# US 10,246,561 B1 · Method of making silver-containing dispersions with nitrogenous bases

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- Number: US 10,246,561 B1
- Document ID: US10246561B1
- Status: Granted
- Kind: B1
- Application number: 15/713,786
- Filed: 2017-09-25
- Published: 2019-03-28
- Granted: 2019-04-02
- Earliest claimed: 2017-09-25
- Assignees: Eastman Kodak Company
- Applicants: Eastman Kodak Company
- Inventors: Deepak Shukla; Kevin M. Donovan
- Web page: https://patentgrep.com/patent/US10246561B1

## CPC

- C08J 3/095: {Oxygen containing compounds}
- C01G 5/006: {Compounds containing silver, with or without oxygen or hydrogen, and containing two or more other elements}
- C08K 3/08: Metals
- C08K 5/16: Nitrogen-containing compounds {(C08K5/0091 takes precedence)}
- C08L 1/12: Cellulose acetate
- C08L 1/14: Mixed esters, e.g. cellulose acetate-butyrate
- C09D 101/12: Cellulose acetate
- C01P 2004/64: Nanometer sized, i.e. from 1-100 nanometer
- C01P 2006/40: Electric properties
- C08K 3/04: Carbon
- C08K 2003/0806: {Silver}
- C08K 2201/005: Additives being defined by their particle size in general
- C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29)
- C01G: COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F (metal hydrides {monoborane, diborane or addition complexes thereof} C01B6/00; salts of oxyacids of halogens C01B11/00; peroxides, salts or peroxyacids C01B15/00; thiosulfates, dithionites, polythionates C01B17/64; compounds containing selenium, or tellurium C01B19/00; binary compounds of nitrogen with metals C01B21/06; azides C01B21/08; {compounds containing nitrogen, other non-metals and metal C01B21/082}; metal amides C01B21/092; nitrites C01B21/50; {compounds of noble gases C01B23/0005}; phosphides C01B25/08; salts of oxyacids of phosphorus C01B25/16; carbides C01B32/90; compounds containing silicon C01B33/00; compounds containing boron C01B35/00; compounds having molecular sieve properties but not having base-exchange properties C01B37/00; compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites, C01B39/00; cyanides C01C3/08; salts of cyanamide C01C3/16; thiocyanates C01C3/20)
- C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09)
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D)
- C01P: INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS

## Abstract

A method is used to prepare silver nanoparticle cellulosic polymer composites. A cellulosic polymer, reducible silver ions in an amount of a weight ratio to the cellulosic polymer of 5:1 to 50:1, and an organic solvent are mixed. Each organic solvent has a boiling point at atmospheric pressure of 100° C. to 500° C. The Hansen parameter (δTPolymer) of the cellulosic polymer is less than or equal to the Hansen parameter (δTSolvent) of the organic solvent. The resulting premix solution is heated to at least 75° C., and a (d) nitrogenous base is added to provide a concentration of the nitrogenous base in an equimolar amount or in molar excess in relation to the amount of reducible silver ions, thereby forming a silver nanoparticle cellulosic polymer composite. After cooling, the silver nanoparticle cellulosic polymer composite is isolated and re-dispersed in an organic solvent to provide a non-aqueous silver-containing dispersion.

## Claims

### Claim 1

A method comprising, in sequence:
A) mixing:
(a) one or more polymers selected from one or more of cellulose acetate, cellulose acetate phthalate, cellulose acetate butyrate, cellulose acetate propionate, cellulose acetate trimellitate, hydroxypropylmethyl cellulose phthalate, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropylmethyl cellulose, and carboxymethyl cellulose;
(b) reducible silver ions present in an amount of a weight ratio of (b) reducible silver ions to the one or more (a) polymers of at least 5:1 and up to and including 50:1; and
(c) one or more organic solvents, each of which has a boiling point at atmospheric pressure of at least 100° C. and up to but less than 500° C., wherein the Hansen parameter (δTPolymer) of each of the one or more polymers is less than or equal to the Hansen parameter (δTSolvent) of each of the one or more organic solvents,
to form a premix solution;
B) heating the premix solution to a temperature of at least 75° C.;
C) while keeping the premix solution at the temperature of at least 75° C., adding a (d) nitrogenous base having a pKa in acetonitrile of at least 15 and up to and including 25 at 25° C., to provide a concentration of the (d) nitrogenous base in an equimolar amount or in molar excess in relation to the amount of (b) reducible silver ions,
to form a silver nanoparticle composite;
D) after cooling, isolating the silver nanoparticle composite; and
E) re-dispersing the silver nanoparticle composite in the same or different one or more (c) organic solvents used in A), to provide a non-aqueous silver-containing dispersion comprising the silver nanoparticle composite.

### Claim 2 (depends on 1)

The method of claim 1, further comprising:
disposing the non-aqueous silver-containing dispersion onto a substrate, and
removing the same or different one or more (c) organic solvents.

### Claim 3 (depends on 2)

The method of claim 2, comprising disposing the non-aqueous silver-containing dispersion onto the substrate in a patternwise manner.

### Claim 4 (depends on 2)

The method of claim 2, comprising disposing the non-aqueous silver-containing dispersion onto the substrate using inkjet printing, screen printing, flexographic printing, or gravure printing.

### Claim 5 (depends on 2)

The method of claim 2, wherein the substrate has a first supporting side and a second opposing supporting side, and the method comprises disposing the non-aqueous silver-containing dispersion onto the substrate in a patternwise manner to form at least one pattern of the non-aqueous silver-containing dispersion on at least the first supporting side.

### Claim 6 (depends on 5)

The method of claim 5, wherein the substrate is a continuous polymeric film, and the method comprises disposing the non-aqueous silver-containing dispersion onto the substrate in a manner to form multiple patterns of the non-aqueous silver-containing dispersion on at least the first supporting side.

### Claim 7 (depends on 6)

The method of claim 6, further comprising disposing the non-aqueous silver-containing dispersion onto the substrate in a manner to form multiple patterns of the non-aqueous silver-containing dispersion on the second opposing supporting side.

### Claim 8 (depends on 6)

The method of claim 6, comprising disposing the non-aqueous silver-containing dispersion onto the substrate to form multiple patterns of the non-aqueous silver-containing composition on both the first supporting side and the second opposing supporting side using one or more flexographic printing members.

### Claim 9 (depends on 2)

The method of claim 2, wherein the substrate is a continuous web that is unrolled from a supply roll and is taken up using a take-up roll, and the method is carried out in a continuous roll-to-roll manner.

### Claim 10 (depends on 1)

The method of claim 1, wherein the silver is present in the non-aqueous silver-containing dispersion at a weight ratio to the one or more (a) polymers of at least 5:1 and up to and including 20:1.

### Claim 11 (depends on 1)

The method of claim 1, wherein the one or more (c) organic solvents is one or more hydroxylic organic solvents each having an α-hydrogen atom and is chosen from the group consisting of n-butanol, n-pentanol, n-hexanol, n-octanol, 2-ethyl-1-hexanol, n-decanol, ethylene glycol, propylene glycol, benzyl alcohol, isobutyl alcohol, isoamyl alcohol, secondary butylcarbinol, secondary butyl alcohol, secondary amyl alcohol, diethyl carbinol, methyl isobutyl carbinol, methyl-3-heptanol, diisobutyl carbinol, dodecanol-Z, methyl allyl carbinol, cyclohexanol, methyl cyclohexyl carbinol, phenyl methyl carbinol, 2-methoxyethanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, methoxy isopropanol, and a combination thereof.

### Claim 12 (depends on 1)

The method of claim 1, wherein the nitrogenous base is an aromatic cyclic compound.

### Claim 13 (depends on 1)

The method of claim 1, wherein the nitrogenous base is selected from the group consisting of 1,4-diazabicyclo[2.2.2]octane (DABCO), cyclohexylamine, piperidine, N-methyl pipperidine, N-methyl-3-piperidinol, ethanol amine, 2-(ethylamino)ethanol, 2-(methylamino)ethanol, 2-(butylamino)ethanol, methyldiethanolamine (MDEA), diethanolamine (DEA), diglycolamine (DGA), diethylaminoethanol (DEAE), substituted or unsubstituted non-polymeric pyridine, picolines, lutidines, quinoline, purine, isoquinoline, imidazole, benzimidazole, benzthiazole, thiazole, oxazole, benzoxazole, 4,4′-bipyridine, pyrazine, triazine, pyrimidine, nicotinic acid, and isonicotinic acid compounds, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), and a combination thereof.

### Claim 14 (depends on 1)

The method of claim 1, wherein the (a) one or more polymer is one or more of carboxymethyl cellulose, cellulose acetate butyrate, ethyl cellulose, cellulose acetate, and cellulose acetate propionate.

### Claim 15 (depends on 1)

The method of claim 1, wherein the non-aqueous silver-containing dispersion further contains (e) a carbon black.

### Claim 16 (depends on 1)

The method of claim 1, wherein the non-aqueous silver-containing dispersion has a viscosity of at least 1 centipoise (0.001 Pascal sec) and up to and including 5000 centipoise (5 Pascal sec) at 25° C.

### Claim 17 (depends on 1)

The method of claim 1, wherein the non-aqueous silver-containing dispersion has a viscosity of at least 3 centipoise (0.003 Pascal sec) and up to and including 10 centipoise (0.01 Pascal sec) at 25° C.