Method of making silver-containing dispersions

• US 10,444,618 B2
• Filed: 09/25/2017
• Issued: 10/15/2019
• Est. Priority Date: 09/25/2017
• Status: Active Grant

• Current Assignee: Eastman Kodak Company
• Original Assignee: Eastman Kodak Company
• Inventors: Shukla, Deepak, Donovan, Kevin M., Klubek, Kevin P.
• Primary Examiner(s): Peng, Kuo Liang
• Application Number:
  US15/713,777
• Publication Number:
  US 20190094679A1
• Time in Patent Office: 750 Days
• CPC Class Codes: B82Y 40/00 Manufacture or treatment of nanostructures
• CPC Class Codes: C01G 5/02 Halides
• CPC Class Codes: C07C 31/02 Monohydroxylic acyclic alcohols
• CPC Class Codes: C08B 3/06 Cellulose acetate , e.g. mono-acetate, di-acetate or tri-acetate
• CPC Class Codes: C08B 3/08 of monobasic organic acids with three or more carbon atoms, e.g. propionate or butyrate
• CPC Class Codes: C08B 3/16 Preparation of mixed organic cellulose esters , e.g. cellulose aceto-formate or cellulose aceto-propionate
• CPC Class Codes: C08K 2003/0806 Silver
• CPC Class Codes: C08K 2201/011 Nanostructured additives
• CPC Class Codes: C08L 1/12 Cellulose acetate
• CPC Class Codes: C08L 1/14 Mixed esters, e.g. cellulose acetate-butyrate
• CPC Class Codes: C08L 1/284 with hydroxylated hydrocarbon radicals
• CPC Class Codes: C08L 1/286 substituted with acid radicals, e.g. carboxymethyl cellulose [CMC] C08L1/282 takes precedence
• CPC Class Codes: C08L 1/32 Cellulose ether-esters
• CPC Class Codes: G03C 1/49809 Organic silver compounds
• CPC Class Codes: G03F 7/00 Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor using photoresist structures for special production processes, see the relevant places, e.g. B44C, H01L, e.g. H01L21/00, H05K
• CPC Class Codes: H01B 1/22 the conductive material comprising metals or alloys

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 (δ_T^Polymer) 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.

Claims

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

(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.

18. An article comprising 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, hydroxypropylmethyl 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.,

which (d) one or more nitrogenous bases are selected from the group consisting of 1,4-diazabicyclo[2.2.2]octane (DABCO), cyclohexylamine, piperidine, N-methyl piperidine, N-methyl-3-piperidinol, 2-(ethylamino)ethanol, 2-(methylamino)ethanol, 2-(butylamino)ethanol, methyldiethanolamine (MDEA), diglycolamine (DGA), diethylaminoethanol (DEAE), substituted non-polymeric pyridine, picolines, lutidines, quinoline, purine, isoquinoline, 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.

19. The article of claim 18, wherein the (d) one or more nitrogenous bases are selected from 2-butyl aminoethanol, 2-methyl aminoethanol, 4-methyl pyridine, and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU).

20. The article of claim 19, wherein the (a) one or more polymers is selected from cellulose acetate and cellulose acetate propionate.