-60-184248.

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

Other examples of compounds which can be used in the present invention include competitive couplers described in U.S. Patent No. 4,130,427, polyequivalent type couplers described in U.S. Patent Nos. 4,283,472, 4,338,393 and 4,310,618, DIR redox compound releasing couplers, DIR coupler releasing couplers, redox compound releasing DIR couplers and redox compound releasing DIR redox compounds as described in JP-A-60-185950 and JP-A-62-24252, dye releasing couplers capable of re-forming color after elimination as described in EP-A-173,302 and EP-A-313,308, bleach accelerator releasing couplers as described in RD No. 11449, RD No. 24241 and JP-A-61-201247, ligand-releasing couplers described in US-PS 4 555 477, leuco dye-releasing couplers described in JP-A-63-75747, and US-PS 4 774 181 described fluorescent dye releasing couplers.

Couplers used according to the invention can be introduced into the photographic materials by various known dispersion processes.

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

Examples of the high boiling organic solvents having a boiling point of not lower than 175ºC at normal pressure used in the oil-in-water dispersion method 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 acid 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 (e.g. isostearyl alcohol, 2,4-di-tert-amylphenol), aliphatic carboxylic acid esters (e.g. bis(2-ethylhexyl)sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate), aniline derivatives (e.g. N,N-dibutyl-2- butoxy-5-t-octylaniline) and hydrocarbons (eg paraffin, dodecylbenzene, diisopropylnaphthalene). Organic solvents having a boiling point of not lower than about 30°C, preferably not lower than about 50°C but not higher than about 160°C can be used as co-solvents. Examples of the co-solvents include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate and dimethylformamide.

Examples of steps in latex dispersion processes, their effects and the impregnating latex are described in US-PS 4 199 363, DE-OSen 2 541 274 and 2 541 230.

It is preferable that germicidal and fungicidal agents, such as 1,2-benzoisothiazolin-3-one, n-butyl-p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol and 2-(4-thiazolyl)benzimidazole as 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 the color photographic materials of the present invention include general-purpose and motion picture color negative films, reversal color films for slides and television, color paper, color positive films or reversal color paper.

Examples of carriers usable in the 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 of the layer thicknesses of the entire hydrophilic colloid layers on the emulsion layer side thereof is preferably not more than 28 µm, more preferably not more than 23 µm, still 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% relative humidity under room air conditioning (2 days). The layer swelling rate T1/2 can be measured by methods known in the field of photography, for example, using a swelling meter as described in A. Green et al, Photogr. Sci. Eng., Vol. 19, No. 2, pages 124 to 129. T1/2 is defined as the time required for the layer thickness to reach half of the saturated layer thickness when processing is carried out with a color developer solution at 30ºC for 3 minutes and 15 seconds, and 90% of the attainable maximum thickness of the swollen layer is called the saturated layer thickness.

The layer swelling rate T1/2 can be controlled by adding a hardener to gelatin as a binder or by changing the conditions with time after coating. A swelling coefficient of 150 to 400% is preferred. The swelling coefficient can be calculated 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 according to the invention can be developed by conventional methods as 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).

Color developing solutions that can be used for processing the photographic materials of the present invention are preferably aqueous alkali solutions composed predominantly of aromatic primary amine color developing agents. Aminophenol compounds are suitable as color developing agents and p-phenyldiamine compounds are preferred as color developing agents. Typical examples thereof 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 sulfate, hydrochloride and p-toluenesulfonate. Among them, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline sulfate is particularly preferred. These compounds may be used either alone or in combination of two or more of them, depending on the purpose of use.

In general, the colour developer solutions contain pH buffering agents such as alkali metal carbonates, borates and phosphates, developed retarders such as chlorides, bromides, iodides, benzimidazoles, benzothiazoles and mercapto compounds, and anti-fogging agents. If desired, the color developer solutions may optionally contain preservatives such as hydroxylamine, diethylhydroxylamine, sulfites, hydrazine 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, competitive couplers; additional developing agents such as 1-phenyl-3-pyrazolidone; coupling agents; and chelating agents such as aminopolycarboxylic acids, aminepolyphosphonic 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 salts thereof.

Usually, when performing reversal processing, 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 of them.

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 the color photographic materials, but is usually not more than 3 l/m² of the photographic material. The replenishment rate can be reduced to 500 ml or less if the concentration of bromide ions in the replenishment solution is reduced. When the replenishment amount is to be reduced, it is desirable that the contact area of the processing solution with air is reduced, thereby preventing the solution from evaporating or being oxidized by air. The contact area of the photographic processing solution with air in the processing tank is indicated by the opening ratio described below.

Opening ratio = Air contact area (cm⁻²) of processing solution/Capacity (cm³) of processing solution

The aperture ratio is preferably not larger than 0.1, more 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 lid is used as described in JP-A-1-82033, and a slit development method as described in JP-A-63-216050. It is preferable that 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 changing 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 processing time can be shortened.

After color development, the photographic emulsion layer is generally bleached. Bleaching may be carried out simultaneously with fixing (bleach-fixing treatment) or separately. After bleaching, bleach-fixing treatment may be carried out to speed up processing. Processing is carried out with a bleach-fixing bath composed of two subsequent baths. Fixing may be carried out before bleach-fixing treatment. After bleach-fixing treatment, bleaching may be carried out depending on the application. 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-diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid), citric acid, tartaric acid and malic acid. Among them, iron(III) complex salts of aminopolycarboxylic acids such as (ethylenediaminetetraacetonato)-iron(III) complex and (1,3-diaminopropanetetraacetonato)-iron(III) complex are preferred for rapid processing and prevention of environmental pollution. In addition, iron(III) complex salts of aminopolycarboxylic acids are useful for bleaching solutions and bleach-fixing solutions. The pH of the bleaching solutions containing the iron(III) complex salts of aminopolycarboxylic acids and the bleach-fixing solutions containing the iron(III) complex salts is usually in the range of 4.0 to 8. A lower pH can be used to accelerate processing.

If desired, the bleaching solution, the bleach-fixing solution and its pre-bath may contain bleaching accelerators. Examples of the bleaching accelerators include compounds having a mercapto group or a disulfide group as 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-53-28425 and Research Disclosure No. 17129 (July 1978); the thiazolidine derivatives described in JP-A-50-140219; the thiourea derivatives described in JP-B-45-8506, JP-A-52-20832, JP-A-53-32735 and US-PS 3 706 561; the thiourea derivatives described in DE-PS 1,127,715 and JP-A-58-16235; the polyoxyethylene compounds described in German Patents 996,410 and 2,748,430; the polyamine compounds described in JP-B-45-8836; the 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 these, the compounds having a mercapto group or disulfide group are preferred because of their high accelerating effect. Particularly preferred are compounds described in US-PS 3,893,858, German-PS 1,290,812 and JP-A-53-95630. Furthermore, the compounds described in US-PS 4,552,834 are preferred. These bleaching accelerators can be incorporated into the photographic materials. These bleaching accelerators are particularly effective in carrying out the bleach-fixing of the color photographic materials for photography.

It is preferable that the bleaching solution and the bleach-fixing solution contain, in addition to the above-described compounds, organic acids for preventing staining that may be caused by bleaching. Particularly preferred organic acids are compounds having an acid dissociation constant (pKa) of 2 to 5. Examples of the organic acids include acetic acid and propionic acid.

Examples of fixing agents used in the fixing solution and the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas and a large amount of an iodide. The thiosulfates are widely used as fixing agents. In particular, ammonium thiosulfate is most 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 as described in EP-A-294 769 are preferred as preservatives for the fixing solution and the bleach-fixing solution. It is also preferred that aminopolycarboxylic acids or organic phosphonic acids are added to the fixing solution or the bleach-fixing solution, thereby stabilizing the solution.

It is preferred that compounds having a pKa of 6. to 9.0, particularly 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 the bleach-fixing solution for adjusting the pH.

A shorter desilvering time (in total) is preferred, as long as it does not cause desilvering failure. The desilvering time is preferably 1 to 3 minutes, more preferably 1 to 2 minutes. The processing temperature is 25 to 50°C, preferably 35 to 45°C. When desilvering is carried out at a temperature within the preferred range, the desilvering speed is increased and staining after processing is effectively prevented.

It is preferred that in the desilvering step the agitation is intensified to the highest possible degree. Methods for intensifying the agitation include Methods in which a jet of the processing solution collides with the surfaces of the emulsions of the photographic materials as described in JP-A-62-183460, a method in which stirring is improved by rotating means as described in JP-A-62-183461; a method in which a wiping blade provided in the solution is brought into contact with the surfaces of the emulsions, the photographic material is agitated, thereby forming a turbulent flow, thereby improving the stirring effect; a method in which the total amount of the circulated processing solution is increased. Such agitation improving means are effectively applicable to the bleaching solution, the bleach-fixing solution and the fixing solution. It is believed that improved agitation accelerates the penetration of the bleaching solution and the fixing solution into the emulsion layers and, as a result, increases the desilvering speed. The agitation improving means described above are more effective when the bleaching accelerators are used. The acceleration effect can be greatly increased, and the problem that inhibition of fixation caused by bleaching accelerators occurs can be solved.

It is preferable that automatic processors for use in processing the photographic materials of the present invention are equipped with transporting means for photographic materials as described in JP-A-60-191257, JP-A-60-191258 and JP-A-60-191259. As stated in JP-A-60-191257, the transporting means can greatly reduce the amount of processing solution discharged from the preceding Bath into the subsequent bath, so that the maintenance of the quality of the processing solution is very high. This is particularly effective in shortening the processing time of each stage or in reducing the replenishment rate of the processing solution. Usually, the silver halide color photographic materials of the present invention are washed and/or stabilized after desilvering. The amount of washing water in the washing stage varies greatly depending on the characteristics (for example, depending on the materials used such as couplers) of the photographic materials, their use, the temperature of the washing water, the number of washing tanks (the number of stages), the replenishment system (countercurrent, direct flow) and other conditions. The relationship between the amount of water and the number of washing tanks in the multi-stage countercurrent system can be determined by the method described in 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 as described in the above article, the amount of washing water can be greatly reduced. However, the residence time of the water in the tanks is prolonged and as a result, bacterial growth occurs and the resulting suspended matter is deposited on the photographic material. A method for reducing calcium ion and magnesium ion concentrations as described in JP-A-62-288838 can be effectively used to solve this problem in the color photographic materials of the present invention. can be used. Further, isothiazolone compounds, thiabendazole compounds, chlorine-containing germicides such as sodium chlorinated isocyanurate and benzotriazole described in JP-A-57-8542, and germicides as 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 washing time are usually 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 stabilizing treatment can be carried out by conventional methods as described in JP-A-57-8543, JP-A-58-14834 and JP-A-60-220345.

A stabilizing treatment can be carried out after washing. The stabilizing treatment can be used as a final bath for the color photographic materials for photography. An example of this includes a stabilizing bath that a dye stabilizer and a wetting agent. Examples of the dye stabilizer include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine and aldehyde-sulfite adducts.

The stabilization bath can contain various chelating agents and anti-fungal agents.

Overflow solution from wash water replenishment and/or stabilization can be reused in other steps, such as the desilvering step.

When processing solutions are concentrated by evaporation in processing with automatic processors, it is preferable that water be added to compensate for the amount of water evaporated.

The color developing agents can be incorporated into the silver halide color developing materials of the present invention for the purpose of simplifying and accelerating processing. It is preferred that precursors of the color developing agents are used for incorporating them into the photographic materials. Examples of the precursors include indoaniline compounds as described in U.S. Patent No. 3,342,597; Schiff bases as described in U.S. Patent No. 3,342,599, Research Disclosure No. 14850 and ibid. No. 15159; aldol compounds as described in Research Disclosure No. 13924; metal complex salts as described in U.S. Patent No. 3,719,492. and urethane compounds as 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 these compounds include those described in JP-A-56-64339, JP-A-57-144547 and JP-A-58-115438.

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

The silver halide photographic materials of the present invention include heat-developable photosensitive materials as 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 described in more detail with reference to the following examples, which, however, should not be construed as limiting the invention in any way. Unless otherwise indicated, parts, percentages and ratios are by weight.

EXAMPLE 1

The surface of a cellulose triacetate film support having an undercoat layer attached thereto was coated with the following layers of the following compositions, thereby preparing 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/m based on silver. The coating weights of couplers, additives and gelatin are given in g/m². The amounts of sensitizing dyes are given in moles per mole of silver halide present in the same layer. First layer: anti-halation layer Second layer: intermediate layer Third layer: low-sensitivity red-sensitive emulsion layer Fourth layer: medium-sensitive red-sensitive emulsion layer Fifth layer: high-sensitivity red-sensitive emulsion layer Sixth layer: intermediate layer Seventh layer: low-sensitivity green-sensitive emulsion layer Eighth layer: medium-sensitive green-sensitive emulsion layer Ninth layer: highly sensitive green-sensitive emulsion layer Tenth layer: yellow filter layer Eleventh layer: low-sensitivity blue-sensitive emulsion layer Twelfth layer: highly sensitive blue-sensitive emulsion layer Thirteenth layer: First protective layer Fourteenth layer: Second protective layer

Furthermore, the following Cpd-3, Cpd-5, Cpd-7, Cpd-8, P-1, P-2, W-1, W-2, W-3 were used to improve the preservability, processability, Pressure resistance, mildew resistance and anti-mold properties, antistatic properties and coatability.

The chemical structural formulas and chemical names of the compounds used in the invention are as follows: (Weight ratio) Molecular weight: about 20,000 (DIR coupler, similar to DC-3 from DE-OS 3 815 469)

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

P-2 Polyethylacrylate

Samples 102 to 104

Each of Samples 102, 103 and 104 was prepared in the same manner as Sample 101, except that a double molar amount of compound (D-14) or (D-29) or an equimolar amount of (D-7) was used instead of ExC-13 in the third layer, fourth layer, eleventh layer and twelfth layer of Sample 101.

Samples 105 to 116:

Each of Samples 105 to 108 was prepared in the same manner as in the preparation of Samples 101 to 104, except that the yellow-colored cyan coupler (YC-28) was added in an amount of 0.02 g/m² and 0.01 g/m², respectively, to the third layer and the fourth layer in each of Samples 101 to 104. Similarly, (YC-32) and (YC-47) were added to prepare Samples 109 to 116.

Samples 117 to 120:

Each of Samples 117 to 120 was prepared in the same manner as in the preparation of Sample 107, except that (YC-24), (YC-26), (YC-30) or (YC-3) was used instead of (YC-28).

Samples 121 to 122:

Each of Samples 121 and 122 was prepared in the same manner as in the preparation of Sample 107, except that ExY-15 in an amount of 1.10 g/m² or 1.20 g/m² was used instead of (Y-1) in the eleventh layer of Sample 107; the amount of gelatin was changed to 1.50 g/m²; the amount of Solv-1 was changed to 0.40 g/m²; and further, ExY-15 or ExY-16 in an amount of 0.18 g/m² was used instead of (Y-1) in the twelfth layer of Sample 107.

The samples prepared above were subjected to red exposure and subsequent 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 subsequent color development after red exposure became 1.2, and the samples were then subjected to red exposure and developed (Condition B).

The relative sensitivity was determined from the logarithm of the reciprocal amount of exposure that gave a density of (Fog + 0.2) under condition A. The color turbidity was determined from a value obtained was calculated by subtracting the yellow density in the red unexposed area from the yellow density in an exposure amount which gives a cyan density of (Fog + 0.5) and (Fog + 1.0) under conditions A and B.

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

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

The processing solution used in each stage had the following composition.

Color developer solution

Sodium nitrilotriacetate 1.0 g

Sodium sulphite 4.0 g

Sodium carbonate 30.0 g

Potassium bromide 1.4 g

Hydroxylamine sulfate 2.4 g

4-(N-ethyl-N-β-hydroxyethylamino)-2- methylaniline sulfate 4.5 g

Water to 1 l

Bleaching solution

Ammanium brcmide 160.0 g

Ammonia water (28%) 25.0 ml

Sodium iron salt of ethylenediaminetetraacetic acid 130 g

Glacial acetic acid 14 ml

Water to 1 l

Fixing solution

Sodium tetrapolyphosphate 2.0 g

Sodium sulphite 4.0 g

Ammonium thiosulfate (70% solution) 175.0 ml

Sodium bisulfite 4.6 g

Water to 1 l

Stabilization solution

Formalin 2.0 ml

Water on 1 litre TABLE 1 TABLE 1 CONTINUED

From Table 1 it is clear that the samples according to the invention are highly sensitive compared to the samples that are outside the range of the invention. For example, all the samples according to the invention are highly sensitive compared to sample 113, which is proposed as a photographic material in DE-PS 3 815 469. The samples according to the invention show low color haze at any exposure amount under both conditions A and B compared to samples 102 to 104, in which only a DIR compound is used, and with samples 105, 109 and 113, in which only a yellow color coupler is used. The effect of the present invention on color haze is remarkable under condition B where color haze occurs during exposure and improvement in chromaticity is desired, in contrast to condition A where exposure is only pure red exposure. Furthermore, it is clear that the effect of the present invention is high in the high density region where the exposure amount is increased. More specifically, Table 1 shows that the present invention has achieved improvement in color reproducibility under various exposure conditions.

Furthermore, it is clear that the MTF values of both the yellow dye image and the blue-green dye image of the samples according to the invention are increased.

It is also clear that sample 107, in which the yellow coupler (Y-1) was used, is highly sensitive, shows little turbidity and has excellent sharpness compared to samples 121 and 122 in which ExY-15 and ExY-16 were used.

EXAMPLE 2

Each of Samples 107, 121 and 122 was cut into 35 mm wide films and processed into a 135 cartridge (24 shots), thereby preparing Photographic Materials 201, 202 and 203. Half the length of a person was photographed by a color checker (manufactured by Macbeth) with a Canon EOS-630 camera using these photographic materials under the setting conditions of ISO speeds 400, 100 and 12, respectively. The same subject was photographed using commercially available Super HG-400 under the setting conditions of ISO speeds 1600, 400 and 50, respectively.

Color development was carried out at 38ºC using an automatic processor under the following conditions:

In the above processing steps, washes (1) and (2) were carried out in a system that ran countercurrently from (2) to (1). Each processing solution had the composition shown below.

The replenishment rate of each processing solution was such that the replenishment rate in the color development step was 1200 ml/m² of the color photographic material, and that in each of the other steps including the washes was 800 ml. The amount of processing solution transferred from the previous bath to the washing step was 50 ml/m² of the color photographic material. Color developer solution Bleaching solution Bleach-fixing solution

Washing water

Tap water containing calcium ions (32 mg/L) and magnesium ions (7.3 mg/L) was passed through a column filled with a strong acidic H-type cation exchange resin and a strong basic OH-type anion exchange resin, reducing calcium ion concentration to 1.2 mg/L and magnesium concentration to 0.4 mg/L. Subsequently, 20 mg/L of sodium isocyanurate dichloride was added to the treated water.

Stabilization solution

The mother solution and the refill solutions were identical

Drying:

The drying temperature was 50ºC.

An auto printer FAP-3500 manufactured by Fuji Photo Film Co. Ltd. was adjusted so that the density of B, G and R of neutral 5 of the Macbeth color checker became 0.75 ± 0.02 respectively in copying under three conditions of Super HG-400. Copying of the photosensitive materials 201 to 203 was carried out under the above conditions. Fuji color paper HG was used for copying. The Macbeth color checker density of these samples was measured on paper. The results are shown in Table 2. TABLE 2

From Table 2, it is clear that Sample 201 containing the yellow coupler (Y-1) shows less change in color density (under any exposure condition, especially under the ISO speed setting of 12, which is an overexposure setting) compared to Samples 202 and 203 obtained using ExY-15 and ExY-16.

EXAMPLE 3

A yellow cyan coupler (YC-1) was added in an amount of 0.015 g/m² and 0.005 g/m² to the fourth and fifth layers of Sample 105 of JP-A-1-214849 (the coupler Ex-10 is the same as the inventive D-29), respectively, to prepare Sample 301. Similarly, (YC-25), (YC-27), (YC-52), (YC-85), (YC-86), (YC-88) and (YC-89) were added to prepare Samples 302 to 308.

These samples were exposed and color developed under conditions A and B in the same manner as in Example 1. The MTF value was measured in the same manner as in Example 1.

The development was carried out using the following processing steps and processing solutions in an automatic cine system processor.

The samples for use in the evaluation of quality were processed after exposed samples were processed until the amount of color developer solution added refill solution was 3 times the tank capacity of the mother solution. PROCESSING STAGE

The washing water was provided by a system flowing countercurrently from (2) to (1). All of the overflow solution of the washing water was added to the fixing bath. The replenishment of the bleach-fixing bath was carried out in such a way that the upper part of the bleaching bath in the automatic processor was connected to the bottom of the bleach-fixing bath by a pipe, the upper part of the fixing bath was connected to the bottom of the bleach-fixing bath by a pipe, and all of the overflow solution resulting from the supply of the replenishment solution through the bleaching bath and the fixing bath was allowed to flow into the bleach-fixing bath. The amount of developing solution charged in the bleaching step, the amount of bleaching solution charged in the bleach-fixing step, the amount of bleach-fixing solution charged in the fixing step, and the amount of fixing solution charged in the washing step were 2.5 ml, 2.0 ml, 2.0 ml, and 2.0 ml, respectively, each amount being given per 35 mm width x 1 m length of the photographic material. The transfer time in all these steps was 5 seconds. The transfer time was included in the processing time of the previous step. Each processing bath was equipped with a device for allowing the jet stream of each processing solution to collide with the surfaces of the emulsion layers as described in JP-A-62-183460.

The processing solutions had the following compositions. Color developer solution Bleaching solution

Mother solution of the bleach-fixing solution

A mixed solution of the mother solution of the above bleaching solution and the mother solution of the following fixing solution (15:85 by volume) Fixing solution

Washing water

Tap water was passed through a mixed bed column filled with a strong acidic H-type cation exchange resin (Amberlite IR-120B, manufactured by Rohm & Haas Co.) and a strong basic OH-type anion exchange resin (Amberlite IRA-400), thereby reducing the calcium ion and magnesium concentrations to 3 mg/L or less. Then, 20 mg/L of sodium isocyanurate dichloride and 150 mg/L of sodium sulfate were added. The pH of the resulting solution was in the range of 6.5 to 7.5.

Stabilization solution

The mother solution and the refill solution are identical TABLE 3

From Table 3, it is clear that Samples 301 to 303 and 305 of the present invention have higher sensitivity, cause less color haze regardless of conditions A and B and a larger exposure amount, and are excellent in sharpness in terms of MTF value, compared with Sample 105 of JP-A-1-214849.

Claims (14)

1. Color photographic silver halide material comprising a support on which there is 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, characterized in that the photographic material contains at least one compound of the following general formula (I) and at least one yellow-colored cyan coupler: A-(TIME)n-B (I) wherein A represents a coupler moiety which is released from (TIME)nB by a coupling reaction with an oxidation product of an aromatic primary amine developing agent; TIME represents a synchronizing group which is bonded to the active coupling site of A and which releases B after A is released by the coupling reaction; B represents a group of the following general formulas (IIa), (IIb), (IIc) (IId), (IId), (IIf), (IIg), (IIh), (IIi), (IIj), (IIk), (IIl), (IIm), (IIn), (IIo) or (IIp); and n represents 0 or 1, and when n is 0, B is directly bonded to A: wherein X₁ represents a substituted or unsubstituted aliphatic group having 1 to 4 carbon atoms or a substituted phenyl group, substituent groups are a hydroxyl group, an alkoxycarbonyl group, an acylamino group, a carbamoyl group, a sulfonyl group, a sulfonamido group, a sulfamoyl group, an acyloxy group, a ureido group, a carboxyl group, a cyano group, a nitro group, amino group, an alkoxycarbonylamino group and acyl group, the number of carbon atoms in these substituent groups is not more than 3, the phenyl group may have one or more substituents; X₂ represents a hydrogen atom, an aliphatic group, a halogen atom, a hydroxyl group, an alkoxy group, an alkylthio group, an alkoxycarbonyl group, an acylamino group, a carbamoyl group, a a sulfonyl group, a sulfonamido group, a sulfamoyl group, an acyloxy group, a ureido group, a cyano group, a nitro group, an amino group, an alkoxycarbonylamino group, an aryloxycarbonyl group or an acyl group; X₃ represents an oxygen atom, a sulfur atom or an imino group having not more than 4 carbon atoms; m represents an integer of 1 or 2; the total number of carbon atoms in X₂ or (X₂)m groups is not more than 8; and when m = 2, the two X₂ groups may be identical or different from each other, wherein the yellow colored cyan coupler is capable of releasing a unit of a water-soluble dye having a group selected from a 6-hydroxy-2-pyridon-5-ylazo group, a 2-acylaminophenylazo group and a 2-sulfonamidophenylazo group through a coupling reaction with an oxidation product of an aromatic primary amine developing agent. 2. The silver halide color photographic material according to claim 1, wherein A in formula (I) is a coupler unit selected from a yellow coupler unit, a magenta coupler unit, a cyan coupler unit and a coupler unit which forms a coupling reaction product having substantially no absorption in the visible light region. 3. A silver halide color photographic material according to claim 1, wherein the compound of formula (I) is incorporated in at least one layer selected from silver halide emulsion layers and a light-insensitive adjacent intermediate layer. 4. A silver halide color photographic material according to claim 1, wherein the ratio of the compound of formula (I) to the main coupler in the same layer, when the compound is incorporated in a silver halide emulsion layer, or in the adjoining silver halide emulsion layer containing a larger amount of silver halide, when the compound is incorporated in a light-insensitive intermediate layer, is 0.1 to 100 mol%. 5. A silver halide color photographic material according to claim 1, wherein the proportion of the compound of formula (I) to silver halide is 0.01 to 20 mol% per mol of silver halide in the same layer when the compound is incorporated in a silver halide emulsion layer, or in that adjacent silver halide emulsion layer which contains a higher amount of silver halide when the compound is incorporated in a light-insensitive intermediate layer. 6. A silver halide color photographic material according to claim 1, wherein the yellow-colored cyan coupler has an absorption maximum at 400 to 500 nm and 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. 7. A silver halide color photographic material according to claim 1, wherein the yellow-colored cyan coupler is selected from the couplers of the formulas (CI) to (CII): wherein Cp represents a cyan coupler unit (T is bonded to the coupling site thereof); T represents a synchronizing group; k represents 0 or 1; X represents an N-, O- or S-containing divalent group which is bonded to (T)k through the N-, O- or S-atom and which is also bonded 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, an alkyl group, a cycloalkyl group, a 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 alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group; the group may be in the form of at least one of other tautomeric forms thereof; R4 is an acyl group or a sulfonyl group; R5 is a group capable of being bonded to a benzene ring; j is an integer of 0 to 4; when j = 2 or more, the two or more R5 groups may be identical or different from each other; and the coupler has at least one water-solubilizing group on T, X, Q, R1, R2, R3, R4 and R5. 8. A 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. 9. A silver halide color photographic material according to claim 1, wherein the yellow-colored cyan coupler is added to a red-sensitive silver halide emulsion layer. 10. The silver halide color photographic material according to claim 1, wherein the yellow-colored cyan coupler is added in an amount of 0.005 to 0.30 g/m². 11. The silver halide color photographic material according to claim 1, wherein at least one yellow coupler contained in the blue-sensitive silver halide emulsion layer is a compound represented by the following general formula (A): wherein M and Q each represent a group or an atom capable of being bonded to the benzene ring; L represents a hydrogen atom, a halogen atom or an aliphatic oxy group; m represents an integer of 0 to 5; n represents an integer of 0 to 4; X represents a group capable of being eliminated by a coupling reaction with an oxidation product of an aromatic primary amine developing agent; when m = 2 or greater, the two or more M groups may be identical or different groups; when n = 2 or greater, the two or more Q groups may be identical or different groups; and M, Q, L or X may be a single-bonding or a bivalent to tetravalent bonding group having a Compound with two to four units of the yellow coupler of formula (A). 12. A silver halide color photographic 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. 13. A silver halide color photographic material according to claim 12, wherein the layer containing the compound of formula (I) is a red-sensitive layer. 14. A silver halide color photographic material according to claim 1, wherein the compound of formula (I) and the yellow-colored cyan coupler are contained in the same red-sensitive layer.