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Publication numberUS3012884 A
Publication typeGrant
Publication dateDec 12, 1961
Filing dateDec 27, 1957
Priority dateDec 31, 1956
Also published asDE1063900B, US3013879
Publication numberUS 3012884 A, US 3012884A, US-A-3012884, US3012884 A, US3012884A
InventorsRamaix Maurice Antoine De, Jaeken Jan
Original AssigneeGevaert Photo Prod Nv
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Production of colored photographic images
US 3012884 A
Abstract  available in
Images(5)
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Claims  available in
Description  (OCR text may contain errors)

3,012,884- PRODUCTION @F COLGRED PHOTOGIHC WAGES The present invention relates to a method of producing colored photographic images, more particularly such images which are free from unwanted secondary images due to undesired absorptions of the dyestuffs.

It is known that by color development a dyestuif image is formed which mostly shows an undesirable side-absorption and that it can be compensated by a mask image of opposite gradation and with an absorption to compensate the undesirable absorption all over the layer.

One means to do this is the use in the emulsion layer of a colored color coupler with a suitable absorption but losing it Where color development takes place, so that afterwards the remaining color coupler automatically forms the desired masking. The filter action of this colored color coupler in the emulsion inevitably involves a loss of sensitivity.

Another means to obtain the desired mask image consists in converting, after color development, the residue of the color coupler into a colored compound with adequate absorption. This often requires supplementary baths and has in no case given satisfactory results.

It is an object of the present invention to provide a method of obtaining masked images without using colored color couplers. It is a further object of the present invention to provide a method of obtaining masked images without special treatments, at least if the substances added to the photographic material have been rendered fast to diffusion. Further objects of the present invention will appear from the following description.

These objects are accomplished by color development of a multilayer material containing color couplers and subsequent treatment with an oxidizing substance in the presence of a compound which after oxidation couples with one of the color couplers.

The oxidizing substance can be present in a special bath or in one of the baths normally used. Preferably, the oxidizing substance normally present in the bleaching bath is used.

The mask-forming compound can be present in a bath between the color developer and the bleaching bath, or in one of the sensitive or non-sensitive layers of the photographic material. It may be advantageous that it be fast to difiusion and preferably it corresponds to the following general formula:

I Rs

wherein R =hydrogen or any substituent, e.g. alkyl including aralkyl, aryl, carboxyl including esterified carboxyl or amino including acyl amino;

R =alky1 including aralkyl, aryl, or a heterocyclic residue;

ice

2 R =hydrogen, alkyl including aralkyl, aryl, acyl, i.e. all

the radicals which can be obtained by withdrawing a hydroxyl group from an acid, or a heterocyclic residue.

It is possible of course to use derivatives of these substances wherein the amino group is substituted by a group which inhibits neither the oxidation nor the coupling.

Mask-forming compounds are for instance:

(I 4-amino-antipyrine 0r 1-phenyl-2:3-dimethyl-4- amino-pyrazolone-S (2) 1,2dfphenyl-3-melhyl-4-amin0-pyrazolone-5 This product can be prepared according to A. Heymans, Ber. 66 (1933), 1654/61.

(3) 2-phenyl-3-methyl-4-amin0-pyraz0I0ne-5 This product can be prepared as follows: 8.7 g. of 1- phenyl-4-phenylazo-S-methyl-pyrazolone-3, prepared according to Michaelis, Ber. 38, 155 and Ann. 338, 228, are reduced in cm. of dioxane in the presence of Raney nickel as catalyst. After elimination of the catalyst by filtration, evaporation of the'solvent to dryness, and washing with ether, 4.1 g. of an amine, melting at 180 C., are obtained. After purification over the benzal compound as described by Michaelis, Ann. 350, 295, an amine, melting at 182 C., is obtained.

(4) 1-benzoyl-2-pheny[-3-methyl-4-amin0-pyrazolone-5- hydrachloride This product can be prepared as follows: to 27.8 g. of 1-phenyl-4-phenylazo-5-methyl-pyrazolone-3 (described by Michaelis as above) dissolved in 100 om. of dioxane, 22 cm. of benzoylchlon'de and 300 cm. of an aqueous solution of sodium hydroxide 5 N are added simultaneously and drop by drop at 10 C. The oil formed is washed with an aqueous solution of sodium hydroxide N until solidification and the product is sucked off, washed with Water, then with ethanol, and recrystallized from ethanol. 29.6 g. of a product, melting at 127 C., are obtained.

9.5 g. of the above compound are dissolved in 70 cm. of ethyl acetate and hydrogenated in the presence of palladium as catalyst. After elimination of the catalyst by filtration, the hydrochloride of the amine is precipitated by means of etheric hydrogen chloride. 8 g. of a product which after recrystallization from methyl ethylketone melts at 160 C. (with decomposition) are obtained.

(5) 1-phenylsulphonyl-Z-phenyl-3-methyl-4-amin0- pyrraz0l0ne-5-hydr0chl0ride This product can be obtained as follows: a solution of 18 g. of 1-phenyl-4-phenylazo-5-methyl-pyrazolone-3 (described by Michaelis as before) in 60 cm. of dioxane is added simultaneously and drop by drop with 28 cm. of benzene sulphochloride to 250 cm. of an aqueous solution of sodium hydroxide N at a temperature of 25-30 C. The precipitate formed is sucked off and washed with water. After recrystallization from ethanol, 21 g. of a product, melting at 132 C. are obtained.

11 g. of this azo compound are hydrogenated in 150 cm? of ethylacetate in the presence of Raney nickel as catalyst at about 50 C. After evaporation of the solvent, treatment with etheric hydrogen chloride and recrystallization from acetonitrile, 7.5 g. of a product, melting at C. (with decomposition), are obtained.

(6) I -phenyZ-2-hexadecyl-3-methyl-4-amino-pyraz0lone-5 This product can be obtained as follows: 174 g. of 1- phenyl-3-methyl-pyrazolone-5 and 500 g. of cetyltoluenesulphonate are melted for 3 h. at 160 C.- The oil obtained is boiled with n-hexane, dissolved in ether and shaken out with sodium hydroxide solution in order to remove unaltered pyrazolone. After evaporation of the ether, the residue is dissolved in 1300 cm. of dioxane and after addition of 150 cm. of water and 95 cm. of concentrated hydrochloric acid nitrosated at 10 C. by means of a solution of 40 g. of sodium nitrite in 275 cm. of water. After thirty minutes extra stirring, the green precipitate is centrifuged and Washed with water and subsequently with methanol. 70 g. of a product, melting at 160 C. (with decomposition), are obtained.

8.5 g. of the nitroso compound in 150 cm. of ethyl acetate are hydrogenated in the presence of Raney nickel as catalyst. After filtration, the amine is precipitated from the solution in the form of sulphate by addition of 1 cm. of concentrated sulphuric acid. After sucking off, the sulphate is Washed with ether. 6.2 g. of a product, melting at 150 C. (with decomposition), are obtained. The free base is obtained by dissolving the sulphate in ethanol and completely precipitating the product with water. This base after recrystallization from cyclohexane melts at 124 C.

(7) 2 [p- (a-hexadecenyI-succinyZ-amido)-phenyl] -3- marhyl-4-amino-pyraz0l0ne-5 This product can be obtained as follows: to 20 g. of alpha-acetyl-beta-(p-nitrphenyl)hydrazine and 14 g. of acetyl acetic acid ethyl ester, 15 cm. of phosphorus trichloride are added whilst stirring at between 0 and 5 C. The mixture is slowly brought to room temperature and then gradually heated to 70 C. When the development of hydrogen chloride is practically finished and the reaction mass has become viscous and stiff, it is dissolved in acetic acid and neutralized with an aqueous solution of sodium carbonate. The sucked off product is washed with water. After drying, 20 g. of a product, melting above 260 C., and which can be recrystallized from acetonitrile or from xylene are obtained.

18.4 g. of this 1-p-nitrophenyl-5-methyl-pyrazolone-3 are hydrogenated in methyl Cellosolve in the presence of Raney nickel as catalyst. After elimination of the catalyst by filtration, the solvent is evaporated. The solid residue is Washed with ether and recrystallized from acetontrile. 13 g. of a product, melting at 220 C., are obtained.

5.7 g. of 1-paminophenyl-5-methyl-pyrazolone-3 are refluxed for 3 h. with 9.7 g. of hexadecenyl succinic acid anhydride in methylethylketone, and after evaporation of the solvent to dryness and recrystallization from acetonitrile, 12.2 g. of a product, melting at 117 C., are obtained.

3.24 g. of dichloroaniline are diazotized in 8 cm. of concentrated sulphuric acid and 20 cm. of water at 0 C. with a solution of 1.6 g. of sodium nitrite in 5 cm. of water. The diazoniurn solution obtained is added drop by drop at 5 C. to 10.22 g. of the foregoing compound dissolved in an aqueous solution of sodium carbonate 10%. The mixture is acidified with acetic acid, the precipitate obtained is washed with water and recrystallized from ethanol. 8.6 g. of a product, melting at142 C., are obtained.

1 g. of the azo compound thus obtained is hydrogenated in methyl Cellosolve in the presence of palladium as catalyst. After filtering, pouring out into water, sucking off and washing with acetonitrile, 0.8 g. of a product, melting at 170 C. is obtained.

phenyl-3pentadecyl-pyrazolone-S and 93 g. of methylp-toluenesulphonate are melted together for 30 h. at

4 140 C. In order to remove the toluenesulphonic acid formed the reaction mixture is fixed together with an aqueous sodium hydroxide solution 5%. After extraction with ether and recrystallization from n-hexane, 99 g. of 1-phenyl-2-methyl-3-pentadecyl-pyrazolone-5 are obtained. Yield: 61%. Melting point: 65 C.

99 g. of the above compound are dissolved in acetic acid, cooled down to 10 C. and nitrosated by dropwise addition of a solution of 20 g. of sodium nitrite in 50 cm. of water Whilst thoroughly stirring with an Ultra Turrax stirrer. The reaction liquid changes into a mass which is further stirred for 15 minutes. After dropwise adding 400 cm. of water, sucking off, washing with water until all acid is removed, drying and recrystallizing from xylene at a temperature not higher than 70, 54.5 g. of 1-phenyl-2 methyl-3-pentadecyl-4-nitroso-pyrazolone-5 are obtained. Yield: 51%. Melting point: C.

80 g. of the above nitroso compound are hydrogenated in 900 cm. of methanol at 40 C. in the presence of Raney nickel as catalyst. After filtration and evaporation of the solvent, the oily residue is covered with 60 cm. of chloroformic acid ethyl ester. After about 2 h., the reaction mass has solidified. After washing with ether and crystallization from n-hexane, 49 g. of l-phenyl- 2 methyl-3-pentadecyl-4-carbethoxyamino-pyrazolone-5 are obtained. Yield: 62%. Melting point: 65 C.

(9) 1 -phenyl-2-methyl-3- ma-lzexadecenybsucciny lumido plzelzyl] -4-amin0pyraz0l0n 8-5 This product can be obtained as follows: 562 g. of 1- phenyl-3-m-nitrophenyl pyrazolone-S and 560 g. of methyl-p-toluene sulphonate are melted together for 20 h. at C. The cooled reaction mass is dissolved in chloroform and the solution is washed with an aqueous sodium carbonate solution 5% in order to split off toluene sulphonic acid. After recrystallization from ethanol, 388 g. of l-phenyl-2-metbyl-3-rn-nitrophenylpyrazolone-S are obtained. Yield: 66%. Melting point: 224 C.

383 g. of the latter nitro compound, dissolved in 2.5 l. of methyl Cellosolve are hydrogenated at 60 C. in the presence of Raney nickel as catalyst. After eliminating the catalyst by filtration, the solution is evaporated to dryness and the residue is crystallized from n-butanol. 255 g. of 1-phenyl-2-methyl-3-m-aminophenyl-pyra2olone-5 are obtained. Yield: 74%. Melting point: 222 C.

40 g. of the above amine and 48 g. of alpha-hexadecenyl succinic acid anhydride are refluxed for 1 /2 h. in 1.5 l. of acetonitrile. The precipitate which is produced on cooling is first washed with ethyl acetate and then crystallized from the same solvent. 43 g. of 1-phenyl-2-methyl-3- [m-(alpha-hexadecenyl succinyl) amido] -phenyl-pyrazolone-5 are obtained. Yield: 49%.

14.5 g. of the above compound are dissolved in cm? of acetic acid. After adding 36 cm. of concentrated hydrochloric acid the solution is nitrosated with 21 cm. of an aqueous sodium nitrite solution 20% at about 5 C. After 20 minutes further stirring, the solution is poured out into water and the green nitroso compound formed is sucked off. The latter is dis-solved in 450 cm? of ethanol and hydrogenated at 35 C. in the presence of Raney nickel as catalyst. After sucking off the catalyst, the solution is evaporated to dryness and the remaining residue is thoroughly washed with acetonitrile. 6 g. of 1 phenyl 2-methyl-3-{m-(alpha-hexadecenyl-succinyl)- amido]-phenyl 4 amino-pyrazolone 5 are obtained. Yield: 41%. Melting point: 140 C. (with decomposition).

(10) Methyl ester of I-(p-succinyl-amido)-phenyZ-2- methyl-3-penJadecyl-4-amino-pyraz0lone-5 This product can be obtained as follows: 382 g. of pnitrophenyl hydrazine and 164 g. of palmitoyl acetic acid off with a part of the isopropanol. After sucking off and crystallizing from ethanol, 850 g. of 1-p-nitr0phenyl-3- pentadecyl-pyrazolone-S are obtained. Yield: 82%. Melting point: 111 C.

519 g. of the above pyrazolone are melted together with 256 g. of methyl-p-toluene sulphonate at 135-140 C. for 30 h. After cooling, the reaction mass is dissolved in about 2.5 l. of chloroform. This solution is shaken with an about 5% aqueous sodium carbonate solution in order to split off the toluene sulphonic acid from the quaternary salt, washed with water until the wash water is neutral and the chloroform solution is evaporated to dryness, and after recrystallization from petroleum solvent, 421 g. of 1-p-nitrophenyl-2-rnethyl-3- pentadecyl-pyrazolone-S are obtained. Yield: 78%. Melting point: 78 C.

121 g. of the above nitroso compound are hydrogenated in 1250 cm. of methyl Cellosolve at 60 C. in the presence of Raney nickel as catalyst, the latter is eliminated by filtration and the solvent is evaporated to dryness. After recrystallization from acetonitrile, 108 g. of l-pamino-phenyl-2-methyl-3-pentadecyl-pyrazolone-5 are obtained. Yield: 95%. Melting point: 104 C.

40 g. of this amine are dissolved in 400 cm. of warm acetonitrile and 15 g. of beta-carbomethoxy-propionyl chloride are added in portions. The solution is refluxed for 10 minutes and after cooling, the product is sucked oif in order to complete the crystallization and recrystallized from acetonitrile. 44 g. of 1-[p-( beta-carbomethoxy propionyl)amino] phenyl-2-methyl-3-pentadecyl-pyrazolone-S are obtained. Yield: 86%. Melting point: 159 C.

40 g. of this compound are dissolved in 400 cm of ethylene chlorohydrine and the temperature of the solution is brought at 15 C. 11 cm. of concentrated hydrochloric acid solution and next, dropwise Whilst stirring at 10-15 C., 60 cm. of an aqueous sodium nitrite solution 20% are added. After 1 to 1 /2 h. stirring, 600 cm. of water are added. Stirring is continued for another 1 h. in order to obtain a more crystalline and filtrable pre cipitate. After sucking E, thoroughly washing with water and crystallizing from ethanol, 25.5 g. of 1-[p-(beta-carb0- methoxy propionyl) amido] phenyl-2-methyl-S-pentadecyl-4-nitroso pyrazolone-S are obtained. Yield: 60%.

48 g. of this nitroso compound in a mixture of 850 cm. of ethanol and 70 cm. of concentrated hydrochloric acid solution are reduced at 30-35 C. with zinc powder until the solution is colorless. The zinc is eliminated by filtration and the filtrate is added whilst stirring to 1 /2 1. of saturated aqueous sodium acetate solution. After sucking off, washing with water and recrystallizing from ethyl acetate and subsequently from acetonitrile, 28 g. of l-[pbeta-carbomethoxy-propionyl) amido]-phenyl-2-rnethyl-3- pentadecyl-4-amino pyrazolone-S are obtained. Yield: 59%. Melting point: 163 C.

(11 1 -phenyl-2-( -sulph0) -pr0pyl-3-pentadecyl-4-acetylamid0-pyraz0l0ne-5 This product can be obtained as follows: a diazonium salt solution prepared from 90 cm. of aniline is dropwise added to 222 g. of 1-phenyl-3-pentadecyl-pyrazolonein 250 cm. of an aqueous sodium hydroxide solution N. After /2 h. stirring the solution is neutralized with about 30 cm. of acetic acid. After sucking ofi the precipitate obtained, washing with water and crystallizing from acetic acid, 220 g. of 1-phenyl-3-pentadecyl4-phen ylazo-pyrazolone-S are obtained. Yield: 77%. Melting point 99 C.

95 g. of this azo compound are dissolved in warm state in a mixture of 600 cm. of acetic acid and 300 cm. of acetic anhydride and whilst the solution is still warm zinc powder is added until the liquid is decolorized. After 1 /2 h. refluxing, the solution is poured into ice. After sucking off the precipitated compound and recrystallizing from petroleum solvent, 33 g. of 1-phenyl-3-pentadecyl-4- 6 diacetylamino-pyrazolone-5 are obtained. Yield; 38%. Melting point: 107 C.

14 g. of this compound are heated for 30 h. at C. with 8 g. of n-propane sultone. After cooling, washing with ether and crystallizing from dioxane, 12 g. of 1-phenyl-2-( gamma-sulpho) -propyl-3 -pentadecyl-4-acetylamino-pyrazolone-S are obtained. Yield: 65%. By recrystallization from acetonitrile the melting point can be increased to 180 C.

By boiling this compound for 2 min. in Water the acetylamino is saponified to a free amino group. The solution thus obtained is added to the photographic emulsion.

(12) 1 -phenyl-2-methyl3- [p- (ot-hexadecenyl-succinyl) amido] -benz0ylamid0-4-amin0-pyraz0l0ne-5 This product can be obtained as follows: 33 g. of finely divided 1 phenyl 2 methyl-3-amino-pyrazolone-5 (prepared according to H. Stenzl, Helv., 33 (1950) 1189); are suspended in cm. of acetone and Whilst stirring 105 cm. of a 40% aqueous sodium hydroxide solution and 65 g. of p-nitrobenzoylchloride in 105 cm. of acetone are simultaneously and dropwise added at 0 C. After further stirring for 1 h., 1 l. of water is added and the suspension is filtered and the filtrate is acidified with acetic acid. After sucking off the precipitate, washing with water and then with acetone and crystallizing from methyl Cellosolve, 47 g. of 1 phenyl-2-methyl-3-p-nitrobenzoylamino-pyrazolone-5 are obtained. Yield: 80%. Melting point: above 260 C.

70 g. of this nitro compound are hydrogenated at 75 in 2 1. of methyl Cellosolve in the presence of Raney nickel as catalyst. After concentrating and recrystallizing the formed crystals from methyl Cellosolve, 56 g. of 1-phenyl-2-rnethyl-3-p-aminobenzoylamino pyrazolone-S are obtained. Yield: 88%. Melting point: 222 C.

18.6 g. of this compound and 21.6 g. of alpha-hexadecenyl succinic acid anhydride are refluxed for 3 h. 700 cm. of acetonitrile. After evaporating the acetonitrile and crystallizing from ethyl acetate, 21 g. of l-phenyl-Z- methyl 3 [-p-(alpha-hexadecenyl succinyl)amido]-benzoyl-amino-pyrazolone-S are obtained. Yield: 55%. Melting point: 190 C. (with decomposition).

11 g. of this compound are dissolved in cold state in 20 cm? of an aqueous sodium carbonate solution 2 N. To this solution is added at between 0 and 5 C. a solution of p-chlorophenyl diazonium sulphate prepared from 23.5 g. of p-chloroaniline. The precipitated yellow azodyestuif is washed with water and dried and 12.5 g. of

1-phenyl-2-methyl 3 -'[p (alpha-hexadecenyl-succinyl)- amido]-benzoyl-amino 4 (p-chloro)phenylazo-pyrazolone-5 are obtained. Yield: 90%. Melting point: 185 C. By recrystallization from ethanol the melting point can be brought to 186 C., however with considerable loss.

4 g. of the above azo compound are dissolved in 60 cm. of ethanol. After adding 6 cm. of concentrated hydrochloric acid solution, the solution is reduced at 45 C. by adding zinc powder until the dyestulf is decolorized. After filtration, the filtrate is poured out into a solution of 16 g. of sodium acetate in'100 cmfi of water, sucked off, Washed with water and then with acetonitrile, and 3 g. of 1 phenyl-2-methyl-3-[p-(alpha-hexadecenyl-succinyl)- amido] benzoyl amino 4 amino-pyrazolone-S are obtained. Yield: 92%. Melting point: about C. (with decomposition).

Hereinafter follow some examples which illustrate our invention Without limiting, however, the scope thereof:

EXAIVIPLE 1 A strip of negative multilayer material, the underlying red-sensitive layer of which contains l-hydroxy-Z- naphthoic acid hexadecylarnide-4-sulphonic acid as color coupler is exposed to a wedge through a red-filter. This exposed film is successively: color developed in a devel- I oper containing N:N diethyl para phenylenediamine, fixed, rinsed, treated for 2 minutes in a bath composed of:

Water to 1000 cm rinsed, fixed, rinsed and dried. The area which should have been white it not subjected to antipyrine treatment, is strongly red colored. If the image of the wedge is measured behind intense red, green and blue filters, it appears that when the red filter densities increase, the green filter densities decrease somewhat and the blue filter densities increase much less than with a test strip which was not treated with the amino antipyrine bath.

EXAMPLE 2 A film support is coated with an emulsion layer which besides theusual red sensitizer and l-hydroxy-Z-naphthoic acid-hexadecylamide-4-sulphonic acid as color coupler also contains 2-(p-alpha-hexadecenyl-succinyl-imidophenyl) -3-1nethyl-4-aminopyrazolone-5. A strip or" this film is exposed through a wedge and after color development, fixed, rinsed, bleached in the same bath as in Example 1, fixed, rinsed and dried. On measurement, a decrease of the greenand blue-filter densities is observed for an increase of the red-filter densities, not observed in a test strip containing no pyrazolone derivative.

EXAMPLE 3 A film support is coated with an emulsion layer which besides a green sensitizer and 4-hexadecenyl-succinylimido-indazolone as color coupler also contains 2-(p-hexadecenylsuccinylimidophenyl) -3-methyl-4-amino pyrazolone-5. After exposure of a strip as in Example 1, color development, fixing, rinsing, bleaching for instance in a bath mentioned in Example 1, again fixing, rinsing and drying, at strong yellow-brown color is observed all over the surface. On measurement of the wedge, a much greater proportion of green to blue-filter density than in a comparable material coated without the pyrazolone derivative is observed.

We claim:

1. Method of forming a color corrected image in a photographic element having superposed silver halide emulsion layers sensitive to difierent regions of the visible spectrum, at least one of said layers containing a color coupler for color development, which is reactive with the oxidation product of an aromatic amino developing agent to form by color development a primary dye image which absorbs a major proportion of light in one region of the visible spectrum, and undesirably absorbs a minor proportion of light in at least one other region of the visible spectrum, which method comprises exposing said layers to light, developing at least said one layer containing said color coupler by color development with an aromatic amino developing agent, whereby said primary image is formed in the developed areas by coupling, leaving in the undeveloped areas of at least said one layer residual color coupler, treating said photo- 8 graphic element with a solution containing a 4-amino-S pyrazolon'e derivative of the formula wherein R is a member selected from the group con sisting of alkyl, phenyl, and benzoylamido, R is a member selected from the group consisting of alkyl, phenyl, and p-(ot-hexadecenyl-succinyl-amido)-phenyl, R is a member selected from the group consisting of hydrogen, phenyl, and p-(succinyl-amido-methylester)-phenyl, and R is a member selected from the group consisting of hydrogen, carbethoxy, and acetyl, and treating at least said one layer containing said residual color coupler with a bleaching bath, the latter treatment resulting in the oxidation of said 4-amino-5-pyrazolone derivative, whereby said secondary dye image is formed by coupling of the oxidized 4amino-5-pyrazolone derivative with said residual color coupler.

2. Method of forming a color corrected image in a photographic element having superposed silver halide emulsion layers sensitive to different regions of the visi ble spectrum, at least one of saidlayers containing a color coupler for color development, which is reactive with the oxidation product of an aromatic amino developing agent to form by color development a primary dye image which absorbs a major proportion of light in one region of the visible spectrum, and undesirably absorbs a minor proportion of light in at least one other region of the visible spectrum, at least said one layer also containing a 4-amino-5-pyrazolone derivative of the formula wherein R is a member selected from the group consisting of alkyl, phenyl, and benzoylamido, R is a member selected from the group consisting of alkyl, phenyl, and p-(whexadeeenyl-succinyl-amido)-phenyl, R is a member selected from the group consisting of hydrogen, phenyl, and p-(succinyl-amido-methylester)-phenyl, and R is a member selected from the group consisting of hydrogen, carbethoxy, and acetyl, said color coupler being also reactive with the oxidation product of said 4- amino-S-pyrazolone derivative to form a secondary dye image having a gradation opposite to that of said primary dye image, and absorbing light in at least one of said unwanted minor absorption regions but transmitting substantially all the light in said major absorption region, which method comprises exposing said layers to light, developing at least said one layer containing said color coupler by color development with an aromatic amino developing agent, whereby said primary dye image is formed in the developed areas by coupling, leaving in the undeveloped areas of at least said one layer residual color coupler, and treating at least said one layer containing said residual color coupler with a bleaching bath, said treatment resulting in the oxidation of said 4-amino- 5-pyrazolone derivative, whereby said secondary dye image is formed by coupling of the oxidized 4-amino-5- pyrazolone derivative with said residual color coupler.

3. Photographic element having superposed silver halide emulsion layers sensitive to different regions of the visible spectrum, at least one of said layers containing a color coupler for color development, which is reactive with the oxidation product of an aromatic amino developing agent to form by color development a primary dye image which absorbs a major proportion of light in one region of the visible spectrum, and undesirably absorbs a minor proportion of light in at least one other region of the visible spectrum, at least said one layer also containing a 4-amino-5-pyrazolone derivative of the formula l Ra wherein R is a member selected from the group consisting of alkyl, phenyl, and benzoylamido, R is a member selected from the group consisting of alkyl, phenyl, and p-(a-hexadecenyl-succinyl-amido)-phenyl, R is a member selected from the group consisting of hydrogen, phenyl, and p-(succinyl-amido-methylester)-phenyl, and R is a member selected from the group consisting of hydrogen, carbethoxy, and acetyl, said color coupler being also reactive with the oxidation product of said 4-amino- 5-pyrazolone derivative to form a secondary dye image having a gradation opposite to that of said primary dye image, and absorbing light in at least one of said unwanted minor absorption regions but transmitting substantially all the light in said major absorption region.

References Cited in the file of this patent UNITED STATES PATENTS 2,163,781 Eggert et a1. June 27, 1939 FOREIGN PATENTS 685,061 Great Britain Dec. 31, 1952 765,286 Great Britain Jan. 9, 1957

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Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3245787 *Nov 14, 1960Apr 12, 1966Gevaert Photo Prod NvProduction of color photographic images
US3245788 *Apr 3, 1961Apr 12, 1966Gevaert Photo Prod NvProduction of color photographic images
US3249431 *Mar 27, 1961May 3, 1966Gevaert Photo Prod NvProduction of color photographic images
US4061498 *May 27, 1976Dec 6, 1977Agfa-Gevaert, N.V.Photographic material containing 2-acyl-2-pyrazolin-5-on-couplers
US4128425 *May 6, 1977Dec 5, 1978Polaroid CorporationPhotographic developers
US7285137Dec 1, 2004Oct 23, 2007L'oreal, S.A.Composition for dyeing keratinous fibers comprising at least one diamino-N,N-dihydropyrazolone derivative
US7642360Sep 12, 2007Jan 5, 2010L'oreal S.A.Composition for dyeing keratinous fibers comprising at least one diamino-N,N-dihydropyrazolone derivative
US7651536Jun 20, 2007Jan 26, 2010L'oreal S.A.Composition for dyeing of keratin fibers, comprising 2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one, at least one oxidation base chosen from para-phenylenediamine and para-tolylenediamine, and a substituted meta-aminophenol
US7651537Jun 20, 2007Jan 26, 2010L'oreal S.A.Composition for dyeing keratin fibers, comprising 2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one, 6-chloro-2-methyl-5-aminophenol and a substituted meta-aminophenol
US7651539Nov 30, 2007Jan 26, 2010L'oreal S.A.Dye composition of acidic pH comprising 2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one, a coupler, a particular surfactant and an oxidizing agent and processes and kits using said composition
US7766977Nov 30, 2007Aug 3, 2010L'oreal S.A.Dye composition of acidic pH comprising 2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one, a para-phenylenediamine, a meta-aminophenol and an oxidizing agent, and processes for dyeing keratin fibers using the composition
US7918900Jun 20, 2007Apr 5, 2011L'oreal S.A.Process for the predictable dyeing of keratinous fibers comprising applying at least one composition comprising at least one diamino-N, N-dihydropyrazolone derivative and at least one composition chosen from fundamental and/or golden-highlights compositions
US20050166335 *Dec 1, 2004Aug 4, 2005Laurent VidalComposition for dyeing keratinous fibers comprising at least one diamino-N,N-dihydropyrazolone derivative
US20080005853 *Jun 20, 2007Jan 10, 2008Francois CottardProcess for the predictable dyeing of keratinous fibers comprising applying at least one composition comprising at least one diamino-N, N-dihydropyrazolone derivative and at least one composition chosen from fundamental and/or golden-highlights compositions
US20080016627 *Jun 20, 2007Jan 24, 2008Francois CottardComposition for dyeing of keratin fibers, comprising 2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one, at least one oxidation base chosen from para-phenylenediamine and para-tolylenediamine, and a substituted meta-aminophenol
US20080016628 *Jun 20, 2007Jan 24, 2008Francois CottardComposition for dyeing keratin fibers, comprising 2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one, 6-chloro-2-methyl-5-aminophenol and a substituted meta-aminophenol
US20080071092 *Sep 12, 2007Mar 20, 2008L'oreal S.A.Composition for dyeing keratinous fibers comprising at least one diamino-N,N-dihydropyrazolone derivative
US20080163883 *Nov 30, 2007Jul 10, 2008Francois CottardDye composition of acidic pH comprising 2,3-diamino-6, 7-dihydro-1H, 5H-pyrazolo[1,2-a]pyrazol-1-one, a coupler, a particular surfactant and an oxidizing agent and processes and kits using said composition
US20090007347 *Nov 30, 2007Jan 8, 2009Francois CottardDye composition of acidic pH comprising 2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one, a para-phenylenediamine, a meta-aminophenol and an oxidizing agent, and processes for dyeing keratin fibers using the composition
CN1660033BNov 30, 2004Jul 17, 2013莱雅公司Composition for dyeing keratinous fibers comprising at least one diamino-n,n-dihydropyrazolone derivative
EP1550656A1 *Nov 22, 2004Jul 6, 2005L'oreal4-5-diamino-n,n-dihydro-pyrazol-3-one derivatives for use in composition for dyeing keratin fibres
EP1764082A3 *Nov 22, 2004May 23, 2007L'oreal4-5-diamino-N,N-dihydro-pyrazol-3-one derivatives for use in composition for dyeing keratin fibres
Classifications
U.S. Classification430/359, 430/361, 430/382
International ClassificationC07D231/48, C07D231/22, C07D231/26, C07D231/46, C07D231/50, G03C7/34, C07D231/52, G03C7/18
Cooperative ClassificationG03C7/344, C07D231/48, C07D231/50, C07D231/46, G03C7/18, C07D231/26, C07D231/52, C07D231/22
European ClassificationC07D231/52, G03C7/18, C07D231/26, C07D231/48, C07D231/22, C07D231/46, G03C7/34N, C07D231/50