# US 10,870,774 B2 · Silver-containing precursor and product articles containing cellulosic polymers

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- Number: US 10,870,774 B2
- Document ID: US10870774B2
- Status: Granted
- Kind: B2
- Application number: 15/456,868
- Filed: 2017-03-13
- Published: 2018-09-13
- Granted: 2020-12-22
- Earliest claimed: 2017-03-13
- Assignees: Eastman Kodak Company
- Applicants: Eastman Kodak Company
- Inventors: Deepak Shukla; Kevin M. Donovan
- Web page: https://patentgrep.com/patent/US10870774B2

## CPC

- C09D 101/12: Cellulose acetate
- C09D 5/24: Electrically-conducting paints {(conductive materials H01B1/00)}
- C09D 7/67: {Particle size smaller than 100 nm}
- C09D 7/68: {Particle size between 100-1000 nm}
- C09D 11/033: characterised by the solvent
- C09D 11/037: characterised by the pigment
- C09D 11/14: based on carbohydrates
- C09D 11/322: Pigment inks
- C09D 11/324: containing carbon black
- C09D 11/36: based on non-aqueous solvents
- C09D 11/38: characterised by non-macromolecular additives other than solvents, pigments or dyes
- C23C 18/1608: {from pretreatment step, i.e. selective pre-treatment}
- C23C 18/165: {Multilayered product (layered product B32B)}
- C23C 18/1831: {Use of metal, e.g. activation, sensitisation with noble metals}
- C23C 18/1879: {Use of metal, e.g. activation, sensitisation with noble metals}
- C23C 18/2053: {only one step pretreatment}
- C23C 18/30: Activating {or accelerating or sensitising with palladium or other noble metal}
- C23C 18/31: Coating with metals
- C23C 18/405: {Formaldehyde}
- C08K 3/04: Carbon
- C08K 2003/0806: {Silver}
- C08K 2201/005: Additives being defined by their particle size in general
- C08K 2201/011: Nanostructured additives
- 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)
- C23C: COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL (making metal-coated products by extrusion B21C23/22; covering with metal by connecting pre-existing layers to articles, see the relevant places, e.g. B21D39/00, B23K; metallising of glass C03C; metallising mortars, concrete, artificial stone, ceramics or natural stone C04B41/00; enamelling of, or applying a vitreous layer to, metals C23D; treating metal surfaces or coating of metals by electrolysis or electrophoresis C25D; single-crystal film growth C30B; by metallising textiles D06M11/83; decorating textiles by locally metallising D06Q1/04)
- C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09)

## Abstract

An article has a substrate and a pattern of a dry silver nanoparticle-containing composition comprising at least 20 weight % of one or more (a) polymers, that are cellulosic polymers; (d) silver nanoparticles having a mean particle size of 25-750 nm and present in an amount of 0.1-400 weight %, based on the total weight of the one or more (a) polymers; and (e) carbon black in an amount of 5-50 weight %, based on the total weight of the one or more (a) polymers. Such patterns can have multiple fine lines of any geometric arrangement. The article can have multiple patterns of this type, and each pattern can be electrolessly plated with a suitable metal such as copper to provide electrically-conductive product articles.

## Claims

### Claim 1

An article comprising a substrate, and having disposed on a supporting surface thereof, a pattern of a dry silver nanoparticle-containing composition comprising:
at least 20 weight % of one or more (a) polymers, based on the total weight of the pattern, which one or more (a) polymers are 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, hydroxypropyl cellulose, hydroxyethyl cellulose, hydroxypropylmethyl cellulose, and carboxymethyl cellulose;
(d) silver nanoparticles having a mean particle size of at least 25 nm and up to and including 750 nm, that are present in the pattern in an amount of at least 0.1 weight % and up to and including 400 weight %, based on the total weight of the one or more (a) polymers;
(e) 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; and
less than 5 mol % of (b) reducible silver ions, based on the total molar amount of dry silver in the silver nanoparticle-containing composition.

### Claim 2 (depends on 1)

The article of claim 1, wherein the (d) silver nanoparticles have a mean particle size of at least 50 nm and up to and including 300 nm.

### Claim 3 (depends on 1)

The article of claim 1, wherein the (d) silver nanoparticles are present in an amount of at least 0.1 weight % and up to and including 5 weight %, based on the total weight of the one or more (a) polymers.

### Claim 4 (depends on 1)

The article of claim 1, wherein the (d) silver nanoparticles are present in an amount of at least 15 weight % and up to and including 200 weight %, based on the total weight of the one or more (a) polymers.

### Claim 5 (depends on 1)

The article of claim 1, wherein the substrate is a continuous flexible polymeric film, a metal foil, or a textile web.

### Claim 6 (depends on 1)

The article of claim 1, wherein the substrate is a transparent continuous polymeric film.

### Claim 7 (depends on 1)

The article of claim 1, wherein the one or more (a) polymers comprise one or more of carboxymethyl cellulose, cellulose acetate butyrate, cellulose acetate propionate, cellulose acetate, and hydroxypropyl cellulose.

### Claim 8 (depends on 1)

The article of claim 1, wherein the pattern of the dry silver nanoparticle-containing composition comprises a combination of fine lines, each fine line having an average dry width of at least 0.1 μm and up to and including 20 μm, which combination of fine lines can be arranged in parallel, crossing at any desired angle, a combination thereof, or in a random arrangement.

### Claim 9 (depends on 1)

The article of claim 1, wherein the substrate has a first supporting surface and a second opposing supporting surface, and one or more patterns of the dry silver nanoparticle-containing composition are disposed on the first supporting surface, and optionally, one or more patterns of the same or different dry silver nanoparticle-containing composition is disposed on the second opposing supporting surface.

### Claim 10 (depends on 1)

The article of claim 1, wherein the substrate is a transparent continuous polyester film that has a first supporting surface and a second opposing supporting surface,
the article further comprising multiple individual patterns formed on the first supporting surface which one or more multiple individual patterns comprise the same or different dry silver nanoparticle-containing compositions, and further comprising multiple opposing patterns formed on the second opposing supporting surface that comprise the same or different dry silver nanoparticle-containing compositions.

### Claim 11 (depends on 10)

The article of claim 10, wherein all of the multiple individual patterns on both the first supporting surface and the second opposing supporting surface comprise the same dry silver nanoparticle-containing composition, the (d) silver nanoparticles in each individual pattern having a mean particle size of at least 50 nm and up to and including 300 nm, and each of the multiple individual patterns comprising fine lines having an average dry width of at least 0.1 μm and up to and including 20 μm.

### Claim 12 (depends on 1)

The article of claim 1, wherein the pattern of the dry silver nanoparticle-containing composition further comprises at least 5 weight % and up to and including 25 weight % of a carbon black, based on the total weight of the one or more (a) polymers.

### Claim 13 (depends on 1)

The article of claim 1, further comprising a pattern of electrolessly plated metal that is disposed solely on the pattern of the dry silver nanoparticle-containing composition.

### Claim 14 (depends on 13)

The article of claim 13, wherein the substrate is a continuous flexible polymeric film, a metal foil, or a textile web.

### Claim 15 (depends on 13)

The article of claim 13, wherein the substrate is a transparent continuous polymeric film.

### Claim 16 (depends on 13)

The article of claim 13, wherein the one or more (a) polymers comprise one or more of carboxymethyl cellulose, cellulose acetate butyrate, cellulose acetate propionate, cellulose acetate, or hydroxypropyl cellulose.

### Claim 17 (depends on 13)

The article of claim 13, wherein the pattern of electrolessly plated metal comprises a combination of fine lines, each fine line having an average dry width of at least 0.1 μm and up to and including 20 μm, which combination of fine lines can be arranged in parallel, crossing at any desired angle, or a combination thereof or in a random arrangement.

### Claim 18 (depends on 13)

The article of claim 13, wherein the substrate has a first supporting surface and a second opposing supporting surface, and comprises one or more patterns of electrolessly plated metal disposed on the first supporting surface, and optionally, one or more patterns of electroless plated metal disposed on the second opposing supporting surface.

### Claim 19 (depends on 13)

The article of claim 13, wherein the substrate is a transparent continuous polyester film that has a first supporting surface and a second opposing supporting surface,
the article further comprising multiple individual patterns of electrolessly plated copper formed on the first supporting surface, and comprising multiple individual patterns of electrolessly plated copper formed on the second opposing supporting surface.

### Claim 20 (depends on 13)

The article of claim 13, wherein the electrolessly plated metal is copper.