US3721565A - Polymeric binders for photographic emulsions - Google Patents

Abstract

A photosensitive silver halide emulsion wherein the emulsion binder comprises a graft copolymer of an amine diamide monomer on a polymer containing a plurality of hydroxyl groups.

Description

United States Patent 1 91 Fitzgerald ]March 20, 1973 I POLYMERIC BINDERS FOR 3,396,030 8/1968 Haas ..96/1 14 PHOTOGRAPHIC EMULSIONS 3,408,199 10/1968 Saleck etal. "96/114 [75] Inventor: naurice J. Fitzgerald, Canton, FOREIGN PATENTS OR APPLICATIONS ass. I 1,500,666 9/1967 France ..96/l14 [73] Asslgnee: Polaroid Corporation, Cambridge, I 9 Mass Primary ExaminerRonald H. Smith [22] Filed: July 6; 1971 Attorney-Charles Mikula et a1.

[211 App]. No.: 160,214

[57] ABSTRACT [52 us. c1. ..96/114, 96/84 R A photosensitive silver halide emulsion h r in h [51] Int. Cl. ..G03c l/04 emulsion binder wmpl'ises a graft copolymer of [58] Field of Search ..96/114 amine iamide monomer n a polymer containing a plurality of hydroxylgroups. 56 R f Ct 11 I e erences l e 23 Claims, No Drawings UNITED STATES PATENTS 2,409,126 8/1946 Kenyon et a]. ..260/83 POLYMERIC BINDERS FOR PHOTOGRAPIIIC EMULSIONS BACKGROUND OF THE INVENTION 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 notfunctioned 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 has now been found which is not susceptible to the deficiencies of the prior I an and which may replace gelatin entirely in photosensitive silver halide emulsions.

Summary of the Invention The present invention is directed to a photosensitive wherein R R and R each is hydrogen, lower alkyl group, e.g., one to four 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 nitrogen; R when Z is oxygen, is an electron pair, and when Z is nitrogen, is hydrogen or lower alkyl, e.g., one to four carbon alkyl group, preferably methyl or ethyl; R, is a lower alkyl or cycloalkyl group, e.g., a one to four carbon alkyl or cycloalkyl group; R, and R each is hydrogen, lower alkyl group or lower cycloalkyl group, e.g., one to four carbons and any combination of R R,, R, and R may be taken together to form a three to seven atom ring structure; on a polymer containing a plurality of hydroxyl groups. In an alternative embodiment, the graft copolymer also includes asecond monomer grafted thereon, i.e., an ethylenically unsaturated monomer. In still another 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 containing a plurality of hydroxyl groups having grafted thereon an amine diamide monomer represented by the formula:

fn. it? (111:6

llm

e.g., one to four carbons, and any combination of R R R and R5 may be taken together to form a three to seven atom ring structure.

Such polymers have been found to substantially provide 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 against degradation, particularly hydrolysis and the growth of microorganisms than gelatin.

With regard to the backbone polymer of the graft copolymer; in general, any organic polymer comprising repeating units comprising structural units containing a plurality of I groupings capable of being oxidized by, e.g., a transition metal ion catalyst is useful in the present invention. Preferred backbones are substituted or unsubstituted cellulosic or polyvinyl polymers, and most preferably, a backbone selected from the group consisting of polymeric polyols, polyvinyl alcohol, gelatin,

. 3 polysaccharides, partial acetals of polyvinyl alcohol,

etc.

It is believed that upon oxidation of the hydroxyl groups, mention may be made of the following:

(1) 7 T115611 "6H l a "if Y J H H1011 cellulose 2 """dmbcfigaabi 'carboxymethyl cellulose hydroxyethyl cellulose carboxymethyl hydroxyethyl cellulose Oll O-GI-IzlICHs H -CHzCHCHa oornonom k y-6p hydroxypropyl cellulose methylcellulose dnr-ommc mona hydroxypropylmethyl cellulose cinz-o-omono'mcm hydroxybutylmethyl cellulose alginic acid COOH OOII

propyleneglycol ,alginate cellulose sulfate kappacarrageenan CIIzOII OOCHzCHCHa (Illa k ii CH: 8 04H lv Jx l (LE Quinuclidine-3 '-y1-2-acrylamido-Z-methylpropionate N-[3 '-(morphol1no)prop-1 -yl]-2-acrylam1do-2- methylpropionamide 13) 111: as) CH3 1H3 CH =CH-CONHCC0N11CH:CH2C Hz-N N-on. 0111:0114; O-NH-JJ-C o-Nu-omcn N g I om N-[ 3 -(N "-methylpiperazino )prop-l '-yl]-2- acrylamido-2-methylpropionamide The monomers employed in forming the graft copolymers suitable for use in the present invention may be prepared by the following general procedure:

N-[2'-(1 -methylpyrrolidin-2"-yl)ethyl]-2- acrylamido-Z-methylpropionamide a9 OH;

0112:011-0 ONH(IJC O-N N-CH;

H R /R7 R1 R2 3 ,1 V y I R: =0 1 N R5 R1 C=0 N-[2'-acrylam1do-2'-methy1prop1onyl]-N'-methyl- 1 piperazine J: I

R3- :CH-R R-|C-Ra R1 CZ-RuN (70) CH3 CH3 ll 1 oHFe-c0-NH (:-co-N' 'N 4111; 0

Oxazolone Reagent Amine Reagent 1 N-[2'-Methacrylamido-2Gmethylpropionyl]-N- The oxazolone reagent may be dissolved in an inert methylpiperazine solvent such as hexane or methylene chloride and a stoichiometric amount of amine reagent may be added (71) 0H3 to the solution. The desired monomer crystallizes out CHFCH CO NH 'JJ COCFCHQCHFN of solution in relatively high yield and purity. The

monomer may be collected by filtration, washed with 3 hexane or methylene chloride and vacuum dried.

The following table illustrates suitable monomers N-[2'-(2."-acrylamido-2"-methylpropionyloxy)ethyl1 prepared according to the above-indicated general azatane procedure.

TABLE 1 Elemental analysis 4 Theoretical Foun Reaction M.P., Percent Oxazolone reagent Amine reagent solvent Appearance C. yield C II N C H N 2-viny1-4-isopropy1-5- N,N-dimethyl ethyl- Hexane White crystals. 118-120 oxazolon'e. enediamine. 2-isopropenyl-4-isopropy1-5- .do Dlethylethen. ..do.. 117-119 oxazolone. 2-viny1-i4,4dimethyl-5- ..d0 IIexane do 76-78 85.0 58.2 9.3 18.5 58.1' 9.4 18.4

oxazo one.

Do fl-(tertiary butylarnino)- Acetone do 157-159 31.0 48.9 7.8 13.2 49.0 8.1 13.1

' ethanol nitrate. Do fl-(diethylamino)ethanol.. Diethylether. Colorless oil. 83.0 Do N,N-diothy1-ethyl- Hexane White crystals... 71-72 60.0 61.1 9.9 16.5 60.8 10.3 16.3 enediamine. 2-vmy.-4-isopropy1-5- do ..d0. .d0 83-84 oxazolone. 2-vinyl-4,4-dimethyl-5- N,N-dlisopropylethylene- .....do ..d0. 74-75 63.0 63.6 10.3 14.8 63.6 10.5 14.7

oxazolone. diamine.

Do 2-(dimethy1amino)-1 ...do ..do.. 54-55 43.0 59.7 9.6 17.4 59.6 9.7 17.4 v

aminopropane. Do B-(dimethylaminQ-l- Diethyl ether. Colorless oil 59 5 9.1 11.6 58 3 9 7 9 2 propane Do 2-pyrrolidinoethylamine. Hexane White crystals... 124-125 92.5 61.6 9.2 16.6 62.0 9.3 16.6 Do 2-piperidinoethylamine ..d0. .....d0 131-132 93 5 62.9 9.4 15.7 62 8 9 4 15 8 Do 3-piperidino-1-aminopro- ..do 1lo 103-104 93 5 64.0 9.7 14. 9 64 0 9 7 14 6 panc. l)o. 3-morph0lino-l-aminopro- .do. 9697 915 59.4 3.9 M x 5') 6 9 K 14 1-1 pane.

2-(l-methylpyrr0l1din-2-yl)- ...d0. .....d0........ 912-94 74.0 62.9 9.4 15.7 62.1; 9.7' 15.6 ethyl amino. Do N-methylpipemzine Diethyletln-r ..11o 72-75 62.0 2-isopropeny1-4,4- 1imethyl-5- .do ..do.... .do 115. 9 64. 0

oxazolone. 2-viny1-4,4-(limethyl-5- 3-(N-methylpiperazino)-1- l1exane. ....(lo.. 113-114 95.5 60.8 9.5 18. 9 60.7 9.9 18.5

oxazolone. aminopropnne.

1 Very high boiling point.

CHFCH-COOH (14) acrylic acid methacrylic acid a-chloroacrylic acid a-bromoacrylic acid CH CH=CHCOOH 7s crotonic acid CH CH=CH-COOH 79 isocrotonic acid B-cliloroacrylic acid BrCH=CH-COOH (81) ,B-bromoacrylic acid B-chloromethacrylic' acid CH =CHCOO-CH;, (as) methyl acrylate CHa ethyl methacrylate n-propyl-a chloroacrylate B1'CH=CH-COOCH+CH3)2 (86) isopropyl-B-bromoacrylate isobutyl methacrylate fi-hydroxyethyl acrylate 'y-hydroxypropyl acrylate 0112:0-0 00CH2?HCHJ 2-hydroxy-n-propyl methacrylate c11 =cH-c0 N11 (91) acrylamide a-bromoacrylamide methacrylamide a-ethylacrylamide ClCH=( JCONHa B-chloromethacrylamide 2,3-dibromoacrylamide CH CH=CH--CONH (98) crotonamide (nu) CH3 om=c co--Nu-cm N-methylmethacrylamide N,N-dimethylacrylamide N-ethyl-a-chloroacrylamide CH,=CH-CONH-C-(-CH N-tertiary butylacrylamide Z-acrylamidopropionamide 2-methacrylamidopropionamide 2-( a-chloroacrylamido 3-methylbutyramide N-( acetamidomethyl)acrylamide N-(propionamidomethyl)methacrylamide N-( n-butyramidomethyl )a-chloroacrylamide maleic anhydride HOOCCH=CHCOOH maleic acid HOOC-CH=Cl-lCONl-l maleic acid amide HOOC-CH=CH-CO-NHCH CH N-ethylmaleic acid amide N-methyl methylmaleate amide CH =CH-0OCl-l vinylformate CH =CH-OOCCl-l vinyl acetate CH =CH-OH vinyl alcohol isopropenyl bromoacetate CH =Cl-IOOCC(-Cl-l vinyl privalate Cl-l -=CHNHCOOC-(-Cl-l N-vinyl-tertiary butylcarbamate ethyl-3-carboxy-3-butenate (lSO) (lSl) fuss) I a-vinylfuran a(-acryloyloxymethyl+tetrahydrofuran p-hydroxystyrene m-hydroxystyrene o-hydroxystyrene p-carboxystyrene m-carboxystyrene N-vinyl-2-pyrrolidone Polymerization of the indicated monomers is achieved by conventional transition metal ion catalyst techniques.

The following non-limiting examples illustrate the preparation of polymers within the scope of the present invention.

EXAMPLE 1 A flask was charged with 10 ml. of water, 1.06 g. of acrylamide and 3.40 g. of 2-acrylamidO-Z-methyI-N-[B- (dimethylamino)ethyl]-propionamide.-20 ml. of a 10 percent aqueous solution of polyvinyl alcohol (Elvanol 70-05, DuPont Company, Wilmington, Delaware) was added to the flask. 1.4 g. of concentrated nitric acid was added and nitrogen was bubbled through the solution for two hours. The solution was then heated to 55 C.; 0.20 g. of ceric ammonium nitrate in 2 ml. of water was added and the solution was stirred for 3 hours. The solution was then cooled, adjusted to a pH of 9 with potassium hydroxide and dialyzed for 28 hours against distilled water. Analysis showed a 1:1:3 graft of acrylamide: Z-acrylamido-2-methyl-N-[B- (dimethylamino)ethyl]-propionamide on polyvinyl alcohol. 1

EXAMPLE [I A 121:3 graft of acrylamide:Z-acrylamido-Z-methyl- N-[3'-(piperidino)-propyl]-propionamide on polyvinyl alcohol was prepared according to the procedure of Example I. Y

The following general procedure may be used for preparing photographic emulsions using the graft copolymers 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 potassium, sodium, or ammonium bromide, preferably together with potassium, sodium or ammonium iodide, in an aqueous solution of the abovedescribed polymer. The emulsion of silver halide thusformed contains water-soluble 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 thisemulsion 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. duPont deNemours & Company, Wilmington, Delaware, 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, New York 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 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 alkyl a-picolinium bromide; and with polyethylene glycols and derivatives thereof. The emulsions of the present invention require only 5 percent as much gold for chemical sensitization as do gelatin emulsions.

The graft copolymers 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.

Cross-linking agents conventionally employed with ,hydroxyl-containing polymers, such as boric acid, may 1 also be employed.

sion.

The emulsions of this invention maybe 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 glycol-terephthalic acid, and cellulose derivatives such as cellulose 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 5-75 mole percent of the grafted monomer; preferably 20 mole percent. The

specific amount employed may be selected by the operator depending upon the grain particle size and habit desired. For example, the grain size distribution of the emulsion may be varied by changing the mole ration and type of monomer grafted on the hydroxyl-containing polymer backbone.

By selecting appropriate monomers to be grafted on the hydroxyl-containing polymers, the instant graft polymers 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. As examples of specific materials whichmay serve as bodying polymers are polyvinyl alcohol, polyacrylamide, polyalkylacrylamides, polyvinyl pyrrolidone, poly(B-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 copolymer may be precipitated by lowering the pH below 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 graft 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. 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. duPont de Nemours & Company, Wilmington, Delaware, 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, commercially available from lnstar Supply Company, New York, New York). This film so prepared was air dried, exposed on a sensitometer, and processed with a processing solution and an imagereceiving sheet from a Type 107C film assembly (Polaroid Corporation, Cambridge, Massachusetts). The negative and image-receiving element were maintained in superposed position for seconds, after which they were stripped apart. The photographic characteristicsof 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.

TABLE 2 Grain Size (microns) Range Average Graft copolymer of Example 111 0.4-3.0 1.3 Graft copolymer of Example 11 0.5-3.1 1.4

The following table shows densitometer readings obtained on a negative prepared from an emulsion of the present invention.

TABLE 3 Grain growing polymer 1:]:3-acrylamidez2-acrylamido-2- methyl-N-{B- dimethylaminoethyllpropionamide on polyvinyl alcohol Bodying polymer polyvinyl alcohol Polyvinyl alcohol silver ratio 1.0 Film base coverage 178.8 mg. Ag/ft. Positive max 1.38 'min 0.50 AD 0.84

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 compatability 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 photoexposed 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 graft copolymer of an amine diamide of the formula:

wherein R R and R each are selected from the group graft copolymer.

23 alkyl, lower cycloalkyl, and any combination of R R R, and R, may be chemically joined to form a three to seven atom ring structure, onto a polymer containing a plurality of hydroxyl groups.

5. The product as 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 graft copolymer further includes a second ethylenically unsaturated monomer grafted onto said polymer containing a plurality of hydroxyl groups.

8. The product as defined in claim 7 wherein said amine diamide is dimethylaminoethyl-2-acrylamido-2- methylpropionamide.

9. The product as defined in claim 7 wherein said amide diamide is dimethylaminoethyl-2-acrylamido-3- methylbutyramide.

10. The product as defined in claim 7 wherein said amine diamide is B-(dimethylamino)-ethyl-2'acryalmido-2-methylpropionate.

11. The product as defined in claim 7 wherein said amine diamide is 2-acrylamido--2-methyl-N-[2'- (piperidino)-ethyl]-propionamide.

12. The product as defined in claim 7 wherein said second monomer is acrylamide.

13. The product as defined in claim 7 wherein said second monomer is N-isopropylacrylamide.

14. The product as defined in claim 7 wherein said second monomer is acrylamidoacetamide.

15. 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 graft copolymer of an amine diamide 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 three to seven atom ring structure, onto a polymer containing a plurality of hydroxyl groups.

16. The method as defined in claim 15 wherein said graft copolymer further includes a second ethylenically unsaturated monomer grafted onto a polymer containing a plurality of hydroxyl groups.

17. The method as defined in claim 16 wherein said amine diamide is dimethylaminoethyl-Z-acrylamido-Z- methylpropionamide.

18. The method as defined in claim 16 wherein said amine diamide is dimethylaminoethyl-Z-acrylamido-3- methylbutyramide. v

19. The methodas defined in claim 16 wherein said amine diamide is B-(dimethylamino)-ethyl-2- acrylamido-2-methylpropionate.

20. The method as defined in claim 16 wherein said amine diamide is 2-acrylamido-2-methyl-N-[2'- (piperidino)-ethyl]-propionamide.

21. The method as defined in claim 16 wherein said second monomer is acrylamide.

22. The method as defined in claim 16 wherein said second monomer is N-isopropylacrylamide.

23. The method as defined in claim 16 wherein said second monomer is acrylamidoacetamide.

' :r k a:

Claims (22)

1. 2. The product as defined in claim 1 wherein substantially all of said emulsion binder comprises said graft copolymer.
2. 3. The product as defined in claim 1 wherein said graft copolymer comprises 5-75 mole percent of said amine diamide.
3. 4. The product as defined in claim 1 wherein said silver halide emulsion is a silver iodobromide emulsion.
4. 5. The product as defined in claim 1 wherein said emulsion includes at least one chemical sensitizing agent.
5. 6. The product as defined in claim 1 wherein said emulsion includes at least one optical sensitizing agent.
6. 7. The product as defined in claim 1 wherein said graft copolymer further includes a second ethylenically unsaturated monomer grafted onto said polymer containing a plurality of hydroxyl groups.
7. 8. The product as defined in claim 7 wherein said amine diamide is dimethylaminoethyl-2-acrylamido-2-methylpropionamide.
8. 9. The product as defined in claim 7 wherein said amide diamide is dimethylaminoethyl-2-acrylamido-3-methylbutyramide.
9. 10. The product as defined in claim 7 wherein said amine diamide is Beta -(dimethylamino)-ethyl-2-acryalmido-2-methylpropionate.
10. 11. The product as defined in claim 7 wherein said amine diamide is 2-acrylamido-2-methyl-N-(2''-(piperidino)-ethyl)-propionamide.
11. 12. The product as defined in claim 7 wherein said second monomer is acrylamide.
12. 13. The product as defined in claim 7 wherein said second monomer is N-isopropylacrylamide.
13. 14. The product as defined in claim 7 wherein said second monomer is acrylamidoacetamide.
14. 15. 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 graft copolymer of an amine diamide of the formula:
15. 16. The method as defined in claim 15 wherein said graft copolymer further includes a second ethylenically unsaturated monomer grafted onto a polymer containing a plurality of hydroxyl groups.
16. 17. The method as defined in claim 16 wherein said amine diamide is dimethylaminoethyl-2-acrylamido-2-methylpropionamide.
17. 18. The method as defined in claim 16 wherein said amine diamide is dimethylaminoethyl-2-acrylamido-3-methylbutyramide.
18. 19. The method as defined in claim 16 wherein said amine diamide is Beta -(dimethylamino)-ethyl-2-acrylamido-2-methylpropionate.
19. 20. The method as defined in claim 16 wherein said amine diamide is 2-acrylamido-2-methyl-N-(2''-(piperidino)-ethyl)-propionamide.
20. 21. The method as defined in claim 16 wherein said second monomer is acrylamide.
21. 22. The method as defined in claim 16 wherein said second monomer is N-isopropylacrylamide.
22. 23. The method as defined in claim 16 wherein said second monomer is acrylamidoacetamide.