KR20220003011A - Pigment/frit mixture - Google Patents

Abstract

The present invention relates to a frit or frit mixture comprising an effect pigment for ceramic glazes which is stable above 1000° C. and produces a liquid-metal effect in the glaze.

Description

Pigment/frit mixture

The present invention relates to a frit or frit mixture comprising an effect pigment for a ceramic glaze that is stable above 900° C. and produces a liquid-metal effect in the ceramic glaze.

Ceramic, metallic or glass-like materials are often decorated with effect pigments. For this purpose, the effect pigment is mixed with the so-called glass frit/flux and applied to the workpiece to be decorated by the medium. The medium depends on the type of application. For screen printing, for example, it may be a screen printing medium, for spray applications it may be a sprayable binder mixture, or for immersion applications it may be a mating slip. The medium is used only for application and has little relevance with regard to coloration. It is common to all methods that the applied decorative layer is finally fired to form a glass-like layer surrounding the effect pigment on the workpiece. The organic components (medium/binder/slip, etc.) decompose during the firing operation and the glass frit/flux becomes fluid. Thus, a unit is formed from a powder mixture consisting of frit powder and effect pigment. A composite layer of effect pigments embedded in a continuous glass matrix is formed.

The use of golden effect pigments based on flake-form substrates to achieve a shiny pearlescent or metallic effect in ceramic glazes is known, for example, from DE 10 2015 013 400 A1 and CN 101462895A.

Matte and satin glazes or glazes with metallic glitter are known, for example, from DE 39 32 424 C1, GB 2 096 592 A, US 5,783,506, US 4,353,991, EP 0 419843 A1.

The known high-gloss and non-glossy surfaces from polished metals are prevented by the rigid flake-like structure of the effect pigments, along with imperfect plane-parallel alignment of the pigment with the glaze surface. The resulting twinkle effect is, in many cases, entirely desirable. However, there is also a need for a high-gloss surface with a metallic feel without any shimmer, such as can be observed in the case of liquid-metals, beyond the currently available technical solutions. Accordingly, this effect is also referred to as the liquid-metal effect. Corresponding decorations (eg, gold rims of crockery) are generally known, for example. Surfaces of this type are not accessible using currently commercially available pigment-based decoration possibilities (the decorations have a satin and shiny appearance, or have metallic effects due to degradation of pigments in aggressive frit environments or during the firing process). is completely lost). Accordingly, in order to achieve the liquid-metal effect, very expensive noble metal preparations based on gold and platinum are used. This type of decoration is expensive and sensitive to washing in the dishwasher and use in the microwave. It is likewise impossible to use noble metal preparations in combination with pigments.

It is an object of the present invention to form, with the aid of effect pigments, a stable ceramic glaze with a high-gloss metallic-gold color and free from shimmer.

Surprisingly, it has been found that the use of special frits in combination with effect pigments having at least two pseudobrookite layers makes it possible to achieve glazes for ceramic surfaces having an appearance very close to shiny metallic surfaces (liquid-metal effect). lost. This type of combination is therefore suitable as a replacement for the gold-based pastes hitherto exclusively used for this purpose. Suitable frits are frits with precisely defined sodium oxide content. Effect pigments break down during firing, where the “breaking up” is that in a very aggressive medium that changes the refractive index of the glaze at the surface of the glaze and is responsible for the so-called liquid-metal effect, the metal oxides of the pigment are extremely small crystals means to form Thus, the actual color body is formed only in situ during firing, since the pigment is destroyed during firing, forming a lustrous glaze surface with a liquid-metal effect in situ. .

Accordingly, the present invention is characterized in that the frit comprises 3 to 7% sodium oxide and the effect pigment is based on a flake-form substrate having at least one following layer sequence on the surface of the substrate, It relates to the effect pigment/frit mixture:

(A) a high-index coating having a refractive index of n ≥ 1.8;

(B) a pseudobrookite layer optionally doped with one or more oxides in an amount of up to 10% by weight, based on layer (B),

(C) a low-index layer having an index of refraction of n < 1.8;

(D) a high-index layer having a refractive index of n ≥ 1.8 and consisting of at least two colorless metal-oxide layers,

(E) a pseudobrookite layer optionally doped with one or more oxides in an amount of up to 10% by weight, based on layer (E),

and optionally,

(F) Outer protective layer.

The effect pigment/frit mixture according to the invention provides a possible glaze for ceramic surfaces with an appearance very close to a shiny metallic surface (eg a gold surface) (liquid-metal effect).

Glazes comprising the pigment/frit mixture according to the invention are abrasion-resistant and stable against detergents and lacuna under normal mechanical loads during dishwashing. Also, it can be used without problems in a microwave oven.

The pigment/frit mixture may be used in porcelain, bone china and earthenware, in particular porcelain stoneware tile, stoneware tile, porcelain tile, hard porcelain, soft porcelain, fine china ( It is suitable for decoration of ceramic articles selected from the group of fine china), biscuit porcelain, porcelain porcelain and porcelain porcelain.

In a preferred embodiment, the pigment/frit mixture according to the invention consists of from 20 to 70% by weight of an effect pigment, and from 30 to 80% by weight of a frit, and optionally from 0 to 10% by weight of one or more additives, wherein The sum of pigments, frits and additives is 100%. A color body is achieved when the proportion by weight of the pigment in the effect pigment/frit mixture is preferably 20 to 70% by weight, very particularly preferably 25 to 60% by weight, based on the pigment/frit mixture.

An essential component of the effect pigment/frit mixture according to the invention is an effect pigment.

Suitable base substrates for the effect pigments according to the invention are translucent and transparent flake-shaped substrates. Preferred substrates are phyllosilicate flakes, SiC, TiC, WC, B ₄ C, BN, graphite, TiO ₂ and Fe ₂ O ₃ flakes, doped or undoped Al ₂ O ₃ flakes, doped or undoped glass flakes. , doped or undoped SiO ₂ flakes, TiO ₂ flakes, BiOCl and mixtures thereof. From the group of phyllosilicates, natural and synthetic mica flakes, muscovite, talc and kaolin are particularly preferred. The synthetic mica used as substrate is preferably fluorophlogopite or Zn phlogopite.

The glass flakes may consist of any type of glass known to the person skilled in the art as long as it is temperature-stable in the firing range used. Suitable glasses are, for example, quartz, A glass, E glass, C glass, ECR glass, recycled glass, alkali metal borate glass, alkali metal silicate glass, borosilicate glass, Duran® glass, laboratory equipment. glass or optical glass.

The refractive index of the glass flakes is preferably 1.45 to 1.80, in particular 1.50 to 1.70. The glass substrate is particularly preferably C glass, ECR glass or borosilicate glass.

Synthetic substrate flakes such as glass flakes, SiO ₂ flakes, Al ₂ O ₃ flakes may be doped or undoped. If doped, the doping is preferably Al, N, B, Ti, Zr, Si, In, Sn or Zn or mixtures thereof. In addition, additional ions from the group of transition metals (V, Cr, Mn, Fe, Co, Ni, Cu, Y, Nb, Mo, Hf, Sb, Ta, W) and ions from the group of lanthanides are plated can act as a trough.

In _{the case of Al 2} O ₃ , the substrate is preferably undoped or doped with TiO ₂ , ZrO ₂ or ZnO. The Al ₂ O ₃ flakes are preferably corundum. Suitable Al ₂ O ₃ flakes are preferably doped or undoped α-Al ₂ O ₃ flakes, in particular α-Al ₂ O ₃ flakes _{doped with TiO 2} or ZrO _{2 .}

If the substrate is doped, the doping ratio is preferably 0.01 to 5% by weight, in particular 0.10 to 3% by weight, based on the substrate.

The size of the base substrate itself is not critical and can be tailored to a particular application. In general, the flake-shaped substrate has a thickness of 0.05 to 5 μm, in particular 0.1 to 4.5 μm.

It is also possible to use substrates with different particle sizes. Particular preference is given to mixtures of mica fractions of mica N (10-60 μm), mica F (5-20 μm) and/or mica M (less than 15 μm). Furthermore, N and S fractions (10 to 130 μm) and F and S fractions (5 to 130 μm) are preferred.

A typical example of a particle-size distribution (determined using a Malvern Mastersizer 2000) is:

D ₁₀ : 1 to 50 μm, in particular 2 to 45 μm, very particularly preferably 5 to 40 μm,

D ₅₀ : 7 to 275 μm, in particular 10-200 μm, very particularly preferably 15 to 150 μm,

D ₉₀ : 15 to 500 μm, in particular 25 to 400 μm, very particularly preferably 50 to 200 μm.

As used herein, "high-index" means a refractive index of ≧1.8, while “low-index” means a refractive index of <1.8.

The layer sequences (A) to (E) or (A) to (F) of the effect pigments according to the invention are essential for the stability and optical properties of the pigments.

The layer (A) is a high-index layer having a refractive index of n≧1.8, preferably n≧2.0. The layer (A) may be absorptive in colorless or visible wavelength light. The layer (A) preferably consists of a metal-oxide or a metal-oxide mixture. The metal-oxide is preferably TiO ₂ , ZrO ₂ , ZnO, SnO ₂ , Cr ₂ O ₃ , Ce ₂ O ₃ , BiOCl, Fe ₂ O ₃ , Fe ₃ O ₄ , FeO(OH), Ti suboxide ( _{Partially reduced TiO 2} and lower oxides having oxidation states of less than 4 to 2, such as Ti ₃ O ₅ , Ti ₂ O ₃ to TiO), titanium oxynitride and titanium nitride, CoO, Co ₂ O ₃ , Co ₃ O ₄ , VO ₂ , V ₂ O ₃ , NiO, WO ₃ , MnO, Mn ₂ O ₃ and mixtures of these oxides. Said layer (A) preferably consists of TiO ₂ , Fe ₂ O ₃ , Cr ₂ O ₃ or SnO ₂ .

Said layer (A) preferably has a layer thickness of 1 to 15 nm, in particular 1 to 10 nm, very particularly preferably 1 to 5 nm.

The pseudobrookite layers (B) and (E) may be the same or different. The layers are preferably identical in composition. The pseudobrookite layer preferably consists entirely _{of Fe 2} TiO _{5 .} However, the Fe ₂ TiO ₅ may be slightly high- or low-stoichiometric due to slight fluctuations in the Fe/Ti ratio and the resulting lattice vacancies.

The layers can be produced by simultaneous addition and precipitation of Fe- and Ti-containing salt solutions or by co-precipitation from a single solution containing Fe and Ti salts.

The pseudobrookite layer should preferably consist of 100% crystalline pseudobrookite.

Said layers (B) and (E) may optionally be further doped with one or more oxides or oxide mixtures, preferably metal oxides, in order to increase the stability and/or color intensity. The oxide is preferably of Al ₂ O ₃ , Ce ₂ O ₃ , B ₂ O ₃ , ZrO ₂ , SnO ₂ , Cr ₂ O ₃ , CoO, Co ₂ O ₃ , Co ₃ O ₄ , and Mn ₂ O ₃ . selected from the group. The proportion by weight of oxides or oxide mixtures in the pseudobrookite layer, based on the layers (B) and (E), is preferably up to 5% by weight, in particular from 1 to 5% by weight, very particularly preferably from 1 to 3% by weight.

Said layers (B) and (E) preferably each independently of one another have a layer thickness in the range from 60 to 120 nm, in particular from 70 to 110 nm, very particularly preferably from 80 to 100 nm.

It is of particular importance for the stability of the effect pigments according to the invention that the layers (B) and (E) are separated from each other by a separating layer (C) and a separating layer (D). The distance between the layers (B) and (E) should preferably be between 40 and 100 nm, in particular between 45 and 90 nm, very particularly preferably between 50 and 80 nm.

The low-index layer (C) having a refractive index of n < 1.8, preferably n < 1.7 is preferably SiO ₂ , MgO*SiO ₂ , CaO*SiO ₂ , Al ₂ O ₃ *SiO ₂ , B ₂ O ₃ * SiO ₂ or a mixture of these compounds. Furthermore, the silicate layer may be doped with additional alkaline-earth or alkali-metal ions. Said layer (C) is preferably a "silicate" layer. Said layer (C) very particularly preferably consists of doped or undoped SiO ₂ .

Said layer (C) preferably has a layer thickness of 40 to 90 nm, in particular 40 to 70 nm, very particularly preferably 50 to 60 nm.

The high-index coating of layer (D) having a refractive index of n≧1.8, preferably n≧2.0 consists of at least two colorless metal-oxide layers. The layer (D) preferably consists of two or three colorless metal-oxide layers. The metal-oxide is preferably selected from the group of SnO ₂ , TiO ₂ , Al ₂ O ₃ , Fe ₂ O ₃ , Cr ₂ O ₃ or mixtures thereof.

The coating of said layer (D) preferably comprises:

The following metal-oxide layers (D1) and (D2):

(D1) SnO ₂ layer, and

(D2) TiO ₂ layer;

or

The following metal-oxide layers (D1), (D2) and (D3):

(D1) Al ₂ O ₃ layers,

(D2) TiO ₂ layer, and

(D3) Al ₂ O ₃ layer;

or

(D1) SnO ₂ layer,

(D2) TiO ₂ layer, and

(D3) SnO ₂ layer

is made of

The coating of said layer (D) preferably has a layer thickness of 10 to 25 nm, in particular 11 to 21 nm, very particularly preferably 12 to 17 nm. The sum of all layer thicknesses of the individual metal-oxide layers (D1), (D2), (D3), and any additional coating layers of layer (D) must not exceed 25 nm.

In order that the layers (C) and (D) can act as separation layers and thus contribute to a reduced phase reaction between the individual pseudobrookite layers (B) and (E), the layers (C) and (D) ) should not exceed the thickness range of 120 nm, preferably in the range from 50 to 115 nm, in particular from 51 to 91 nm, very particularly preferably from 62 to 77 nm.

When the layer (A) or (D) _{consists of TiO 2} , the TiO ₂ may be present as rutile or anatase modification.

Particularly preferred effect pigments have the structure:

- substrate + TiO ₂ + pseudobrookite + SiO ₂ + SnO ₂ + TiO ₂ + SnO ₂ + pseudobrookite,

- substrate + Fe ₂ O ₃ + pseudobrookite + SiO ₂ + SnO ₂ + TiO ₂ + SnO ₂ + pseudobrookite,

- substrate + Cr ₂ O ₃ + pseudobrookite + SiO ₂ + SnO ₂ + TiO ₂ + SnO ₂ + pseudobrookite,

- substrate + TiO ₂ + pseudobrookite + MgO*SiO ₂ + SnO ₂ + TiO ₂ + SnO ₂ + pseudobrookite,

- substrate + Fe ₂ O ₃ + pseudobrookite + MgO*SiO ₂ + SnO ₂ + TiO ₂ + SnO ₂ + pseudobrookite,

- substrate + Cr ₂ O ₃ + pseudobrookite + MgO*SiO ₂ + SnO ₂ + TiO ₂ + SnO ₂ + pseudobrookite,

- substrate + TiO ₂ + pseudobrookite + CaO*SiO ₂ + SnO ₂ + TiO ₂ + SnO ₂ + pseudobrookite,

- substrate + Fe ₂ O ₃ + pseudobrookite + CaO*SiO ₂ + SnO ₂ + TiO ₂ + SnO ₂ + pseudobrookite,

- substrate + Cr ₂ O ₃ + pseudobrookite + CaO*SiO ₂ + SnO ₂ + TiO ₂ + SnO ₂ + pseudobrookite,

- substrate + TiO ₂ + pseudobrookite + Al ₂ O ₃ *SiO ₂ + SnO ₂ + TiO ₂ + SnO ₂ + pseudobrookite,

- substrate + Fe ₂ O ₃ + pseudobrookite + Al ₂ O ₃ *SiO ₂ + SnO ₂ + TiO ₂ + SnO ₂ + pseudobrookite,

- substrate + Cr ₂ O ₃ + pseudobrookite + Al ₂ O ₃ *SiO ₂ + SnO ₂ + TiO ₂ + SnO ₂ + pseudobrookite,

- substrate + TiO ₂ + pseudobrookite + SiO ₂ + TiO ₂ + SnO ₂ + pseudobrookite,

- substrate + TiO ₂ + pseudobrookite + SiO ₂ + SnO ₂ + TiO ₂ + pseudobrookite,

- substrate + TiO ₂ + pseudobrookite + SiO ₂ + TiO ₂ + SnO ₂ + pseudobrookite + SnO ₂ ,

- substrate + TiO ₂ + pseudobrookite + SiO ₂ + SnO ₂ + TiO ₂ + pseudobrookite + SnO ₂ ,

- substrate + TiO ₂ + pseudobrookite + SiO ₂ + SnO ₂ + Fe ₂ O ₃ + SnO ₂ + pseudobrookite,

- substrate + TiO ₂ + pseudobrookite + SiO ₂ + SnO ₂ + Cr ₂ O ₃ + SnO ₂ + pseudobrookite, or

- substrate + TiO ₂ + pseudobrookite + SiO ₂ + Al ₂ O ₃ + TiO ₂ + Al ₂ O ₃ + pseudobrookite.

Very particularly preferred effect pigments have the following layer structure:

- natural mica flakes + TiO ₂ + pseudobrookite + SiO ₂ + SnO ₂ + TiO ₂ + SnO ₂ + pseudobrookite;

- natural mica flakes + Fe ₂ O ₃ + pseudobrookite + SiO ₂ + SnO ₂ + TiO ₂ + SnO ₂ + pseudobrookite,

- natural mica flakes + Cr ₂ O ₃ + pseudobrookite + SiO ₂ + SnO ₂ + TiO ₂ + SnO ₂ + pseudobrookite,

- natural mica flakes + TiO ₂ + pseudobrookite + MgO*SiO ₂ + SnO ₂ + TiO ₂ + SnO ₂ + pseudobrookite,

- natural mica flakes + Fe ₂ O ₃ + pseudobrookite + MgO*SiO ₂ + SnO ₂ + TiO ₂ + SnO ₂ + pseudobrookite,

- natural mica flakes + Cr ₂ O ₃ + pseudobrookite + MgO*SiO ₂ + SnO ₂ + TiO ₂ + SnO ₂ + pseudobrookite,

- natural mica flakes + TiO ₂ + pseudobrookite + CaO*SiO ₂ + SnO ₂ + TiO ₂ + SnO ₂ + pseudobrookite,

- natural mica flakes + Fe ₂ O ₃ + pseudobrookite + CaO*SiO ₂ + SnO ₂ + TiO ₂ + SnO ₂ + pseudobrookite,

- natural mica flakes + Cr ₂ O ₃ + pseudobrookite + CaO*SiO ₂ + SnO ₂ + TiO ₂ + SnO ₂ + pseudobrookite,

- natural mica flakes + TiO ₂ + pseudobrookite + Al ₂ O ₃ *SiO ₂ + SnO ₂ + TiO ₂ + SnO ₂ + pseudobrookite,

- natural mica flakes + Fe ₂ O ₃ + pseudobrookite + Al ₂ O ₃ *SiO ₂ + SnO ₂ + TiO ₂ + SnO ₂ + pseudobrookite,

- natural mica flakes + Cr ₂ O ₃ + pseudobrookite + Al ₂ O ₃ *SiO ₂ + SnO ₂ + TiO ₂ + SnO ₂ + pseudobrookite,

- natural mica flakes + TiO ₂ + pseudobrookite + SiO ₂ + TiO ₂ + SnO ₂ + pseudobrookite,

- natural mica flakes + TiO ₂ + pseudobrookite + SiO ₂ + SnO ₂ + TiO ₂ + pseudobrookite,

- natural mica flakes + TiO ₂ + pseudobrookite + SiO ₂ + TiO ₂ + SnO ₂ + pseudobrookite + SnO ₂ ,

- natural mica flakes + TiO ₂ + pseudobrookite + SiO ₂ + SnO ₂ + TiO ₂ + pseudobrookite + SnO ₂ ,

- natural mica flakes + TiO ₂ + pseudobrookite + SiO ₂ + SnO ₂ + Fe ₂ O ₃ + SnO ₂ + pseudobrookite,

- natural mica flakes + TiO ₂ + pseudobrookite + SiO ₂ + SnO ₂ + Cr ₂ O ₃ + SnO ₂ + pseudobrookite,

- natural mica flakes + TiO ₂ + pseudobrookite + SiO ₂ + Al ₂ O ₃ + TiO ₂ + Al ₂ O ₃ + pseudobrookite,

- synthetic mica flakes + TiO ₂ + pseudobrookite + SiO ₂ + SnO ₂ + TiO ₂ + SnO ₂ + pseudobrookite,

- synthetic mica flakes + Fe ₂ O ₃ + pseudobrookite + SiO ₂ + SnO ₂ + TiO ₂ + SnO ₂ + pseudobrookite,

- synthetic mica flakes + Cr ₂ O ₃ + pseudobrookite + SiO ₂ + SnO ₂ + TiO ₂ + SnO ₂ + pseudobrookite,

- synthetic mica flakes + TiO ₂ + pseudobrookite + MgO*SiO ₂ + SnO ₂ + TiO ₂ + SnO ₂ + pseudobrookite,

- synthetic mica flakes + Fe ₂ O ₃ + pseudobrookite + MgO*SiO ₂ + SnO ₂ + TiO ₂ + SnO ₂ + pseudobrookite,

- synthetic mica flakes + Cr ₂ O ₃ + pseudobrookite + MgO*SiO ₂ + SnO ₂ + TiO ₂ + SnO ₂ + pseudobrookite,

- synthetic mica flakes + TiO ₂ + pseudobrookite + CaO*SiO ₂ + SnO ₂ + TiO ₂ + SnO ₂ + pseudobrookite,

- synthetic mica flakes + Fe ₂ O ₃ + pseudobrookite + CaO*SiO ₂ + SnO ₂ + TiO ₂ + SnO ₂ + pseudobrookite,

- synthetic mica flakes + Cr ₂ O ₃ + pseudobrookite + CaO*SiO ₂ + SnO ₂ + TiO ₂ + SnO ₂ + pseudobrookite,

- synthetic mica flakes + TiO ₂ + pseudobrookite + Al ₂ O ₃ *SiO ₂ + SnO ₂ + TiO ₂ + SnO ₂ + pseudobrookite,

- synthetic mica flakes + Fe ₂ O ₃ + pseudobrookite + Al ₂ O ₃ *SiO ₂ + SnO ₂ + TiO ₂ + SnO ₂ + pseudobrookite,

- synthetic mica flakes + Cr ₂ O ₃ + pseudobrookite + Al ₂ O ₃ *SiO ₂ + SnO ₂ + TiO ₂ + SnO ₂ + pseudobrookite,

- synthetic mica flakes + TiO ₂ + pseudobrookite + SiO ₂ + TiO ₂ + SnO ₂ + pseudobrookite,

- synthetic mica flakes + TiO ₂ + pseudobrookite + SiO ₂ + SnO ₂ + TiO ₂ + pseudobrookite,

- synthetic mica flakes + TiO ₂ + pseudobrookite + SiO ₂ + TiO ₂ + SnO ₂ + pseudobrookite + SnO ₂ ,

- synthetic mica flakes + TiO ₂ + pseudobrookite + SiO ₂ + SnO ₂ + TiO ₂ + pseudobrookite + SnO ₂ ,

- synthetic mica flakes + TiO ₂ + pseudobrookite + SiO ₂ + SnO ₂ + Fe ₂ O ₃ + SnO ₂ + pseudobrookite,

- synthetic mica flakes + TiO ₂ + pseudobrookite + SiO ₂ + SnO ₂ + Cr ₂ O ₃ + SnO ₂ + pseudobrookite,

- synthetic mica flakes + TiO ₂ + pseudobrookite + SiO ₂ + Al ₂ O ₃ + TiO ₂ + Al ₂ O ₃ + pseudobrookite,

- Al ₂ O ₃ flakes + TiO ₂ + pseudobrookite + SiO ₂ + SnO ₂ + TiO ₂ + SnO ₂ + pseudobrookite,

- Al ₂ O ₃ flakes + Fe ₂ O ₃ + pseudobrookite + SiO ₂ + SnO ₂ + TiO ₂ + SnO ₂ + pseudobrookite,

- Al ₂ O ₃ flakes + Cr ₂ O ₃ + pseudobrookite + SiO ₂ + SnO ₂ + TiO ₂ + SnO ₂ + pseudobrookite,

- Al ₂ O ₃ flakes + TiO ₂ + pseudobrookite + MgO*SiO ₂ + SnO ₂ + TiO ₂ + SnO ₂ + pseudobrookite,

- Al ₂ O ₃ flakes + Fe ₂ O ₃ + pseudobrookite + MgO*SiO ₂ + SnO ₂ + TiO ₂ + SnO ₂ + pseudobrookite,

- Al ₂ O ₃ flakes + Cr ₂ O ₃ + pseudobrookite + MgO*SiO ₂ + SnO ₂ + TiO ₂ + SnO ₂ + pseudobrookite,

- Al ₂ O ₃ flakes + TiO ₂ + pseudobrookite + CaO*SiO ₂ + SnO ₂ + TiO ₂ + SnO ₂ + pseudobrookite,

- Al ₂ O ₃ flakes + Fe ₂ O ₃ + pseudobrookite + CaO*SiO ₂ + SnO ₂ + TiO ₂ + SnO ₂ + pseudobrookite,

- Al ₂ O ₃ flakes + Cr ₂ O ₃ + pseudobrookite + CaO*SiO ₂ + SnO ₂ + TiO ₂ + SnO ₂ + pseudobrookite,

- Al ₂ O ₃ flakes + TiO ₂ + pseudobrookite + Al ₂ O ₃ *SiO ₂ + SnO ₂ + TiO ₂ + SnO ₂ + pseudobrookite,

- Al ₂ O ₃ flakes + Fe ₂ O ₃ + pseudobrookite + Al ₂ O ₃ *SiO ₂ + SnO ₂ + TiO ₂ + SnO ₂ + pseudobrookite,

- Al ₂ O ₃ flakes + Cr ₂ O ₃ + pseudobrookite + Al ₂ O ₃ *SiO ₂ + SnO ₂ + TiO ₂ + SnO ₂ + pseudobrookite,

- Al ₂ O ₃ flakes + TiO ₂ + pseudobrookite + SiO ₂ + TiO ₂ + SnO ₂ + pseudobrookite,

- Al ₂ O ₃ flakes + TiO ₂ + pseudobrookite + SiO ₂ + SnO ₂ + TiO ₂ + pseudobrookite,

- Al ₂ O ₃ flakes + TiO ₂ + pseudobrookite + SiO ₂ + TiO ₂ + SnO ₂ + pseudobrookite + SnO ₂ ,

- Al ₂ O ₃ flakes + TiO ₂ + pseudobrookite + SiO ₂ + SnO ₂ + TiO ₂ + pseudobrookite + SnO ₂ ,

- Al ₂ O ₃ flakes + TiO ₂ + pseudobrookite + SiO ₂ + SnO ₂ + Fe ₂ O ₃ + SnO ₂ + pseudobrookite,

- Al ₂ O ₃ flakes + TiO ₂ + pseudobrookite + SiO ₂ + SnO ₂ + Cr ₂ O ₃ + SnO ₂ + pseudobrookite,

- Al ₂ O ₃ flakes + TiO ₂ + pseudobrookite + SiO ₂ + Al ₂ O ₃ + TiO ₂ + Al ₂ O ₃ + pseudobrookite,

- SiO ₂ flakes + TiO ₂ + pseudobrookite + SiO ₂ + SnO ₂ + TiO ₂ + SnO ₂ + pseudobrookite,

- SiO ₂ flakes + Fe ₂ O ₃ + pseudobrookite + SiO ₂ + SnO ₂ + TiO ₂ + SnO ₂ + pseudobrookite,

- SiO ₂ flakes + Cr ₂ O ₃ + pseudobrookite + SiO ₂ + SnO ₂ + TiO ₂ + SnO ₂ + pseudobrookite,

- SiO ₂ flakes + TiO ₂ + pseudobrookite + MgO*SiO ₂ + SnO ₂ + TiO ₂ + SnO ₂ + pseudobrookite,

- SiO ₂ flakes + Fe ₂ O ₃ + pseudobrookite + MgO*SiO ₂ + SnO ₂ + TiO ₂ + SnO ₂ + pseudobrookite,

- SiO ₂ flakes + Cr ₂ O ₃ + pseudobrookite + MgO*SiO ₂ + SnO ₂ + TiO ₂ + SnO ₂ + pseudobrookite,

- SiO ₂ flakes + TiO ₂ + pseudobrookite + CaO*SiO ₂ + SnO ₂ + TiO ₂ + SnO ₂ + pseudobrookite,

- SiO ₂ flakes + Fe ₂ O ₃ + pseudobrookite + CaO*SiO ₂ + SnO ₂ + TiO ₂ + SnO ₂ + pseudobrookite,

- SiO ₂ flakes + Cr ₂ O ₃ + pseudobrookite + CaO*SiO ₂ + SnO ₂ + TiO ₂ + SnO ₂ + pseudobrookite,

- SiO ₂ flakes + TiO ₂ + pseudobrookite + Al ₂ O ₃ *SiO ₂ + SnO ₂ + TiO ₂ + SnO ₂ + pseudobrookite,

- SiO ₂ flakes + Fe ₂ O ₃ + pseudobrookite + Al ₂ O ₃ *SiO ₂ + SnO ₂ + TiO ₂ + SnO ₂ + pseudobrookite,

- SiO ₂ flakes + Cr ₂ O ₃ + pseudobrookite + Al ₂ O ₃ *SiO ₂ + SnO ₂ + TiO ₂ + SnO ₂ + pseudobrookite,

- SiO ₂ flakes + TiO ₂ + pseudobrookite + SiO ₂ + TiO ₂ + SnO ₂ + pseudobrookite,

- SiO ₂ flakes + TiO ₂ + pseudobrookite + SiO ₂ + SnO ₂ + TiO ₂ + pseudobrookite,

- SiO ₂ flakes + TiO ₂ + pseudobrookite + SiO ₂ + TiO ₂ + SnO ₂ + pseudobrookite + SnO ₂ ,

- SiO ₂ flakes + TiO ₂ + pseudobrookite + SiO ₂ + SnO ₂ + TiO ₂ + pseudobrookite + SnO ₂ ,

- SiO ₂ flakes + TiO ₂ + pseudobrookite + SiO ₂ + SnO ₂ + Fe ₂ O ₃ + SnO ₂ + pseudobrookite,

- SiO ₂ flakes + TiO ₂ + pseudobrookite + SiO ₂ + SnO ₂ + Cr ₂ O ₃ + SnO ₂ + pseudobrookite, or

- SiO ₂ flakes + TiO ₂ + pseudobrookite + SiO ₂ + Al ₂ O ₃ + TiO ₂ + Al ₂ O ₃ + pseudobrookite.

The metal-oxide layer(s) is preferably applied by a wet-chemical method, it is possible to use wet-chemical coating methods developed for the production of pearlescent pigments, methods of this type being described, for example, in U.S. 3087828, U.S. 3087829, U.S. 3553001, DE 14 14 67 468, 19 19 59 988, DE 20 20 09 566, DE 22 22 14 545 DE 22 22 15 15 37 191 808 31 DE 1 37 298 DE 13 25 23 22 809, DE 31 31 51 343 DE 31 31 51 568 DE 31 31 51 355 DE32 32 11 602 DE 32 0 17 35 DE 196 18 0 568 Additional or other publications known to those skilled in the art EP 659 is described in

In the case of wet coating, the substrate flakes are suspended in water and one or more hydrolyzable metal salts are added at a pH suitable for hydrolysis, wherein the pH is such that metal oxides or metal oxide hydrates precipitate directly on the flakes without secondary precipitation occurring. chosen to be The pH is kept constant, usually by simultaneous metered addition of base and/or acid. The effect pigment is subsequently separated off, washed, dried and optionally calcined, wherein the calcination temperature can be optimized in each case for the coating present. In general, the calcination temperature is 250 to 1000 °C, preferably 350 to 900 °C. Optionally, the pigment can be separated off, dried and optionally calcined after application of the individual coatings and then re-suspended for precipitation of further layers.

For _{the application of the SiO 2} layer, the process described in DE 196 18 569 is preferably used. For the _{production of the SiO 2} layer, preferably a sodium water-glass solution or a potassium water-glass solution is used.

Furthermore, the coating can also be carried out by vapor phase coating in a fluidized bed reactor, wherein the processes proposed for the production of pearlescent pigments of, for example, EP 0 045 0 851 and EP 0 0 106 235 can be used correspondingly.

The hue of the pigment can be varied widely by various choices of the amount of coating or the thickness of the resulting layer. Fine tuning for a particular hue can be achieved beyond the pure selection of quantities by approaching the desired color with visual or measurement technique adjustments.

, Philips Technical Review, Vol. 44, No. 3, 81 ff.] 및 문헌[P.H. Harding J.C. Berg, J. Adhesion Sci. Technol. Vol. 11 No. 4, pp. 471-493]에 기재된 바와 같이 가능하다. 상기 층 (F)는 바람직하게는 SnO₂의 층이다.In order to increase light, moisture and weather stability, it is often recommended to treat the effect pigments according to the invention, depending on the area of application, with an inorganic or organic post-coating or post-treatment (layer (F) above). Suitable post-coatings or post-treatments are, for example, the methods described in DE-A 22 15 191, DE-A 31 51 354, DE-A 32 35 017 or DE-A 33 34 598. Said post-coating further increases the chemical and photochemical stability or simplifies the handling of the effect pigments, in particular their incorporation into various media. To improve wettability, dispersibility and/or compatibility with user media, _{a functional coating of SnO 2} , Al ₂ O ₃ or ZrO ₂ or mixtures thereof may be applied to the pigment surface. Furthermore, organic post-coating can be applied, for example with silane, for example EP 0090259, EP 0 634 459, WO 99/57204, WO 96/32446, WO 99/57204, US 5,759,255, US 5,571,851, WO 01/ 92425 or JJ Ponje

, Philips Technical Review, Vol. 44, No. 3, 81 ff.] and PH Harding JC Berg, J. Adhesion Sci. Technol. Vol. 11 No. 4, pp. 471-493]. Said layer (F) is preferably a layer of _{SnO 2 .}

A coating(s) herein is considered to mean the complete covering/sheathing of a flake-shaped substrate.

The optimal orientation of the color body in the glaze _{is supported by a Na 2} O-containing frit. The higher the proportion of pigment in the frit, preferably less than 30% by weight, the better the orientation of the desired color body is supported. The effect generally increases continuously by increasing the pigment concentration by at least 30 wt%, at least 50 wt%, at least 70 wt%.

In addition to the optimal alignment of the color bodies, temperature stability and stability to chemically highly reactive media (frit melts) play an important role in the application of pigment/frit mixtures. The use of Na ₂ O-containing frits significantly improves the temperature stability. The _{proportion of Na 2} O in the frit is 3 to 7% by weight, in particular 4 to 6.5% by weight, very particularly preferably 5 to 6% by weight, based on the frit.

Suitable commercially available frits include, in _{addition to Na 2} O, components common to frits (eg, Al ₂ O ₃ , SiO ₂ , B ₂ O ₃ , TiO ₂ , ZrO ₂ , Sb ₂ O ₃ , P _{2 ).} O ₅ , Hf ₂ O, Fe ₂ O ₃ , ZnO, PbO, alkali metal oxides such as Li ₂ O, K ₂ O; alkaline earth metal oxides such as CaO, BaO, MgO, SrO; and rare earth oxides).

A preferred frit is

- (Na ₂ O + K ₂ O + Li ₂ O) ≤ 10% by weight,

- Al ₂ O ₃ ≥ 4.5% by weight,

- SiO ₂ ≥ 45% by weight

wherein the total proportion of all components of the frit is 100%.

The frit mixture contains, as an additional component, 0 to 10% by weight, based on the pigment/frit mixture, of an inorganic coloring pigment clay, kaolin, bentonite or an organic component, in order to adjust the stability of the glaze slip. may include

The particles of the frit preferably have a particle size of 1 to 20 μm, in particular 3 to 15 μm, very particularly preferably 5 to 12 μm.

_{Suitable frits/fluxes having a Na 2} O ratio in the range of 3 to 7% by weight, based on the frit, are commercially available, for example from Ferro, Sicer or Zschimmer & Schwarz. do. By way of example and without limiting the number of frits/fluxes that can be used, the following frits are mentioned:

Cycer STDA450-76AT, Torrecid EPS06321A, Ferro 101911, 101915, 101600, 101650 840, Cycer-SM112/SM114/SM140.

The pigment/frit mixture is suitable for decoration of ceramic articles based on porcelain, bone china and porcelain.

Suitable workpieces for the pigment/frit mixture according to the invention are given in the table below.

The application of the pigment/frit mixture according to the invention to the workpiece is, for example,

- Direct rotary screen printing;

- Direct flat screen printing;

- Indirect rotary screen printing via decals

- Indirect flat screen printing via decals,

- rotocolor,

- spray application,

- (hand) painting,

- immersion,

- waterfall,

- Air-free spray application;

- optional application (eg pre-printed stickers) with decorative powder (eg Vetrosa grit), followed by scattering decoration powder on top, and finally removal by inhalation or insufflation can be performed.

The frit used in the pigment/frit mixture, or a frit similar in composition and melting behavior, is applied as an intermediate layer (the so-called “underlay”) between a ceramic or glaze and the pigment/frit mixture, which is particularly pronounced liquid-metal The effect is achieved. Both of these layers (lower layer and frit mixture) are applied separately, but then fired together.

The underlying layer and pigment/frit mixture may be applied to the glazed or non-glazed ceramic surface, for example by spray application, brush application, knife coating, screen printing and decaling. The total layer thickness measured after firing is between 5 and 30 μm depending on the application.

The firing temperature depends on the frit used. Typical firing temperatures for pigment/frit mixtures according to the invention are in the range from 950°C to 1150°C.

In order to change the color tone, stable inorganic color pigments or color pigments can be added to the pigment/frit mixture according to the invention. The proportion of the colored pigments is 0 to 30% by weight, in particular 0 to 15% by weight, very particularly preferably 0 to 10% by weight, based on the pigment/frit mixture. Suitable and stable color pigments are, for example, green chromium oxide pigments, black spinel pigments, yellow-brown rutile pigments, cadmium red and yellow, cobalt blue pigments. Colored pigments of this type are commercially available, for example, from Ferro and Shepard.

The fired effect glazes comprising the pigment/frit mixture according to the invention are characterized by a particularly high gloss in combination with a low sparkle value and exhibit the desired liquid-metal effect.

The invention also relates to the use of the pigment/frit mixture according to the invention for ceramic glazes on fired or non-fired roof, floor and wall tiles, sanitary ceramics, porcelain, pottery and ceramic articles for indoor or outdoor use it's about

Accordingly, the invention also relates to formulations comprising the effect pigment/frit mixture according to the invention.

The following examples are intended to illustrate the present invention, but do not limit it.

Example

Example 1

100 g of natural mica having a particle size of 10 to 60 μm is heated to 80° C. with stirring in 2 L of demineralized water. When this temperature is reached, 44 g of TiCl ₄ solution (400 g/L of TiCl ₄ ) are metered in at pH 1.8, while maintaining the pH constant using 32% sodium hydroxide solution. The pH is subsequently adjusted to pH 2.8 with sodium hydroxide solution, 600 mL of aqueous FeCl ₃ solution (w(Fe) = 7%) and 462 mL of aqueous TiCl ₄ solution (200 g of TiCl ₄ /L) It is added simultaneously at the above pH and 75°C. Throughout the addition time, the pH is kept constant by the simultaneous dropwise addition of 32% sodium hydroxide solution. After stirring for a further 0.5 h, the pH is raised to 7.5 and 650 mL of sodium water-free solution (13% by weight of SiO ₂ ) is slowly metered in at this pH, during which time the pH is increased with 10% hydrochloric acid. keep constant. After stirring for a further 0.5 h, the pH is lowered to pH 1.8 with 10% hydrochloric acid, and 5 g of SnCl ₄ x 5 H ₂ O and 41 mL of hydrochloric acid (20%) solution are metered in. Then 105 mL of TiCl ₄ solution (400 g/L of TiCl ₄ ) is slowly metered in at the same pH. A solution consisting of 5 g of SnCl ₄ x 5 H ₂ O and 41 mL of hydrochloric acid (20%) is then further added. The pH is kept constant at 1.8 using in each case 32% sodium hydroxide solution. The pH is subsequently adjusted back to pH 2.8 with sodium hydroxide solution. Finally, 650 mL of aqueous FeCl ₃ solution (w(Fe) = 7%) and 499 mL of aqueous TiCl ₄ solution (200 g of TiCl ₄ /L) were added side by side and mixed with sodium hydroxide solution (w = 10%). Apply the outermost layer by titrating at the same time. After stirring at pH 3.0 for a further 0.5 h, the coated mica substrate is filtered off, washed and dried at 110° C. for 16 h. Finally, the effect pigment obtained is calcined at 850° C. for 0.5 h and sieved.

A temperature-stable gold multilayer pigment with high luminance is obtained.

Example 2

100 g of natural mica having a particle size of 10 to 25 μm is heated to 80° C. with stirring in 2 L of demineralized water. When this temperature is reached, 44 g of TiCl ₄ solution (400 g/L of TiCl ₄ ) are metered in at pH 1.8, while maintaining the pH constant using 32% sodium hydroxide solution. The pH is subsequently adjusted to pH 2.8 with sodium hydroxide solution, 600 mL of aqueous FeCl ₃ solution (w(Fe) = 7%) and 462 mL of aqueous TiCl ₄ solution (200 g of TiCl ₄ /L) It is added simultaneously at the above pH and 75°C. Throughout the addition time, the pH is kept constant by the simultaneous dropwise addition of 32% sodium hydroxide solution. After stirring for a further 0.5 h, the pH is raised to 7.5 and 650 mL of sodium water-free solution (13% by weight of SiO ₂ ) is slowly metered in at this pH, during which time the pH is increased with 10% hydrochloric acid. keep constant. After stirring for a further 0.5 h, the pH is lowered to pH 1.8 with 10% hydrochloric acid, and 5 g of SnCl ₄ x 5 H ₂ O and 41 mL of hydrochloric acid (20%) solution are metered in. Then 105 mL of TiCl ₄ solution (400 g/L of TiCl ₄ ) is slowly metered in at the same pH. A solution consisting of 5 g of SnCl ₄ x 5 H ₂ O and 41 mL of hydrochloric acid (20%) is then further added. The pH is kept constant at 1.8 using in each case 32% sodium hydroxide solution. The pH is subsequently adjusted back to pH 2.8 with sodium hydroxide solution. Finally, 650 mL of aqueous FeCl ₃ solution (w(Fe) = 7%) and 499 mL of aqueous TiCl ₄ solution (200 g of TiCl ₄ /L) were added side by side and mixed with sodium hydroxide solution (w = 10%). Apply the outermost layer by titrating at the same time. After stirring at pH 3.0 for a further 0.5 h, the coated mica substrate is filtered off, washed and dried at 110° C. for 16 h. Finally, the effect pigment obtained in this way is calcined at 850° C. for 0.5 h and sieved.

A temperature-stable gold multilayer pigment having high luminance and good hiding power is obtained.

Example 3

100 g of natural mica having a particle size of < 15 μm is heated to 80° C. with stirring in 2 L of demineralized water. When this temperature has been reached, 53 g of TiCl ₄ solution (400 g/L of TiCl ₄ ) are metered in at pH 1.8, during which time the pH is kept constant using 32% sodium hydroxide solution. The pH is subsequently adjusted to pH 2.8 with sodium hydroxide solution, and 640 mL of aqueous FeCl ₃ solution (w(Fe) = 7%) and 501 mL of aqueous TiCl ₄ solution (200 g of TiCl ₄ /L) are added. It is added simultaneously at the above pH and 75°C. Throughout the addition time, the pH is kept constant by the simultaneous dropwise addition of 32% sodium hydroxide solution. After stirring for a further 0.5 h, the pH is raised to 7.5 and 650 mL of sodium water-free solution (13% by weight of SiO ₂ ) is slowly metered in at this pH, during which time the pH is increased with 10% hydrochloric acid. keep constant. After stirring for a further 0.5 h, the pH is lowered to pH 1.8 with 10% hydrochloric acid, and 5 g of SnCl ₄ x 5 H ₂ O and 41 mL of hydrochloric acid (20%) solution are metered in. Then 105 mL of TiCl ₄ solution (400 g/L of TiCl ₄ ) is slowly metered in at the same pH. A solution consisting of 5 g of SnCl ₄ x 5 H ₂ O and 41 mL of hydrochloric acid (20%) is then further added. The pH is kept constant at 1.8 using in each case 32% sodium hydroxide solution. The pH is subsequently adjusted back to pH 2.8 with sodium hydroxide solution. Finally, 650 mL of aqueous FeCl ₃ solution (w(Fe) = 7%) and 499 mL of aqueous TiCl ₄ solution (200 g of TiCl ₄ /L) were added side by side and mixed with sodium hydroxide solution (w = 10%). Apply the outermost layer by titrating at the same time. After stirring at pH 3.0 for an additional 0.5 h, the coated mica substrate is filtered off, washed and dried at 110° C. for 16 h. Finally, the effect pigment is calcined at 850° C. for 0.5 h and sieved.

A temperature-stable gold multilayer pigment with high hiding power is obtained.

Example 4

100 g of borosilicate glass flakes having a particle size of 20 to 200 μm are heated to 80° C. with stirring in 2 L of demineralized water. When this temperature has been reached, 38 g of TiCl ₄ solution (400 g/L of TiCl ₄ ) are metered in at pH 1.8, during which time the pH is kept constant using 32% sodium hydroxide solution. The pH was subsequently adjusted to pH 2.8 with sodium hydroxide solution, and 508 mL of aqueous FeCl ₃ solution (w(Fe) = 7%) and 431 mL of aqueous TiCl ₄ solution (200 g of TiCl ₄ /L) were added. It is added simultaneously at the above pH and 75°C. Throughout the addition time, the pH is kept constant by the simultaneous dropwise addition of 32% sodium hydroxide solution. After stirring for a further 0.5 h, the pH is raised to 7.5 and 650 mL of sodium water-free solution (13% by weight of SiO ₂ ) is slowly metered in at this pH, during which time the pH is increased with 10% hydrochloric acid. keep constant. After stirring for a further 0.5 h, the pH is lowered to pH 1.8 with 10% hydrochloric acid, and 5 g of SnCl ₄ x 5 H ₂ O and 41 mL of hydrochloric acid (20%) solution are metered in. Then 105 mL of TiCl ₄ solution (400 g/L of TiCl ₄ ) is slowly metered in at the same pH. A solution consisting of 5 g of SnCl ₄ x 5 H ₂ O and 41 mL of hydrochloric acid (20%) is then further added. The pH is kept constant at 1.8 using in each case 32% sodium hydroxide solution. The pH is subsequently adjusted back to pH 2.8 with sodium hydroxide solution. Finally, 650 mL of aqueous FeCl ₃ solution (w(Fe) = 7%) and 499 mL of aqueous TiCl ₄ solution (200 g of TiCl ₄ /L) were added side by side and mixed with sodium hydroxide solution (w = 10%). Apply the outermost layer by titrating at the same time. After stirring at pH 3.0 for a further 0.5 h, the glass flakes coated in this way are filtered, washed and dried at 110° C. for 16 h. Finally, the effect pigment obtained in this way is calcined at 850° C. for 0.5 h and sieved.

A temperature-stable gold multilayer pigment with a very strong shimmering effect is obtained.

Example 5

_{100 g of SiO 2} flakes having a particle size of 10 to 40 μm are heated to 80° C. with stirring in 2 L of demineralized water. When this temperature is reached, 44 g of TiCl ₄ solution (400 g/L of TiCl ₄ ) are metered in at pH 1.8, while maintaining the pH constant using 32% sodium hydroxide solution. The pH is subsequently adjusted to pH 2.8 with sodium hydroxide solution, 600 mL of aqueous FeCl ₃ solution (w(Fe) = 7%) and 462 mL of aqueous TiCl ₄ solution (200 g of TiCl ₄ /L) It is added simultaneously at the above pH and 75°C. Throughout the addition time, the pH is kept constant by the simultaneous dropwise addition of 32% sodium hydroxide solution. After stirring for a further 0.5 h, the pH is raised to 7.5 and 650 mL of sodium water-free solution (13% by weight of SiO ₂ ) is slowly metered in at this pH, during which time the pH is increased with 10% hydrochloric acid. keep constant. After stirring for a further 0.5 h, the pH is lowered to pH 1.8 with 10% hydrochloric acid, and 5 g of SnCl ₄ x 5 H ₂ O and 41 mL of hydrochloric acid (20%) solution are metered in. Then 105 mL of TiCl ₄ solution (400 g/L of TiCl ₄ ) is slowly metered in at the same pH. A solution consisting of 5 g of SnCl ₄ x 5 H ₂ O and 41 mL of hydrochloric acid (20%) is then further added. The pH is kept constant at 1.8 using in each case 32% sodium hydroxide solution. The pH is subsequently adjusted back to pH 2.8 with sodium hydroxide solution. Finally, 650 mL of aqueous FeCl ₃ solution (w(Fe) = 7%) and 499 mL of aqueous TiCl ₄ solution (200 g of TiCl ₄ /L) were added side by side and mixed with sodium hydroxide solution (w = 10%). Apply the outermost layer by titrating at the same time. After stirring at pH 3.0 for a further 0.5 h, the SiO ₂ flakes coated in this way are filtered, washed and dried at 110° C. for 16 h. Finally, the effect pigment obtained is calcined at 850° C. for 0.5 h and sieved.

A temperature-stable gold multilayer pigment having high luminance and good hiding power is obtained.

Example 6

100 g of synthetic mica having a particle size of 10 to 40 μm is heated to 80° C. with stirring in 2 L of demineralized water. When this temperature is reached, 44 g of TiCl ₄ solution (400 g/L of TiCl ₄ ) are metered in at pH 1.8, while maintaining the pH constant using 32% sodium hydroxide solution. The pH is subsequently adjusted to pH 2.8 with sodium hydroxide solution, 600 mL of aqueous FeCl ₃ solution (w(Fe) = 7%) and 462 mL of aqueous TiCl ₄ solution (200 g of TiCl ₄ /L) It is added simultaneously at the above pH and 75°C. Throughout the addition time, the pH is kept constant by the simultaneous dropwise addition of 32% sodium hydroxide solution. After stirring for a further 0.5 h, the pH is raised to 7.5 and 650 mL of sodium water-free solution (13% by weight of SiO ₂ ) is slowly metered in at this pH, during which time the pH is increased with 10% hydrochloric acid. keep constant. After stirring for a further 0.5 h, the pH is lowered to pH 1.8 with 10% hydrochloric acid, and 5 g of SnCl ₄ x 5 H ₂ O and 41 mL of hydrochloric acid (20%) solution are metered in. Then 105 mL of TiCl ₄ solution (400 g/L of TiCl ₄ ) is slowly metered in at the same pH. A solution consisting of 5 g of SnCl ₄ x 5 H ₂ O and 41 mL of hydrochloric acid (20%) is then further added. The pH is kept constant at 1.8 using in each case 32% sodium hydroxide solution. The pH is subsequently adjusted back to pH 2.8 with sodium hydroxide solution. Finally, 650 mL of aqueous FeCl ₃ solution (w(Fe) = 7%) and 499 mL of aqueous TiCl ₄ solution (200 g of TiCl ₄ /L) were added side by side and mixed with sodium hydroxide solution (w = 10%). Apply the outermost layer by titrating at the same time. After stirring at pH 3.0 for a further 0.5 h, the coated mica substrate is filtered off, washed and dried at 110° C. for 16 h. Finally, the effect pigment obtained in this way is calcined at 850° C. for 0.5 h and sieved.

A temperature-stable gold multilayer pigment having high luminance and moderate hiding power is obtained.

Example 7

100 g of talc having a particle size of <10 μm is heated to 80° C. with stirring in 2 L of demineralized water. When this temperature is reached, 44 g of TiCl ₄ solution (400 g/L of TiCl ₄ ) are metered in at pH 1.8, while maintaining the pH constant using 32% sodium hydroxide solution. The pH is subsequently adjusted to pH 2.8 with sodium hydroxide solution, 600 mL of aqueous FeCl ₃ solution (w(Fe) = 7%) and 462 mL of aqueous TiCl ₄ solution (200 g of TiCl ₄ /L) It is added simultaneously at the above pH and 75°C. Throughout the addition time, the pH is kept constant by the simultaneous dropwise addition of 32% sodium hydroxide solution. After stirring for a further 0.5 h, the pH is raised to 7.5 and 650 mL of sodium water-free solution (13% by weight of SiO ₂ ) is slowly metered in at this pH, during which time the pH is increased with 10% hydrochloric acid. keep constant. After stirring for a further 0.5 h, the pH is lowered to pH 1.8 with 10% hydrochloric acid, and 5 g of SnCl ₄ x 5 H ₂ O and 41 mL of hydrochloric acid (20%) solution are metered in. Then 105 mL of TiCl ₄ solution (400 g/L of TiCl ₄ ) is slowly metered in at the same pH. A solution consisting of 5 g of SnCl ₄ x 5 H ₂ O and 41 mL of hydrochloric acid (20%) is then further added. The pH is kept constant at 1.8 using in each case 32% sodium hydroxide solution. The pH is subsequently adjusted back to pH 2.8 with sodium hydroxide solution. Finally, 650 mL of aqueous FeCl ₃ solution (w(Fe) = 7%) and 499 mL of aqueous TiCl ₄ solution (200 g of TiCl ₄ /L) were added side by side and mixed with sodium hydroxide solution (w = 10%). Apply the outermost layer by titrating at the same time. After stirring at pH 3.0 for a further 0.5 h, the talc flakes coated in this way are filtered, washed and dried at 110° C. for 16 h. Finally, the effect pigment obtained in this way is calcined at 850° C. for 0.5 h and sieved.

A temperature-stable gold multilayer pigment with high hiding power is obtained.

Example 8

100 g of natural mica having a particle size of 20 to 180 μm is heated to 80° C. with stirring in 2 L of demineralized water. When this temperature has been reached, 38 g of TiCl ₄ solution (400 g/L of TiCl ₄ ) are metered in at pH 1.8, during which time the pH is kept constant using 32% sodium hydroxide solution. The pH was subsequently adjusted to pH 2.8 with sodium hydroxide solution, and 508 mL of aqueous FeCl ₃ solution (w(Fe) = 7%) and 431 mL of aqueous TiCl ₄ solution (200 g of TiCl ₄ /L) were added. It is added simultaneously at the above pH and 75°C. Throughout the addition time, the pH is kept constant by the simultaneous dropwise addition of 32% sodium hydroxide solution. After stirring for a further 0.5 h, the pH is raised to 7.5 and 650 mL of sodium water-free solution (13% by weight of SiO ₂ ) is slowly metered in at this pH, during which time the pH is increased with 10% hydrochloric acid. keep constant. After stirring for a further 0.5 h, the pH is lowered to pH 1.8 with 10% hydrochloric acid, and 5 g of SnCl ₄ x 5 H ₂ O and 41 mL of hydrochloric acid (20%) solution are metered in. Then 105 mL of TiCl ₄ solution (400 g/L of TiCl ₄ ) is slowly metered in at the same pH. A solution consisting of 5 g of SnCl ₄ x 5 H ₂ O and 41 mL of hydrochloric acid (20%) is then further added. The pH is kept constant at 1.8 using in each case 32% sodium hydroxide solution. The pH is subsequently adjusted back to pH 2.8 with sodium hydroxide solution. Finally, 650 mL of aqueous FeCl ₃ solution (w(Fe) = 7%) and 499 mL of aqueous TiCl ₄ solution (200 g of TiCl ₄ /L) were added side by side and mixed with sodium hydroxide solution (w = 10%). Apply the outermost layer by titrating at the same time. After stirring at pH 3.0 for a further 0.5 h, the coated mica substrate is filtered off, washed and dried at 110° C. for 16 h. Finally, the effect pigment obtained in this way is calcined at 850° C. for 0.5 h and sieved.

A temperature-stable, golden multilayer pigment having a strong shimmering effect is obtained.

Use Examples

Process description for the decoration of ceramic workpieces

A - ceramic substrate,

B - Engobe,

C - glazing,

D - decoration/application;

E - firing.

A = non-fired, pre-fired (biscuit), glazed porcelain porcelain tile, porcelain/porcelain tile, porcelain (eg hard porcelain, soft porcelain, fine china, bone china, free porcelain, porcelain, porcelain) ).

B = Commercially available engoves with a variety of different functions (eg, to hide substrate color, influence chemical and physical reactions, and improve adhesion between glaze and substrate).

C = eg commercially available glazes, glazes with effect pigments, colored glazes.

D = For example, rotary and flat screen printing, both indirect and indirect printing via decals, rotocolor, spray application, (hand) painting, immersion, waterfall, air-free spray application, decorative powder (eg, batten) Optional application (eg, pre-printed stickers) with rosa grit), followed by sprinkling of decorative powder thereon, and finally removal by inhalation or insufflation.

In the case of point D, the decoration preferably has, in addition to the ceramic color, one or more pre-prints (referred to as lower layers hereinafter), which may lie over all or part of the area. The latter can produce interesting effects (relief printing). The degree of gloss of the colored glaze can be affected by the choice of the underlying layer. The lower layer can be colored with inorganic pigments and effect pigments.

E = Firing can be performed at various different temperatures and temperature profiles and at various times between individual applications. Oven atmosphere also plays a role in the final effect, the more oxygen present during the firing process, the better the effect.

Points A to E are not necessarily used, and points may be omitted or replaced in some cases. In general, the individual points A to E may be combined as desired and/or may be used twice to achieve the described effect.

All combinations of A to E (Table) can produce a liquid-metal effect with the effect pigments according to Examples 1 to 8. Possible combinations are schematically illustrated in FIG. 3 .

Also, in addition to the effect pigments of Examples 1 to 8, commercially available effect pigments presented below were similarly tested in combinations A to E:

Kuncai KC305 (Kuncai),

Kunkai KC306,

Kunkai KC307,

Kunkai KC300,

Kunkai 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,

Iriodin® 305 (Merck KGaA);

Iriodin (registered trademark) 306 (Merck Kagea),

Iriodin (registered trademark) 326 (Merck Kagea),

Kunkai KC302,

Kunkai KC303,

oxen 307,

Pretty Iridisium 3325,

Xirallic(R) Leonis Gold(Merck Kagea);

Miraval (registered trademark) Cosmic Gold (Merck Kagea).

Only the effect pigments of Examples 1 to 8 can produce the liquid-metal effect, since only these pigments are destroyed during firing to form a glossy glaze surface with a liquid-metal effect in situ .

Screen Printing—Example A1: Screen Printing Application Using Under Layer, Indirect Application to Fine China (Decal)

material:

- screen printing the "bottom layer formulation" according to table 4,

- Screen printing of "Liquid-Metal Decorative Formulations" according to Table 3.

The lower layer is pre-printed on decal paper and intermediately dried at 0-40° C. until no wiping. A decorative paste is subsequently printed on the lower layer in the registry. Then, intermediate drying is performed again at 0 to 40° C. until no wiping. The cover coat (Ferro 80 450) is then overprinted and dried again at 0-40° C. until not wiped. The finished decal is peeled off with water, applied to a fine china (dish from Villeroy & Boch), and finally fired at 1060°C with a holding time of 3 minutes.

Screen Printing—Example A2: Application of screen printing with an underlying layer, direct application to porcelain porcelain tiles

material:

- screen printing the "bottom layer formulation" according to table 4,

- Screen printing of "Liquid-Metal Decorative Formulations" according to Table 3.

The lower layer is pre-printed on porcelain porcelain tiles and intermediately dried at 0-40° C. until not wiped. Subsequently, a decorative paste is printed on the underlying layer in an overlapping manner. Then, it is dried again at 0-40° C. until not wiped. Finally, calcination is performed at 1050° C. with a holding time of 10 minutes. Overprinting a decorative layer on the underlying layer results in a relief effect comprising matte areas and glossy areas.

Screen Printing—Example A3: Screen Printing Application with Pre-fired Underlayer, Direct Application to Ceramic Tiles

material:

- screen printing the "bottom layer formulation" according to table 4,

- Screen printing of "Liquid-Metal Decorative Formulations" according to Table 3.

The lower layer is pre-printed on the ceramic tile, intermediate-dried at 0-40° C. until not wiped, and then fired at 1050° C. with a hold time of 10 minutes. Subsequently, a decorative paste is printed in an overlapping manner on the pre-fired underlying layer. It is then dried again at 0-40° C. until not wiped. Finally, calcination is performed at 1050° C. with a holding time of 10 minutes. Overprinting a decorative layer on the underlying layer results in a relief effect comprising matte areas (without underlying layer) and glossy areas (with underlying layer).

Screen Printing—Example A4: Application of Indirect Screen Printing to Additional Decals Using an Underlying Layer

material:

- screen printing the "bottom layer formulation" according to table 4,

- Screen printing of "Liquid-Metal Decorative Formulations" according to Table 3.

The lower layer is printed on decal paper, and intermediately dried at 0-40° C. until not wiped. Subsequently a cover coat (Ferro 80 450) is overprinted and dried again at 0-40° C. until not wiped. The decorative paste is printed on decal paper, and intermediately dried at 0 to 40° C. until no wiping. A cover coat (Ferro 80 450) is then overprinted and dried again at 0-40° C. until not wiped.

The finished decal with the lower layer is separated with water and applied to the hard porcelain. The finished decal with the decorative color is peeled off with water and applied to the applied lower layer decal on the hard porcelain. Finally, it is fired at 1115 DEG C with a holding time of 3 minutes.

Screen Printing—Example A5: Direct Screen Printing Application to Oil-Free Porcelain Tiles Using Engobe and Non-fired Glaze

material:

- screen printing the "bottom layer formulation" according to table 4,

- Screen printing of "Liquid-Metal Decorative Formulations" according to Table 3.

Pre-fired oil-free porcelain tiles are coated with engobe and subsequently glazed with an underlying layer. A screen printing “liquid-metal decorative formulation” is then printed on the non-fired glaze.

The coated, glazed and printed tiles are then fired at 1090° C. [Heat Ball] with a hold time of 8 minutes.

Screen Printing—Example A6: Direct Screen Printing Application to Non-fired Tiles (Greenware) and Non-Fired Glaze with Engobe

material:

- screen printing the "bottom layer formulation" according to table 4,

- Screen printing of "Liquid-Metal Decorative Formulations" according to Table 3.

The non-fired tiles are coated with engobe and subsequently glazed with an underlying layer. A screen-printed “liquid-metal decorative formulation” is then printed over the non-fired glaze. The coated, glazed and printed tiles are then fired at 1090° C. [Heat Ball] with a hold time of 8 minutes.

Rotocolor - Example A7: Direct Rotocolor Application to Non-Fired Tiles (Greenware) and Non-Fired Glaze with Engobe

material:

- screen printing the "bottom layer formulation" according to table 4,

- Screen printing of "Liquid-Metal Decorative Formulations" according to Table 3.

The non-fired tiles are coated with engobe and subsequently glazed with an underlying layer. A Rotocolor "Liquid-Metal Decorative Formulation" is then printed on the non-fired glaze. The coated, glazed and printed tiles are then fired at 1090° C. [Heat Ball] with a hold time of 8 minutes.

Rotocolor—Example A8: Direct Rotocolor Application to Unfired Tiles (Greenware) with Engobe and Non-Fired Glaze with Lower Interlayer Interlayer

material:

- screen printing the "bottom layer formulation" according to table 4,

- Screen printing of "Liquid-Metal Decorative Formulations" according to Table 3.

The non-fired tiles are coated with engobe and subsequently glazed with a commercially available glaze. The Rotocolor underlayer is then printed, and the Rotocolor "Liquid-Metal Decorative Formulation" is overprinted onto the non-fired glaze comprising the underlayer. The coated, glazed and double-printed tiles are fired at 1100°C [heat hole] with a hold time of 8 minutes.

Rotocolor - Example A9: Pre-fired tile (biscuit) racket with Engobe and direct Rotocolor application to non-fired glaze with lower layer interlayer

material:

- screen printing the "bottom layer formulation" according to table 4,

- Screen printing of "Liquid-Metal Decorative Formulations" according to Table 3.

The pre-fired tiles are coated with engobe and subsequently glazed with a glaze. The rotocolor underlayer is then printed and the rotocolor "liquid-metal decorative formulation" is subsequently overprinted onto the non-fired glaze comprising the underlayer. The coated, glazed and double-printed tiles are fired at 1040° C. [Heat Ball] with a hold time of 10 minutes.

Spray application—Example A10: Spray application with non-fired tiles (greenware) and effect glazes with Engobe

material:

- screen printing the "bottom layer formulation" according to table 4,

- Screen printing of "Liquid-Metal Decorative Formulations" according to Table 3.

The non-fired tiles are coated with engobe and subsequently glazed with a “liquid-metal decorative formulation”. The coated, glazed and sprayed tiles are then fired at 1090° C. [heat hole] with a hold time of 8 minutes.

The fired effect glaze with the pigment/frit mixture according to the invention is characterized by a particularly high gloss in combination with a low brilliance value and exhibits the desired liquid-metal effect. The luster is [Rhopoint] using Rhopoint IQ mini 2.0. The liquid-metal glaze is characterized by the following gloss values.

The fired effect glaze is characterized by a particularly high gloss in combination with a low brilliance value. The gloss was determined using a Ropoint IQ Mini 2.0 (goniometer). The liquid-metal glaze is characterized by the following gloss values.

The brilliance (glitter) is measured using a BYK mac meter. The brilliance is below the measurable range at illumination angles of 45° and 75°. The non-uniformity of the glaze surface can lead to measurements of up to 2 (Sa and Si) at a 15° illumination angle. However, nevertheless, the SG value is zero.

Claims (22)

An effect pigment/frit mixture comprising:
The frit comprises 3 to 7% by weight of Na ₂ O based on the frit,
The effect pigment/frit mixture, wherein the effect pigment is based on a flake-form matrix having on its surface at least one of the following layer sequences (A) to (E) or (A) to (F) :
(A) a high-index coating having a refractive index of n ≥ 1.8;
(B) a pseudobrookite layer optionally doped with one or more oxides in an amount of up to 10% by weight, based on layer (B),
(C) a low-index layer having an index of refraction of n <1.8;
(D) a high-index coating consisting of at least two colorless metal-oxide layers,
(E) a pseudobrookite layer optionally doped with one or more oxides in an amount of up to 10% by weight, based on layer (E),
and optionally,
(F) Outer protective layer. According to claim 1,
The flake-form matrix of the effect pigment is phyllosilicate, BiOCl, SiC, TiC, WC, B ₄ C, BN, graphite, TiO ₂ , Fe ₂ O ₃ flakes, doped or undoped Al ₂ O ₃ Effect pigment/frit mixture, characterized in that it is selected from the group of flakes, doped or undoped glass flakes, doped or undoped SiO _{2 flakes or mixtures thereof.} 3. The method of claim 1 or 2,
Effect pigment/frit mixture, characterized in that the phyllosilicate flakes are natural mica, synthetic mica, kaolin or talc. 4. The method according to any one of claims 1 to 3,
Effect pigment/frit mixture, characterized in that the layer (A) of the effect pigment consists of at least one metal oxide. 5. The method according to any one of claims 1 to 4,
The metal oxide of the layer (A) is TiO ₂ , Fe ₂ O ₃ , Fe ₃ O ₄ , Fe(O)OH, BiOCl, Cr ₂ O ₃ , ZnO, Ce ₂ O ₃ , ZrO ₂ , SnO ₂ , Co ₂ O _{3 , Ti suboxide (partially reduced TiO 2} and lower oxides or mixtures thereof having oxidation states of less than 4 to 2), titanium oxynitride, titanium nitride, CoO, Co ₂ O ₃ , Co ₃ O ₄ Effect pigment/frit mixture, characterized in that it is selected from the group of , VO ₂ , V ₂ O ₃ , NiO, WO ₃ , MnO, Mn ₂ O _{3 and mixtures of these oxides.} 6. The method according to any one of claims 1 to 5,
Said layer(s) (B) and/or (E) are: Al ₂ O ₃ , Ce ₂ O ₃ , B ₂ O ₃ , ZrO ₂ , SnO ₂ , Cr ₂ O ₃ , CoO, Co ₂ O ₃ , Co Effect pigment/frit mixture, characterized in that it is doped with one or more oxides or mixtures of oxides selected from the group of ₃ O ₄ and Mn ₂ O _{3 .} 7. The method according to any one of claims 1 to 6,
The effect, characterized in that the layer (C) of the effect pigment consists of SiO ₂ , MgO*SiO ₂ , CaO*SiO ₂ , Al ₂ O ₃ *SiO ₂ , B ₂ O ₃ *SiO ₂ or mixtures of these compounds. Pigment/frit mixture. 8. The method according to any one of claims 1 to 7,
The layer (D) of the effect pigment consists of at least two metal-oxide layers, wherein the metal-oxide comprises SnO ₂ , TiO ₂ , Al ₂ O ₃ , Cr ₂ O ₃ , Fe ₂ O ₃ and mixtures thereof. Effect pigment/frit mixture, characterized in that it is selected from the group. 9. The method according to any one of claims 1 to 8,
Effect pigment/frit mixture, characterized in that the layer (D) of the effect pigment consists of the following metal-oxide layers (D1) and (D2):
(D1) SnO ₂ layer,
(D2) TiO ₂ layer. 9. The method according to any one of claims 1 to 8,
Effect pigment/frit mixture, characterized in that the layer (D) of the effect pigment consists of the following metal-oxide layers (D1), (D2) and (D3):
(D1) Al ₂ O ₃ layers,
(D2) TiO ₂ layer,
(D3) Al ₂ O ₃ layer. 9. The method according to any one of claims 1 to 8,
Effect pigment/frit mixture, characterized in that said layer (D) consists of the following metal-oxide layers (D1), (D2) and (D3):
(D1) SnO ₂ layer,
(D2) TiO ₂ layer,
(D3) SnO ₂ layer. 12. The method according to any one of claims 1 to 11,
Effect pigment/frit mixture, characterized in that the outer protective layer (F) of the effect pigment _{consists of SnO 2 .} 13. The method according to any one of claims 1 to 12,
An effect pigment/frit mixture, characterized in that the effect pigment has the structure:
- substrate + TiO ₂ + pseudobrookite + SiO ₂ + SnO ₂ + TiO ₂ + SnO ₂ + pseudobrookite,
- substrate + Fe ₂ O ₃ + pseudobrookite + SiO ₂ + SnO ₂ + TiO ₂ + SnO ₂ + pseudobrookite,
- substrate + Cr ₂ O ₃ + pseudobrookite + SiO ₂ + SnO ₂ + TiO ₂ + SnO ₂ + pseudobrookite,
- substrate + TiO ₂ + pseudobrookite + MgO*SiO ₂ + SnO ₂ + TiO ₂ + SnO ₂ + pseudobrookite,
- substrate + Fe ₂ O ₃ + pseudobrookite + MgO*SiO ₂ + SnO ₂ + TiO ₂ + SnO ₂ + pseudobrookite,
- substrate + Cr ₂ O ₃ + pseudobrookite + MgO*SiO ₂ + SnO ₂ + TiO ₂ + SnO ₂ + pseudobrookite,
- substrate + TiO ₂ + pseudobrookite + CaO*SiO ₂ + SnO ₂ + TiO ₂ + SnO ₂ + pseudobrookite,
- substrate + Fe ₂ O ₃ + pseudobrookite + CaO*SiO ₂ + SnO ₂ + TiO ₂ + SnO ₂ + pseudobrookite,
- substrate + Cr ₂ O ₃ + pseudobrookite + CaO*SiO ₂ + SnO ₂ + TiO ₂ + SnO ₂ + pseudobrookite,
- substrate + TiO ₂ + pseudobrookite + Al ₂ O ₃ *SiO ₂ + SnO ₂ + TiO ₂ + SnO ₂ + pseudobrookite,
- substrate + Fe ₂ O ₃ + pseudobrookite + Al ₂ O ₃ *SiO ₂ + SnO ₂ + TiO ₂ + SnO ₂ + pseudobrookite,
- substrate + Cr ₂ O ₃ + pseudobrookite + Al ₂ O ₃ *SiO ₂ + SnO ₂ + TiO ₂ + SnO ₂ + pseudobrookite,
- substrate + TiO ₂ + pseudobrookite + SiO ₂ + TiO ₂ + SnO ₂ + pseudobrookite,
- substrate + TiO ₂ + pseudobrookite + SiO ₂ + SnO ₂ + TiO ₂ + pseudobrookite,
- substrate + TiO ₂ + pseudobrookite + SiO ₂ + TiO ₂ + SnO ₂ + pseudobrookite + SnO ₂ ,
- substrate + TiO ₂ + pseudobrookite + SiO ₂ + SnO ₂ + TiO ₂ + pseudobrookite + SnO ₂ ,
- substrate + TiO ₂ + pseudobrookite + SiO ₂ + SnO ₂ + Fe ₂ O ₃ + SnO ₂ + pseudobrookite,
- substrate + TiO ₂ + pseudobrookite + SiO ₂ + SnO ₂ + Cr ₂ O ₃ + SnO ₂ + pseudobrookite, or
- substrate + TiO ₂ + pseudobrookite + SiO ₂ + Al ₂ O ₃ + TiO ₂ + Al ₂ O ₃ + pseudobrookite. 14. The method according to any one of claims 1 to 13,
Pigment/frit mixture, characterized in that the frit particles have a particle size of 1 to 500 μm. 15. The method according to any one of claims 1 to 14,
The frit is, in _{addition to Na 2} O, Al ₂ O ₃ , SiO ₂ , B ₂ O ₃ , TiO ₂ , Fe ₂ O ₃ , MgO, MnO, Cr ₂ O ₃ , P ₂ O ₅ , PbO, HfO ₂ , ZnO , ZrO ₂ , A pigment/frit mixture, characterized in that it comprises as a further component at least one component selected from the group of alkali metal oxides, alkaline earth metal oxides and rare earth oxides. 16. The method according to any one of claims 1 to 15,
wherein the pigment/frit mixture consists of 20 to 70% by weight of an effect pigment, and 30 to 80% by weight of a frit, and optionally 0 to 10% by weight of one or more additives, wherein the pigment, the frit and the additive Pigment/frit mixture, characterized in that the sum of (s) is 100%. 17. A method according to any one of claims 1 to 16, in non-fired or fired roof tiles, non-fired or fired earthenware and ceramicware, and ceramic glazes. Use of pigment/frit mixtures. 17. The method of claim 16,
Use of pigment/frit mixtures for decorative tiles or for decoration of porcelain, bone china or pottery. 19. The method of claim 18,
Use of pigment/frit mixtures for porcelain glazes. A formulation comprising the pigment/frit mixture according to claim 1 . 21. The method of claim 20,
A formulation characterized in that it has the following luster values (determined using a Rhopoint IQ mini 2.0 goniophotometer):
Gloss (20°) > 100,
Gloss peak value (R _spec ) ≥ 20. 17. A pigment/frit mixture according to any one of claims 1 to 16 and optionally a frit as an intermediate layer (=underlayer) is applied between the ceramic or glaze and the pigment/frit mixture, wherein the lower A method for producing a ceramic glaze, characterized in that the layers and the pigment/frit mixture are applied separately and subsequently fired together.

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