PIGMENT/FRIT MIXTURES

Abstract

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

Claims

1. A pigment/frit mixture, comprising a mixture of a pearlescent pigment and a frit, 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.sub.2O.sub.3, based on the weight of the frit.

2. The pigment/frit mixture according to claim 1, wherein the pearlescent pigment is based on a flake substrate.

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

4. The pigment/frit mixture according to claim 2, 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.

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

6. The pigment/frit mixture according to claim 2, wherein the flake substrate has a particle thickness of 0.05-5.0 m.

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

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

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

10. 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.sub.2; substrate flake+Fe.sub.2O.sub.3; substrate flake+Fe.sub.3O.sub.4; substrate flake+TiO.sub.2/Fe.sub.2O.sub.3 substrate flake+FeTiO.sub.3; substrate flake+Fe.sub.2TiO.sub.5 substrate flake+ZrO.sub.2; substrate flake+ZnO; substrate flake+SnO.sub.2; substrate flake+Cr.sub.2O.sub.3; substrate flake+Ce.sub.2O.sub.3; substrate flake+TiO.sub.x (reduced), where x=1.50-1.95; substrate flake+TiO.sub.2+Fe.sub.2O.sub.3; substrate flake+TiO.sub.2+Fe.sub.3O.sub.4; substrate flake+Fe.sub.2O.sub.3+TiO.sub.2; substrate flake+TiO.sub.2+SiO.sub.2+TiO.sub.2; substrate flake+TiO.sub.2+SnO.sub.2+TiO.sub.2; substrate flake+TiO.sub.2+Al.sub.2O.sub.3+TiO.sub.2; substrate flake+Fe.sub.2O.sub.3+SiO.sub.2+TiO.sub.2; substrate flake+TiO.sub.2/Fe.sub.2O.sub.3+SiO.sub.2+TiO.sub.2; substrate flake+TiO.sub.2/Fe.sub.2O.sub.3+SiO.sub.2+TiO.sub.2/Fe.sub.2O.sub.3; substrate flake+TiO.sub.2/Fe.sub.2O.sub.3+SiO.sub.2+TiO.sub.2+TiO.sub.2/Fe.sub.2O.sub.3; substrate flake+TiO.sub.2+SiO.sub.2+TiO.sub.2/Fe.sub.2O.sub.3; substrate flake+TiO.sub.2+SiO.sub.2; substrate flake+TiO.sub.2+Al.sub.2O.sub.3; substrate flake+TiO.sub.2+MgOSiO.sub.2+TiO.sub.2; substrate flake+Fe.sub.2O.sub.3+MgOSiO.sub.2+TiO.sub.2; substrate flake+TiO.sub.2/Fe.sub.2O.sub.3+MgOSiO.sub.2+TiO.sub.2; substrate flake+TiO.sub.2/Fe.sub.2O.sub.3+MgOSiO.sub.2+TiO.sub.2/Fe.sub.2O.sub.3; substrate flake+TiO.sub.2/Fe.sub.2O.sub.3+MgOSiO.sub.2+TiO.sub.2+TiO.sub.2/Fe.sub.2O.sub.3; substrate flake+TiO.sub.2+MgOSiO.sub.2+TiO.sub.2/Fe.sub.2O.sub.3; substrate flake+SnO.sub.2+TiO.sub.2+SiO.sub.2+SnO.sub.2+TiO.sub.2; substrate flake+SnO.sub.2+TiO.sub.2+SnO.sub.2+TiO.sub.2; substrate flake+SnO.sub.2+TiO.sub.2+Fe.sub.2O.sub.3+SiO.sub.2+SnO.sub.2+TiO.sub.2+Fe.sub.2O.sub.3; substrate flake+Fe.sub.2O.sub.3+SnO.sub.2+TiO.sub.2; substrate flake+Fe.sub.2O.sub.3+SnO.sub.2+Fe.sub.2O.sub.3; substrate flake+TiO.sub.2+SnO.sub.2+TiO.sub.2; substrate flake+TiO.sub.2/Fe.sub.2O.sub.3+SnO.sub.2+TiO.sub.2; substrate flake+TiO.sub.2/Fe.sub.2O.sub.3+SnO.sub.2+TiO.sub.2/Fe.sub.2O.sub.3; substrate flake+SnO.sub.2+TiO.sub.2+Fe.sub.2O.sub.3+SnO.sub.2+TiO.sub.2+Fe.sub.2O.sub.3; substrate flake+Fe.sub.2TiO.sub.5+SnO.sub.2+Fe.sub.2TiO.sub.5; substrate flake+Fe.sub.2TiO.sub.5+SiO.sub.2+Fe.sub.2TiO.sub.5.

11. 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.sub.2O.sub.3, SiO.sub.2, zirconium silicate ZrSiO.sub.4, mullite 3Al.sub.2O.sub.32SiO.sub.2 or 2Al.sub.2O.sub.3SiO.sub.2 (sintered or fused mullite) or alkaline-earth metal silicate (MSiO.sub.3, where M=Mg.sup.2+, Ca.sup.2+, Sr.sup.2+ or Ba.sup.2+, or M.sub.2Si.sub.3O.sub.8, where M=Mg.sup.2+, Ca.sup.2+, Sr.sup.2+ or Ba.sup.2+).

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

13. 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.

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

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

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

17. 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.

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

19. The method of claim 17, wherein the article is a porcelain glaze.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0102] FIGS. 1 and 2 show sectional side views through a pigmented frit layer before the firing operation, the particles of the frit are represented as round or oval particles and the pearlescent pigments are represented as rods.

[0103] FIGS. 3-5 diagrammatically show the plane-parallel alignment of the pearlescent pigments in the glaze.

[0104] FIG. 6 shows the temperature profile used for firing the printed and dried tiles in the Examples.

[0105] From the foregoing description, one skilled in the art can easily ascertain the essential characteristics of this invention and, without departing from the spirit and scope thereof, can make various changes and modifications of the invention to adapt it to various usages and conditions.