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
  • G03C7/32—Colour coupling substances
  • G03C7/34—Couplers containing phenols
  • G03C7/342—Combination of phenolic or naphtholic couplers

Definitions

• the present invention relates to silver halide col­or photographic materials and, more particularly, to silver halide color photographic materials which contain a specific combination of cyan couplers.
• a silver image is pro­duced by means of an aromatic primary amino-type devel­oper compound in the presence of color couplers which react with the oxidized developing substance to form a dye in the areas corresponding to the silver image.
• light sensitive color photographic materials which include, coated on a support, one or more red-sensitive silver halide emulsion layers, one or more green-sensitive silver halide emulsion layers, and one or more blue-sensitive silver halide emulsion layers, each layer comprising color couplers, wherein upon color development cyan, magenta and yellow dye images are re­spectively formed.
• couplers used to produce cyan image dyes gener simplyally derive from phenols and naphthols (as described, for example, in US patents 2,367,351, 2,423,730, 2,474,293, 2,772,161, 2,772,162, 2,895,826, 2,920,961, 3,002,836, 3,466,622, 3,476,563, 3,880,661, 3,996,253, 3,758,308, in FR patents 1,478,188 and 1,479,043, and in GB patent 2,070,000).
• These types of couplers can be used either in photographic layers or in the processing baths. In the former case, when it is desired that they do not migrate from a layer into another, they can have ballasting substituents.
• couplers can bear also hydrophilic or hydrophobic substituents if they must be introduced into photographic layers, respectively, dissolved in water or in an organic solvent.
• such couplers Upon reaction with the oxidation products of the aromatic primary amino-type developing agents, such couplers give indoaniline dyes with consumption of four equivalents of silver ions per mole of dye and, preferably, two equivalents of silver ions per mole of dye when the reactive methine group (in the para position to the phenolic hydroxylic group) is substituted with atoms or groups which are split off during the coupling reaction.
• naphthol cyan couplers have been used in the red sensitive layers of silver halide photograph­ic materials because they give a cyan dye, formed by the reaction with an oxidized product of a color developing agent, having absorptions at longer wavelength region respect to dyes given by phenol type couplers, that be­ing preferred in connection with color reproduction.
• cyan couplers for use in color photography, said combination comprising cyan cou­plers having the following Formula (I) and cyan couplers having the following Formula (II): wherein R1 is an aryl group, R2 is an alkyl group or an aryl group, R3 is a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group, and Z1 is a hydrogen atom, a halogen atom or a group which can be split off by the reaction of said coupler with the oxidized pro­duct of an aromatic primary amine-type color developing agent, wherein A is a -NHCO- group or a -CONH- group, R4 is an alkyl group, R5 is an alkyl group, R6 is a hydrogen at­om, a halogen atom, an alkyl group or an alkoxy group or R5 and R6 can combine to form a benz
• Such a combination of cyan couplers when associat­ed with silver halide color photographic materials, gives high sensitivity and, upon coupling with the oxi­dized aromatic primary amine-type color developing agents, cyan indoaniline dyes very stable to light, heat and humidity. They are also stable to bleaching solu­tions which have a weak oxidation power or are exhaust­ed.
• the present invention relates to a silver halide color photographic material comprising a support having coated thereon one or more silver halide emulsion lay­ers, wherein at least one of said layers comprises in combination at least one of the cyan couplers having the following Formula (I) and at least one of the cyan cou­plers having the following Formula (II): wherein R1 is an aryl group, R2 is an alkyl group of up to 20 carbon atoms (such as methyl, ethyl, butyl, do­decyl, etc.) or an aryl group of up to 20 carbopn atoms, R3 is a hydrogen atom, a halogen atom (such as fluorine, bromine, chlorine, etc.), an alkyl group of up to 20 carbon atoms (such as methyl, ethyl, butyl, dodecyl, etc.) or an alkoxy group of up to 20 carbpn atoms (such as methoxy,
• the aryl group represented by R1 of Formula (I) is, e.g., a phenyl group, a naphthyl group, or other aryl group of up to 30 carbon atoms, and preferably is a phenyl group.
• This group is allowed to have a single substituent or a plurality of substituents; for example, typical substituents introducible to the aryl group in­clude halogen atoms (such as fluorine, chlorine, bro­mine, etc.), alkyl groups (such as methyl, ethyl, propyl, butyl, dodecyl, etc.), hydroxyl group, cyano group, nitro group, alkoxy groups (such as methoxy, ethoxy, etc.), alkylsulfonamido groups (such as methyl­sulfonamido, octylsulfonamido, etc.), arylsulfonamido groups (such as phenylsulfonamido, naphthylsulfonamido, etc.), alkylsulfamoyl groups (such as butylsulfamoyl), arylsulfamoyl (such as phenyl
• the preferred group represented by R1 is a phenyl group, the more pre­ferred is a phenyl group having one or more substituents including halogen atoms and cyano groups.
• alkyl group inherently includes the basic group and that group with conventional substitution.
• moiety inherently describes a chemical compound or substituent, only an unsubstituted chemical material is intended to be included.
• alkyl group inherently includes not only alkyl moieties as methyl, ethyl, octyl, dodecyl, etc., but also such moieties bearing sustituent groups such as halogen, cyano, hydroxyl, nitro, amine, carboxylate, etc.
• alkyl moiety in­cludes only methyl, ethyl, octyl, dodecyl, etc.
• the preferred cyan cou­plers having Formula (I) are the compounds having the following Formula (III): wherein X1 is a hydrogen atom, a halogen atom or a mono­valent organic group, R7 is a hydrogen atom or a substi­tuent exemplified by a halogen atom (such as fluorine, bromine, chlorine, etc.), a hydroxyl group, a nitro group, an alkyl group of up to 20 carbon atoms (such as methyl, ethyl, iso-propyl, tert.-butyl, n-octyl, n-do­decyl, etc.), an alkyloxycarbonyl group (such as methyl­oxycarbonyl), an aryloxycarbonyl group (such as phenyl­oxycarbonyl), an alkoxy group of up to 20 carbon atoms (such as methoxy, ethoxy, etc.), an aryl
• Examples of monovalent organic group represented by X1 include a halogen atom (such as fluorine, chlorine, bromine, etc.), a nitro group, an amino group, a cyano group, a hydroxy group, a carboxy group, an alkyl group (such as methyl, ethyl, propyl, isopropyl, t-butyl, octyl, etc.), an aralkyl group (such as benzyl, phen­ethyl, etc.), an alkoxy group (such as methoxy, ethoxy, benzyloxy, etc.), an aryloxy group (such as phenoxy, p-nitrophenoxy, etc.), an acylamino group (such as acetylamino, propionylamino, benzoylamino, phenoxy­acetylamino, etc.), a carbamoyl group (such as methyl­carbamoyl, dimethylcarbam
• the more preferred cyan couplers having Formula (I) are the compounds having the following formula (V): wherein X2 is a hydrogen atom or a halogen atom (such as fluorine, chlorine, bromine, etc.), R13 is a hydrogen atom or an alkyl group of up to 20 carbon atoms (such as methyl, ethyl, propyl, butyl, octyl, dodecyl, etc.), R14 and R15 may be either the same or different and each is a hydrogen atom, an alkyl group of up to 20 carbon atoms (such as methyl, ethyl, butyl, dodecyl, etc.) or an alkoxy group of up to 20 carbon atoms (such as methoxy, ethoxy, etc.), provided that the sum of carbon atoms of R13, R14 and R15 is from 8 to 20, p is an integer of 0 to 2, and Z5 is a hydrogen atom or a chlorine
• the preferred cyan cou­plers having Formula (II) are the compounds having the following Formula (IV): wherein A is a -NHCO- group or a -CONH- group, R9 is a branched-chain or a straight chain alkylene group, R10 is a hydrogen atom or a substituent of the type de­scribed for R7 of Formula (III), X is an oxygen atom or a sulfur atom, R11 is an alkyl group of up to 20 carbon atoms (such as methyl, ethyl, propyl, butyl, dodecyl, etc.) R12 is a hydrogen atom, a halogen atom (such as fluorine, chlorine, bromine, etc.) or an alkyl group of up to 20 carbon atoms (such as methyl, ethyl, propyl, butyl, dodecyl, etc.) or R11 and R12 can combine to form a benzene ring, 1 is
• the more preferred cyan couplers having Formula (II) in the present invention include those compounds having the following Formula (VI): wherein R16 and R17 may be either the same or different and each is a hydrogen atom, an alkyl group of up to 20 carbon atoms (such as methyl, ethyl, propyl, butyl, pentyl, dodecyl, etc.) or an alkoxy group of up to 20 carbon atoms (such as methoxy, ethoxy, etc.), R18 is a hydrogen atom or an alkyl group of up to 20 carbon atoms (such as methyl, ethyl, propyl, butyl, pentyl, dodecyl, etc.), provided that the sum of carbon atoms of R16, R17 and R18 is from 8 to 20, R19 is an alkyl group of 1 to 2 carbon atoms (such as methyl or ethyl), q is an integer of 0 to 2, and Z6 is a hydrogen atom
• os such groups include, for example, alkoxy groups, aryloxy groups, arylazo groups, thiether, carbamoyloxy groups, acyloxy groups, imido groups, sulfonamido groups, thio­cyano group or heterocyclic groups (such as oxazolyl, diazolyl, triazolyl, tetrazolyl, etc.), and the like.
• the particularly preferred examples represented by Z are a hydrogen atom or a chlorine atom.
• the cyan couplers used in combination according to the present invention are incorporated in a silver halide emulsion layer of the color photographic materi­al.
• the skilled in the art knows that, if the cyan cou­plers are incorporated into the silver halide emusion layer, they are, in most instances, required not to dif­fuse within the layers themselves.
• a group bearing a ballasting group such as a hydrophobic residue with 8 to 20 carbon atoms is introduced into the coupler molecules in order to avoid said diffusing process.
• ballasting group is linked, di­rectly or through one or more of imino, ether, carbon­amido, sulfonamido, ureido, ester, imido, carbamoyl, sulfamoyl, phenylene, etc. groups, to the coupler mole­cule.
• ballasting group is preferably comprised by the group R2 of Formula (I) and R4 of Formula (II).
• ballasting groups are illustrated in US pat­ent 4,009,038, in European patents 87,930, 84,100, 87,931, 73,146, 88,563, in German patents 3,300,412, 3,351,012, in Japanese patents J5 8033248, J5 8033250, J58031334, J5 8106539.
• ballasting groups comprise alkyl chains, the total carbon atoms of which are from 8 to 20.
• the cyan couplers of Formula (I) and (II) can read­ily be synthesized by use of methods well known in the art such as described, for example, in US Patents 3,758,308, 4,333,999 and 4,451,559 for couplers of For­mula (I) and in US patents 2,369,929 and 3,772,002 for couplers of Formula (II).
• cyan couplers represented by the Formulas (I) and (II) are illustrated below, but the present invention is not limited thereby.
• the silver halide color photographic materials of the present invention comprise at least one blue-sen­sitive silver silver halide emulsion layer, at least one green-sensitive silver halide emulsion layer and at least one silver-halide red-sensitive silver halide emulsion layer, said layers being associated with yel­low, magenta and cyan dye-forming couplers.
• the word "associated" means that the cyan dye-­forming couplers according to the present invention and the silver halide emulsions are positioned in such a way as to image-wise produce in the photographic layers upon coupling with the oxidized aromatic primary amine-type developing agents very stable cyan indoaniline dyes.
• Such cyan couplers may be incorporated in the silver halide emulsion layers, in an adjacent layer or in the processing solutions. In a preferred form, the cyan cou­plers are incorporated in the silver halide emulsion layer.
• the silver halide emulsion layer com­prising the combination of cyan couplers of general For­mula (I) and (II) described above is a red-sensitive silver halide emulsion layer.
• the couplers of Formula (I) and (II) can be used in an arbitrary proportion in the combination thereof, but it is desirable that the cyan coupler of Formula (I) is used in an amount of from 10 to 90 mol % based on the total amount of said cou­plers in the silver halide emulsion layer, and more preferably from 25 to 85 mol %.
• said cyan couplers of Formula (I) and (II) are present in a total amount of from about 6.5x10 ⁇ 3 to about 80x10 ⁇ 3 mol per mol of silver halide contained in said silver halide emulsion layer, and preferably from about 13.5x10 ⁇ 3 to about 53.5x10 ⁇ 3 mol per mol of silver halide.
• the couplers of the present invention can be incorporated into the silver halide emulsion layer by the dispersion technique, which consists of dissolving the coupler in a water-immiscible high-boiling organic solvent and then dispersing such a solution in a hydro­philic colloidal binder under the form of very small droplets.
• the preferred colloidal binder is gelatin, even if some other kinds of binders can be used.
• Another type of introduction of the couplers into the silver halide emulsion layer consists of the so-­called "loaded-latex technique".
• a detailed description of such technique can be found in BE patents 853,512 and 869,816, in US patents 4,214,047 and 4,199,363 and in EP patent 14,921. It consists of mixing a solution of the couplers in a water-miscible organic solvent with a polymeric latex consisting of water as a continous phase and of polymeric particles having a mean diameter rang­ing from 0.02 to 0.2 micrometers as a dispersed phase.
• couplers having a water-soluble group such as a carboxyl group, a hydroxy group, a sulfonic group or a sulfonamido group, can be added to the photographic layer for example by dissolv­ing them in an alkaline water solution.
• the cyan couplers of the combination of the present invention are generally incorporated into a red-sensi­tive silver halide emulsion layer to form one of the differently sensitized silver halide emulsion layers of a multilayer color photographic material.
• Such material generally comprises a support base having coated thereon one or more red-sensitive silver halide emulsion layers, one or more green-sensitive silver halide emulsion lay­ers, one or more blue-sensitive silver halide emulsion layers and additionally filter layers, interlayers, pro­tective layers and sub-layers.
• the layer units can be coated in any conventional order, but in a preferred layer arrangement the red-sensitive layes are coated nearest the support and are overcoated by the green-sen­sitive layers, a yellow filter layer and the blue-sensitive layers.
• the red-sensitive silver halide emulsion layer associated according to this invention with the combination of the cyan couplers of Formulae (I) and (II), is composed of two or more silver halide emulsion layers sensitized to the same spectral region of the visible spectrum, the uppermost silver halide emulsion layer of which having the highest sensitivity and the lowermost silver halide emulsion layer having the lowest sensitivity, as described in GB patent 923,045, in FR patent 2,043,433 and in US patent 4,582,780.
• the uppermost red-sensitive silver halide emulsion layer having the highest sensi­tivity comprises the combination of the cyan couplers of Formulae (I) and (II), the other red-sensitive silver halide emulsion layers comprising the cyan couplers of Formula (I).
• the sensitive layers are each associated with at least one image dye forming compound.
• Incorporated dye forming couplers constitute exemplary preferred image-­dye providing compounds.
• the blue, green and red-respon­sive layers preferably contain yellow, magenta and cyan image-dye providing couplers, respectively.
• yellow-forming couplers are conven­tional open-chain ketomethylene type couplers. Particu­lar examples of such couplers are benzoylacetanilide type and pivaloyl acetanilide type compounds. Yellow-­forming couplers that can be used are specifically de­scribed in US patents 2,875,057, 3,265,506, 3,408,194, 3,551,151, 3,682,322, 3,725,072 and 3,891,445, in DE patents 2,219,917, 2,261,361 and 2,414,006, in GB patent 1,425,020, in JP patent 10,783/76 and in JP patent ap­plications 26,133/72, 73,147/73, 102,636/76, 6,341/75, 123,342/75, 130,442/75, 1,827/76, 87,650/75, 82,424/77 and 115,219/77.
• magenta-forming couplers are con­ventional pyrazolone type compounds, indazolone type compounds, cyanoacetyl compounds, pyrazoletriazole type compounds, etc, and particularly preferred couplers are pyrazolone type compounds.
• Magenta-forming couplers are described for example in US patents 2,600,788, 2,983,608, 3,062,653, 3,127,269, 3,311,476, 3,419,391, 3,519,429, 3,558,319, 3,582,322, 3,615,506, 3,834,908 and 3,891,445,in DE patent 1,810,464, in DE patent ap­plications 2,408,665, 2,417,945, 2,418,959 and 2,424,467 and in JP patent applications 20,826/76, 58,922/77, 129,538/74, 74,027/74, 159,336/75, 42,121/77, 74,028/74, 60,233/75, 26,541/76 and 55,122/78.
• Colored couplers can be used which include those described for example in US patents 3,476,560, 2,521,908 and 3,034,892, in JP patent publications 2,016/69, 22,335/63, 11,304/67 and 32,461/69, in JP patent appli­cations 26,034/76 and 42,121/77 and in DE patent appli­cation 2,418,959.
• DIR (Development Inhibitor Releasing) couplers can be used which include those described for example in US patents 3,227,554, 3,617,291, 3,701,783, 3,790,384 and 3,632,345, in DE patent applications 2,414,006, 2,454,301 and 2,454,329, in GB patent 953,454, in JP patent applications 69,624/77, 122,335/74 and 16,141/76.
• DIR couplers In addition to DIR couplers, some other compounds which release development inhibitors upon development can also be present in the light-sensitive material. Such kind of DIR compounds is described for example in US patents 3,297,445 and 3,379,529, in DE patent appli­cation 2,417,914, in JP patent applications 15,271/77 and 9,116/78.
• Couplers described above can be incorporated in the same layer, or the same cou­pler can also be present in two or more layers.
• Said couplers can be introduced into the silver halide emulsion layers of the photographic materials by using some of the methods described above. Moreover, said couplers are made non-diffusing by means of the above described ballasting groups.
• the present invention is not limited to photograph­ic materials with a particular type of emulsion or sil­ver halides. It can therefore find an application with photographic materials containing different types of emulsions or silver halides, such as for example those described in Research Disclosure 17643, I, December 1978.
• the emulsions which can be used in the present in­vention can be chemically and optically sensitized as described in Research Disclosure 17643, III and IV, De­cember 1978. They can contain optical brighteners, anti­fogging agents and stabilizers, filtering and antihalo dyes, hardeners, coating aids, plasticizers and lubri­cants and other auxiliary substances as described for example in Research Disclosure 17643, V, VI, VIII, X, XI and XII, December 1978.
• the layers of the photographic material can contain various colloids, alone or in combination, such as bind­ing materials, as for example described in Research Dis­closure 17643, IX, December 1978.
• the photographic materials which can be used in the present invention can contain orthochromatic or panchro­matic emulsions, as well as unsensitized emulsions. In particular and more preferably, they can be emulsions for color photography as described in Research Disclo­sure 17643, VII, December 1978.
• Such photographic mate­rials in particular, can be of the negative color print type or of the reversal type, of the color paper type or of the movie positive type.
• unconventional photographic materials of the transfer type which make use of negative or direct positive emulsions, such as for example those described in US patents 3,277,550 and 3,227,551, can use the couplers of the present inven­tion.
• emulsions can be coated onto several support bases (cellulose triacetate, paper, resin-coated paper, polyester, and the like) by adopting various methods, as described in Research Disclosure 17643, XV and XVI, December 1978.
• the silver halide emulsion layers exposed to light radiation to form a la­tent image are developed with a compound of the aromat­ic amine type in the presence of the color couplers.
• Suitable developing compounds are in particular the p-­phenylenediamine derivatives, for example 2-amino-5-di­ethylamino-toluene chlorydrate (called CD2), 2-amino-N-­ethyl-N-( ⁇ -methanesulfonamido)-m-toluidine sesquisulfate monohydrate (called CD3), 4-amino-3-methyl-N-ethyl-N-­( ⁇ -hydroxyethyl)-aniline sulfate (called CD4).
• CD2 2-amino-5-di­ethylamino-toluene chlorydrate
• CD3 2-amino-N-­ethyl-N-( ⁇ -methanesulfonamido)-m-toluidine sesquisulfate monohydrate
• CD4 4-amino-3-methyl-N-ethyl-N-­( ⁇ -hydroxyethyl)-aniline
• the bleaching bath is a water solution having a pH equal to 5.60 and containing an oxidizing agent, normally a complex salt on an alkali metal or of ammonium and of trivalent iron with an or­ganic acid, e. g. EDTA.Fe.NH4, wherein EDTA is the ethylenediaminotetracetic acid.
• an oxidizing agent normally a complex salt on an alkali metal or of ammonium and of trivalent iron with an or­ganic acid, e. g. EDTA.Fe.NH4, wherein EDTA is the ethylenediaminotetracetic acid.
• this bath is continously aired to oxidize the divalent iron which forms while bleching the silver image and regener­ated, as known in the art, to maintain the bleach ef­fectiveness.
• the bad working of these operations may cause the drawback of the loss of cyan density of the dyes.
• the blix bath contains known fixing agents, such as for example ammonium or alkali metal thiosulfates.
• Both bleaching and fixing baths can contain other additives, e. g. polyalkyleneoxide derivatives, as described in GB patent 933,008 in order to increase the effectiveness of the bath, or thioethers known as bleach accelerators.
• Film A was prepared by coating a cellulose tri­acetate support base, subbed with gelatin, with the fol­lowing layers in the following order:
• Film B was prepared by coating a cellulose tri­acetate support base, subbed with gelatin, with the fol­lowing layers in the following order:
• Film C was prepared by coating a cellulose tri­acetate support base, subbed with gelatin, with the fol­lowing layers in the following order:
• Film D was prepared by coating a cellulose tri­acetate support base, subbed with gelatin, with the fol­lowing layers in the following order:
• the couplers used are as follows:
• Samples of the four films were exposed to 5500° K light through a grey step wedge, then subjected to a standard Kodak C41 process for color negative films.
• the following table reports the wavelengths of the absorption maxima of the spectrophotometric curves of the cyan dyes formed in the coupling reaction, the fog, sensitivity and maximum density values of the cyan sen­sitometric HD curves and the color loss percentage ac­cording to the bleach-leuco test.
• the spectrophotometric and sensitometric curves of the developed cyan images and the bleach-leuco test show how the combination of couplers according to the present invention has absorption maxima shifted towards high wavelengths, as desired, high sensitivity and good re­sistance to the bleach-leuco processing.

Landscapes

• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)

Applications Claiming Priority (2)

Related Child Applications (1)

Publications (1)

Family

ID=11160542

Family Applications (2)

Family Applications Before (1)

Country Status (4)

Cited By (3)

Families Citing this family (1)

Citations (3)

Family Cites Families (4)

• 1989
  • 1989-03-09 IT IT8919706A patent/IT1229993B/it active
• 1990
  • 1990-03-01 EP EP91117859A patent/EP0476710A1/fr not_active Withdrawn
  • 1990-03-01 EP EP90103931A patent/EP0389817A1/fr not_active Withdrawn
  • 1990-03-08 JP JP2057816A patent/JPH02272541A/ja active Pending
  • 1990-03-08 CA CA002011730A patent/CA2011730A1/fr not_active Abandoned

Patent Citations (3)

Also Published As

Similar Documents

Legal Events