US3713834A - Polymeric binders for photographic emulsions - Google Patents

Polymeric binders for photographic emulsions Download PDF

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US3713834A
US3713834A US00160092A US3713834DA US3713834A US 3713834 A US3713834 A US 3713834A US 00160092 A US00160092 A US 00160092A US 3713834D A US3713834D A US 3713834DA US 3713834 A US3713834 A US 3713834A
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acrylamido
methyl
acrylamide
emulsion
copolymer
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M Fitzgerald
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Polaroid Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/12—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms
    • C07D295/125—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms with the ring nitrogen atoms and the substituent nitrogen atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
    • C07D295/13—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms with the ring nitrogen atoms and the substituent nitrogen atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
    • 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
    • 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

  • This invention relates to photography and more particularly, to novel photosensitive photographic elements, particularly novel photosensitive emulsions.
  • a class of synthetic polymers have now been found which is not susceptible to the deficiencies of the prior art and which may replace gelatin entirely in photosensitive silver halide emulsions.
  • R R and R each is hydrogen, lower alkyl group, e.g., 1-4 carbon alkyl group, preferably methyl or ethyl, or halogen, e.g., chloro, bromo or iodo; R is hydrogen, lower alkyl, halogen or cyano; Z is oxygen or against degradation,
  • R is a lower alkyl or cycloalkyl group, e.g., a 1-4 carbon alkyl or cycloalkyl group;
  • R and R each is hydrogen, lower alkyl group or lower cycloalkyl group, e.g., 1-4 carbons and any combination of R R R and R may be taken together to form a 37 atom ring structure, and n is a positive integer greater than 1.
  • the above-described polymer comprises only a portion of the binder, the remainder constituting gelatin or a second synthetic polymer.
  • R R R and R each is hydrogen, lower alkyl group, e.g., 14 carbon alkyl group, preferably methyl or ethyl, or halogen, e.g., chloro, bromo or iodo; and R is additionally cyano;
  • Z is oxygen or nitrogen;
  • R is a lower alkyl or cycloalkyl group, e.g.
  • R and R each is hydrogen, lower alkyl group or lower cycloalkyl group, e.g., l-4 carbons, and any combination of R R R and R may be taken together to form a 3-7 atom ring structure, and n is a positive integer greater than 1.
  • Such polymers have been found to substantially pro vide all of the basic requirements for a gelatin substitute, as delineated above.
  • the emulsions of the present invention are readily sensitized by conventional sensitizing agents and are characterized by excellent latent image stability and excellent film speed.
  • the emulsions of the present invention are much more stable particularly hydrolysis and the growth of microorganisms than gelatin.
  • the monomer 2 CHZCHNH may be collected by filtration, washed with hexane or n'propyl'a'cmmoacrylate 0 methylene chloride and vacuum dried.
  • Examples of typical (44) C 0CH2CH2OH comonomers which may be employed in forming the B-Hydtoxyethyl acrylate polymers suitable for use in the present inventlon in- (45)
  • EXAMPLE 1 A 1:1 copolymer of acrylamide/Z-acrylamido-3-methyl- N-[B- (dimethylamino) ethyl] butyramide was prepared according to the procedure of Example I.
  • EXAMPLE VII A 4:1 copolymer of methacrylic acid/2-methacrylamido-3-methyl-dimethylaminoethyl b-utyramide was prepared according to the procedure of Example I.
  • EXAMPLE XIII A 38:1 copolymer of acrylamide/N-[B-(dimethylamino)ethyl] 2 acrylamido-Z-methyl-propionamide was prepared by dissolving 13.5 g. of acrylamide and 1.14 g. of the diamide in 80 ml. of dimethylformamide with 0.01 g. of a-zobisisobutyronitrile. The mixture was heated to 60 C. for 18 hours. The thus-formed polymer was precipitated into acetone, washed, dried and redissolved for use in making an emulsion.
  • a water-soluble silver salt such as silver nitrate, may be any water-soluble silver salt.
  • the emulsion of silver halide thus-formed contains watersoluble 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 100,000 (commercially available from E. I. do Pont de Nemours & 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 slot coated onto a base of cellulose triacetate sheet 5 mls. thick having a coating of 30 mg./sq. ft. of hardened gelatin.
  • the soluble salts may be removed by adding to the emulsion a solution of polyacid such as 1:1 ethylenezmaleic acid copolymer and lowering the pH to below 5, thereby bringing about precipitation of the polyacid carrying the silver halide grains along with the precipitate, and then to wash and resuspend the resulting precipitate by redissolving the polyacid at pH 6-7.
  • polyacid such as 1:1 ethylenezmaleic acid copolymer and lowering the pH to below 5, thereby bringing about precipitation of the polyacid carrying the silver halide grains along with the precipitate, and then to wash and resuspend the resulting precipitate by redissolving the polyacid at pH 6-7.
  • the emulsions may be chemically sensitized with sulfur compounds such as sodium thiosulfate or thiourea, with reducin 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 alkyl a-picolinium bromide; and with polyethylene glycols and derivatives thereof.
  • sulfur compounds such as sodium thiosulfate or thiourea
  • reducin substances such as stannous chloride
  • salts of noble metals such as gold, rhodium and platinum
  • With amines and polyamines with quaternary ammonium compounds such as alkyl a-picolinium bromide
  • polyethylene glycols and derivatives thereof The emulsions of the present invention require only 5% as much gold for chemical sensitization as do gelatin emulsions.
  • polymers employed as the binders in the emulsions of the present invention may be cross-linked according to conventional procedures.
  • polymers containing amine groups may be cross-linked with zirconium salts under alkaline conditions wherein amine-containing polymer is coated With a zirconium salt, for example, zirconium sulfate, and the pH is raised cross-linking the polymer.
  • zirconium salt for example, zirconium sulfate
  • the emulsions of the present invention may also be optically sensitized with cyanine and merocyanine dyes more easily than are gelatin emulsions. Cyanine dyes tend to aggregate less on the polymers of the instant invention than with gelatin providing less light filtering and speed loss. Where desired, suitable antifoggants, toners, restrainers, developers, accelerators, preservatives, coating aids, plasticizers, hardeners and/or stabilizers may be included in the composition of the emulsion. l
  • 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 glycolterephthalic acid, and cellulose derivatives such as cellu lose acetate, triacetate, nitrate, propionate, butyrate, acetate propionate, and acetate butyrate.
  • These novel emulsions of the instant invention have been found to adhere to supports in a most satisfactory manner.
  • the polymers employed in the practice of the instant invention may contain from -100 mole percent of the repeating units represented in Formula A.
  • the specific amount employed may be selected by the operator depending upon the grain particle size and habit desired.
  • Emulsions within the scope of the present invention may also be prepared employing polymers such as:
  • the instant copolymers may be made to be compatible with all watersoluble 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.
  • specific materials which may serve as bodying polymers are polyvinyl alcohol, polyacrylamide, polyalkylacrylamides, polyvinyl pyrrolidone, poly(fl-hydroxyethyl acrylate), polyethylene imine and cellulose derivatives such as hydroxypropyl cellulose and methyl cellulose. It has been found that using only a small amount of one or more of the instant polymers, large amounts of photosensitive silver halide grains may be obtained.
  • An emulsion made from one of these polymers of the instant invention may therefore be bodied with a watersoluble polymer such that the polymeric constitution of the resulting emulsion comprises a relatively large percentage of the bodying polymer.
  • copolymers with selected diffusion characteristics may be prepared.
  • the instant polymers containing acidic comonomers may be pH flocculated in order to remove the soluble salts formed as a byproduct of the double decomposition reaction between the water-soluble silver salt and the water-soluble halide, in addition to any unreacted excess of the initial salts.
  • an acid copolyrner may be precipitated by lowering the pH below 5 and then washed and resuspended by raising the pH to above 7.
  • Procedure A A solution of 4.15 g. of the dry copolymer in 266 ml. of distilled water was adjusted to pH 6.30 with dilute nitric acid and maintained at a temperature of 55 C. To this solution, 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 with continuous agitation to the polymer-halide solution and an additional 396 ml. was added over a period of 22 minutes. Thereafter, the emulsion was ripened for 30 minutes at 55 C., and then rapidly cooled to below 20 C.
  • Procedure B In an alternative procedure for preparing the emulsion, the pH of the polymer solution was adjusted to 3.0; the amount of dry potassium bromide used was 88.0 g. and the amount of dry potassium iodide used was 1.0 g. In addition, the emulsion was ripened for 60 minutes instead of for 30 minutes.
  • the emulsion mixture in both procedures was centrifuged and washed with water to a low conductance. The emulsion was then redispersed in distilled water. To an aliquot of this emulsion was added a known quantity of a solution of bodying or thickening polymer of polyvinyl alcohol having an average molecular weight of about 100,000 (commercially available from E. I. du Pont de Nemours & Company, Wilmington, Del., designated Type 72-60). A surfactant, such as Aerosol OT, was added and the emulsion was slot coated onto a base of cellulose triacetate sheet 5 mils thick having a coating of 30 mg./ sq. ft.
  • a surfactant such as Aerosol OT
  • 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 form usable images when photo-exposed by radiation.
  • a photosensitive silver halide emulsion wherein the emulsion binder comprises a polymer having in its structure repeating units of the formula:
  • R R and R each are selected from the group consisting of hydrogen, lower alkyl and halogen; R is selected from the group consisting of hydrogen, lower alkyl, halogen and cyano; Z is selected from the group consisting of oxygen and nitrogen; when Z is oxygen R is an electron pair and when Z is nitrogen R is selected from the group consisting of hydrogen and lower alkyl; R is selected from the group consisting of lower alkyl and lower cycloalkyl groups; R and R each are selected from the group consisting of hydrogen, lower alkyl, lower cycloalkyl, and any combination of R R R and R may be chemically joined to form a 3-7 atom ring structure, and n is a positive integer greater than 1.
  • JJH- -(il 0 R; O 11- -Z-R -N and a second ethylenically unsaturated monomer.
  • 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 polymer having in its structure repeating units of the formula:
  • R R and R each are selected from the group consisting of hydrogen, lower alkyl and halogen; R is s lected from the group consisting of hydrogen, lower alkyl, halo-gen and cyano; Z is selected from the group consisting of oxygen and nitrogen; when Z is oxygen R is an electron pair and when Z is nitrogen R is selected from the group consisting of hydrogen and lower alkyl; R is selected from the group consisting of lower alkyl and lower cycloalkyl groups; R, and R each are selected from the group consisting of hydrogen, lower alkyl, lower cycloalkyl, and any combination of R R R and R may be chemically joined to form a 3-7 atom ring structure, and n is a positive integer greater than 1.

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Abstract

A PHOTOSENSITIVE SILVER HALIDE EMULSION WHEREIN THE EMULSION BINDER COMPRISES AN AMINE-DIAMIDE POLYMER OR COPOLYMER.

Description

United States Patent 3,713,834 POLYMERIC BINDERS FOR PHOTOGRAPHIC EMULSIONS Maurice J. Fitzgerald, Canton, Mass., assignor to Polaroid Corporation, Cambridge, Mass. No Drawing. Filed July 6, 1971, Ser. No. 160,092
Int. Cl. G03c N04 US. Cl. 96114 24 Claims ABSTRACT OF THE DISCLOSURE A photosensitive silver halide emulsion wherein the emulsion binder comprises an amine-diamide polymer or copolymer.
BACKGROUND OF THE INVENTION This invention relates to photography and more particularly, to novel photosensitive photographic elements, particularly novel photosensitive emulsions.
As a result of the known disadvantages of gelatin, in particular, its variable photographic properties and its fixed physical properties, for example, its diffusion characteristics; much effort has been expended in the past in order to replace gelatin with a suitable synthetic colloid binder for photographic silver halide emulsions. Many synthetic polymeric materials have heretofore been suggested as peptizers for silver halide emulsions, however, these have generally not functioned satisfactorily and frequently have not fulfilled all of the basic requirements for a photosensitive silver halide emulsion binder listed following:
(1) Absent (or constant) photographic activity;
(2) Ability to form an adsorption layer on microcrystals of silver halide permitting stable suspensions to be obtained;
(3) Ability to form adsorption layers as described in (2) above which do not prevent growth of silver halide microcrystals during physical ripening; and
(4) Solubility in water solution.
In addition, hithertofore, much emphasis has been placed on the ability of the synthetic polymeric material to mix with gelatin, as this property has been critical for employment in partial substitution reactions with gelatin. Consequently, many synthetic polymers of the prior art have been materials which allow for the growth of silver halide crystals only in the presence of gelatin.
A class of synthetic polymers have now been found which is not susceptible to the deficiencies of the prior art and which may replace gelatin entirely in photosensitive silver halide emulsions.
SUMMARY OF THE INVENTION The present invention is directed to a photosensitive silver halide emulsion wherein the silver halide crystals are disposed in a synthetic polymeric binder comprising a polymer having in its structure repeating units represented by the formula:
wherein R R and R each is hydrogen, lower alkyl group, e.g., 1-4 carbon alkyl group, preferably methyl or ethyl, or halogen, e.g., chloro, bromo or iodo; R is hydrogen, lower alkyl, halogen or cyano; Z is oxygen or against degradation,
3,713,834 Patented Jan. 30, 1973 ice nitrogen; R when Z is oxygen, is an electron pair, and when Z is nitrogen, is hydrogen or lower alkyl, e.g., l-4 carbon alkyl group, preferably methyl or ethyl; R is a lower alkyl or cycloalkyl group, e.g., a 1-4 carbon alkyl or cycloalkyl group; R and R each is hydrogen, lower alkyl group or lower cycloalkyl group, e.g., 1-4 carbons and any combination of R R R and R may be taken together to form a 37 atom ring structure, and n is a positive integer greater than 1. In an alternative embodiment, the above-described polymer comprises only a portion of the binder, the remainder constituting gelatin or a second synthetic polymer.
DETAILED DESCRIPTION OF THE INVENTION The present invention is directed to photosensitive silver halide emulsions wherein photosensitive silver halide crystals are disposed in a synthetic polymeric binder comprising a polymer having in its structure repeating units represented by the formula:
wherein R R R and R each is hydrogen, lower alkyl group, e.g., 14 carbon alkyl group, preferably methyl or ethyl, or halogen, e.g., chloro, bromo or iodo; and R is additionally cyano; Z is oxygen or nitrogen; R when Z is oxygen, is an electron pair and when Z is nitrogen, is hydrogen or lower alkyl, e.g., l-4 carbon alkyl group, preferably methyl or ethyl; R is a lower alkyl or cycloalkyl group, e.g. a 1-4 carbon alkyl or cycloalkyl group; R and R each is hydrogen, lower alkyl group or lower cycloalkyl group, e.g., l-4 carbons, and any combination of R R R and R may be taken together to form a 3-7 atom ring structure, and n is a positive integer greater than 1.
Such polymers have been found to substantially pro vide all of the basic requirements for a gelatin substitute, as delineated above. The emulsions of the present invention are readily sensitized by conventional sensitizing agents and are characterized by excellent latent image stability and excellent film speed. In addition, the emulsions of the present invention are much more stable particularly hydrolysis and the growth of microorganisms than gelatin.
As examples of monomers suitable for providing the amine-diamide polymers, mention may be made of the following:
(29) on. arpon-0011 CHz=CH--CONHA7CONH-CHCH2CH2P6 N-CHa Acrylic acid H (3].) EH;
C N- [3'- (N -methylpiperazino )prop-l '-yl] -2-acrylam1do-2- H2 0 O OH methylpropionamide Methacrylie acid (32) C1 The monomers employed in forming the polymers sui't- CHz=0-O00H able for use in the present invention may be prepared by a chloroacrylic acid the following general procedure: (33) R7 CHz=JJ-COOH R4 0 I] a-Bromoacrylic acid 1 i 34) CH3CH=CH- COOH Crotonic acid (35) CHsCH:CHCOOH R2C=CH-Ri Isocrotonic acid Oxazolone Reagent Amine Reagent (36) 'CI'CH=CHCOOH R1 R2 fl-Chloroacrylic acid I I 37 GH=C Br C CH COOH BBr0moacry1ic acid (3:0 (as CH I o1on=b-ooorr R4(|]Ra R1 B-Chloromethacrylic acid (39) CH2=CH-COOCH3 ll 5 R8 Methyl acrylate (40) CH; The oxazolone reagent may be dissolved in an inert 30 CH2=0Co0-CH2GHa solvent such as hexane or methylene chloride and a stoi- Ethyl methacrylate chiometric amount of amine reagent may be added to (41) or the solution. The desired monomer crystallizes out of I OH =c000 solution in relatively high yield and purity. The monomer 2 CHZCHNH may be collected by filtration, washed with hexane or n'propyl'a'cmmoacrylate 0 methylene chloride and vacuum dried. L
The following table illustrates surtable monomers prepared according to the above-indicated general procedure. Isopropyl-B-bromoacrylate TABLE 1 Elemental analysis Theoretic 1 F Reaction M.P., Percent 01L Oxazolone reagent Amine reagent solvent Appearance 0. yield 0 H N C H N 2-viny1--L-isopropyl-5-oxazolone. N,N-dimethyl ethylenediamine- Hexane Wiliiie crys- 118-120 8. S. 2-1sopropenyl-4-isopropyl-5-oxa- -...-do Diethyl ..d0 117-119 zolone. ether 2-vinyl-4-,4-dimethyl-5oxazolone --do Hexane ..do 76-78 85.0 58.2 9.3 18.5 58.1 9.4 13.4 D p-(Ttertiary butylamino)ethanol Acetone .-do... 157-159 31.0 48.9 7.8 13.2 49.0 8.1 13,1
I11 I 9. D B-(Diethylamino) ethanol Die t hyl Colr arless 83.0
e 61. 01 D N,N-diethyl-ethylenediamine.-.. Hexane.-- W151i? orys- 71-72 60.0 61.1 9.9 16.5 60.8 10 3 16,3
21 S. 2-vinyl-4-isopropyl-fi-oxazolone H 83-84 2-vinyl-4,4-dimethyl-5-oxazolone N,N-dusopropylethylenedlado --..d0 74-75 63.0 63 6 10.3 14.8 63.6 10.5 14.7
1111116. D0 2-(dimethylamino)-1-aminopto- ..do .do 54-55 43 0 69 7 9.6 17.4 59.6 9,7 17,4
8H6. D0 3-?dimethylamino)1-pr0pan0l- Die t hyl Goh rrless 59.5 9.1 11.6 58.3 9.7 9 2 8 er. 01 D zyrrolidinoethylamine- Hexane--. wgi e crys- 124-126 92.5 616 9.2 16.6 62.0 9.3 16,6
a S. Do. 2-pipeiidinoet-hylamine-- 93.5 62.9 9.4 15.7 62.8 9.4 15.3 D0 3-pipend1no-1-am1nopr0pa 93.5 64.0 9.7 14.9 64.0 9.7 14.8 DQ 3-morphol1no-1-azn1nopropan 91.5 59.4 8.9 14.8 59.6 8.8 14.8 Do 2(1-methy1pyrrohdm-2-y1) 74.0 62.9 9.4 15.7 62.8 9.7 15.6
- ethylalmne. D N-methylpiperazine Diethyl 62.0
ether. 2-iso1pr0penyl-4,4dimethyl-5-0Xa- -J!" 64.0
Z0 one. 2-vinyl-4,4-dimethyl-5-oxazolone 3-(N-methylpiperazino)-1- Hexane -.do 113-114 95.5 608 9.5 18.9 60.7 9.9 18.5
amlnopropane.
Very high boiling point.
The instant polymers may be homopolymers or inter- (43) cm polymers having, in addition to the repeating units del fined above, any compatible repeating unit or various re- OH2=O O0O CH2HTCH I peating units which are not detrimental to photographic 70 silver halide emulsions and which allow the resultant Isbutyl methacrylate polymer to be soluble in water. Examples of typical (44) C 0CH2CH2OH comonomers which may be employed in forming the B-Hydtoxyethyl acrylate polymers suitable for use in the present inventlon in- (45) cH2=cH-CO0-CH2CH2CH2OH clude the following ethylenically-unsaturated monomers:
'y-flydroxypropyl acrylate Maleic anhydride HOOC-CHzCH- COOH Maleic acid HOOC'CH:CH-CONH2 H00C=CH=CHCONHCH2CH:1
Maleic acid amide N-ethylmaleic acid amide CI-Is0OC-CH:CH-CO-NH-CH3 N-methyl methylmaleate amide CH= CH-OOCH Vinylformate CH2:CHOOC-CH::
Vinyl acetate CH2:CH-OH Vinyl alcohol CH;=C-OOCCHBr Isopropenyl bromoacetate CH2=CH0OCC- (CHa) 3 Vinyl pivalate 'CH2:CHNH'COOC- (-CH3) 3 N-vinyl-tertiary butylcarbamate CHg=CCHr-COO-CHzCH OOOH Ethy1-3-carboxy-3-butcnate afaeryloyloxyrncthy1-)-tetrahydr0furan p-Hydroxystyrene I OH mHydroxystyrene o-Hydroxystyrene p-Carboxystyrene 6 O O H m-Carboxys tyrcne 1 COOH o-Carboxystyrene Polymerization of the indicated monomers is achieved by conventional free radical polymerization techniques. The following non-limiting examples illustrate the preparation of polymers within the scope of the present invention.
EXAMPLE 1 EXAMPLE II A 1:1 copolymer of acrylamide/Z-acrylamido-3-methyl- N-[B- (dimethylamino) ethyl] butyramide was prepared according to the procedure of Example I.
EXAMPLE III A 121 copolymer of N-isopropylacrylamide/2-methacrylamido-3-methyl N [fi-(dimethylamino)ethyl]butyramide was prepared according to the procedure of Example I.
EXAMPLE 'IV A 1:1 copolymer af acrylamide 2-methacrylamido-3- methyl-N-[fl-dimethylamino)ethyl]butyramide was prepared according to the procedure of Example I.
EXAMPLE V A 4:1 copolymer of aerylamide/Z-aerylamido B-methyl- N [5 (dimethylamino)ethyl]butyramide was prepared according to the procedure of Example 1.
EXAMPLE VI A 1:1 copolymer of N-isopr0pylacrylamide/Z-acrylamide was prepared according to the procedure of Example I.
EXAMPLE VII A 4:1 copolymer of methacrylic acid/2-methacrylamido-3-methyl-dimethylaminoethyl b-utyramide was prepared according to the procedure of Example I.
EXAMPLE VIII A 1:1 copolymer of acrylamide/N-[B-(dimethylamino) ethyl]-2-acrylamido-2-methyl propionamide was prepared according to the procedure of Example I.
EXAMPLE IX A 4:1 copolymer of acrylamide/N-[[i-(dimethylamino) ethyl]-2-acrylamido-2-methylpropionamide was prepared according to the procedure of Example I.
1 1 EXAMPLE X A :2 copolymer of acrylamide/N- [p-(dimethylamino) ethyl]-2-acrylamido-Z-methyl-propionamide was prepared according to the procedure of Example I.
EXAMPLE XI A 1:1 copolymer of acrylamide/Z acrylamido-2- methyl N [Z-pyrrolidinoethyl]-propionamide was prepared according to the procedure of Example 1.
EXAMPLE XII A 1:1 copolymer of acry1amide/3'-(dimethylamino) propyl-2-acrylamido 2 methylpropionate was prepared according to the procedure of Example I.
EXAMPLE XIII A 38:1 copolymer of acrylamide/N-[B-(dimethylamino)ethyl] 2 acrylamido-Z-methyl-propionamide was prepared by dissolving 13.5 g. of acrylamide and 1.14 g. of the diamide in 80 ml. of dimethylformamide with 0.01 g. of a-zobisisobutyronitrile. The mixture was heated to 60 C. for 18 hours. The thus-formed polymer was precipitated into acetone, washed, dried and redissolved for use in making an emulsion.
EXAMPLE XIV A 3:4 copolymer of acrylamide/N- [13- (dimethylamino)ethyl] 2 acrylamido 2-methyl-propionamide was prepared according to the procedure of Example XIII.
EXAMPLE XV A :1 copolymer of acrylamide/N-[fi-(dimethylamino)ethyl] 2 acrylamide-Z-methyl-propionamide was prepared according to the procedure of Example XHI.
EXAMPLE XVI EXAMPLE XVII A 1:1 copolymer of acrylamide/fi-(tert-butylamino9- ethyl-Z-acrylamido-Z-methylpropionate nitrate was prepared employing the procedure of Example I.
EXAMPLE XVIII A 1:1 copolymer of acrylamide/2 acrylamino-Z- methyl-N-[piperidinopropyl]propionamide was prepared according to the procedure of Example XVI.
EXAMPLE XIX A 1:1 copolymer of acrylamide/2 acrylamino-Z- methyl N [3-morpholinopropyl]propionamide was prepared according to the procedure of Example XVI.
EXAMPLE XX A 9:5 copolymer of acrylamide/2-acrylamido-2-methyl- N [N'-methyl-2'-pyrridinoethyl]propionamide was prepared according to the procedure of Example XVI.
EXAMPLE XXI A 12:5 copolymer of acrylamide/2 acrylamido-2- methyl-N- [N,N' dimethyl-Z-aminopropyl]propionamide was prepared according to the procedure of Example XVI.
EXAMPLE XXII A 18:5 copolymer of N'-[methyl] -N-[(2-methylacrylamido-Z-methyl) propionyl] piperazine/methacrylamide was prepared according to the procedure of Example XVI.
12 The following general procedure may be used for preparing photographic emulsions using the polymers of the instant invention as the colloid binders.
A water-soluble silver salt, such as silver nitrate, may
be reacted with at least one water-soluble halide, such as Y potassium, sodium, or ammonium bromide, preferably together with potassium, sodium or ammonium iodide, in an aqueous solution of the above-described polymer. The emulsion of silver halide thus-formed contains watersoluble salts, as a by-product of the double decomposition reaction in addition to any unreacted excess of the initial salts. To remove these soluble materials, the emulsion may be centrifuged and washed with distilled water to a low conductance. The emulsion may then be redispersed in distilled water. To an aliquot of this emulsion may be added a known quantity of a solution of bodying or thickening polymer, such as polyvinyl alcohol having an average molecular weight of about 100,000 (commercially available from E. I. do Pont de Nemours & 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 slot coated onto a base of cellulose triacetate sheet 5 mls. thick having a coating of 30 mg./sq. ft. of hardened gelatin.
Alternatively, the soluble salts may be removed by adding to the emulsion a solution of polyacid such as 1:1 ethylenezmaleic acid copolymer and lowering the pH to below 5, thereby bringing about precipitation of the polyacid carrying the silver halide grains along with the precipitate, and then to wash and resuspend the resulting precipitate by redissolving the polyacid at pH 6-7.
The emulsions may be chemically sensitized with sulfur compounds such as sodium thiosulfate or thiourea, with reducin 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 alkyl a-picolinium bromide; and with polyethylene glycols and derivatives thereof. The emulsions of the present invention require only 5% as much gold for chemical sensitization as do gelatin emulsions.
The polymers employed as the binders in the emulsions of the present invention may be cross-linked according to conventional procedures. As an example, polymers containing amine groups may be cross-linked with zirconium salts under alkaline conditions wherein amine-containing polymer is coated With a zirconium salt, for example, zirconium sulfate, and the pH is raised cross-linking the polymer.
The emulsions of the present invention may also be optically sensitized with cyanine and merocyanine dyes more easily than are gelatin emulsions. Cyanine dyes tend to aggregate less on the polymers of the instant invention than with gelatin providing less light filtering and speed loss. Where desired, suitable antifoggants, toners, restrainers, developers, accelerators, preservatives, coating aids, plasticizers, hardeners and/or stabilizers may be included in the composition of the emulsion. l
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. As examples of 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 glycolterephthalic acid, and cellulose derivatives such as cellu lose acetate, triacetate, nitrate, propionate, butyrate, acetate propionate, and acetate butyrate. These novel emulsions of the instant invention have been found to adhere to supports in a most satisfactory manner.
The polymers employed in the practice of the instant invention may contain from -100 mole percent of the repeating units represented in Formula A. The specific amount employedmay be selected by the operator depending upon the grain particle size and habit desired.
Emulsions within the scope of the present invention may also be prepared employing polymers such as:
N- 8- diethylamino) ethyl] -2-acrylarnido-3-methyl-butynamide) :N-methyl-N- [2-acrylamido-2-methylpropionyl] -piperazine and methacrylamide :N-methyl-N- [2-acrylamido-2-methylpropionylJ-piperazine copolymer.
By selecting appropriate comonomers, the instant copolymers may be made to be compatible with all watersoluble 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. As examples of specific materials which may serve as bodying polymers are polyvinyl alcohol, polyacrylamide, polyalkylacrylamides, polyvinyl pyrrolidone, poly(fl-hydroxyethyl acrylate), polyethylene imine and cellulose derivatives such as hydroxypropyl cellulose and methyl cellulose. It has been found that using only a small amount of one or more of the instant polymers, large amounts of photosensitive silver halide grains may be obtained.
An emulsion made from one of these polymers of the instant invention may therefore be bodied with a watersoluble polymer such that the polymeric constitution of the resulting emulsion comprises a relatively large percentage of the bodying polymer.
By selecting appropriate comonomers, copolymers with selected diffusion characteristics may be prepared.
The instant polymers containing acidic comonomers may be pH flocculated in order to remove the soluble salts formed as a byproduct of the double decomposition reaction between the water-soluble silver salt and the water-soluble halide, in addition to any unreacted excess of the initial salts. As an example, an acid copolyrner may be precipitated by lowering the pH below 5 and then washed and resuspended by raising the pH to above 7.
The instant invention will be further illustrated by reference to the following nonlimiting examples in which the preparation of the emulsion was carried out in the following general manner.
Procedure A A solution of 4.15 g. of the dry copolymer in 266 ml. of distilled water was adjusted to pH 6.30 with dilute nitric acid and maintained at a temperature of 55 C. To this solution, 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 with continuous agitation to the polymer-halide solution and an additional 396 ml. was added over a period of 22 minutes. Thereafter, the emulsion was ripened for 30 minutes at 55 C., and then rapidly cooled to below 20 C.
Procedure B In an alternative procedure for preparing the emulsion, the pH of the polymer solution was adjusted to 3.0; the amount of dry potassium bromide used was 88.0 g. and the amount of dry potassium iodide used was 1.0 g. In addition, the emulsion was ripened for 60 minutes instead of for 30 minutes.
The emulsion mixture in both procedures was centrifuged and washed with water to a low conductance. The emulsion was then redispersed in distilled water. To an aliquot of this emulsion was added a known quantity of a solution of bodying or thickening polymer of polyvinyl alcohol having an average molecular weight of about 100,000 (commercially available from E. I. du Pont de Nemours & Company, Wilmington, Del., designated Type 72-60). A surfactant, such as Aerosol OT, was added and the emulsion was slot coated onto a base of cellulose triacetate sheet 5 mils thick having a coating of 30 mg./ sq. ft. of hardened gelatin (Celfa, commencially available from Instar Supply Company, New York, N.Y.). This film so prepared was air dried, exposed on a sensitometer, and processed with a processing solution and an imagereceiving sheet from a Type 42 film assembly (Polaroid Corporation, Cambridge, Mass). The negative and imagereceiving element were maintained in superposed position for 15 seconds, after which they were stripped apart. The photographic characteristics of the resulting positive print were measured on an automatic recording densitometer.
The following table summarizes silver halide grain sizes obtained in emulsions prepared with polymers of the present invention.
TAB LE 2 Grain size (microns) Polymer Range Average Dimethylaminoethyl-2-acrylamido-Z- methylpropionamide 0.2-2. 0 0.5 3 .4 Acrylarnide, dirnethylaminoethyl-2- acrylamido-Z-rnethylpropionamide 0. 3-2. 1 l. 0 1:1 Acrylarnide, dimethylaminoethyl-Z- acrylamido-Z-methylpropionamide 0. 4-1. 4 0. 8 4: 1 Acrylamide, dimethylaminoethyl-Z- acrylarnido-2methy1propionamide.-- 0. 53. 7 1. 8 38:1 Acrylamide, dimethylamineothyl-2 acrylamido-2-methylpropionamide. 0. 3-2. 2 1. 3 Dimethylaminoethyl-2-acrylamido-3- methylbutyramide 0.2-2. 0 0,5 1: 1 Acrylamide, dimethylarninoethyl-Z- acrylamido-S-methylbutyramide 0. 4-2. 3 1, 5 6: 1 Aerylamide, dimethylaminoethyl-Z- acrylamido-El-rnethylbutyramide 0. 2-2. 0 0, 8 1: 1 N-isopropylacrylamide, dimethylaminoethyl-Z-acrylamido-3-methylbutymrnid n 0. 1-2. 0 0. 9 9:1 Aerylamidoacetamide, dimethylami noethyl-Z-acrylamido-3-methylbutyramrde 0. 1-1. 5 0. 6 8:1: 1 Methacrylamidoacetamide, methaeryloxglycine, dimethylaminoethyl- 2-acrylamido-3-methylbutyramide 0.2-2. 0 0. 8 2: 1:2 Acrylamide: acryloylvaline, di-
methylaminoethyl-2-acrylamidQ-B-methylbutyrmnir ln 0. 1-0. 8 0. 3 4: 3: 3 Acrylamide: acryloylvaline,
dimethylaminoethyl-2-acrylamido-3- methylbutyrarnide 0. 2-1. 0 0. 5 2:2: 1 Acrylamide:aeryloylvaline,
dimethylaminoethyl-2-acrylamido-3- methylbutyramide 0. 1-1. 5 0, 8 2: 2: 1 Methacrylamide:methacryloylvaline,
dimethylaminoethyl-2-acrylamido-3- methylbutyramide 0. 22. 0 1. 0 4: 3: 3 Methacrylamide: mothacryloylvalme,
dimethylaminoethyl-2-acrylamid0-3- methylbutyrarnide 0.1-2.0 0. 5 6: 1 Acrylamidezfi-(tert-butylamino)-ethyl-aacrylamido-2-methylpropionate.. 0. 2-1 1 0.4 7: 7: 1 AerylamidezB- (diethylamino) aorylarnldo-2-methylpropionate. 0. 4-1. 6 0. 7 N-[fl-(diethylamino) ethyl1-2-acrylam1do-2- methylpropionamide 0.2-1.1 0. 5 1: 77: 1 Acrylarnide, Z-acrylamido-Z-rnethyl-N- [2-(diisopropylamino) ethyl] proplonarnide 0. 4 12:5 Acrylamide, 2-acrylarnido-2-methyl-N:
[Z-(dimethylamino)-prop-1-yl]propionam1de- 0. 2-2. 4 1. 0 4: 8: 1 Acrylamide23(dimethylamino) -proop- 1-yl-2-acrylamido-3-methylprop1onate 0. 4-4. 5 1. 5 1:1 Acrylamide: Z-aerylamido-Z-methyl- N-[2-pyrro1idiuo) ethyl1propionamide 0. 2-0. 9 0.4 2; 6: 1 Acrylamide, Z-acrylarnido-Z-methyl-N- [2-(piperidino)-ethyl]propionarnide 0. 2-0. 8 0. 4 1: 1 Acrylamide, 2-aerylamido-2-methyllpiperidinopropyl]propionamlde 0. 2-0. 8 0.4 9:5 Acrylann'de, 2-acrylarnido-2-methyl-N- propionamide 0. 21.4 0. 6 1:08: 1 Acrylamide, 2-acrylam do-2-methyl-N- [3-morpholino)propyl]propronamide 0. 31. 2 0. 7 1:1 Acrylamide, 2-acrylamido-2-methyl-N- lN"-methyl-N-piperazinopropyl] pro 0. 2-1. 1 0. 6
The following table shows densitometer readings obtained on negatives prepared from emulsions within the scope of the present invention.
TABLE 3 Silver/ Silver,
olymer rng./ Gram growing polymer Bodying polymer ratio it. Dmax. Dmin. A D
21:1 acrylamide/N-[B-(dimethylamino)ethyl]-2racrylamido-2-methylpropionamide None oo 81. 0. 81 0. 0. 66 Do Polyvinyl alcohol. 0. 91 105. 5 1. 62 0.09 1. 53 10:1 acrylarnide/dimethy]amino-ethyl-2-acrylamido-Z-methylproplonamide None co 52. 5 0.65 0. 00 0. 65 4:1 acrylamide/dimethylazmino-ethyl2-aerylamido-2methylpropionamide do eo 143. 3 0.90 0.00 0. 90 6:1 acrylamide/Z-acrylamido-3 methyl-N-[B-(dimethylamino) ethyllbutyramide do ee 29. 6 1. 14 0 29 0. 85
In certain photographic applications, it may be desirable to replace part, but not all, of the gelatin in the photosensitive emulsion. In view of the characteristics of these polymers described above, and further, in view of their compatibility with gelatin in substantially all proportions, it will be obvious that these polymers are ideally suited for such work.
The term 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 form usable images when photo-exposed by radiation.
Since certain changes may be made in the above products and processes without departing from the scope of the invention herein involved, it is intended that all matter contained in the above description shall be interpreted as illustrative only and not in a limiting sense.
What is claimed is:
1. A photosensitive silver halide emulsion wherein the emulsion binder comprises a polymer having in its structure repeating units of the formula:
wherein R R and R each are selected from the group consisting of hydrogen, lower alkyl and halogen; R is selected from the group consisting of hydrogen, lower alkyl, halogen and cyano; Z is selected from the group consisting of oxygen and nitrogen; when Z is oxygen R is an electron pair and when Z is nitrogen R is selected from the group consisting of hydrogen and lower alkyl; R is selected from the group consisting of lower alkyl and lower cycloalkyl groups; R and R each are selected from the group consisting of hydrogen, lower alkyl, lower cycloalkyl, and any combination of R R R and R may be chemically joined to form a 3-7 atom ring structure, and n is a positive integer greater than 1.
2. The product as defined in claim 1 wherein substantially all of said emulsion hinder comprises said polymer.
3. The product as defined in claim 1 wherein said polymer comprises 5-100 mole percent of said repeating segments.
4. The product as defined in claim 1 wherein said silver halide emulsion is a silver iodobromide emulsion.
5. The product was defined in claim 1 wherein said emulsion includes at least one chemical sensitizing agent.
6. The product as defined in claim 1 wherein said emulsion includes at least one optical sensitizing agent.
7. The product as defined in claim 1 wherein said polymer is a homopolymer.
8. The product as defined in claim 1 wherein said polymer comprises a copolymer of a first monomer of the formula:
JJH- -(il =0 R; O 11- -Z-R -N and a second ethylenically unsaturated monomer.
9. The product as defined in claim 8 wherein said fir monomer is dimethylaminoethyl-Z-acrylamido-2-methylpropionamide.
10. The product as defined in claim 8 wherein said first monomer is dimethylaminoethyl-Z-acrylamido-3-methylbutyramide.
11. The product as defined in claim 8 wherein said first monomer, is fi-(dimethylamino)-ethyl 2 acrylamido-Z- methylpropionate.
12. The product as defined in claim 8 wherein said first monomer is 2 acrylamido-Z-methyl-N-[2-(piperidino)- ethyl]-propionamide.
13. The product as defined in claim 8 wherein said co monomer is acrylamide.
14. The product as defined in claim 8 wherein said comonomer is N-isopropylacrylamide.
15. The product as defined in claim 8 wherein said comonomer is acrylamidoacetamide.
16. 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 polymer having in its structure repeating units of the formula:
iti
wherein R R and R each are selected from the group consisting of hydrogen, lower alkyl and halogen; R is s lected from the group consisting of hydrogen, lower alkyl, halo-gen and cyano; Z is selected from the group consisting of oxygen and nitrogen; when Z is oxygen R is an electron pair and when Z is nitrogen R is selected from the group consisting of hydrogen and lower alkyl; R is selected from the group consisting of lower alkyl and lower cycloalkyl groups; R, and R each are selected from the group consisting of hydrogen, lower alkyl, lower cycloalkyl, and any combination of R R R and R may be chemically joined to form a 3-7 atom ring structure, and n is a positive integer greater than 1.
17. The method as defined in claim 16 wherein said polymer comprises a copolymer of a first monomer of the formula:
/ =0 R: 0 R imaaam b Ru and a second ethylenically unsaturated monomer.
18. The method as defined in claim 17 wherein said first monomer is dimethylaminoethyl-2-acrylamido-2-methylpropionamide.
19. The method as defined in claim 17 wherein said first monomer is dimethylaminoethyl 2 acrylamido 3- methylbutyramide.
20. The method as defined in claim 17 wherein said first monomer is fi-(dimethylamino) -ethy1 2 acrylamido-Z- methylpropionate.
21. The method as defined in claim 17 wherein said first monomer is 2-acrylamido-2-methyl-N-[2-(piperidino) -ethy1] -propionamide.
22. The method as defined in claim 17 wherein said comonomer is acrylamide.
23. The method as defined in claim 17 wherein said comonomer is N-isopropylacrylamide.
24. The method as defined in claim 17 wherein said c0- monomer is acrylamidoacetamide.
References Cited UNITED STATES PATENTS 2,409,126 8/1946 Kenyon et a1. 260--83 5 3,396,030 8/1968 Haas 96-114 3,408,199 10/1968 Saleck et a1 96-114 FOREIGN PATENTS 1,500,666 9/1967 France 96-1 14 10 RONALD H. SMITH, Primary Examiner US. Cl. X.R. 96-84 R
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US3904418A (en) * 1974-08-15 1975-09-09 Eastman Kodak Co Hardenable vehicles for silver halide emulsions
US4030929A (en) * 1975-09-19 1977-06-21 Agfa-Gevaert, A.G. Photographic silver halide emulsion
US4131471A (en) * 1975-12-08 1978-12-26 Polaroid Corporation Synthetic polymeric silver halide peptizer
US4315071A (en) * 1981-03-30 1982-02-09 Polaroid Corporation Polystyryl amine polymeric binders for photographic emulsions
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US4350759A (en) * 1981-03-30 1982-09-21 Polaroid Corporation Allyl amine polymeric binders for photographic emulsions
WO1983001617A1 (en) * 1981-10-29 1983-05-11 Minnesota Mining & Mfg Acrylamidoacylated oligomers
US4546159A (en) * 1980-03-14 1985-10-08 Polaroid Corporation Eliminating polymers useful in diffusion control layers
US4694103A (en) * 1986-05-19 1987-09-15 Minnesota Mining And Manufacturing Company Method of preparing N-acryloyl-α-amino acids
USRE32952E (en) * 1986-05-19 1989-06-13 Minnesota Mining And Manufacturing Company Method of preparing N-acryloyl-α-amino acids
US5157108A (en) * 1989-12-12 1992-10-20 Minnesota Mining And Manufacturing Company Thermally sensitive linkages
US20020042377A1 (en) * 1995-06-07 2002-04-11 Steiner Joseph P. Rotamase enzyme activity inhibitors
US20020052410A1 (en) * 1995-06-07 2002-05-02 Steiner Joseph P. Rotamase enzyme activity inhibitors
US20120065616A1 (en) * 2007-10-09 2012-03-15 Lynn David M Ultrathin Multilayered Films for Controlled Release of Anionic Reagents
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US3879205A (en) * 1971-10-08 1975-04-22 Polaroid Corp Method of preparing photosensitive silver halide emulsions
USB320452I5 (en) * 1973-01-02 1975-01-28
US3925083A (en) * 1973-01-02 1975-12-09 Polaroid Corp Synthetic silver halide emulsion binder
US3904418A (en) * 1974-08-15 1975-09-09 Eastman Kodak Co Hardenable vehicles for silver halide emulsions
US4030929A (en) * 1975-09-19 1977-06-21 Agfa-Gevaert, A.G. Photographic silver halide emulsion
US4131471A (en) * 1975-12-08 1978-12-26 Polaroid Corporation Synthetic polymeric silver halide peptizer
US4546159A (en) * 1980-03-14 1985-10-08 Polaroid Corporation Eliminating polymers useful in diffusion control layers
WO1982003131A1 (en) * 1981-03-02 1982-09-16 Corp Polaroid Cleavable polymers and photographic products and processes employing same
US4315071A (en) * 1981-03-30 1982-02-09 Polaroid Corporation Polystyryl amine polymeric binders for photographic emulsions
US4350759A (en) * 1981-03-30 1982-09-21 Polaroid Corporation Allyl amine polymeric binders for photographic emulsions
WO1983001617A1 (en) * 1981-10-29 1983-05-11 Minnesota Mining & Mfg Acrylamidoacylated oligomers
USRE32952E (en) * 1986-05-19 1989-06-13 Minnesota Mining And Manufacturing Company Method of preparing N-acryloyl-α-amino acids
US4694103A (en) * 1986-05-19 1987-09-15 Minnesota Mining And Manufacturing Company Method of preparing N-acryloyl-α-amino acids
US5157108A (en) * 1989-12-12 1992-10-20 Minnesota Mining And Manufacturing Company Thermally sensitive linkages
US20020042377A1 (en) * 1995-06-07 2002-04-11 Steiner Joseph P. Rotamase enzyme activity inhibitors
US20020052410A1 (en) * 1995-06-07 2002-05-02 Steiner Joseph P. Rotamase enzyme activity inhibitors
US7056935B2 (en) 1995-06-07 2006-06-06 Gpi Nil Holdings, Inc. Rotamase enzyme activity inhibitors
US8524368B2 (en) 2003-07-09 2013-09-03 Wisconsin Alumni Research Foundation Charge-dynamic polymers and delivery of anionic compounds
US20120065616A1 (en) * 2007-10-09 2012-03-15 Lynn David M Ultrathin Multilayered Films for Controlled Release of Anionic Reagents
US8574420B2 (en) * 2007-10-09 2013-11-05 Wisconsin Alumni Research Foundation Ultrathin multilayered films for controlled release of anionic reagents
US10807069B2 (en) 2009-03-31 2020-10-20 3M Innovative Properties Company Hydrophobic monomers, hydrophobically-derivatized supports, and methods of making and using the same
US9958364B2 (en) 2013-10-03 2018-05-01 3M Innovative Properties Company Ligand functionalized substrates with enhanced binding capacity
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