Method of making silver-containing dispersions

Patent metadata

Field	Value
Publication number	US-10444618-B2
Application number	US-201715713777-A
Country	US
Kind code	B2
Filing date	Sep 25, 2017
Priority date	Sep 25, 2017
Publication date	Oct 15, 2019
Grant date	Oct 15, 2019

Abstract

A method is used to prepare silver nanoparticles in the form of a silver nanoparticle cellulosic polymeric composite. A cellulosic polymer, organic solvent having a boiling point at atmospheric pressure of 100° C. to 500° C. and a Hansen parameter (δTPolymer) equal to or greater than that of the cellulosic polymer, and a nitrogenous base are mixed to form a premix solution. Upon heating the premix solution to a temperature of at least 75° C., a solution of reducible silver ions is added that is equimolar or less in relation to the nitrogenous base. The weight ratio of reducible silver ions to the cellulosic polymer is 5:1 to 50:1. The resulting silver nanoparticle composite is cooled, isolated, and re-dispersed in an organic solvent, providing a non-aqueous silver-containing dispersion comprising the silver nanoparticle cellulosic polymeric composite.

First claim

The invention claimed is:

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;
(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 (δ T Polymer ) of each of the one or more polymers is less than or equal to the Hansen parameter (δ T Solvent ) of each of the one or more organic solvents; and
(d) a nitrogenous base having a pKa in acetonitrile of at least 15 and up to and including 25 at 25° C.,
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 solution of (b) reducible silver ions in (c) the one or more organic solvents to provide an amount of (b) the reducible silver ions in the premix solution that is equimolar or less in relation to the (d) nitrogenous base, and to provide a weight ratio of (b) the reducible silver ions to the one or more (a) polymers of at least 5:1 and up to and including 50:1,
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.

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

3. 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 manner to form at least one pattern of the silver nanoparticle composite on at least the first supporting side.

4. The method of claim 3 , 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 silver nanoparticle composite on at least the first supporting side.

5. The method of claim 4 , 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.

6. 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.

7. 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.

8. 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 ethanol, n-propanol, 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, isopropyl alcohol, 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.

9. The method of claim 1 , wherein the (d) nitrogenous base is selected from the group consisting of 1,4-diazabicyclo[2.2.2]octane (DABCO), cyclohexylamine, piperidine, N-methyl piperidine, 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, isonicotinic acid, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), and a combination thereof.

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

11. 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) as measured at 25° C.

12. An article a substrate having a silver nanoparticle composite composition disposed thereon, which silver nanoparticle composite composition comprises:
a silver nanoparticle composite comprised of silver and (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, carboxymethyl cellulose, and combinations thereof; and (d) one or more nitrogenous bases having a pKa in acetonitrile of at least 15 and up to and including 25 at 25° C., and
the silver nanoparticle composite composition further comprises carbon black in an amount of at least 5 weight % and up to and including 50 weight %, based on the total weight of the one or more (a) polymers.

13. The article of claim 12 , wherein the silver nanoparticle composite has a mean particle size (d50) of at least 20 nm and up to and including 500 nm.

14. The article of claim 12 , wherein the substrate is a transparent polymeric film.

15. The article of claim 12 , wherein the substrate has a first supporting surface and a second opposing supporting surface, and one or more dry patterns of the silver nanoparticle composite composition disposed on the first supporting surface, and optionally, one or more dry patterns of the same or different silver nanoparticle composite composition disposed on the second opposing supporting surface.

16. The article of claim 12 that has a flexible transparent polymeric substrate in the form of a continuous web or roll.

17. 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;
(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 (δ T Polymer ) of each of the one or more polymers is less than or equal to the Hansen parameter (δ T Solvent ) of each of the one or more organic solvents; and

Assignees

• Eastman Kodak Co

Inventors

• Shukla Deepak
• Donovan Kevin M
• Klubek Kevin P

Classifications

• C08K2201/011

  Nanostructured additives · CPC title

• C08L1/32

  Cellulose ether-esters · CPC title

• C08L1/284

  with hydroxylated hydrocarbon radicals · CPC title

• H01B1/22

  the conductive material comprising metals or alloys · CPC title

• C01G5/02

  Halides · CPC title