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
  • G03C7/36—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
• • 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

Definitions

• a sharp color image can be repro- UNITED STATES PATENTS prised from the photographic material according to a 3,127,269 3/1964 Greenhalgh et al. 96/100 color Subtracm? process' 3,623,871 11/1971 Poucke et al. 96/100 20' Claims, No Drawings MAGENTA COUPLER-CONTAINING PHOTOGRAPIIIC SILVER I-IALIDE MATERIALS BACKGROUND OF THE INVENTION 1.
• This invention relates to silver halide photographic materials containing at least one novel magenta coupler.
• acylacetamide or dibenzoylmethane type couplers are used for the formation of yellow images
• phenol type couplers such as phenols and naphthols are used for the formation of cyan images.
• the couplers for forming dyes are either added in the developers employed or incorporated in photographic light-sensitive emulsion layers.
• the reaction of the oxidation products of the color developing agents formed in the development of latent images with couplers happens during development.
• 2-pyrazol-5-one derivatives for forming magenta images in trichromatic color photography are known.
• an alkoxy group as described in U.S. Pat. No. 2,439,098
• an' acylamino group as described in U.S. Pat. Nos. 2,369,489 and 2,600,78
• a ureido group as described in U.S. 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.
• Anilino-5-pyrazolone type couplers have often been described since the issuance of U.S.
• 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
• Couplers having water-soluble groups such as carboxyl group'or 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 in the form of fine colloidal particles, and then the resulting dispersion is added to a 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
• the following characteristics are required: (1) the' couplers should have high coupling reactivity with the oxidation products ofdeveloping 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 coup'lers should not advers'ly affect photographic emulsions; and (5) the couplers should be easily soluble in organic solvents for dispersing the couplers, and further should be difi'icult 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 difiicult using the oil solution system to obtain green-sensitive emulsion layers having excellent photographic properties.
• a magenta color image in trichromatic subtractive color photography absorbs light in the range of wave length of maximum luminosity, and therefore, the light absorption characteristic thereof is an extremely im portant 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.
• v Magenta color images obtained from most 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 .object of this invention is to provide novel magenta couplers which are suitable for the preparation of photographic materials in an oil solution system.
• a second object of this invention is to provide photographic materials having excellent color reproducibility forreproducing sharp color tone according to a subtractive process, L
• a third object of this invention is to providecolor photographs having excellent magenta color images which are stableand are deteriorated only slightly even under severe conditions and even after being stored for a long period of time.
• a fourth object-of this invention is to provide photographic -materials suitable for simple development treatment, which does not require any stabilization treatment with formaldehyde or the like.
• -A fifth object of this invention is to vmanufacture 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,
• the 4-position of the 2-pyrazol-5-one derivative can be substituted by a residue which may be removed by means of an oxidation product of a 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, :1 nitro group,- a hydroxy group, a carboxy group, an amino group (e.g., amino, N-alkylamino, N,N-dialkylamino, N-arylamino, N-alkyl-N-aryl-amino, etc.), a carboxyester (e.g.,-carbomethoxy, carboethoxy, carbophenoxy, etc.), a sulfo group, a sulfo ester (e.g., methoxysulfonyl, butoxysulfonylphenoxysulfonyl, etc.) an amido group (e.g., acetamido, butyramido, [oz-( 2,4-di-t-amylphenoxy )aceta
• a sulfonic acid group for example, a sulfonyl group (for example, a methylsulfonyl group, an octadecylsulfonyl group, an ethoxysulfonyl group, a decyloxysulfonyl group, a phenylsulfonyl group, a tolylsulfonyl group, a phenoxysulfonyl group, etc.) or the like;
• X and Y each represents an alkyl group (for example, a methyl group, a tert-butyl group, an octyl group, a dodecyl group, etc.), 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,
• an arylazo group for example, a substituted or unsubstituted phenylazo or naphthylazo group, etc.
• a 2-aryltriazolyl group for example, a 2-benzotriazolyl 2-naphthotriazolyl or the like group
• an alkylthio group for example, containing an alkyl group of 4 to carbon atoms
• an arylthio group for example, a phenylthio, naphthylthio or the like group
• a heterothio group for example, a 2-benzothiazolylthio, l-phenyl-5-tetrazolylthio, 2-benzoxazolylthio, 2-benzimidazolylthio, S-phenyl-1,3,4-oxadiazolyl-2-thio or the like group
• a cycloalkylthio group for example, a cyclohexylthio group, etc.
• U represents a halogenatom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group or acyano 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 or a cyano group; and 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, arylthio group,-a' cyano group, anacylamino group, a carbamyl 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-(l) preferably contains therein at least one hydrophobic group having 8 to 32 carbon 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.
• 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 difficult ly soluble in organic solvents.
• Use of couplers containing ballast groups outside of the range of 8 to 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 tel-phenyl group, etc.
• These 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, acarbamyl group, a sulfonamido group, etc.
• hydrophobic groups are, for example, n-octyl, 2-ethylhexyl, tertoctyl, n-nonyl, n-decyl, n-dodecyl, l,l-dimethyldecyl, 2,2-dimethyldecyl, n-octadecyl, 2-(n-hexyl)-decyl; noctadecyl, 9,lO-dichlorooctadecyl, heptyloxyethyl, 2,4-di-tert-pentylcyclohexyldodecyloxypropyl, oleyl, 2,4-di-tert-butylphe'nyl, 2,4-di-tert-pentylphenyl, 2,4- di-tert-pentyl-6-chlorophenyl, S-n-pentadecyl, 2-
• hydrophobic residues are included in at least one of the groups represented by R R X, Y and Z in the above formula (I). These hydrophobic residues can constitute the R R X, Y and Z groups, by themselves or in combination with other aliphatic or aromatic groups or heterocyclic groups bonded with the hydrophobic residues directly or via a divalent bond such as an ether bond, a thioether bond, an amido bond, an ureido bond, a sulfonamido bond, a carbonyl bond, an oxycarbonyl bond or an amino bond.
• a divalent bond such as an ether bond, a thioether bond, an amido bond, an ureido bond, a sulfonamido bond, a carbonyl bond, an oxycarbonyl bond or an amino bond.
• Couplers which have in the R R X, Y and Z groups of the formula (I) strongly hydrophilic groups, such as a carboxyl group, a sulfonic acid group or a sulfonoxy group, can be added to photographic emulsions using a water solution process.
• magenta couplers used in the present invention also include derivatives of S-pyrazolone compounds of the formula (I), such as 3-anilino-5-acyloxypyrazoles obtained by reacting the S-pyrazolone compounds with acylating agents, and the alkylidene-bis-pyrazolones and the arylidene-bis-pyrazolones obtained by reacting I the S-pyrazolone compounds with aldehydes.
• S-pyrazolone compounds of the formula (I) such as 3-anilino-5-acyloxypyrazoles obtained by reacting the S-pyrazolone compounds with acylating agents, and the alkylidene-bis-pyrazolones and the arylidene-bis-pyrazolones obtained by reacting I the S-pyrazolone 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 invention.
• 3-(2-methoxy-5-tetradecyloxycarbonylanilino) derivative 5. 3-(2-chloro-5-tetradecyloxycarbonylanilino) derivative, 6. 3-(2-methylthio-5-hexadecyloxycarbonylanilino) derivative, 7. 3- ⁇ 2-methoxy-5-[ 2-( 2,4-di-tert-pentylphenoxy)ethoxycarbonyl]anilino derivative, 8. 3- 2-chloro-5-[2-( ,4-di-tert-pentylphenoxy)ethoxycarbonyl] anilino ⁇ derivative, 9.
• magenta couplers which are used in the present invention can be synthesized using conventional methods. Some examples to show the synthesis synthesizing representative couplers will be given below. Other couplers according to the present invention can also be prepared in a similar manner.
• the crystals separated from the cooled mixture were collected by filtration and then recrystallized from acetonitrile to obtain colorless crystals as the desired product, the melting point of which was 219 220C.
• the recrystallized crystals were mixed with the 1-(2,4,6-trichlorophenyl)-3-(2-chloro-5-methoxycarbonylanilino)-2-pyrazol-5-one obtained in the above Method a), and no melting point depression thereof was observed.
• the infrared absorption spectra of the two were completely same.
• the resulting reaction product was recrystallized from ethanol to obtain colorless crystals, l-(2,4,6-trichlorophenyl)-3- (2-chloro-5-tetradecyloxycarbonylanilino)-2-pyrazol- 5-one, which is the desired coupler.
• the melting point of the obtained coupler was 95 98C.
• 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 couplers have excellent photographic properties such as good sensitivity, gradation, etc. and further, these structurally different from known couplers as disclosed in British Pat. No. 956,261 and US. Pat. No. 3,419,391 and Japanese Pat. No. 19032/71, in that the couplers of the formula (I) of the invention contain an alkoxycarbonyl group on the anilino group thereof while the known couplers contain an acylamino group on the anilino group.
• the couplers of the present invention which have an alkoxycarbonyl yield color images of more excellent spectroabsorption characteristics than the other known couplers having an acylaminoanilino group. This is because 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-5-one type couplers which have an alkoxycarbonyl group and which are used in the present invention can more easily be made soluble, in general, in organic solvents 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 may 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 after treatment is necessary for stabiliz ing the color images obtained due to the high heat durability thereof.
• the spectroabsorption characteristics of azomethine dyes which form color images were compared in the formof an ethyl acetate solution thereof.
• the dyes subjected to this comparison experiment were the oxidation coupling products of the following couplers and 4- N-ethyl-N-( 2-methanesulfonarnidoethyl )-amino -2'- methylaniline.
• Coupler (5) of the present invention is:
• Coupler (A) (containing acylaminoanilino group):
• Dialkylphenoxyalkylcarbonyl groups which are most spectroabsorption curve of the colo i a e bt i d generally used as a ballast residue of oil-soluble coufrom the magenta coupler of the present invention is sharply cut at the long wavelength side and further has plers were selected as the acyl group of these known couplers.
• the spectroabsorption of color images formed therefrom is markedly inclined to the long wavelength side as a whole with a decrease in the amount of non-volatile organic solvents of high boiling points incorporated in emulsions, as compared with the color images formed using a large amount of non-volatile organic solvents of high boiling points, and therefore, the ability to reduce the amount of solvents for these known couplers is limited from the point of spectroabsorption characteristics.
• the couplers of the present invention are extremely advantageous in that the thickness of emulsion layers can be thin, e.g., l to 8 ,u, more preferably 3 to 6 pa ii. Solubility of couplers in organic solvents:
• Couplers (4) and (5) 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 C, and the results obtained are shown in the following Table 2.
• Couplers (4) and (5) of the present invention show a heat of solution absorption of 7.37 kcal/mole and 7.84 kcal/mole, respectively, when dissolved in a large amount of ethyl acetate at 25C.
• 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 therefore, when non-volatile coupler solvents are used, the amount of solvent remaining in coated emulsion films is consequently small. Accordingly, 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 formed, and further, couplers are difficultly crystallized in the emulsions as well as in the coated and dried films.
• Coupler (5) of the present invention and the known Couplers (A) and (B) were competitively subjected to an oxidation coupling reaction with 4-[N-ethyl-N-(Z-methane-sulfonamidoethyl- )amino]-2-methylaniline in the presence of a cyan forming coupler 2-[2-(2,4-di-tert-pentylphenoxy)acetamido]-4,6-dichloro-S-methylphenol, and the relative coupling speed was calculated therefrom in each case.
• the relative coupling speed is calculated as follows: A 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 dyes, to an emulsion in the form of a mixture of these 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 D respectively
• the ratio of the reactivities of the both couplers R /R is represented by the following formula:
• Coupler (5) of the present invention reacts with the oxidation product of the color developing agent used at a higher speed than the other known Couplers (A) and (B).
• Couplers (A) and (B) As a result, color photographic materials of the present invention have high green-sensitivity, high magenta density and good gradation, and further can form excellent color images.
• 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 that color images derived from conventional 2-pyrazol- 5-one type magenta couplers containing 3-acylamino or 3-ureido groups are seriously deteriorated by heat. This is believed because the dyes formed react with the remaining couplers to form colorless products. For the 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 invention do not require any chemical treatment, for example, with formaldehyde, for the improvement of the heat durability of images formed, and conse- 16 quently, 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 difficultly soluble in water and which has a high boiling point (of 200C or more, for example, up to a boiling point of 250C/ 1 mm Hg), 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, for example, carboxylic acid esters such as the alkyl or aryl esters of phthalic acid or citric acid, e.g., dibutyl phthalate, phosphoric aicd esters such as the alkyl or aryl esters of phosphoric acid, e.g., tricresyl phosphate, amides such as alkyl or aryl amides of carboxylic acids, e.g., N,N-diethyl caproic acid amide, ethers such as the alkyl or aryl phenyl ethers, alkyl or aryl phenols, e.g., p-n-nonylphenol, 2-methyl-4-n-octylphenol, glycerin esters such as glycerides, etc.
• carboxylic acid esters such as the alkyl or aryl esters of phthalic acid or citric acid, e.g
• the organic solvent used is removed during the preparation of photographic materials.
• solvents which are suitable for this method are ethyl acetate, cyclohexanone, betabutylethoxyethyl 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 form of fine colloidal particles.
• the solvent used can be removed during 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, dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, glycerin, tetrahydrofuran, etc.
• Suitable solvents for methods (a) to (c) are disclosed in US. Pat. Nos. 2,322,027; 2,835,579; 3,253,921; and 3,574,627.
• the solvents of the above described methods (a), (b) and (c) can be used optionally in the form of a mixture thereof, whereby the dispersion condition of the couplers can be improved.
• a 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 (0) is mixed with water and a base such as sodium hydroxide is further added thereto to from a mixing 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 emulsion.
• couplers having a water-soluble group such as carboxyl group in anyone of the residues R R X, Y and Z of the above formula (I) are particularly suitable.
• the couplers of the present invention represented by the 17 above formula (1) can be used singly, or in the form of a mixture of couplers, or moreover, the couplers of the present invention can also be used together with magenta couplers other than those of the formula (1), for
• magenta color couplers disclosed in U.S.
• 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 photographic materials such as color positive films, color negative film, color reversal films, color photographic papers, etc. can be prepared.
• the above described photographic emulsions silver halides such as silver chloride, silver bromide, silver iodide, silver bromoiodide', silver iodochloride, silver iodobromochloride, etc.
• the so-called converted halide silver halide grains as described in U.S. Pat. No. 3,622,318 and British Pat. No. 635,841 can be used, and these photographic emulsions can optionally contain the natural sensitizers present in gelatin, sulfur sensitizers, noble metal salts and reduction sensitizers as disclosed in U.S. Pat. Nos.
• these emulsions can further contain optical sensitizers for imparting thereto appropriate color sensitivity as disclosed, for example, in U.S. Pat. Nos. 2,519,001; 2,666,761; 2,739,964; and 3,481,742, and can also contain conventional photographic additives such as anti-fogging agents, stabilizers, anti-irradiation dyes, anti-staining agents, coating auxiliaries, polymers, gelatin plasticizers, gelatin hardeners, etc.
• optical sensitizers for imparting thereto appropriate color sensitivity as disclosed, for example, in U.S. Pat. Nos. 2,519,001; 2,666,761; 2,739,964; and 3,481,742
• conventional photographic additives such as anti-fogging agents, stabilizers, anti-irradiation dyes, anti-staining agents, coating auxiliaries, polymers, gelatin plasticizers, gelatin hardeners, etc.
• Suitable antifoggants or stabilizers whichcan be used are disclosed in U.S. Pat. Nos. 2,728,663 2,728,667; 2,131,038; 2,377,375; 2,394,198; 2,403,927; 2,691,588; 2,708,162; and 3,163,536; suitable anti-staining agents are disclosed in U.S. Pat. Nos. 2,360,290; 2,403,721; 2,704,713; 2,732,300; and 2,735,765; suitable antiirradiation dyes in U.S. Pat. No. 3,615,546; suitable gelatin plasticizers in U.S. Pat. Nos.
• 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.
• p-substituted phenol derivatives which are particularly suitable for the color photographic materials of the 18 present invention are, for example, the hydroquinone derivatives as described in U.S. Pat. Nos. 2,360,290; 2,418,613; 2,675,314; 3,701,179; 2,704,713; 2,728,659; 2,732,300; 2,735,765; 2,710,801; 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-hydroxycoumaran; a hexahydrodibenzofuran-S-01; and a 6,6- dihydroxy-spirochroman. Examples of such compounds are 1. 2,2-dimethyl-4-methyl-6-hydroxy-7-octyl-chroman 2. 2,2-dimethyl-4-isopropyl-6-hydroxy-7-octyl-chroman 3.
• colloids such as gelatin, acylated gelatin (e.g., acetylated gelatin, phthalated gelatin, succinated gelatin, etc.), graft gelatin (e.g., vinylic monomergelatin graft polymer, etc.), albumin, gum arabic, agar-agar, alginates, cellulose derivatives (e.g., hydroxyethyl cellulose, carboxymethyl cellulose, etc.), polyvinylpyrrolidone, polyvinylalcohol, a copolymer of alkyl acrylate and acrylic acid.
• colloids such as gelatin, acylated gelatin (e.g., acetylated gelatin, phthalated gelatin, succinated gelatin, etc.), graft gelatin (e.g., vinylic monomergelatin graft polymer, etc.), albumin, gum arabic, agar-agar, alginates, cellulose derivatives (e.g., hydroxyethy
• hydrophilic colloids examples are illustrated in US. Pat. Nos. 2,286,215; 2,322,085; 2,327,808, 2,541,474; 2,563,791; 2,768,154; 2,808,331; 2,831,767; and 2,852,382.
• hydrophilic collid layers containing the 3- anilino-2-pyrazol-5-one couplers of the present invention can be hardened with various kinds of crosslinking agents, as disclosed in US. Pat. Nos. 1,574,944; 2,399,083; 2,410,689; 2,487,850; 2,521,925; 2,540,085; 2,642,361; and 2,983,609.
• crosslinking agents such as chromic acid and zirconium salts and aldehyde type crosslinking agents such as mucochloric acid and 2- phenoxy-3-chloro-malealdehyde acid as described in Japanese Pat. No.
• non-aldehyde type crosslinking agents such as polyepoxy compounds, as described in Japanese Pat. No. 7133/59, poly-( l-aziridinyl) compounds, as described in Japanese Pat. No. 8790/62, and active halogen compounds, as described in US. Pat. Nos. 3,362,827 and 3,325,287, are especially useful in the actual practice of the present invention.
• Photographic materials containing couplers of the present invention are treated according to conventional methods. More precisely, these materials after exposure thereof, are developed with a developer containing a p-phenylenediamine type developing agent, and then are bleach-fixed to form color images having excellent spectroabsorption characteristics and transparency.
• developing agents suitable for development of the color photographic materials of the present invention are, for example, 4-( N,N-diethyl )aminoaniline, 4-N-ethyl-N-( 2- methanesulfonamidoethyl)amino-2-methylaniline, 4- N-ethyl-N-( beta-hydroxyethyl )amino-2-methylaniline, 4-(N,N-diethyl)amino-2-methylaniline, etc., as disclosed in J. Am. Chem. Soc., vol 73, pages 3100 3125 (1951), J. Prol. Sci, Eng, vol 8, No. 3, pages 125 137 (1964), C. E. K. Mees and T. H. James, The Theory of the Photographic Process, lllrd Ed., pages 294 295, and US. Pat. 2,592,364; 2,193,015.
• EXAMPLE 1 A solution obtained by heating and dissolving 5 g of the above described Coupler (4) of the present invention, 4 ml of tricresyl phosphate and ml of ethyl acetate at 60C was added to 50 ml of an aqueous solution (60C) containing 5 g of gelatin and 0.15 g of sodium dodecyl-benzene sulfonate, and the solution mixture was stirred with a homogenizer to form a coupler dispersion.
• an aqueous solution 60C
• This coupler dispersion was mixed with g of a photographic emulsion containing 5.6 X 10 mole of silver bromochloride (silver chloride; 55 mol%) and 10 g of gelatin, and then 5 ml 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 triacetate film base and then dried (thickness of dried film; 4.5 a). The thus prepared 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 537 mp. was obtained.
• This coupler dispersion was mixed with 100 g of a photographic emulsion containing 4.7 X 10 mole of silver bromochloride (silver chloride; 50 mol%) and 9 g of gelatin, and then 5 ml 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 7.0, this was applied on a resin coated paper and then dried (thickness of dried film: 2.6 u).
• Step-exposure was imparted to each of the thus prepared color photographic papers, and then the following development treatments were performed:
• N (zmethuncsulmmmidg 8 g dispersion thus formed was mixed with 100 g of a phoahyl ⁇ -aminol;2methylaniline-sesquisulfatc tographic emulsion containing 5.0 X 10 mole of silver atcr to ma 0 l l't I Emmi-1mg Solution: bromochloride.(silver chloride.
• Coupler (5) of the present invention yields good color images of excellent transparency even though the amount of the non-volatile solvent of high boiling point used is decreased, and further, the Coupler (5) did not separate out in the dispersion as well as in the coated film.
• 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-[2-(2,4-di-tert-pentyl-phenoxy)butylamido]- acetoanilide to form a first layer having a thickness of 3.0 u, and then gelatin was applied thereupon to form a second layer of a thickness of 1.5 p"
• This coupler dispersion was mixed with 100 g of a green-sensitive photographic emulsion containing 4.7 X mole of silver bromochloride (silver chloride: 50 mol%) and 9 g of gelatin, and then 5 ml of a 3% acetone solution of triethylene phosphamide were added thereto as a hardener, and finally, after the pH of the resulting mixture was adjusted at 7.0, this was applied on the above coated material to form a third layer of a thickness of 3.5 it.
• a green-sensitive photographic emulsion containing 4.7 X mole of silver bromochloride (silver chloride: 50 mol%) and 9 g of gelatin, and then 5 ml of a 3% acetone solution of triethylene phosphamide were added thereto as a hardener, and finally, after the pH of the resulting mixture was adjusted at 7.0, this was applied on the above coated material to form a third layer of a thickness of 3.5 it.
• gelatin containing 2-(5'-chlorobenzotriazol-2-yl)-4-methyl-6-tert-butylphenol and 2-(benzotriazol-2-yl)-4-tert-butylphenol was further applied thereupon to form a fourth layer ofa thickness of 1.5 p, and on this fourth layer was applied further a red-sensitive emulsion containing 2- 2-(2,4-di-tert-pentylphenoxy)butylamido -4,6-dichloro-5-methyl-phenol to form a fifth layer of a thickness of 2.5 p., and then gelatin was superposed thereon to form an uppermost layer of a thickness of l a, whereby a color print paper was prepared (Sample a).
• Coupler (5) In place of the above Coupler (5) were used 4.0 g of a known coupler l-(2,4,6-trichlorophenyl)-3- ⁇ 3-[2- (2,4-di-tert-pentylphenoxy)butylamido]benzamide ⁇ -2- 24 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 (Sample b).
• EXAMPLE 5 On a cellulose triacetate film base were coated a first layer of a red-sensitive silver bromoidide emulsion containing l-hydroxy-2-tetradecylnaphthamide (thickness: 5 p.) and a second layer of gelatin containing 2,5-di-tert-octylhydroquinone (thickness: 1.0 n).
• This coupler dispersion was mixed with 1 kg of a green-sensitive photographic emulsion containing 6 X 10 mole of silver bromoiodide (silver iodide: 6 mol%) and 60 g of gelatin, and then 5 ml of a 3% acetone solution of 2-hydroxy-4,6- dichloro-S-triazine sodium salt were added thereto, and finally, after the pH of the resulting mixture was adjusted to 7.0, this was applied on the above coated film base to form a third layer of a dried thickness of 5.5 1..
• This film was developed, after exposure, according to the following treatment steps, whereby an excellent color negative was obtained having high sensitivity, good gradation and excellent image quality. in addition, it was shown that the blue light density thereof was almost constant regardless of the degree of green light exposure and that a proper color correction was completed.
• Z represents a hydrogen atom, a halogen 27 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 represents 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 represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, 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, 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 ary
• a silver halide photographic element comprising a support and having thereon at least one silver halide photographic emulsion layer of claim 1.
• Z represents a hydrogen atom, a halogen atom, a thiocyano group, an acyloxy group, aryloxy group, an arylazo group, a heteroazo group, 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 represents 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 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
• 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.
• the silver halide photographic emulsion of claim 1 wherein said coupling removable residue is selected from the class consisting ot a thiocyano group, an acyloxy group, an aryloxy group, a halogen atom, an arylazo group, a 2-aryl triazolyl group, an alkylthio 20.
• the silver halide photographic element of claim 8 wherein said coupling removable residue is selected from the class consisting of a thiocyano group, an acyloxy group, an aryloxy group, a halogen atom, an arylazo group, a 2-aryl triazolyl group, an alkylthio group, an arylthio group, a heterothio group, a cycloalkylthio group and a cycloalkoxy group.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)

Applications Claiming Priority (1)

Publications (1)

Family

ID=14637925

Family Applications (1)

Country Status (5)

Cited By (10)

Families Citing this family (8)

Citations (5)

• 1972
  • 1972-11-15 JP JP11444672A patent/JPS5529420B2/ja not_active Expired
• 1973
  • 1973-11-14 US US415853A patent/US3928044A/en not_active Expired - Lifetime
  • 1973-11-15 GB GB5316173A patent/GB1420637A/en not_active Expired
  • 1973-11-15 FR FR7340675A patent/FR2206530B1/fr not_active Expired
  • 1973-11-15 DE DE2357102A patent/DE2357102A1/de not_active Withdrawn

Patent Citations (5)

Also Published As

Similar Documents