Process for producing a shiny laminate structure at low temperatures

Patent metadata

Field	Value
Publication number	US-10384266-B2
Application number	US-201415023961-A
Country	US
Kind code	B2
Filing date	Sep 24, 2014
Priority date	Sep 24, 2013
Publication date	Aug 20, 2019
Grant date	Aug 20, 2019

Abstract

Process for producing a layer structure, which comprises the steps:
E1. provision of a composition comprising
i. gold (Au) particles in an amount in the range from 0.1 to 50% by weight; ii. a balance to 100% by weight of a polar, protic organic solvent; iii. less than 5% by weight of water, where the % by weight, in each case based on the total mass of the composition, add up to 100% by weight;
E2. application of the composition to a substrate to give a precursor; E3. heating of the precursor to a temperature in the range from 25 to 200° C. to give the layer structure.

First claim

The invention claimed is:

1. A process for producing a layer structure, which comprises the steps:
E1. providing a composition comprising
i. gold (Au) particles in an amount in the range from 0.1 to 50% by weight;
ii. a balance to 100% by weight of a polar, protic organic solvent;
iii. less than 5% by weight of water; and
iv. a mercapto-carboxyl compound of the general formula (I), or a salt thereof,
wherein the general formula (I) is: SH—R 1 —COOH,
where R 1 is a substituted, unsubstituted, branched or unbranched, cyclic or polycyclic C 1 -C 20 -hydrocarbon radical,

where the % by weight, in each case based on the total mass of the composition, add up to 100% by weight; and wherein the composition has a pH in the range from 3 to 8;
E2. applying the composition to a substrate to give a precursor; and
E3. heating the precursor to a temperature in the range from 25 to 300° C. to give the layer structure.

2. The process as claimed in claim 1 , wherein the gold particles have a diameter in the range from 1 to 25 nm.

3. The process as claimed in claim 1 , wherein the viscosity of the composition is selected in the range from 1 to 100000 mPas at a temperature of 20° C.

4. The process as claimed in claim 1 , wherein the protic, polar organic solvent comprises at least 20% by weight of a polyalcohol.

5. The process as claimed in claim 4 , wherein the polyalcohol has from 2 to 20 carbon atoms.

6. The process as claimed in claim 4 , wherein the polyalcohol is selected from the group consisting of 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2,3-propanetriol (glycerol), 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,2,3-butanetriol, 1,2-dihydroxybenzene, 1,3-dihydroxybenzene, 1,4-dihydroxybenzene, 1,2,3-trihydroxybenzene, 1,2,4-trihydroxybenzene, 1,4-dihydroxy-2,5-dinitrobenzene, L-adrenaline, a monosaccharide, a disaccharide, a monosaccharide or disaccharide in mixtures with a liquid polyol, 1,1,1-tris(hydroxymethyl)propane, 2,2-dimethylpropane-1,3-diol, a polyethylene glycol, and mixtures of at least two thereof.

7. The process as claimed in claim 1 , wherein the substituted, unsubstituted, branched or unbranched, cyclic or polycyclic C 1 -C 20 -hydrocarbon radical has at least one, preferably two or all, of the following properties:
e1. at least one of the carbon atoms of the C 1 -C 20 -hydrocarbon radical has been replaced by at least one nitrogen atom, an oxygen atom, a phosphorus atom, a sulfur atom, a hydroxyl group, a carboxyl group, a halide, an amine, an amide, a phosphate group, a sulfate group or a combination of at least two thereof; or
e2. the C 1 -C 20 -hydrocarbon radical can be substituted by a substituted, unsubstituted, branched or unbranched, cyclic or polycyclic C 1 -C 20 -hydrocarbon radicals or the C 1 -C 20 -hydrocarbon radical can be branched; or
e3. at least one of the carbon atoms of the C 1 -C 20 -hydrocarbon radical has been replaced by an aromatic radical or in the case of a 5-, 6- or 7-membered heteroaromatic ring by 1, 2, 3 or 4 nitrogen, oxygen and sulfur atoms, wherein the heteroaromatic radical can be substituted by halogen atoms, hydroxyl, nitro, amino groups, protected amino radicals, cyano, trifluoromethyl groups, hydrocarbon radicals having from 1 to 4 carbon atoms, alkoxy radicals having from 1 to 4 carbon atoms.

8. The process as claimed in claim 1 , wherein the composition comprises from 0.1 to 4% by weight of the mercapto-carboxyl compound, based on the total mass of the composition.

9. The process as claimed in claim 1 , wherein the mercapto-carboxyl compound is selected from the group consisting of L-cysteine, D-cysteine, γ-L-glutamyl-L-cysteinylglycine (glutathione), (RS)—N-(2-mercapto-1-oxopropyl)glycine (tiopronin), mercaptosuccinic acid, N-acetylcysteine, thiosalicylic acid, dimercaptosuccinic acid, L-methionine, D-methionine, thiourea, 2-mercaptopropionic acid, thioglycerol, thiodipropionic acid, cystine, methyl 3-mercaptopropionate, Na thioglycolate and mixtures of at least two thereof.

10. The process as claimed in claim 1 , wherein the composition comprises at least one further metal selected from the group consisting of silver (Ag), platinum (Pt), palladium (Pt), copper (Cu), rhodium (Rh) and combinations of at least two thereof.

11. The process as claimed in claim 1 , wherein the composition further comprises a surface-active substance.

12. The process as claimed in claim 1 , wherein a protective layer is applied at least to a part of the layer structure in a further step E4.

13. The process as claimed in claim 1 , wherein the substrate is selected from the group consisting of a paper, a wood, a textile, a glass, a polymer, a metal, a ceramic, a keratinized layer and combinations of at least two thereof.

14. The process as claimed in claim 1 , wherein the substrate has a conductivity of less than 10 13 S/cm.

15. The process as claimed in claim 1 , wherein the application of the composition in step E2 is carried out by means of a brush, a screen, a felt pen, a fountain pen or a nozzle.

16. A precursor of a layer structure obtained by means of process steps E1 and E2 of the process as claimed in claim 1 .

17. The precursor as claimed in claim 16 , wherein the precursor has at least one of the following properties:
V1. a thickness of the substrate in the range from 0.1 mm to 5 cm;
V2. a thickness of the composition applied in step E2 in the range from 0.1 μm to 70 μm;
V3. a conductivity of the substrate of less than 10 13 S/cm; or
V4. a conductivity of the composition applied in step E2 in the range from 10 −1 S/cm to 10 −8 S/cm.

18. A composition comprising:
z1. gold (Au) particles in an amount in the range from 0.1 to 50% by weight;
z2. water in the range from 0 to 5% by weight;
z3. a polar, protic, organic solvent as balance to 100% by weight; and
z4. a mercapto-carboxyl compound of the general formula (I), or a salt thereof,
wherein the general formula (I) is: SH—R 1 —COOH,
where R 1 is a substituted, unsubstituted, branched or unbranched, cyclic or polycyclic C 1 -C 20 -hydrocarbon radical,

where the % by weight, in each case based on the total mass of the composition, add up to 100% by weight; and wherein the composition has a pH in the range from 3 to 8.

19. The composition as claimed in claim 18 , wherein the composition comprises at least one further component selected from:
z4. polyvinylpyrrolidone in an amount in the range from 0 to 10% by weight, based on the total mass of the composition; or
z5. a polyalcohol in an amount in the range from 0 to 90% by weight, based on the total mass of the composition.

20. The composition as claimed in claim 19 , wherein the polyalcohol is selected from the group consisting of 1,2-ethanediol, 1,2-propanediol, 1,2,3-propanetriol (glycerol), 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,2,3-butanetriol, 1,2-dihydroxybenzene, 1,3-dihydroxybenzene, 1,4-dihydroxybenzene, 1,2,3-trihydroxybenzene, 1,2,4-trihydroxybenzene, 1,4-dihydroxy-2,5-dinitrobenzene, L-adrenaline, a monosaccharide, a disaccharide, a monosaccharide or disaccharide in mixtures with a liquid polyol, 1,1,1-tris(hydroxymethyl)propane, 2,2-dimethylpropane-1,3-diol, a polyethylene glycol, and mixtures of at least two thereof.

21. The composition as claimed in claim 18 , wherein the gold particles have a particle size D 50 of 20 nm or less.

Assignees

• Heraeus Deutschland Gmbh & Co Kg

Inventors

• Behl Susanne
• Boldt Kai-Ulrich

Classifications

• B22F1/107

  containing organic material comprising solvents, e.g. for slip casting · CPC title

• B22F1/0545

  Dispersions or suspensions of nanosized particles · CPC title

• B22F1/054

  Nanosized particles · CPC title

• B22F7/04 Primary

  with one or more layers not made from powder, e.g. made from solid metal · CPC title

• B22F2009/245

  Reduction reaction in an Ionic Liquid [IL] · CPC title