Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
  • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
  • C08F20/52—Amides or imides
  • C08F20/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
  • C08F20/60—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen
• • 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
  • G03C7/327—Macromolecular coupling substances
  • G03C7/3275—Polymers obtained by reactions involving only carbon-to-carbon unsaturated bonds, e.g. vinyl polymers

Definitions

• the present invention relates to novel polymeric compounds and to their use in photographic colour elements as competing couplers for improving theimage quality.
• novel polymerisable' monomeric -2-pyrazoline-5-one compounds are provided carrying in the 4-position an alkyl group which may be substituted. From these: monomers, polymeric competing couplers can be formed having a high coupling activity. Moreover, these monomeric 2-pyrazolin-5-one compounds are easily polymerisable, so that polymers can be formed comprising a high content of active substance which is favourable for the formation of very thin intermediate hydrophilic colloid layers comprising the polymeric competing couplers. Polymerisation proceeds better with these monomeric competing couplers than withthe corresponding monomeric colou'r' couplers havingno substituent in the 4-position. 'f
• the monomeric 2 -pyrazo lin, 5 -.one compounds according tothe'p resent; invention can be represented by the formula: 4
• R represents a substituent of the type well known in the 1-position of 2-pyrazolin-5-one colour couplers e.g. alkyl, especially C --C -alkyl, which may be substituted e.g. by fluoro such as 2-trifluoroethyl, I cyano such as cyanoethyl and aryl such as benzyl,
• phenyl which may be substituted e.g. phenyl substituted by alkyl such as methyl, halogen such as chlorine and bromine, sulpho, alkoxy such'as methoxy, alkylsulphonyl such as methylsulphonyl, alkylthio such as m'ethylthio, haloalkyloxy, haloalkylthio,
• R represents a C -C alkyl group including a substituted C -C alkyl group e.g. benzyl, R being preferably methyl, and
• R represents hydrogen, C -C alkyl e.g. methyl or chlorine.
• polymeric competing couplers comprise recurring units of the formula:
• R R and R have the same significances given above, and are derived from the above monomeric 2-pyrazolin-5-one compunds by homopolymerization or by copolymerization of the monomeric 2- pyrazolin-S-one compounds with one or more monomers that are not capable of oxidative coupling with aromatic primary amino compounds and that contain at least one ethylenic group, for example acrylic acid, a-chloro acrylic acid, a-alkacrylic acid e.g. methacrylic acid, the estersand amides preferably lower alkyl esters and amides derived from these acrylic acids e.g.
• acrylamide methacrylamide, t-bhtylacrylamide, ethyl acrylate, n-butyl acrylate, Z-ethylhexyl acrylate, and lauryl methacrylate
• vinyl esters such as vinyl'acetate, vinyl propionate, and vinyl laurate,acrylonitrile, methacrylonitrile, aromatic vinyl compounds, such as stryrene and its derivatives e.
• Two or more of the above comonomeric compounds can be used together e.g. n-butyl acrylate and divinylbenzene, styrene and methacrylic acid, nbutylacrylate and methacrylic acid, etc.
• the ethylenically unsaturated monomers for being copolymerized with the monomeric 2-pyrazolin-5-one compounds corresponding to the above general formula can be chosen so that the physical and/or chemical propertiesof the resulting .copolymer e.g. its solubility, ,its compatibility with the binder of the photographic colloid composition e.g. gelatin, its flexiblity, its thennal stability etc., are favourable influenced.
• polymeric colour couplers form dyestuffs that should have favourable spectral properties and high stability so that the substituents on the colour coupler units should be selected to meet these require ments
• the polymeric competing couplers of the invention form colourless compounds so that the substituents on the competing coupler units are of minor importance in so far as they do not impair the coupling activity to a noteworthy extent.
• the monomeric 2-pyrazolin-5-one competing couplers corresponding to the above general formula can be prepared by allowing to react an acid halide of acrylic acid or an a-substituted acrylic acid such as acryloyl and methacryloyl chloride with the appropriate 3-amino-2-pyrazolin-5-one compound.
• the acylation can be effected in the presence of a Lewis acid as described in US. Pat. No. 3,325,482.
• the 3-amino-2- pyrazolin-S-one compounds can be prepared by cyclisation of the appropriate N-substituted aliphatic or aromatic hydrazine e.g. of the type described in US. Pat. No. 2,376,380 of Henry D.
• the polymeric competing couplers according to the present invention are preferably prepared by emulsion polymerisation techniques according to which latices are obtained which can be used as such for incorporating the polymeric competing couplers into lightsensitive materials.
• interesting emulsion polymerisation techniques are for instance described in Belgian Pat. Specification No. 669,971 filed Sept. 22, 1965 by du Pont de Nemours, according to which latices are formed of polymeric colour couplers by emulsion polymerisation in aqueous gelatin, and in United Kingdom Pat. No. 1,130,581 filed June 23, 1964 by Gevaert Photo-Production N.V. according to which latices are formed of polymeric colour couplers by emulsion polymerisation in water.
• the processes can be applied to the fonnation of homopolymers and to the formation of co-polymers.
• the comonomer may be a liquid comonomer and may in some cases serve as solvent for the normally solid monomer.
• persulphates such as ammonium and potassium persulphate, azonitrile compounds such as 4,4'-azo-bis(4-cyanovaleric acid) as well as peroxide compounds such as benzoyl peroxide, hydrogen peroxide.
• the latices obtained generally comprise between about 2 and about 50% by weight of polymeric competing coupler in respect of the total amount of latex.
• the polymeric competing couplers according to the present invention can be characterized by their socalled equivalent molecular weight.
• equivalent molecular weight is understood the number of grams of polymer containing 1 mole of polymerized monomeric competing coupler. It can be compared with the molecular weight of the non-polymeric classical nonmigratory competing couplers.
• the equivalent molecular weight of the polymeric competing couplers accord: ing to the invention can vary within very wide limits, preferably from about 250 to 2000.
• A. MONOMERIC COMPOUNDS Preparation 1 1-phenyl-3-methacryloylamino-4-methyl-2-pyrazolin- 5-one a. A suspension of 251 g 1.2 mole) of the ethyl ester of a-methyl-B-ethoxy-B-iminopropionic acid hydrochloride in 500 ml of hexane was neutralized at 0-5C against phenolphthaleine by means of a solution of 65 g of sodium methylate in 400 ml of methanol. While introducing nitrogen, 60 ml of acetic acid and 108 g( 1 mole) of phenylhydrazine were added at room temperature. The mixture was stirred for 1 hour whereupon 500 ml of 2N sodium hydroxide were added and the mixture was stirred for 15 min. The pH was adjusted to 4 by addition of 2N hydrochloric acid and the precipitate formed was filtered off and dried.
• Preparations 8-12 The following polymers were prepared in a similar way as the copolymer of preparation 7 using the monomer of preparation 1 as monomeric competing coupler.
• a suspension of 800 ml of demineralized water, 50 ml of a 10% aqueous solution of the sodium salt of oleyl methyl tauride, and 70 g of l-pmethylsulphonylphenyl-3-methacryloylamino-4- methyl-2-pyrazolin-5-one was stirred for 30 min. while introducing nitrogen.
• the suspension was heated to 70C and 10 g of n-butyl acrylate were added.
• the temperature was raised to 90C and 12.5 ml of a 1% aqueous solution of the sodium salt of 4,4-azo-bis(4- cyanovaleric acid) were added. Polymerization started after a few minutes and the temperature rose to 95C.
• Preparations 14-17 The following polymers were prepared in a similar way as the copolymer of preparation 13 using the monomer of preparation 3 as monomeric competing coupler.
• red-sensitized gelatino silverbromoiodide emulsion layer comprising per sq.m an amount of silver halide equivalent to 3 g of silver nitrate and containing no colour coupler
• the material was exposed to red light and processed in a common colour developing bath.
• the developer oxidation products diffuse inter alia through the intermediate layer to form a magenta dye in layer 4).
• the density formed is proportional to the amount of diffused developer oxidation products and is reduced by the presence in the intermediate layer of a competing coupler.
• a film support 2 a gelatino silverbromoiodide emulsion (4 mole of iodide) comprising per sq.m an amount of silver halide equivalent to 4 g of silver nitrate and containing no colour coupler,
• the competing couplers of the present invention can be used in one or more silver halide emulsion layers or non-lightsensitive hydrophilic colloid layers in water-permeable relationship with the emulsion layers e.g. intermediate layers and surface coatings.
• a hydrophilic colloid surface coating they can be used to react with developer oxidation products which are present in the developing composition and thus prevent these oxidation products from reacting with colour coupler in underlying emulsion layers which would cause colour fog and falsification of colour reproduction.
• intermediate layers they can be used to couple with the oxidation products formed during colour development that diffuse from an emulsion layer into an intermediate layer so that these oxidation products are prevented from diffusing in adjacent emulsion layers where they would cause colour fog and falsification of colour reproduction. It is also possible to use the competing couplers in an emulsion layer itself to reduce colour fog or to regulate the gradation which is important for correct colour reproduction. They can also be used in the emulsion layers to reduce graininess e.g. in colour reversal materials.
• the polymeric competing couplers of the present invention lend themselves particularly for use in intermediate gelatin layers. As a matter of fact intermediate layers comprising competing couplers should be as thin aspossible and it was found that the polymeric competing couplers of the invention have a high percentage of active units so that little gelatin can be used for coating the layer.
• Intermediate layers comprising polymeric competing couplers of the present invention are particularly suitable for use in photographic colour materials of the type described in Belgian Pat. No. 776,272 filed Dec. 6, 1971 by Agfa-Gervaert N.V.
• the incorporation of the polymeric colour couplers according to the present invention in the form of latices into silver halide emulsions or hydrophilic colloid e.g. gelatin compositions for the formation of intermediate layers offers several advantages. Indeed, the latices may contain a high percentage of polymer and nevertheless still possess a relatively low viscosity so that the viscosity of the hydrophilic colloid coating composition is not influenced. Moreover, by the use of latices there can be dispensed with the use of organic solvents or alkaline solutions as well as with special dispersing techniques as commonly employed for incorporating colour couplers and competing couplers.
• the polymeric competing couplers of the present invention may be used in various kinds of photographic colour materials which include negative, positive as well as reversal material.
• Photographic multilayer colour materials usually comprise a blue-sensitive silver halide emulsion layer with colour coupler for yellow, a green-sensitized silver halide emulsion layer with colour coupler for magenta and a red-sensitized silver halide emulsion layer with colour coupler for cyan.
• These colour materials may further comprise one or more intermediate layers, filter layers and protective surface layers.
• Colour couplers for yellow are usually of the acylacetamide type, expecially the acylacetanilide type for example benzoyl acetanilide colour couplers wherein both aryl groups may be substituted by groups well known in yellow-forming colour couplers e.g. alkyl, alkoxy, halogen, alkylthio, alkylsulphonyl etc. and wherein the active methylene group may carry a substituent conferring to the colour coupler a 2-equivalent character e.g. a halogen atom such as chlorine, an acyloxy group, an alkoxy, aryloxy or heterocycloxy group, an alkylthio, arylthio or heterocyclic thio group, etc.
• a halogen atom such as chlorine, an acyloxy group, an alkoxy, aryloxy or heterocycloxy group, an alkylthio, arylthio or heterocyclic thio group, etc.
• Colour couplers for magenta are usually of the 2- pyrazolin-S-one type carrying in the l-position an alkyl including substituted alkyl group e.g. haloalkyl such as fluor'oalkyl, cyanoalkyl and benzyl, or aryl including substituted aryl e.g. phenyl which may be substituted by alkyl, halogen, alkoxy, haloalkoxy, alkylsulphonyl,
• active methylene group may also carry a substituent as described above conferring to the colour coupler a 2- equivalent character.
• Particularly suitable magenta forming colour couplers can be found in U.S. Pat. Nos. 3,325,482 of Marcel Jacob Monbaliu, Arthus Henri De Cat and Raphael Karel Van Poucke, issued June 13,
• 2-equivalent or 4-equivalent colour couplers for cyan are usually of the phenol or naphthol type. Particularly suitable are the colour couplers described in French Pat. No. 2,078,920 filed Feb. 22, 1971 by Gevaert- Agfa N.V., in British Pat. No. 1,004,281 filed Feb. 15, 1961 by Gevaert Photo-Producten N.V. and in U.S. Pat. Nos. 3,079,256 of Raphael Karel Van Poucke, Arthur Henri De Cat and Marcel Hendrik Verbrugghe, issued Feb. 26, 1963, 3,226,230 of Raphael Karel Van Poucke, Hector Alfons Vanden Eynde and Arthur Henri De Cat, issued Dec. 28, 1965, and 3,488,] 93 of Hector Alfons Vanden Eynde and Arthur Henri De Cat, issued Jan. 6, 1970.
• the hydrophilic colloid used as the vehicle for the silver halide emulsion layer and the other hydrophilic colloid layers may be, for example, gelatin, colloidal albumin, zein, casein, a cellulose drivative, a synthetic hydrophilic colloid such as polyvinyl alcohol, poly-N- vinyl pyrrolidone, etc., gelatin being preferred. If desired compatible mixtures of two or more of these colloids may be employed.
• the silver halide emulsion layer may comprise various silver salts as the sensitive salt such as silver bromide, silver chloride, silver chlorobromide, silver bromoiodide and silver chlorobromoiodide.
• the photographic colour elements comprising the polymeric competing couplers of the present invention may comprise as supports paper, glass, cellulose ester film, polyvinyl acetal film, polystyrene film, polyethylene terephthalate film and related films of resinous materials.
• aromatic primary amino developing agents are used forming dyestuffs with the colour couplers incorporated in the photographic material and colourless compounds with the polymeric competing couplers of the present invention.
• Suitable developing agents are p-phenylene diamine and derivatives e.g. N,N-diethyl-p-phenylene diamine, N-butyl-N- sulphobutyl-p-phenylene diamine, 2-amino-5- 4-amino-N-ethyl-N( B-me thane N-hydroxyethyl-N- EXAMPLE
• a photographic multilayer negative material A was composed as follows:
• a material B was prepared in exactly the same way as material A with the only difference that both the gelatin-intermediate layer and the filter layer comprise per sq.m an amount of polymeric competing coupler according to preparation 13 corresponding to l millimole of polymerized monomeric coupler.
• the separation images of material B showed markedly purer colours than those of material A.
• a photographic colour element comprising in a lightsensitive silver halide emulsion layer or in a nonlightsensitive hydrophilic colloid layer in waterpermeable relationship with the said emulsion layer a polymeric compound comprising recurring units of the fonnula:
• R represents an alkyl group or an aryl group
• R represents a C -C alkyl group
• R is hydrogen, C -C alkyl or chlorine.
• Photographic element according to claim 1 wherein R is a phenyl group and R is methyl.
• Photographic element according to claim 1 wherein the said polymeric compound is a homopolymer.
• Photographic element according to claim 1 wherein the said polymeric compound is a copolymer comprising recurring units derived from one or more monomeric compounds containing an ethylenic group and being incapable of oxidative coupling with an aromatic primary amino compound.
• Photographic element according to claim 1 wherein the said polymeric compound is a copolymer comprising recurring units derived from one or more monomeric compounds selected from the group consisting of acrylic acid, methacrylic acid, esters and amides of these acrylic acids, styrene, vinyl toluene and divinyl benzene.
• a photographic element comprising at least one blue-sensitive silver halide emulsion layer containing a colour coupler for yellow, at least one green-sensitized silver halide emulsion layer containing a colour coupler for magenta, at least one red-sensitized silver halide emulsion layer containing a colour coupler for cyan and one or more intermediate or filter layers wherein the said intermediate and- /or filter layers comprise the said polymeric compound.

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Citations (3)

• 1973
  • 1973-01-30 DE DE2304319A patent/DE2304319A1/de active Pending
• 1974
  • 1974-01-10 CA CA189,824A patent/CA1023898A/en not_active Expired
  • 1974-01-11 GB GB137674A patent/GB1454054A/en not_active Expired
  • 1974-01-11 US US432533A patent/US3912513A/en not_active Expired - Lifetime
  • 1974-01-18 BE BE1005654A patent/BE809893A/xx unknown
  • 1974-01-19 IT IT86207/74A patent/IT1016464B/it active
  • 1974-01-22 FR FR7402449A patent/FR2215420B1/fr not_active Expired
  • 1974-01-29 JP JP49012149A patent/JPS5083031A/ja active Pending

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