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Publication numberUS3369905 A
Publication typeGrant
Publication dateFeb 20, 1968
Filing dateMar 19, 1963
Priority dateMar 19, 1963
Publication numberUS 3369905 A, US 3369905A, US-A-3369905, US3369905 A, US3369905A
InventorsJones Jean E, Wilson Charles V
Original AssigneeEastman Kodak Co
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Photographic silver halide emulsions containing polyamine sensitizing agents
US 3369905 A
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Description  (OCR text may contain errors)

3,369,905 PHGTOGRAPHIC SILVER HALIDE EMUL- SIONS CONTAINING POLYAMINE SEN- SITIZING AGENTS Jean E. Jones and Charles V. Wilson, Rochester, N.Y., assignors to Eastman Kodak Company, Rochester, N.Y., a corporation of New Jersey No Drawing. Filed Mar. 19, 1963, Ser. No. 266,192 11 Claims. (Cl. 96-107) This invention relates to photography and particularly to sensitizers for photosensitive colloid-silver halide emulsion layers.

Polyalkyleneimino compounds (polyamines) having primary amino end groups are described for use as chemical sensitizers for photographic silver halide emulsions in US. Patents No. 2,743,182, patented Apr. 24, 1956, and No. 2,518,698, patented Aug. 15, 1950. Many of these a chemical sensitizers increase speed of photographic emulsions but have the disadvantage of substantially increasing fog in the emulsions, especially in emulsions sensitized with sulfur and gold.

An object of the present invention is to provide novel photographic colloid-silver halide emulsions containing a polyamine sensitizing agent which will increase the speed of the emulsion with only very slight or no increase in fog, even in emulsions sensitized with sulfur and gold.

This and other objects of the invention are obtained by incorporating into a photographic colloid-silver halide emulsion a polyalkyleneimino compound having at least one secondary or tertiary amino end group. Even better results are obtained when all of the nitrogen atoms in the polyamine chain are fully substituted. Effective amounts of sensitizer in the emulsion are usually in the range from 0.03 to 5.0 grams sensitizer per mole silver.

Polyalkyleneimino compounds that are useful as sensitizers according to the present invention have the formula:

wherein each of R and R represents a member selected from the group consistihg of hydrogen, alkyl containing 1-4 carbon atoms, hydroxyalkyl, aryl, aralkyl, alkyl substituted aryl and alkoxy substituted aryl; R represents a member selected from the group consisting of alkyl containing 1-4 carbon atoms, hydroxyalkyl, aryl, aralkyl, alkyl substituted aryl and alkoxy substituted aryl; each R is an alkylene chain having from 2-3 carbon atoms in the chain with each of said carbon atoms having attached thereto members selected from the group consisting of hydrogen, alkyl containing 1-4 carbon atoms, aryl of 6- carbon atoms and aralkyl, the alkyl group in each said aralkyl being of 1-2 carbon atoms; n is a positive whole integer from 1-3 and the radical I ls] is a unit in the linear chain of the polyamine.

Specific examples of compounds having the above formula are:

( 1 N,N'-di-beta-hydroxyethylethylenediamine (2) 8-amino-3,6-diazaoctanol (3) 3,6,9-triaza-1,1l-undecanediol (4) 3,6,9-trimethyltriaza-1,1l-undecanediol (5) 4,15-diazaoctadecane-1,18-bisdimethylamine Compounds 1 and 3 in the above list may be represented by the formula:

wherein R and R are members selected from the group consisting of alkyl containing 1-4 carbon atoms, hydroxy United States Patent 0 "ice alkyl, aryl, aralkyl, alkyl substituted aryl and alkoxy substituted aryl, R is an alkylene chain having from 2-3 carbon atoms in the chain with each of said carbon atoms having attached thereto members selected from the group consisting of hydrogen, alkyl containing 14 carbon atoms, aryl of 610 atoms and aralkyl, the alkyl group in said aralkyl being of 1-2 carbon atoms, and n is a positive whole integer from 1-3 and the radical NHR is a unit in the linear chain of the polyamine.

Additional specific examples of compounds having the last formula above are:

(6) N,N"'-dimethyltriethylenetetramine (7) N,N"-dimethyldiethylenetriamine (8) N,N'-dimethylethylenediamine (9) N,N'-dibenzylethylenediamine (10) N,N'-di-n-butylethylenediamine l1 N,N'-dimethyltrimethylenediamine 12) N,N-dimethyl-1,2-propanediamine (l3 N,N'-diphenylethylenediamine The invention may be better understood by reference to the following examples which describe in detail some preferred embodiments of the invention.

Example I Conventional fast silver bromoiodide-gelatin emulsions, chemically sensitized with sulfur and gold compounds and spectrally sensitized with cyanine dyes were prepared by conventional procedures and each of the compounds numbered 1-5 above was added respectively to a separate sample of emulsion in the concentrations shown in Table 1. Control samples of each emulsion were also kept. The sensitized and control emulsion samples were coated by conventional melt coating procedures on cellulose acetate film, then chill-set and dried. Respective samples of the film were exposed on an Eastman sensitometer Type IB to light of daylight quality for 1. second and were developed for 5 minutes in Kodak Developer DK-50 at 68 F., then fixed and dried. Relative speed was determined at the exposure necessary to produce density of 0.2 above fog. Results of the tests in terms of relative speed, gamma and fog are tabulated in Table 1.

Emulsion number as above) and Con- Relative Gam- Fog centration in Grams Per Speed ma Density Mole Silver Data in Table 1 show results obtained using different sensitizers of the class described at concentrations from 0.03 to 3.0 grams per mole silver in the emulsion. Optimum results were obtained at concentrations in the magnitude of 0.3 gram per mole, however, the sensitizing effect was appreciable at other concentrations.

Variations from the colloid-silver halide emulsion compositions described in the examples herein may be made within the scope of the present invention. The class of sensitizers defined above are effective to increase speed in a wide variety of photosensitive silver halide emulsions familiar to those skilled in the art. The invention includes photographic emulsions made from suitable colloids other than gelatin and containing other functional addenda as will be familiar to emulsion makers.

The invention has been described with reference to cer- Q a tain preferred embodiments but it will be understood that variations and modifications of the invention as described can be made within the scope of the invention as defined in the following claims.

We claim: 1 1. A colloid-silver halide photographic emulsion containing at least one linear polyamine sensitizing agent having the formula:

U n Rt N-Ra "NR2 wherein each of R and R represents a member selected from the group consisting of hydrogen, alkyl containing 14 carbon atoms, hydroxyalkyl, aryl, aralkyl, alkyl substituted aryl and alkoxy substituted aryl; R represents a member selected from the group consisting of alkyl containing 1-4 carbon atoms, hydroxyalkyl, aryl, aralkyl, alkyl substituted aryl and alkoxy substituted aryl; each R is an alkylene chain having from 23 carbon atoms in the chain with each of said carbon atoms having attached thereto members selected from the group consisting of hydrogen, alkyl containing 1-4 carbon atoms, aryl of 6- 10 carbon atoms and aralkyl, the alkyl group in each said aralkyl being of 1-2 carbon atoms; n is a positive whole integer from 13 and the radical is a unit in the linear chain of the polyamine.

2. A colloidsilver halide photographic emulsion containing at least one linear polyamine sensitizing agent having the general formula:

wherein R and R are selected from the group consisting of alkyl of 1 to 4 carbon atoms, aryl, aralkyl, hydroxy substituted alkyl and'alkyl substituted aryl and alkoxy substituted aryl; R is an alkylene chain having from 2 to 3 carbon atoms in the chain with each of said carbon atoms having attached thereto members selected from the group consisting of hydrogen, alkyl of 1 to 4 carbon atoms, aryl of 6 to 10 carbon atoms and aralkyl, the alkyl group in said aralkyl being of 1 to 2 carbon atoms; and n is a positive whole number from 1 to 3 and the radical, NHR is a unit in the linear chain of the polyamine.

3. An emulsion as set forth in claim 2 wherein said \colloid is gelatin.

4. A colloid-silver halide photographic emulsion containing a linear amine sensitizing agent having the formula:

wherein R is selected from the group consisting of an alkyl radical of 1 to 4 carbon atoms and hydroxy substituted alkyl and R is an alkylene chain having 2 to 3 carbon atoms in the chain with each of said carbon atoms having attached thereto members selected from the group consisting of hydrogen and an alkyl of 1 to 4 carbon atoms.

5. A colloid-silver halide photographic emulsion containing at least one linear polyamine sensitizing agent having the formula:

wherein R and R are hydroxy substituted alkyl, R is an alkylene chain having 2 carbon atoms, n is a positive whole integer from 1 to 2, and the radical NHR is a unit of the linear chain of the polyamine.

6. An emulsion as defined in claim 5 wherein said colloid is gelatin.

7. An emulsion as defined in claim 2 wherein said sensitizing agent is N,N-di-beta-hydroxyethylethylenediamine.

8. An emulsion as defined in claim 1 wherein said sensitizing agent is 8-amino-3,6-diazaoctanol.

9. An emulsion as defined in claim 2 wherein said sensitizing agent is 3,6,9-triaza-1,11-undecanediol.

10. An emulsion as defined in claim 1 wherein said sensitizing agent is 3,6,9-trimethyltriaza-1,1l-undecanediol.

11. A colloid-silver halide photographic emulsion containing 4,15-diazaoctadecane 1,18 bisdimethylamine as a linear polyamine sensitizing agent.

References Cited UNITED STATES PATENTS 3,026,203 3/1962 Chamber et al. 96-107 2,016,471 10/1935 Wilmanns et al 96-107 2,518,698 8/1950 Lowe et al. 96107 NORMAN G. TORCHIN, Primary Examiner.

J. T. BROWN, Assistant Examiner.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2016471 *Mar 2, 1934Oct 8, 1935Agfa Ansco CorporationStabilizing silver halide emulsions
US2518698 *Nov 18, 1948Aug 15, 1950Eastman Kodak CoChemical sensitization of photographic emulsions
US3026203 *Aug 17, 1959Mar 20, 1962Du PontSilver halide photographic emulsions containing linear polyamine sensitizing agents
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US5677352 *Jun 7, 1995Oct 14, 1997University Of Florida Research Foundation, Inc.Polyamines and anti-diarrheal and gastrointestinal anti-spasmodic pharmaceutical compositions and methods of treatment
US5679682 *Sep 18, 1996Oct 21, 1997University Of Florida Research Foundation, Inc.Anti-neoplastic, anti-viral or anti-retroviral spermine derivatives
US5681837 *Sep 18, 1996Oct 28, 1997University Of Florida Research Foundation, Inc.Anti-neoplastic, anti-viral or anti-retroviral spermine derivatives
US5753714 *Mar 15, 1994May 19, 1998Merrell Pharmaceuticals Inc.Antiprotozoa agents
US5827894 *Sep 18, 1996Oct 27, 1998University Of Florida Research Foundation, Inc.Antitumor agents, antigrowth agents for treatment of psoriasis, insecticides
US5834439 *Jan 13, 1997Nov 10, 1998Life Technologies, Inc.Highly packed polycationic ammonium, sulfonium and phosphonium lipids
US5866613 *Jun 7, 1995Feb 2, 1999University Of Florida Research Foundation, Inc.Diethyltris/trimethylene/tetramine and salts
US6034139 *Sep 18, 1996Mar 7, 2000University Of Florida Research Foundation, Inc.Polyamine compound
US6110916 *Nov 6, 1998Aug 29, 2000Life Technologies, Inc.For transfection/drug delivery of macromolecules and other compounds into cells
US6114394 *Oct 14, 1997Sep 5, 2000Merrell Pharmaceuticals Inc.Protecting mammalian cells from harmful cellular effects caused by exposure to ionizing radiation
US6399663Aug 25, 2000Jun 4, 2002Invitrogen CorporationDrug delivery
US6455591 *Jun 7, 1995Sep 24, 2002University Of FloridaDiethylhomospermine or other polyamine derivatives and salts as anti-secretory, nitric oxide agonist, nitric oxide synthase activating or gastrointestinal anti-spasmodic agents
US6716882Apr 23, 2002Apr 6, 2004Invitrogen CorporationHighly packed polycationic ammonium, sulfonium and phosphonium lipids
US7145039Jan 21, 2005Dec 5, 2006Invitrogen Corp.Transfection reagents
US7166745Nov 12, 1999Jan 23, 2007Invitrogen CorporationAcyclic and macrocyclic, aliphatic diammonium surfactants for use in forming lipid aggregates for drug delivery of macromolecules; improved versatility among different cell types and broadened range of molecules to be carried
US7173154Jul 28, 2003Feb 6, 2007Invitrogen Corp.Transfection reagents
US7323594Dec 28, 2006Jan 29, 2008Invitrogen CorporationAcyclic and macrocyclic, aliphatic diammonium surfactants for use in forming lipid aggregates for drug delivery of macromolecules; improved versatility among different cell types and broadened range of molecules to be carried
US7470817Dec 28, 2006Dec 30, 2008Invitrogen CorporationAcyclic and macrocyclic, aliphatic diammonium surfactants for use in forming lipid aggregates for drug delivery of macromolecules; improved versatility among different cell types and broadened range of molecules to be carried
US7479573Jan 21, 2005Jan 20, 2009Invitrogen CorporationCationic lipids capable of facilitating transport of biologically active agents or substances into cells; lipid aggregate macromolecular complex interacts with cells making the polyanionic macromolecule available for absorption and uptake by the cell
US7501542Jan 21, 2004Mar 10, 2009Invitrogen CorporationHighly-packed polycationic ammonium, sulfonium and phosphonium lipids
US7601872Jan 21, 2005Oct 13, 2009Life Technologies CorporationCationic lipids capable of facilitating transport of biologically active agents or substances into cells; lipid aggregate macromolecular complex interacts with cells making the polyanionic macromolecule available for absorption and uptake by the cell
US7915450Dec 15, 2009Mar 29, 2011Life Technologies CorporationTransfection reagents
US8158827Jan 14, 2009Apr 17, 2012Life Technologies CorporationTransfection reagents
Classifications
U.S. Classification430/599
International ClassificationG03C1/10
Cooperative ClassificationG03C1/10
European ClassificationG03C1/10