Classifications

• • 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

Definitions

• polymers of the instant invention are to be distinguished from the polymers of the instant invention in that the former polymers are inner salts or betaines" having a carboxy or sulfo anion which is covalently bonded through a carbon chain to the quatemized nitrogen atom, whereas the instant invention is directed to silver halide emulsions employing polymeric salts whose anions are only bonded to the polymer by ionic forces and which may be relatively easily removed or interchanged in ways well known to those skilled in the art.
• R is hydrogen, a lower alkyl group, i.e., l4 carbon alkyl group, preferably methyl or ethyl, or a halogen, i.e., chloro, bromo, or iodo;
• R is hydrogen, a lower alkyl group, a halogen or cyano group;
• R is a lower alkylene, i.e., l4 carbon alkylene group or a lower cycloalkylene group, i.e., 3-6 carbon cycloalkylene group; and
• R R and R each is a lower alkyl or a lower cycloalkyl group, i.e., a 3-6 carbon cycloalkyl group; or R and/0r R and/or R and/or R taken together represent the atoms necessary to complete a 3 to S-membered heterocyclic ring structure;
• X is a salt-forming anion, e.g., halide,
• the polymeric salts may comprise only a portion of the binder, the remainder constituting gelatin or a second synthetic polymer.
• the present invention is directed to photosensitive silver halide emulsions wherein photosensitive silver halide crystals are disposed in a synthetic polymeric binder comprising a water-soluble film-forming quaternary ammonium alkyl acrylate polymeric salt having in its structure repeating units represented by the formula set forth above.
• filmforming is intended to designate a molecular weight sufficiently high to form a film, for example, a molecular weight comparable to that of gelatin (i.e. around 15,000).
• the polymers of the present invention have been found to substantially meet all of the basic require ments of a gelatin substitute without possessing the above-described deficiencies of gelatin. More specifically, the emulsions of the present invention are more stable against degradation than gelatin; particularly against hydrolysis of the polymeric backbone in acidic or basic media. This stability is due, in large part, to the carbon-carbon linkages in the polymeric backbone of the instant polymers, as opposed to the relatively easily hydrolyzed ester and amide linkages found in the polymeric backbone of gelatin. The emulsions of this inven tion also show a resistance to the growth of microorganisms which is not exhibited by gelatin.
• An important feature of the polymers of this invention is the presence of a mobile anion or counter-ion" 3 4 which is free to diffuse in the aqueous medium of the B-(methacryloyloxy)ethyl(ethyl dimethyl ammosilver halide emulsion.
• the instant polymers may be homopolymers or inter- 2 2 I polymers having, in addition to the repeating units de- CH fined above, any compatible repeating unit or various repeating units which are not detrimental to photoacryloyloxy methyl trimethyl ammonium chloride graphic silver halide emulsions and which allow the re- CH CH B-(acryloyloxy )ethyl trimethyl ammonium p-tolsultant polymer to be soluble in water.
• Examples of typuenesulfonate ical comonomers which may be employed in forming the polymers suitable for use in the present invention 3 il 3 include the following ethylenically-unsaturated monomers.
• CH CC0O-CH CH (+9 0 socrr 10.
• CH Cl-l-COOH fi-(methacryloyloxy)ethyl trimethyl ammonium acrylic acid methyl sulfate lC1 C? /CH e 4.
• cr-1 ccoocH cH --b
• HOOC-CH CHCONl-lCl-l,Cl-l
• N-ethylmaleic acid amide 81 Cl-l OOCCl-l Cl-l-CO--Nl-l--CH N-methyl methylmaleate amide 82.
• CH, CHOOCH vinylformate a-vinylfuran 9o, ca-ca-coo-cn O a-acryloyloxymethyl-tetrahydrofuran p-hydroxy styrene m-hydroxystyrene 93.
• the following non-limiting examples illustrate the preparation of polymers within the scope of the present invention.
• the numerical ratio before the word copolymer in the following examples refers to the molar ratio of monomers in the reaction mixture forming the copolymer.
• Example 1 EXAMPLES ll VIIl Copolymers of acrylamide/B-(methacryloyloxy) ethyl trimethylammonium methyl sulfate
• the procedure of Example 1 was followed except that, in addition to the reagents already present in the polymerization solution, various quantities of acrylamide were included.
• the amounts of acrylamide added in Example 11, 111, IV and V were 0.71 g, 1.42 g, 2,84 g and 5.69 g respectively.
• Vl 8.54 g of acrylamide, 10.62 g of the Sipomer Q-S and 0.01 g of the catalyst were dissolved in the E o-isopropanol solution, polymerized and separated according to the procedure of Example I.
• Example VII 8.54 g of acrylamide, 7.08 g of the Sipomer Q6 and 0.01 g of the catalyst were dissolved in the l-l O-isopropanol solution, polymerized and separated according to the procedure of Example 1. ln Example Vlll a solution of 5.69 g of acrylamide, 14.17 g of Sipomer (2-5, and 0.01 g of the catalyst in mls of H 0 and 5 mls of isopropanol was polymerized and separated according to the procedure of Example 1.
• EXAMPLE Xl 2:3 copolymer of diacetone acrylamide and 3-(methacryloyloxy )-2-hydroxy-proplyl trimethylammonium chloride 46.62 g of the above-mentioned Sipomer Q-l and 20.32 g of diacetone acrylamide were added to 500 ml of distilled H O in a 3-neck one liter round-bottom flask with stirrer and under nitrogen.
• the pH was adjusted to 6.5 with HNO and 0.05 g of X 8 and 0.05 g of NaHSO were added to the solution.
• the solution was stirred until viscous and then dialyzed for 36 hours to yield a milky viscous liquid which was analyzed to have 7.3% solids.
• EXAMPLE Xlll 3:1 copolymer of acrylamide/ ⁇ Hmethacryloyloxy)ethyl (ethyl dimethylammonium) ethylsulfate 7.1 l g of acrylamide, 10.38 g of [3-( methacryloyloxy) ethyl (ethyldimethylammonium) ethylsulfate (commercially available from Alcolac Chemical Corporation under the designation DV-364) and 0.01 g of 2,2- azobis-[Z-methylpropionitrile] catalyst were dissolved in ml of dimethylformamide. This solution was polymerized in a sealed tube at 65 C for 12 hours under N The result was a white paste which was filtered and dried under vacuum at 45 C for 12 hours.
• a water-soluble silver salt such as silver nitrate, may be reacted with at least one water-soluble halide, such as potassium, sodium, or ammonium bromide, preferably together with potassium, sodium or ammonium iodide, in an aqueous solution of the polymer.
• the emulsion of silver halide thus-formed contains water-soluble salts, as a by-product of the double decomposition reaction, in addition to any unreacted excess of the initial salts.
• the emulsion may be centrifuged and washed with distilled water to a low conductance. The emulsion may then be redispersed in distilled water.
• a solution of bodying or thickening polymer such as polyvinyl alcohol having an average molecular weight of about l00,000 (commercially available from E. l. duPont deNemours & Company, Wilmington, Del, designated Type 72-60).
• a surfactant such as dioctyl ester of sodium sulfosuccinic acid, designated Aerosol OT, (commercially available from American Cyanamid Company, New York, N.Y.,) may be added and the emulsion coated onto a film base of cellulose triacetate sheet having a hardened gelatin.
• the emulsions may be chemically sensitized with sulfur compounds such as sodium thiosulfate or thiourea, with reducing substances such as stannous chloride, with salts of noble metals such as gold, rhodium and platinum; with amines and polyamines; with quaternary ammonium compounds such as alkyla-picolinium bromide; and with polyethylene glycols and derivatives thereof.
• sulfur compounds such as sodium thiosulfate or thiourea
• reducing substances such as stannous chloride
• salts of noble metals such as gold, rhodium and platinum
• amines and polyamines with quaternary ammonium compounds such as alkyla-picolinium bromide
• polyethylene glycols and derivatives thereof may be chemically sensitized with sulfur compounds such as sodium thiosulfate or thiourea, with reducing substances such as stannous chloride, with salts of noble metals such as gold, rhodium
• the polymers employed as the binders in the emulsions of the present invention may be cross-linked according to conventional procedures.
• the polymers may be ionically cross-linked with a dibasic acid or cross-linked with succinaldehyde.
• the emulsions of the present invention may also be optically sensitized with cyanine and merocyanine dyes.
• strainers developers, accelerators, preservatives, coating aids, plasticizers, hardeners and/or stabilizers may be included in the composition of the emulsion.
• the emulsions of this invention may be coated and processed according to conventional procedures of the art. They may be coated, for example, onto various types of rigid or flexible supports, such as glass, paper, metal, and polymeric films of both the synthetic type and those derived from naturally occurring products.
• rigid or flexible supports such as glass, paper, metal, and polymeric films of both the synthetic type and those derived from naturally occurring products.
• specific materials which may serve as supports mention may be made of paper, aluminum, polymethacrylic acid, methyl and ethyl esters, vinylchloride polymers, polyvinyl acetal, polyamides such as nylon, polyesters such as polymeric film derived from ethylene glycol-terephthalic acid, and cellulose derivatives such as cellulose acetate, triacetate, nitrate, propionate, butyrate, acetate propionate, and acetate butyrate.
• Suitable subcoats may be provided on the supports, for example a layer of gelatin, if necessary or desirable for adherence, as
• the polymeric salts employed in the practice of the instant invention may contain from -100 mole of the above-indicated repeating units.
• the specific amount employed may be selected by the operator depending upon the grain particle size and habit desired.
• the copolymers of this invention may be made to be compatible with all water-soluble bodying polymers. Emulsions made from these novel polymers, may be bodied with any water-soluble polymers, overcoming the disadvantage encountered with gelatin which is only compatible with a very few polymers in a most limited pH range.
• gelatin polyvinyl alcohol, polyacrylamide, polyalkylacrylamides, polyvinyl pyrrolidone, polymethacrylamidoacetamide, vinyl alcohol/N- vinylpyrrolidone copolymers, poly-N-ethylaziridine, poly-N-(2-hydroxyethyl)aziridine, poly-N-(Z-cyanoethyl) aziridine, poly (B-hydroxy-ethyl acrylate), polyethylene imine and cellulose derivatives such as bydroxyethyl cellulose, hydroxypropyl cellulose and methyl cellulose.
• copolymers with selected diffusion characteristics may be prepared.
• the rate of diffusion of alkali ion or a dye-developer through an emulsion comprising one of the copolymers of this invention may be modified by varying the composition of the copolymer.
• a solution of 55.0 g of silver nitrate in 500 mls of distilled water was prepared. From this silver nitrate solu- 5 tion, 100 mls were rapidly added to the polymerhalide solution and the remainder was added over a period of 22 minutes. Thereafter, the emulsion was ripened for 60 minutes at 55 C, with continuous agitation, at the end of which it was rapidly cooled to below 20 C.
• Example XVI The procedure of Example XIV was followed to prepare a silver halide emulsion employing as the emulsion binder a 1 1:1 copolymer of acylamide/B-(metha- 15 cryloyloxy) ethyl trimethylammonium methylsulfate (commercially available from Hercules Powder Co., Wilmington Del. under the designation Reten Lot. No.
• a solution of 4.15 g of the dry polymer in 266 ml of distilled water was adjusted to pH 6.30 with dilute nitric acid and maintained at a temperature of 55 C.
• 44.0 g of dry potassium bromide and 0.50 g of dry potassium iodide were added.
• a solution of 55 g of silver nitrate in 500 ml of distilled water was prepared. From this silver nitrate solution, 100 ml was rapidly added to the polymer-halide solution and the remainder was added over a period of 22 minutes. Thereafter, the emulsion was ripened for 30 minutes at 55 C., with continuous agitation, at the end of which it was rapidly cooled to below 20 C.
• EXAMPLE XVIII A silver halide emulsion employing the polymeric salt of Example XlV as the colloid binder was prepared by the following procedure:
• a solution of 3.10 g of the dry polymer in 200 ml of distilled water was adjusted to pH 3.0 with dilute nitric acid and maintained at a temperature of C.
• 66.0 g of dry potassium bromide and 0.375 g 55 of dry potassium iodide were added.
• a solution of 41.25 g of silver nitrate in 375 ml of distilled water was prepared. From this silver nitrate solution, 75 ml was rapidly added to the polymer-halide solution and the remainder was added over a period of 50 13.5 minutes. Thereafter, the emulsion was ripened for 46.5 minutes at 55 C., with continuous agitation, at the end of which it was rapidly cooled to below 20C.
• EXAMPLE XIX (CONTROL) A control silver halide emulsion employing gelatin as the colloid binder was prepared by following the procedures of Example XVII substituting gelatin for the synthetic polymeric salt.
• photosensitive and other terms of similar import are herein employed in the generic sense to describe materials possessing physical and chemical properties which enable them to fon'n usable images when photoexposed by radiation actinic to silver halide.
• a photosensitive silver halide emulsion wherein the emulsion binder consists essentially of a water-soluble film-forming copolymer of a first monomer of the formula:
• R is hydrogen, a lower alkyl group or a halogen;
• R is hydrogen, a lower alkyl group, halogen or cyano group;
• R is a lower alkylene or lower cycloalkylene group and R R and R each is a lower alkyl, or lower cycloalkyl group; or R and/or R and/or R and- /or R taken together represent the atoms necessary to complete a 3 to S-membered heterocyclic ring structure; and
• X is a salt-forming anion;
• a method of preparing a photosensitive silver halide emulsion which comprises reacting a water-soluble silver salt with a water-soluble halide salt in an aqueous solution containing a water-soluble film-forming copolymer of a first monomer of the formula:
• R is hydrogen, a lower alkyl group or a halogen;
• R is hydrogen, a lower alkyl group, a halogen or cyano group;
• R is a lower alkylene or lower cycloalkyl' ene group and R R and R each is a lower alkyl group or lower cycloalkyl group; or R and/or R and/or R taken together represent the atoms necessary to complete a 3 to 8membered heterocyclic ring structure; and
• X is a salt-forming anion;
• R is hydrogen, a lower alkyl group or-a halogen
• R is hydrogen, a lower alkyl group, halogen or cyano group
• R; is a lower alkylene or lower cycloalkylene group and R R and R each is a lower alkyl, or lower cycloalkyl group; or R and/or R and/or R and- /or R taken together represent the atoms necessary to complete a 3 to S-membered heterocyclic ring structure
• X is a salt-forming anion.
• a method of preparing a photosensitive silver halide emulsion which comprises reacting a water-soluble silver salt with a water-soluble halide salt in an aqueous solution containing a water-soluble film-forming homopolymer consisting essentially of repeating units of the formula:
• R is hydrogen, a lower alkyl group or a halogen
• R2 is hydrogen, a lower alkyl group, a halogen or cyano group
• R is a lower alkylene or lower cycloalkylene group and R R and R each is a lower alkyl group or lower cycloalkyl group; or R and/or R and/or R and/or R taken together represent the atoms necessary to complete a 3 to S-membered heterocyclic ring structure
• X is a salt-forming anion.

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• 1973
  • 1973-01-02 US US320452A patent/US3925083A/en not_active Expired - Lifetime

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