JP2020514511A - Effect pigments - Google Patents

Abstract

The present invention is a glaze- and enamel-stable effect pigment having a surface layer of antimony oxide or a mixture of antimony oxides, which has improved stability in glazes, enamel or ceramics or glass-like materials, especially at temperatures above 1000. Related to effect pigments having properties.

Description

  The present invention is a glaze-stable and enamel-stable effect pigment having an antimony oxide surface layer, which has improved stability in glazes, enamel or ceramics or glass-like materials, in particular above 1000 ° C. Related to effect pigments that are stable at temperature.

  Mixtures of effect pigments, such as pearlescent pigments and ceramic frits, are commonly used for decorative applications in ceramic glazes. In particular, in a high temperature region higher than 1000 ° C., particularly when used as a ceramic glaze in a so-called single-firing-Verfahren, and when used, oxide melting (frit component) and high temperature during the firing process. In an intense situation consisting of, the problem arises that the effect pigment cannot withstand without damage. Therefore, hitherto, attempts have been made to stabilize effect pigments by covering them with a heat-insulating protective layer for such applications. The second starting point for stabilization is a suitable combination of frit and pearlescent pigment.

  It is known from the prior art that with the use of pearlescent pigments in ceramic glazes used in the> 1000 ° C. range, a considerable loss of tinting strength and pearlescent effect must be expected. To prevent this, these pigments are encapsulated in an additional protective layer, or the use of pearlescent pigments in the high temperature range for this application has been investigated, especially iron oxides in modified soils and fluxes. Must be limited to coated pearlescent pigments.

EP 220509 A1 describes the stabilization of pearlescent pigments, for example with a layer of SnO ₂ and / or CeO ₂ .
EP307771A1 discloses stabilized and novel decoration for a combination of effects, Au- doped encapsulation pearlescent pigment according to the SnO ₂ layer. In order to achieve the desired stabilization, a considerable amount of the stated oxide / oxide combinations must be applied in both cases. Therefore, it has proved advantageous to apply the protective coat at about 5 to 30% by weight, based on the total pigment.
DE 3933424 C1 discloses pearlescent pigment / frit combinations with and without additional absorbent pigments. However, the range of use of pigment glass frits is only 700-900 ° C. at maximum.
GB2096592A discloses the use of pearlescent pigments in frit-containing ceramic fluxes. Neither the target firing temperature nor the specific problems with the use of pearlescent pigments at temperatures> 1000 ° C. are discussed here.

US Pat. No. 5,783,506 discloses a "leafing" capable ceramic flux in a formulation consisting of a frit, a dispersant, a binder, mica and a pearlescent pigment based on mica having a defined viscosity, The use of mica pigments coated with TiO ₂ or Fe ₂ O ₃ is disclosed. The invention in this US patent resides in the transfer of the pearlescent pigment to the surface of the glaze (leafing) due to the addition of mica.
US Pat. No. 4,353,991 discloses pearlescent pigments having a particle size of 1 to 200 μm in "fritted glass enamel" in concentrations ranging from 0.5 to 25.0% by weight, based on the weight of the frit / pigment mixture. Discloses the use of. However, these mixtures can only be used at temperatures up to 538-760 ° C.
EP0419843A1 discloses the use of pearlescent pigments in glass frits at working concentrations of 5 to 20% by weight. The service temperature is 800-900 ° C for rapid firing or 700-800 ° C for standard firing.

で構成される。
専ら雲母をベースとする特定の黄金色の真珠光沢顔料に使用が限定され、当該黄金色の真珠光沢顔料の層構造が開示されていないことは、ここでは不利である。したがって利用可能な顔料の数及び色の選択は、ＣＮ１０１４６２８９５Ａにおいては非常に、大いに限定されている。 CN10146285A discloses the use of 10-60% by weight of golden pearlescent pigments in glaze at 1000-1200 ° C. The frit used here is

Composed of.
It is a disadvantage here that the use is limited to certain golden pearlescent pigments exclusively based on mica and the layer structure of the golden pearlescent pigment is not disclosed. Therefore, the number of pigments available and the choice of colors are very limited in CN10146285A.

DE 19859420A1 discloses a modified facing soil having a pearlescent effect. The coating of ceramics (Keramikwaren) and ceramics (Keramikwaren) in order to modify (prime) the surface by fineness or color is usually carried out with vase. The modified facing soil achieves better adhesion of the facing soil to fired or unfired tiles, grills and ceramics. The make-up soil comprises a frit with a firing range of 600-1200 ° C. and one or more pearlescent pigments.
DE-A 1952538 and EP 0130272A1 describe that Sb ₂ O ₃ is used as a coating for absorbing pigments such as chrome yellow or lead chromate, in order to increase the thermal and light stability. Here, temperatures up to 175 ° C. and 325 ° C. are described, respectively.

  Use of effect pigments, for example pearlescent pigments in glazes, enamels, ceramics or glass-like materials, wherein a temperature of 1000 ° C. or higher is used and stability compared to unprotected pigments. No effective and universal protective layer is known from the prior art for use in which the conversion is achieved in the application without technical modifications such as frit composition.

Therefore, it is an object of the present invention to stabilize effect pigments which are stable at temperatures of 1000 ° C. and above, and by which effect pigments can be utilized without problems, for example in decorative glazes, enamel and the like, At the same time, the optical properties of the effect pigments are not impaired by the stabilization or only slightly impaired.
The stabilization is intended here to be achieved exclusively by the protective layer, without having to make any changes to the production method of the frit or the workpiece.

Surprisingly, for example, at least one layer of TiO ₂ and / or titanium oxynitride and / or other titanium-containing mixed oxides known to the person skilled in the art, based on a flaky substrate, and optionally It has been found that effect pigments, such as pearlescent pigments, which comprise an additional layer at, are stabilized when they have an antimony oxide surface layer on their surface. Due to this surface layer, the effect pigment is stable at a temperature of 1000 ° C. or higher, and can be incorporated into enamel, glaze, baked goods, ceramics, etc. without any problem, and does not adversely affect the optical characteristics.

The present invention is therefore distinguished by the fact that they are covered with a surface layer containing one or more antimony oxides or antimony oxide mixtures in order to achieve improved thermal and temperature stability in glazes, ceramics, enamel etc. , Effect pigments based on flaky substrates.
The invention also relates in particular to formulations, coatings, glazed tiles, enamels, glazes, baked goods, glassware and ceramics containing effect pigments stabilized according to the invention.

The coating of effect pigments with one or more antimony oxides results in a considerably improved stability of the pigment in ceramic applications compared to unstabilized pigments. This stability is evident especially at firing temperatures of 600 to 1200 ° C., but temperatures of 1000 to 1200 ° C. are particularly preferred.
The surface layer of antimony oxide may be composed of various modifications of antimony oxide. The surface layer is preferably composed of Sb _x O _y , where x = 2 and y = 3, 4, 5, especially Sb ₂ O ₃ , Sb ₂ O ₄ or Sb ₂ O ₅ or mixtures of said antimony oxides. Is. Preferred mixtures are composed of Sb ₂ O ₃ and Sb ₂ O ₄ , Sb ₂ O ₄ and Sb ₂ O ₅ , and of Sb ₂ O ₃ , Sb ₂ O ₄ and Sb ₂ O ₅ . The antimony oxide layer preferably consists of only one antimony oxide, in particular Sb ₂ O ₃ or Sb ₂ O ₄ or Sb ₂ O ₅ .

Particularly preferred is the surface layer of Sb ₂ O ₄ . Among the modifications of Sb ₂ O ₄ , especially alpha-cervantes stone (alpha-Sb ₂ O ₄ ) is sometimes said to be particularly preferred, which provides maximum protection of the effect pigments against temperatures of 1000 ° C. and above, At the same time, in addition to the stabilizing effect, it is also considered to be less important than, for example, Sb ₂ O ₃ from a toxicological viewpoint.
For stabilization, the effect pigment is preferably 5 to 50% by weight, in particular 5 to 50% by weight, based on the effect pigment, depending on the type of effect pigment to be stabilized and / or in accordance with the particle size of the cross section. The surface is coated with 30% by weight, and very particularly preferably 10-15% by weight of antimony oxide or antimony oxide mixture. It is particularly preferred to coat with 10-15% by weight of Sb ₂ O ₄ , especially alpha-Sb ₂ O ₄ .

Depending on the particle size, the surface layer on the effect pigments generally has a thickness of 1-100 nm, in particular 2-70 nm, and very particularly preferably 5-50 nm.
Surface in this patent application means the complete coating of the surface of the effect pigment.
Application to surface effect pigments is simple and easy to carry out. The antimony oxide and the antimony oxide mixture used for stabilization are applied to the effect pigments, preferably from one or more soluble antimony salts by wet chemical precipitation. Subsequent calcination of the coated effect pigments at 400-1000 ° C. results in the formation of modifications such as antimony oxide, eg Sb ₂ O ₃ , Sb ₂ O ₄ or Sb ₂ O ₅ , depending on the calcination temperature. Each modification can be easily detected using XRD.

In the case of wet coating, the effect pigment is suspended in water and one or more hydrolyzable antimony salts, preferably antimony (III) salts such as SbCl ₃ are secondary precipitated with antimony oxide or antimony oxide hydrate. Is added at a pH suitable for hydrolysis, chosen to precipitate directly on the effect pigments without generating. The pH is kept constant, usually by simultaneous metered addition of base and / or acid. The effect pigments are subsequently separated, washed and dried and optionally calcined. Generally, the firing temperature is in the range of 250 to 1000 ° C, preferably 350 to 900 ° C. If desired, the pigment can also be sieved to finally adjust the particle size to the appropriate particle size.

In principle, the preparation is of course also possible by the one-pot method, in which case the coating with antimony oxide according to the invention is carried out in the process for preparing the effect pigment itself without pre-firing the effect pigment.
In addition, the coating can also be carried out in a fluidized bed reactor, in which case the methods for the preparation of pearlescent pigments, which are proposed, for example, in EP0045851 and EP0106235, can be used accordingly.
The following Sb-containing precursors, for example those which hydrolyze with H ₂ O vapor, namely SbCl ₃ , SbF ₃ , Sb (III) n-butoxide, Sb (III) ethoxide or tris (dimethylamino) antimony, are used for this purpose. Can be used for.

The invention also relates to a method for preparing effect pigments stabilized according to the invention.
The stabilizing effect pigments are preferably pearlescent pigments, interference pigments, multilayer pigments with transparent, translucent and / or opaque layers, or hologram pigments. A particular stabilizing effect is that of interference or silver-white effect pigments composed of flaky substrates coated with TiO ₂ and / or titanium oxynitride and / or other titanium-containing mixed oxides and optionally further layers. If achieved.
In the present application titanium oxynitride means the compound of the TiO _x N _y formulation, where x = 0 to 2 and y = 0 to 1 and in all cases 1 ≦ x + y ≦ 2.
Particularly preferred are effect pigments having layers of TiO _x N _y , where x> 1.5 and y <0.5. The layer of titanium oxynitride can also be a mixture of two or more titanium oxynitride compounds or other titanium-containing mixed oxides. In this case, the titanium oxynitride compounds can be mixed with one another in any proportion.

Suitable effect pigments are, inter alia, pearlescent pigments, interference pigments or multilayer pigments with transparent, translucent and / or opaque layers, especially based on the support, the support being preferably flaky. For example, flake TiO ₂ , synthetic mica (eg fluorophlogopite) or natural mica, doped or undoped glass flakes, flake SiO ₂ , flake Al ₂ O ₃ or flake iron oxide are suitable. Glass flakes are types of glass known to those skilled in the art, such as A glass, E glass, C glass, ECR glass, used glass, window glass, borosilicate glass, Duran® glass, laboratory equipment. It can be composed of glass or optical glass. The refractive index of the glass flakes is preferably 1.45 to 1.80, especially 1.50 to 1.70. The glass substrate is particularly preferably composed of C glass, ECR glass or borosilicate glass.

High temperature resistance flakes such as Al ₂ O ₃ , SiC, B ₄ C, BN, graphite, TiO ₂ and Fe ₂ O ₃ flakes are particularly suitable.
Suitable substrate flakes for pearlescent pigments can be doped or undoped. If they are doped, the doping is preferably Al, N, B, Ti, Zr, Si, In, Sn or Zn or mixtures thereof. In addition, ions from the further transition metal groups (V, Cr, Mn, Fe, Co, Ni, Cu, Y, Nb, Mo, Hf, Ta, W) and ions from the lanthanide group act as dopants. obtain.
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 TiO ₂ -doped α-Al ₂ O ₃ flakes. When doping the substrate, 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 supporting substrate is not critical per se and can be adapted to the particular application. In general, the flake-like substrate has a thickness of 0.1 to 5 μm, especially 0.2 to 4.5 μm. The other two dimensions are usually 1 to 1000 μm, preferably 2 to 200 μm, especially 5 to 60 μm.
The thickness of each layer of metal oxide, metal oxide hydrate, metal suboxide, metal, metal fluoride, metal nitride, metal oxynitride or mixtures thereof on the supporting substrate is preferably 3 to 300 nm, especially 20 to 200 nm.

  In a preferred embodiment, the effect pigment support is a metal oxide, a metal oxide hydrate, a metal suboxide, a metal, a metal fluoride, a metal nitride, a metal oxynitride or a mixture of these materials. It may be coated with one or more transparent, translucent and / or opaque layers including. Layers of metal oxides, metal oxide hydrates, metal suboxides, metals, metal fluorides, metal nitrides or metal oxynitrides or mixtures thereof have a low refractive index (refractive index <1.8) or It may have a high refractive index (refractive index ≧ 1.8). Suitable metal oxides and metal oxide hydrates are all metal oxides or metal oxide hydrates known to those skilled in the art, such as aluminum oxide, aluminum oxide hydrate, silicon oxide, Silicon oxide hydrate, iron oxide, tin oxide, cerium oxide, zinc oxide, zirconium oxide, chromium oxide, titanium oxide, especially titanium dioxide, titanium oxide hydrate and mixtures thereof, such as ilmenite or pseudoplate titanite Is. A metal oxide that can be used is, for example, titanium suboxide. A suitable metal fluoride is, for example, magnesium fluoride. Available metal nitrides or metal oxynitrides are, for example, nitrides or oxynitrides of the metals titanium, zirconium and / or tantalum. Layers of metal oxides, metals, metal fluorides and / or metal oxide hydrates, and very particularly preferably metal oxide and / or metal oxide hydrate layers, are preferably applied to the support. It In addition, there may also be multi-layer structures comprising layers of high and low refractive index metal oxides, metal oxide hydrates, metals or metal fluorides, high and low birefringence layers. Are preferably alternating. Particularly preferred is a layer package comprising a high refractive index layer and a low refractive index layer, one or more of these layer packages being applicable to the support. The order of the high refractive index layer and the low refractive index layer here can be adapted to the support in order to incorporate it into a multilayer structure. In a further embodiment, the layer of metal oxide, metal silicate, metal oxide hydrate, metal suboxide, metal, metal fluoride, metal nitride or metal oxynitride is mixed with a colorant or Can be doped.

  Suitable colorants or other elements are, for example, inorganic color pigments such as magnetite, colored metal oxides such as chromium (III) oxide, or color pigments such as tenard blue (Co / Al spinel), or Pigments from the structural classes of elements such as yttrium or antimony, and generally perovskite, pyrochlore, rutile, and spinel. Pearlescent pigments containing these layers additionally exhibit a great variety of colors with respect to color and, in many cases, can exhibit angle-dependent color changes due to interference (color flop).

In a preferred embodiment, the outer layer on the support is a high index metal oxide. This outer layer is furthermore on top of the layer package or, in the case of high-index supports, part of the layer package and is, for example, TiO ₂ , titanium suboxide, Fe ₂ O ₃ , SnO ₂ , ZnO, ZrO. ₂ , Ce ₂ O ₃ , CoO, Co ₃ O ₄ , V ₂ O ₅ , Cr ₂ O ₃ and / or mixtures thereof, such as ilmenite or pseudolite. TiO ₂ is particularly preferable, and Fe ₂ O ₃ is further preferable. If the support flakes are coated with TiO _2, TiO ₂ is preferably rutile modification, more preferably anatase modification. The method for preparing rutile is described, for example, in U.S.P. S. 5,433,779, U.S.P. S. 4,038,099, U.S.S. S. 6,626,989, DE2522572C2 and EP0271767B1 in the prior art. A thin (<10 nm) tin oxide layer, which acts as an additive for converting TiO ₂ to rutile, is preferably applied to the substrate flakes prior to precipitation of TiO ₂ .

  Effect pigments are known and in most cases commercially available and can be prepared by standard methods known to the person skilled in the art. The effect pigments are preferably prepared by wet chemistry methods, for example DE 1467468, DE 1959998, DE 2009566, DE 21066613, DE 2214545, DE 2215191, DE 2244298, DE 23133331, DE 2429762, DE 2522572, DE3137808, DE3137809, DE3151553, DE35015, DE315153, DE315153, DE31515, Known wet chemical coating techniques developed for the preparation of pearlescent pigments, such as those described in WO 98/53011, can be used.

Particularly preferred effect pigments have the following structure:
Base material flake + TiO ₂
Base material flake + titanium oxynitride base material flake + SiO ₂ + TiO ₂
Base material flakes + SnO ₂ + TiO ₂
Base material flakes + Cr ₂ O ₃ + TiO ₂
Base material flake + Ce ₂ O ₃ + TiO ₂
Base material flakes + ZrO ₂ + TiO ₂
Base material flake + TiO ₂ + Cr ₂ O ₃
Base material flakes + TiO ₂ + SiO ₂ + TiO ₂
Base material flakes + TiO ₂ + SiO ₂
Base material flake + TiO ₂ + SnO ₂ + TiO ₂
Base material flake + TiO ₂ + Fe ₂ O ₃
Base material flakes + Fe ₂ O ₃ + TiO ₂
Base material flakes + TiO ₂ + Al ₂ O ₃ + TiO ₂
Base material flake + TiO ₂ + ZrO ₂ + TiO ₂
Have.

Very particularly preferred effect pigments have the following layer structure:
Natural mica flakes + TiO ₂
Natural Mica Flake + Titanium Oxynitride Synthetic Mica Flake + TiO ₂
Synthetic mica flakes + titanium oxynitride Al ₂ O ₃ flakes + TiO ₂
Al ₂ O ₃ flakes + titanium oxynitride SiO ₂ flakes + TiO ₂
SiO ₂ flakes + titanium oxynitride glass flakes + TiO ₂
Glass flakes + titanium oxynitride Fe ₂ O ₃ flakes + TiO ₂
Fe ₂ O ₃ flakes + titanium oxynitride TiO ₂ flakes + TiO ₂
TiO ₂ flakes + ZrO ₂ + TiO ₂
TiO ₂ flakes + SiO ₂ + TiO ₂
Have.

The commercially available effect pigments which can be coated, for example with the surface layer according to the invention, are given below.

  In the present patent application, “high refractive index” means a refractive index of 1.8 ≧, while “low refractive index” means a refractive index of <1.8.

  In order to improve the wettability, dispersibility and / or compatibility with the application medium, the finished effect pigments, depending on the application area, can be post-coated or post-treated with inorganic and / or organic substances, for example with silanes. , Often a good idea. Suitable post-coatings or post-treatments are, for example, the methods described in DE patents 2215191, DE-A3151354, DE-A3235017 or DE-A3334598. This post-coating simplifies the handling of the pigment, especially its incorporation into various media.

  The effect pigments according to the invention have increased temperature and thermal stability compared to unstabilized effect pigments. Stabilized effect pigments can be incorporated into cosmetic soils and glazes without problems. The glaze can be matte to glossy or clear to opaque, depending on the desired effect.

Coatings for baking, glassware and ceramics to improve (prime) the surface through fineness or color are usually done with ceramic coating compositions. Generally, the soil is composed of glass frits, a binder and optionally pigments. Generally, cosmetic soil contains a frit having a firing range of 600 to 1200 ° C., and the frit is, for example, Al ₂ O ₃ , SiO ₂ , B ₂ O ₃ , TiO ₂ , ZrO ₂ , Sb ₂ O ₃ , P ₂ O ₅ , Fe. _It is composed of components normally contained in a frit, such as ₂ O ₃ , alkali metal oxides and alkaline earth metal oxides. Besides the effect pigments according to the invention, for example (encapsulated) Co, Cr, Cu, Mn, Fe, Zr, V, Al, Ni, Si, Sb, Pr, Ca or CdSSe and mixtures thereof 0 to 30% by weight, preferably 5 to 20% by weight, and especially 5 to 15% by weight, based on the inorganic components, of inorganic coloring pigments such as colored metal oxides and / or metal hydroxides selected from the group Can be further added to the frit.

In addition to the effect pigments, the cosmetic soil may further comprise a binder in an amount of 0 to 70% by weight, preferably 10 to 60% by weight, in particular 20 to 50% by weight. The choice of binder depends on the technical requirements of the coating produced. Suitable binders are, in particular, all binders or binder mixtures normally considered for ceramics, in particular screen printing media. Therefore, cellulose, polyethylene glycol, cellulose nitrate, alkyl cellulose, hydroxycellulose, hydroxyalkyl cellulose ether, hydroxyalkyl cellulose, cellulose acetopropionate and butyrate cellulose, polyacrylate resin, polymethacrylate resin, polyester resin, polyphenol resin, urea resin, Melamine resin, polyterpene resin, polyvinyl resin, polyvinyl chloride resin, polyvinylpyrrolidone resin, polystyrene resin and modified polystyrene, polyalpha-methylstyrene, hydrogenated colophony ester, polyolefin, coumarone-indene resin, hydrocarbon resin, ketone It is possible to use binders based on resins, aldehyde resins, aromatic resins, formaldehyde resins, carbamic acid resins, sulfonamide resins, epoxy resins, polyurethanes and / or natural oils or derivatives of said substances. Further, conventional surface coating binders such as, for example, polyurethane acrylate resins, acrylate melamine resins, alkyd resins, polyester resins, polyurethanes, nitrocellulose, ketone resins, aldehyde resins and polyvinyl butyral, acrylate resins or epoxy resins and mixtures thereof. ..
However, the application can also be applied without a binder, for example in the form of dust. In this case, the effect pigment and the frit powder are mixed in dry form, for example by spraying.

  If a solvent is required, the solvent component in the make-up soil must be adapted to the respective binder by expert methods. During the preparation, it is possible to utilize water and all organic solvents, preferably those which are emulsifiable or miscible with water. Suitable solvents include pine oil, terpineol, ester alcohols, toluene, naphtha, mineral oils, aliphatic or aromatic hydrocarbons, esters, vegetable oils such as ethanol, butanol, ester alcohols, tridecyl alcohol, isopropanol, 2 to 4 Aliphatic alcohols having carbon atoms of, or ketones such as acetone or ethyl methyl ketone, glycols or glycol ethers such as tripropylene glycol methyl ether, propylene glycol monoethyl ether, or ethylene glycol and propylene glycol, for example. A diol, or a polyether diol such as polyethylene glycol and polypropylene glycol, or such as trimethylolethane, trimethylolpropane, glycerin, 1,2,4-butanetriol, 1,2,6-hexanetriol and pentaerythritol, Conventionally used in the field of ceramic coating compositions such as polyols such as aliphatic triols and tetraols having 2 to 6 carbon atoms and all other solvents from other classes of compounds or mixtures of the above solvents. It is a thing. Preferred is the use of the solvents listed in Karsten, Lackrohofftabellellen [Coating Raw Material Tables], 8th Edition 1987. In particular, solvents that are highly miscible with water are used.

Lotions generally comprise from 0 to 90% by weight, preferably from 5 to 80% by weight, in particular from 20 to 70% by weight, based on the lotion, of water and / or organic solvents or solvent mixtures.
As an additional further ingredient, the cosmetic soil may contain up to 15% by weight, preferably 0.1 to 5% by weight, of one or more viscosity modifiers. Such regulators are likewise known from the prior art and examples thereof are ethylcellulose, nitrocellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, acrylic resins, poly (vinyl) butyral resins, carboxymethylcellulose and ethylhydroxyethylcellulose. is there.
Lozenges may also contain further modifying ingredients such as dispersants, wetting agents, antisettling agents, flow aids and the like.

The frit, optionally containing further additives, colorants or coloring pigments, is used to grind to a fineness of 0.1-300 μm, preferably 10-20 μm, preferably wet-milled. Finally, the effect pigment is mixed.
The finished facing soil can be applied to the tile, clay, glass or ceramic surface by conventional application methods such as spraying, brushing, flow coating or dipping. This is preferably applied to fired or non-fired tiles, fired or non-fired ceramics and ceramics. Makeup soil is preferably applied to unbaked products. The applied soil is subsequently dried, preferably at 50-200 ° C. for 0.5-5 hours. Finally, the coated product is calcined at 400-1200 ° C for several hours, preferably 2-48 hours.

Cosmetic soils containing effect pigments according to the present invention provide baked goods such as unfired roof tiles, and ceramic coatings such as glazed tiles and non-glaze tiles, providing color and luster and accents of new and interesting colors. It has significantly improved optical properties in terms of possibilities.
The effect pigments according to the invention are furthermore flowable pigment preparations and dry preparations, in particular printing inks and surface coatings, preferably automotive paints, which consist of the effect pigments according to the invention, a binder and optionally one or more additives. Suitable for the preparation of

The invention further relates to the use of the effect pigments according to the invention for the laser marking of paints, coatings, printing inks, plastics, ceramic materials, glass, plastics and papers and in cosmetic formulations, especially in printing inks. .. The effect pigments according to the invention are furthermore suitable for the preparation of pigment preparations, such as, for example, granules, particles, pellets, briquettes and for the preparation of dry preparations. The dry preparations are particularly suitable for surface coatings and printing inks.
The invention therefore also relates to formulations containing the effect pigments according to the invention.

  The following examples are intended to illustrate the invention without, however, limiting it.

Example 1
100 g of Iriodin® 103 (TiO ₂ / mica pigment from Merck) are stirred in 2 l of pure water and heated to 70 ° C. Then 60 g of 32% antimony (III) chloride solution are weighed in, while keeping pH 4.5 constant by simultaneous dropwise addition of 32% aqueous sodium hydroxide solution. When the addition is complete, the mixture is stirred for another 30 minutes. The product is filtered, washed and dried at 110 ° C. for 10 hours, followed by calcination at 850 ° C. for 30 minutes, then sieving, white overtone, high gloss and the following particle size distribution:
D ₁₀ = 10 μm
D ₉₀ = 60 μm
An effect pigment having is obtained.
The effect pigment of Example 1 is stable at temperatures> 1000 ° C.

Example 2
100 g of Xrallic® Crystal Silver (Al ₂ O ₃ flakes coated with TiO ₂ , effect pigment from Merck) are suspended in 2 l of pure water and the suspension is heated to 85 ° C. Then 55 g of 32% antimony (III) chloride solution are weighed in, while keeping pH 4.5 constant by simultaneous dropwise addition of 32% aqueous sodium hydroxide solution. When the addition is complete, the mixture is stirred for another 30 minutes. The product is filtered, washed and dried at 110 ° C. for 12 hours, followed by calcination at 850 ° C. for 45 minutes and then sieving, white overtone, very high gloss, very strong glitter effect (Sparkle-). Effekt) and the following particle size distribution:
D ₁₀ = 5 μm
D ₉₀ = 30 μm
An effect pigment having is obtained.
The effect pigment of Example 2 is stable at temperatures> 1100 ° C.

Example 3
100 g of Miraval® Cosmic Silver (TiO ₂ coated glass flakes, effect pigment from Merck) are suspended in 2 l of pure water and the suspension is heated to 85 ° C. Then 55 g of 32% antimony (III) chloride solution are weighed in, while keeping pH 4.5 constant by simultaneous dropwise addition of 32% aqueous sodium hydroxide solution. When the addition is complete, the mixture is stirred for another 30 minutes. The product is filtered, washed and dried at 110 ° C. for 12 hours, followed by calcination at 850 ° C. for 45 minutes and then sieving, white overtone, very high gloss, very strong shine effect (Glitzereffekt). And the following particle size distribution:
D ₁₀ = 20 μm
D ₉₀ = 200 μm
An effect pigment having is obtained.
The effect pigment of Example 3 is stable at temperatures> 1000 ° C.

Example 4
100 g of mica flakes are stirred in 2 l of pure water and heated to 70 ° C. 90 g of tin (IV) chloride solution are then weighed in, while keeping pH 2.3 constant by simultaneous dropwise addition of 32% aqueous sodium hydroxide solution. Then 200 g of titanium (IV) chloride solution is weighed in, while keeping the pH 1.9 constant by simultaneous dropwise addition of 32% aqueous sodium hydroxide solution. Then 60 g of 32% antimony (III) chloride solution is added dropwise, while keeping the pH 4.5 constant by the simultaneous addition of 32% aqueous sodium hydroxide solution. When the addition is complete, the mixture is stirred for another 30 minutes. The product is filtered, washed and dried at 110 ° C. for 10 hours, followed by calcination at 850 ° C. for 30 minutes, then sieving, white overtone, high gloss and the following particle size distribution:
D ₁₀ = 10 μm
D ₉₀ = 60 μm
An effect pigment having is obtained.
The effect pigment of Example 4 is stable at temperatures> 1000 ° C.

Example 5
100 g of mica flakes are stirred in 2 l of pure water and heated to 70 ° C. 90 g of tin (IV) chloride solution are then weighed in, while keeping pH 2.3 constant by simultaneous dropwise addition of 32% aqueous sodium hydroxide solution. Then 200 g of titanium (IV) chloride solution is weighed in, while keeping the pH 1.9 constant by simultaneous dropwise addition of 32% aqueous sodium hydroxide solution. Then 60 g of 32% antimony (III) chloride solution is added dropwise, while keeping the pH 4.5 constant by the simultaneous addition of 32% aqueous sodium hydroxide solution. When the addition is complete, the mixture is stirred for another 30 minutes. The product is filtered, washed and dried at 110 ° C. for 10 hours, followed by calcination at 850 ° C. for 30 minutes and then sieving, white overtone, medium gloss and the following particle size distribution:
D ₁₀ = 5 μm
D ₉₀ = 25 μm
An effect pigment having is obtained.
The effect pigment of Example 5 is stable at temperatures> 1000 ° C.

Example 6
100 g of Iriodin® 100 (TiO ₂ coated mica flakes, effect pigment from Merck) are stirred in 2 l of pure water and heated to 70 ° C. Then 60 g of 32% antimony (III) chloride solution is weighed in and pH 4.5 is kept constant by simultaneous dropwise addition of 32% aqueous sodium hydroxide solution. When the addition is complete, the mixture is stirred for another 30 minutes. The product is filtered, washed and dried at 110 ° C. for 10 hours, followed by calcination at 1000 ° C. for 30 minutes, then sieving, white overtone, high gloss and the following particle size distribution:
D ₁₀ = 10 μm
D ₉₀ = 60 μm
An effect pigment having is obtained.
The effect pigment of Example 6 is stable at temperatures> 1000 ° C.

Example 7
100 g of Iriodin® 123 (TiO ₂ coated mica flake, effect pigment from Merck) are stirred in 2 l of pure water and heated to 70 ° C. Then 60 g of 32% tin (IV) chloride / antimony (III) solution are weighed in, while keeping pH 4.5 constant by simultaneous dropwise addition of 32% aqueous sodium hydroxide solution. When the addition is complete, the mixture is stirred for another 30 minutes. The product is filtered, washed and dried at 110 ° C. for 10 hours, followed by calcination at 850 ° C. for 30 minutes, then sieving, white overtone, medium gloss and glitter effect and the following particle size distribution:
D ₁₀ = 5 μm
D ₉₀ = 25 μm
An effect pigment having is obtained.
The effect pigment of Example 7 is stable at temperatures> 1000 ° C.

Example 8
100 g of Iriodin® 6163 (synthetic mica flake coated with TiO ₂ , effect pigment from Merck) are suspended in 2 l of pure water and the suspension is heated to 85 ° C. Then 55 g of 32% antimony (III) chloride solution are weighed in, while keeping pH 4.5 constant by simultaneous dropwise addition of 32% aqueous sodium hydroxide solution. When the addition is complete, the mixture is stirred for another 30 minutes. The product is filtered, washed and dried at 110 ° C. for 12 hours, followed by calcination at 850 ° C. for 45 minutes, then sieving, white overtone, high gloss effect and strong shimmer effect and the following particle size distribution:
D ₁₀ = 20 μm
D ₉₀ = 180 μm
An effect pigment having is obtained.
The effect pigment of Example 8 is stable at temperatures> 1000 ° C.

Example 9
100 g of Colorstream® Viola Fantasy (SiO ₂ flakes coated with TiO ₂ , effect pigment from Merck) are suspended in 2 l of pure water and the suspension is heated to 85 ° C. Then 55 g of 32% antimony (III) chloride solution are weighed in, while keeping pH 4.5 constant by simultaneous dropwise addition of 32% aqueous sodium hydroxide solution. When the addition is complete, the mixture is stirred for another 30 minutes. The product is filtered, washed and dried at 110 ° C. for 12 hours, followed by calcination at 850 ° C. for 45 minutes and then sieving, white overtone, very high gloss, color flop and the following particle size distribution:
D ₁₀ = 5 μm
D ₉₀ = 50 μm
An effect pigment having is obtained.
The effect pigment of Example 9 is stable at temperatures> 1000 ° C.

Example 10
100 g of Iriodin® 183 (TiO ₂ coated mica flake, effect pigment from Merck) are stirred in 2 l of pure water and heated to 70 ° C. Then 60 g of antimony (III) chloride solution are weighed in, while keeping pH 4.5 constant by simultaneous dropwise addition of 32% aqueous sodium hydroxide solution. When the addition is complete, the mixture is stirred for another 30 minutes. The product is filtered, washed and dried at 110 ° C. for 10 hours, followed by calcination at 1000 ° C. for 30 minutes, then sieving, white overtone, high gloss, strong glitter effect and the following particle size distribution:
D ₁₀ = 45 μm
D ₉₀ = 500 μm
An effect pigment having is obtained.
The effect pigment of Example 10 is stable at> 1000 ° C.

  The improved stability of the effect pigments prepared in Examples 1 to 10 was demonstrated in each case by an undungspezifischen Test in comparison with unstabilized pigments. To this end, unstabilized pigments (for example Iriodin® 103 in Example 1) and in each case stabilized pigments are used in the same way and two workpieces are used for the color and pearl luster. Visually evaluate the effect. The stabilized pigments in each case show less discoloration and better pearlescent effect compared to the corresponding commercial or unstabilized effect pigments.

  Here, the use for screen printing of a porcelain workpiece divided into three steps will be described as a representative.

1) Preparation of printing paste In order to create fine color grid and relief-like printing on a ceramic substrate using ceramic colors, screen printing that prevents the flow of color paste after printing and produces printing with sharp contours. Use oil. For this purpose, known binders are used, which are incorporated into finely divided natural or synthetic waxes and / or finely divided inorganic silicates or into the solvent silicate structure during firing. It is composed of oxidizable substances. Pearlescent pigments with corresponding amounts of frits and print media (screen printing oil 221-ME and Screenprint Bulk 803035, both commercially available from Ferro-in the examples) were used in a series of experiments. Weigh out and homogenize.

以下の工程は、印刷ペーストの組成から独立している。 The effect pigments according to Examples 1 to 10 were weighed out and homogenized with corresponding amounts of frits of the following compositions:

The following steps are independent of the composition of the printing paste.

2) Printing of tiles The resulting printing paste can be applied to tiles by standard printing methods, slip methods (Schlickverfahren), spray application or transfer printing. In all cases, the printed tiles are dried in a drying cabinet or draft at a temperature of 60-110 ° C. in order to evaporate the solvent present in the printing oil. In an example according to the invention, the printing paste is applied to the tiles using a doctor blade and screen printing.

3) Baking of printed tiles The printed and dried tiles are then fired using a temperature profile in a baking oven.

Claims (14)

  An effect pigment based on a flaky substrate, characterized in that the pigment has on its surface a surface layer comprising one or more antimony oxides and a mixture of antimony oxides. The effect pigment according to claim 1, characterized in that the effect pigment has a surface layer containing Sb _x O _y on the surface, where x = 2 and y = 3, 4, 5. The effect pigment according to claim 1, wherein the surface layer is made of Sb ₂ O ₄ .   Effect pigment according to any one of claims 1 to 3, characterized in that the surface layer is in an amount of 5 to 50% by weight, based on the total pigment.   Effect pigment according to any one of claims 1 to 4, characterized in that the surface layer has a thickness of 1 to 100 nm.   The effect pigment according to any one of claims 1 to 5, characterized in that the effect pigment is selected from the group of pearlescent pigments, interference pigments, multilayer pigments and hologram pigments. 7. The effect pigments according to claim 1, wherein the effect pigments are based on natural or synthetic mica flakes, SiO ₂ flakes, glass flakes, TiO ₂ flakes or Al ₂ O ₃ flakes. Effect pigments. 8. The effect pigment according to claim 1, characterized in that it comprises at least one TiO ₂ layer and / or at least one titanium oxynitride layer on the flaky substrate. Effect pigments. The effect pigment has the following structure:
Base material flake + TiO ₂
Base material flake + titanium oxynitride base material flake + SiO ₂ + TiO ₂
Base material flakes + SnO ₂ + TiO ₂
Base material flakes + Cr ₂ O ₃ + TiO ₂
Base material flake + Ce ₂ O ₃ + TiO ₂
Base material flakes + ZrO ₂ + TiO ₂
Base material flake + TiO ₂ + Cr ₂ O ₃
Base material flakes + TiO ₂ + SiO ₂ + TiO ₂
Base material flakes + TiO ₂ + SiO ₂
Base material flake + TiO ₂ + SnO ₂ + TiO ₂
Base material flake + TiO ₂ + Fe ₂ O ₃
Base material flakes + Fe ₂ O ₃ + TiO ₂
Base material flakes + TiO ₂ + Al ₂ O ₃ + TiO ₂
Base material flake + TiO ₂ + ZrO ₂ + TiO ₂
The effect pigment according to any one of claims 1 to 8, which comprises: The effect pigments are the following groups of effect pigments:
Natural mica flakes + TiO ₂
Natural Mica Flake + Titanium Oxynitride Synthetic Mica Flake + TiO ₂
Synthetic mica flakes + titanium oxynitride Al ₂ O ₃ flakes + TiO ₂
Al ₂ O ₃ flakes + titanium oxynitride SiO ₂ flakes + TiO ₂
SiO ₂ flakes + titanium oxynitride glass flakes + TiO ₂
Glass flakes + titanium oxynitride Fe ₂ O ₃ flakes + TiO ₂
Fe ₂ O ₃ flakes + titanium oxynitride TiO ₂ flakes + TiO ₂
TiO ₂ flakes + ZrO ₂ + TiO ₂
TiO ₂ flakes + SiO ₂ + TiO ₂
Effect pigment according to any one of claims 1 to 9, characterized in that it is selected from   A method for preparing an effect pigment according to any one of claims 1 to 10, characterized in that the antimony oxide layer is applied to the effect pigment by a wet chemical method or a gas phase coating.   Use of the effect pigments according to any one of claims 1 to 10, for the laser marking of paints, coatings, printing inks, plastics, ceramic materials, glass, plastics and papers, in cosmetic preparations, pigment preparations. And for use in the preparation of dry preparations.   Use of the effect pigments according to claim 12 for the coloring of glazes, cosmetic soils and enamel.   A preparation comprising the effect pigment according to any one of claims 1 to 10.