FORMULATION FOR APPLICATION ONTO GLASS, PORCELAIN, TILES, METALS AND PLASTIC FOIL

Abstract

The invention relates to a composition containing at least the two following components: a) a silver carboxylate, and b) a terpene, an ink for ink jet printing and a paste for printing with a screen printing method, wherein the ink or the paste, respectively, each contains the composition according to the invention. The invention also relates to a method for producing a pattern on a substrate, at least comprising the following steps: A) providing a substrate and a composition containing at least one silver carboxylate and one terpene; B) applying the composition to the substrate while preserving a precursor with the pattern; C) treating the precursor with the pattern according to a treatment step that is selected from the group consisting of: a) at a temperature of more than 200° C. for at least 10 minutes, wherein the treatment is preferably carried out in an atmosphere of air; b) a photonic sintering process; c) a combination of a) and b), wherein the substrate to which the pattern is applied is preserved. The invention further relates to a printer, an item that is coated at least in part, and a use of the composition according to the invention for applying a pattern.

Claims

1. A composition comprising: a) silver carboxylate; and b) a terpene.

2. The composition according to claim 1, wherein the terpene is selected from the group consisting of orange terpene, limonene and pinene, or a combination thereof.

3. The composition according to claim 1, further comprising at least one elemental metal selected from the group consisting of gold, rhodium, vanadium, palladium, platinum, osmium and tungsten, and wherein the at least one elemental metal is present at an amount of is less than 10 wt. %, based on the total weight of the composition.

4. The composition according to claim 1, further comprising at least one carboxylic acid.

5. The composition according to claim 1, wherein the sum of percentages by weight of a) and b) is within a range from 20 to 95 wt. %, based on the total weight of the composition and the composition further comprises at least one component selected from the group consisting of an organic solvent, an adhesion promoter, and a viscosity aid.

6. The composition according to claim 1, wherein the silver carboxylate is silver neodecanoate.

7. The composition according to claim 1, wherein the composition further comprises at least one component selected from the group consisting of an organic solvent, an adhesion promoter, and a viscosity aid.

8. An ink for ink jet printing, wherein the ink comprises contains a composition according to claim 1.

9. A paste for printing with a screen printing method, wherein the paste comprises contains a composition according to claim 1.

10. A method for producing a pattern on a substrate, the method comprising the following steps: A) providing a substrate and a composition comprising silver carboxylate and terpene; B) applying the composition to the substrate while preserving a precursor with the pattern; C) treating the precursor with the pattern according to a treatment step selected from the group consisting of a) at a temperature of more than 200° C. for at least 10 minutes, wherein the treatment is carried out in an atmosphere of air, b) a photonic sintering process, and c) a combination of a) and b).

11. The method according to claim 10, wherein the pattern is an element selected from the group consisting of (A) a glossy decor, and (B) an electrically conducting structure.

12. The method according to claim 10, wherein the applying step is carried out by means of a printer.

13. The method according to claim 10, wherein the pattern includes at least one of the following properties: a gloss of at least 1300 GU; and an electrical conductivity of at least 30%, based on the conductivity of silver, at 20° C.

14. A printer comprising a printer head and a reservoir, wherein the reservoir contains a composition according to claim 1.

15. (canceled)

16. A printed pattern comprising a silver-containing coating, wherein the coating comprises a total percentage by weight of at least one element selected from the group consisting of gold, rhodium, vanadium, palladium, platinum, osmium and tungsten, wherein the at least one element is present in the coating at a percentage of less than 5 wt. %, based on the total weight of the coating.

17. (canceled)

18. A printer comprising a printer head and a reservoir, wherein the reservoir contains an ink according to claim 7.

19. A printer comprising a printer head and a reservoir, wherein the reservoir contains, or a paste according to claim 9.

20. The composition of claim 4 wherein the carboxylic acid is a tertiary carboxylic acid.

Description

FIGURES

[0162] In the following, the invention will be illustrated by way of examples based on figures. The invention is not limited to the embodiments and details shown in the figures.

[0163] FIG. 1 shows a flow diagram for a method for producing a pattern.

DESCRIPTION OF THE FIGURES

[0164] FIG. 1 shows a flow diagram for a method for producing a pattern. In step A), a substrate and a composition, which is a glossy ink in the illustrated instance, are provided. In step B), the composition is applied to the substrate in a previously selected pattern. In the subsequent step C), the substrate thus treated is treated at an increased temperature for a certain time, in the illustrated instance at 230° C. for 10 minutes. Therein, the pattern is applied to the substrate durably and permanently.

Test Methods

[0165] a. Gloss Measurement

[0166] The gloss was measured as per the DIN EN ISO 2813:2015-02 standard, using the gloss measuring instrument PolyGloss GL0030, available from TQC B.V. Netherlands, at an angle of 20° and a temperature of 23° C. Calibration was carried out as specified in the user guide (designated as V1.01 092013). The measuring geometries defined in the standard were complied with. Glass and polyimide film were used as substrates. The samples were planar and did not have any anisotropism. The dry coat thickness was <5 μm in the case of liquid samples and <5 μm in the case of pasty samples.

b. Electrical Conductivity

[0167] The electrical conductivity was measured using a resistance meter, LCR Meter, by Rhode & Schwarz HM 8118 (four-point measurement), Germany.

c. Viscosity

[0168] The viscosity of pasty samples was determined as per the DIN 53019 standard, using a Brookfield rheometer type DV3, spindle no. 14, at 10 RPM and at 25° C.

[0169] The viscosity of liquid samples was determined as per the DIN 53019 standard, using a Brookfield rheometer type DV3, spindle no. 21, at 100 RPM and at 20° C.

d. Determination of Metal Contents (ICP Analysis)

[0170] The inductively coupled plasma (ICP) is coupled to optical emission spectrometry (OES) for evaluation purposes. Typical determination limits according to the method used here are at 1 ppm (each based on the weighed-in sample quantity). The determination of the element concentration using the measuring instrument is carried out as specified by the manufacturer of the device (ICP-OES: VARIAN Vista MPX) and using certified reference liquids for calibration purposes. The element concentrations in the solution (100 ml) determined by the devices are then converted to the original weighted sample (0.1 g).

[0171] Note: The sample to be analysed is decomposed with aqua regia (a mixture consisting of 3 parts of HCl, 37 wt. %, and 1 part of HNO.sub.3, 65 wt. %) in a microwave reaction system, MultiwavePro, by Anton Paar.

[0172] The following elements can be determined in this way: Ag, Au, B, Bi, Ce, Co, Cr, Cu, Fe, In, Ir, Mn, Ni, Pd, Pt, Rh, Ru, Sb, Si, Sn, Ti, V, Zn, Zr.

Examples

[0173] In the following, the invention is further illustrated by way of various examples. The invention is not limited to these examples.

Example Compositions

[0174] The following compositions were produced (each specified in wt. % of the component):

TABLE-US-00001 Example Component I II III IV V VI Pine oil − 24.80  − 11.25  − − Orange terpenes 12.00  − 19.80  10.00  50.00 − Glycol ether − − − − − 70.00 Silver neo 57.90  40.00  40.00  60.00  47.00 27.00 decanoate 38% Colophony - PO 2:1 21.00  28.00  − − − − Bakelite LA751 − − 33.00  − − − Colophony − − − 9.00 − − Rhodium(III) 2.60 2.00 2.00 3.5  − − solution, 5% Carboxylic acid 0.50 0.50 − 1.00  3.00  3.00 HF8028 DS 0.20 0.20 0.20 0.25 − − HAN 8572 5.80 4.50 5.00 5.00 − − Substrate Float glass Float glass Float glass Float glass Polyimide Polyimide film film Conditioning of Preliminary Preliminary Preliminary Preliminary Cleaning with Cleaning with the substrate cleaning with cleaning with cleaning with cleaning with purified water, purified water, prior to being purified water, purified water, purified water, purified water, lint-free cloth lint-free cloth used subsequent subsequent subsequent subsequent cleaning with a cleaning with a cleaning with a cleaning with a lint-free cloth lint-free cloth lint-free cloth lint-free cloth soaked with soaked with soaked with soaked with ethanol ethanol ethanol ethanol Gloss (GU) ++ + + +++ +++ + Conductivity (L) + + + + +++ + Storage stability + + ∘ + + − Gloss: + = 1000-1300 GU; ++ = >1300 to 1500 GU; +++ = >1500 GU. Conductivity: + = <20%, ++ = 20-<40%; +++ = ≥40%, each based on the conductivity of silver at 20° C. Storage stability: + = excellent (>12 weeks); ∘ = adequate (4-12 weeks); − = insufficient (<4 weeks).

[0175] Compositions nos. I-II as well as nos. IV-VI are according to the invention.

[0176] Composition no. III is a comparative example.

[0177] Ag Versatic 38% is a silver neo decanoate with 38 wt. % silver content, based on the total quantity of the composition. Purified water is demineralised water. This water has a conductivity within a range from 0 to 50 μS.

[0178] Orange terpene (CAS: 68647-72-3) has about 95% D-limonene and is available from Frey & Lau GmbH in Henstedt-Ulzburg, Germany.

[0179] Versatic® carboxylic acids are tertiary carboxylic acids and are available from HEXION Rotterdam, Netherlands, and others.

[0180] Colophony (CAS: 8050-09-7) is a mixture consisting of various rosin acids and is available from H. Reynaud & Fils (Germany) GmbH, Hamburg.

[0181] Rh(III) solution is a rhodium nonanoate which is produced by Heraeus Deutschland GmbH, Hanau. In the present case, a solution with 5 wt. % of rhodium is used, based on the total weight of the solution.

[0182] HF8028DS is a silicone-containing additive which is produced by Heraeus Deutschland GmbH, Hanau.

[0183] HAN8572 is an aromatic-aliphatic hydrocarbon mixture and available from EXXON MOBIL CHEMICAL, Antwerp.

Producing a Coated Item

[0184] Test pieces 10 cm×0.2 cm×0.8 cm in size (W×H×D) and made of glass were chosen as substrate. The test pieces were cleaned with purified water and ethanol. A coat of a silver-containing composition (see above, types I-IV) having a wet coat thickness of >20 μm was applied by screen printing. The coat was sintered on the substrate in an oven at a temperature of >350° C. for 10 minutes.

[0185] Test pieces 10 cm×0.1 cm×10 cm in size (W×H×D) and made of polyimide film were chosen as substrate. The test pieces were cleaned with purified water and a lint-free cloth. A coat of a silver-containing composition (see above, types V and VI) having a wet coat thickness of >5 μm was applied by ink jet printing. The coat was sintered on the substrate in an oven at a temperature of 230° C. for 10 minutes.