US3576813A - Bis(pyridinium salts) useful as gelatin hardeners - Google Patents

Bis(pyridinium salts) useful as gelatin hardeners Download PDF

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US3576813A
US3576813A US702508A US3576813DA US3576813A US 3576813 A US3576813 A US 3576813A US 702508 A US702508 A US 702508A US 3576813D A US3576813D A US 3576813DA US 3576813 A US3576813 A US 3576813A
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gelatin
perchlorate
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hardeners
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Donald M Burness
Burton D Wilson
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Eastman Kodak Co
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
    • C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
    • C07D213/20—Quaternary compounds thereof
    • 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
    • C07D295/08—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 bound oxygen or sulfur atoms
    • C07D295/084—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 bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
    • C07D295/088—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 bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/08—Bridged systems
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16D—COUPLINGS FOR TRANSMITTING ROTATION; CLUTCHES; BRAKES
    • F16D3/00—Yielding couplings, i.e. with means permitting movement between the connected parts during the drive
    • F16D3/16—Universal joints in which flexibility is produced by means of pivots or sliding or rolling connecting parts
    • F16D3/20—Universal joints in which flexibility is produced by means of pivots or sliding or rolling connecting parts one coupling part entering a sleeve of the other coupling part and connected thereto by sliding or rolling members
    • F16D3/22—Universal joints in which flexibility is produced by means of pivots or sliding or rolling connecting parts one coupling part entering a sleeve of the other coupling part and connected thereto by sliding or rolling members the rolling members being balls, rollers, or the like, guided in grooves or sockets in both coupling parts
    • 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
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/30—Hardeners

Definitions

  • This invention relates to certain compounds found useful as photographic hardeners and to gelatin compositions containing those hardeners.
  • One object of our invention is to provide hardeners for photographic gelatin. Another object of our invention is to provide gelatin compositions useful photographically. A further object of our invention is to provide certain compounds which are useful in the preparation of photographic products. Other objects of our invention will appear herein.
  • the compounds of our invention are conveniently prepared by the alkylation of the appropriate tertiary amine with an appropriate bis(alpha-chloroalkyl carboxylate).
  • these compounds may be prepared by the direct condensation of acid halide, aldehyde and tertiary amine by the procedure described by Iakubovics et al., J. Gen. Chem. U.S.S.R. Engl. Transl. 28, 1971 (1958).
  • Compounds which have been found to be useful for hardening gelatin or some other polymeric material hav- 3,576,813 Patented Apr. 27, 1971 ing carboxyl groups therein have the following general structural formula:
  • X is an acid anion such as halide, perchlorate or other suitable acid anion
  • R is hydrogen or a lower alkyl radical such as of 1-4 carbon atoms
  • B+ is a quaternary nitrogen residue from one of the following bases: (1) pyridine or simple derivatives thereof as for example picolines, 2-benzylpyridine, 2-(4-pyridyl) ethanol and the like, (2) a compound with a tertiary nitrogen in a bridgehead position as for example quinuclidine, (3) an aliphatic or cyclic tertiary base as for example trimethylamine, triethylamine, N-methylpiperidine and the like.
  • Z represents a linking structure which may be either a valence bond, a saturated or unsaturated carbon chain or a heterogeneous chain composed predominantly of carbon. It may be a cyclocarbon such as cyclohexylene or phenylene, a chain including phenylene, cyclohexylene, or some other radical or a chain having simple alkyl substituents thereon such as methyl, ethyl, propyl, butyl and the like.
  • the linking structure is most conveniently (CH where n equals 110.
  • a bifunctional amine for example, N,N'-dimethylpiperazine, or where the nitrogen residue is derived from 1,4-diazabicyclo[2. 2.2[octane polymeric salts will be formed having good hardening activity.
  • the following recurring structure represents polymers of this nature which are useful as hardeners in accordance with our invention:
  • R and R are hydrogen or lower alkyl or together they may form the hydrocarbon portion of a ring.
  • the hardeners in accordance with our invention they may be employed in gelatin compositions either where gelatin is the main substituent or in compositions in which gelatin is a carrier for suspended material such as in gelatin-silver halide photographic emulsions, gelatinbarium sulfate compositions or other cases where some pigment or insoluble material is in suspension in the gelatin.
  • Useful compositions are also prepared by incorporating these hardeners into solutions or emulsions of polymers containing carboxyl groups as for example acrylic acid copolymers. These hardeners are conveniently used in proportions of 0.55%, based on the weight of the gelatin or other polymer to be hardened. However, it is to be understood that the invention is not limited to these proportions as effective amounts outside of this range may occasionally be employed.
  • Example l.-Adipoylbis (N-oxymethylpyridinium perchlorate) 4.86 grams of bis(chlormethyl) adipate were dissolved in 25 ml. of dry pyridine and the solution was heated on a steam bath for 2 hours. The precipitate was isolated and converted to the perchlorate by a double decomposition reaction with sodium perchlorate. Recrystallization from water gave colorless crystals, M.P. 206-207 (corn).
  • Example 2 Adipoylbis(N-oxymethyl-4-picolinium perchlorate) This compound was prepared in the same manner as described in Example 1 except that 'y-picoline was substituted for the pyridine. The melting point of the crystals obtained was 123425 (corn).
  • Example 3 Adipoylbis(N-alpha-oxyethylpyridinium perchlorate) The method described in Example 1 was followed except that an equivalent amount of bis(alpha-chloroethyl)adipate was substituted for the bis(chlormethyl) adipate. The material obtained had no definite melting point and tended to oil out on recrystallization.
  • Example 4 Sebacoylbis (N-oxymethylpyridinium perchlorate) This material was prepared by the procedure of Example 1 but using an equivalent amount of bis(chloromethyl) sebacate therein. The material obtained had a melting point of 168-171 (corn).
  • Example .Adipoylbis( l-oxymethyl-4-azal-azoniabicyclo [2.2.2] octane chloride) A solution was prepared of 4.86 grams of bis(chlormethyl)adipate and 11.2 grams of l,4-diazabicyclo[2.2.2] octane in 25 ml. of acetonitrile. This solution was stirred at 25 C. Dense precipitation and an exothermic reaction set in after 35 minutes. The precipitate was collected the next day and recrystallized from alcohol-acetone. The product obtained had a melting point of l25l26.5 (corn).
  • Example 6 Poly(1,4 diazoniabicyclo[2.2.2]0ctane-1,4- dimethyl adipate dichloride) A solution of equimolar quantities of the reagents of Example 5 in acetonitrile was heated on the steam bath for one hour. The material was purified by repeated dissolution in water and precipitation into acetone.
  • Example -8.-Adipolybis(oxyrnethyltriethylammonium perchlorate) A solution as prepared of 30 ml. of triethylamine (dried over calcium hydride) and 4.86 grams of bis(chloromethyl) adipate in 25 ml. of acetonitrile. The solution was stirred for 2 days for anhydrous conditions. The solids which precipitated (triethylamine hydrochloride) were filtered off and discarded. The filtrate was concentrated to remove volatiles and the residual oil obtained was converted to the perchlorate by a double decomposition reaction.
  • X is an inorganic nonmetallic halo anion
  • each R is the same substituent selected from the group consisting of hydrogen and an alkyl group having 1 to 4 carbon atoms
  • each B is the same member selected from the group consisting of a pyridinium group and a picolinium group and wherein said members are joined through their nitrogen atom to the carbon atom of the UNITED STATES PATENTS 2,023,075 12/1935 Harris 260295 2,089,602 8/ 1937 Granacher 260295 2,402,526 6/ 1946 Pikl 260 -295 3,241,972 3/1966 Wilson 96111 3,312,711 4/1967 Koch 260295 3.144,45 6 8/ 1964 Motfett 260268 3,213,098 10/ 1965 Miller 260268 3,345,177 10/1967 Wilson 260297 3,369,076 2/ 1968 Kaniecki 260567.'6 3,396,127 8/1968 Burness et a1 2608 3,406,005 10/1968 Whitfield

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • General Engineering & Computer Science (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Pyridine Compounds (AREA)
  • Hydrogenated Pyridines (AREA)

Abstract

CERTAIN BIS(PYRIDINUM SLATS) ARE USEFUL FOR HARDENING GELATIN, SUCH AS PHOTOGRAPHIC GELATIN. ADIPOLYBIS (NOXYMETHYLPYRIDINUM PERCHLORATE), ADIPOLYBIS(N-OXYMETHYL - 4 - PICOLINIUM PRCHLORATE), ADIPOLYBIS(N - ALPHA-OXYETHYLPYRIDINIUM PERCHLORATE) AND SEBACOYLBIS(N-OXYMETHYLPYRIDINIUM PERCHLORATE) ARE ILLUSTRATIVE OF THE NOVEL HARDENER COMPOUNDS.

Description

United States Patent C) No n'awin Original application May 22, 1964, Ser. No. 369,629, now Patent No. 3,396,127, dated Aug. 6, 1968. Divided and this application Feb. 2, 1968, Ser.
Int. Cl. C07d 31/34 US. Cl. 260-295 6 Claims ABSTRACT OF THE DISCLOSURE Certain bis(pyridinium salts) are useful for hardening gelatin, such as photographic gelatin. Adipolybis (N- oxymethylpyridinium perchlorate), adipolybis(N-oxymethyl 4 picolinium perchlorate), adipolybis(N alpha-oxyethylpyridinium perchlorate) and sebacoylbis(N-oxymethylpyridinium perchlorate) are illustrative of the novel hardener compounds.
This application is a division of our copending applicaiton Ser. No. 369,629, filed May 22, 1964, now US Pat. 3,396,127 issued Aug. 6, 1968.
This invention relates to certain compounds found useful as photographic hardeners and to gelatin compositions containing those hardeners.
Some compounds which have been suggested as hardeners for photographic emulsions or other gelatin solutions have been insufficiently effective for that purpose.
One object of our invention is to provide hardeners for photographic gelatin. Another object of our invention is to provide gelatin compositions useful photographically. A further object of our invention is to provide certain compounds which are useful in the preparation of photographic products. Other objects of our invention will appear herein.
We have found that certain quaternary nitrogen type compounds, which compounds are free of deleterious photographic effects, are useful for hardening photographic emulsions or gelatin compositions generally. We have found that bis(alphacarbonyloxyalkyl quaternary nitrogen) salts and polymeric analogs thereof are useful for hardening purposes in photographic compositions. These hardeners are not only useful in gelatin compositions but also have been found to be effective for hardening polymers containing hydroxyl groups generally when incorporated in compositions thereof prior to coating out onto a support. We have found that several of the compounds in accordance with out invention, in addition to having a hardening effect on gelatin-silver halide photographic emulsions, also exert a sensitizing effect thereon.
The compounds of our invention are conveniently prepared by the alkylation of the appropriate tertiary amine with an appropriate bis(alpha-chloroalkyl carboxylate). In lieu thereof these compounds may be prepared by the direct condensation of acid halide, aldehyde and tertiary amine by the procedure described by Iakubovics et al., J. Gen. Chem. U.S.S.R. Engl. Transl. 28, 1971 (1958). Compounds which have been found to be useful for hardening gelatin or some other polymeric material hav- 3,576,813 Patented Apr. 27, 1971 ing carboxyl groups therein have the following general structural formula:
in which X is an acid anion such as halide, perchlorate or other suitable acid anion; R is hydrogen or a lower alkyl radical such as of 1-4 carbon atoms and B+ is a quaternary nitrogen residue from one of the following bases: (1) pyridine or simple derivatives thereof as for example picolines, 2-benzylpyridine, 2-(4-pyridyl) ethanol and the like, (2) a compound with a tertiary nitrogen in a bridgehead position as for example quinuclidine, (3) an aliphatic or cyclic tertiary base as for example trimethylamine, triethylamine, N-methylpiperidine and the like. Z represents a linking structure which may be either a valence bond, a saturated or unsaturated carbon chain or a heterogeneous chain composed predominantly of carbon. It may be a cyclocarbon such as cyclohexylene or phenylene, a chain including phenylene, cyclohexylene, or some other radical or a chain having simple alkyl substituents thereon such as methyl, ethyl, propyl, butyl and the like. The linking structure is most conveniently (CH where n equals 110.
Where a bifunctional amine is used in preparing the hardener, for example, N,N'-dimethylpiperazine, or where the nitrogen residue is derived from 1,4-diazabicyclo[2. 2.2[octane polymeric salts will be formed having good hardening activity. The following recurring structure represents polymers of this nature which are useful as hardeners in accordance with our invention:
In this structure Z and X represent substituents as listed above and n represents the degree of polymerization,
' being a number from 2 to 20 or even more. R and R are hydrogen or lower alkyl or together they may form the hydrocarbon portion of a ring.
In using the hardeners in accordance with our invention they may be employed in gelatin compositions either where gelatin is the main substituent or in compositions in which gelatin is a carrier for suspended material such as in gelatin-silver halide photographic emulsions, gelatinbarium sulfate compositions or other cases where some pigment or insoluble material is in suspension in the gelatin. Useful compositions are also prepared by incorporating these hardeners into solutions or emulsions of polymers containing carboxyl groups as for example acrylic acid copolymers. These hardeners are conveniently used in proportions of 0.55%, based on the weight of the gelatin or other polymer to be hardened. However, it is to be understood that the invention is not limited to these proportions as effective amounts outside of this range may occasionally be employed.
The following examples illustrate the preparation of hardeners useful in accordance with our invention.
Example l.-Adipoylbis (N-oxymethylpyridinium perchlorate) 4.86 grams of bis(chlormethyl) adipate were dissolved in 25 ml. of dry pyridine and the solution was heated on a steam bath for 2 hours. The precipitate was isolated and converted to the perchlorate by a double decomposition reaction with sodium perchlorate. Recrystallization from water gave colorless crystals, M.P. 206-207 (corn).
Example 2.Adipoylbis(N-oxymethyl-4-picolinium perchlorate) This compound was prepared in the same manner as described in Example 1 except that 'y-picoline was substituted for the pyridine. The melting point of the crystals obtained was 123425 (corn).
Example 3.Adipoylbis(N-alpha-oxyethylpyridinium perchlorate) The method described in Example 1 was followed except that an equivalent amount of bis(alpha-chloroethyl)adipate was substituted for the bis(chlormethyl) adipate. The material obtained had no definite melting point and tended to oil out on recrystallization.
Example 4.Sebacoylbis (N-oxymethylpyridinium perchlorate) This material was prepared by the procedure of Example 1 but using an equivalent amount of bis(chloromethyl) sebacate therein. The material obtained had a melting point of 168-171 (corn).
Example .Adipoylbis( l-oxymethyl-4-azal-azoniabicyclo [2.2.2] octane chloride) A solution was prepared of 4.86 grams of bis(chlormethyl)adipate and 11.2 grams of l,4-diazabicyclo[2.2.2] octane in 25 ml. of acetonitrile. This solution was stirred at 25 C. Dense precipitation and an exothermic reaction set in after 35 minutes. The precipitate was collected the next day and recrystallized from alcohol-acetone. The product obtained had a melting point of l25l26.5 (corn).
Example 6.Poly(1,4 diazoniabicyclo[2.2.2]0ctane-1,4- dimethyl adipate dichloride) A solution of equimolar quantities of the reagents of Example 5 in acetonitrile was heated on the steam bath for one hour. The material was purified by repeated dissolution in water and precipitation into acetone.
The salts obtained in the above examples had the following structural formula:
Samples of the compounds prepared by the above examples were added to separate portions of a high-speed silver bromoiodide emulsion which had been panchromatically sensitized with a cyanine dye. Each emulsion sample was coated on a cellulose acetate film support at a coverage of 432 mg. of silver and 980 mg. of gelatin per square foot. A sample of each film coating was exposed on an Eastman 1B sensitometer, processed for five minutes in Kodak DK-SO developer, fixed, washed and dried with the following results:
TABLE II Percent Hardener of Cone, Rel. vertical g./100 swell Example g. of gel speed Gamma Fog in water 1 Control 100 1. 24 0. 10 609 1 89 1. 18 09 349 5 87 1. 15 09 214-281 10 87 1. 07 08 102-256 2 Control 100 1. 13 12 850 1 118 1. 17 14 570 3 107 1. I0 13 360 3 Control 100 1.30 16 750 1 97 1. 33 15 700 3 102 1. 27 15 530 6 102 l. 13 17 490 4 Control 100 1. 27 17 990 3 1.05 20 370 6 53 93 29 230 5 Control 1. 23 13 860 1 107 1. 30 14 640 3 89 1. l5 13 260 6 Control 100 1. 37 13 731 3 91 1. 13 11 278 6 74 1. 07 11 10 71 97 .10 148 Example 7.Adipoylbis(oxymethyltrimethylammonium perchlorate) A solution was prepared by dissolving 7.29 grams of bis(chloromethyl)adipate and 45 grams of trimethylamine in 25 ml. of acetonitrile. The solution was stirred for 8 hours under reflux (using a Dry-Ice condenser) following which it was allowed to stand over night at room temperature. The thick slurry which resulted was diluted with ether and the solids were collected. The chloride obtained was dried and then converted to the perchlorate by a double decomposition reaction with sodium perchlorate. The product obtained was recrystallized from water, giving colorless crystals of the above mentioned compounds, M.P. 235236 C.
Example -8.-Adipolybis(oxyrnethyltriethylammonium perchlorate) A solution as prepared of 30 ml. of triethylamine (dried over calcium hydride) and 4.86 grams of bis(chloromethyl) adipate in 25 ml. of acetonitrile. The solution was stirred for 2 days for anhydrous conditions. The solids which precipitated (triethylamine hydrochloride) were filtered off and discarded. The filtrate was concentrated to remove volatiles and the residual oil obtained was converted to the perchlorate by a double decomposition reaction. Evaporation gave a saturated aqueous solution of the perchlorate which yielded seed crystals by means of which the Whole could be recrystallized froml methanol with seeding. Colorless crystals of the above mentioned compound were obtained, M.P. 139-141 C.
Samples of the compounds prepared in Examples 7 and 8 were added to separate portions of a high-speed silver bromoiodide emulsion which had been panchromatically sensitized with a cyanine dye. Each emulsion sample was coated on cellulose acetate film support at a coverage of 459 mg. of silver and 1040 mg. of gelatin per square foot. A sample of each film coating and control samples were exposed on an Eastman 1B sensitometer, processed for 5 minutes in Kodak DK-SO developer, fixed, washed, and dried with the following results:
Percent C0nc., vertical Hardener of g./l00 Rel. swell Example g of gel speed Gamma Fog in water 7 Control 100 1.10 .11 810 100 1. 13 410 8 Control 100 1. 25 12 810 106 1. 28 12 460 Examples 9, 10 and 11 Hardening amounts of hardeners in accordance with the invention were added to gelatin containing coating composition as indicated below. Each of the compositions was coated on cellulose acetate film support at the rate of 750 mg. (dry weight) of composition per square footand dried as was also a sample of composition without hardener. The swell in water of each coating was determined with the following results:
Percent Hardener Percent hardener Percent hardener 1n compo- Swell Example example in gelatin sition 1 in water Control 500 7 5 150 1 20 5 150 5 20 5 120 1 Layer consisted of the designated percent hardener in a composition %)5'75 gelatin and 75% ethyl acrylate-acrylic acid copolymer (sodium The invention has been described in considerable detail with particular reference to certain preferred embodiments thereof, but it will be understood that variations that modifications can be effected within the spirit and scope of the invention as described hereinabove, and as defined in the appended claims.
We claim:
1. A compound having the formula:
wherein X is an inorganic nonmetallic halo anion, each R is the same substituent selected from the group consisting of hydrogen and an alkyl group having 1 to 4 carbon atoms, each B is the same member selected from the group consisting of a pyridinium group and a picolinium group and wherein said members are joined through their nitrogen atom to the carbon atom of the UNITED STATES PATENTS 2,023,075 12/1935 Harris 260295 2,089,602 8/ 1937 Granacher 260295 2,402,526 6/ 1946 Pikl 260 -295 3,241,972 3/1966 Wilson 96111 3,312,711 4/1967 Koch 260295 3.144,45 6 8/ 1964 Motfett 260268 3,213,098 10/ 1965 Miller 260268 3,345,177 10/1967 Wilson 260297 3,369,076 2/ 1968 Kaniecki 260567.'6 3,396,127 8/1968 Burness et a1 2608 3,406,005 10/1968 Whitfield 260268UX DONALD G. DAVIS, Primary Examiner US. Cl. X.R.
gggg UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3, 516 ,81'3 Dated April 21, 1971 Inventor) Donald M. Burness and Burton D. Wilson It is certified that error appears in the above-identified patent and that said Letters Potent are hereby corrected as shown below:
Column 6, line 3H, "3,213,098 should read 3 3: 9
Column 6, line 36, "3, 369,076" should read 3:3 9s
Signed and sealed this 18th day of April 1972.
(SEAL) Attest:
EDWARD M.FLETCHER,JR. ROBERT GOTTSCHALK Attesting Officer Commissioner of Patents
US702508A 1964-05-22 1968-02-02 Bis(pyridinium salts) useful as gelatin hardeners Expired - Lifetime US3576813A (en)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
US369629A US3396127A (en) 1964-05-22 1964-05-22 Photographic hardeners
GB45958/66A GB1214451A (en) 1964-05-22 1966-10-14 Quaternary nitrogen compounds suitable as gelatin hardeners
FR86775A FR1503463A (en) 1964-05-22 1966-12-09 New tanners and their photographic use
DEE0033113 1966-12-28
US70251268A 1968-02-02 1968-02-02
US70250868A 1968-02-02 1968-02-02

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US702512A Expired - Lifetime US3542558A (en) 1964-05-22 1968-02-02 Hardeners for photographic gelatin emulsions

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4014862A (en) * 1972-07-12 1977-03-29 Ilford Limited Production of hardened gelatin layers by the addition of quaternary carbamoyl pyridinium compounds
US4160099A (en) * 1974-06-24 1979-07-03 Interx Research Corporation Labile, non-heterocyclic quaternary ammonium salt/esters as transient derivatives

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3951940A (en) * 1974-09-30 1976-04-20 Ciba-Geigy Ag Method of producing a hardened gelatin layer using aqueous solution of a 2-halogeno pyridinium compound
DE3105777A1 (en) * 1981-02-17 1982-09-02 Agfa-Gevaert Ag, 5090 Leverkusen IMAGE RECEIVING ELEMENT FOR THE COLOR DIFFUSION TRANSFER METHOD
JPS5993442A (en) * 1982-11-19 1984-05-29 Fuji Photo Film Co Ltd Photosensitive silver halide material
US5286450A (en) * 1992-06-01 1994-02-15 Eastman Kodak Company Bilirubin assay using crosslinkable polymers
GB2408937A (en) * 2003-12-09 2005-06-15 Johnson & Johnson Medical Ltd pH dependent medicinal compositions
GB201121133D0 (en) 2011-12-08 2012-01-18 Dow Corning Hydrolysable silanes
GB201121132D0 (en) 2011-12-08 2012-01-18 Dow Corning Modifying polymeric materials by amines
GB201121128D0 (en) 2011-12-08 2012-01-18 Dow Corning Treatment of filler with silane
GB201121124D0 (en) 2011-12-08 2012-01-18 Dow Corning Hydrolysable silanes
GB201121122D0 (en) 2011-12-08 2012-01-18 Dow Corning Hydrolysable silanes and elastomer compositions containing them

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2858329A (en) * 1955-11-30 1958-10-28 Abbott Lab Preparation of bis-diloweralkylaminoalkyl loweralkyl dicarboxylates
US3169870A (en) * 1961-12-04 1965-02-16 Eastman Kodak Co Photographic gelatin layers containing the salts of various alkyl and alkenyl succinamates as coating aids

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4014862A (en) * 1972-07-12 1977-03-29 Ilford Limited Production of hardened gelatin layers by the addition of quaternary carbamoyl pyridinium compounds
US4160099A (en) * 1974-06-24 1979-07-03 Interx Research Corporation Labile, non-heterocyclic quaternary ammonium salt/esters as transient derivatives

Also Published As

Publication number Publication date
FR1503463A (en) 1967-11-24
US3396127A (en) 1968-08-06
US3542558A (en) 1970-11-24
DE1547768A1 (en) 1969-11-20
GB1214451A (en) 1970-12-02

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