Pigment/frit mixtures

Patent metadata

Field	Value
Publication number	US-10214651-B2
Application number	US-201615282061-A
Country	US
Kind code	B2
Filing date	Sep 30, 2016
Priority date	Oct 19, 2015
Publication date	Feb 26, 2019
Grant date	Feb 26, 2019

Abstract

Frits or frit mixtures with pearlescent pigments for materials, such as ceramic glazes, which are stable above 1000° C.

First claim

The invention claimed is:

1. A pigment/frit mixture, comprising a mixture of a pearlescent pigment and a frit in the form of particles, wherein the proportion of pearlescent pigment in the mixture is 5-95% by weight and the frit comprises at least 5% by weight of Al 2 O 3 , based on the weight of the frit, wherein the pearlescent pigment is based on a flake substrate and the ratio of the thickness of the flake substrate to the size of the frit particles is from 0.01 to 0.2.

2. The pigment/frit mixture according to claim 1 , wherein the flake substrate is selected from: synthetic mica flakes, natural mica flakes, Al 2 O 3 flakes, SiO 2 flakes, Fe 2 O 3 flakes, B 4 C flakes, TiO 2 flakes, SiC flakes, BN flakes and graphite flakes.

3. The pigment/frit mixture according to claim 1 , wherein the flake substrate is covered with one or more layers of metal oxide(s), metal sulfides, rare-earth metal oxides and/or metal(s) or mixtures thereof.

4. The pigment/frit mixture according to claim 3 , wherein the flake substrate is covered on the surface with one or more layers selected from: TiO 2 , Fe 2 O 3 , ZrO 2 , SnO 2 , TiO 2 /Fe 2 O 3 , Fe 2 TiO 5 , FeTiO 3 , FeOOH, Fe 3 O 4 , Cr 2 O 3 and TiO x , where x=1.50-1.95.

5. The pigment/frit mixture according to claim 1 , wherein the flake substrate has a particle thickness of 0.05-5.0 μm.

6. The pigment/frit mixture according to claim 1 , wherein the frit has a particle size of 1-500 μm.

7. The pigment/frit mixture according to claim 1 , wherein the frit comprises CaO, Na 2 O, K 2 O, BaO, SiO 2 or B 2 O 3 .

8. The pigment/frit mixture according to claim 1 , wherein the frit comprises ≥5% by weight of Al 2 O 3 and ≥50% by weight of SiO 2 , based on the weight of the frit, where the totality of all constituents of the frit is 100%.

9. The pigment/frit mixture according to claim 1 , wherein the pearlescent pigment is selected from pigments having one of the following combinations of substrate and layer(s) thereon:
substrate flake+TiO 2 ;
substrate flake+Fe 2 O 3 ;
substrate flake+Fe 3 O 4 ;
substrate flake+TiO 2 /Fe 2 O 3
substrate flake+FeTiO 3 ;
substrate flake+Fe 2 TiO 5
substrate flake+ZrO 2 ;
substrate flake+ZnO;
substrate flake+SnO 2 ;
substrate flake+Cr 2 O 3 ;
substrate flake+Ce 2 O 3 ;
substrate flake+TiO x (reduced), where x=1.50-1.95;
substrate flake+TiO 2 +Fe 2 O 3 ;
substrate flake+TiO 2 +Fe 3 O 4 ;
substrate flake+Fe 2 O 3 +TiO 2 ;
substrate flake+TiO 2 +SiO 2 +TiO 2 ;
substrate flake+TiO 2 +SnO 2 +TiO 2 ;
substrate flake+TiO 2 +Al 2 O 3 +TiO 2 ;
substrate flake+Fe 2 O 3 +SiO 2 +TiO 2 ;
substrate flake+TiO 2 /Fe 2 O 3 +SiO 2 +TiO 2 ;
substrate flake+TiO 2 /Fe 2 O 3 +SiO 2 +TiO 2 /Fe 2 O 3 ;
substrate flake+TiO 2 /Fe 2 O 3 +SiO 2 +TiO 2 +TiO 2 /Fe 2 O 3 ;
substrate flake+TiO 2 +SiO 2 +TiO 2 /Fe 2 O 3 ;
substrate flake+TiO 2 +SiO 2 ;
substrate flake+TiO 2 +Al 2 O 3 ;
substrate flake+TiO 2 +MgO×SiO 2 +TiO 2 ;
substrate flake+Fe 2 O 3 +MgO×SiO 2 +TiO 2 ;
substrate flake+TiO 2 /Fe 2 O 3 +MgO×SiO 2 +TiO 2 ;
substrate flake+TiO 2 /Fe 2 O 3 +MgO×SiO 2 +TiO 2 /Fe 2 O 3 ;
substrate flake+TiO 2 /Fe 2 O 3 +MgO×SiO 2 +TiO 2 +TiO 2 /Fe 2 O 3 ;
substrate flake+TiO 2 +MgO×SiO 2 +TiO 2 /Fe 2 O 3 ;
substrate flake+SnO 2 +TiO 2 +SiO 2 +SnO 2 +TiO 2 ;
substrate flake+SnO 2 +TiO 2 +SnO 2 +TiO 2 ;
substrate flake+SnO 2 +TiO 2 +Fe 2 O 3 +SiO 2 +SnO 2 +TiO 2 +Fe 2 O 3 ;
substrate flake+Fe 2 O 3 +SnO 2 +TiO 2 ;
substrate flake+Fe 2 O 3 +SnO 2 +Fe 2 O 3 ;
substrate flake+TiO 2 +SnO 2 +TiO 2 ;
substrate flake+TiO 2 /Fe 2 O 3 +SnO 2 +TiO 2 ;
substrate flake+TiO 2 /Fe 2 O 3 +SnO 2 +TiO 2 /Fe 2 O 3 ;
substrate flake+SnO 2 +TiO 2 +Fe 2 O 3 +SnO 2 +TiO 2 +Fe 2 O 3 ;
substrate flake+Fe 2 TiO 5 +SnO 2 +Fe 2 TiO 5 ;
substrate flake+Fe 2 TiO 5 +SiO 2 +Fe 2 TiO 5 .

10. The pigment/frit mixture according to claim 1 , wherein the pearlescent pigment is on a flake substrate and has a first low-refractive-index layer (=LRL) on the flake substrate comprising Al 2 O 3 , SiO 2 , zirconium silicate ZrSiO 4 , mullite 3Al 2 O 3 ×2SiO 2 or 2Al 2 O 3 ×SiO 2 (sintered or fused mullite) or alkaline-earth metal silicate (MSiO 3 , where M=Mg 2+ , Ca 2+ , Sr 2+ or Ba 2+ , or M 2 Si 3 O 8 , where M=Mg 2+ , Ca 2+ , Sr 2+ or Ba 2+ ).

11. The pigment/frit mixture according to claim 10 , wherein the pearlescent pigment is selected from pigments having one of the following combinations of substrate and layer(s) thereon: substrate flake+LRL+TiO 2 ;
substrate flake+LRL+Fe 2 O 3 ;
substrate flake+LRL+Fe 3 O 4 ;
substrate flake+LRL+TiO 2 /Fe 2 O 3 ;
substrate flake+LRL+FeTiO 3 ;
substrate flake+LRL+Fe 2 TiO 5 ;
substrate flake+LRL+ZrO 2 ;
substrate flake+LRL+ZnO;
substrate flake+LRL+SnO 2 ;
substrate flake+LRL+Cr 2 O 3 ;
substrate flake+LRL+Ce 2 O 3 ;
substrate flake+LRL+TiO x (reduced), where x=1.50-1.95;
substrate flake+LRL+TiO 2 +Fe 2 O 3 ;
substrate flake+LRL+TiO 2 +Fe 3 O 4 ;
substrate flake+LRL+Fe 2 O 3 +TiO 2 ;
substrate flake+LRL+TiO 2 +SiO 2 +TiO 2 ;
substrate flake+LRL+TiO 2 +SnO 2 +TiO 2 ;
substrate flake+LRL+TiO 2 +Al 2 O 3 +TiO 2 ;
substrate flake+LRL+Fe 2 O 3 +SiO 2 +TiO 2 ;
substrate flake+LRL+TiO 2 /Fe 2 O 3 +SiO 2 +TiO 2 ;
substrate flake+LRL+TiO 2 /Fe 2 O 3 +SiO 2 +TiO 2 /Fe 2 O 3 ;
substrate flake+LRL+TiO 2 /Fe 2 O 3 +SiO 2 +TiO 2 +TiO 2 /Fe 2 O 3 ;
substrate flake+LRL+TiO 2 +SiO 2 +TiO 2 /Fe 2 O 3 ;
substrate flake+LRL+TiO 2 +SiO 2 ;
substrate flake+LRL+TiO 2 +Al 2 O 3 ;
substrate flake+LRL+TiO 2 +MgO×SiO 2 +TiO 2 ;
substrate flake+LRL+Fe 2 O 3 +MgO×SiO 2 +TiO 2 ;
substrate flake+LRL+TiO 2 /Fe 2 O 3 +MgO×SiO 2 +TiO 2 ;
substrate flake+LRL+TiO 2 /Fe 2 O 3 +MgO×SiO 2 +TiO 2 /Fe 2 O 3 ;
substrate flake+LRL+TiO 2 /Fe 2 O 3 +MgO×SiO 2 +TiO 2 +TiO 2 /Fe 2 O 3 ;
substrate flake+LRL+TiO 2 +MgO×SiO 2 +TiO 2 /Fe 2 O 3 ;
substrate flake+LRL+SnO 2 +TiO 2 +SiO 2 +SnO 2 +TiO 2 ;
substrate flake+LRL+SnO 2 +TiO 2 +SnO 2 +TiO 2 ;
substrate flake+LRL+SnO 2 +TiO 2 +Fe 2 O 3 +SiO 2 +SnO 2 +TiO 2 +Fe 2 O 3 ;
substrate flake+LRL+Fe 2 O 3 +SnO 2 +TiO 2 ;
substrate flake+LRL+Fe 2 O 3 +SnO 2 +Fe 2 O 3 ;
substrate flake+LRL+TiO 2 +SnO 2 +TiO 2 ;
substrate flake+LRL+TiO 2 /Fe 2 O 3 +SnO 2 +TiO 2 ;
substrate flake+LRL+TiO 2 /Fe 2 O 3 +SnO 2 +TiO 2 /Fe 2 O 3 ;
substrate flake+LRL+SnO 2 +TiO 2 +Fe 2 O 3 +SnO 2 +TiO 2 +Fe 2 O 3 ;
substrate flake+LRL+Fe 2 TiO 5 +SnO 2 +Fe 2 TiO 5 ;
substrate flake+LRL+Fe 2 TiO 5 +SiO 2 +Fe 2 TiO 5 .

12. An unfired or fired brick, unfired or fired earthenware, unfired or fired ceramicware or a ceramic glaze, which comprises a pigment/frit mixture according to claim 1 .

13. A decorative tile, which comprises a pigment/frit mixture according to claim 1 .

14. A porcelain glaze, which comprises a pigment/frit mixture according to claim 1 .

15. A composition comprising the pigment/frit mixture according to claim 1 and a dispersant, binder and/or printing oil.

16. A method of making an article which is an unfired or fired brick, unfired or fired earthenware, unfired or fired ceramicware or a ceramic glaze, wherein the article is prepared by firing it to a temperature above 1000° C., wherein, before firing, a pigment/frit mixture according to claim 1 is incorporated into a composition used to prepare the article.

17. The method of claim 16 , wherein the article is a decorative tile.

18. The method of claim 16 , wherein the article is a porcelain glaze.

19. The pigment/frit mixture according to claim 1 , wherein the Al 2 O 3 content in the frit is ≥7% by weight based on the weight o

Assignees

• Merck Patent Gmbh

Inventors

• Hamm Lukas
• Handrosch Carsten
• Nelischer Nicole

Classifications

• C09C2200/1087

  the core consisting of bismuth oxychloride, magnesium fluoride, nitrides, carbides, borides, lead carbonate, barium or calcium sulfate, zinc sulphide, molybdenum disulphide or graphite · CPC title

• C09C2200/102

  the core consisting of glass or silicate material like mica or clays, e.g. kaolin · CPC title

• C09C2200/1004

  the core comprising at least one inorganic oxide, e.g. Al2O3, TiO2 or SiO2 · CPC title

• C09C1/0051

  comprising a stack of coating layers with alternating low and high refractive indices, wherein the first coating layer on the core surface has the low refractive index · CPC title

• C09C1/0021

  comprising a core coated with only one layer having a high or low refractive index · CPC title