阅读说明：本技术 颜料/玻璃料的混合物 (Pigment/glass frit mixtures ) 是由 J·克斯滕 C·普拉策 E(K)·张 S(T)·唐 R·白 于 2020-04-28 设计创作，主要内容包括：本发明涉及玻璃料或玻璃料的混合物,其包含用于陶瓷釉的效果颜料,其在1000℃以上是稳定的并在陶瓷釉中产生液体金属效果。(The invention relates to a glass frit or a mixture of glass frits, comprising an effect pigment for a ceramic glaze, which is stable above 1000 ℃ and produces a liquid metallic effect in the ceramic glaze.)

1. Effect pigment/glass frit mixture, characterized in that the glass frit contains 3 to 7 wt.% Na₂O, based on the glass frit, based on the flake-form substrate, which has at least one layer sequence (A) to (E) or (A) to (F) on the surface,

(A) the high-refractive-index coating has a refractive index n of not less than 1.8,

(B) pseudobrookite layer, which may optionally be doped with one or more oxides in an amount of < 10% by weight, based on layer (B),

(C) a low refractive index layer having a refractive index n <1.8,

(D) a high refractive index coating consisting of at least two colourless metal oxide layers,

(E) pseudobrookite layer, which may optionally be doped with one or more oxides in an amount of ≦ 10 wt.%, based on layer (E), and optionally,

(F) an outer protective layer.

2. The effect pigment/glass frit mixture according to claim 1, wherein the flake-like substrate of the effect pigment is selected from the group consisting of phyllosilicate flakes, BiOCl flakes, SiC flakes, TiC flakes, WC flakes, B flakes₄C flake, BN flake, graphite flake, TiO flake₂Flake, Fe₂O₃Flake, doped or undoped Al₂O₃Flakes, doped or undoped glass flakes, doped or undoped SiO₂Flakes or mixtures thereof.

3. The effect pigment/glass frit mixture of claim 1 or 2, wherein the phyllosilicate platelets are natural mica, synthetic mica, kaolin or talc.

4. The effect pigment/glass frit mixture according to one or more of claims 1 to 3, characterized in that the layer (A) of effect pigments consists of one or more metal oxides.

5. The effect pigment/glass frit mixture according to one or more of claims 1 to 4, characterized in that the metal oxide of the layer (A) is selected from TiO₂、Fe₂O₃、Fe₃O₄、Fe(O)OH、BiOCl、Cr₂O₃、ZnO、Ce₂O₃、ZrO₂、SnO₂、Co₂O₃Titanium suboxide (partially reduced TiO)₂Which has a structure selected from<4 to 2 oxidation state, and lower oxides or mixtures thereof), titanium oxynitride, titanium nitride, CoO, Co₂O₃、Co₃O₄、VO₂、V₂O₃、NiO、WO₃、MnO、Mn₂O₃Or mixtures of the above oxides.

6. The effect pigment/glass frit mixture according to one or more of claims 1 to 5, characterized in that the layers (B) and/or (E) are doped with one or more oxides or mixtures of oxides selected from the following: al (Al)₂O₃,Ce₂O₃,B₂O₃,ZrO₂,SnO₂,Cr₂O₃,CoO,Co₂O₃,Co₃O₄,Mn₂O₃。

7. The effect pigment/glass frit mixture according to one or more of claims 1 to 6, characterized in that the layer (C) of effect pigment consists of SiO₂,MgO*SiO₂,CaO*SiO₂,Al₂O₃*SiO₂,B₂O₃*SiO₂Or a mixture of said compounds.

8. The effect pigment/glass frit mixture according to one or more of claims 1 to 7, characterized in thatThe layer (D) of effect pigments is then composed of at least two metal oxide layers, the metal oxides being selected from SnO₂,TiO₂,Al₂O₃,Cr₂O₃,Fe₂O₃Or mixtures thereof.

9. The effect pigment/glass frit mixture according to one or more of claims 1 to 8, characterized in that the layer of effect pigments (D) consists of metal oxide layers (D1) and (D2)

(D1)SnO₂Layer(s)

(D2)TiO₂And (3) a layer.

10. The effect pigment/glass frit mixture according to one or more of claims 1 to 8, characterized in that the layer of effect pigments (D) consists of metal oxide layers (D1), (D2) and (D3)

(D1)Al₂O₃Layer(s)

(D2)TiO₂Layer(s)

(D3)Al₂O₃And (3) a layer.

11. The effect pigment/glass frit mixture according to one or more of claims 1 to 8, characterized in that the layer (D) consists of a metal oxide layer (D1), (D2) and (D3)

(D1)SnO₂Layer(s)

(D2)TiO₂Layer(s)

(D3)SnO₂And (3) a layer.

12. The effect pigment/glass frit mixture according to one or more of claims 1 to 11, characterized in that the outer protective layer (F) of the effect pigment consists of SnO₂And (4) forming.

13. The effect pigment/glass frit mixture according to one or more of claims 1 to 12, wherein the effect pigment has the following structure:

substrate + TiO₂+ AlkyaniteSiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

Base material + Fe₂O₃+ pseudobrookite + SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

-substrate + Cr₂O₃+ pseudobrookite + SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

Substrate + TiO₂+ pseudobrookite + MgO SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

Base material + Fe₂O₃+ pseudobrookite + MgO SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

-substrate + Cr₂O₃+ pseudobrookite + MgO SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

Substrate + TiO₂+ pseudobrookite + CaO × SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

Base material + Fe₂O₃+ pseudobrookite + CaO × SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

-substrate + Cr₂O₃+ pseudobrookite + CaO × SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

Substrate + TiO₂+ pseudobrookite + Al₂O₃*SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

Base material + Fe₂O₃+ pseudobrookite + Al₂O₃*SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

-substrate + Cr₂O₃+ pseudobrookite + Al₂O₃*SiO₂+SnO₂+TiO₂+SnO₂+ pseudobrookite

Substrate + TiO₂+ pseudobrookite + SiO₂+TiO₂+SnO₂+ pseudobrookite

Substrate + TiO₂+ pseudobrookite + SiO₂+SnO₂+TiO₂+ pseudobrookite

Substrate + TiO₂+ pseudobrookite + SiO₂+TiO₂+SnO₂+ pseudobrookite + SnO₂

Substrate + TiO₂+ pseudobrookite + SiO₂+SnO₂+TiO₂+ pseudobrookite + SnO₂

Substrate + TiO₂+ pseudobrookite + SiO₂+SnO₂+Fe₂O₃+SnO₂+ pseudobrookite

Substrate + TiO₂+ pseudobrookite + SiO₂+SnO₂+Cr₂O₃+SnO₂+ pseudobrookite

Substrate + TiO₂+ pseudobrookite + SiO₂+Al₂O₃+TiO₂+Al₂O₃+ pseudobrookite.

14. The pigment/glass frit mixture according to one or more of claims 1 to 13, wherein the glass frit particles have a particle size of 1 to 500 μ ι η.

15. Pigment/glass frit mixture according to one or more of claims 1 to 14, characterized in that, except for Na, it is present₂O, the glass frit further comprises at least one component selected from the group consisting of: al (Al)₂O₃,SiO₂,B₂O₃,TiO₂,Fe₂O₃,MgO,MnO,Cr₂O₃,P₂O₅,PbO,HfO₂,ZnO,ZrO₂Alkali metal oxides, alkaline earth metal oxides and rare earth element oxides.

16. The pigment/glass frit mixture according to one or more of claims 1 to 15, characterized in that the pigment/glass frit mixture consists of 20 to 70 wt. -% of effect pigment and 30 to 80 wt. -% of glass frit and optionally 0 to 10 wt. -% of one or more additives, wherein the sum of the pigments, glass frit and additives is 100%.

17. Use of the pigment/glass frit mixture according to one or more of claims 1 to 16 in unfired or fired roof tiles, unfired or fired crockery and ceramics, ceramic glazes.

18. Use of the pigment/glass frit mixture according to claim 16 for decorating tiles, for decorating porcelain, bone china and pottery.

19. Use of the pigment/glass frit mixture according to claim 18 for porcelain glaze.

20. Formulation comprising a pigment/glass frit mixture according to one or more of claims 1 to 16.

21. The preparations according to claim 20, characterized in that they have the following gloss values (determined using Rhopoint IQ mini 2.0 goniophotometer)

Gloss value (20 degree > 100)

The peak value of the glossiness Rspec is more than or equal to 20.

22. Process for producing ceramic glazes, characterized in that a pigment/glass frit mixture according to one or more of claims 1 to 16 and optionally a glass frit as an intermediate layer (lining layer) are applied between the ceramic or glaze and the pigment/glass frit mixture, wherein the lining layer and the pigment/glass frit mixture are applied separately and subsequently fired together.

Detailed Description

Examples

Example 1

100 grams of natural mica with a particle size of 10-60 microns was heated to 80C in 2 liters of deionized water and stirred. When this temperature had been reached, 44 g of TiCl were metered in at a pH of 1.8₄Solution (400 g/l TiCl₄) During this period, the pH is maintained constant with 32% sodium hydroxide solutionAnd (6) changing. The pH is subsequently adjusted to 2.8 with the aid of sodium hydroxide solution, and 600 ml of FeCl are added simultaneously at this pH and 75 ℃₃Aqueous solution (w (fe) ═ 7%) and 462 ml of TiCl₄Aqueous solution (200 g TiCl)₄L). The pH was maintained throughout the addition by the simultaneous dropwise addition of 32% sodium hydroxide solution. After stirring for a further 0.5 h, the pH was raised to 7.5 and 650 ml of an aqueous sodium silicate solution (13% by weight SiO) were slowly metered in at this pH₂) During this time, the pH was kept constant with 10% hydrochloric acid. After stirring for a further 0.5 h, the pH is lowered to 1.8 with 10% hydrochloric acid and 5 g of SnCl are metered in₄x5H₂O and 41 ml of hydrochloric acid (20%). 105 ml of TiCl are then slowly metered in at the same pH₄Solution (400 g/l TiCl₄). Then 5 g of SnCl is added₄x5H₂O and 41 ml hydrochloric acid (20%). In each case, the pH was maintained at 1.8 using 32% sodium hydroxide solution. The pH is subsequently adjusted to 2.8 again with the aid of sodium hydroxide solution. Finally, 650 ml of FeCl were added in parallel₃Aqueous solution (w (fe) ═ 7%) and 499 ml of TiCl₄Aqueous solution (200 g TiCl)₄/l) and titrated simultaneously with sodium hydroxide solution (w ═ 10%) to apply the outermost layer. After stirring at pH 3.0 for an additional 0.5 hours, the coated mica substrate was filtered off, washed and dried at 110 ℃ for 16 hours. Finally, the effect pigments obtained were calcined at 850 ℃ for 0.5 h and sieved.

A temperature-stable, golden multilayer pigment with high brightness is obtained.

Example 2

100 grams of natural mica with a particle size of 10-25 microns was heated to 80C in 2 liters of deionized water and stirred. When this temperature had been reached, 44 g of TiCl were metered in at a pH of 1.8₄Solution (400 g/l TiCl₄) The pH was kept constant during this process with 32% sodium hydroxide solution. The pH is subsequently adjusted to 2.8 with the aid of sodium hydroxide solution, and 600 ml of FeCl are added simultaneously at this pH and 75 ℃₃Aqueous solution (w (fe) ═ 7%) and 462 ml of TiCl₄Aqueous solution (200 g TiCl)₄L). The pH was maintained throughout the addition by the simultaneous dropwise addition of 32% sodium hydroxide solution. After stirring for a further 0.5 h, the pH was raised to 7.5 and 650 ml of an aqueous sodium silicate solution (13% by weight SiO) were slowly metered in at this pH₂) During this time, the pH was kept constant with 10% hydrochloric acid. After stirring for a further 0.5 h, the pH is lowered to 1.8 with 10% hydrochloric acid and 5 g of SnCl are metered in₄x5H₂O and 41 ml of hydrochloric acid (20%). 105 ml of TiCl are then slowly metered in at the same pH₄Solution (400 g/l TiCl₄). Then 5 g of SnCl is added₄x5H₂O and 41 ml hydrochloric acid (20%). In each case, the pH was maintained at 1.8 using 32% sodium hydroxide solution. The pH is subsequently adjusted to 2.8 again with the aid of sodium hydroxide solution. Finally, 650 ml of FeCl were added in parallel₃Aqueous solution (w (fe) ═ 7%) and 499 ml of TiCl₄Aqueous solution (200 g TiCl)₄/l) and titrated simultaneously with sodium hydroxide solution (w ═ 10%) to apply the outermost layer. After stirring at pH 3.0 for an additional 0.5 hours, the coated mica substrate was filtered off, washed and dried at 110 ℃ for 16 hours. Finally, the effect pigments obtained in this way were calcined at 850 ℃ for 0.5 h and sieved.

A temperature-stable, golden multilayer pigment having high brightness and good hiding power is obtained.

Example 3

100 grams of natural mica with a particle size of less than 15 microns was heated to 80C in 2 liters of deionized water and stirred. When this temperature had been reached, 53 g of TiCl were added at a pH of 1.8₄Solution (400 g/l TiCl₄) Metered in, during which the pH is kept constant with 32% sodium hydroxide solution. The pH is subsequently adjusted to 2.8 with the aid of sodium hydroxide solution, and 640 ml of FeCl are added simultaneously at this pH and 75 ℃₃Aqueous solution (w (fe) ═ 7%) and 501 ml of TiCl₄Aqueous solution (200 g TiCl)₄L). During the whole addition process, the pH value is kept constant by simultaneously dropwise adding 32% sodium hydroxide solutionAnd (6) changing. After stirring for a further 0.5 h, the pH was raised to 7.5 and 650 ml of an aqueous sodium silicate solution (13% by weight SiO) were slowly metered in at this pH₂) During this time, the pH was kept constant with 10% hydrochloric acid. After stirring for a further 0.5 h, the pH is lowered to 1.8 with 10% hydrochloric acid and 5 g of SnCl are metered in₄x5H₂O and 41 ml of hydrochloric acid (20%). 105 ml of TiCl are then slowly metered in at the same pH₄Solution (400 g/l TiCl₄). Then 5 g of SnCl is added₄x5H₂O and 41 ml hydrochloric acid (20%). In each case, the pH was maintained at 1.8 using 32% sodium hydroxide solution. The pH is subsequently adjusted to 2.8 again with the aid of sodium hydroxide solution. Finally, 650 ml of FeCl were added in parallel₃Aqueous solution (w (fe) ═ 7%) and 499 ml of TiCl₄Aqueous solution (200 g TiCl)₄/l) and simultaneously titrated with sodium hydroxide solution (w ═ 10%) to apply the outermost layer. After stirring at pH 3.0 for an additional 0.5 hours, the coated mica substrate was filtered off, washed and dried at 110 ℃ for 16 hours. Finally, the effect pigments obtained in this way were calcined at 850 ℃ for 0.5 hours and then sieved.

A temperature-stable, golden multilayer pigment having high hiding power is obtained.

Example 4

100 grams of borosilicate glass flakes having a particle size of 20-200 microns were heated to 80C in 2 liters of deionized water and stirred. When this temperature had been reached, 38 g of TiCl were added at a pH of 1.8₄Solution (400 g/l TiCl₄) Metered in, during which the pH is kept constant using 32% sodium hydroxide solution. The pH is subsequently adjusted to 2.8 by means of sodium hydroxide solution, at which pH and 75 ℃ 508 ml of FeCl are simultaneously added₃Aqueous solution (w (fe) ═ 7%) and 431 ml of TiCl₄Aqueous solution (200 g TiCl)₄L). The pH was maintained throughout the addition by the simultaneous dropwise addition of 32% sodium hydroxide solution. After stirring for 0.5 h, the pH was raised to 7.5 and 650 ml of an aqueous sodium silicate solution (13% by weight SiO) were slowly metered in at this pH₂) During this time, the pH was kept constant with 10% hydrochloric acid. After stirring for a further 0.5 h, the pH is lowered to 1.8 with 10% hydrochloric acid and 5 g of SnCl are metered in₄x5H₂O and 41 ml of hydrochloric acid (20%). 105 ml of TiCl are then slowly metered in at the same pH₄Solution (400 g/l TiCl₄). Then adding 5 g SnCl₄x5H₂O and 41 ml hydrochloric acid (20%). In each case, the pH was maintained at 1.8 using 32% sodium hydroxide solution. The pH is subsequently adjusted to 2.8 again with the aid of sodium hydroxide solution. Finally, 650 ml of FeCl were added in parallel₃Aqueous solution (w (fe) ═ 7%) and 499 ml of TiCl₄Aqueous solution (200 g TiCl)₄/l) and simultaneously titrated with sodium hydroxide solution (w ═ 10%) to apply the outermost layer. After stirring at a pH of 3.0 for a further 0.5 h, the glass flakes coated in this way were filtered off, washed and dried at 110 ℃ for 16 h. Finally, the effect pigments were calcined at 850 ℃ for 0.5 h and sieved.

A temperature-stable, gold-coloured multilayer pigment is obtained with a very strong glittering effect.

Example 5

100 grams of silica flakes having a particle size of 10-40 microns were heated to 80C in 2 liters of deionized water and stirred. When this temperature had been reached, 44 g of TiCl were metered in at a pH of 1.8₄Solution (400 g/l TiCl₄) During this time, the pH was kept constant with 32% sodium hydroxide solution. The pH is subsequently adjusted to 2.8 with the aid of sodium hydroxide solution, and 600 ml of FeCl are added simultaneously at this pH and 75 ℃₃Aqueous solution (w (fe) ═ 7%) and 462 ml of TiCl₄Aqueous solution (200 g TiCl)₄L). The pH was maintained throughout the addition by the simultaneous dropwise addition of 32% sodium hydroxide solution. After stirring for a further 0.5 h, the pH was raised to 7.5 and 650 ml of an aqueous sodium silicate solution (13% by weight SiO) were slowly metered in at this pH₂) During this time, the pH was kept constant with 10% hydrochloric acid. After stirring for a further 0.5 h, the pH is lowered to 1.8 with 10% hydrochloric acid and 5 g are then metered inSnCl₄x5H₂O and 41 ml of hydrochloric acid (20%). 105 ml of TiCl are then slowly metered in at the same pH₄Solution (400 g/l TiCl₄). Then further adding 5 g SnCl₄x5H₂O and 41 ml hydrochloric acid (20%). In each case, the pH was maintained at 1.8 using 32% sodium hydroxide solution. The pH is subsequently adjusted to 2.8 again with the aid of sodium hydroxide solution. Finally, 650 ml of FeCl were added in parallel₃Aqueous solution (w (fe) ═ 7%) and 499 ml of TiCl₄Aqueous solution (200 g TiCl)₄/l) and titrated simultaneously with sodium hydroxide solution (w ═ 10%) to apply the outermost layer. After stirring for a further 0.5 h at a pH of 3.0, the SiO coated in this way is applied₂The flakes were filtered off, washed and dried at 110 ℃ for 16 hours. Finally, the effect pigments were calcined at 850 ℃ for 0.5 h and sieved.

A temperature-stable, golden multilayer pigment having high brightness and good hiding power is obtained.

Example 6

100 grams of synthetic mica having a particle size of 10-40 microns was heated to 80C in 2 liters of deionized water and stirred. When this temperature had been reached, 44 g of TiCl were added at a pH of 1.8₄Solution (400 g/l TiCl)₄) Metered in, during which the pH is kept constant with 32% sodium hydroxide solution. The pH is subsequently adjusted to 2.8 with the aid of sodium hydroxide solution, and 600 ml of FeCl are added simultaneously at this pH and 75 ℃₃Aqueous solution (w (fe) ═ 7%) and 462 ml of TiCl₄Aqueous solution (200 g TiCl)₄Per liter). The pH was maintained throughout the addition by the simultaneous dropwise addition of 32% sodium hydroxide solution. After stirring for 0.5 h, the pH was raised to 7.5 and 650 ml of an aqueous sodium silicate solution (13% by weight SiO) were slowly metered in at this pH₂) During this time, the pH was kept constant with 10% hydrochloric acid. After stirring for a further 0.5 h, the pH is lowered to 1.8 with 10% hydrochloric acid and 5 g of SnCl are metered in₄x5H₂O and 41 ml of hydrochloric acid (20%). 105 ml of TiCl are then slowly metered in at the same pH₄Solution (400 g/l TiCl₄). Then adding 5 g SnCl₄x5H₂O and 41 ml hydrochloric acid (20%). In each case, the pH was maintained at 1.8 using 32% sodium hydroxide solution. The pH is subsequently adjusted to 2.8 again with the aid of sodium hydroxide solution. Finally, 650 ml of FeCl were added in parallel₃Aqueous solution (w (fe) ═ 7%) and 499 ml of TiCl₄Aqueous solution (200 g TiCl)₄/l) and simultaneous titration with sodium hydroxide solution (w ═ 10%) were carried out to coat the outermost layer. After stirring at pH 3.0 for an additional 0.5 hours, the coated mica substrate was filtered off, washed and dried at 110 ℃ for 16 hours. Finally, the effect pigments obtained in this way were calcined at 850 ℃ for 0.5 h and sieved.

A temperature-stable, golden multilayer pigment having high brightness and moderate hiding power is obtained.

Example 7

100 g of talc having a particle size of less than 10 μm are heated to 80 ℃ in 2 l of deionized water and stirred. When this temperature had been reached, 44 g of TiCl were metered in at a pH of 1.8₄Solution (400 g/l TiCl₄) During this time, the pH was kept constant with 32% sodium hydroxide solution. The pH is subsequently adjusted to 2.8 with the aid of sodium hydroxide solution, and 600 ml of FeCl are added simultaneously at this pH and 75 ℃₃Aqueous solution (w (fe) ═ 7%) and 462 ml of TiCl₄Aqueous solution (200 g TiCl)₄L). The pH was maintained throughout the addition by the simultaneous dropwise addition of 32% sodium hydroxide solution. After stirring for 0.5 h, the pH was raised to 7.5 and 650 ml of an aqueous sodium silicate solution (13% by weight SiO) were slowly metered in at this pH₂) The pH was kept constant during this process with 10% hydrochloric acid. After stirring for a further 0.5 h, the pH is lowered to 1.8 with 10% hydrochloric acid and 5 g of SnCl are metered in₄x5H₂O and 41 ml of hydrochloric acid (20%). 105 ml of TiCl are then slowly metered in at the same pH₄Solution (400 g/l TiCl₄). Then adding 5 g SnCl₄x5H₂O and 41 ml hydrochloric acid (20%) And (3) forming a solution. In each case, the pH was maintained at 1.8 using 32% sodium hydroxide solution. The pH is subsequently adjusted to 2.8 again with the aid of sodium hydroxide solution. Finally, 650 ml of FeCl were added in parallel₃Aqueous solution (w (fe) ═ 7%) and 499 ml of TiCl₄Aqueous solution (200 g TiCl)₄/l) and simultaneously titrated with sodium hydroxide solution (w ═ 10%) to apply the outermost layer. After stirring for a further 0.5 h at a pH of 3.0, the talc flakes coated in this way were filtered off, washed and dried at 110 ℃ for 16 h. Finally, the effect pigments obtained in this way were calcined at 850 ℃ for 0.5 h and sieved.

A temperature-stable, golden multilayer pigment having high hiding power is obtained.

Example 8

100 grams of natural mica with a particle size of 20-180 microns was heated to 80C in 2 liters of deionized water and stirred. When this temperature had been reached, 38 g of TiCl were added at a pH of 1.8₄Solution (400 g/l TiCl₄) Metered in, during which the pH is kept constant using 32% sodium hydroxide solution. The pH is subsequently adjusted to 2.8 by means of sodium hydroxide solution, at which pH and 75 ℃ 508 ml of FeCl are simultaneously added₃Aqueous solution (w (fe) ═ 7%) and 431 ml of TiCl₄Aqueous solution (200 g/l TiCl)₄). The pH was maintained throughout the addition by the simultaneous dropwise addition of 32% sodium hydroxide solution. After stirring for 0.5 h, the pH was raised to 7.5 and 650 ml of an aqueous sodium silicate solution (13% by weight SiO) were slowly metered in at this pH₂) During this time, the pH was kept constant with 10% hydrochloric acid. After stirring for a further 0.5 h, the pH is lowered to 1.8 with 10% hydrochloric acid and 5 g of SnCl are metered in₄x5H₂O and 41 ml of hydrochloric acid (20%). 105 ml of TiCl are then slowly metered in at the same pH₄Solution (400 g/l TiCl₄). Then further adding 5 g SnCl₄x5H₂O and 41 ml hydrochloric acid (20%). In each case, the pH was maintained at 1.8 using 32% sodium hydroxide solution. The pH is subsequently brought again by means of sodium hydroxide solutionThe value was adjusted to 2.8. Finally, 650 ml of FeCl were added in parallel₃Aqueous solution (w (fe) ═ 7%) and 499 ml of TiCl₄Aqueous solution (200 g TiCl)₄/l) and simultaneously titrated with sodium hydroxide solution (w ═ 10%) to apply the outermost layer. After stirring at pH 3.0 for a further 0.5 hours, the coated mica substrate was filtered off, washed and dried at 110 ℃ for 16 hours. Finally, the effect pigments were calcined at 850 ℃ for 0.5 h and sieved.

A temperature-stable, golden multilayer pigment with a strong glittering effect is obtained.

Examples of the use

Process description for decorating ceramic workpieces

A-ceramic substrate

B-glaze

C-glaze

D-decoration/application

E-firing

A ═ unfired, pre-fired (green), glazed porcelain stoneware tile, stoneware/pottery tile, porcelain (e.g. hard porcelain, soft porcelain, fine porcelain, bone porcelain, celadon, stoneware, pottery).

TABLE 1

B ═ commercially available glaze, has a variety of functions such as hiding the color of the substrate, affecting chemical and physical reactions, improving the adhesion between the glaze and the substrate.

C-for example commercially available glazes, glazes with effect pigments, coloured glazes

For example rotary and planar screen printing (directly or indirectly by means of decals), pad printing, spraying, (hand) painting, dipping, waterfall, airless spraying, any application with a decorative powder (for example Vetrosa sand), for example preprinted decals, followed by spreading with decorative powder and finally removal by suction or blowing.

Table 2: administration of

Example application

1 direct rotary screen printing

2 direct planar Screen printing

Indirect rotary screen printing by decals

Indirect flat screen printing by decals

5 blanket printing

6 spray coating

7 (hand) drawing

8 Dip coating

9 waterfall type

10 airless spray coating

11 application of any decorative powder (for example Vetrosa sand), for example preprinted stickers, followed by spreading with decorative powder and finally removal by suction or blowing.

In the case of point D, the decoration can preferably have, in addition to the ceramic colour, one or more preprints (hereinafter referred to as underlayers), which can be carried out over all or part of the area. The latter can give rise to interesting effects (relief printing). The gloss of the pigmented enamel can be influenced by the choice of the backing layer. The backing layer may be pigmented with inorganic pigments and effect pigments.

Table 3: examples of liquid Metal decorative formulations

Such as Sicer STD450-76AT or Torrecid EPS06321A

Pigment the effect pigments of examples 1 to 8

E.g., Ferro-221-ME/80850/80840, siser-SM 112/SM114/SM140,

zschimmer & Schwarz-WB110, CMC thickener

Table 4: examples of liner formulations

E ═ firing can be carried out different times, at different temperatures and temperature profiles, or between applications. The furnace atmosphere also has an influence on the final effect, and the more oxygen is in the firing process, the better the effect is.

The points a-E need not all be present in use and may be omitted or replaced as the case may be. In general, the individual points A-E can be combined as desired and/or can also be used twice to achieve the stated effect.

All combinations of A-E (tables) can be used to produce liquid metal effects with the effect pigments according to examples 1-8. Fig. 3 schematically depicts a possible combination.

In addition, in addition to the effect pigments of examples 1 to 8, the commercially available effect pigments shown below were similarly tested in the combination A to E:

Kuncai KC305(Kuncai)

Kuncai KC306

Kuncai KC307

Kuncai KC300

Kuncai KC3501

Kunwei KW302

Mearlin Aztec Gold(Engelhard)

BASF majestic gold(BASF)

BASF Symic OEM Medium Space Gold

Mearlin majestic gold

Sudarshan bright gold Lot 186

CQV chaos super gold(C-603S)

CQV blondiee satin gold

CQV 6001S

Oxen 3311

305(Merck KGaA)

306(Merck KGaA)

326(Merck KGaA)

Kuncai KC302

Kuncai KC303

Oxen 307

Pritty Iridisium 3325

Leonis Gold(Merck KGaA)

Cosmic Gold(Merck KGaA)

the liquid metallic effect can only be produced with the effect pigments of examples 1 to 8, since only these pigments crack during firing and form in situ a glossy glaze with a liquid metallic effect.

Screen printing-example a 1: screen-printing application with underlayer, indirect on fine porcelain (applique)

Materials:

screen printing "lining formulations" according to table 4.

-screen printing a "liquid metal decorating formulation" according to table 3.

The backing layer is preprinted on a decal paper and intermediate dried at 0-40 ℃ until wipe resistant. The decorative paste is then printed in register on the backing layer. Then intermediate drying is carried out again at 0-40 ℃ until wiping resistance is achieved. The cover (Ferro 80450) was then printed and dried again at 0-40 ℃ until resistant to wiping.

The finished applique was separated with the aid of water and applied to fine porcelain (dish from Villeroy & Boch) and finally fired at 1060 ℃ for a3 minute hold time.

Screen printing-example a 2: screen printing with a lining directly on porcelain stoneware tile

Materials:

screen printing "lining formulations" according to table 4.

-screen printing a "liquid metal decorating formulation" according to table 3.

Pre-printing the lining on porcelain stoneware tiles, and performing intermediate drying at 0-40 ℃ until the ceramic stoneware tiles are resistant to wiping. The decorative paste is then printed in an overlapping manner on the backing layer. Drying is then carried out again at 0-40 ℃ until resistance to wiping. Finally, firing was carried out at 1050 ℃ and 10 minutes holding time. The overprinting of the decorative layer on the backing layer produces a relief effect comprising matte areas and glossy areas.

Screen printing-example a 3: screen printing application with pre-fired lining directly on ceramic tiles

Materials:

screen printing "lining formulations" according to table 4.

-screen printing a "liquid metal decorating formulation" according to table 3.

The lining is preprinted on a ceramic tile and intermediate dried at 0-40 ℃ until resistant to rubbing, and then fired at 1050 ℃ for a10 minute hold time. The decorative paste is then printed in an overlapping manner on the pre-fired backing layer. Drying is then carried out again at 0-40 ℃ until resistance to wiping. Finally, firing was carried out at 1050 ℃ and 10 minutes holding time. The overprinting of the decorative layer on the backing layer produces a relief effect comprising matte areas (no backing layer) and glossy areas (backing layer).

Screen printing-example a 4: indirect screen printing application with underlayers on additional decals

Materials:

screen printing "lining formulations" according to table 4.

-screen printing a "liquid metal decorating formulation" according to table 3.

The backing layer is printed on a decal paper and intermediate dried at 0-40 ℃ until wipe-resistant. The cover (Ferro 80450) was then printed and dried again at 0-40 ℃ until resistant to wiping. The decorative paste is printed on a decal paper and intermediate dried at 0-40 ℃ until resistant to rubbing. The cover (Ferro 80450) was then blanket printed and dried again at 0-40 ℃ until resistant to wiping.

The finished, lined applique was separated by water and applied to hard porcelain. The finished applique bearing the decorative colour was separated by water and applied to the liner applique on the hard porcelain and finally fired at 1115C for 3 minutes.

Screen printing-example a 5: glazed plain tile and direct screen-printing application on unfired glaze

Materials:

screen printing "lining formulations" according to table 4.

-screen printing a "liquid metal decorating formulation" according to table 3.

The pre-fired plain brick is glazed and then glazed with a liner. The screen printed "liquid metal decorative formulation" was then printed over the unfired glaze.

The coated, glazed and printed tile was then fired at 1090C ° [ voided, lacuna ] for 8 minutes.

Screen printing-example a 6: glazed unfired bricks (greenware) and direct screen-printing application on the unfired glaze

Materials:

screen printing "lining formulations" according to table 4.

-screen printing a "liquid metal decorating formulation" according to table 3.

The unfired tile is glazed and then glazed with a backing layer. The screen printed "liquid metal decorating formulation" was then printed over the unfired glaze.

The coated, glazed and printed tile was then fired at 1090C ° [ voided, lacuna ] for 8 minutes.

Offset roll printing-example a 7: glazed unfired bricks (greenware) and direct offset-printing application of the unfired glaze

Materials:

screen printing "lining formulations" according to table 4.

-screen printing a "liquid metal decorating formulation" according to table 3.

The unfired tile is glazed and then glazed with a backing layer. The "liquid metal decorating formulation" printed in a roll was then printed over the unfired glaze.

The coated, glazed and printed tile was then fired at 1090C ° [ voided, lacuna ] for 8 minutes.

Offset roll printing-example 8: glazed unfired bricks (greenware) and direct offset printing application of unfired glaze with interliner interlayer

Materials:

screen printing "lining formulations" according to table 4.

-screen printing a "liquid metal decorating formulation" according to table 3.

The unfired tile is glazed and then glazed with a commercially available glaze. The offset printed under-layer is then printed, followed by the offset printed "liquid metal decorative formulation" being printed over the unfired glaze containing the under-layer.

The coated, glazed and double printed tile was then fired at 1100C ° [ voided, lacuna ] for 8 minutes.

Offset roll printing-example a 9: glazed pre-fired tile (biscuit) bat and direct offset pad-printing application of unfired glaze with interliner interlayer

Materials:

screen printing "lining formulations" according to table 4.

-screen printing a "liquid metal decorating formulation" according to table 3.

Glazing the pre-fired brick and then glazing the glaze. The offset printed liner is then printed, followed by the offset printed "liquid metal decorative formulation" being printed over the unfired liner-containing glaze.

The coated, glazed and double printed tile was then fired at 1040C ° [ voided, lacuna ] for 10 minutes.

Spray-example a 10: glazed unfired bricks (greenware) and spray-coating with effect glaze

Materials:

screen printing "lining formulations" according to table 4.

-screen printing a "liquid metal decorating formulation" according to table 3.

The unfired tile is glazed and subsequently glazed with a "liquid metal decorating formulation". The coated, glazed and sprayed tile was then fired at 1090C ° [ voided, lacuna ] for 8 minutes.

The fired effect frits with the pigment/glass frit mixtures according to the invention are characterized by a particularly high gloss and low flash value and exhibit the desired liquid metal effect. Gloss is measured using Rhopoint IQ mini 2.0 (goniophotometer) [ void, lacuna ]. The liquid metal enamel is characterized by the following gloss values:

fired effect glazes are characterized by a particularly high gloss and low flash value. Gloss was measured using Rhopoint IQ mini 2.0 (goniophotometer). The liquid metal enamel is characterized by the following gloss values:

evaluation of liquid Metal Effect	Gloss value (20 degree)	Peak gloss value Rspec
			Is excellent in color	>140	≥28
Is excellent in	>120	≥25
			Good effect	>100	≥20

Flashes (shinks) were measured with a BYK mac gauge. At illumination angles of 45 ° and 75 °, the sparkle here is below the measurable range. Irregularities in the glaze result in measurements of up to 2(Sa and Si) at 15 ° illumination angle. However, even so, the SG value is 0.