US3907571A - Magenta coupler-containing silver halide photographic materials - Google Patents

Magenta coupler-containing silver halide photographic materials Download PDF

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US3907571A
US3907571A US415864A US41586473A US3907571A US 3907571 A US3907571 A US 3907571A US 415864 A US415864 A US 415864A US 41586473 A US41586473 A US 41586473A US 3907571 A US3907571 A US 3907571A
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silver halide
anilino
halide photographic
chloro
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Atsuaki Arai
Yasushi Oishi
Akio Okumura
Minoru Yamada
Yukio Yokota
Kozo Inouye
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/44—Oxygen and nitrogen or sulfur and nitrogen atoms
    • C07D231/52—Oxygen atom in position 3 and nitrogen atom in position 5, or vice versa
    • 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
    • G03C7/36—Couplers containing compounds with active methylene groups
    • G03C7/38—Couplers containing compounds with active methylene groups in rings
    • G03C7/384—Couplers containing compounds with active methylene groups in rings in pyrazolone rings

Definitions

  • acylacetamide or dibenzoylmethane type couplers are used for the formation of yellow images
  • pyrazolone, cyanoacetyl or indazolone type couplers are used for the formation of magenta images
  • phenol type couplers such as phenols and naphthols are used for the formation of cyan images.
  • the couplers for forming the dyes are either added in the developers employed or incorporated in photo-sensitive emulsion layers.
  • the reaction of the oxidation products of the color developing agents formed in thedev'elopment of latent images with couplers happens during development.
  • 2-pyrazol-5-one derivatives for forming magenta images are known.
  • an alkoxy group as described in US. Pat. No. 2,439,098
  • an aeylamino group as described in US. Pat. Nos. 2,369,489 and 2,600,788
  • a ureido group as described in US. Pat. No. 3,558,319
  • an alkyl group, an aryl group and :an anilino group are known as substituents in the 3-position of the S-pyrazolone ring of these derivatives.
  • 3-Anilino-5-pyrazolone type couplers have often been described since the issuance of US. Pat. No.
  • D CONH wherein D represents an aryl group, D CO represents an acyl group.
  • D represents hydrogen atom or a coupling off group removed by the oxidation product of a primary aromatic amine developing agent, such as phenoxy group.
  • L represents a chlorine atom or a methoxy group.
  • these couplers When these couplers are used by addition previously to silver halide photographic emulsions during the preparing of the photographic materials (incorporated couplers), these couplers must be non-diffusing cou plers in order to prevent such an unfavorable phenomenon in which the incorporated couplers diffuse between emulsion layers of different spectral sensitivities and mutually admix together consequently decreasing the color reproducibility thereof. For this reason, it is necessary to introduce into the coupler molecule a hydrophobic group having 8 or more carbon atoms as a ballast group, which serves to decrease the diffusibility of the coupler.
  • Couplers having watersoluble groups such as a carboxyl group or a sulfonic acid group are soluble in alkaline aqueous media, and after the coupler is added to an emulsion in the form of a neutral or alkaline aqueous solution, this is neutralized with an acid.
  • Oil solution system A coupler is dissolved in an organic solvent and the resulting organic solution containing the coupler is emulsified and dispersed in an aqueous medium inthe form of fine colloidal particles, and then the resulting dispersion is added to av photographic emulsion.
  • a coupler is heated and melted, and the molten coupler is directly added to an emulsion or an aqueous medium to disperse the same.
  • magenta couplers suitable for the oil solution system 1 the couplers should have high coupling reactivity with the oxidation products of developing agents; 2) the magenta color images formed through color development should have suitable light absorption characteristics in accordance with the color reproduction principles of the trichromatic subtractive process; (3) the magenta color images should not deteriorate but, should be fast even when stored under any severe conditions; (4) the couplers shouldnot adversely affect photographic emulsions; and (5) the couplers should be easily soluble in organic solvents for dispersing the couplers, and further should be difficult to crystallize in organic solvents.
  • Magenta couplers for the oil solution system which have heretofore been known do not have sufficient coupling reactivity with the oxidation products of developing agents in the form of a dispersion in an emulsion layer, and thus, it has been difficult using the oil solution system to obtain greensensitive emulsion layers having excellent photographic properties.
  • a magenta color image in trichromatic subtractive color photography absorbs light in the range of wavelength of maximum luminosity, and therefore, the light absorption characteristic thereof is an extremely important factor for determining the properties of color photographs for color reproduction.
  • improvement in sharpness of the spectroabsorption curve and a decrease of specific secondary absorption of the pyrazolone type magenta couplers will result in good absorption characteristics of the magenta color image in question, and various efforts have been directed toward attaining such advantages,
  • Magenta color images obtained from conventional magenta couplers tend to be deteriorated when stored under conditions of high temperature and high moisture for a long period of time, and the use of formalin has been inevitable during development treatment for preventing this deterioration.
  • a fourth object of this invention is to provide photographic materials suitable for simple development treatment which do not require any stabilization treatment with formaldehyde or the like.
  • a fifth object of this invention is to manufacture photographic materials by using magenta couplers which may be synthesized relatively easily from easily available materials.
  • the objects of this invention can be attained by incorporating at least one 3-anilino-2-pyrazol-5-one derivative as a magenta coupler into at least one silver halide emulsion layer of a photographic material, in which the anilino group of the derivative is substituted in at least one ortho-position thereof, with a halogen atom or an alkyl, aryl, alkoxy, aryloxy, alkylthio, arylthio, amino, amido, hydroxyl, cyano or nitro group, and in at leastone of metaand para-positions thereof, with a sulfamoyl group.
  • the 4-position of the 2- pyrazol-S-one derivative can be substituted by a residue which may be removed by means of an oxidation product ofa primary aromatic amine developing agent.
  • Especially preferred couplers of this invention include compounds of the following general formula (I):
  • R represents an aryl group in which the aryl groups include any of the substituted groups used in couplers, such as a halogen atom, a cyano group, a nitro group, a hydroxy group.
  • a earboxy group an amino group (e.g.. amino, N-alkylamino, N,N- dialkylamino, N-arylamino, N-alkyl-N-aryl-amino. etc.), a earboxy ester (e.g., carbomethoxy, carboethoxy, carbophenoxy.
  • a sulfo group e.g., methoxysulfonyl, butoxysulfonylphenoxysulfonyl, etc.
  • an amido group e.g., acetamido, butyramido, [a-(2,4-di-t-amylphenoxy)acetamido1benzamido.
  • R and R each represents a hydrogen atom, a straight or branched alkyl group having I to 32 carbon atoms, a cycloalkyl group (for example, a cyclohexyl group, terpenyl group, norbornyl group, etc.), an aryl group (for example, a phenyl group, a naphthyl group, etc.) or a heterocyclic group (for example, a benzimidazolyl group, a benzothiazolyl group, etc.), or represents a group of non-metal atoms necessary for forming, together with the N-atom of tthe sulfamoyl group, a heterocyclic ring such as morpholine or piperidine; the alkyl, aryl and heterocyclic groups, etc.
  • a cycloalkyl group for example, a cyclohexyl group, terpenyl group, norbornyl group, etc.
  • an aryl group
  • a substituent such as a halogen atom, a nitro group, a hydroxyl group, a carboxyl group, an amino group (for example, an unsubstituted amino group, an alkylamino group. a dialkylamino group.
  • an anilino group, an N-alkylanilino group, etc. an aryl group, a carboxy ester group (for example, a earboalkoxy group, a carboaryloxy group, etc.), an amido group (for example, an acetamido group, a butylamido group, an ethylsulfonamido group, an N- mcthylbenzamido group, an N-propylbenzamido group, a 4-tert-butylbenzamido group, a diaeylamido group, etc.
  • a earbamyl group for example, an unsubstituted carbarnyl group, an N-octadecylcarbamyl group, an N,Ndihexylcarbamyl group, an N-methyl-N-phenyl-carbamyl group, a 3pentadecylphenylcarbamyl group, etc.
  • a sulfamyl group for example.
  • X and Y each represents an alkyl group (for example, a methyl group,a ter
  • an aryl group for example, a phenyl group, a tolyl group, etc.
  • an alkoxy group for example, a methoxy group, an octyloxy group, etc.
  • an aryloxy group for example, a phenoxy group, a p-tertbutylphenoxy group, a naphthoxy group, etc.
  • an alkylthio group for example, a methylthio group, an octylthio group, etc
  • an arylthio group for example, a phenylthio group, etc.
  • an amino group for example, an unsubstituted amino group, a methylamino group, a diethylamino group, an anilino group, etc.
  • an amido group for example, an acetamido group, a butylamido group, a methylsulfonamido group, a diacylamido group, etc.
  • a Z-aryltriazolyl group for example, a Z-benzotriazolyl, 2- naphthotriazolyl or the like group
  • an alkylthio group for example. containing an alkyl group of 4 to 1() carbon atoms
  • an arylthio group for example, a phenylthio, naphthylthio or the like group
  • a heterothio group for example. a 2.-benzothiazolythio, l-phenyl-S- tetrazolylthio, Z-benzoxazolylthio, 2- benzimidazolythio. 5-phenyl-l,3, 4-oxadiazolyl-2-thio or the like group).
  • a cycloalkylthio group for example, a cyclohexylthio group. etc
  • a eycloalkoxy group for example. a cyclohexyloxy group, etc.
  • U represents a halogen atom.
  • U represents a halogen atom.
  • U U and U each represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group or a cyano group; and U U and U each represents a hydrogen atom, a halogenatom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, arylthio group, a cyano group, an acylamino group, a earbamyl group, an ureido group, a sulfonamido group, a sulfamyl group, an alkylsulfonyl group, a alkylcarbonyl group, an alkoxycarbonyl group, an aralkoxycarbonyl group, a carboxy group or an arylcarbonyl group.
  • the magenta coupler molecule represented by the above formula (1) preferably contains therein at least one hydrophobic group having 8 to 32 atoms as a ballast group.
  • the hydrophobic group makes the coupler easily soluble in an organic solvent making the coupler solution easily dispersible in a hydrophilic colloid, as well as preventing the coupler from being crystallized thereby stabilizing the resulting photographic material. If the number of carbon atoms of the hydrophobic group is less than 8, the coupler will dissolve in a treating solution such as developer and will move in the photographic material consequently decreasing the color reproducibility thereof, while, on the contrary, if the number of carbon atoms is more than 32, the mutual interaction between coupler molecules becomes too great and the couplers become difficultly soluble in organic solvents.
  • ballast groups outside of the range of 8 to b 32 carbon atoms is disadvantageous.
  • hydrophobic ballast groups are, for example, an alkyl group, an alkoxyalkyl group, an alkenyl group, an aryl group substituted with alkyl group(s), an aryl group substituted with alkoxy group(s), a terphenyl group, etc.
  • hydrophobic groups can be substituted with, for example, a halogen atom such as a fluorine atom or a chlorine atom, or a nitro group, a cyano group, an alkoxycarbonyl group, an amido group, a earbamyl group, a sulfonamido group, etc.
  • hydrophobic groups are, for example, n-octyl, 2- ethylhexyl, tert-octyl, n-nonyl, n-decyl, n-dodecyl, 1,1- dimethyldeeyl, 2,2-dimethyldecyl, n-octadeeyl, 2-(nhexyl)-decyl, n-oetadecyl, 9,10-dichlorooctadecyl, heptyloxyethyl, 2,4-di-tert-pentylcyclohexyldodecyloxypropyl, oleyl.
  • hydrophobic residues are included in at least one of the groups represented by R, R R X, Y and Z in the above formula (I). These hydrophobic residues can constitute the R. R R X, Y and Z groups, by themselves or in combination with other aliphatic or aromatic groups or hcterocyclic groups bonded with the hydrophobic residues directly or via a divalent bond such as an ether bond, a thioether bond, an amide least one ortho-position thereof an alkyl, alkoxy or I alylthio group or a halogen atom or acyano group as a substituent having excellent heat and light stability, those in which one or both of R and R are unsubstitued alkyl groups or alkyl groups substituted with an alkoxy, aryloxy, acyloxy, alkoxycarbonyl, acylamino,
  • atoms included in these groups R, and R is in the range of 8 to 32 are advantageously synthesized, those in which X is a halogen atom, an alkoxy group having or less carbon atoms or an aryloxy group having '12 or less carbon atoms are advantageous in that the spectroabsorption characteristics of magenta images formed therefrom are excellent, those in which Y is a hydrogen atom have the advantage that the raw materials forsynthesis of the couplers are readily available and that the synthesis thereof is advantageous, and those in which the R R NsO -moiety in the anilino I group is in the 5-position are excellent in that they are easily soluble in solvents for couplers.
  • magenta couplers used in the present invention also include derivatives of S-pyrazolotie compounds of the formulatl), such as 3-anilino-5-acyloxypyrazoles obtained by reacting the S-pyrazolone compounds, with acylating agents, and the alkylidene-bispyrazolones and arylidene-bis-pyraiolones obtained by reacting the S-pyrazolorie compounds with aldehydes.
  • S-pyrazolotie compounds of the formulatl such as 3-anilino-5-acyloxypyrazoles obtained by reacting the S-pyrazolone compounds, with acylating agents, and the alkylidene-bispyrazolones and arylidene-bis-pyraiolones obtained by reacting the S-pyrazolorie compounds with aldehydes.
  • magenta couplers which can be used in the present invention are described below, the listing of which, however, should not be interpreted as limiting the scope of the present inventionl-(2,4,6-Trichlorophenyl)-2-pyrazol 5 one 'cornpounds having the following 3-substituent:
  • magenta couplers which are used in the present invention can be prepared using conventional methods. Some examples to show the synthesis of representative couplers will be given below. Other couplers according to the present invention can also be prepared in a similar manner.
  • the magenta couplers according to the present invention have high coupling reactivity and sufficient solubility in organic solvents, and thus, photographic materials for color photography prepared using these couon the anilino group.
  • the couplers of the present inventhe form of an ethyl acetate solution thereof.
  • the dyes plers have excellent photographic properties such as good sensitivity, gradation, etc. and further. these materials are advantageous'in that they can easily be prepared.
  • JphOtOgr'aphic color images obtained after development of the materials have'advantageous spectroabsorption characteristics and sufficient fastness in color reproduction, and they are stable on storage for a long period of time under severe conditions.
  • the 3-anilino-2-pyrazol-5-one type couplers of the formula (I) which are used in the present invention are structurally different from known couplers as disclosed in British Patent No. 956,261 and US. Pat. No. 3,419,391 and Japanese Patent Publn. No. 19032/71, in that the couplers of the formula (I) of the invention contain a sulfamoyl group on the anilino group thereof while the known couplers contain an acylamino group tion which have a sulfamoylanilino group yield color images of more excellent spectroabsorption characteristics than the other known couplers having an acylaminoanilino group.
  • the couplers of the present invention form azomethine dyes having less undesirable absorption of red light and blue light, and thus, photographic materials for color photography can be prepared using the advantageous couplers of the present invention which can reproduce light and sharp red color and blue color.
  • the 2-pyrazol- S-one type couplers which have a sulfamoylanilino group and which areused in the present invention can more easily be made soluble, in general, in organic s01- vents than the other couplers containing an acylamino group and corresponding to those of the present invention.
  • the couplers used in the present invention are improved in that they yield images of more excellent spectroabsorption characteristics, that they have higher reactivity with the oxidation products of primary aromatic amine developing agents, that the color images obtained have more excellent heat durability, and that no specific aftertreatment is necessary for stabilizing the color images obtained due to the high heat durability thereof.
  • the couplers of the present invention are extremely advantageous in that the thickness of emulsion layers can be thin. e.g., 1 to 8 u, more preferably 3 to 6 1.,
  • Couplers (l). (3), (6) and (23) of the present invention were compared with the following known Couplers (A), (C), (D) and (E) which have an acylaminoanilino group, with respect to the solubility thereof in ethyl acetate at 25C, and the results obtained are shown in the following Table 2. 7
  • Dialkylphenoxy-alkylcarbonyl groups which are most generally used as a ballast residue of oil-soluble couplers were
  • Couplers have sufficient solubility to attain the objects of the present invention even at a low temperature.
  • the couplers which are used in the present invention are easily dispersible and the amount of coupler solvents necessary for dissolving the couplers can be small. and theregfore, when non-volatile coupler solvents are used.
  • the thickness of the coated emulsion films can be reduced, whereby scattering of light in the thinner emulsion films decreases with the result that sharp images can be methanesulfonamidoethyl)amino ⁇ - 2-methylaniline in i the presence of a cyan forming coupler T22-[2- (2.4-di-tertpentylphenoxy)-acetamido]-4,6-dichloro- 5-methylphenol. and the relative coupling speed was calculated therefrom in each case.
  • the relative coupling speed is calculated as follows:
  • the coupling reactivity of a coupler is determined relatively by measuring each content of dyes in color images which are obtained by adding two kinds of Couplers M and N. which yield mutually clearly separated different dycs. to an emulsion in the form of a mixture ofthese two couplers and then subjecting the resulting photographic material to color development.
  • the Coupler M yields an image having a maximum density of (D and a midway density of D
  • the Coupler N an image having (D and Dy, respectively.
  • the ratio of the reactivities of the both couplers R /R is represented by the following formula:
  • magenta color images obtained from the new couplers of the present invention have various favorable characteristics such that they are fast to the action of heat and moisture and that they are hardly deteriorated even after exposure to strong light. It is known prevention of such deterioration.treatment with reagents such as formaldehyde has generally been practiced.
  • the couplers of the present invention do not require such a treatment. inherently having sufficient fastness. With respect, to stability against heat. experimental data for comparison are given in Example 2 hereinafter.
  • the color photographic materials of the present inv'ention do not require any chemical treatment, lor example, with formaldehyde. for the improvement of the heat durability of images formed, and consequently, the development treatment can be simplified as a whole, which is one of the advantages of the present invention.
  • a coupler is dissolved in an organic solvent which is dillicultly soluble in water and which has a high boiling point (of 200C or more, for example, up to a boiling point of 250C/l mmHg), and the resulting coupler solution is emulsified and dispersed in an aqueous medium and then added to a photographic emulsion.
  • organic solvents which are suitable for this method are,
  • carboxylic acid esters such as the alkyl or I aryl esters of phthalic acid or citric acid, e.g., dibutyl phthalate
  • phosphoric acid esters such as the alkyl or aryl esters of phosphoric acid,e.g., tricresyl phosphate
  • amides such as alkyl or aryl amides of carboxylic acid, e.g., N,N-diethyl caproic acid amide
  • ethers such as the alky-lor aryl phenyl .ethers,'a1ky1 or aryl phenols, c.g., p-n-nonylpheno1,- 2-methy1-4-n-octy1pheno1, glycerin esters such as glycerides, etc.
  • These classes and examples are merely cxemplary of suitable solvents having a high boiling point, the important functional characteristic.
  • a coupler is dissolved in a solvent which is relatively difficultly soluble'in water and which has a low boiling point, c.g., about 35 to 160C, preferably 60 to 130C. and the resulting'coupler solution is emulsitied and dispersed in an aqueous medium and then added to a photographic emulsion.
  • the organic solvent used is removed during the preparation of photographic materials.
  • solvents which are suitable for this method are ethyl acetate, cyclohexanone. beta-butylethoxyethyl acetate, etc.
  • a coupler is dissolved in an organic solvent which is easily miscible with water and the resulting coupler solution is added to a photographic emulsion, whereby the coupler is dispersed therein in the formof fine colloidal particles.
  • the solvent used can be removedduring the preparation of photographic materials or can be retained in'the emulsion layer.
  • Solvents easily'miscible with water which are suitable for this method are, for example, dimethylformamidc, dimethylsulfoxide, N-' methylpyrrolidone ,glycerin, tet rahydrofuran, etc.
  • ln additioi iia coupler can also be added according to another method which is similar to a water solution system, where a solvent as used in the above method (c) is mixed with wa ter and a base such as sodium hydroxide is further added thereto to form a mixed solvent.
  • the coupler is'dissolved in the resulting mixed solvent to form an aqueous solution, and the resulting coupler aqueous solution is mixed with a photographic emulsionf
  • couplers having a water-soluble group ' such as a carboxyl group in any of the residues R, R R- X, Y and Z of the above formula (1) are particularly suitable.
  • the couplers ofthepresentinvention represented by the above formula (1) can be used singly or in the form 01' a mix- .ture of the couplers, or moreover, the couplers of the present invention can also be used together with magcnta couplers other than those of the formula (1), for example, the magenta color couplers disclosed in U.S. Pat. Nos.
  • magenta coupler of the present invention represented by the formula (I) can be used together with other cyan or yellow couplers in the same emulsion layer, for the purpose of improving the color reproductivity of color photographic materials, as described in Japanese P atent Publn. No. 391/65.
  • a photographic emulsion containing one or more couplers of the present invention is applied on a conventional photographic support such as a film base or .baryta paper, and consequently, various color photopapers, etcQcan be prepared.
  • the above described phtog raphic emulsions silver halides such as silver chloride, silver bromide, silver iodide, silver bromoiodide, silver iodochloride, silver iodobromochlori'de, ctc.
  • silver halides such as silver chloride, silver bromide, silver iodide, silver bromoiodide, silver iodochloride, silver iodobromochlori'de, ctc.
  • the so-called converted halide silver halide grains as described in 1 Pat. No. 3,622,318 andBritish Patent 635,841 can i be used, and these photographic emulsions can optionally contain natural sensitizers present in gelatin, noble metal salts as well as reduction sensitizers, as disclosed in U.S. Pat, Nos.
  • these emulsions can further contain optical scnsitiyers for imparting thereto appropriate color sensitivity as disclosed, for example, in U.S. Pat. Nosl 2,519,001;]2,666,761; 2,739,964; and
  • I 3,481,742 can also contain conventional photographic additives 'such as antifogging agents, stabilizers, anti-staining agents, anti-irradiation dyes, gelatin plasticizers, gelatin hardeners,'coating auxiliaries, poly- I mers, etc.
  • Suitable anti-fog'gants or stabilizers which 2,360,290; 2,403,721;1,704,713; 2,732,300; and
  • the color photographic materials of the present invention advantageously contain a p-substituted phenol derivative together with a 3-anilino-2-pyrazol-5-one compound of the formula (1), for increasing the stability of color photographs
  • psubstitutcd phenol derivatives which are particularly suitable for the color photographic materials of the present invention are, for example, the hydroquinone derivatives as described in U.S. Pat, Nos. 2,360,290, 2,418,613, 2,675,314, 2,701,197, 2,704,713, 2,728,659, 2,732,300, 2,735,765, 2,710,801, and 2,816,028; the gallic acid derivatives as described in U.S. Pat, Nos.
  • A is a substituted phenyl radical, including a phenyl having a fused heterocyclic group in the 4-5 position relative to the OH group. More specifically, A is defined as the residue of a hydroxy phenyl ether; a 6-hydroxy chroman; a 5-hydroxy coumaran; a hexahydro dibenzo furan-5-ol; and a 6,6- dihydroxy spirochroman.
  • Examples of such compounds are 1, 2,2-dimethyl-4-methyl-6-hydroxy-7octylchroman 2. 2,2-dimethyl-4-isopropyl-6-hydroxy-7-oetylchroman 3, 2'methy
  • 2,2,4,5-tetramcthyl-6-hydroxy-7.8-dimethoxychroman 8. 2'methyl2-hexadecyl-6-hydroxy-8-t-butyl chroman 9 2-methyl-2-( 4,8-dimethyl )nonyl-5 -methyl-6" hydroxy-7,8-dimethoxy chroman 2,2'-spirochroman 17. 2-hydroxy 3-octyl-5a-methyl-8-isopropyl- 5a,6,7,8,9,9a-hexahydrodibenzofuran l8 2-1N-methyl-N-tp-carboxy methyl )benzyl lamino-3,3-dimethyl-5-hydroxy-6-t-octyl coumaran 19.
  • hydrophilic colloid layers containing the 3- anilino2-pyrazol-5-one couplers of the present invention can be hardened with various kinds of crosslinking agents, as disclosed in U.S. Pat. Nos.
  • inorganic compounds such as chromic acid and zirconium salts and aldehyde type cross-linking agents such as mucocliloric acid and 2- phenoxy'3-chloromalealdehyde acid as described in Japanese Patent Publn. No, 1872/71 can be used effectively in the present invention in many cases; and in particular, non-aldehyde type crosslinking agents such as polyepoxy compounds, as described in Japanese Patent Publn. No.
  • developing agents suitable for development ofthe color photographic materials of the present invention are, for example, 4-(N,N-diethyl)aminoaniline, 4- N-ethyl-N-(Z- methanesulfonamidoethyl)amino -2-methylaniline, 4- N-ethyl-N-( heta-hydroxyethyl )amino-2-methylaniline, 4-(N,N-diethyl)amino-2-methy1aniline, etc, as disclosed in J.Am, Chem, 800., vol 73, pages 3100 3125 (1951), 1. Plan, Sci, Eng, vol 8, No. 3, pages 137 (1964), C. E. K. Mees and T. H. James, The Theory of the Photographic Process, lllrd Ed., pages 294 295 (1966), and U.S. Pat. Nos. 2,592,364; 2,193,015.
  • EXAMPLE 1 A solution obtained by heating and dissolving 5g of the above described Coupler (22) of the present invention, 4ml of tricresyl phosphate and 15ml of ethylacetate at 60C was added to 50ml of an aqueous solution (60C) containing 5g of gelatin and 0.15g of sodium dodecyl-benzene sulfonate, and the solution mixture was stirred with a homogenizer to form a coupler dispersion.
  • This coupler dispersion was mixed with 100g of a photographic emulsion containing 5.6 X 10 mole of silver bromochloride (silver chloride; 55mol /r) and 10g of gelatin, and then, 5ml of a 3% acetone solution of triethylene phosphamide was further added thereto as a hardener, and finally, after the PH of the resulting mixture was adjusted to 6.5, this was applied on a cellulose t riacetate film base and then dried (thickness of dried film: 3.4 The thus manufactured photographic film was exposed in a conventional manner and then subjected to the following treatments, whereby a sharp magenta color image having a maximum absorption of 542 mu was obtained.
  • EXAMPLE 2 A solution obtained by heating and dissolving 5.0g of the above described Coupler (7) of the present'invention, 0.4g of 2.S-di-tert-octylhydroquinone, 7.0ml of tricresyl phosphate and 14ml of ethyl acetate at 60C was added to 50ml of an aqueous solution (60C) containing 5g of gelatin and O. 10g of sodium dodecylbenzene sulfonate, and the resulting solution mixture was stirred with a homogenizer to form a coupler dispersion.
  • This coupler dispersion was mixed with 100g of a photographic emulsion containing 4.7 X 10 mole of silver bromochloride (silver chloride: 50 molVr) and 9g of gelatin, and then, 5ml of a 3% acetone solution of tricthylene phosphamide was further added thereto as a hardener, and finally, after the pH of the resulting mixture was adjusted to 7.0, this was applied on a resin coated paper and then dried (thickness of dried film: 2.9 t).
  • Couplers (l), (3) and (6) of the present invention were prepared using the above described Couplers (l), (3) and (6) of the present invention and the above described known Couplers (A) and (B).
  • Coupler Sta- 120C 4Hours 60C,75'/1RH Fluorescent bil- Initial 2 Weeks Lamp iz- Density initial 2 Weeks ing 0.5 1.0 Density Initial Bath 0.5 1.0 Density invention (a) 7 5 5 4 21 Coupler (7) lnvention (a) 8 7 2 0 18 Coupler (l lnvention (a) 7 6 6 4 l9 Coupler (3) lnvention (a) 6 4 5 3 20 Coupler (6) Known (a) 10 7 9 7 23 Coupler (A) Known (a) 67 40 33 19 25 Coupler (B) Known (b) 8 3 9 6 23 Coupler (B) As is apparent from the results contained in Table 4 above, the couplers of the present invention yield color images having a fastness to heat which is equal to or higher than that of the known Coupler (A), and further they do not require any stabilization
  • a plurality of coupler dispersions was prepared by using (a) 4.4g of the above described known Coupler (B) and (b) 8.8ml, 6.16ml, 3.52mi, 2.2ml, 0.88m] and Oml of tricresyl phosphate and (e) 9ml, 12ml, 14ml, 16ml, 17ml and 18ml of ethyl acetate, respectively, and each of the resulting coupler dispersions was mixed with [g of the above described photographic emulsion and then coated and dried.
  • Each of the resulting photographic films thus prepared was treated with the following developer for 12 minutes at 21C, and then the same treatments, fixation, bleaching and fixation, as described in Example I were performed consequently to obtain magenta color images.
  • the main absorption wavelength peak of the resulting magenta color images was as shown in the following Table 5.
  • Coupler (6) of the present invention yields good color images of excellent transparency even through the amount of the non-volatile solvent of high boiling point used is decreased, and further. the Coupler (6) did not separate out in the dispersion as well as in the coated film.
  • a decrease in the amount of nonvolatile solvents of high boiling points used for the couplers of the present invention scarcely causes any variation in the spectroabsorption characteristics of the resulting color images, and therefore, it is possible to decrease the amount of the solvents for the couplers of the present invention with the result that the thickness of the coated films can be decreased.
  • EXAMPLE 4 On a polyethylene coated paper was applied a bluesensitive silver bromochloride emulsion containing alpha-pivaloyl-alpha-(5,5-dimethyl-3-hydantoinyl)-2- chloro-5-[alpha-(2,4-di-tert-pentylphenoxy)- butylamido1-acetoanilide to form a first layer having a thickness of 3.0 11., and then gelatin was applied thereupon to form a second layer of a thickness of 1.5 ,u.
  • an aqueous solution 60C containing 5g of gelatin and 0.16g of sodium dodecylbenzenesulfonate
  • This coupler dispersion was mixed with g of a green-sensitive photographic emulsion containing 4.7 X 10' mole of silver bromochloride (silver chloride: 50 mol%) and 9g of gelatin, and then 5ml of a 3% acetone solution of triethylene phosphamide was added thereto as a hardener, and finally, after the pH of the resulting mixture was adjusted to 7.0, this was applied on the above coated material to form a third layer of a thickness of 3.5 ;1.
  • gelatin containing 2-( 5 chlorobenzotriazol-Z-yl)-4-methyl-6tert-butylphenol and 2-(benzotriazol-2-yl)-4-tert-butylphenol was further applied thereupon to form a fourth layer of a thickness of 1.5 u, and on this fourth layer was applied further a red-sensitive emulsion containing 2-[alpha- (2,4-di-tert-pentylphenoxy)butylamido]-4,6 -dichloro- S-methyl-phenol to form a fifth layer of a thickness of 2.5 ,u. and then gelatin was superposed thereon to form an uppermost layer of a thickness of l .1., whereby a color print paper was prepared (Sample a).
  • Coupler (7) In place of the above Coupler (7) were used 4.0g of a known coupler 1-(2,4,6-trichlorophenyl)-3- 3-[2- (2,4-di-tert-pentylphenoxy )butylamido]benzamide-2- pyrazol-S-one, as a magenta coupler, and otherwise the same procedures used in the preparation of Sample a were carried out to form another color print paper (Sample b).
  • EXAMPLE 5 On a cellulose triacetate film base were coated a first layer of a red-sensitive: silver vbromoiodide emulsion containing l-hydroxy-2-tetradecyl naphthamide (thickness: 5p.) and a second layer of gelatin containing 2,5-di-tert-octylhydroquinone (thickness: l.0 a).
  • R represents an aryl group or a heterocyclic group selected from the group consisting of a 2- thiazolyl, a Z-benzothiazolyl, a 2-benzoxazoly, a 2- oxazolyl, a 2-imidazolyl or a 2benzimidazolyl group
  • R, and R cach represents a hydrogen atom or an alkyl group, an aryl group, or a heterocyclic group selected from the group consisting of a benzimidazolyl group or a benzothiazolyl group or a group of non-metallic atoms necessary for forming a heterocyclic group together with the N-atom of the sulfamoyl group selected from the group consisting of a morpholine or piperidine ring
  • X and Y each represents an alkyl group, an aryl group, alkoxy group, an aryloxy group, an alkylthio
  • R represents a phenyl group substituted, in at least one ortho-position thereof, by an alkyl group, an alkoxy group, an alkylthio group, a cyano group or a halogen atom;
  • R, and R each represents a hydrogen atom or an alkyl group or an alkyl group substituted with an alkoxy group, an aryloxy group, an acyloxy group, an alkoxycarbonyl group, an acylamino group "or a carbamoyl group, with both R, and R not being simultaneously hydrogen atom and with the total numher of carbon atoms included in both R, and R ranging from 8 to 32;
  • X represents a halogen atom, or an alkoxy group having 5 or less carbon atoms or an aryloxy group having 12 or less carbon atoms; and
  • Y represents hydrogen atom.
  • Z represents ahydrogen atom, a halogen 5 atom, a thiocyano group,'an acyloxy group, an aryloxy group, an arylazo group, a heteroazo group, an arylthio group or a heterothio group.
  • X represents a methoxy group, an cthoxy group, a propoxy group, a'fluorine atom, a chlorine atom, a bromine atom or a phenoxy group.
  • U represents a halogen atom, or an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group or a cyano group
  • U represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group or a cyano group
  • U U and U each represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, a cyano group, an acylamino group, a carbamyl group, an ureido group, a sulfonamido group, a sulfamyl group, an alkylsulfonyl group, an
  • a silver halide photographic element comprising a support and having thereon at least one silver halide photographic emulsion layer of claim 1.
  • R and R each represehts a hydrogen atom or an alkyl group.- or an alkyl group substituted with'an alkoxy group,.an aryloxy group, an acyloxy group, an alkoxycarbonyl group, an acylamino group or a carbamoyl group, with both R and R not being simultaneously a hydrogen atom and with the total number of carbon atoms included in both R and R ranging from 8 to 32;
  • X represents a halogen atom, an alkoxy group having or less carbon atoms or an aryloxy group having 12 or less carbon atoms; and Y represents a hydrogen atom.
  • Z represents a hydrogen atom, a halogen atom, a thiocyano group, an acyloxy group, an aryloxy group, an arylazo group, a heteroazo group, an arylthio group or a heterothio group.
  • X represents a methoxy group, an ethoxy group, a propoxy group, a fluorine atom, a chlorine atom, a bromine atom or a phenoxy group.
  • U U and U each represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, a cyano group, an acylamino group, a carbamyl group, an ureido group, a sulfonamido group, a sulfamyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aralkoxycarbonyl group, a carboxy group or an arylcarbonyl group.
  • R represents a phenyl group substituted, in at least one ortho-position thereof, with an alkyl group, an alkoxy group, an alkylthio group, a cyano group or a halogen atom
  • R and R each represents a hydrogen atom or an alkyl group or an alkyl group substituted with an alkoxy group, an aryloxy group, an acyloxy group, an alkoxycarbonyl group, an acylamino group or a carbamoyl group, with both R, and R not being simultaneously hydrogen atoms and with the total number of carbon atoms included in both R and R ranging group
  • U represents a hydrogen atom, a halogen atom
  • X represents a halogen atom, or an alkoxy group having 5 or less carbon atoms or an aryloxy group having 12 or less carbon atoms
  • Y represents a hydrogen atom
  • Z represents a hydrogen atom or .

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4120723A (en) * 1976-06-11 1978-10-17 Fuji Photo Film Co., Ltd. Color photographic light-sensitive element
US4199361A (en) * 1977-10-14 1980-04-22 Fuji Photo Film Co., Ltd. Color photographic light-sensitive element
US4243747A (en) * 1978-01-17 1981-01-06 Fuji Photo Film Co., Ltd. Color photographic light-sensitive material
US4273864A (en) * 1978-12-28 1981-06-16 Fuji Photo Film Co., Ltd. Color photographic light-sensitive materials
US5256528A (en) * 1992-04-23 1993-10-26 Eastman Kodak Company Magenta image-dye couplers of improved hue
EP0686873A1 (en) 1994-06-08 1995-12-13 Eastman Kodak Company Color photographic element containing new epoxy scavengers for residual magenta coupler
EP0711804A2 (de) 1994-11-14 1996-05-15 Ciba-Geigy Ag Kryptolichtschutzmittel
US5646297A (en) * 1995-09-18 1997-07-08 Imation Corp. Process for preparation of 2-equivalent 4-arylthio-5-pyrazolone magenta couplers
US6365334B1 (en) 1993-10-22 2002-04-02 Eastman Kodak Company Photographic elements containing aryloxypyrazolone couplers and sulfur containing stabilizers

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5850537A (ja) * 1981-09-21 1983-03-25 Konishiroku Photo Ind Co Ltd カラ−写真画像の形成方法
JPS59188641A (ja) 1983-04-11 1984-10-26 Fuji Photo Film Co Ltd ハロゲン化銀写真乳剤
JPS60143331A (ja) 1983-12-29 1985-07-29 Fuji Photo Film Co Ltd ハロゲン化銀写真感光材料
AU590563B2 (en) 1985-05-16 1989-11-09 Konishiroku Photo Industry Co., Ltd. Method for color-developing a silver halide color photographic light-sensitive material
AU588878B2 (en) 1985-05-31 1989-09-28 Konishiroku Photo Industry Co., Ltd. Method for forming direct positive color image
AU591540B2 (en) 1985-12-28 1989-12-07 Konishiroku Photo Industry Co., Ltd. Method of processing light-sensitive silver halide color photographic material

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2343703A (en) * 1942-09-04 1944-03-07 Eastman Kodak Co Pyrazolone coupler for color photography
US3127269A (en) * 1961-09-11 1964-03-31 Colour photography
US3623871A (en) * 1968-07-18 1971-11-30 Agfa Gevaert Nv Photographic color process utilizing 2-pyrazolin-5-one couplers

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2343703A (en) * 1942-09-04 1944-03-07 Eastman Kodak Co Pyrazolone coupler for color photography
US3127269A (en) * 1961-09-11 1964-03-31 Colour photography
US3623871A (en) * 1968-07-18 1971-11-30 Agfa Gevaert Nv Photographic color process utilizing 2-pyrazolin-5-one couplers

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4120723A (en) * 1976-06-11 1978-10-17 Fuji Photo Film Co., Ltd. Color photographic light-sensitive element
US4199361A (en) * 1977-10-14 1980-04-22 Fuji Photo Film Co., Ltd. Color photographic light-sensitive element
US4243747A (en) * 1978-01-17 1981-01-06 Fuji Photo Film Co., Ltd. Color photographic light-sensitive material
US4273864A (en) * 1978-12-28 1981-06-16 Fuji Photo Film Co., Ltd. Color photographic light-sensitive materials
US5256528A (en) * 1992-04-23 1993-10-26 Eastman Kodak Company Magenta image-dye couplers of improved hue
US6365334B1 (en) 1993-10-22 2002-04-02 Eastman Kodak Company Photographic elements containing aryloxypyrazolone couplers and sulfur containing stabilizers
EP0686873A1 (en) 1994-06-08 1995-12-13 Eastman Kodak Company Color photographic element containing new epoxy scavengers for residual magenta coupler
EP0711804A2 (de) 1994-11-14 1996-05-15 Ciba-Geigy Ag Kryptolichtschutzmittel
US5646297A (en) * 1995-09-18 1997-07-08 Imation Corp. Process for preparation of 2-equivalent 4-arylthio-5-pyrazolone magenta couplers

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FR2206529A1 (en(2012)) 1974-06-07
DE2357122A1 (de) 1974-05-22
JPS4974027A (en(2012)) 1974-07-17
GB1397483A (en) 1975-06-11
FR2206529B1 (en(2012)) 1977-10-28
JPS5531460B2 (en(2012)) 1980-08-18

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