US3008827A - Production of colored photographic images - Google Patents

Production of colored photographic images Download PDF

Info

Publication number
US3008827A
US3008827A US742756A US74275658A US3008827A US 3008827 A US3008827 A US 3008827A US 742756 A US742756 A US 742756A US 74275658 A US74275658 A US 74275658A US 3008827 A US3008827 A US 3008827A
Authority
US
United States
Prior art keywords
radical
thiazolyl
color
silver halide
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US742756A
Inventor
Jaeken Jan
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Gevaert Photo Producten NV
Original Assignee
Gevaert Photo Producten NV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Gevaert Photo Producten NV filed Critical Gevaert Photo Producten NV
Application granted granted Critical
Publication of US3008827A publication Critical patent/US3008827A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom 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
    • C07D213/72—Nitrogen atoms
    • C07D213/75—Amino or imino radicals, acylated by carboxylic or carbonic acids, or by sulfur or nitrogen analogues thereof, e.g. carbamates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D211/68—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
    • C07D211/72—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D277/32—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole 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
    • C07D277/38—Nitrogen atoms
    • C07D277/44—Acylated amino or imino radicals
    • C07D277/46—Acylated amino or imino radicals by carboxylic acids, or sulfur or nitrogen analogues thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D277/32—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole 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
    • C07D277/56—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D307/18—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no 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
    • C07D307/22—Nitrogen atoms not forming part of a nitro radical
    • 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
    • G03C7/362—Benzoyl-acetanilide couplers

Definitions

  • the color couplers may be provided with a molecule enlarging group. Yellow colored images are :usually obtained by development in the presence of color couplers containing a methylene group free to react with an aromatic amino silver halide developing agent, more particularly in the presence of compounds containing an acylacetarnide group. In this way, it has been proposed to use color couplers of the formula wherein Y represents a heterocyolic nucleus.
  • the dyestuffs formed from benzoyl acetanilide couplers containing an alkoxy group on the benzoyl group are hypsochromic as distinguished from the dyestuffs formed from the couplers without alkoxy substituent, and therefore cannot be used for the manufacture of a positive material, it was to be expected that the alkoxy-substituted couplers of the present invention also should produce hypsochromic dyestuifs on color development.
  • the dyestuffs obtained on color development from the couplers according to the present invention are bathochromic and thus differ from the dyestuffs obtained from the corresponding acetarylide coupler not containing an alkoxy phenyl group. It has further been found that the dye;
  • the color couplers which have been found to be especially suitable for accomplishing the objects of the present invention are compounds having the formula wherein R represents an alkyl group containing a linear chain comprising at least ten carbon atoms and preferably not more than twenty carbon atoms such as a dodecyl group, a hexadecyl group or an octadecyl group or a substituted alkyl group, the substituent containing at least eight carbon atoms, such as p-isooctyl-phenoxy-ethyl group, and Y represents a heterocyclic radical selected from those of the thiophene series e.g.
  • a S-carbethoxythiophenyl-(2)-radical those of the furane series, e.g. a S-carbethoxy-furyl radical, those of the thiazole series, e.g. a 4-methyl-thiazolyl-(2)-, a 4-phenyl-thiazolyl-(2)-, a 4-furyl-thiazolyl-(2)-, a 4-methyl-5-carboXyethyl-thiazolyl-(2)-, a 4,5-diphenyl-thiazolyl-(2)-, a 4-carboxymethyl-thiazoly1-(2)-, a 4-mor p-acylaminophenyl-thiazolyl- (2)-, a 4,S-dicarbethoxy-thiazolyl-(2-)-, a 4methyl-5-car-' benzimidazyl-(2)-radical, those of the pyridine series, e.g.
  • a. 5-acylazmino-pyridyl-(2)-, a pyridyl-(4)- or a chinolyl- (2)-radical those of the 1,3- or 1,4-diazine series, e.g. a 2,6-dihydroxy-4-methyl-pyrimidyl-(5)-radical, those of the 1,3,4thiadiazole series, e.g. a 5-carbomethoxyethyl-- 1,3,4-thiadiazolyl-(2)-radical, those of the 1,3,4-oxodiazole series, those of the 1,2,4-triazole series, e.g.
  • the methylene group attached to the two carbonyl groups is reactive with aromatic amino developing agents in the development process.
  • One or both of the hydrogen atoms of the methylene group may, in general, be substituted by certain groups without destroying the chemical activity of the methylene group. It is necessary, however, that the substituents are groups capable of splitting off either before development occurs, for instance by the action of the alkali in the developing solution, or during the color development.
  • the color couplers according to the present invention possess a central p-oxybenzoyl acetamide part conferring a coupler function to which is attached through the acid amide linkage a heterocyclic nucleus Y which preferably contains a group conferring solubility to the coupler, and to'which is attached through the ether linkage an alkyl group or a substituted alkyl group which serves to prevent wandering of the coupler the new color couplers are incorporated into a colloid 3 layer of a light-sensitive photographic element; preferably they are incorporated into the silver halide emulsion layer but in some cases useful results can be attained when the coupler is incorporated in a layer adjacent to the silver halide emulsion layer or separated therefrom by a water-permeable colloid layer.
  • the aromatic amino compounds which in the present invention are used as developing agent for the silver halide comprise monodi-, and tri-amino aryl compounds, particularly N,N-dia-lkylparaphenylene diamincs, and their derivatives such as N,N-dialkyl-N-sulphomethyl-pphenylene diamine, and N,N-dialkyl-N'-carboxymethyl p-phenylene di-amines.
  • mono-amino developing agents are considered compounds such as aminophenols, aminocresols, aminonaphthols and halogen derivatives of these compounds.
  • the couplers of the invention may be employed for the production of colored photographic images in layers of gelatin or other carriers for the silver halide such as collodium, cellulose organic acid esters or synthetic resins such as pclyvinylalcohol.
  • the support for the emulsion may be a transparent material such as glass, cellulose ester or a synthetic film forming resin such as polystyrene or polyester, or a non-transparent reflecting material such as paper or an opaque cellulose ester layer.
  • the emulsion containing the couplers of the present invention may be coated as a single layer on a support or as a layer of a photographic material containing 'a plurality of emulsion layers coated on one or both sides of the support.
  • the emulsion layers of the multilayer material may be differentially sensitized for the formation of a natural color image in the well known manner.
  • the couplers of the present invention advantageously may be incorporated into the blue sensitive emulsion layer of a multi-layer color film of the positive type such as e.g. the cine film Gevacolor Positive Type 952, the general properties of which together with a method for the production of color prints on this film and a method for processing the exposed film are described in the booklet Motion Picture Films for Professional Use, issued June 1957 by Gevaert Photo-Producten N.V., Mortsel Antwerp, Belgium, pages 60-64 and 77-84.
  • the positive type such as e.g. the cine film Gevacolor Positive Type 952
  • Example 1 32.3 g. of 4- ⁇ fi-[4-(1,1,3,3-tetramethylbutyl)-phenoxy]- ethoxy ⁇ -benzoyl acetic methyl ester (prepared according to British specification 774,421) and 18.3 g. of Z-amino- 4,5-dicarbethoxythiaZ/ole (prepared according to L. Conover, I. Am. Chem. Soc. 72 (1950), 5221/25) dissolved in 800 can. of xylene are refluxed for 3 h.
  • Example 3 The 2-amino-4,S-dicarbethoxythiazole used in the synthesis of the coupler of Example 1 is replaced by a product corresponding to the following formula:
  • Example 4 The 2-arnino-4,S-dicarbethoxythiazole used in the synthesis of the coupler of Example 1 is replaced by a product corresponding to the following formula:
  • Example 5 910 g. of keto ester according to Example 1, and 262 g. of 2-amino-5-nitropyridine (prepared according to Plazek, Ber. 61 (1928), 1815) dissolved in 3 lit. of toluene and 3 lit. of xylene are refluxed for 24 h. in such a way that part of the toluene can distill oil with the methanol formed. On cooling the reaction mixture, 21 compound crystallizes out which after recrystallization from acetonitrile melts at 143 C.
  • 140 g. of this compound are reduced in the presence of g. of iron powder in a boiling mixture of 625 cm. of acetonitrile, 625 cm. of glacial acetic acid and 1125 cm. of water.
  • the filtrate is poured into a mixture of 1250 g. of ice and 1250 cm. of concentrated hydrochloric acid.
  • the precipitate obtained is sucked off, Washed with an aqueous 2.5 N hydrochloric acid solution until no iron is present any longer and then dissolved in chloroform.
  • the solution is Washed with an aqueous sodium carbonate solution until free of acid, filtered through a dry sodium sulphate layer and evaporated to dryness.
  • the residue is washed with ether and after recrystallization from benzene an amine is obtained. Melting point: 137 C.
  • a color coupler is obtained corresponding to the following formula:
  • colloid layers coated thereon at least one of said colloid layers being a light-sensitive silver halide emulsion layer,
  • a solution of 4 g. of this color coupler is added to 1 kg. of a photographic silver halide emulsion. After coating this emulsion onto a layer support, exposing and developing, a yellow image is obtained with an absorption maximum at 445 mu.
  • Example 6 8.6 g. of 2-amino-5-carbethoxythiazole and 25 g. of p-cetyl-oxybenzoyl acetic ethyl ester (prepared according to British patent application 23,2'67/ 56) are refluxed for 6 h., dissolved in 200 cm. of xylene. After cooling the precipitate is sucked ofit' and washed with benzene. A color coupler is obtained with a melting point of 150 C. By recrystallization from methylcellosolve, the melting point is not increased.
  • the color coupler corresponds to the following formula:
  • a solution of 4 g. of this color coupler is added to 1 kg. of a photographic silver halide emulsion. After coating this emulsion onto a layer support, exposing and developing, a yellow image is obtained with an absorption maximum at 455 mg.
  • a light-sensitive photographic material for forming a colored image comprising a support, a plurality of colloid layers coated thereon, at least one of said colloid layers being a light-sensitive silver halide emulsion layer, and a color coupler incorporated in one of the colloid layers, the color coupler containing a methylene group free to react with an aromatic amino silver halide de veloping agent to form a dye, and having the formula wherein R represents a member selected from the group consisting of an alkyl radical and a substituted alkyl radical, said alkyl radical consisting of a linear chain of at least ten carbon atoms and more than twenty carbon atoms, said substituted alkyl radical being a p-isooctylphenoxy ethyl radical, and Y represents a substituted thiazolyl radical selected from the group consisting of a 4-methyl-thiazolyl-(2)-radical, a 4-phenyl-thiazolyl- (2)-radical, a
  • a light-sensitive photographic material for forming a colored image comprising a support, a plurality of and a color coupler incorporated in one of the colloid layers, the color coupler containing a methylene group free to react with an aromatic amino silver halide developing agent to form a dye, and having the formula wherein R represents a member selected from the group consisting of an alkyl radical and a substituted alkyl radical, said alkyl radical consisting of a linear chain of at least ten carbon atoms and not more than twenty carbon atoms, said substituted alkyl radical being a p-isooctylphenoxy ethyl radical, and Y represents a radical of the pyridine series selected from the group consisting of a S-acylamino-pyridyMZ)-radical, a pyridy1-(4)-radical, and a quinolyl-(2) -radical.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
  • Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)

Description

United States Patent 3,008,827 PRODUCTION OF COLORED PHOTOGRAPHIC IMAGES Jan Jaeken, Hove-Antwerp, Belgium, assignor to Gevaert Photo-Producten N.V., Mortsel, Belgium, a Belgian company No Drawing. Filed June 18, 1958, Ser. No. 742,756 Claims priority, application Germany June 19, 1957 5 Claims. (Cl. 96-55) The present invention relates to a process for the. production of colored photographic images by color development in the presence of a color coupler, to photographic material containing a color coupler, and to photographic images produced according to this process.
It is known to produce a colored photographic image by developing a reducible silver salt image formed in a silver halide emulsion layer, with an aromatic amino developing agent in the presence of a color coupler, i.e. a compound which during developing couples with the oxidation product of the developing agent, to form a dyestuff.
It is further known to incorporate the color couplers in the light-sensitive emulsion layer, or in an adjacent layer thereto, of a photographic material. In order to prevent wandering of these couplers out of the layer wherein they initially were incorporated, the color coupler may be provided with a molecule enlarging group. Yellow colored images are :usually obtained by development in the presence of color couplers containing a methylene group free to react with an aromatic amino silver halide developing agent, more particularly in the presence of compounds containing an acylacetarnide group. In this way, it has been proposed to use color couplers of the formula wherein Y represents a heterocyolic nucleus.
The practical value of these couplers, however, is rather low, since the color density of the colored images obtained from these couplers is not sufficiently high, but the substitution of an aryl or a higher alkyl group for the methyl group does not eliminate this deficiency.
It is therefore an object of the present invention toprovide a light-sensitive photographic material for forming colored images having incorporated in a colloid layer of this material a non-diffusing color coupler forming a dye image of increased color density. It is a further object of this invention to provide a photographic silver halide emulsion containing such coupler. A still further object is to provide a method of producing colored images from such color couplers. Still further objects will appear from the following description and examples.
These objects are accomplished by using a benzoyl acetamide color coupler, the benzoyl group of which contains an alkoxy substituent containing a group rendering the color coupler fast to diffusion, and the amino group of which contains a heterocyclic nucleus as substituent.
Since it is known that the dyestuffs formed from benzoyl acetanilide couplers containing an alkoxy group on the benzoyl group are hypsochromic as distinguished from the dyestuffs formed from the couplers without alkoxy substituent, and therefore cannot be used for the manufacture of a positive material, it was to be expected that the alkoxy-substituted couplers of the present invention also should produce hypsochromic dyestuifs on color development.
Surprisingly it has now been found, however, that the dyestuffs obtained on color development from the couplers according to the present invention are bathochromic and thus differ from the dyestuffs obtained from the corresponding acetarylide coupler not containing an alkoxy phenyl group. It has further been found that the dye;
3,008,827 Patented Nov. 14,1961
"ice
stuffs image obtained from the coupler, according to the invention are very intensive.
In consequence of the outstanding properties of the color couplers of the present invention, and of the particularly valuable results which are attained when using them, especially in the manufacture of a positive material, they are substantially different from those known in the art.
The color couplers which have been found to be especially suitable for accomplishing the objects of the present invention are compounds having the formula wherein R represents an alkyl group containing a linear chain comprising at least ten carbon atoms and preferably not more than twenty carbon atoms such as a dodecyl group, a hexadecyl group or an octadecyl group or a substituted alkyl group, the substituent containing at least eight carbon atoms, such as p-isooctyl-phenoxy-ethyl group, and Y represents a heterocyclic radical selected from those of the thiophene series e.g. a S-carbethoxythiophenyl-(2)-radical, those of the furane series, e.g. a S-carbethoxy-furyl radical, those of the thiazole series, e.g. a 4-methyl-thiazolyl-(2)-, a 4-phenyl-thiazolyl-(2)-, a 4-furyl-thiazolyl-(2)-, a 4-methyl-5-carboXyethyl-thiazolyl-(2)-, a 4,5-diphenyl-thiazolyl-(2)-, a 4-carboxymethyl-thiazoly1-(2)-, a 4-mor p-acylaminophenyl-thiazolyl- (2)-, a 4,S-dicarbethoxy-thiazolyl-(2-)-, a 4methyl-5-car-' benzimidazyl-(2)-radical, those of the pyridine series, e.g.
a. 5-acylazmino-pyridyl-(2)-, a pyridyl-(4)- or a chinolyl- (2)-radical, those of the 1,3- or 1,4-diazine series, e.g. a 2,6-dihydroxy-4-methyl-pyrimidyl-(5)-radical, those of the 1,3,4thiadiazole series, e.g. a 5-carbomethoxyethyl-- 1,3,4-thiadiazolyl-(2)-radical, those of the 1,3,4-oxodiazole series, those of the 1,2,4-triazole series, e.g. a 1-(pcarbethoxyphenyl)-3-amino-triazolyl-(5)- or a l-(p-carbethoxy-phenyl)-triaxolyl-(5)-radical and those of the 1,3,5-triazine series.
In these compounds the methylene group attached to the two carbonyl groups is reactive with aromatic amino developing agents in the development process. One or both of the hydrogen atoms of the methylene group may, in general, be substituted by certain groups without destroying the chemical activity of the methylene group. It is necessary, however, that the substituents are groups capable of splitting off either before development occurs, for instance by the action of the alkali in the developing solution, or during the color development.
It will be noted that the color couplers according to the present invention possess a central p-oxybenzoyl acetamide part conferring a coupler function to which is attached through the acid amide linkage a heterocyclic nucleus Y which preferably contains a group conferring solubility to the coupler, and to'which is attached through the ether linkage an alkyl group or a substituted alkyl group which serves to prevent wandering of the coupler the new color couplers are incorporated into a colloid 3 layer of a light-sensitive photographic element; preferably they are incorporated into the silver halide emulsion layer but in some cases useful results can be attained when the coupler is incorporated in a layer adjacent to the silver halide emulsion layer or separated therefrom by a water-permeable colloid layer.
The aromatic amino compounds which in the present invention are used as developing agent for the silver halide comprise monodi-, and tri-amino aryl compounds, particularly N,N-dia-lkylparaphenylene diamincs, and their derivatives such as N,N-dialkyl-N-sulphomethyl-pphenylene diamine, and N,N-dialkyl-N'-carboxymethyl p-phenylene di-amines. As mono-amino developing agents are considered compounds such as aminophenols, aminocresols, aminonaphthols and halogen derivatives of these compounds.
The couplers of the invention may be employed for the production of colored photographic images in layers of gelatin or other carriers for the silver halide such as collodium, cellulose organic acid esters or synthetic resins such as pclyvinylalcohol. The support for the emulsion may be a transparent material such as glass, cellulose ester or a synthetic film forming resin such as polystyrene or polyester, or a non-transparent reflecting material such as paper or an opaque cellulose ester layer. The emulsion containing the couplers of the present invention may be coated as a single layer on a support or as a layer of a photographic material containing 'a plurality of emulsion layers coated on one or both sides of the support. The emulsion layers of the multilayer material may be differentially sensitized for the formation of a natural color image in the well known manner.
The couplers of the present invention advantageously may be incorporated into the blue sensitive emulsion layer of a multi-layer color film of the positive type such as e.g. the cine film Gevacolor Positive Type 952, the general properties of which together with a method for the production of color prints on this film and a method for processing the exposed film are described in the booklet Motion Picture Films for Professional Use, issued June 1957 by Gevaert Photo-Producten N.V., Mortsel Antwerp, Belgium, pages 60-64 and 77-84.
The following examples illustrate the present invention without limiting, however, in any way the scope thereof. Example 1 32.3 g. of 4-{fi-[4-(1,1,3,3-tetramethylbutyl)-phenoxy]- ethoxy}-benzoyl acetic methyl ester (prepared according to British specification 774,421) and 18.3 g. of Z-amino- 4,5-dicarbethoxythiaZ/ole (prepared according to L. Conover, I. Am. Chem. Soc. 72 (1950), 5221/25) dissolved in 800 can. of xylene are refluxed for 3 h. The methanol formed is distilled oil with part of the xylene whereby the level of the reacting liquid is kept at the same height by addition of fresh xylene. On cooling, the amide crystallizes out. After recrystallization from n-butanol a product is obtained corresponding to the following formula:
Melting point: 181 C.
A solution of 4 g. of this color coupler is added to 1 kg. of a photographic silver halide emulsion. After coating this emulsion onto a layer support, exposing and developing, a yellow image is obtained with an absorption maximum at 460 m Example 2 The 2-amino-4,5-dicarbethoxythiazole used in the 0 synthesis of the coupler of Example 1 is replaced by a 7 product corresponding to the following formula:
SCGHr-C O O C2Ht HzN- C 4 (prepared according to Conrad, Ann. 285 (1895), 208) and the n-butanol used for recrystallization by acetonitrile. A color coupler is obtained yielding after color development a yellow image with an absorption maximum at 450 m Mel-ting point: 178 C.
Example 3 The 2-amino-4,S-dicarbethoxythiazole used in the synthesis of the coupler of Example 1 is replaced by a product corresponding to the following formula:
(prepared according to Dodson, J. Am. Chem. Soc. 67 (1945), 2242) and the n-butanol used for recrystallization by ethanol. A color coupler is obtained yielding after color development a yellow image with an absorption maximum at 460 mp. Melting point: 181 C.
Example 4 The 2-arnino-4,S-dicarbethoxythiazole used in the synthesis of the coupler of Example 1 is replaced by a product corresponding to the following formula:
(prepared according to Erlenmeyer, Helv. Chim. Acta 27 (1944), 1432, or Dann, Ber. 76 (1943), 419) and the n butanol used for the recrystallization by acetic acid. A color coupler is obtained yielding after color development a yellow image with an absorption maximum at 460 m Melting point: 195 C.
Example 5 910 g. of keto ester according to Example 1, and 262 g. of 2-amino-5-nitropyridine (prepared according to Plazek, Ber. 61 (1928), 1815) dissolved in 3 lit. of toluene and 3 lit. of xylene are refluxed for 24 h. in such a way that part of the toluene can distill oil with the methanol formed. On cooling the reaction mixture, 21 compound crystallizes out which after recrystallization from acetonitrile melts at 143 C.
140 g. of this compound are reduced in the presence of g. of iron powder in a boiling mixture of 625 cm. of acetonitrile, 625 cm. of glacial acetic acid and 1125 cm. of water. After sucking off the iron which has not reacted, the filtrate is poured into a mixture of 1250 g. of ice and 1250 cm. of concentrated hydrochloric acid. The precipitate obtained is sucked off, Washed with an aqueous 2.5 N hydrochloric acid solution until no iron is present any longer and then dissolved in chloroform. The solution is Washed with an aqueous sodium carbonate solution until free of acid, filtered through a dry sodium sulphate layer and evaporated to dryness. The residue is washed with ether and after recrystallization from benzene an amine is obtained. Melting point: 137 C.
89 g. of the amine are dissolved in 1 liter of boiling benzene. After adding 37 g. of maleic anhydride dissolved in 270 cm. of benzene, the mixture is refluxed for /2 11., cooled off, sucked off and washed with ether.
.'. -LAR.
A color coupler is obtained corresponding to the following formula:
colloid layers coated thereon, at least one of said colloid layers being a light-sensitive silver halide emulsion layer,
Melting point: 190 C. (decomposition). After recrystallization from benzene, the melting point remains unchanged.
A solution of 4 g. of this color coupler is added to 1 kg. of a photographic silver halide emulsion. After coating this emulsion onto a layer support, exposing and developing, a yellow image is obtained with an absorption maximum at 445 mu.
Example 6 8.6 g. of 2-amino-5-carbethoxythiazole and 25 g. of p-cetyl-oxybenzoyl acetic ethyl ester (prepared according to British patent application 23,2'67/ 56) are refluxed for 6 h., dissolved in 200 cm. of xylene. After cooling the precipitate is sucked ofit' and washed with benzene. A color coupler is obtained with a melting point of 150 C. By recrystallization from methylcellosolve, the melting point is not increased.
The color coupler corresponds to the following formula:
S-C-C O O 02H,
A solution of 4 g. of this color coupler is added to 1 kg. of a photographic silver halide emulsion. After coating this emulsion onto a layer support, exposing and developing, a yellow image is obtained with an absorption maximum at 455 mg.
I claim:
1. A light-sensitive photographic material for forming a colored image, comprising a support, a plurality of colloid layers coated thereon, at least one of said colloid layers being a light-sensitive silver halide emulsion layer, and a color coupler incorporated in one of the colloid layers, the color coupler containing a methylene group free to react with an aromatic amino silver halide de veloping agent to form a dye, and having the formula wherein R represents a member selected from the group consisting of an alkyl radical and a substituted alkyl radical, said alkyl radical consisting of a linear chain of at least ten carbon atoms and more than twenty carbon atoms, said substituted alkyl radical being a p-isooctylphenoxy ethyl radical, and Y represents a substituted thiazolyl radical selected from the group consisting of a 4-methyl-thiazolyl-(2)-radical, a 4-phenyl-thiazolyl- (2)-radical, a 4-furyl-thiazolyl-(2)-radical, a 4-methyl- S-carbethoxy ethyl-thiazolyl-(2)-radical, a 4,5-diphenylthiazoly1-(2)-radical, a 4-carboxymethyl-thiazolyl-(2)- radical, a 4-rn-acylaminophenyl-thiazolyl-(2)-radical, a 4 p acylaminophenyl thiazolyl (2) radical, a 4,5-dicarbethoxy-thiazolyl-(2)-radical, a 4-methyl-5-carbethoxy-methyl-thiazolyl-(2)-radical, a 4-methyl-5-carbethoxy-thiazolyl-(2)-radical, a 5-carboxy-thiazolyl-(2)- radical, a S-carbomethoxy-thiazolyl-(2)-radical, a S-carbethoxy-thiazolyl-(Z)-radical, and a S-carbethoxy-thiazolyl-( 2) -radical.
2. A light-sensitive photographic material for forming a colored image, comprising a support, a plurality of and a color coupler incorporated in one of the colloid layers, the color coupler containing a methylene group free to react with an aromatic amino silver halide developing agent to form a dye, and having the formula wherein R represents a member selected from the group consisting of an alkyl radical and a substituted alkyl radical, said alkyl radical consisting of a linear chain of at least ten carbon atoms and not more than twenty carbon atoms, said substituted alkyl radical being a p-isooctylphenoxy ethyl radical, and Y represents a radical of the pyridine series selected from the group consisting of a S-acylamino-pyridyMZ)-radical, a pyridy1-(4)-radical, and a quinolyl-(2) -radical.
3. In the method of producing a colored photographic image, the steps of treating, in the presence of a color coupler, a photographic material containing a silver halide emulsion layer wherein a reducible silver salt image has been formed with a developer containing an aromatic amino silver halide developing agent, said color coupler containing a methylene group free to react with an arcmatic amino silver halide developing agent to form a dye, and having the formula 11-0-00 0-0112-0 O-NHY wherein R represents a member selected from the group consisting of an alkyl radical and a substituted alkyl radical, said alkyl radical consisting of a linear chain of at least ten carbon atoms and not more than twenty carbon atoms, said substituted alkyl radical being a p-isooctylphenoxy ethyl radical, and Y represents a heterocyclic radical selected from the group consisting of a 4-methyl-thiazolyl-(2)-radica1, a 4-phenyl-thiazolyl-(2)- radical, a 4-furyl-thiazoly1-(2)-radical, a 4methyl-5- carbethoxy ethyl-thiazolyl-(2)-radical, a 4,5-diphenylthiazolyl-(2)-radical, a 4-carboxymethyl-thiazolyl-(2) radical, a 4-m-acylaminophenyl-thiazolyl-(2)-radical, a 4-p-acylaminophenyl-thiazolyl-(2)-radical, a 4,5-dicarbethoxy-thiazolyl(2)-radical, a 4-methyl-5-carbethoxymethyl-thiazolyl-(2)-radical, a 4-methyl-5-carbethoxythiazolyl-(2)-radical, a S-carboxy-thiazolyl-(Z)-radical, a S-carbomethoxy-thiazolyl-(2)-radical, a S-carbethoxythiazolyl-(2)-radical, a S-carbethoxy-thiazolyl-(2)-radical, a S acylamino-pyridyl-(Z)-radical, a pyn'dyl-(4)-radical and a quinolyl-(2)-radical.
4. The light-sensitive photographic material according to claim 2, the light-sensitive silver halide emulsion layer having said color coupler incorporated therein.
5. The light-sensitive photographic material according to claim 1, the light-sensitive silver halide emulsion layer having said color coupler incorporated therein.
References Cited in the file of this patent UNITED STATES PATENTS

Claims (1)

1. A LIGHT-SENSITIVE PHOTOGRAPHIC MATERIAL FOR FORMING A COLORED IMAGE, COMPRISING A SUPPORT, A PLURALITY OF COLLOID LAYERS COATED THEREON, AT LEAST ONE OF SAID COLLOID LAYERS BEING A LIGHT-SENSITIVE SILVER HALIDE EMULSION LAYER, AND A COLOR COUPLER INCORPORATED IN ONE OF THE COLLOID LAYERS, THE COLOR COUPLER CONTAINING A METHYLENE GROUP FREE TO REACT WITH AN AROMATIC AMINO SILVER HALIDE DEVELOPING AGENT TO FORM A DYE, AND HAVING THE FORMULA
US742756A 1957-06-19 1958-06-18 Production of colored photographic images Expired - Lifetime US3008827A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEG22339A DE1038916B (en) 1957-06-19 1957-06-19 Process for producing color photographic images

Publications (1)

Publication Number Publication Date
US3008827A true US3008827A (en) 1961-11-14

Family

ID=7121923

Family Applications (1)

Application Number Title Priority Date Filing Date
US742756A Expired - Lifetime US3008827A (en) 1957-06-19 1958-06-18 Production of colored photographic images

Country Status (5)

Country Link
US (1) US3008827A (en)
BE (1) BE568688A (en)
DE (1) DE1038916B (en)
FR (1) FR1239317A (en)
GB (1) GB873125A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3186846A (en) * 1960-06-10 1965-06-01 Polaroid Corp Process for producing silver halide emulsions containing gelatin derivatives
US3278306A (en) * 1960-08-29 1966-10-11 Ilford Ltd Colour couplers and their production and use in colour photography
US3393041A (en) * 1963-07-09 1968-07-16 Gevaert Photo Prod Nv Multilayer silver halide elements containing thiazole color couplers for yellow
US3841880A (en) * 1973-04-03 1974-10-15 Eastman Kodak Co Silver halide emulsion containing ketomethylene photographic color-forming couplers

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2166181A (en) * 1937-09-21 1939-07-18 Pont Film Mfg Company Du Color photography
US2186849A (en) * 1935-08-07 1940-01-09 Agfa Ansco Corp Manufacture of photographic silver halide emulsions
US2296306A (en) * 1938-10-26 1942-09-22 Eastman Kodak Co Nondiffusing metallic salt coupler compound
US2395776A (en) * 1943-10-01 1946-02-26 Gen Aniline & Film Corp Color photography

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH227990A (en) * 1940-07-17 1943-07-31 Ig Farbenindustrie Ag Process for the preparation of color photographic images.
US2357776A (en) * 1942-02-16 1944-09-05 Colt S Mfg Co Barrel support for automatic firearms
BE543742A (en) * 1954-12-20

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2186849A (en) * 1935-08-07 1940-01-09 Agfa Ansco Corp Manufacture of photographic silver halide emulsions
US2166181A (en) * 1937-09-21 1939-07-18 Pont Film Mfg Company Du Color photography
US2296306A (en) * 1938-10-26 1942-09-22 Eastman Kodak Co Nondiffusing metallic salt coupler compound
US2395776A (en) * 1943-10-01 1946-02-26 Gen Aniline & Film Corp Color photography

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3186846A (en) * 1960-06-10 1965-06-01 Polaroid Corp Process for producing silver halide emulsions containing gelatin derivatives
US3278306A (en) * 1960-08-29 1966-10-11 Ilford Ltd Colour couplers and their production and use in colour photography
US3393041A (en) * 1963-07-09 1968-07-16 Gevaert Photo Prod Nv Multilayer silver halide elements containing thiazole color couplers for yellow
US3841880A (en) * 1973-04-03 1974-10-15 Eastman Kodak Co Silver halide emulsion containing ketomethylene photographic color-forming couplers

Also Published As

Publication number Publication date
GB873125A (en) 1961-07-19
BE568688A (en)
DE1038916B (en) 1958-09-11
FR1239317A (en) 1960-12-16

Similar Documents

Publication Publication Date Title
US3615506A (en) Silver halide emulsions containing 3-cyclicamino-5-pyrazolone color couplers
US2875057A (en) Benzoylacet-o-alkoxyanilide couplers for color photography
JPS6145247A (en) Color graphic recording material having yellow-dir coupler
CH628161A5 (en) COLOR PHOTOGRAPHIC MATERIAL.
US3891445A (en) Color photographic light-sensitive materials
US3384657A (en) Acetoacetamide couplers in which the non-oxo carbon atom of the aceto group is a tertiary carbon atom
US2998314A (en) Color photography
US2294909A (en) Chemical process and composition
US4157919A (en) Silver halide emulsions containing yellow-dye-forming couplers
US3563745A (en) Silver halide photographic materials containing 1-arylmethyl-2-pyrazolin-5-one color couplers
US3615505A (en) Silver halide emulsion containing 2-pyrazolin-5-one color coupler
US4617256A (en) Color photographic color coupler-containing recording material
US3677764A (en) Silver halide emulsion containing purple coupler for color photography and process of making the same
US3222176A (en) Photographic colour images from amino substituted phenols
US3008827A (en) Production of colored photographic images
US3684514A (en) Light-sensitive silver halide color photographic emulsions
US4095983A (en) Photographic material comprising cyclic sulfonamide substituted yellow color couplers
US2902366A (en) Acylated 3-aminopyrazolone couplers
US2673801A (en) Production of color photographic images
US2439098A (en) Alkoxy pyrazolone couplers
JPS585732A (en) Generation of photographic image
US3622328A (en) Process for producing photographic color images
US2865751A (en) 1-alkyl-3-acylamido-5-pyrazolone couplers for color photography
US3462270A (en) Color photography utilizing 1-fluoroalkyl - 2 - pyrazoline - 5 - one colour couplers
JPS58167572A (en) Pyrazolone compound and manufacture