US2829053A - Copolymers and photographic emulsions containing the same - Google Patents

Copolymers and photographic emulsions containing the same Download PDF

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US2829053A
US2829053A US467641A US46764154A US2829053A US 2829053 A US2829053 A US 2829053A US 467641 A US467641 A US 467641A US 46764154 A US46764154 A US 46764154A US 2829053 A US2829053 A US 2829053A
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parts
copolymers
weight
emulsion
copolymer
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US467641A
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Weaver Clay
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EIDP Inc
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EI Du Pont de Nemours and Co
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Priority to BE542633D priority Critical patent/BE542633A/xx
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Priority to US467641A priority patent/US2829053A/en
Priority to GB27396/55A priority patent/GB788955A/en
Priority to DEP14966A priority patent/DE1018306B/de
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C08G59/3209—Epoxy compounds containing three or more epoxy groups obtained by polymerisation of unsaturated mono-epoxy compounds
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/12—Hydrolysis
    • 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
    • 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
    • C08F218/00—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 an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
    • C08F218/02—Esters of monocarboxylic acids
    • C08F218/04—Vinyl esters
    • C08F218/08—Vinyl acetate

Definitions

  • This invention relates to photographic emulsions and more particularly to silver halide emulsions containing amine and quaternary ammonium derivatives of vinyl alcohol/allyl glycidyl ether copolymers.
  • Gelatin has generally been employed as the protective colloid for photosensitive silver halide since it has the ability to form a thin coating containing dispersed silver halide. Gelatin has good water permeability coupled with insolubility at relatively low temperatures. However, photographic'emulsions based on gelatin are somewhat brittle, unstable, susceptible to decomposition by bacteria andvfungi, difficult to maintain and process under conditions of high humidity and temperature.
  • An object of this invention is to provide new synthetic colloid-silver halide emulsions. Another object is to provide such emulsions which have good sensitivity and speed characteristics. I A further object is to provide such emulsions to which substantial amounts of water-permeabl'e colloids can be added. A related object is to provide such emulsions which can be made ready for coating by the addition of substantial amounts of polyvinyl alcohol or water-soluble or hydrophilic acetals. Still other objects will be apparent from the folowing description of the invention.
  • photosensit ive emulsions are obtained by the dispersion of a photosensitive silver halide in a protective colloid system that is substantially gelatin free and contains at least 1% and preferably 10-50% or more of an ammonia, monoamine, or quaternary ammonium derivative of a hydrolyzed polyvinyl ester/allyl glycidyl ether copolymer in which the copolymer ratio of allyl glycidyl ether to vinyl ester groups is within the range of from A to A.
  • hydrolyzed copolymers just described by reason of the large initial proportion of vinyl ester units, may be called amineor quaternary ammonium-modified polyvinyl alcohols. Theyare'98 to100% hydrolyzed and consist essentially of recurringintralinear units of the formulae: 1
  • the photosensitive compositions can be prepared by precipitating light-sensitive silver halide in an aqueous solution of the'hydrolyzed copolymers described above or by admixing an aqueous dispersion of silver halide with an aqueous solution of such copolymers.
  • the resulting solution can be admixed with or bulked up with additional copolymer or with a different Water-permeable colloid and made ready for coating on a suitable sheet support, e. g., film or paper, by admixing therewith a sensitizing dye or dyes, color-former, sulfur sensitizer and other emulsion adjuvants.
  • the solutions can be admixed with polyvinyl acetal color-formers to form color-forming emulsion layers.
  • Example I A solution containing 50 parts of a 2.5% solution of the quaternary ammonium-modified polyvinyl alcohol prepared by hydrolysis from vinyl acetate/allyl glycidyl ether of 91.4/ 8.6 composition (described in Webers U. S. Patent 2,676,166) and dimethylaminoacetamide, 23 parts of 3 N ammonium bromide, 1.2 parts of 0.5 N potassium iodide and 50 parts of water is treated with a solution of the soluble complex formed by adding 20% ammonium hydroxide to 10 parts 3 N silver nitrate until the precipitate which is originally formed is completely redissolved and 50 parts of water.
  • the emulsion is ripened essed bystandard photographic methods, a black and white, image of good gradation is obtained and the photographic speed of the emulsion is found to be four times as fast as a control emulsion made in completely hydrolyzed polyvinyl alcohol without the amine-modified polyvinyl alcohol.
  • Example II Photographic silver halides are prepared as described in assignees Weaver application Ser. No. 362,151, filed June 16, 1953, now U. S. Patent No. 2,752,246, by stirring a solution consisting of 46 parts of 3 N ammonium bromide, 2.5 parts 0.5 N potassium iodide, 50 parts of distilled water and 25 parts of a solution of the condensation product of moles of ethylene oxide with 1 mole of oleyl alcohol and adding a solution consisting of the soluble complex formed by adding 20% ammonium hydroxide to 20 parts of 3 N silver nitrate until the precipitate which is originally formed is completely redissolved and 'sufiicient distilled water to make a total volume of 250 parts.
  • the silver halides are ripened by stirring slowly at 30 C. for 30 minutes.
  • the precipitate of silver halides is allowed to settle and separated by decantation and Washed with water, again al lowing to settle and decanting.
  • To /2 of the silver halide precipitate is added a solution consisting of 5 parts (by weight) of the quaternary ammonium-modified polyvinyl alcohol derived from a vinyl acetate/allyl glycidyl ether copolymer (91.4/ 8.6) and a mixture of dimethylaminoacetamide and triethylamine (1/ 3) followed by hydrolysis, dissolved in 10 parts of ethanol and parts of water.
  • the dispersion is stirred for one hour at C., treated with 70 parts of a 5% aqueous solution of completely hydrolyzed polyvinyl alcohol, having a viscosity between 12 and 50 poises, and stirred an additional hour at 60 C.
  • Coating aids are added, the viscosity of the emulsion is adjusted by adding 20% ethanol, and a coating is made on a transparent film support.
  • the speed of this film is about ten times that of a control emulsion in which the second half of the silver halides was dis persed in polyvinyl alcohol alone and no quaternary ammonium-modified polyvinyl alcohol was employed.
  • Example III A mixture of 200 parts of isopropyl alcohol and 100 parts of a 55.5% solution of a vinyl acetate/allyl glycidyl ether copolymer (4.6% allyl glycidyl ether) in methyl ethyl ketone is stirred at room temperature and treated with a solution of 8 parts (by weight) of triethylamine in 50 parts of isopropyl alcohol and 5 parts of distilled water. The reaction mixture is heated under reflux for 5 hours to bring about amination (quaternization) of the glycidyl ether groups.
  • Hydrolysis of the vinyl acetate groups is accomplished by adding a solution of 10 parts (by weight) of sodium methylate in 50 parts of isopropyl alcohol and stirring at room temperature for 15-30 minutes.
  • the hydrolysis can be carried. out. by adding the polymer solution to a methanol solution of sodium methylate.
  • the product is separated by filtration and purified by dissolving in a small amount of water and precipitating with methanol and acetone.
  • the product is finally washed with methanol and acetone and when dried, about parts (by weight) of slightly yellow-colored polymer is obtained. From the nitrogen content of the polymer, 76% of the allyl glycidyl ether groups in this polymer are substituted with quaternary ammonium groups.
  • Silver halides are preparedas described in Example H and the precipitate retained after decantation is treated with 10 parts of a 5% aqueous solution of the hydrolyzed quaternary copolymer, and a suitable sulfur sensitizer and stirred. at 40?. C. for. 15 minutes; The dispersion is treated. with lparts:of a 5% solution of a yellow color-forming polyvinyl acetal (i. e., one of those described in the examples of U. S; Patent 2,465,067) and stirred at 50 C. for 15 minutes.
  • a yellow color-forming polyvinyl acetal i. e., one of those described in the examples of U. S; Patent 2,465,067
  • the viscosity of the emulsion is adjusted with 20% ethanol, 4 parts of a 1% solution of C-cetyl betaine (coating assistant) and an antifogging agent are added and the emulsion is coated on a transparent support. Exposure in a camera and standard photographic processing produces negatives of good gradation from which acceptable photographic prints can be made.
  • Example IV A solution consisting of 100 parts (by weight) of.
  • Example V A solution of 100 parts (by weight) of vinyl ace tate/allyl glycidyl ether (95 5) copolymer solution(%, in methyl ethyl ketone), 200 parts of methyl ethyl-ketone and 5 parts of water is stirred at room temperature, and 20 parts (by weight) of gaseous dimethylamine introduced. stream of dimethylamine for one hour, allowed to stand for 12 hours at room temperature and is again saturated.
  • Example Ive When the dimethylamine-modified polyvinyl alcohol is employed in. a photographic emulsionas described in Example. III, the speed, gamma and fogvalues arercon siderably improved over those of a. control. emulsion containing no amine polymer.
  • Example VI The amine of ExampleIII is replaced by an equivalent amount of methylamine and the reaction mixture is stirred and refluxed while a slow stream of methylamine is introduced during a period of 6 hours. The reaction mixture is allowed to stand overnight and refluxed an additional hour. The aminated copolymer is hydrolyzed and isolated as described in Example III. Analysis for nitro gen indicates that about 78% of the glycidyl groups are converted to methylamino groups. When the: amino polymer is employed in the preparation of'a photographic emulsion utilizing preformed silver halides as described in Example III, emulsion coatings are obtained which can be exposed and processed to images of good density and gradation which. are superior to a control emulsion.
  • Example VII A mixture of 100'parts' (by weight) of vinyl acetate/ allyl glycidyl ether (/5) polymer solution (66% solids in methyl ethyl ketone), 105 parts of isopropyl alcohol and parts of concentrated ammonium hydroxide is stirred at room temperature for one hour and allowed to stand overnight. After heating at 70-75 C. for one The mixture is refluxed under a constant hour, the reaction mixture is concentrated under partial vacuum to remove ammonia and solvent. Isopropyl alcohol (100 parts) is added and the solution again concentrated under vacuum. Methanol (200 parts) is added speed, gamma, fog and density characteristics as compared to-a control emulsion containing no amino polymer.
  • the copolymer of allyl glycidyl ether and a vinyl ester, preferably vinyl acetate, employed in the preparation of the hydrolyzed amine-modified or trialkylamino-cation modified polyvinyl esters consists of from 3 to 30% of the allyl glycidyl ether and from 70 to 97% of vinyl acetate (this corresponds to a molar ratio of between 1/45 to V3).
  • the preferred copolymers contain 5 to of allyl glycidyl ether and 80 to 95% of vinyl acetate, or on a molar basis of between 1/ to 1/5.
  • the copolymers are prepared by polymerizing together in suitable proportions allyl glycidyl ether and vinyl acetate in a homogeneous medium in the presence of a free radical-generating catalyst, e. g., benzoyl peroxide.
  • the monomers are gen- 'erally converted to copolymers in high yields, e. g. 75- 99%.
  • the resulting copolymers have molecular weights of the order of 1000 to 10,000.
  • the allyl glycidyl ether copolymer obtained as described above contains epoxy or oxirane groups.
  • Ammonia and monoamines react with the epoxy group to give polyamines which contain an alcoholic hydroxyl group on the carbon adjacent to the carbon bearing the amino group.
  • the following equations illustrate (1) the reaction of a hydrogen-bearing amine with the epoxy group and (2) the reaction of a tertiary amine with the epoxy group in the presence of an acid:
  • R represents an organic radical, i. e.,.a hydrocarbon radical or a substituted-hydrocarbon radical wherein the substituent is unreactive with epoxy of the R groups is hydrogen, the compound is a secondary amine and useful amines of this class include dipropylamine, dibutylamine, and diamylamine.
  • useful amines that can be employed include tri-n-octylamine, Z-ethylpyridine, and dimethylaminodimethylacetamide.
  • the aminesremployed have only one basic nitrogen group per molecule.
  • the basicity equivalent corresponds to an ionization constant of at least 1X10-
  • the nitrogen-containing compounds included preferably contain no more than 24 carbons and generally less than 8 carbons. Preferably they are saturated (i. e., free from ethylenic unsaturation).
  • at least 0.5 equivalent of ammonia or amine is present per epoxy group.
  • the amine is present in considerable excess,'wit h 2 to 5 or more equivalents of amine per epoxy group usually being employed. Inert solvents or diluents can be present but are not necessary.
  • the epoxy groups are reacted with ammonia or an amine.
  • the resulting polymer has a nitrogen, content of generally between 0.3
  • the hydrolyzed copolymers form thin layers which are strong, smooth, coherent, but freely water-permeable.
  • the hydrolyzed copolymers are also useful as water-permeable colloid binding agents in filter and anti-halation layers in photographic films and as textile sizing agents.
  • the photographic emulsions of this invention contain silver halides in dispersed form in the hydrolyzed vinyl ester/allyl glycidyl ether-amine or quaternary derivative. They are prepared by dispersing precipitated light-sensitive silver halides in an aqueous medium which contains 15% or more on a Weight basis of the amine or quaternary ammonium polymeric material.
  • the emulsions which contain the silver halide and polymer are prepared and coated on a film support in the substantial absence of actinic light;
  • the emulsions of this invention may be coated onto various types of rigid or flexible supports, e. g., glass, paper, metal, films, super-polymers, resins, cellulose derivatives, etc.
  • Suitable materials include paper, aluminum, polymethacrylic acid methyl and ethyl esters, vinyl chloride polymers, polyvinylacetals, nylon, polyesters, e. g., ethylene glycol-terephthalic acid polymers, cellulose acetate, cellulose nitrate, cellulose propionate, etc.
  • the hydrolyzed copolymers of this invention are not only useful as the sole protective colloid in photographic silver halide dispersions or emulsions but can be advantageously used in the preparation of silver halide dispersions or emulsions to be bulked with another colloid prior to coating in the form of a photographic layer.
  • the initial silver halide dispersion can be admixed with a different bulking colloid, e. g., gelatin, a watersoluble or Water-permeablle polyvinyl alcohol, polyvinyl acetal, cellulose derivative, polyamide or other synthetic resin or superpolymcr.
  • Suitable polyvinyl acetals which bcnzaldehyde polyvinyl acetals which contain a large number "of recurring intralinear.
  • Another advantage of the invention is that it enables one to prepare silver halide dispersions or emulsions with sensitive well-formed grains and in the absence of gelatin.
  • the silver halide emulsions are uniform in properties and have a high degree of photosensitivity for gelatin-free systems. Still further advantages of the invention will be apparent from the above description.
  • .A is a member taken from the group consisting of OH and esterified OH, the esterification being in an amount from 0% to 2% based on the weight of the copolymer, and one of the radicals X and Y is hydroxyl and the other is a nitrogen-containing radical taken from the group consisting, of amino radicals and trialkylamino cation radicals, said first unit constituting 94 to 51% and the second unit constituting 6 to 49% by weight .of the copolymer.
  • A is a member taken from the group consisting 8 of OH and esterified OH, the esterification being in an amount from 0% to 2% based on the weight of the copolymer, and of the radicals Q and Z is hydroxyl and the other is amino, said first unit constituting 94 to 51% and the second unit constituting 6 to 49% by weight of the copolymer.
  • A is a member taken from the group consisting of --OH and esterified OH, the esterification being in an amount from 0% to 2% based on the weight of the copolymer, and one of the radicals R and R is hydroxyl and the other is trialkylarnino cation, said first unit 0011- stituting 94 to 51% and the second unit constituting 6 to 49% by weight of the copolymer.
  • A is a member taken from the group consisting of --OH and esterified OH, the esterification being in an amount from 0% to 2% based on the Weight of the copolymer, and one of the radicals A and B is hydroxyl and the other is a dimethylaminoacetamide halide group, said first unit constituting 94 to 51% and the second unit constituting 6 to 49% by weight of the copolymer.

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US467641A 1954-11-08 1954-11-08 Copolymers and photographic emulsions containing the same Expired - Lifetime US2829053A (en)

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BE542633D BE542633A (enrdf_load_html_response) 1954-11-08
US467641A US2829053A (en) 1954-11-08 1954-11-08 Copolymers and photographic emulsions containing the same
GB27396/55A GB788955A (en) 1954-11-08 1955-09-26 Improvements in or relating to copolymers their production and use
DEP14966A DE1018306B (de) 1954-11-08 1955-10-13 Lichtempfindliche Halogensilberemulsion

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3047394A (en) * 1958-08-01 1962-07-31 Eastman Kodak Co Photosensitive products containing therein layers hardened by bisepoxides
US3425836A (en) * 1965-04-15 1969-02-04 Eastman Kodak Co Photographic emulsions
US3684784A (en) * 1969-10-15 1972-08-15 Rhone Poulenc Sa Quaternary nitrogen-containing random copolymers
US20050049149A1 (en) * 2003-09-03 2005-03-03 M I Llc High performance water-based drilling mud and method of use

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2248639A (en) * 1935-01-04 1941-07-08 Miksits Reinhold Rotary piston machine
US2321728A (en) * 1939-12-11 1943-06-15 Du Pont Interpolymerized substance containing unsaturated methylene groups
US2461023A (en) * 1944-10-25 1949-02-08 Gen Aniline & Film Corp Photographic silver halide emulsions
US2522771A (en) * 1944-11-03 1950-09-19 Gen Aniline & Film Corp Photographic silver halide emulsions

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2248639A (en) * 1935-01-04 1941-07-08 Miksits Reinhold Rotary piston machine
US2321728A (en) * 1939-12-11 1943-06-15 Du Pont Interpolymerized substance containing unsaturated methylene groups
US2461023A (en) * 1944-10-25 1949-02-08 Gen Aniline & Film Corp Photographic silver halide emulsions
US2522771A (en) * 1944-11-03 1950-09-19 Gen Aniline & Film Corp Photographic silver halide emulsions

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3047394A (en) * 1958-08-01 1962-07-31 Eastman Kodak Co Photosensitive products containing therein layers hardened by bisepoxides
US3425836A (en) * 1965-04-15 1969-02-04 Eastman Kodak Co Photographic emulsions
US3684784A (en) * 1969-10-15 1972-08-15 Rhone Poulenc Sa Quaternary nitrogen-containing random copolymers
US20050049149A1 (en) * 2003-09-03 2005-03-03 M I Llc High performance water-based drilling mud and method of use
US7192907B2 (en) * 2003-09-03 2007-03-20 M-I L.L.C. High performance water-based drilling mud and method of use

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DE1018306B (de) 1957-10-24
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