EP0267618A2

EP0267618A2 - Silver halide color photographic material containing hydroquinone derivative

Info

Publication number: EP0267618A2
Application number: EP87116734A
Authority: EP
Inventors: Keiji Fuji Photo Film Co. Ltd. Mihayashi; Nobutaka Fuji Photo Film Co. Ltd. Ohki
Original assignee: Fuji Photo Film Co Ltd
Current assignee: Fujifilm Holdings Corp
Priority date: 1986-11-13
Filing date: 1987-11-12
Publication date: 1988-05-18
Anticipated expiration: 2007-11-12
Also published as: JPH0648372B2; DE3789001D1; EP0267618B1; JPS63123042A; EP0267618A3; DE3789001T2

Abstract

A silver halide color photographic material comprising a support having thereon a red-sensitive silver halide emulsion layer containing a cyan coupler, a green-sensitive silver halide emulsion layer containing a magenta coupler, a blue -sensitive silver halide emulsion layer containing a yellow coupler, at least one of said light-sensitive silver halide emulsion layers containing a 2-equivalent coupler; and at least one light-insensitive layer containing at least one compound selected from the group consisting of compounds represented by formula (I), bis- and tris compounds and polymers derived therefrom, and an alkali-labile precursor thereof: wherein R₁ and R₂ each represents a hydrogen atom, a halogen atom, -SO₃M, -COOM (wherein M represents H, alkali metal atom or -NH₄), an alkyl group, an acylamino group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a sulfonyl group, an acyl group, a carbamoyl group or a sulfamoyl group, R₁ and R₂ amy be linked to form a ring; X represents -CO- or -SO₂-; R₃ represents an alkyl group, an aryl group, a heterocyclic group, a cycloalkyl group, an alkoxy group, an aryloxy group, or an amino group; at least one of R₁, R₂ and R₃ may be a 2-valence group to form a bis- or tris-compound or a polymer; and the sum of the carbon atoms contained in R₁, R₂ and R₃ is at least 10. The photographic material has superior sensitivity, sharpness, contrast and grain characteristics, and exhibits low color staining and color fog.

Description

FIELD OF THE INVENTION

This invention relates to a silver halide color light-sensitive material and, more particularly, to a photographic material having improved sharpness and reduced color stain and color fog, as well as to light-sensitive materials having improved graininess.

BACKGROUND OF THE INVENTION

In recent years, super-high sensitivity light-sensitive materials such as ISO-1600 films, and light-sensitive materials with high image quality and high sharpness suited for small-sized cameras such as 110-size cameras or disc cameras, have been required in the field of silver halide color protographic materials, particularly those for photographic use. Additionally silver-saving, inexpensive light-sensitive materials containing a low amount of coated silver have also been required.
2-Equivalent couplers have been proposed for various purposes: reducing the thickness of emulsion layers by enhancing the color-forming efficiency of couplers in light-sensitive materials; improving image sharpness by reducing blurring which is caused by light scattering; reducing the amount of silver; and increasing sensitivity. Such 2-equivalent couplers have been put into use, as described in T. H. James; The Theory of the Photographic Process, Chap. 12 (4th ed. MacMillan Co.). While these 2-equivalent couplers can reduce the thickness of emulsion layers and the amount of silver required, they involve certain disadvantages. Since they produce dyes in high yield even from a slight amount of an oxidation product of a developing agent (quinonediimine), the effect of quinone-diimine produced in other color-sensitive layers by color development, or color stain, is increased to deteriorate color reproduction. The effect of quinonediimine from other layers of the same color sensitivity is also increased to deteriorate graininess and sharpness.
As one technique for preventing such undesirable color stain, it has been proposed to use hydroquinone compounds as quinonediimine scavengers.
For example, U.S. Pats. 2,360,290, 2,419,613, 2,403,721, 3,960,570, etc. describe mono-n-alkylhydroquinones, U.S. Pat. 3,700,453, Japanese Patent Application (OPI) Nos. 106,329/74 and 156,438/75 (the term "OPI" as used herein means an "unexamined published Japanese patent Japanese patent application"), West German Pat. Application Application (OLS) No. 2,149,789, etc. describe mono-branched alkylhydroquinones; U.S. Pats. 2,728,659, 2,732,300, 3,243,294, 3,700,543, British Pat. No. 752,146, Japanese Patent Application (OPI) Nos. 156,438/75, 9,528/78, 29,637/79, Japanese Patent Publication No. 21,249/75, etc. describe dialkyl-substituted hydroquinones, and U.S. Pat. 2,418,613 describes arylhydroquinones.
These compounds can prevent color fog and color stain to some extent, but they have the disadvantage that they do not completely prevent color fog and color stain, and that, after exhibiting the effect, they produce colored materials.
Therefore, Japanese Patent Application (OPI) No. 22,237/82 proposes a hydroquinone nucleus substituted with an electron attractive group such as an acyl group, a nitro group, a cyano group, a formyl group, a halogenated alkyl group, etc. These possess excellent color stain-preventing ability, but still have the disadvantage that they produce colored materials; that they deteriorate during preparation and storage of light-sensitive materials, and that they fog silver halide emulsions.
On the other hand, some of the compounds included in the compounds of the present invention have been already proposed. For example, U.S. Patent 4,198,239 discloses hydroquinones substituted by an aliphatic acylamino group, a ureido group, a urethane group, etc., Japanese Patent Application (OPI) No. 202,465/84 proposes hydroquinones substituted by a sulfonamido group, and U.S. Pat. 2,701,197 proposes hydroquinones having a sulfonic acid group and substituted by an acylamino group.
These compounds have a large color stain-preventing ability when used with 2-equivalent couplers, but otherwise have only a small effect and produce only poor sharpness.
Japanese Patent Publication No. 7578/80 discloses compounds containing in the same molecule both a hydroquinone residue analogous to the compounds of the present invention and a coupler residue. However, these compounds form color image by a coupling reaction during development processing, thus failing to prevent color stain.
Recently, Japanese Patent Application (OPI) Nos. 77,052/86, 83,536/86, etc. suggest combined use of a 2-equivalent coupler-containing layer and a quinonediimine scavenger-containing adjacent layer. However, in the combinations, most of the quinonediimine scavengers are alkylhydroquinones, and novel hydroquinone derivatives as used in the present invention have not been used.

SUMMARY OF THE INVENTION

An object of the present invention is to provide a light-sensitive material having excellent sharpness.
Another object of the present invention is to provide a light-sensitive material undergoing less color stain and less color fog and providing excellent color reproduction.
A further object of the present invention is to provide a light-sensitive material having high sensitivity and forming a high contrast image.
Still a further object of the present invention is to provide a light-sensitive material having excellent graininess.
Still a further object of the present invention is to provide a light-sensitive material which does not deteriorate (with respect to sensitivity and increase of fog) during preparation and storage.
Still a further object of the present invention is to provide a less costly light-sensitive material containing a reduced amount of silver.
It has now been discovered that these and other objects of the present invention can be attained by a silver halide photographic material composed of a support having thereon a red-sensitive silver halide emulsion layer containing a cyan coupler, a green- sensitive silver halide emulsion layer containing a magenta coupler, a blue-sensitive silver halide emulsion layer containing a yellow coupler, at least one of the light-sensitive silver halide emulsion layers containing a 2-equivalent coupler; at least one light-insensitive layer containing at least one of compound represented by formula (I), bis- and tris-compounds and polymers derived therefrom, and an alkali-labile precursor thereof (hereinafter all of these compounds are referred to "compounds represented by formula (I)"):
wherein R₁ and R₂ each represents a hydrogen atom, a halogen atom, -SO₃M, -COOM (wherein M represents H, alkali metal atom or -NH₄), an alkyl group, an acylamino group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a sulfonyl group, an acyl group, a carbamoyl group or a sulfamoyl group, R₁ and R₂ may be linked to form a ring; X represents -CO- or -SO₂-; R₃ represents an alkyl group, an aryl group, a heterocyclic group, a cycloalkyl group, an alkoxy group, an aryloxy group, or an amino group; at least one of R₁, R₂ and R₃ may be a 2-valence group to form a bis- or tris-compound or a polymer; and the sum of the carbon atoms contained in R₁, R₂ and R₃ is at least 10.

DETAILED DESCRIPTION OF THE INVENTION

In the present invention, the light-insensitive layers containing the compounds represented by general formula (I) are preferably in close proximity to the 2-equivalent coupler-containing emulsion layers. The term "in close proximity" as used herein means a directly adjacent layer or a layer separated by a single light-insensitive layer.
Alkali-labile precursors of the compounds of the present invention represented by general formula (I) are compounds in which the hydroxy groups at the 1- and 4-positions of the hydroquinone skeleton in the compound represented by general formula (I) is protected by a group capable of being cleaved under alkaline conditions of a developing process.
The light-insensitive layer may contain a silver halide emulsion that is not chemically sensitized, a fine-grain silver halide emulsion, and/or colloidal silver grains. The light-insensitive layer may be a protective layer, an inter layer, a filter layer, an antihalation layer or a layer specifically provided for incorporating the compound. When such layer is specifically provided a hydrophilic material which is usually used as a binder in a photographic material (e.g., gelatin, a synthetic hydrophilic polymer) may be used.
The light-insensitive layer containing the compound of general formula (I) may be provided in any position in a light-sensitive material as long as it is in close proximity to a 2-equivalent coupler-containing emulsion layer. Preferably, however, it is provided between emulsion layers having different color sensitivities or between two emulsion layers having substantially the same color sensitivity and, more preferably, between a layer having the maximum sensitivity in a color sensitive layer unit and a layer sensitive in different color and having the minimum sensitivity, between layers one having a higher sensitivity and the other having a lower sensitivity and a each having substantially the same color sensitivity, or between layers one having a intermediate sensitivity and the other having a lower or a higher sensitivity and each having substantially the same color sensitivity.
The compound of the present invention represented by the general formula (I) can be added to a light-sensitive material in the same manner as for dispersing and adding couplers as described hereinafter.
These compounds are added to layers in close proximity to 2-equivalent couplers in a total amount of about 0.005 to 2.0 g/m², preferably about 0.01 to 1.0 g/m², more preferably about 0.03 to 0.3 g/m².
The thickness of the light-insensitive layer such as protective layer, an inter layer, a filter layer and an antihalation layer generally is from about 0.05 to 2.0 µm, preferably from about 0.1 to 1.5 µm, and more preferably from about 0.2 to 1.0 µm.
The thickness of the layer containing the compound is generally from about 0.1 to 2.0 µm, preferably from about 0.2 to 1.5 µm, and more preferably from about 0.3 to 1.0 µm.
2-equivalent couplers used in the present invention are preferably added to layers in close proximity to light-insensitive layers to which the compounds of the present invention are added. When the color-sensitive layers to which they are added are constituted by two layers having different light-sensitivities, it is preferred to add them at least to the less sensitive layer thereof, and, when constituted by three layers, at least to the least sensitive layer or to the least and the intermediate sensitivity layers. The 2-equivalent coupler is usually added in an amount of from about 0.01 to 2.0 g/m², preferably from about 0.03 to 1.5 g/m², and more preferably from about 0.05 to 1.2 g/m².
The ratio of the amount of the 2-equivalent coupler to the amount of the compound is preferably about 0.001 to 100, and more preferably about 0.05 to 2.0 by weight.
The compounds represented by the general formula (I) are described in greater detail below.
In descriptions with respect to compounds used in the present invention numbers in parenthesis show preferable carbon numbers, and each of the acylamino group, sulfonyl group, and sulfamoyl group may be comprised of either aliphatic (C₁∼C₃₂), alicyclic (C₄∼C₃₂), aromatic (C₆∼C₃₂) or heterocyclic (C₁∼C₃₂) atomic group, and each of acyl group and carbamoyl group may be comprised of either aliphatic (C₂∼C₃₂), alicyclic (C₅∼C₃₂) aromatic (C₇∼C₃₂) or heterocyclic (C₂∼C₃₂) atomic group.
In the above formula, R₁ and R₂ which may be the same or different, each represents hydrogen atom, a halogen atom (e.g., a chlorine atom, a bromine atom), -SO₃M, -COOM (wherein M represents H, an alkali metal atom or -NH₄), an alkyl group (C₁∼C₃₂; e.g., a methyl group, a pentadecyl group, a t-hexyl group, etc.), an acylamino group (C₁∼C₃₂; e.g., an acetylamino group, a benzoylamino group, etc.), an alkoxy group (C₁∼C₃₂; e.g., a methoxy group, a butoxy group, etc.), an aryloxy group (C₆∼C₃₂; e.g., a phenoxy group, etc.), an alkylthio group (C₁∼C₃₂; e.g., an octylthio group, a hexadecylthio group, etc.), an arylthio group (C₆∼C₃₂; e.g., a phenylthio group, etc.), a sulfonyl group (e.g., a dodecanesulfonyl group, a p-toluenesulfonyl group, etc.), an acyl group (e.g., an acetyl group, a benzoyl group, etc.), a carbamoyl group (e.g., an N,N-dibutylcarbamoyl group, etc.) or a sulfamoyl group (e.g., an N,N-diethylsulfamoyl group, etc.), provided that R₁ and R₂ may be linked to form a ring such as a cycloalkyl group, an indene nucleus, a naphthalene nucleus, a quinoline nucleus and an isoquinoline nucleus. The above-described groups, an alkyl group, an acylamino group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a sulfonyl group, an acyl group, a carbamoyl group, and a sulfamoyl group may be substituted or unsubstituted. Examples for substituents for the alkyl group, the alkoxy group, the aryloxy group, the alkylthio group, the arylthio group, the sulfonyl group, the acyl group include groups recited above as R₁ and R₂, and examples for substituents for the carbamoyl group and the sulfamoyl group include an alkyl group and aryl group. X represents -CO- or -SO₂-. R₃ represents an alkyl group (C₁∼C₃₂; e.g., a heptadecyl group, a 1-hexylnonyl group, a 1-(2,4-di-t-amylphenoxy)propyl group, etc.), an aryl group (C₆∼C₃₂; e.g., a phenyl group, a 3,5-bis(2-hexyldecanamido)phenyl group, a 3,4-bis(hexadecyloxycarbonyl)phenyl group, a 2,4-bis(tetradecyloxy)phenyl group, etc.), a heterocyclic group, preferably 5- to 7-membered heterocyclic group having at least one of N, O and S atom as a hetero atom, such as, a pyridinyl group, a pyrrolidinyl group piperidinyl group, a 2-thienyl group, a 2-furyl group, a 4-thiazolyl group, a 6-pyrimidyl group and a 8-quinolyl group (e.g., a 2,6-dihexyloxypyridin-4-yl group, an N-tetra-decylpyrrolidin-2-yl group, an N-octadecylpiperidin-3-yl group, etc.), a cycloalkyl group (C₃∼C₃₂; e.g., a 3-decanamido-cyclohexyl group, a 3-((2,4-di-t-amylphenoxy)butanamido)-cyclohexyl group, etc.), an alkoxy group (C₁∼C₃₂; e.g., a hexadecyloxy group, etc.), an aryloxy group (C₆∼C₃₂; e.g., a 4-t-octylphenoxy group, etc.) or an amino group (e.g., an octadecylamino group, etc.), which may be unsubstituted or substituted. Examples for substituents include a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, a carbonamido group, a sulfonamido group, an alkylthio group, an arylthio group, an aryl group, an alkoxycarbonyl group, and a carbamoyl group, and these groups may be further substituted with such groups.
The sum of the carbon atoms contained in R₁, R₂, and R₃ should be 10 or more to provide non-diffusibility to the compound. The sum of the carbon atoms preferably at least 15, and it is preferably not more than 64.
The compounds of the general formula (I) may be linked at at least one of R₁, R₂ and R₃ to form a bis compound, a tris compound or a polymer thereof.
In general formula (I), R₁ and R₂ preferably each represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or an alkylthio group. Of these, a hydrogen atom, a halogen atom, and an alkyl group are more preferred, and a hydrogen atom is most preferred.
As X in general formula (I), -CO- is preferred.
In general formula (I), preferred R₃ groups include an alkyl group and an aryl group, with an aryl group being most preferred.
When R₃ in the general formula (I) represents an aryl group, substituents for the aryl group are not particularly limited, and preferred substituents include: a halogen atom, an alkyl group, an amido group, a sulfonamido group, an alkoxy group, an alkoxycarbonyl group, and a carbamoyl group. The aryl group preferably does not contain a sulfo group (-SO₃M), a carboxyl group (-COOM), or other such water-soluble group, because these groups can adversely affect preservability of light-sensitive materials.
Since the compounds used in the present invention are agents for preventing color stain and color fog in photographic light-sensitive materials, good color reproduction of the photographic light-sensitive materials is adversely affected if the compounds themselves is colored or form a color image in the course of development processing. According, the compounds of the present invention must first be substantially colorless. The term "substantially colorless" as used herein means not having an absorption of 5,000 or more in molar extinction coefficient in the visible wavelength region from 400 nm to 700 nm. Second, the compounds to be used in the present invention must not possess within the molecule coupler residues capable of undergoing a coupling reaction with an oxidation product of a color developing agent to form color image (e.g., an acylacetanilide residue, a 5- pyrazolone residue, a 1-naphthol residue, etc.) and therefore do not form a color image by a coupling reaction in the development processing step.
Typical examples of the protective group, include an acyl group (e.g., an acetyl group, a chloroacetyl group, a benzoyl group, an ethoxy-carbonyl group, etc.) and a β-eliminatable group (e.g., a 2-cyanoethyl group, a 2-methanesulfonylethyl group, a 2-toluenesulfonylethyl group, etc.).
Specific examples of compounds represented by formula (1) are given below, but the present invention is not to be construed as being limited thereto.
The compounds of the present invention represented by general formula (I), bis-, tris-compounds and polymers derived therefrom, and the alkali-labile precursors thereof can be readily synthesized according to processes described in U.S. Pat. 2,701,197, Japanese Patent Publication No. 37,497/84 (corresponding to U.S. Pat. 4,198,239) and Japanese Patent Application (OPI) No. 202,465/84 (corresponding to U.S. Pat. 4,584,264).
Referred 2-equivalent couplers used in the present invention are represented by the following general formuale (Cp-1) to (Cp-9).
R₅₁ to R₅₉, Z₁, Z₂, Z₃, Y, ℓ, m, and p in the above general formulae (Cp-1) to (Cp-9) are described below.
In the general formulae, R₅₁ represents an aliphatic group, an aromatic group, an alkoxy group or a heterocyclic group, and R₅₂ and R₅₃, which may be the same or different each represents an aromatic group or a heterocyclic gruop.
The aliphatic group represented by R₅₁ contains preferably 1 to 22 carbon atoms, and may be substituted or unsubstituted, and may be in a chain form or cyclic form. Substituents for an alkyl group represented by R₅₁ include an alkoxy group, an aryloxy group, an amino group, an acylamino group, a halogen atom, etc.,which themselves may further be substituted. Specific examples of the aliphatic group represented by R₅₁ include an isopropyl group, an isobutyl group, a tert-butyl group, an isoamyl group, a tert-amyl group, a 1,1-dimethylbutyl, 1,1-dimethylhexyl, 1,1-diethylhexyl gruop, a dodecyl group, a hexadecyl group, an octadecyl group, a cyclohexyl group, a 2-methoxyisopropyl group, a 2-phenoxyisopropyl group, 2-p-tert-butyl-phenoxy-isopropyl group, an α-aminoisopropyl group, an α-(diethylaminoisopropyl group,an α-(succinimido)isopropyl group, an α-(phthalimido)isopropyl group, an α-(benzenesulfonamido)isopropyl group, etc.
When R₅₁, R₅₂ or R₅₃ represents an aromatic group (particularly a phenyl group), the aromatic 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 alkyureido group, an alkyl-substituted succinimido group, etc., containing up to 32 carbon atoms. In such cases, the alkyl group may contain in its chain an aromatic group such as a phenylene group. The phenyl group in the aromatic group may also be substituted by an aryloxy group, an aryloxycarbonyl group, an arylcarbamoyl group, an arylamido group, an arylsulfamoyl group, an arylsulfonamido group, an arylureido group, etc., with the aryl moiety of these substituents being optionally substituted by one or more alkyl groups containing a total of 1 to 22 carbon atoms.
The phenyl group in the aromatic group represented by R₅₁, R₅₂ or R₅₃ may further be substituted by an amino group including those substituted by a lower alkyl group or groups containing 1 to 6 carbon atoms, a hydroxyl group, a carboxyl group, a sulfo group, a nitro group, a cyano group, a thiocyano group or a halogen atom.
Further, R₅₁, R₅₂ or R₅₃ may represent a substituent in which a phenyl group is fused with an other ring, such as a naphthyl group, a quinolyl group, an isoquinolyl group, a chromanyl group, a coumaranyl group, a tetrahydronaphthyl group, etc. These substituents themselves may further have a substituent or substituents.
When R₅₁ represents an alkoxy group, the alkyl moiety includes a straight or branched alkyl, alkenyl, cyclic alkyl or cyclic alkenyl group containing 1 to 32, preferably 1 to 22, carbon atoms, which may further be substituted by a halogen atom, an aryl group, an alkoxy group, etc.
When R₅₁, R₅₂ or R₅₃ represents a heterocyclic group, the heterocyclic group is linked to the carbon atom of the carbonyl group in the acyl group of the α-acylacetamido group, or to the nitrogen atom of the amido group of the α-acylacetamido group, through one carbon atom contained in the ring. Such hetero rings include thiophene, furan, pyran, pyrrole, pyrazole, pyridine, pyrazine, pyrimidine, pyridazine, indolidine, imidazole, thiazole, oxazole, triazine, thiadiazine, oxazine, etc. These may further have a substituent or substituents in the ring.
In general formula (Cp-3), R₅₅ represents a straight or branched alkyl group containing 1 to 32, preferably 1 to 22, carbon atoms (e.g., a methyl group, an isopropyl group, a tert-butyl group, a hexyl group, a dodecyl group, etc.), an alkenyl group (e.g., an allyl group, a cyclic alkyl group (e.g., a cyclopentyl group, a cyclohexyl group, a norbornyl group, etc.), an aralkyl group (e.g., a benzyl group, a β-phenylethyl group, etc.), or a cyclic alkenyl group (e.g., a cyclopentenyl group, a cyclohexenyl group, etc.), which may further be substituted by a halogen atom, a nitro group, a cyano group, an aryl group, an alkoxy group, an aryloxy group, a carboxyl 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 hydroxy group, a mercapto group, etc.
Further, R₅₅ may represent an aryl group (e.g., a phenyl group, an α-or β-naphthyl group, etc.). The aryl group may have one or more substituents. Examples of the substituents 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, a urethane 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, a hydroxy group, etc.
Still further, R₅₅ may represent a heterocyclic group (for example, a 5- or 6-membered heterocyclic group or fused heterocyclic group containing a sulfur atom, an oxygen atom or a nitrogen atom as a hetero atom, such as a pyridyl group, a quinolyl group, a furyl group, a benzothiazolyl group, an oxazolyl group, an imidazolyl group, a naphthoxazolyl group, etc.), a heterocyclic group substituted with a substituents for the aryl group represented by R₅₅, 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.
In the general formulae, R₅₄ represents a hydrogen atom, a straight or branched alkyl or alkenyl group containing 1 to 32, preferably 1 to 22, carbon atoms, a cyclic alkyl group, an aralkyl group, a cyclic alkenyl group (these groups optionaly having substituents mentioned with respect to R₅₅), an aryl group and a heterocyclic group (these optionally having substituents mentioned with respect to R₅₅), an alkoxycarbonyl group (e.g., a methoxycarbonyl group an ethoxycarbonyl group, a stearyloxycarbonyl group, etc.), an aryloxycarbonyl group (e.g., a phenoxycarbonyl group, a naphthoxycarbonyl group, etc.), an aralkyloxycarbonyl group (e.g., a benzyloxycarbonyl group, etc.), an alkoxy group (e.g., a methoxy group, an ethoxy group, a heptadecyloxy group, etc.), an aryloxy group (e.g., a phenoxy group, a tolyloxy group, etc.), an alkylthio group (e.g., an ethylthio group, a dodecylthio group, etc.), an arylthio group (e.g., a phenylthio group, an α-naphthylthio group, etc.), a carboxyl group, an acylamino group (e.g., an acetylamino group, a 3-[(2,4-di-tert-amylphenoxy)- acetamido]benzamido group, etc.), a diacylamino group, an N-alkylacylamino group (e.g., an N-methylpropionamido group, etc.), an N-arylacylamino group (e.g., an N-phenylacetamido group, etc.), a ureido group (e.g., a ureido group, an N-arylureido group, an N-alkylureido group, etc.), a urethane group, a thio-urethane group, an arylamino group (e.g., a phenylamino group, an N-methylanilino group, a diphenylamino group, an N-acetylanilino group, a 2-chloro-5-tetradecanamidoanilino group, etc.), an alkylamino group (e.g., an n-butylamino group, a methylamino group, a cyclohexylamino group, etc.), a cycloamino group (e.g, a piperidino group, a pyrrolidino group, etc.), a heterocyclic amino group (e.g., a 4-pyridyl-amino group, a 2-benzoxazolylamino group, etc.) an alkylcarbonyl group (e.g., a methylcarbonyl group, etc.), an arylcarbonyl group (e.g., a phenylcarbonyl group, a sulfonamido group (e.g., an alkylsulfonamido group, an arylsulfonamido group, etc.), a carbamoyl group (e.g., an ethylcarbamoyl group, a dimethylcarbamoyl group, an N-methylphenylcarbamoyl group, an N-phenylcarbamoyl group, etc.), a sulfamoyl group (e.g., an N-alkylsulfamoyl group, an NN-dialkylsulfamoyl group, an N-arylsulfamoyl group, an N-alkyl-N-arylsulfamoyl group, an N,N-diarylsulfamoyl group, etc.), a cyano group, a hydroxyl group, and a sulfo group.
In the general formulae, R₅₆ represents a hydrogen atom or a straight or branched chain alkyl or alkenyl group containing 1 to 32, preferably 1 to 22, carbon atoms, a cyclic alkyl group, an aralkyl group or a cyclic alkenyl group, which may be substituted by the substituents for R₅₅.
Further, R₅₆ may represent an aryl group or a heterocyclic group, which may be substituted by the substituents for R₅₅.
Still further, R₅₆ may represent a cyano group, an alkoxy group, an aryloxy group, a halogen atom, a carboxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, a sulfo group, a sulfamoyl group, a carbamoyl group, an acylamino group, a diacylamino group, a ureido group, a urethane group, a sulfonamido 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 or a hydroxyl group.
R₅₆ may be substituted at any position of the benzen ring. R₅₇, R₅₈, and R₅₉, which may be the same or different each represents a group present ordinary 4-equivalent phenolic or α-naphtholic couplers, specifically a hydrogen atom, a halogen atom, an alkoxy-carbonylamino group, an aliphatic hydrocarbon group, an N-arylureido group, an acylamino group, -O-R₆₂ or -S-R₆₂ (provided that R₆₂ represents an aliphatic hydrocarbon group). Plural R₅₇ groups in the same molecule may be the same or different. The aliphatic hydrocarbon group includes those which have a substituent or substituents.
When these substituents include an aryl moiety, the aryl moiety may have one or more substituent for R₅₅.
R₅₈ and R₅₉ include aliphatic hydrocarbon groups, aryl groups, and hetero ring groups, or one of them may be a hydrogen atom. The groups may have a substituent or substituents. In addition, R₅₈ and R₅₉ may be linked to form a nitrogen-containing hetero ring nucleus.
The aliphatic hydrocarbon residue represented by R₅₈ and R₅₉ may be saturated or unsaturated, and may be in a straight chain form, a branched chain form or a cyclic form. Preferred examples thereof include an alkyl group (e.g., a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, an isobutyl group, a dodecyl group, an octadecyl group, a cyclobutyl group, a cyclohexyl group, etc.), and an alkenyl group (e.g., an allyl group, an octenyl group, etc.). The aryl group represented by R₅₈ and R₅₉ includes a phenyl group, a naphthyl group, etc., and the hetero ring group represented by R₅₈ and R₅₉ typically includes a pyridinyl group, a quinolyl group, a thienyl group, a piperidyl group, an imidazolyl group, etc. The substituents for these aliphatic hydrocarbon groups, aryl groups, and hetero ring groups include a halogen atom, a nitro group, a hydroxyl 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, an acyl group, an acyloxy group, a sulfonamido group, a sulfamoyl group, a sulfonyl group, a morpholino group, etc.
In the formulas, ℓ represents an integer of 1 to 4, m represents an integer of 1 to 3, and p represents an integer of 1 to 5.
Of the above-described couplers preferred yellow couplers are those represented by general formula (Cp-1), in which R₅₁ represents a t-butyl group or a substituted or unsubstituted aryl group, and R₅₂ represents a substituted or unsubstituted aryl group; and those represented by general formula (Cp-2), in which R₅₂ and R₅₃ each represents a substituted or unsubstituted aryl group.
Preferred magenta couplers are those represented by general formula (Cp-3), in which R₅₄ represents an acylamino group, a ureido group or an arylamino group and R₅₅ represents a substituted aryl group; those represented by general formula (Cp-4) in which R₅₄ represents an acylamino group, a ureido group or an arylamino group and R₅₆ represents a hydrogen atom; and those represented by general formulae (Cp-5) and (Cp-6) in which R₅₄ and R₅₆ each represents a straight or branched alkyl or alkenyl group, a cyclic alkyl or aralkyl group or a cyclic alkenyl group.
Preferred cyan couplers are those represented by general formula (Cp-7), in which R₅₇ represents a 2-position acylamino or ureido group, a 5-position acylamino or alkyl group, or a 6-position hydrogen or chlorine atom; and those represented by general formula (Cp-9) in which R₅₇ represents a 5-position hydrogen atom, acylamino group, sulfonamido group or alkoxycarbonyl group, R₅₈ represents a hydrogen atom, and R₅₉ represents a phenyl group, an alkyl group, an alkenyl group, a cyclic alkyl group, an aralkyl group or a cyclic alkenyl group.
In the general formulas, Z₁ represents a halogen atom, a sulfo group, an acyloxy group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group or a heterocyclic thio group, which may be further substituted by such substitutents as an aryl group (e.g., a phenyl group), a nitro group, a hydroxyl group, a cyano group, a sulfo group, an alkoxy group (e.g., a methoxy group), an aryloxy group (e.g., a phenoxy group), an acyloxy group (e.g., an acetoxy group), an acylamino group (e.g., an acetylamino group), a sulfonamido group (e.g., a methanesulfonamido group), a sulfamoyl group (e.g., a methlsulfamoyl group), a halogen atom (e.g., a fluorine atom, a chlorine atom, or a bromine atom), a carboxy group, a carbamoyl group (e.g., a methylcarbamoyl group), an alkoxycarbonyl group (e.g., a methoxycarbonyl group, etc.), a sulfonyl group (e.g., a methylsulfonyl group), etc.
In the formulae, Z₂ and Y, which may be the same or different each represents a coupling-off group bonded to the coupling site through an oxygen atom, a nitrogen atom or a sulfur atom. When Z₂ and Y are bonded to the coupling site through an oxygen atom, a nitrogen atom or a sulfur atom, these atoms are bound to an alkyl group, an aryl group, an alkylsulfonyl group, an arylsulfonyl group, an alkylcarbonyl group, an arylcarbonyl group or a heterocyclic group. With respect to the nitrogen atom, Z₂ or Y represents a 5- or 6-membered ring containing the nitrogen atom to form a coupling-off group, (e.g., an imidazolyl group, a pyrazolyl group, a triazolyl group, a tetrazolyl group, etc.).
The above-described alkyl, aryl, and hetorocyclic groups contained in Z₂ and Y may have substituents. Specific examples of the substituents include an alkyl group (e.g., a methyl group, an ethyl group, etc.), an alkoxy group (e.g., a methoxy group, an ethoxy group, etc.), an aryloxy group (e.g., a phenyloxy group, etc.), an alkoxycarbonyl group (e.g., a methoxycarbonyl group, etc.), an acylamino group (e.g., an acetylamino group, etc.), a carbamoyl group, an alkylcarbamoyl group (e.g., a methylcarbamoyl group, an ethylcarbamoyl group, etc.), a dialkylcarbamoyl group (e.g., a dimethlcarbamoyl group, etc.), an arylcarbamoyl group (e.g., a phenylcarbamoyl group, etc.), alkylsulfonyl group (e.g., a methylsulfonyl group, etc.) an arylsulfonyl group (e.g., a phenylsulfonyl group, etc.), an alkylsulfonamido group (e.g., a methanesulfonamido group, etc.), an arylsulfonamido group (e.g., a phenylsulfonamido group, etc.), a sulfamoyl group, an alkylsulfamoyl group (e.g., an ethylsulfamoyl group, etc.), a dialkylsulfamoyl group (e.g., a dimethylsulfamoyl group, etc.), an alkylthio group (e.g., a methylthio group, etc.), an arylthio group (e.g., a phenylthio group, etc.), a cyano group, a nitro group, a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, etc.), etc. When two or more substituents are present, they may be the same or different.
Particularly preferred substituents include a halogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, and a cyano group.
Preferable examples of Z₂ are groups which are bonded to the coupling site through a nitrogen atom or a sulfur atom, and preferred examples of Y are a chlorine atom and groups which are bonded to the coupling site through an oxygen atom, a nitrogen atom or a sulfur atom.
In the formulae, Z₃ represents a hydrogen atom or a group represented by the following general formulae (R-I), (R-II), (R-III) or (R-IV):

R₆₃ (R-I)
wherein R₆₃ represents substituted or unsubstituted aryl or heterocyclic group;
wherein R₆₄ and R 65, which may be the same or different, each represents a hydrogen atom, a halogen atom, a carboxylic acid ester group, an amino group, an alkyl group, an alkylthio group, an alkoxy group, an alkylsufonyl group, an alkylsulfinyl group, a carboxylic acid group, a sulfonic acid group, an unsubstituted or substituted phenyl or hetero cyclic group;
wherein W₁ represents a non-metallic atomic group necessary for forming a 4-, 5- or 6-membered ring together with
therein.
Of groups represented by general formula (IV), those represented by the following formulae (R-V) to (R-VII) are preferable:
wherein R₆₆ and R₆₇, which may be the same or different each represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group or a hydroxy group, R₆₈, R₆₉, and R₇₀, which may be the same or different, each represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group or an acyl group, and W₂ represents an oxygen atom or a sulfur atom.
In the silver halide photographic material of the present invention, 2-equivalent magenta couplers or 2-equivalent cyan couplers are preferably used, and especially 2-equivalent magenta coupers are preferably used.
2-Equivalent yellow couplers include the following examples, but the present invention is not to be consumed as being limited thereto.
Preferable silver halides incorporated in the photographic emulsion layers of photogrpahic light-sensitive materials of the present invention are silver bromoiodide, silver chloroiodide, and silver chlorobromoiodide containing up to about 30 mol % of silver iodide. A particularly preferable silver halide is silver bromoiodide containing about 2 to about 25 mol % of silver iodide.
The silver halide grains to be used in the photographic emulsion may have a regular crystal form such as cubic, octahedral or tetradecahedral form, an irregular form such as a spherical form or tabular form, a form having crystal defect such as a twin plane, or a composite form thereof.
As to the grain size of silver halide, fine grains of up to about 0.1 µm and large grains of from about 0.1 to 10 µm in projected area diameter may be used. Polydisperse emulsions and monodisperse emulsions may be used.
The silver halide photographic emulsions used in the present invention may be prepared by the processes described in, for example, Research Disclosure (RD), No. 17643 (Dec., 1978), pp.22-23, "1. Emulsion preparation and types", ibid., No. 18716 (Nov., 1979), p.648, P. Glafkides; Chimie et Physique Photographique (Paul Montel, 1967), G. F. Duffin; Photographic Emulsion Chemistry (Focal Press, 1966), V. L. Zelikman et al; Making and Coating Photographic Emulsion (Focal Press, 1964), etc. Monodisperse emulsions described in U.S. Pats. 3,574,628 and 3,655,394, British Pat. No. 1,413,748, etc. are also preferable.
Tabular grains of about 5 or more in aspect ratio are also usable. Such tabular grains may be easily prepared according to processes described in Gutoff; Photographic Science and Engineering, vol. 14, pp.248-257 (1970), U.S. Pats. 4,434,226, 4,414,310, 4,433,048, 4,439,520, British Pat. No. 2,112,157, etc.
The crystal structure of the silver halide grains may be a uniform structure, a structure wherein the inner portion and the outer portion are different from each other in halide composition, or a layered structure, or silver halide crystals different from each other may be joined to each other by epitaxial junction or, further, crystals joined to other compounds than silver halide such as silver rhodanide or lead oxide may be used.
In addition, a mixture of grains of various crystal forms may also be used.
The silver halide emulsions are usually subjected to physical a ripening, chemical ripening, and spectral sensitization before use. Additives used in these steps are described in Research Disclosure Nos. 17643 and 18716. Places where such additives are described are summarized in the following Table.
Known photographic additives used in the present invention are also described in the above-mentioned two Research Disclosures, and places where they are described are also tabulated in the following Table.
Various couplers may be used in the present invention, and specific examples thereof are described in the patents described in the foregoing Research Disclosure (RD), No. 17643, VII-C to G.
As yellow couplers, those described in, for example, U.S. Pats. 3,933,501, 4,022,620, 4,326,024, 4,401,752, Japanese Patent Publication No. 10739/83, British Pat. 1,425,020 and 1,476,760 are preferable.
As magenta couplers, 5-pyrazolone type and pyrazoloazole type compounds are preferable, with those described in U.S. Pats. 4,310,619, 4,351,897, European Pat. No. 73,636, U.S. Pats. 3,061,432, 3,725,067, Research Disclosure No. 24,220 (June 1984), Japanese Patent Application (OPI) No. 33,552/85, Research Disclosure No. 24230 (June 1984), Japanese Patent Application (OPI) No. 43,659/85, U.S. Pats, 4,500,630, 4,540,654, being particularly preferred.
Cyan couplers include phenolic and naphtholic couplers, and those described in U.S. Pats, 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, 4,327,173, West German Patent Application (OLS) No. 3,329,729, European Pat. No. 121,365A, U.S. Pats. 3,446,622, 4,333,999, 4,451,559, 4,427,767, European Pat. No. 161,626A are preferred.
As colored couplers for correcting unnecessary absorption of colored dyes, those which are described in Research Disclosure No. 17643, Item VII-G, U.S. Pats. 4,163,670, Japanese Patent Publication No. 39,413/82, U.S. Pats, 4,004,929, 4,138,258, and British Pat. No. 1,146,368 are preferred. As couplers capable of forming colored dyes with a suitable controlled diffusibility, those which are described in U.S. Pat. 4,366,237, British Pat. No. 2,125,570, European Pat. No. 96,570, West German Patent Application (OLS) No. 3,234,533 are preferred.
Typical examples of polymerized dye-forming couplers are described in U.S. Pats. 3,451,820, 4,080,211, 4,367,282, and British Pt. No. 2,102,173.
Couplers capable of releasing a photographically useful group upon a coupling reaction are also preferably used in the present invention. As DIR couplers capable of releasing a development inhibitor, those which are described patents referred to in the foregoing RD 17643, Item VII-F; Japanese Patent Application (OPI) Nos. 151,944/82, 154,234/82, 184,248/85, and U.S. Pat. 4,248,962 are preferred.
Preferred couplers capable of imagewise releasing a nucleating agent or a development accelerator, include those described in British Pat. Nos. 2,097,140, 2,131,188, and Japanese Patent Application (OPI) Nos. 157,638/84, and 170,840/84.
Further couplers used in the light-sensitive material of the present invention include competing couplers described in U.S. Pat. 4,130,427; polyequivalent couplers described in U.S. Pats. 4,283,472, 4,338,393, and 4,310,618; DIR redox compound-releasing couplers described in Japanese Patent Application (OPI) No. 185,950/85; couplers capable of re-acquiring color after being released described in European Pat. No. 173,302A, and the like.
The couplers used in the present invention may be introduced into light-sensitive materials by various known processes.
Examples of high-boiling organic solvents used in the oil-in-water dispersion process are described in U.S. Pat. 2,322,027.
The latex dispersion process and specific examples of latexes for impregnation are described in U.S. Pat. 4,199,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.
Suitable supports to be used in the present invention are described in, for example, the above Research Disclosure No. 17643, pp. 28; and id. No. 18716, p. 647, right col. to p. 648, left col.
The color photographic material in accordance with the present invention may be development processed according to common processes described in the foregoing Research Disclosure No. 17643, pp. 28 - 29; and id. No. 18716, p. 651, left col. to right col.
The color developer used for developing the light-sensitive material of the present invention is generally an alkaline aqueous solution containing an aromatic primary amine color-developing agent as a major component. As this color-developing agent, p-phenylenediamine compounds are preferably used, although aminophenol compounds are also useful. Typical examples of the p-phenylenediamine compounds 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 sulfates, hydrochlorides, and p-toluenesulfonates thereof. These compounds may be used as a combination of two or more depending upon the particular material.
The color developer generally contains a pH buffer such as a carbonate, borate or phosphate of an alkali metal; and a development inhibitor or antifoggant such as a bromide, an iodide, a benzimidazole, a benzothiazole or a mercapto compound. If desired, various preservatives (e.g., hydroxylamine, diethylhydroxylamine, hydrazine sulfates, phenylsemicarbazides, triethanolamine, catecholsulfonic acids, triethylenediamines (e.g., 1,4-diazabicyclo (2,2,2)-octane), etc.); organic solvents (e.g., ethylene glycol, diethylene glycol, etc.); development accelerators (e.g., benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines, etc.); dye-forming couplers; competing couplers; fogging agents (e.g., sodium borohydride, etc.); auxiliary developing agents (e.g., 1-phenyl-3-pyrazolidone, etc.); viscosity-increasing agents; various chelating agents such as aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, and phosphonocarboxylic acids (e.g., ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,Nʹ,Nʹ-tetramethylenephosphonic acid, ethylenediamine-di(o-hydroxyphenylacetic acid), and salts thereof may be used.
In conducting reversal processing, color development is usually performed after black-and-white development. As this black-and-white developer, known black-and-white developing agents such as dihydroxybenzenes (e.g., hydroquinone, etc.); 3-pyrazolidones (e.g., 1-phenyl-3-pyrazolidone); or aminophenols (e.g., N-methyl-p-aminophenol) may be used alone or in combination.
The color developer and the black-and-white developer generally have a pH of about 9 to 12.
Color-developed photographic emulsion layers are usually bleached. Bleaching may be conducted separately or simultaneously with fixing (bleach-fixing processing). In order to accelerate the processing, bleaching may be followed by bleach-fixing processing. Further, processing using two continuous bleach-fixing baths, processing in which fixing is conducted before bleach-fixing, and processing in which bleaching is conducted after bleach-fixing may optionally be employed depending upon. Bleaching agents include for example, compounds of polyvalent metals such as iron(III), cobalt(III), chromium(VI), copper(II), etc., peracids, quinones, nitro compounds, etc. Typical bleaching agents used include ferricyanides; dichromates; organic complex salts of iron(III) or cobalt(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, etc.) or organic acids (e.g., citric acid, tartaric acid, malic acid, etc.); persulfates; formates; permanganates; nitrobenzenes; etc. Of these, iron(III) aminopolycarboxylate complex salts including iron(III) ethylenediaminetetraacetate and persulfates are preferred form the standpoint of rapid processing and prevention of environmental pollution. Further, iron(III) aminopolycarboxylate complex salts are particularly useful in both bleaching solutions and bleach-fixing solutions. The bleaching or bleach-fixing solutions containing these iron(III) aminopolycarboxylate complex sales usually have a pH or about 5.5 to 8 but, in order to accelerate the processing, the solution may be a lower pH.
Bleaching accelerators may be used in the bleaching solution, bleach-fixing solution, and pre-baths thereof as desired. Specific examples of useful bleaching accelerators include mercapto group- or disulfido group-containing compounds described in U.S. Pat. 3,893,858, West German Patent Nos. 1,290,812, 2,059,988, Japanese Patent Application (OPI) Nos. 32,736/78, 57,831/78, 37,418/78, 72,623/78, 95,630/78, 95,631/78, 104,232/78, 124,424/78, 141/623/78, 28,426/78, Research Disclosure, No. 17,129 (July 1978); thiazolidine derivatives described in Japanese Patent Application (OPI) No. 140,129/75; thiourea derivatives described in Japanese Patent Publication No. 8,506/70, Japanese Patent Application (OPI) Nos. 20,832/77 and 32,735/78 and U.S. Pat. 3,706,561; iodide salts described in West German Pat. No. 1,127,715 and Japanese Patent Application (OPI) No. 16,235/83; polyoxyethylene compounds described in West German Pat. Nos. 966,410 and 2,748,430; polyamine compounds described in Japanese Patent Publication No. 8836/70; compounds described in Japanese Patent Application (OPI) Nos. 42,434/74, 59,644/74, 94,927/78, 35,727/79, 26,506/80, and 163,940/83; and bromide ions. Of these, mercapto group- or disulfido group-containing compounds are preferred due to their large accelerating effect, and compounds which are described in U.S. Pat. 3,893,858, West German Pat. No. 1,290,812, and Japanese Patent Application (OPI) No. 95,630/78 are particularly preferred. Further, compounds which are described in U.S. Pat. 4,552,834 are also preferred. These bleaching accelerators may be added to light-sensitive materials. These bleaching accelerators are particularly effective in bleach-fixing color light-sensitive materials for photographic use.
Fixing agents include thiosulfates, thiocyanates, thioether compounds, thioureas, a large amount of iodide salt, etc. Of these, thiosulfates are commonly used, with ammonium thiosulfate being most widely used. As preservatives for bleach-fixing solutions, sulfites, bisulfites or carbonyl-bisulfurous acid adducts are preferable.
After being subjected to the bleaching and fixing the silver halide color photographic light-sensitive material of the present invention is generally subjected to water-washing and/or a stabilizing step. Further, the light sensitive material of the present invention may be processed directly with a stabilizing solution in place of the above-described washing water. In such stabilizing processing, all of the techniques described in Japanese Patent Application (OPI) Nos. 8,543/82, 14,834/83, and 220,345/85 may be employed.
In addition, the water-washing step is in some cases followed by stabilizing. An example thereof is a stabilizing bath containing formalin and a surfactant, which is used as a final bath for processing color light-sensitive materials for photographic use. Various chelating agents and anti-fungal agents may also be added to this stabilizing bath.
In the present invention, the various processing solutions are used at temperatures of about 10°C to 50°C. usually, temperatures of about 33°C to 38°C are standard, but higher temperatures may be employed for accelerating the processing and shortening processing times or lower temperatures may be employed to improve image quality and the stability of processing solutions.
The present invention is now illustrated in greater detail by reference to the following examples which, however, are not to be construed as limiting the present invention in any way. Unless otherwise indicated all parts, percents and ratios are by weight.

Example 1

A multi-layer color light-sensitive material, sample 101, was prepared by multi-coating the layers of the following formulations of a subbed cellulose triacetate film support.

Formulation of light-sensitive layer:

The numerical values refer to the respective components as coated amounts in terms of g/m². For silver halide, the numerical values refer to the amounts of coated silver and, for sensitizing dyes, the numerical values refer to the amounts of coted dye per mol of silver halide contained in the same layer.

Sample 101

In addition to the above-described ingredients, gelatin hardener H-1, and surfactant were added to each of the layers.
The chemical structural formula or names of the compounds used in the present invention are shown below. (Samples 102 to 136)
Samples 102 to 136 were prepared by replacing the couplers used in the 5th and the 7th layers of sample 101 by equimolar amounts of the couplers shown in Table 1 and adding to the 6th layer the additives shown in Table 1.
A-1, compound (13) of the present invention, and HBS-1 each added to the composition of the 6th layer in an amount of 0.035 g/m² by emulsification-dispersion.
These samples were imagewise exposed through a red filter (made by Fuji Photo Film Co., Ltd.; SC-62), then subjected to the color development processing described below. The densities of the thus-processed samples were measured using red, green, and blue interference filters, respectively. Color stain values were calculated by subtracting from each fog density the magenta density at an exposure amount which provided a cyan density of (fog + 1.5) measured through a red filter.
Separately, the sample were subjected to the following color development processing immediately after white imagewise exposure (condition A) or after standing for 14 days under conditions of 40°C and 80 % RH (condition B). The difference in the red filter sensitivity of condition B samples and condition A samples (relative sensitivity at a cyan density of fog + 0.2) are tabulated in Table 1 as changes in sensitivity after standing and the relative sensitivities of cyan and magenta images for condition A are also tabulated in Table 1.
Further, MTF values of magenta color images at 40 cycles/mm were measured by first uniformaly exposing the samples in an exposure amount of 0.02 CMS using a red filter, then exposing the samples to a MTF-measuring pattern using white light and developing them. Measurement of MTF was conducted according to Mees, The Theory of the Photographic Process, (3rd ed. Mcmillan Co.).
The color development processing was conducted at 38°C according to the following processing steps.
Color development: 3'15"
Bleaching 6'30"
Washing with water 2'10"
Fixing 4'20"
Washing with water 3'15"
Stabilizing 1'05"
The formulations of the processing solutions used in respective steps are as follows.
It is seen from Table 1 that samples of the present invention exhibited less color stain and less change in photographic properties under incubation conditions, and had better sharpness (MTF value) than samples without compound (13) of the present invention, and higher sensitivity than samples without 2-equivalent couplers.

Example 2

Sample 201 was prepared in the same manner as sample 125 except for providing the following DC (dye conpensator) layer between the 7th and the 8th layers.
DC layer (interlayer)
Gelatin 0.80
EX-6 0.10
A-2 0.03
HBS-1 0.20

(Samples 202 to 228)

Sample 208 was prepared in the same manner as sample 201 except for changing coupler EX-6 in the 7th, 8th, and DC layers to 0.8 time mol of coupler M-7 in accordance with the present invention and changing the amounts of HBS-1 and gelatin to 0.6 time and 0.7 time, respectively. Sample 215 was prepared in the same manner except for changing coupler EX-6 to 0.5 time mol of coupler M-16 in accordance with the present invention and changing the amounts of HBS-1 and gelatin to 0.5 time and 0.6 time, respectively. Sample 222 was prepared in the same manner except for changing coupler EX-6 to 0.4 time of coupler M-3 in accordance with the present invention and changing the amounts of HBS-1 and gelatin to 0.3 time and 0.5 time respectively.
Samples shown in Table 2 were prepared by replacing Compound A-2 added to the DC layer of samples 201, 208, 215, and 222 to equimolar amounts of A-3, A-4, compound (11), compound (15), compound (17), and compound (30) of the present invention, respectively.
These samples were scratched using a sapphire needle with a tip diameter of 0.1 mm while changing the load from 0 to 200 g to determine the scratch strength of each sample which was at the same level of about 130 g.
When the magenta densities obtained by subjecting the samples to white imagewise exposure and to color development processing described below using an automatic developing machine were evaluated, the densities of all samples were found to be about the same.
Further, the samples were exposed through a step wedge for measuring RMS graininess and subjected to the same color development to determine RMS values of the magenta images using an aperture 48 µm in diameter.
The MTF values of the magenta images were also measured by exposure with white light.
Processing
Color development 3'15"
Bleaching 1'
Bleach-fixing 3'15"
Washing with water (1) 40"
Washing with water (2) 1'
Stabilizing 40"
Drying (50°C) 1'15"
In the above-described processing step, washing (1) and washing (2) were conducted by counter current washing from (2) to (1). Formulations of the respective processing solutions are shown below. Additionally, replenishing amounts of the processing solutions were as follows: Replenishing amount of the color developer was 1,200 ml per m² of color light-sensitive material, and that of other solutions was 800 ml per m² of color light-sensitive material. The amount of the processing solution carried over from the bleach-fixing to the washing step was 50 ml per m² of color light-sensitive material.

Washing water

City water containing 32 mg/liter or calcium ions and 7.3 mg/liter of magnesium ions was passed through a column filled with a H-type strongly acidic cation exchange resin and a OH-type strongly basic anion exchange resin to reduce the calcium ion level and the magnesium ion level to 1.2 mg/liter and 0.4 mg/liter, respectively. To the thus-processed water was added 20 mg/liter of sodium dichloroisocyanurate.

Drying

Drying temperature was 50°C.
It is apparent from Table 2 that the samples of the present invention had better sharpness (MTF value) than samples using couplers outside the scope of the present invention and the compounds of the present invention in a DC layer, and had better graininess than the samples using the couplers of the present invention and compounds outside the scope of the present invention in DC layer.
The structures of the compounds used in Examples 1 and 2 were as follows:
While the present invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and the scope of the present invention.

Claims

1. A silver halide color photographic material comprising a support having thereon a red-sensitive silver halide emulsion layer containing a cyan coupler, a green-sensitive silver halide emulsion layer containing a magenta coupler, a blue-sensitive silver halide emulsion layer containing a yellow coupler, at least one of said light-sensitive silver halide emulsion layers containing a 2-equivalent coupler; and at least one light-insensitive layer containing at least one compound selected from the group consisting of compounds represented by formula (I), bis- and tris compounds and polymers derived therefrom, and an alkali-labile precursor thereof:

wherein R₁ and R₂ each represents a hydrogen atom, a halogen atom, -SO₃M, -COOM (wherein M represents H, alkali metal atom or -NH₄), an alkyl group, an acylamino group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a sulfonyl group, an acyl group, a carbamoyl group or a sulfamoyl group, R₁ and R₂ amy be linked to form a ring; X represents -CO- or -SO₂-; R₃ represents an alkyl group, an aryl group, a heterocyclic group, a cycloalkyl group, an alkoxy group, an aryloxy group, or an amino group; at least one of R₁, R₂ and R₃ may be a 2-valence group to form a bis- or tris-compound or a polymer; and the sum of the carbon atoms contained in R₁, R₂ and R₃ is at least 10.

2. The silver halide color photographic material as described in claim 1, wherein said light-insensitive layer is in close proximity to said light-sensitive silver halide emulsion layer contatining at least one 2-equivalent coupler.

3. The silver halide color photographic material as described in claim 2, wherein said light-insensitive layer is adjacent to at least one light-sensitive silver halide emulsion layer containing said 2-equivalent coupler.

4. The silver-halide color photographic material as described in claim 1, wherein said light-insensitive layer is selected from the group consisting of a protective layer, an inter layer, a filter layer, an antihalation layer and a layer provided for incorporating the compound.

5. The silver halide color photographic material as described in claim 1, wherein said compound is incorporated to a layer between emulsion layer having different color sensitivities or between two emulsion layers having substantially the same color sensitivity.

6. The silver halide color photographic material as described in claim 1, wherein said compound is incorporated to a layer between a layer having the maximum sensitivity in a color sensitive layer unit and a layer sensitive in different color and having the minimum sensitivity, between layers one having a higher sensitivity and the other having a lower sensitivity and each having substantially the same color sensitivity, or between layers one having intermediate sensitivity and the other having a lower of a higher sensitivity and each having substantially the same color sensitivity.

7. The silver halide color photographic material as described in claim 1, wherein the thickness of light-insensitive layer containing the compound is from about 0.1 to 2.0 µm.

8. The silver halide color photographic material as described in claim 1, wherein the amount of said compound is from about 0.005 to 2.0 g/m².

9. The silver halide color photographic material as described in claim 1, wherein the amount of said 2-equivalent coupler is from about 0.01 to 2.0 g/m².

10. The silver halide color photographic material as described in claim 1, wherein the ratio of the amount of the 2-equivalent coupler to the amount of said compound is from about 0.001 to 100.

11. The silver halide color photographic material as described in claim 1, wherein the substituent for each group represented by R₁ or R₂ is a substituent selected from the group consisting of halogen atom, -SO₃M-, -COOM (wherein M represents H, an alkali metal atom or -NH₄), an alkyl group, an acylamino group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an acyl group, a carbamoyl group, a sulfamoyl group, and a ring obtained by linking these groups when each of R₁ and R₂ is an alkyl group, an acylamino group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a sulfonyl group, an acyl group, a carbamoyl group, or a sulfamoyl group, and a substituent selected from the group consisting of an alkyl group and an aralkyl group when each of R₁ and R₂ is an alkyl or an aryl group.

12. The silver halide color photographic material as described in claim 1, wherein the substituent for R₃ is a substituent selected from the group consisting of a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, a carbonamido group, a sulfonamido group, an alkylthio group, an arylthio group, an aryl group, an alkoxycarbonyl group, and a carbamoyl group, and groups derived from these groups and which are obtained by further substitution with a substituent selected from these groups.

13. The silver halide color photographic material as described in claim 1, wherein said alkali-labile precursors of said compound is a compound selected from the group consiting of compounds in which the hydroxy groups at the 1- and 4-positions of the hydroquinone skeleton in the compound represented by general formula (I) is protected by a group capable of being cleaved under alkaline conditions of a developing process.

14. The silver halide color photographic material as described in claim 13, where said protective group is a group selected from the group consisting of an acyl group and β-eliminatable groups.

15. The silver halide color photorgraphic material as described in claim 1, wherein X is CO.

16. The silver halide color photographic material as described in claim 1, wherein R₃ represents an alkyl group or an aryl group.

17. The silver halide color photographic material as described in claim 16, wherein R₃ is an aryl group.