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
  • C08F220/00—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
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C255/00—Carboxylic acid nitriles
• • 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
  • C08F20/10—Esters
  • C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
  • C08F20/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
• • 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
  • C08F220/00—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
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
  • C09D133/04—Homopolymers or copolymers of esters
  • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
  • C09D133/062—Copolymers with monomers not covered by C09D133/06
• • 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
  • G03C1/00—Photosensitive materials
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/04—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with macromolecular additives; with layer-forming substances
  • G03C1/053—Polymers obtained by reactions involving only carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
• • 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
  • G03C1/00—Photosensitive materials
  • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
• • 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
  • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
• • 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
  • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
  • G03C8/02—Photosensitive materials characterised by the image-forming section
• • 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
  • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
  • G03C8/24—Photosensitive materials characterised by the image-receiving section
  • G03C8/26—Image-receiving layers
  • G03C8/28—Image-receiving layers containing development nuclei or compounds forming such nuclei

Definitions

• R is alkylene and X is aliphatic acyl or cyano; and R is alkyl, cycloalkyl, aryl or Where R is alkylene and X is aliphatic acyl or cyano, provided that one and only one of R, and R is always i -RaOC--CH2X
• polymers containing units of monomers of the above formula can be utilized to provide improved photographic compositions.
• This invention relates to organic materials which are particularly useful in the photographic field.
• this invention relates to the preparation and use of such organic materials, particularly polymeric materials which can be incorporated into photographic elements and emulsions to obtain a desirable combination of properties.
• this invention relates to photographic materials, their preparation and use.
• Photographic elements employed in photography must have good physical and photographic properties. Due to its unique properties, including its good dispersing property and its excellent protective colloid properties, gelatin has been used as the binding agent in layers of photographic elements for many years. Gelatin is however subject to dimensional change when subjected to varying temperature, humidity and like conditions. Many natural and synthetic materials have been proposed as substitutes for gelatin in one or more layers of a photographic element to improve dimensional stability. For example, as shown in US. Patent 3,062,674, issued Nov. 6, 1962 and U.S. Patent 3,142,568 issued July 28, 1964, vinyl or addition polymers are employed in binding agents in layers of photographic elements to improve physical properties, including dimensional stability.
• a film-forming, addition interpolymer containing at least about 0.1%, by weight, of active methylene groups in aliphatic side chains can be used in binding agents in photographic materials to give products having good dimensional stability and resistance to abrasion.
• a particularly effective class of interpolymers useful for this purpose is prepared from acrylic type esters having active methylene groups in the ester moiety or in a substituent alpha to the carbonyl group. Such compounds can be represented by the formula:
• R is hydrogen, alkyl or o Ro( ioH2X where R is alkylene and X is aliphatic acyl or cyano and R is alkyl, cycloalkyl, aryl or Where R and X are as defined, provided that one and only one R and R is always
• the ethylenically unsaturated polymerizable monomers having the above formula can be prepared using any procedure suitable for this purpose. In general, the reaction of acid chlorides, acid anhydrides or mixed anhydrides containing active methylene groups with acrylic esters containing hydroxyalkyl substituents can be employed.
• a preferred synthesis for preparing the esters having an active methylene group in the ester moiety involves the reaction of a hydroxyalkyl ester of acrylic or an alphaalkyl acrylic acid with diketene or cyanoacetyl chloride.
• the esters having active methylene groups in the alphasubstituent in the above formula can be obtained by reacting the alpha-hydroxyalkyl substituted acrylic esters with diketene or cyanoacetyl chloride.
• Such reactions are not particularly pressure sensitive and, therefore, can be carried out at atmospheric, superatmospheric or subatmospheric pressure.
• the temperature range is subject to Wide variation depending, for example, upon the particular reactants employed, solvents and like considerations, but generally temperatures up to about C.
• the reaction can be carried out in the absence of solvent or using a suitable vehicle, for example, diethyl ether, ethyl acetate or the like and is generally completed in less than 20 hours, often less than 4 hours.
• a suitable vehicle for example, diethyl ether, ethyl acetate or the like and is generally completed in less than 20 hours, often less than 4 hours.
• the acrylic esters containing the active methylene groups are generally viscous liquids or oils and can be separated from the reaction medium by any means suitable for this purpose, for example, by distillation.
• the interpolymers employed in photographic materials according to the practice of this invention are film-forming, addition interpolymers containing at least about 0.1%, generally about 0.1 to about 1.4%, by weight, of active methylene groups in aliphatic side chains of the interpolymers.
• Active methylene groups are methylene groups between two activating groups, for example electronegative groups such as carbonyl. Such methylene groups exhibit unusual chemical activity and are said to be active.
• Malonic esters, acetoacetic esters, cyanoacetic esters and 1,3-diketones are examples of compounds containing such groups.
• the active methylene groups are usually separated from the main polymer chain by at least three atoms and can be introduced into the side chains of an interpolymer by copolymerizing a monomer containing at least one active methylene group, for example a o o II it --COH2--G group, and an independently polymerizable unsaturated methylene group with at least one other copolymerizable monomer containing, for example, at least one group.
• a monomer containing at least one active methylene group for example a o o II it --COH2--G group
• an independently polymerizable unsaturated methylene group with at least one other copolymerizable monomer containing, for example, at least one group.
• the molecular weights of the interpolymers employed in photographic emulsions and elements according to the practice of this invention are subject to wide variation, but are often in the range of about 5,000 to about 500,000.
• Useful gelatin substitutes include, therefore, interpolymers of acrylic monomrs having the above formula with other ethylenically unsaturated polymerizable monomers which form addition polymers, such as vinyl esters, amides, nitriles, ketones, halides, ethers, alpha-beta-unsaturated acids or esters thereof, olefins, diolefins and the like, as exemplified by acrylonit-rile, methacrylonitrile, styrene, alpha-methylstyrene, acrylamide, vinyl chloride, vinylidene chloride, methyl vinyl ketone, fumaric, maleic and itaconic esters, 2-chloroethyl vinyl ether, acrylic acid, methacrylic acid, dimethylaminoethyl methacrylate, 4,4, 9-trimethyl 8 oxo-7-oxa-4-azonia-9-decen
• a preferred class of vinyl or addition interpolymers which can be employed as gelatin substitutes in photographic materials are interpolymers of (A) about 50 to about by weight, of a monomer (1) having the formula:
• R is hydrogen or methyl and R is alkyl, desirably containing up to about 10 carbon atoms, as exemplified by methyl, propyl, isobutyl, octyl, decyl and the like, (B) about 3 to about 20%, by weight, of a sulfoester monomer (2) having the formula:
• R is hydrogen or alkyl, desirably containing up to about 12 carbon atoms, often 1-8 carbon atoms, as exemplified by methyl, pentyl, octyl, dodecyl and the like
• R has its valence bonds on ditferent carbon atoms and can be a divalent hydrocarbon radical or divalent aliphatic hydrocarbon radical in which a chain of carbon atoms joining the oxygen and sulfur atoms in the above formula is interrupted by an atom from Group IV-A of the Periodic Table having an atomic weight of less than about 33, i.e., at least one -O-- and/or -S radical interrupts the carbon chains and M is a cation and (C) about 2 to about 20%, by weight, of a monomer (3) having the formula:
• oI-I2 C-iio1t 1'1.
• R is hydrogen, alkyl, desirably containing up to 12 carbon atoms as exemplified by methyl, n-butyl, octyl, dodecyl and the like, or
• R is alkylene, desirably containing up to 10, preferably 1-8 carbon atoms, as exemplified by ethylene, tetramethylene, 1,3-isobutylene, octamethy-lene and the like and X is aliphatic acyl containing up to about 8 carbon atoms, such as alkyl carbonyl groups exemplified by acetyl, butyryl, caprylyl and the like, or cyano and R is alkyl, desirably containing up to about 10 carbon atoms, as exemplified by methyl, butyl, octyl, decyl and the like, cycloalkyl, desirably containing up to about 10 carbon atoms, as exemplified by cyclopentyl, cyclo'butyl, cyclohexyl and the like, aryl, desirably containing up to about
• R radicals are alkylene radicals, generally those containing 2-4 carbons.
• R can also be a divalent aliphatic hydrocarbon radical in which there is an O-- and/or S- radical and generally contains up to 12 carbon atoms.
• Such R radicals can, therefore, be saturated or unsaturated, although saturated divalent alkylene groups in which the carbon chain is interrupted by oxygen and sulfur atoms are preferred.
• Suitable R radicals include, for example, ethylene, 1,3- propylene, 1,2-propylene, tetramethylene, 1,3-isobutylene, pentamethylene, hexamethylene, octamethylene, phenylene, bisphenylylene, naphthylene, cyclopentylene, cyclohexylene, Z-butylene, butynylene, 2-oxatrimethylene, 3-
• M in the sulfoester monomer (2) is a cation, as exemplified by hydrogen, an alkali metal such as sodium or potassium, ammonium, the cation of an organic amine such as t-riethylene amine, diethanol amine and the like.
• interpolymers in which acrylic acid is used in place of the sulfoester monomer (2).
• interpolymers are film-forming, addition interpolymers of (A) about 50 to about 90%, by Weight, of a monomer (1) having the formula:
• R and R are as defined hereinbefore for monomer (1), (B), about 3 to about 20%, by weight, of acrylic acid and (C) about 2 to about 20%, by weight, of a monomer (3) having the formula:
• the preferred class of interpolymers containing sulfoester units preferably contain, in polymerized form, at least about 65%, by weight, of monomer (1), at least about 3%, by weight, of sulfoester monomer (2) and at least about 2%, by weight, of monomer (3).
• the preferred class of interpolymers containing acrylic acid units preferably contain, in polymerized form, at least about 65%, by Weight, of monomer (1), at least about by weight, of acrylic acid and at least about 5%, by weight, of monomer 3).
• the temperature at which the interpolymers described herein are prepared is subject to wide variation since this temperature depends upon such variable features as the specific monomer used, duration of heating, pressure employed and like considerations.
• the polymerization temperature generally does not exceed about 110 C., and most often it is in the range of about to about C.
• the polymerization can be carried out in a suitable vehicle, for example, water or mixtures of water with Water miscible solvents, as exemplified by methanol, ethanol, propanol, isopropyl, alcohol, butyl alcohol, and the like.
• the pressure employed in the polymerization, if any, is usually only sufficient to maintain the reaction mixture in liquid form, although either superatmospheric or subatmospheric pressures can be used.
• the concentration of polymerizable monomer in the polymerization mixture can be varied widely with concentrations up to about 40%, by weight, and preferably about 20 to about 40%, by weight, based on the Weight of the vehicle, being satisfactory.
• Suitable catalysts for the polymerization reaction include, for example, the free radical catalysts, such as hydrogen peroxide, cumene hydroperoxide, water soluble azo type initiators and the like. In redox polym erization systems the usual ingredients can be employed. If desired, the polymer can be isolated from the reaction vehicle by freezing, salting out, precipitation or any other procedure suitable for this purpose.
• Suitable wetting agents include the non-ionic, ionic and amphoteric types as exemplified by the polyoxyalkylene derivatives, amphoteric amino acid dispersing agents, including sulfobetaines and the like.
• Such Wetting agents are disclosed in U.S. Patent 2,600,831, issued June 17, 1952; U.S. Patent 2,271,622, issued Feb. 3, 1942; U.S. Patent 2,271,623, issued Feb. 3, 1942; U.S. Patent 2,275,727, issued Mar. 10, 1942 and U.S.
• the Wetting agents are generally employed in the polymer preparation in concentrations in the range of about 1% to about 5% based on polymerizable monomer and in coating photographic elements at concentrations in the range of about 0.1 to about 5%, by Weight, based on binding agent. Particularly suitable non-ionic wetting agents or coating aids are disclosed in Belgian Patent 652,862 as having the formula:
• Dispersions of the photographic silver halide containing the film-forming, addition interpolymers containing active methylene groups, in combination with photographic binding agents, such as gelatin can be made in a variety of Ways.
• an aqueous gelatin dispersion of the photographic silver halide can be mixed with an aqueous dispersion or solution of the interpolymer.
• the photographic silver halide can be precipitated in an aqueous dispersion or solution of the interpolymer with or without another colloid, depending upon the dispersing characteristics of the interpolymer.
• a water-soluble silver salt such as silver nitrate is admixed with a water-soluble halide such as potassium bromide in the presence of the mixture.
• the photographic silver halide is precipitated in an aqueous gelatin solution and digested in the conventional manner known to the art. After digestion, but prior to coating. there is added to the emulsion an aqueous dispersion of the interpolymer containing active methylene groups in its side chains.
• the bulk of the resulting dispersion can be increased by the addition of more of the interpolymer and/or natural or synthetic colloids or other binding agents suitable for use in photographic silver halide emulsions.
• Satisfactory colloids include, for example, gelatin, protein derivatives e.g. carboxy methylated proteins, colloidal albumin, cellulose derivatives, synthetic resin such as polyvinyl compounds e.g. polyacrylamide and the like.
• the gelatin substitutes described herein can be employed in the binding agent in one or more layers of a photographic silver halide element.
• photographic silver halides are generally precipitated in the presence of binding agents such as gelatin or other colloids which exhibit very good peptizing action. Therefore, the photographic silver halide emulsions or layers of this invention will generally contain some binding agent such as gelatin which exhibits this very good peptizing action.
• concentration of the interpolymers described herein will be in the range of about 20 to about 85%, often in the range of about 50 to about 85%, by weight, based on total binding agent (dry weight), employed in photographic emulsions, photographic emulsion layers or other layers of a photographic element.
• the remainder of the binding agent is gelatin, although other colloids also give good results.
• the polymers are used in photographic elements in layers other than the emulsion layers, for example, in filter layers, antihalation layers, antiabrasion layers, antistatic layers, barrier layers, receiving layers for diffusion transfer processes and the like; they can be used as the sole vehicle or in admixture with natural or synthetic colloids such as are mentioned hereinbefore.
• the silver halide employed in the preparation of light sensitive coatings described herein includes any of the photographic silver halides as exemplified by silver bromide, silver chloride and silver iodide, or mixed silver halides such as silver chlorobromide, silver bromoiodide, and the like.
• halide comprises at least 50 mole percent chloride.
• Preferred emulsions of this type contain at least 60 mole percent chloride; less than 40 mole percent bromide and less than mole percent iodide.
• Typical supports include polymeric films such as cellulose acetate film, polyvinyl acetal film, polystyrene film, polypropylene film and other polyolefin film, polycarbonate film, polyethylene terephthalate film and other polyester film as well as glass, paper, wood and the like.
• Supports such as paper which are coated with alpha-olefin polymers, particularly polymers of alpha-olefins containing 2-l0 carbon atoms, as exemplified by polyethylene, polypropylene, ethylenebutene copolymers and the like give good results.
• the emulsions containing the interpolymers can be chemically sensitized with compounds of the sulfur group, noble metal salts such as gold salts, reduction sensitized with reducing agents, and combinations of these.
• emulsion layers and other layers present in photographic elements made according to thi invention can be hardened with any suitable hardener such as aldehyde hardeners, such as formaldehyde, mucochloric acid and the like, aziridine hardeners, hardeners which are derivatives of dioxane, oxypolysaccharides such as oxystarch, oxy plant gums and the like.
• Such hardened layer will have a melting point in Water greater than about F. and preferably greater than 200 F.
• the emulsion can also contain additional additives, particularly those known to be beneficial in photographic emulsions, including for example, stabilizers or antifoggants, particularly the water-soluble inorganic acid salts of cadmium, cobalt, manganese and zinc as disclosed in U.S. Patent 2,829,404, the substituted triazaindolizines as disclosed in U.S. Patents 2,444,605 and 2,444,607, speed increasing materials, absorbing dyes, plasticizers and the like.
• Sensitizers which give particularly good results in the photographic compositions disclosed herein are the alkylene oxide polymers which can be employed alone or in combination with other materials, such as quaternary ammonium salts, as disclosed in U.S. Patent 2,886,437 or with mercury compounds and nitrogen containing compounds, as disclosed in U.S. Patent 2,751,299.
• the interpolymers containing at least about 0.1%, by weight, of active methylene groups in their side chains can be used in various kinds of photographic emulsions.
• they can be used in direct positive silver halide emulsions, X-ray and other non-spectrally sensitized emulsions as well as in orthochromatic, panchromatic and infrared sensitive emulsions, particularly those sensitized with merocyanine dyes, cyanine dyes, carbocyanine dyes and the like.
• these polymers can be used in emulsions intended for color photography, for example, emulsions containing color forming couplers or emulsions to be developed by solutions containing couplers or other color generating materials.
• these polymers can be used in photographic emulsions containing developers, e.g. polyhydroxybenzenes as well as in emulsions intended for use in diffusion transfer processes which utilize the non-developed silver halide in the non-image areas of the negative to form a positive by dissolving the undeveloped silver halide and precipitating it on a receiving layer in close proximity to the original silver halide emulsion layer.
• developers e.g. polyhydroxybenzenes
• emulsions intended for use in diffusion transfer processes which utilize the non-developed silver halide in the non-image areas of the negative to form a positive by dissolving the undeveloped silver halide and precipitating it on a receiving layer in close proximity to the original silver halide emulsion layer.
• Such processes are described in Rott U.S. Patent 2,352,014, Land U.S. Patent 2,543,181 and Yackel et al. U.S. Patent 3,020,155.
• the polymers described herein can also be used in color transfer processes which utilize the diffusion transfer of an image-wise distribution of developer, coupler or dye from a light sensitive layer to a second layer while the two layers are in close proximity to one another. Color transfer processes of this type are described in Yutzy U.S. Patent 2,856, 142, Land et al. U.S. Patent 2,983,606, Whitmore et al. British Patents 904,364 and 840,731 and Whitmore et al. U.S. application Ser. No. 392,471. These polymers can also be used in unhardened colloid layers, particularly those designed for processing in hardening developers, as disclosed in British Patent 825,544, published Dec. 16, 1959. Silver halide emulsions containing these polymers can be processed in monobath processes such as described in Haist et al. U.S. Patent 2,875,048 or in stabilization type processes.
• Example 1 Twenty-seven grams of 2-hydroxyethyl methacrylate is mixed with 20 g. of diketene. After the addition of 1 g. of hydroquinone (polymerization inhibitor) the mixture is heated to 100 C. After four hours the mixture is distilled in vacuo and the fraction boiling at 100-130 C./ 1 mm. is collected. This fraction is redistilled from hydroquinone and the principal fraction is collected at 110- 120 C./ 0.3 mm. There is obtained 30 g. of Z-acetoacetoxyethyl methacrylate.
• hydroquinone polymerization inhibitor
• Example 2 A solution of 24 g. of Z-hydroxyethyl acrylate and 17 g. of diketene in 100 ml. of ethyl acetate is treated with 0.2 g. of triethylamine. The temperature rises gradually to 33 C. over one hour. The solution is heated at reflux for two hours and concentrated in vacuo to an oil which is submitted to molecular distillation at 9 microns. A yield of 15.8 g. of 2-acetoacetoxyethyl acrylate is obtained at a pot temperature of 73 C.
• Example 3 To a solution of 82 g. of freshly distilled diketene in 400 ml. of ethyl acetate is added 127 g. of ethyl or- (hydroxymethyl)acrylate. One gram of p-(p-toluenesulfonamido) diphenylamine (polymerization inhibitor) is added and the solution stirred at room temperature. In the course of three hours the temperature gradually rises to a maxmium of 47 C. The solution is kept for approximately 15 hours at room temperature, treated with 2 g. of anilinophenol and submitted to molecular distillation. Several fractions, shown to be similar by infrared spectroscopy, are collected between 84 C. and 94 C. at 500- 505 microns. The total weight of the fractions, which are substantially ethyl a-acetoacetoxymethyl acrylate is 107 g.
• Example 4 A suspension of 104 g. of phosphorus pentachloride in 200 ml. of ether is cooled to 10 C. and treated dropwise with 42.5 g. of cyanoacetic acid in 450 ml. of diethylether. The resulting clear solution is concentrated in vacuo to a weight of 54 g. of crude cyanoacetyl chloride. The crude cyanoacetyl chloride is added to a solution of 65 g. of 2-hydroxyethyl methacrylate in 125 ml. of diethyl ether containing 25 g. of acrylonitrile. After two hours at room temperature the solution is refluxed for 1 /2 hours and concentrated to an oil in vacuo.
• Example 1 compounds of the type prepared according to Examples 1-4 will polymerize with other monomers to form interpolymers containing active methylene groups in the side chains of the interpolymers.
• Triton 770 a 40% solution of a surfactant composition composed of a sodium salt of an alkyl aryl polyether sulfate in isopropanol
• potassium persulfate 0.5 g. of potassium persulfate and 0.05 g. of sodium bisulfite.
• the addition is completed in ten minutes under a constant stream of nitrogen with the flask maintained at C. After heating for an additional fifteen minutes, the latex is cooled.
• the copolymer latex has the molar composition of 75.7% butyl acrylate, 14.9% acrylic acid, and 9.4% Z-acetoacetoxyethyl acrylate and is prepared at two pH levels5.0 and 6.2.
• Example 6 A solution of 4 ml. of Triton 770 in 375 ml. of water is purged with nitrogen and heated to C. 1.0 g. of potassium persulfate and 0.1 g. of sodium bisulfite are added with stirring, followed immediately by the gradual addition from two funnels of the following:
• Example 7 A solution of 7.5 g. of ethyl acrylate, 2.0 g. of acrylic acid and 1.0 g. of Z-acetoacetoxyethyl methacrylate in 10 ml. of dioxane is mixed with 0.05 g. of 2,2'-azobis(2- methylpropionitrile) and kept at 80 C. for one hour.
• the copoly(ethyl acrylate-acrylic acid-Z-acetoacetoxyethyl methacrylate) is isolated by precipitation in Water.
• Example 8 A solution of 4.0 ml. of Triton 770 in 350 ml. of water is swept with nitrogen and heated to 80 C. 1.0 g. of potassium persulfate and 0.1 g. of sodium bisulfite is added. The following two solutions are added simultaneously over ten minutes with stirring:
• the resulting latex of copoly(methyl acrylate-acrylic acid ethyl OL'HCCtOBCEllOXY methyl acrylate) is kept at 80" C. for two hours and cooled to room temperature.
• a portion of the latex is diluted with an equal volume of water and treated with sodium hydroxide (10% solution) to give a solution at pH 5.0 containing 9.8% solids.
• Example 9 As previously pointed out, surface active compounds of the type listed in Table I can be employed during the preparation of a polymer. To illustrate, a solution of 4 ml. of surface active compound No. 9 of Table I in 365 ml. of distilled water purged with nitrogen is heated to 94 C. To this solution is added 1.0 g. of potassium persulfate and 0.1 g. of sodium bisulfite. Immediately after this addition there is begun the simultaneous addition of the following two solutions:
• the resulting latex contains copoly (butyl acrylate sodium acryloyloxy propane sulfonate-Z-acetoacetoxyethyl methacrylate).
• Example 10 The procedure of Example 9 is followed employing the following reactants: 222 g. of methyl acrylate, 12 g. of sodium acryloyloxypropane sulfonate, 16 g. of 2-acetoacetoxyethyl methacrylate, 2.0 g. potassium persulfate, 0.6 g. sodium bisulfite, 16 ml. of surface active compound and a total of 1000 ml. of water. A latex having 19.8% solids and pH 3.5 is obtained. This latex is adjusted to pH 5.0 with dilute sodium hydroxide before coating in photographic materials.
• the latex comprises coply(methyl acrylate sodium acryloyloxypropane sulfonate 2 acetoacetoxyethylmethacrylate)
• Example 11 To a solution of 2 ml. of Triton 770 in 190 ml. of water at 95 C. is added 0.5 g. of potassium persulfate and 0.05 g. sodium bisulfite. Immediately thereafter there is added simultaneously the following two solutions over a period of ten minutes:
• the latex is cooled, diluted with an equal volume of water and converted to a solution at pH 6.5 by the addition of 10% sodium hydroxide solution.
• Example 12 As previously indicated, interpolymers containing active methylene groups in the side chains can be incorporated into photographic materials to improve resistance to abrasion.
• copoly(methyl acrylate/ sodium 3- acryloyloxy-l methylpropane-l sulfonate/Z-acetoacetoxyethyl acrylate) latex of Example 6 is incorporated into a fine grain silver chlorobromide emulsion (80 mole percent chloride).
• the emulsion contains 70 g. of gelatin and 70 g. of copolymer per mole of silver halide.
• the emulsion is coated on conventional polyester film support at a silver coverage of 412 mg./ft.
• Coating 1 support (Coating 1) with formaldehyde hardening agent.
• copoly(methyl acrylate-sodium 3-acryloyloxypropane-1- sulfonate) (95:5 weight percent) is incorporated into another sample of the emulsion and coated in the same manner (Coating 2).
• the coatings are exposed on an Eastman 1b sensitometer, developed in Kodak DK-SO developer for approximately minutes at 68 F., fixed in Kodak F-5 fix for approximately minutes and washed.
• the resistance to abrasion for the coatings is determined by drawing a pointed stylus under constant pressure across the surface of the coating which is wet with developer, fix or wash water.
• the resistance to abrasion is rated as follows:
• the coating is easily punctured by the stylus and easily tears away from the support.
• Example 13 The use of the interpolymers described herein in photographic materials has no substantial adverse effect on photographic properties.
• copoly(methyl acrylate-sodium 3 acryloyloxypropane 1 sulfonate-2- acetoacetoxyethyl methacrylate) latex of Example 10 is incorporated into a portion of a coarse grain gelatin, silver bromoiodide emulsion which is panchromatically sensitized.
• the emulsion portion is coated (Coating B) on conventional cellulose acetate film support at a coverage of 460 mg. of silver and 1040 mg. of gelatin/ft. of support.
• Coating A another portion of the emulsion containing no copolymer is coated in the same manner (Coating A).
• the interpolymers described herein can be used in layers other than photographic silver halide emulsion layers.
• copoly(methyl acrylate-sodium-3-acryloyloxypropane 1 sulfonate 2 acetoacetoxyethyl methacrylate) latex prepared according to Example 10
• copoly(butyl acrylate-sodium-3-acryloyloxypropane 1- sulfonate 2 acetoacetoxyethyl methacrylate) latex prepared according to Example 9 are mixed with an equal quantity of gelatin and coated on a conventional polyester film support at 674 mg. of vehicle per square foot of support.
• These coatings are designated 4 and 8, respectively, in the following table.
• coatings are prepared using copoly(methyl acrylate sodium 3 acryloyloxypropane 1 sulfonate) (:5 wt. percent), (designated Coatings 1-3 below) and copoly(butyl acrylate sodium 3 acryloyloxypropanel-sulfonate) (95:5 Wt. percent) (designated Coatings 5-7 below) in place of the copolymers in Coatings 4 and 8. All coatings contain formaldehyde hardener.
• the coatings are immersed in Kodak DK-50 developer (2 minutes), Kodak F-5 Fix (3 minutes) and wash water (10 minutes).
• the resistance to abrasion is determined using the procedure of Example 12. The results are as follows:
• R is a hydrogen atom, an alkyl group containing up to 12 carbon atoms, or
• R is an alkylene group containing up to 10 carbon atoms and X is alkylcarbonyl containing up to 8 carbon atoms, provided that one and only one of R and R is always ti Rto-ooH2X 2.
• X is an acetyl group.
• R is an alkylene group containing up to 10 carbon atoms
• R is a hydrogen atom or an alkyl group containing up to 12 carbon atoms
• X is an alkylcarbonyl group containing up to 8 carbon atoms. 5.
• R is an alkyl group containing up to 10 carbon atoms, a cycloalkyl group containing up to 10 carbon atoms or a phenyl group
• R i an alkylene group containing up to 10 carbon atoms
• X is an alkylcarbonyl group containing up to 8 carbon atoms.

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• 1965
  • 1965-12-20 US US525272A patent/US3459790A/en not_active Expired - Lifetime
• 1966
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