Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
  • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
  • G03C1/825—Photosensitive materials characterised by the base or auxiliary layers characterised by antireflection means or visible-light filtering means, e.g. antihalation
  • G03C1/83—Organic dyestuffs therefor
  • G03C1/832—Methine or polymethine dyes
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
  • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
  • G03C7/32—Colour coupling substances
  • G03C7/3225—Combination of couplers of different kinds, e.g. yellow and magenta couplers in a same layer or in different layers of the photographic material
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
  • G03C1/08—Sensitivity-increasing substances
  • G03C1/10—Organic substances
  • G03C1/12—Methine and polymethine dyes

Definitions

• This invention relates to a positive working silver halide color photographic material and, more particularly, to a positive working silver halide color photographic material having improved color reproducibility.
• positive working silver halide color photographic materials means those materials which can produce reflex, semi-transmission or transmission type positive images (copies) using reflex or transmission type positive images (originals).
• Photographic emulsion layers or other layers in silver halide photographic materials are often colored so that light in specific wave ranges is absorbed.
• a colored layer is provided farther from support than the photographic emulsion in the photographic materials when it is necessary to control the spectral composition of incident light on the photographic emulsion layers.
• Such a colored layer is called a filter layer.
• the filter layer is interposed therebetween.
• a colored layer is often provided between a photographic emulsion layer and a support or on the opposite side of the support to the photographic emulsion for the purpose of preventing image blurring, that is, preventing "halation" from occurring, this blurring or halation being caused by the fact that light which is scattered during or after passage through the photographic emulsion is reflected at the interface between the emulsion layer and the support or on the opposite side of the photographic material to the emulsion layer and again enters the emulsion layer.
• Such a colored layer is called an antihalation layer.
• the antihalation layer is often interposed between the layers.
• Photographic emulsion layers are often colored to prevent image sharpness from being reduced by the scattering of light in the photographic emulsion (this phenomenon is generally called "irradiation").
• Patent 4255,326 and JP-A-59-211043 azomethine dyes as described in JP-A-50-100116, JP-A-54-118247, British Patents 2,014,598 and 750,031; anthraquinone dyes as described in U.S. Patent 2.865,752; arylidene dyes as described in U.S.
• the oxonol dyes having two pyrazolone nuclei have properties such that they are decolorized in developing solutions containing sulfites and have little adverse effects on the photographic emulsions. Therefore, they have been used as useful dyes for the photographic materials.
• an object of the present invention is to provide a positive working color photographic material which has improved color reproducibility and is scarcely colored by dye remaining after processing.
• a positive working silver halide color photographic material comprising a support having thereon at least one silver halide emulsion layer wherein the photographic material contains (a) at least one dye having a maximum absorption wavelength of 480 to 530 nm in a gelatin film and/or (b) at least one dye having a maximum absorption wavelength of 580 to 630 nm in a gelatin film, with the proviso that an oxonol dye having a hydroxypyridone nucleus is excluded when only a dye (a) or a dye (b) is present in the photographic material.
• the silver halide color photographic material of the present invention contains (a) at least one dye having a maximum absorption wavelength of 480 to 530 nm in a gelatin film and/or (b) at least one dye having a maximum absorption wavelength of 580 to 630 nm in a gelatin film.
• the half width of absorption is 90 nm or above and with regard to the dyes (b) having a maximum absorption wavelength of 580 to 630 nm in a gelatin film, the half width of absorption is 100 nm or below.
• oxonol dyes having a pyrazolone nucleus oxonol dyes having a hydroxypyridone nucleus, oxonol dyes having a barbituric acid nucleus, and oxonol dyes having a pyrazolidinedione nucleus are preferred and compounds represented by the following general formula (I), (la), (II), (Ila), (III) or (IV) are particularly preferred.
• R 1 and R 3 which may be the same or different, each represents an aliphatic group, an aromatic group or a heterocyclic ring
• R 2 and R 4 which may be the same or different, each represents an aliphatic group, an aromatic group, -ORs, -COOR s , -NR 5 R 6 , -CONR S Rs, -NRsCONRsR 6 , -S0 2 R 7 , -COR 7 , -NR 6 COR 7 , -NR G S0 2 R 7 , or a cyano group
• Rs and Rs which may be the same or different, each represents a hydrogen atom, an aliphatic group or an aromatic group
• R 7 represents an aliphatic group or an aromatic group
• Rs and Rs or Rs and R 7 may combine together to form a 5-membered or 6- membered ring
• n 1 and n 2 each represents 0 or 1
• M 9 represents a hydrogen atom or a monovalent cation
• R 11 and R 14 each represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, -NR 17 R 18 , -NR 17 CONR 17 R 18 , -NR 18 COR 19 , or -NR 18 SO 2 R 19 ;
• R 12 and R 15 which may be the same or different, each represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, a cyano group, a sulfo group, -NR 17 R 18 , -NR 18 COR 19 , -NR 18 SO 2 R 19 , -NR 17 CONR 17 R 18 , -COOR 17 , -CONR 17 R 18 , -COR 19 , -SO 2 R 19 or -SO 2 NR 17 R 18 ;
• R 13 and R 16 which may be the same or different, each represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, -NR 17 R 18
• R 19 is an aliphatic group or an aromatic group
• R 17 and R 18 or R 18 ⁇ and R 19 may combine together to form a 5-membered or 6-membered ring
• L 1 , L 2 , L 3 , L 4 , Ls, n 1 , n 2 and M 6 are as defined above in the formula (I).
• R 31 , R 32 , R 33 and R 34 which may be the same or different, each represents a hydrogen atom, an aliphatic group or an aromatic group
• L 1 , L 2 , L 3 , L 4 , Ls, n 1 , n 2 and M 9 are as defined in the formula (I).
• R 3 s, R 36 , R 37 and R 38 which may be the same or different, each represents an aliphatic group, an aromatic group or a heterocyclic group; L 41 , L 42 and L 43 each represents a methine group; n 41 represents 1, 2 or 3; and one or more of R 3s , R 36 , R 37 and R 38 have a carboxyl group or a sulfo group and the total of the carboxyl groups and/or the sulfo groups is at least two.
• the dyes represented by the formula (I) are illustrated in greater detail below.
• Examples of suitable aliphatic groups represented by R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 include a straight chain or branched alkyl group having 1 to 6 carbon atom, a cyclic alkyl group having 5 to 10 carbon atoms, aralkyl group having 7 to 10 carbon atoms, and alkenyl group having 2 to 6 carbon atoms, such as methyl, ethyl, n-butyl, benzyl, 2-sulfoethyl, 4-sulfobutyl, 2-sulfobenzyl, 2,4-disulfobenzyl, 4-sulfophenethyl, 2-carboxyethyl, carboxymethyl, trifluoromethyl, dimethylaminoethyl and 2-hydroxyethyl.
• Suitable aromatic groups represented by R 1 , R 2 , R 3 , R 4 , R s , Rs and R 7 include phenyl, naphthyl, 4-sulfophenyl, 3-sulfophenyl, 2,5-disulfophenyl, 4-carboxyphenyl and 5,7-disulfo-3-naphthyl.
• aromatic groups aryl groups having 6 to 10 carbon atoms are preferred.
• Suitable 5-membered or 6-membered rings formed when R 5 and Rs or R 6 and R 7 combine together include a pyrrolidine ring, a piperidine ring, a pyrrolidone ring and a morpholine ring.
• Examples of suitable monovalent cations represented by M ⁇ other than hydrogen include Na ⁇ , K ⁇ , Lie and HN(C 2 H 5 )3 ⁇ .
• R, and R 3 are an alkyl group having 1 to 6 carbon atoms and having at least 1 sulfo group or carboxyl group or an aryl group having 6 to 10 carbon atoms and having at least 1 sulfo group or carboxyl group are preferred.
• Particularly preferred compounds are those where R 2 and R 4 are -OR s or -NR 5 R 6 , in which R 5 and R s are the same as defined in the formula (I).
• Examples of dyes represented by the formula (I) include the following compounds.
• a mixture of 5 g of 3-ethoxy-1-(3'-sulfopropyl)-5-pyrazolone, 2.8 g of glutacondialdehydodianil hydrochloride, 100 ml of methanol and 4 g of triethylamine was stirred at a temperature of 30 to 40° C for 3 hours.
• 20 ml of a methanol solution of 2 g of anhydrous potassium acetate was added thereto with stirring to form a blue precipitate. After stirring for 1 hour, the precipitate was collected by filtration, thoroughly washed with acetone and dried to obtain 4.3 g of the desired dye.
• An aqueous solution of the dye was blue and had a maximum absorption wavelength of 596 m ⁇ .
• the dyes represented by the formula (II) are illustrated in greater detail below.
• Examples of suitable aliphatic groups represented by R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 or R 19 are alkyl groups having 1 to 6 carbon atoms and aralkyl groups having 7 to 10 carbon atoms and include methyl, ethyl, isopropyl, 2-chloroethyl, trifluoromethyl, benzyl, 2-sulfobenzyl, 4-sulfophenethyl, carboxymethyl, 2-carboxyethyl, 2-sulfoethyl, 2-hydroxyethyl, dimethylaminoethyl and cyclopentyl.
• Suitable aromatic groups represented by R 11 , R 13 , R 14 , R 16 , R 17 , R 18 or R 19 are aryl groups having 6 to 10 carbon atoms and include phenyl, naphthyl, 3-sulfophenyl, 4-sulfophenyl, 2,5- disulfophenyl, 4-(3-sulfopropyloxy)phenyl, 3-carboxyphenyl and 2-carboxyphenyl.
• heterocyclic groups represented by R 11 , R 13 , R 14 or R 16 include 2-pyridyl, morpholino and 5-sulfobenzimidazole-2-yl.
• Examples of suitable 5-membered or 6-membered rings formed when R 17 and R 18 , or R 18 and R 19 combine together include piperidine, pyrrolidine, morpholine and pyrrolidone.
• Examples of dyes represented by the formula (II) include the following compounds.
• Dyes having the formula (II) can be synthesized according to the methods described in British Patents 1,278,621, 1,512,863 and 1,579,899 and in accordance with the following synthesis examples.
• the dyes represented by the formula (III) are illustrated in greater detail below.
• Suitable aliphatic groups represented by R 31 , R 32 , R 33 and R 34 are the same as those described for R 1 , R 2 , R 3 and R 4 in the formula (I).
• Suitable aromatic groups represented by R 31 , R 32 , R 33 and R 34 are the same as those described for Ri, R 2 , R 3 and R 4 . in the formula (I).
• Suitable heterocyclic groups represented by R 31 , R 32 , R 33 and R 34 are the same as those described for Ri, R 2 , R 3 and R 4 in the formula (I).
• Examples of the dyes having the formula (III) include the following compounds.
• the dyes represented by the formula (IV) are illustrated in greater detail below.
• R 35 , R 36 , R 37 and R 38 in the dyes having the formula (IV) each represents an alkyl group having 1 to 6 carbon atoms (e.g., methyl, ethyl, carboxymethyl, 2-carboxyethyl, 2-hydroxyethyl, methoxyethyl, 2-chloroethyl, benzyl, 2-sulfobenzyl, 4-sulfophenethyl), an aryl group having 6 to 10 carbon atoms (e.g., phenyl, 4-sulfophenyl, 3-sulfophenyl, 2-sulfophenyl, 4-carboxyphenyl, 3-carboxyphenyl, 4-hydroxyphenyl) or a residue of a heterocyclic ring (e.g., 2-pyridyl, 2-imidazolyl).
• a heterocyclic ring e.g., 2-pyridyl, 2-imidazolyl
• L 41 Lx2 and Lx3 each represents a methine group. These methine groups may be independently substituted by methyl, ethyl, phenyl, sulfoethyl, carboxyethyl or the like.
• n 41 represents 1, 2 or 3.
• R 35 , Ras, R 37 and R 38 have at least one carboxyl or sulfo group and the total of the carboxyl groups and/or sulfo groups is at least 2.
• the carboxyl group and the sulfo group may be in the free form or in the form of a salt (e.g., Na salt, K salt, ammonium salt).
• dyes having the formula (IV) which can be used in the present invention include the following compounds.
• the dyes of the present invention are used as filter dyes, irradiation-preventing dyes or antihalation dyes, the dyes are used in such an amount that the desired results can be obtained. It is preferred that the dyes are used in an amount so as to give an optical density in the range of 0.05 to 3.0.
• the dyes may be added in any stage before coating.
• the dyes of the present invention can be dispersed in emulsion layers and other hydrophilic colloid layers (e.g., an intermediate layer, a protective layer, an antihalation layer, a filter layer, etc.) using conventional methods.
• hydrophilic colloid layers e.g., an intermediate layer, a protective layer, an antihalation layer, a filter layer, etc.
• the dyes can be dispersed in these layers using the following methods.
• Useful surfactants may be oligomers or polymers.
• Suitable polymers are fully described in JP-A-60-158437 (pages 19 to 27).
• a hydrosol of a lipophilic polymer described in JP-B-51-39835 may be added to the hydrophilic colloid dispersion obtained as described above.
• hydrophilic colloid A typical example of a suitable hydrophilic colloid is gelatin. However, other hydrophilic colloid which are conventionally used in the field of photography can also be used.
• Silver halide color photographic materials generally comprise three kinds of silver halide emulsion layers which are sensitized so as to be selectively sensitive to blue light, green light and red light, respectively.
• Each emulsion layer contains a coupler capable of reacting with the oxidation product of aromatic primary amine developing agents to form a dye.
• a coupler capable of reacting with the oxidation product of aromatic primary amine developing agents to form a dye.
• yellow, magenta and cyan colors, respectively are formed.
• couplers have good color forming properties such that the coupling rate is as high as possible and they give a high color density within a restricted period of time. Further, it is required that color forming dyes scarcely give rise to any secondary absorption.
• the formed color images have good preservability under various conditions.
• Suitable magenta couplers which meet these requirements include known couplers, which scarcely cause secondary absorption, as described in U.S. Patents 3,369,897 and 3,725,067, JP-A-59-162548, JP-A-59-171956, JP-A-59-228252, JP-A-60-33552, WO-86/1915 and JP-A-61-65245.
• pyrazolone couplers have excellent color reproducibility with regard to red color and are practically used in the field of some color photographic materials.
• Suitable yellow couplers are known couplers which have excellent color forming properties and have high activity as described in JP-A-60-229029.
• Suitable cyan couplers are known couplers as described in U.S. Patents 2,801,171, 2,895,826 and 3,772,002, JP-A-59-124341, JP-A-58-105229, JP-A-60-24547, JP-A-60-237448, JP-A-61-39045 and JP-A-61-77245.
• the above-described dyes are used in combination with couplers which have good color forming properties and scarcely cause secondary absorption, whereby a positive silver halide color photographic material which has excellent sharpness and color reproducibility can be obtained.
• the silver halide color photographic material of the present invention contains at least one of each of a magenta coupler represented by the following formula (V), a yellow coupler represented by the following formula (VI) and a cyan coupler represented by the following formula (VII) or (VIII).
• X represents a hydrogen atom or a substituent group
• Z 2 represents a hydrogen atom or a coupling elimination group (a group which is eliminated by coupling)
• W represents a hydrogen atom, an acyl group or an aliphatic or aromatic sulfonyl group
• R 8 represents a substituted or unsubstituted N-phenylcarbamoyl group
• Y 3 represents a group which is bonded through an oxygen atom or a nitrogen atom and is eliminated by the coupling reaction with the oxidation product of a primary amine color development agent.
• R 131 represents an alkyl group, an aryl group, an amino group or a heterocyclic group
• R 132 represents an acylamino group or an alkyl group
• R 133 represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group
• R 133 and R' 32 may combine together to form a 5-membered to 7-membered ring
• Z' 31 represents a hydrogen atom or a group which is eliminated by reaction with the oxidation product of an aromatic primary amine color developing agent.
• R131- represents an alkyl group, an aryl group or a heterocyclic group
• R 135 represents an acyl group, a sulfonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group or an alkoxysulfonyl group
• R 136 represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an amido group, an imido group, an alkylthio group, an arylthio group, a ureido group, an alkylsulfonyl group or an arylsulfonyl group
• p represents 0 or 1
• Z 131 represents a hydrogen atom or a group which is eliminated by the reaction with the oxidation product of an aromatic primary amine developing agent.
• Magenta couplers having the formula (V) are illustrated in more detail below.
• the term "dimer or polymer” as used herein refers to compounds having at least 2 groups represented by the formula (V) per molecule. Accordingly, the term “dimer or polymer” includes bis compound couplers and polymer couplers.
• the polymer couplers may be homopolymers composed of a monomer 'having a moiety represented by the formula (V) (preferably a monomer having a vinyl group, hereinafter referred to as a vinyl monomer) or copolymers of this monomer with a non-color-forming ethylenic monomer which is not coupled with the oxidation product of aromatic primary amine color developing agents.
• couplers having the formulae (Va) to (Ve) Of the couplers having the formulae (Va) to (Ve), the couplers having the formulae (Va), (Vb) and (Vc) are preferred. The couplers having the formula (Vc) are most preferred.
• X1, X 2 and X 3 which may be the same or different, each is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an acyloxy group, a carbamoyloxy group, a silyloxy group, a sulfonyloxy group, an acylamino group, an anilino group, a ureido group, an imido group, a sulfamoylamino group, a carbamoylamino group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonamido group, a carbamo
• Z 2 is a hydrogen atom, a halogen atom or a group which is bonded through an oxygen atom, a nitrogen atom or a sulfur atom to the carbon atom at the coupling position and is eliminated on coupling.
• X 1 , X 2 , X 3 or Z 2 may be a divalent group to form a bis compound.
• Couplers may be in the form of polymer couplers wherein the main chain comprises units composed of a residue of couplers having the formulae (Va) to (Ve) or polymers having side chains comprising units composed of a residue of the couplers having the formulae (Va) to (Ve).
• Polymers derived from a vinyl monomer with a moiety having the formula (Va), (Vb), (Vc), (Vd) or (Ve) are particularly preferred.
• X 1 , X 2 , X 3 or Z 2 is a vinyl group or a bonding group.
• Xi, X 2 and X 3 are each a hydrogen atom, a halogen atom (e.g., chlorine, bromine), an alkyl group (e.g., methyl, propyl, isopropyl, t-butyl, trifluoromethyl, tridecyl, 3-(2,4-di-t-amylphenoxy)propyl, 2-(2-octyloxy-5-t-octylbenzenesulfonamido)ethyl, allyl, 2-dodecyloxyethyl, 3-phenoxypropyl, 2-hexylsul- fonylethyl, cyclopentyl, benzyl, etc.), an aryl group (e.g., phenyl, 4-t-butylphenyl, 2,4-di-t-amylphenyl, 4-tetradecanamidophenyl, etc.), a heterocyclic group
• X 2 and X 3 may combine together to form a 5-membered to 7-membered ring.
• Xi, X 2 and X 3 are each preferably a substituted or unsubstituted alkylene group (e.g., methylene, ethylene, 1,10-decylene, -CH 2 CH 2 -O-CH 2 CH 2 - , etc.), a substituted or unsubstituted phenylene group (e.g., 1,4-phenylene, 1,3-phenylene, etc.), an -NHCO-X 4 -CONH group (wherein X4.
• alkylene group e.g., methylene, ethylene, 1,10-decylene, -CH 2 CH 2 -O-CH 2 CH 2 - , etc.
• a substituted or unsubstituted phenylene group e.g., 1,4-phenylene, 1,3-phenylene, etc.
• an -NHCO-X 4 -CONH group wherein X4.
• X s is a substituted or unsubstituted alkylene or phenylene group, such as -NHCOCH 2 CH 2 CONH-, etc.), or an -S-Xs-S- group (wherein X s is a substituted or unsubstituted alkylene group, such as -S-CH 2 CH 2 -S-, etc.), and Z 2 is a divalent group derived from a member selected from the monovalent groups described above for Z 2 .
• the bonding group represented by X 1 , X 2 , X 3 or Z 2 is a group selected from the group consisting of a substituted or unsubstituted alkylene group (e.g., methylene, ethylene, 1,10-decylene, -CH 2 CH 2 OCH 2 CH 2 -, etc.), a substituted or unsubstituted phenylene group (e.g., 1,4-phenylene, 1,3-phenylene, etc.), -NHCO-, -CONH-, -0-, -OCO-, and an aralkylene group (e.g., etc.), or a combination thereof.
• a substituted or unsubstituted alkylene group e.g., methylene, ethylene, 1,10-decylene, -CH 2 CH 2 OCH 2 CH 2 -, etc.
• a substituted or unsubstituted phenylene group e.g., 1,4-phenylene
• bonding groups are the following groups:
• a vinyl group may have one or more substituent groups in addition to the moiety represented by the formula (Va), (Vb), (Vc), (Vd) or (Ve).
• Preferred substituent groups are a chlorine atom and a lower alkyl group having from 1 to 4 carbon atoms (e.g., methyl, ethyl).
• Monomers containing a moiety represented by the formula (Va), (Vb), (Vc), (Vd) or (Ve) may be copolymerized with non-color-forming ethylenic monomers which do not couple with the oxidation product of aromatic primary amine developing agents to form copolymers.
• non-color-forming ethylenic monomers which do not couple with the oxidation product of aromatic primary amine developing agents ' include acrylic acid, a-chloroacrylic acid, a-alkylacrylic acid (e.g., methacrylic acid) and esters and amides derived from these acrylic acids (e.g., acrylamide, n-butylacrylamide, t-butylacrylamide, diacetone acrylamide, methacrylamide, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and ,B-hydroxy methacrylate), methylenedibisacrylamide, vinyl
• non-color-forming ethylenically unsaturated monomers may be used either alone or as a combination of two or more of them.
• a combination of n-butyl acrylate and methyl acrylate, a combination of styrene and methacrylic acid, a combination of methacrylic acid and acrylamide and a combination of methyl acrylate and diacetone acrylamide can be used.
• the ethylenically unsaturated monomers to be copolymerized with the solid water-insoluble monomer couplers can be chosen so as to provide copolymers having good physical properties and/or chemical properties such as solubility, compatibility with binders (e.g., gelatin) in photographic colloid compositions, flexibility, thermal stability, etc., well known in the field of polymer color couplers.
• binders e.g., gelatin
• the polymer couplers which are used in the present invention may be water-soluble or water-insoluble. Among them, polymer coupler latexes are particularly preferred.
• couplers can be synthesized by the methods described in JP-A-59-171596, JP-A-60-172982, JP-A-60-190779, JP-A-60-197688 and JP-A-60-215687.
• magenta couplers which can be used in the present invention include, but are not limited to, the following compounds.
• Couplers having the formula (V) can be synthesized according to the methods described in U.S. Patents 3,369,897 and 3,725,067, JP-A-59-162548, JP-A-59-171956, JP-A-59-228252, JP-A-60-33552, WO 86/1915 and JP-A-61-65245 and similar methods.
• couplers of the formula (V) are used in an amount of 1 x 10- 3 to 1 mol, preferably 5 x 10- 2 to 5 x 10- 1 mol, per mol of silver halide in the emulsions.
• Yellow couplers represented by the formula (VI) are illustrated in greater detail below.
• R s is an N-phenylcarbamoyl group.
• the phenyl group may optionally have one or more substituent groups. When two or more substituent groups are present, they may be the same or different groups.
• substituent groups examples include an aromatic group (e.g., phenyl, naphthyl), a heterocyclic group (e.g., 2-pyridyl, 2-imidazolyl, 2-furyl, 6-quinolyl, etc.), an aliphatic oxy group (e.g., methoxy, 2-methoxyethoxy, 2-propenyloxy, etc.), an aromatic oxy group (e.g., 2,4-di-tert-amylphenoxy, 4-cyanophenoxy, 2-chlorophenoxy, etc.), an acyl group (e.g., acetyl, benzoyl, etc.), an ester group (e.g., butoxycarbonyl, phenoxycarbonyl, acetoxy, benzoyloxy, butoxysulfonyl, toluenesulfonyloxy, etc.), an amido group (e.g., acetylamino, methanesul
• an aromatic group
• R s is a group represented by the following formula (A): wherein G 1 is a halogen atom or an alkoxy group; G 2 is a hydrogen atom or an alkoxy group which may be optionally substituted; and R 11 o is an alkyl group which may be optionally substituted.
• substituent groups for G 2 and R 11 in the formula (A) include an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a dialkylamino group, a heterocyclic group (e.g., N-morpholino, N-piperidino, 2-furyl, etc.), halogen, a nitro group, a hydroxyl group, a carboxyl group, a sulfo group and an alkoxycarbonyl group.
• a heterocyclic group e.g., N-morpholino, N-piperidino, 2-furyl, etc.
• halogen e.g., a nitro group, a hydroxyl group, a carboxyl group, a sulfo group and an alkoxycarbonyl group.
• Y 3 is a group which is eliminated.
• Y 3 is a group selected from groups represented by the following formulae (B) to (E): -OR 111 (B)
• R 111 is a substituted or unsubstituted aryl or heterocyclic group
• R 112 and R 113 are each a hydrogen atom, a halogen atom, a carboxylic ester group, an amino group, an alkyl group, an alkylthio group, an alkoxy group, an alkylsulfonyl group, an alkylsulfinyl group, a carboxyl group, a sulfo group, an unsubstituted or substituted phenyl group or an unsubstituted or substituted heterocyclic group and R 112 and R 113 3 may be the same or different groups; wherein W, is a nonmetallic atomic group required for the formation of a 4-membered, 5-membered or 6- membered ring together with Of the groups of the formula (E), the groups represented by the following formulae (E-1) to (E-3) are preferred.
• R 114 and R 115 are each a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group or a hydroxyl group
• R 116 , R, 17 and R 118 are each a hydrogen atom, an alkyl group, an aryl group, an aralkyl group or an acyl group
• W 2 is an oxygen atom or a sulfur atom.
• alkyl moiety and the aryl moiety in the groups represented by the above formulae may be optionally substituted by the substituent groups already described above.
• Suitable yellow couplers which can be used in the present invention include, but are not limited to, the following compounds.
• Couplers having the formula (VI) are disclosed in JP-A-54-48541, JP-B-58-10739, U.S. Patent 4,326,024 and Research Disclosure, 18053, Vol. 180 (April, 1979).
• the couplers having the formula (VI) are used in an amount of 0.1 to 1.1 mol, preferably 0.1 to 0.5 mol per mol of silver halide in the blue-sensitive silver halide emulsion.
• suitable alkyl groups represented by R 131 are a straight chain, branched or cyclic alkyl group having from 1 to 32 carbon atoms and suitable aryl groups are an aryl group having from 6 to 42 carbon atoms.
• R 131 is an amino group
• the group R 131 can be an alkylamino group or an arylamino group with a substituted or unsubstituted phenylamino group being preferred.
• the alkyl group, the aryl group or the phenylamino group represented by R 131 may be substituted by one or more substituent groups selected from the group consisting of an alkyl group, an aryl group, an alkyl, or aryloxy group, a carboxyl group, an alkyl- or arylcarbonyl group, an alkyl- or aryloxycarbonyl group, an acyloxy group, a sulfamoyl group, a carbamoyl group, a sulfonamido group, an acylamino group, an imido group, a sulfonyl group, a hydroxy group, a cyano group and halogen.
• substituent groups selected from the group consisting of an alkyl group, an aryl group, an alkyl, or aryloxy group, a carboxyl group, an alkyl- or arylcarbonyl group, an alkyl- or aryloxycarbony
• R 133 and R 132 may combine together to form a 5-membered to 7-membered ring.
• Preferred examples of such rings include an oxyindole ring, a 2-oxobenzimidazoline ring and a carbostyryl ring.
• Z 131 is a hydrogen atom or a group which is eliminated on coupling (a coupling eliminable group).
• groups which are eliminated on coupling include a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, a sulfonyloxy group, an amido group, an alkoxycarbonyloxy group, an aryloxycar- bonyloxy group, an aliphatic or aromatic thio group, a heterocyclic thio group, an imido group, an N-substituted heterocyclic ring and an aromatic azo group.
• These groups may contain photographically useful groups.
• a dimer or polymer may be formed by R 131 , R 132 or Z 131 in the formula (VII).
• couplers having the formula (VII) couplers where R 132 is an alkyl group having from 2 to 4 carbon atoms and couplers where R 132 is a phenoxy-substituted alkanamido when R 132 is an acylamino group are preferred.
• R 132 and R 133 combine together to form a ring, 5-membered oxyindole ring couplers are preferred.
• Suitable alkyl groups represented by R 134 are a straight chain, branched or cyclic alkyl group having from 1 to 32 carbon atoms, suitable aryl groups are an aryl group having from 6 to 42 carbon atoms and suitable heterocyclic groups are a 4-membered to 7-membered ring containing at least one of oxygen, nitrogen and sulfur atoms. These groups may be optionally substituted by substituent groups already described above for R 131 in the formula (VII).
• Z 131 is a hydrogen atom or a group which is eliminated on coupling and as defined above for Z 131 in the formula (VII).
• a dimer or polymer may be formed by R 134 , R 135 , R136 or Z 131 in the formula (VIII).
• couplers having the formula (VIII) Of the couplers having the formula (VIII), couplers where R 136 is a hydrogen atom, p is 1, and R 135 is an acyl group or an alkoxycarbonyl group are particularly preferred.
• the couplers having the formula (VII) are compared with the couplers having the formula (VIII), the couplers having the formula (VII) are preferable for the purpose of the present invention.
• couplers having the formulae (VII) and (VIII) which can be used in the present invention include, but are not limited to, the following compounds.
• Couplers having the formula (VII) or (VIII) are described in U.S. Patents 2,801,171, 2,895,862 and 3,772,002, JP-A-59-124341, JP-A-58-105229, JP-A-60-24547, JP-A-60-237448, JP-A-61-39045 and JP-A-6 1 -77245.
• these couplers are used in an amount of generally 0.01 to 2.0 mol, preferably 0.1 to 1.0 mol, per mol of silver halide.
• Couplers having the formula (V), (VI), (VII) or (VIII) can be dispersed in hydrophilic colloids by dissolving them in high boiling organic solvents (e.g., phthalic esters, phosphoric acid esters, fatty acid esters, etc.).
• organic solvents e.g., phthalic esters, phosphoric acid esters, fatty acid esters, etc.
• silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride can be used as the silver halide in the photographic emulsion layers of the photographic material of the present invention.
• the silver halide grains of the present invention may be regular grains having a regular crystal form such as that of a cube, an octahedron or a tetradecahedron, irregular grains having an irregular crystal form such as that of a sphere, grains having crystalline defects such as a twin plane, or grains having a composite form thereof.
• a mixture of gains having various crystal forms may be used, if desired.
• the silver halide grains may have such a wide grain size range of fine grains having a grain size of not greater than about 0.1 u.m to large sized grains having a projected area diameter of about 10 um.
• a monodisperse emulsion having a narrow grain size distribution or a polydisperse emulsion having a wide grain size distribution may be used.
• Silver halide photographic emulsions which can be used in the present invention can be prepared by conventional methods, for example, the methods described in Research Disclosure, Vol. 176, No. 17643, pages 22 and 23 (December, 1978), "I. Emulsion Preparation and Types", and ibid., Vol. 187, No. 18716, page 648 (November, 1979).
• the photographic emulsions of the present invention can be prepared according to the methods described in P. Glafkides, Chimie et Physique Photographique (Paul Montel, 1967), G.F. Duffin, Photographic Emulsion Chemistry (Focal Press, 1966) and V.L. Zelikman et al., Making and Coating Photographic Emulsion (Focal Press, 1964). Namely, any of an acid process, a neutral process and an ammonia process can be used. A soluble silver salt and a soluble halogen salt can be reacted in accordance with a single jet process, a double jet process or a combination thereof. A reverse mixing method in which grains are formed in the presence of excess silver ion can also be used.
• a controlled double jet process in which the pAg in a liquid phase in which the silver halide is formed is maintained constant can be used. According to this method, a silver halide emulsion in which crystal form is regular and grain size is approximately uniform can be obtained.
• Physical ripening can be carried out in the presence of conventional solvents for silver halide (for example, ammonia and potassium rhodanide or thioethers or thione compounds described in U.S. Patent 3,271,157, JP-A-51-12360, JP-A-53-82408, JP-A-53-144319, JP-A-54-100717 or JP-A-54-155828).
• solvents for silver halide for example, ammonia and potassium rhodanide or thioethers or thione compounds described in U.S. Patent 3,271,157, JP-A-51-12360, JP-A-53-82408, JP-A-53-144319, JP-A-54-100717 or JP-A-54-155828.
• Silver halide emulsions comprising the above-described regular grains can be obtained by controlling the pAg and the pH during the formation of the grains. These methods are described in, for example, Photographic Science and Engineering, Vol. 6, pages 159 to 165 (1962), Journal of Photographic Science, Vol. 12, pages 242 to 251 (1964), U.S. Patent 3,665,394 and British Patent 1,413,748.
• Typical examples of monodisperse emulsions which can be used in the present invention include emulsions comprising silver halide grains having a mean grain size of not smaller than about 0.05 u.m wherein at least 95 wt% thereof comprises grains having a grain size within ⁇ 40% of the mean grain size. Further, emulsions comprising grains having a means grain size of 0.15 to 2 u.m wherein at least 95 wt% of the grains or at least 95% of the number of the grains comprises grains having a grain size within means grain size ⁇ 20% can be used. Methods of preparing such emulsions are described in U.S. Patents 3,574,628 and 3,655,394 and British Patent 1,413,748.
• Monodisperse emulsions as described in JP-A-48-8600, JP-A-51-39027, JP-A-51-83097, JP-A-53-137133, JP-A-54-48521, JP-A-54-99419, JP-A-58-37635 and JP-A-58-49938 are preferably used.
• tabular (plate-form) grains having an aspect ratio of 5 or more can be used in the present invention.
• These tabular grains can be easily prepared by methods described in Gutoff, Photographic Science and Engineering, Vol. 14, pages 248 to 257 (1970), U.S. Patents 4,434,226, 4,414,310, 4,433,048 and 4,439,520 and British Patent 2,112,157.
• U.S. Patent 4,434,226 discloses that when tabular grains are used, there are the advantages that covering power is increased and the color sensitizing efficiency of sensitizing dyes is improved.
• Grains whose crystals form is controlled using sensitizing dyes or certain additives during the formation of grains also can be used.
• the crystal structure may be uniform or a different halogen composition may exist between the interior of grain and the surface thereof.
• the crystal structure may be a laminar structure. These grains are disclosed in British Patent 1,027,146, U.S. Patents 3,505,068 and 4,444,877 and JP-A-60-143331. Silver halide grains having different halogen compositions may be joined together by epitaxial bonding. Silver halide grains may be joined to compounds other than silver halide such as silver rhodanide and lead oxide. These grains are described in U.S. Patents 4,094,684, 4,142,900 and 4,459,353, British Patent 2,038,792, U.S. Patents 4,349,622, 4,395,478, 4,433,501, 4,463,087, 3,656,962 and 3,852,067 and JP-A-59-162540.
• Grains having an internal latent image type grain structure formed by forming sensitivity specks (e.g., Ag 2 S, Agn, Au, etc.) on the surface of crystal by chemical ripening and then growing silver halide around the specks can be used.
• sensitivity specks e.g., Ag 2 S, Agn, Au, etc.
• Cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts thereof, rhodium salts or complex salts thereof, iron salts or complex salts thereof may be present during the formation of the silver halide grains.or during physical ripening.
• the emulsions of the present invention may be a surface latent image type emulsion wherein a latent image is mainly formed on the surfaces of the grains, or an internal latent image type emulsion wherein a latent image is mainly formed in the interior of the grains.
• direct reversal emulsions may be used.
• the direct reversal emulsions may be any of a solarization type, an internal latent image type, a light fogging type and a type using a nucleating agent. A combination of these types of emulsions can also be used.
• an internal latent image type emulsion which was previously not fogged be used and fogged by light before or during processing or by using a nucleating agent to obtain a direct positive image.
• Internal latent image type silver halide emulsions previously not fogged which can be used in the present invention are emulsions in which the surfaces of silver halide grains are previously not fogged and which comprise silver halide grains in which a latent image is predominantly formed in the interior of the grains. More specifically, these emulsions have the following properties.
• a transparent support is coated with a given amount of the silver halide emulsion and the coated support is exposed for a fixed period of 0.01 to 10 seconds to prepare a sample.
• the emulsion has properties such that the maximum density obtained by developing the sample in the following Developing Solution A (internal developing solution) at 20*C for. 60 minutes and measuring the maximum density by a conventional photographic density measuring method is preferably at least 5 times, more preferably 10 times, the maximum density obtained by developing the sample in the following Developing Solution B (surface developing solution) at 18° C for 5 minutes and measuring the maximum density.
• Examples of internal latent image type emulsions include conversion type silver halide emulsions as described in British Patent 1,011,062 and U.S. Patents 2,592,250 and 2,456,942 and core/shell type silver halide emulsions.
• Examples of core/shell type silver halide emulsions include emulsions as described in JP-A-47-32813, JP-A-47-32814, JP-A-52-134721, JP-A-52-156614, JP-A-53-60222, JP-A-53-66218, JP-A-53-66727, JP-A-55-127549, JP-A-57-136641, JP-A-58-70221, JP-A-59-208540, JP-A-59-216136, JP-A-60-107641, JP-A-60-247237, JP-A-61-2148, JP-A-61-3137, JP-B-56-18939, JP-B-58-1412, JP-B-58-1415, JP-B-58-6935, JP-B-58-108528, JP-A-62-194248, U.S.
• Soluble silver salt can be removed from the emulsions before or after physical ripening by water washing with noodle, flocculation precipitation method or ultrafiltration.
• the emulsions of the present invention are generally subjected to physical ripening, chemical ripening and spectral sensitization and then used. Additives for these stages are described in Research Disclosure, No. 17643 (December, 1978) and ibid., No. 18716 (November, 1979) and are shown in the following Table.
• color couplers can be used to form direct positive color image in the present invention.
• the color couplers are compounds which are coupled with the oxidation product of aromatic primary amine color developing agents to form or release a dye which is substantially nondiffusing. It is preferred that the color couplers themselves are nondiffusing compounds.
• Typical examples of useful color couplers include naphthol or phenol compounds, pyrazolone or pyrazoloazole compounds and cyclic or heterocyclic ketomethylene compounds. Examples of these cyan, magneta and yellow couplers which can be used in the present invention include compounds as described in Research Disclosure, No. 17643, page 25, Item VII-D (December, 1978), ibid., No. 18717 (November, 1979), JP-A-62-215272 and the patent specifications cited therein.
• Couplers couplers whose forming dye is appropriately diffusing, non-color-forming couplers, DIR couplers which release restrainers by coupling reaction and polymerized couplers can be used to correct unnecessary absorption in the region of short wavelength which the formed dye has.
• Gelatin is advantageous as a binder or protective colloid which can be used for the emulsion layers and intermediate layers of the photographic material of the present invention.
• other hydrophilic colloids can be used.
• the photographic material of the present invention may contain antifogging agents and color mixing inhibitors. Typical examples thereof are described in JP-A-62-215272 (pages 185 to 193).
• Supersensitizing agents can be used in the present invention to improve the color forming properties of the couplers.
• Typical examples of such compounds include those described in JP-A-62-215272 (pages 121 to 125).
• Couplers which release photographically useful residues on coupling can be used in the present invention.
• Preferred DIR couplers which release restrainers are described in the patent specifications cited in RD, 17643, Item VII-F, JP-A-57-151944, JP-A-57-154234, JP-A-60-184248 and U.S. Patent 4,248,962.
• the couplers of the present invention can be incorporated in the photographic material using conventional dispersion methods.
• the photographic material of the present invention may contain dyes for preventing irradiation and halation, ultraviolet light absorbers, plasticizers, fluorescent brighteners, matting agents, aerial fog inhibitors, coating aids, hardening agents, antistatic agents, slipperiness improvers and development accelerators in addition to the dyes described above.
• dyes for preventing irradiation and halation ultraviolet light absorbers, plasticizers, fluorescent brighteners, matting agents, aerial fog inhibitors, coating aids, hardening agents, antistatic agents, slipperiness improvers and development accelerators in addition to the dyes described above.
• Typical examples of these additives are described in Research Disclosure, No. 17643, Item VIII-XIII, pages 25 to 27 (December, 1978) and ibid., No. 18716, pages 647 to 651 (November, 1979).
• Multilayer color photographic materials comprise generally at least one of each of a red-sensitive emulsion layer, a green-sensitive emulsion layer and a blue-sensitive emulsion layer provided on a support.
• the order of these layers may be arbitrarily changed.
• these layers are arranged in order of a red-sensitive layer, a green-sensitive layer and a blue-sensitive layer from the support or in order of a green-sensitive layer, a red-sensitive layer and a blue-sensitive layer from the support.
• Each emulsion layer may comprise two or more layers having different sensitivity.
• a nonsensitive layer may be interposed between two or more emulsion layers having the same color sensitivity.
• the red-sensitive layer contains a cyan-forming coupler
• the green-sensitive emulsion layer contains a magenta-forming coupler
• the blue-sensitive emulsion layer contains a yellow- forming coupler.
• auxiliary layers such as a protective layer, an intermediate layer, a filter layer, an antihalation layer, a back layer, a white color reflecting layer, etc., in addition to the silver halide emulsion layers.
• the photographic emulsion layers and other layers of the photographic material of the present invention are coated on a support as described in Research Disclosure, No. 17643, Item V-VII, page 28 (December, 1978), European Patent 0102253 or JP-A-61-97655. Further, coating methods as described in Research Disclosure, No. 17643, Item XV, pages 28 and 29 can be used.
• the present invention can be applied to various color photographic materials.
• the present invention can be used in the fields of color reversal papers, color autopositive papers, color reversal films, color autopositive films, color diffusion transfer reversal papers (films), silver dye bleach process (film/papers), and dry silver color papers (films).
• the fogging treatment is carried out using a light fogging method and/or a chemical fogging method.
• Overall surface exposure that is, fogging exposure in the light fogging method, is carried out after imagewise exposure and/or during development.
• the imagewise exposed photographic material is exposed in a developing solution, or immersed in the previous bath of the developing solution. Alternatively, the imagewise exposed material is removed from these solutions and exposed before the material is dried. It is most preferred that the exposure be conducted in the developing solution.
• Any light sources within the light-sensitive wavelengths of the photographic materials can be used as a light source for the fogging exposure.
• a fluorescent lamp, a tungsten lamp, a xenon lamp, a sunlamp, etc. can be used.
• Specific methods are described in British Patent 1,151,363, JP-B-45-12710, JP-B-45-12709, JP-B-58-6936, JP-A-48-9727, JP-A-56-137350, JP-A-57-129438, JP-A-58-62652, JP-A-58-60739, JP-A-58-70223 (corresponding to U.S.
• Patent 4,440,851 and JP-A-58-120248 (corresponding to European Patent 89101 A2).
• Light sources having a high color rendering (near white color, if possible) as described in JP-A-56-137350 or JP-A-58-70223 are suitable for photographic materials with sensitivity to light in all wave ranges, for example, color photographic materials.
• the illuminance of light is in the range of 0.01 to 2,000 lux, preferably 0.05 to 30 lux, more preferably 0.05 to 5 lux. Lower illuminance is preferred for photographic materials containing higher sensitivity emulsions.
• the adjustment of illuminance may be made by changing the luminous intensity of the light source, reducing the intensity of light through filters or changing the distance between the photographic material and the light source or the angle therebetween. It is possible that the illuminance of the fogging light is increased continuously or stepwise from lower illuminance to higher.illuminance.
• the photographic material prefferably be immersed in the developing solution or a solution in the previous bath to thereby allow the solution to penetrate thoroughly into the photographic material and light irradiation is then conducted.
• the time taken for the light fogging exposure after the penetration of the solution is in the range of generally 2 seconds to 2 minutes, preferably 5 seconds to 1 minute, more preferably 10 seconds to 30 seconds.
• the exposure time for fogging is generally 0.01 second to 2 minutes, preferably 0.1 second to 1 minute, more preferably 1 second to 40 seconds.
• Nucleating agents which are used in the chemical fogging method can be incorporated in the photographic materials or in the processing solutions for the photographic materials in the present invention.
• nucleating agent refers to substances which react in the surface development of the internal latent image type silver halide emulsion previously not fogged to form a direct positive image. It is particularly preferred in the present invention that the fogging treatment be carried out by using the nucleating agents.
• the nucleating agents When the nucleating agents are incorporated in the photographic materials, it is preferred to add them to an internal latent image type silver halide emulsion. If desired, the agents may be added to other layers such as an intermediate layer, an undercoat layer and a back layer so long as the nucleating agents are diffused during coating or processing and allowed to be adsorbed by silver halide.
• nucleating agents When the nucleating agents are added to the processing solutions, they may be present in the developing solution or in a previous bath having a low pH as described in JP-A-58-178350.
• the nucleating agents may be used either alone or as a combination of two or more of them.
• Z 100 represents a nonmetallic atomic group required for the formation of a 5-membered or 6- membered heterocyclic group which may be optionally substituted;
• R 119 represents an aliphatic group;
• R 120 represents a hydrogen atom, an aliphatic group or an aromatic group;
• R 119 or R 120 may be optionally substituted;
• R 120 may combine together with the heterocyclic ring formed by Z 100 to form a ring; at least one of R 119 , R 120 and Z 100 has an alkynyl group, an acyl group, a hydrazine group or a hydrazone group, or R 119 and R 120 form a 6-membered ring to thereby form a dihydropyridinium skeleton; at least one of R 119 , R' 20 and Z 100 may have an accelerating group for adsorption to silver halide
• Examples of suitable compounds having the formula (N-I) include the following compounds.
• Examples of compounds having the formula (N-II) include the following compounds.
• the nucleating agents may be incorporated in the photographic materials or the processing solutions for the photographic materials. However, it is preferred for the nucleating agents to be incorporated in the photographic materials.
• the agents are added to the internal latent image type silver halide emulsion layers.
• the agents may be added to other layers, such as an intermediate layer, an undercoat layer and a back layer, so long as the nucleating agents are diffused during coating or processing and are adsorbed by silver halide.
• the agents may be present in the developing solution or the previous bath having a low pH as described in JP-A-58-178350.
• the agents are used in an amount of preferably 10- 8 to 10- 2 mol, particularly 10- 7 to 10- 3 mol per mol of silver halide.
• the agents are used in any amount of preferably 10- 5 to 10 -1 moliliter, more preferably 10 -4 to 10 -2 mol/liter.
• nucleating accelerators can be used in the present invention to accelerate the function of the nucleating agents.
• Tetraazaindenes, triazaindenes and pentaazaindenes, these indenes having at least one mercapto group which may be optionally substituted by an alkali metal or ammonium group can be used as the nucleating accelerators. Further, the compounds described in JP-A-63-106656 (pp. 6 to 16) can be used.
• nucleating accelerators examples include, but are not limited to, the following compounds.
• the nucleating accelerators may be incorporated in the photographic materials or the processing solutions. It is preferred for the nucleating accelerators to be incorporated in the internal latent image type silver halide emulsion layers or hydrophilic colloid layers (e.g., an intermediate layer, a protective layer) of the photographic materials. It is particularly preferred for the accelerators to be incorporated in the silver halide emulsion layers or layers adjacent thereto.
• the color developing solutions which can be used for the development of the photographic materials in the present invention are preferably aqueous alkaline solutions mainly containing aromatic primary amine color developing agents. Aminophenol compounds are useful as color developing agents and p-phenylenediamine 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-Q-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-S-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-,6-methoxyethylaniline and salts thereof such as sulfate, hydrochloride and p-toluenesulfonate. These compounds may be used either alone or as a combination of two or more of them.
• Black-and-white developing solutions may contain conventional developing agents, such as hydroquinones (e.g., dihydroxybenzenes), 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 as a combination of two or more of them.
• hydroquinones e.g., dihydroxybenzenes
• 3-pyrazolidones e.g., 1-phenyl-3-pyrazolidone
• aminophenols e.g., N-methyl-p-aminophenol
• 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 types of color photographic materials, but is usually not more than 3 liters per m 2 of the photographic material.
• the replenishment rate can be reduced to 500 ml or less when the concentration of bromide ion in the replenisher is reduced.
• the photographic emulsion layer is generally bleached.
• Bleaching may be carried out simultaneously with fixing (bleaching-fixing treatment) or they can be separately carried out.
• a bleaching-fixing treatment may be conducted to expedite processing.
• Treatment may be conducted with a bleach-fixing bath composed of two consecutive tanks. Fixing may conducted before the bleaching-fixing treatment.
• bleaching may be conducted depending on the purpose. Examples of bleaching agents include compounds of polyvalent metals such as iron(III), cobalt(III), chromium(VI) and copper(II), peracids, quinones and nitro compounds.
• fixing agents include thiosulfates, thiocyanates, thioether compounds, thioureas and various iodides.
• the thiosulfates are widely used as the fixing agents. Particularly, ammonium thiosulfate is most widely used. Sulfites, bisulfites and carbonyl bisulfite adducts are preferred as preservatives for the bleaching-fixing solutions.
• the positive working silver halide color photographic materials of the present invention are subjected to washing and/or stabilization stage after desilverization.
• the amount of rinsing water in the washing stage varies widely depending on the characteristics (e.g., depending on materials used such as couplers) of the photographic materials, use, the temperature of the rinsing water, the number of rinsing tanks (the number of stages), replenishing system (countercurrent, direct flow) and other conditions.
• the relationship between the amount of water and the number of rinsing tanks in the multistage 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).
• the color developing agents may be incorporated in the positive working silver halide color photographic materials of the present invention for the purpose of simplifying and expediting processing. It is preferred for precursors of color developing agents to be used when they are incorporated in the photographic materials.
• developing agents can be used for the development of black-and-white photographic materials in the present invention.
• the developing agents include polyhydroxybenzenes such as hydroquinone, 2-chlorohydroquinone, 2-methylhydroquinone, catechol and pyrogallol; aminophenols such as p-aminophenol, N-methyl-p-aminophenol and 2,4-diaminophenol; 3-pyrazolidones such as 1-phenyl-3-pyrazolidones, 1-phenyl-4,4 -dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone and 5,5-dimethyl-1-phenyl-3-pyrazolidone; and ascorbic acids. These compounds may be used either alone or as a combination of two or more of them.
• the developing solution described in JP-A-58-55928 can also be used.
• a paper support (thickness: 100 u.m, both sides thereof being laminated with polyethylene) was coated with the following first to fourteenth layers and the back thereof was coated with the following fifteenth and sixteenth layers to prepare a multilayer color photographic material.
• Polyethylene on the side of the first layer to be coated contained titanium oxide as a white pigment and a very small amount of ultramarine as a bluing dye (the chromaticity of the surface of the support was 88.0, -0.20, -0.75 in L * , a", b * , system).
• the following components in the following coating weights (unit: g/m 2 ) were used.
• the amount of silver halide is represented as a coating weight in terms -of silver.
• the emulsions used in each layer were prepared according to the method of preparation of Emulsion EMI.
• As the emulsion of the fourteenth layer a Lippmann emulsion which was not subject to surface chemical sensitization was used.
• aqueous solution of silver nitrate and potassium bromide were simultaneously added to an aqueous gelatin solution with vigorous stirring at 75 C over a period of 15 minutes to obtain octahedral silver bromide grains having a mean grain size of 0.40 ⁇ m.
• 0.3 g of 3,4-dimethyl-1,3-thiazoline-2-thione, 6 mg of -sodium thiosulfate and 7 mg of chloroauric acid (tetrahydrate) in order were added to the emulsion, each amount being per mol of silver.
• the emulsion was heated at 75°C for 80 minutes to carry out chemical sensitization.
• the thus-obtained grains were grown as a core under the same precipitation conditions as those initially used to obtain finally an octahedral monodisperse core/shell type silver bromide emulsion having a mean grain size of 0.7 ⁇ m.
• the coefficient of variation in grain size was about 10%.
• 1.5 mg of sodium thiosulfate and 1.5 mg of chloroauric acid (tetrahydrate) were added to the emulsion, each amount being per mol of silver.
• the emulsion was heated at 60°C for 60 minutes to carry out chemical sensitization, thus obtaining an internal latent image type silver halide emulsion.
• the replenishment system of rinsing water was a countercurrent system such that the rinsing bath (2) was replenished and overflow solution from the rinsing bath (2) was introduced in the rinsing bath (1).
• the amount of the bleaching-fixing solution brought over from the bleaching-fixing bath to the rinsing bath (1) was 35 ml/m 2 and the ratio of the replenishment rate of rinsing water to the amount of the bleaching-fixing solution brought over from the bleaching-fixing bath was 9.1.
• Each processing solution had the following composition.
• Tap water was passed through a mixed bed system column packed with an H-type strongly acidic cation exchange resin (Amberlite IR-120B, a product of Rohm & Haas Co.) and an OH-type anion exchange resin (Amberlite IR-400) to reduce the concentration of each of calcium ion and magnesium ion to 3 mg/liter or lower. Subsequently, sodium dichloroisocyanurate (20 mg / liter) and sodium sulfate (1.5 g/liter) were added thereto. The pH of the resulting solution was in the range of 6.5 to 7.5.
• H-type strongly acidic cation exchange resin Amberlite IR-120B, a product of Rohm & Haas Co.
• Amberlite IR-400 OH-type anion exchange resin
• Samples 2 to 10 were prepared in the same manner as in the preparation of Sample 1 except that the compounds of the present invention and comparative compound were used in combination with or in place of the irradiation preventing dyes of the Thirteenth Layer of Sample 1.
• the structures of Samples 2 to 10 are shown in Table 1 below.
• Macbeth color checker was photographed using a color negative film (SHR-100, a product of Fuji Photo Film Co., Ltd.) and printed on color paper (02A, a product of Fuji Photo Film Co., Ltd.) to prepare the original.
• the original was printed on each of Samples 1 to 10 by using a reflection type printer and development was carried out using the processing stages described above to prepare color prints.
• the density and color of the prints were adjusted so that a gray patch of neutral 5 of Macbeth color checker on the color paper original became a gray color having a density of 1.0 on the print.
• Corrective Munsell notation HVC values of color patches red, green and blue of Macbeth color chart on the resulting prints were measured.
• the C values are shown in Table 1 below. A higher C value means that the color of the sample is reproduced with higher saturation. It was confirmed that large and small values corresponded to the brightness of each color when prints were visually examined.
• a paper support (both sides thereof being laminated with polyethylene) was coated with the following first layer to twelfth layer to prepare a color photographic material (Sample 11).
• Polyethylene on the side of the first layer contained titanium white as a white pigment and a very small amount of ultramarine as a bluing dye.
• the following components in the following coating weights (unit: g/m 2 ) were used.
• the amounts of silver halide are represented as a coating weight in terms of silver.
• Samples 12 to 18 were prepared in the same manner as in the preparation of Sample 11 except that the compounds of the present invention were added.
• a Macbeth color checker was photographed using a coupler incorporated color reversal film RDP (a product of Fuji Photo Film Co., Ltd.) and the film was processed with CR-56P to obtain a color positive film which was then used as the color positive original.
• the original was printed on the color reversal paper of Samples 11 to 18 using subtractive color photography. Printing was adjusted using a YMC filter so that the gray color of neutral 5 of a Macbeth color checker became a gray color having a density of 1.0 on the print. Development was carried out in the stages described below.
• the HVC values of the Munsell notation were measured to examine the red, green and blue color reproducibility of the resulting image.
• the resulting C values are shown in Table 2 below.
• Samples 11 to 18 were exposed through plain glass by using a sensitometer (500 CMS, color temperature: 3,200 K) and processed. The cyan density of each of the resulting samples was measured using a Macbeth densitometer.
• the samples were processed with the following processing solutions in the following processing stages using an automatic processor until the accumulated replenishment rate of the processing solutions reached three times the tank capacity.
• the first rinsing stage and the third rinsing stage were a countercurrent rinsing system such that rinsing water was allowed to flow into the first rinsing (2), overflow solution therefrom was fed to the first rinsing (1), rinsing water was allowed to flow into the third rinsing (3), overflow solution therefrom was fed to the third rinsing (2) and overflow solution from the third rinsing (2) was fed to the third rinsing (1).
• Each processing solution had the following composition.
• Sample 19 was prepared in the same way as in Example 1 except that the compositions of the sensitive layers were modified in the following manner.
• Example 1 Each sample was subjected to a running test in the same manner as in Example 1 using the same processing solutions and stages as those in Example 1.
• Samples 20 to 27 were prepared in the same manner as in the preparation of Sample 19 except that the compounds of the present invention and comparative compounds were used in combination with or in place of the irradiation preventing dye of the Thirteenth Layer of Sample 19.
• the structures of Samples 19 to 27 are shown in Table 3 below.
• Samples 19 to 27 were exposed through an optical wedge using white light of 3,200 K.
• the exposed samples were processed in the manner described above.
• the relative sensitivity at an optical density of 1.0 and maximum density (Dmax) were measured.
• Samples 19 to 27 were stored at 50 C and RH of 80% for 3 days. Samples 19 to 27 were stored in a refrigerator at 0° C for the same period of time. These samples were exposed and developed in the same manner as those described above. The relative sensitivity of each sample (stored at 50 C and RH of 80%) to the sensitivity of each sample (stored in the refrigerator) was determined.
• the samples of the present invention have high Dmax values and scarcely cause deterioration (reduction in sensitivity) during photographic material storage conditions as compared with the comparative samples. Further, the samples of the present invention show high C values and have excellent color reproducibility as compared with the comparative samples.
• Sample 28 was prepared in the same manner as in Example 1 except that C-2, C-9 (a ratio of 1/1) as cyan couplers in an amount of 0.30 g/m 2 were used for the Third and Fourth Layers, Cpd-18, Cpd-19, Cpd-20, Cpd-21 (a ratio of 10/10/14/16) as irradiation preventing dyes in an amount of 0.05 g/m 2 were used for the Thirteenth Layer and Fifteenth Layer contained no dye.
• Example 1 Each sample was subjected to a running test in the same manner as in Example 1 using the same processing stages and processing solutions as those in Example 1.
• Samples 29 to 36 were prepared in the same manner as in the preparation of Sample 28 except that the compounds of the present invention and the comparative compounds were used in combination with or in place of the irradiation preventing dye of the Thirteenth Layer of Sample 28.
• Samples 28 to 36 are shown in Table 4 below. The samples were tested in the same manner as in Example 1 to evaluate color reproducibility.
• Sample 37 was prepared in the same manner as in Example 1 except that the Thirteenth Layer contained no irradiation preventing dye and. the Fifteenth Layer contained no dye.
• Example 1 This sample was subjected to a running test in the same manner as in Example 1 using the same processing stages and processing solutions as those in Example 1.
• Samples 38 to 46 were prepared in the same manner as in the preparation of Sample 37 except that the dyes of the present invention and comparative compound were added to the Thirteenth Layer, these dyes and comparative compound being shown in Table 5 below. These samples were processed in the same manner as in Sample 37.

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• 1989
  • 1989-09-22 EP EP19890117586 patent/EP0360289A3/fr not_active Withdrawn

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