Pigment mixture

The present invention relates to pigment mixtures consisting of at least two components, where component A comprises multilayered pigments (Multilayer pigments) based on mica, SiO₂platelets, Glass flakes, Al₂O₃Flakes or polymer flakes and component B platelet-shaped, needle-shaped or spherical colorants and / or Fillers, and their use in coatings, paints, printing inks, Plastics, powder coating materials, ceramic glazes, plastic films and cosmetic formulations.

Opacity and gloss are in platelet-shaped pigments often difficulties at the same time realize a satisfactory extent. So are characterized as having one or more thin metal mica platelets covered or SiO₂Platelets by interference colors and high gloss, at the same time but also owing to the transparent Substrate by a high transparency and hence a comparatively poor hiding power from.

From DE-A-42 40 511 a pigment mixture is known, the off an interference pigment and a platelet-shaped color pigment composed. The interference pigment are coated with metal oxides Mica or SiO₂Platelets and the color pigment, colored SiO₂be flakes. This pigment mixture is in coatings, printing inks, Plastics or cosmetics incorporated.

Object of the present invention is to provide a pigment mixture which is characterized by a relatively high coverage and can be readily incorporated into the respective application system and at the same time a separation of pigment / colorant in the system is largely excluded.

Surprisingly, a pigment blend was found that has none of the above disadvantages. The invention Pigment mixture consisting of at least two components, wherein Component A multilayered pigments (multilayer pigments) based on Mica, SiO₂Flakes, glass flakes, Al₂O₃Platelets or polymer platelets, and component B flaky, needle-like or spherical colorants and / or fillers.

The admixing of one or more colorants to the multilayered pigments (Multilayer pigments) can the application systems awarded a color flop (strongly angle-dependent color impression) be, the color effect is amplified and novel color effects achieved.

The invention thus relates to a pigment mixture consisting of at least two components, where component A comprises multilayered pigments (Multilayer pigments) based on mica, SiO₂platelets, Glass flakes, Al₂O₃Flakes or polymer flakes and component B platelet-shaped, needle-shaped or spherical colorants and / or Fillers.

The invention relates also to formulations, such as. B. Paints, varnishes, printing inks, plastics, powder coatings, ceramic Glazes, plastic and cosmetic preparations which the Pigment mixture according to the invention contain.

The multilayer pigments can be used in any ratio with the colorant or filler are mixed. Preferably, the ratio of Component A to component B is 1: 20 to 20: 1, especially 1: 10 to 10: 1.

The example from German Offenlegungsschriften DE 196 18 563, DE 196 18 566, DE 196 18 569, DE 197 07 805 DE 197 07 806 EN based 197 46 067 known multilayered pigments on a platelet-shaped, transparent, colored or colorless matrix, consisting of mica (synthetic or natural), SiO₂Flakes, glass flakes, Al₂O₃Flakes, polymer flakes, and generally have a thickness between 0.3 and 5 .mu.m, in particular between 0.4 and 2.0 .mu.m. is the expansion in the other two dimensions usually between 1 and 250 microns, preferably between 2 and 100 microns, and in particular between 5 and 40 microns. The multilayer pigments consist of the matrix (substrate) coated with metal oxides (At least 2). The coating of the substrate flakes mica, SiO₂platelets, Glass flakes, Al₂O₃done flakes with several layers so that a layer structure consisting of alternating high- and low refractive index layers is formed. Preferably contain Multilayered pigments 2, 3, 4, 5, 6 or 7 layers, in particular 3, 4 or 5 layers. Suitable highly refractive metal oxides are, for example, Titanium dioxide, zirconium oxide, zinc oxide, iron, iron-titanium oxides (Iron titanates) and / or chromium oxide, in particular TiO₂ and / or Fe₂O₃, As low refractive metal oxides are SiO₂ and Al₂O₃ for use. It can also, however, this MgF₂ or an organic polymer (for example, Acrylate) are used. The coating of the substrate flakes can eg carried out as described in WO 93/08237 (wet chemical coating) or DE-OS-196 14 637 (CVD) method described.

Preferred multilayered pigments have the following structure:<sl><li>Substrate + Fe₂O₃Layer + SiO₂Layer + Fe₂O₃-Layer</li><li>Substrate + Fe₂O₃Layer + SiO₂Layer + TiO₂-Layer</li><li>Substrate + TiO₂Layer + SiO₂Layer + Fe₂O₃-Layer</li><li>Substrate + TiO₂Layer + SiO₂Layer + TiO₂/ Fe₂O₃-Layer</li><li>Substrate + TiO₂/ Fe₂O₃Layer + SiO₂Layer + TiO₂/ Fe₂O₃-Layer</li><li>Substrate + TiO₂Layer + SiO₂Layer + Cr₂O₃-Layer</li></sl>

Instead of the outer metal oxide layer may also be a semi-transparent Layer of metal can be used. Suitable metals for this are For example, Cr, Ti, Mo, W, Al, Cu, Ag, Au or Ni.

To achieve special color effects in the high- and low-refractive Layers additionally finely divided particles in the nanometer size range are introduced. Suitable for this purpose prove for example finely divided TiO₂ or finely divided carbon (carbon black) with Particle sizes in the range of 10-250 nm. The light-diffusing Properties of such particles can be targeted on luster and hiding power Be influenced.

The multilayer pigments can also improve the lighting, Weather and chemical stability or to increase compatibility in different media be provided with a protective layer. As Post-coatings or post-treatments are, for example, in DE 22 15 191, DE 31 51 354, DE 32 35 017 or DE 33 34 598 described method in question. The additionally applied substances make up only about 0.1 to 5 wt .-%, preferably 0.5 to 3.0 wt .-%, of the Multilayer pigment from.

As component B for the pigment mixture according to the invention are all known to those skilled flaky, needle-shaped and spherical Colorants or fillers capable of a particle size 0.001 to 10 microns, preferably 0.01 to 1 .mu.m. Prefers the pigment mixtures of the invention as a colorant Absorption pigments and platelet-shaped or spherical as fillers Powder. Component B preferably comprises coated or uncoated SiO₂Balls. With one or more metal oxides coated SiO₂Balls are known for example from EP 0803550 A2.

Preferred pigment mixtures in addition to component A as a colorant (Component B) in particular a pearlescent pigment. The pearlescent Pigments on platelet-shaped base, transparent or semitransparent substrates comprising, for example phyllosilicates, such as Mica, synthetic mica, talc, sericite, kaolin, glass or other silicate materials, the colorless or colored with Metal oxides such as TiO₂, Titanium suboxides, titanium oxynitrides, Fe₂O₃. Fe₃O₄, SnO₂, Cr₂O₃, ZnO, CuO, NiO and other metal oxides, alone or in a mixture in a uniform layer or in successive Layers are coated. Pearlescent pigments are, for example from the German Patents and Patent Applications 14 67 468, 19 59 998 20 09 566 22 14 454 22 15 191, 22 44 298, 23 13 331, 25 22 572, 31 37 808 31 37 809 31 51 343 31 51 354 31 51 355 32 11 602 32 35 017 and P 38 42 330 and are commercially available, eg under the trade name Iriodin® from Merck KGaA, Darmstadt, Germany. Particularly preferred pigment preparations comprise TiO₂/Mica-, Fe₂O₃/ Mica and / or TiO₂/ Fe₂O₃Mica pigments.

Also preferred are TiO₂ and / or Fe₂O₃ coated SiO₂- or Al₂O₃Platelets. The coating of SiO₂Flakes with one or more metal oxides can be done for example as described in WO 93/08237 (wet-chemical Coating) or DE-A 196 14 637 (CVD) described.

The flake-form colorants are, in particular pearlescent pigments in particular based on mica, SiO₂Flakes, Al₂O₃flakes or glass flakes that are coated with a metal oxide layer, Metallic effect pigments (Al flakes, bronzes), optically variable pigments (OVP's), liquid crystal polymer pigments (LCPs) or holographic Pigments.

The spherical colorants include, in particular TiO₂, Colored SiO₂, CaSO₄, Iron oxides, chromium oxides, carbon black, organic color pigments, such as anthraquinone pigments, quinacridone pigments, diketopyrrolopyrrole pigments, Phthalocyanine pigments, azo pigments, isoindoline pigments. The needle-shaped pigments are preferably BiOCl, colored glass fibers, α-FeOOH, organic colored pigments, such as azo pigments, β-phthalocyanine CI Blue 15.3, Cromophtalgelb 8GN (Ciba-Geigy), Irgalith Blue PD56 (Ciba-Geigy), Azomethinkupferkomplex CI Yellow 129, Irgazingelb 5GT (Ciba-Geigy).

The pigment mixture according to the invention is simple and easy to handle. The pigment mixture can be prepared by simply stirring in the Application system are incorporated. Complex grinding and Dispersing the pigments is not necessary.

The pigment mixture according to the invention can for pigmenting Paints, printing inks, plastics, agricultural films, seed coating, Food colorings, button pastes, medicament coatings or cosmetic formulations, such as lipsticks, nail varnishes, compact powders, Shampoos, loose powders and gels, are used. The concentration the pigment mixture in the application system to be pigmented is generally between 0.1 and 70 wt.%, preferably between 0.1 and 50 wt.% And in particular between 1.0 and 10 wt.%, Based on the total solids content of the system. It depends generally the specific application.

Plastics comprising the pigment mixture according to the invention in quantities from 0.01 to 50. wt.%, preferably 0.1 to 7 wt%, characterized often by a particular color flop effect, but also by an Sparkle effect from.

In the coatings sector, in particular in automobile paints, the pigment mixture, also for 3-layer structures in amounts of 0.1-10 wt.%, preferably 1 to 3 wt.%, are used. The mixing ratio of Multilayered pigments with component B depends on the desired effect from. Preferably, the multilayer pigments are mixed with component B in Ratio of 10: 1 to 1: 10, are used.

In the varnish, the pigment mixture of the invention has the advantage that the desired color flop effect by a single finish ( or base coat in 2-Schichaufbau) is achieved. This Color flop is extremely pronounced even under diffuse light. Compared with paint containing an interference pigment based on mica instead of multilayer pigments, finishes comprising the inventive Pigment mixture a clearer depth effect and a glitter effect.

The pigment mixture according to the invention can also be beneficial in the decorative and care cosmetics are used. The concentration and the mixing ratio of multilayer pigments with Component B, in particular organic and inorganic color pigments and coloring agents, natural or synthetic origin, such as eg chromium oxide, ultramarine, spherical SiO₂- Or TiO₂Pigments are, depending on the application medium and the effect that can be achieved should. The mixture of multilayer pigments with other pigments or dyes can be carried out in all ratios, preferably the ratio is 1: 10 to 10: 1. The use concentration extends from 0.01.% In shampoo to 70 wt.% In compact powders. At a Mixture of multilayer pigments with spherical fillers, z. B. SiO₂, The concentration at 0.01-70 wt can.% In the formulation lie. The cosmetic products, such as nail varnishes, lipsticks, Compact powders, shampoos, loose powders and gels, are distinguished by particularly interesting gloss and / or color effects, depending on the structure of the can be multi-layer pigment highly angle dependent. The glitter effect in nail polish can over conventional nail varnishes with the help of The pigment mixtures according to the invention can be increased significantly. furthermore may pigment mixture of the invention in bath products, toothpastes and for the finishing of foods, eg. example mass coloring or be used as a coating.

In the pigmentation of binder systems, for. Example for paints and Printing inks for gravure, offset or screen printing, or as Precursor for printing inks, for example in the form of highly pigmented pastes, Granules, pellets, etc., pigment mixtures have consisting of multilayer pigments with spherical colorants, such as eg TiO₂, Chromium oxide, iron oxide and organic "colored pigments" proved to be particularly suitable. The pigment mixture is generally in the printing ink in amounts of 2-35.%, preferably 5-25 wt.%, and in particular 8-20 wt.% incorporated. Offset printing inks the pigment mixture up to 40 wt.% and contain more. The precursors for printing inks, for example in the form of granules, pellets, briquettes, etc., in addition to the binder and additives up to 95 wt.% of Pigment mixture according to the invention. The mixing ratio of Component A to component B is preferably in the range of 1: 10 to 10: 1. The printing inks comprising the pigment mixture according to the invention exhibit purer hues and are due to the good values ​​for the viscosity of improved printability.

The invention thus also relates to formulations comprising the Pigment mixture according to the invention.

The following examples illustrate the invention without however, limiting.

<b>Examples</b>

Example 1: - ink

The pigment was at 600 rpm in the solvent-containing binder stirred and the inks were subsequently on black and white card knife.

Color no. 1:

<dl tsize="7" compact="compact"><dt>88.0 g</dt><dd>Gebr. Schmidt 95 MB 011 TW</dd><dt>10.0 g</dt><dd>Multilayered pigment consisting of mica flakes Particle size 5-40 microns, both sides with 3 layers in the sequence Fe₂O₃, SiO₂, Fe₂O₃</dd><dt>2.0g</dt><dd>Gebr. Schmidt 95 MB 022-TW (Green)</dd></dl>

Color no. 2: Comparison

<dl tsize="7" compact="compact"><dt>88.0 g</dt><dd>Gebr. Schmidt 95 MB 011 TW</dd><dt>10.0 g</dt><dd>with Fe₂O₃ coated mica of particle size 10 to 60 microns (Fa. Merck KGaA)</dd><dt>2.0g</dt><dd>Gebr. Schmidt 95 MB 022-TW (Green)</dd></dl>

The color chart with color no. 1 is visually a much better Color flop than the color card with the comparison color no. 2,.

Example 2: - Car Paint

<dl tsize="8" compact="compact"><dt>2.0g</dt><dd>SiO₂Flakes 5-40μm particle size, both sides coated with 3 layers in the sequence Fe₂O₃, SiO₂, Fe₂O₃</dd><dt>1.5 g</dt><dd>Heliogenblau L 6930</dd><dt>0.2 g</dt><dd>Hostapermgrün 8G</dd><dt>0.05 g</dt><dd>Color black FW 200</dd><dt>66.6 g</dt><dd>Basecoat (A4) MP system (FK = 19%)</dd><dt>29.65 g</dt><dd>Verdünnermischung</dd></dl>

It is a color with a pronounced blue-green envelope and reached golden highlights that even up toward dark violet can oscillate.

Example 3: - Plastic

The plastic granules Polypropylene PP Stamylan PPH10 (Fa. DSM) or polystyrene 143E (Fa. BASF) are each<sl><li>a) 1% SiO₂Flakes of particle size 5-40 microns, both sides coated with 3 layers of consequence Fe₂O₃, SiO₂, Fe₂O₃</li><li>b) a mixture of 1% SiO₂Flakes of particle size 5-40 microns, both sides coated with 3 layers in the sequence Fe₂O₃, SiO₂, Fe₂O₃ and 0.1 % PV Fast Blue B2G01 (Pigment Blue 15.3 Fa. Clariant)</li><li>c) 1% with Fe₂O₃ coated mica of particle size 10-60 microns (Merck KGaA)</li><li>d) a mixture of 1% with Fe₂O₃ coated mica of particle size 10-60 microns (Merck KGaA) and 0.1% PV Fast Blue B2G01 (Pigment Blue 15.3 Fa. Clariant)</li></sl>added.

The pigmented granules are then at a spraying machine Stepped plates processed.

is with the use of the pigment in a) and in the mixture under b) achieved a strong angle-dependent color impression of the plastic. This in the case of b) are considerably more varied and can be, for. example, for a strong blue-green envelope used.

Example 4: - Eyeshadow

phase 1

<dl tsize="8" compact="compact"><dt>5.00%</dt><dd>silica</dd><dt>25.00%</dt><dd>SiO₂Flakes of particle size 5-40 microns coated with 3 Layers in the sequence Fe₂O₃, SiO₂, Fe₂O₃</dd><dt>5.00%</dt><dd>CI Pigment Green 18 (CI77289)</dd><dt>47.42%</dt><dd>Talc</dd><dt>7.18%</dt><dd>Solanum tuberosum (Potato Starch)</dd><dt>2.40%</dt><dd>magnesium Stearate</dd></dl>

phase II

<dl tsize="7" compact="compact"><dt>6.96%</dt><dd>isopropyl Stearate</dd><dt>0.40%</dt><dd>Cetyl Palmitate</dd><dt>0.40%</dt><dd>petrolatum</dd><dt>0.08%</dt><dd>preservation</dd></dl>

The components of Phase I are combined and premixed. Subsequently, the powder mixture with stirring dropwise with molten phase II added. The powders are at 40-50 bar pressed.

The eye shadow obtained is characterized by an intense shine and a strong iridescent color impression when you from viewing angle.

Example 5: - Lipstick

phase I

<dl tsize="12" compact="compact"><dt>8.25%</dt><dd>Cera alba</dd><dt>4.95%</dt><dd>Ceresin, Copernica Cerifera</dd><dt>3.30%</dt><dd>lanolin Oil</dd><dt>5.28%</dt><dd>isopropyl Myristate</dd><dt>1.98%</dt><dd>mineral Oil</dd><dt>0.03%</dt><dd>Tocopherol, Ascorbyl Palmitate, Ascorbic Acid, Citric Acid, PEG-8</dd><dt>0.06%</dt><dd>preservation </dd><dt>0.50%</dt><dd>aroma</dd><dt>1.00%</dt><dd>Lithalrubin BK, CI Pigment Red 57: 1 (CI 15850)</dd><dt>100.00%</dt><dd>Ricinus communis (20% in Castor Oil)</dd></dl>

phase II

<dl tsize="8" compact="compact"><dt>2.00%</dt><dd>silica</dd><dt>15.00%</dt><dd>SiO₂Flakes of particle size 5-40 microns coated with 3 Layers in the sequence Fe₂O₃, SiO₂, Fe₂O₃</dd></dl>

The components of Phase I are heated to 75 ° C and melted. The pigments of phase II is added and stirred everything well. The lipstick composition is then in the temperature-controlled at 65 ° C casting apparatus 15 min stirred.. The homogeneous melt into the 65 ° C preheated molds cast. It is then cooled, the molds and removes the castings cold.

The lipstick is characterized by an intense shine and a strong iridescent color impression when you from viewing angle.

Example 6 - Shower Gel

phase A

<dl tsize="7" compact="compact"><dt>0.10%</dt><dd>Mica pigment of particle size 10-60 microns, both sides coated with TiO₂, SiO₂, TiO₂ (1)</dd><dt>0.75%</dt><dd>Xanthan Gum (2)</dd><dt>62.10%</dt><dd>water</dd></dl>

phase B

<dl tsize="8" compact="compact"><dt>20.00%</dt><dd>Decyl Glucoside (3)</dd><dt>6.65%</dt><dd>Texapon.RTM ASV (Sodium Laureth Sulfate, Magnesium Laureth Sulfate, Sodium Laureth-8 Sulfate, Magnesium Laureth-8 Sulfate, Sodium Oleth Sulfate, Magnesium Oleth Sulfate (3)</dd><dt>0.20%</dt><dd>Bronidox L (Propylene Glycol, 5-bromo-5-nitro-1,3-dioxane) (3)</dd><dt>0.05%</dt><dd>Perfume (perfume oil Everest 79658 SB) (4)</dd></dl>

phase C

<dl tsize="7" compact="compact"><dt>0.15%</dt><dd>Citric Acid (1)</dd><dt>0.10%</dt><dd>Sicovit Green Z 6120 (1% in water) [CI 19140/42051] (5)</dd><dt>10.00%</dt><dd>water</dd></dl>

Sources:

<sl><li>(1) Merck KGaA</li><li>(2) Monsanto</li><li>(3) Henkel KGaA</li><li>(4) Haarmann &amp; Reimer</li><li>(5) BASF</li></sl>

For Phase A, the pigment is stirred into water. Xanthan Gum is slowly sprinkled with stirring into the suspension and stirred until it is resolved. Phases B and C are successively added and then, as long is stirred until everything is distributed homogeneously.

The shower gel is characterized by intensive interference glitter effects.

Example 7: - Eyeliner Gel

phase A

<dl tsize="8" compact="compact"><dt>15.00%</dt><dd>Mica pigment of particle size 10-60 microns, both sides coated with TiO₂, SiO₂, TiO₂ (1)</dd><dt>5.0%</dt><dd>Mica pigment of particle size 10-60 microns coated with Fe₃O₄ (1)</dd><dt>2.00%</dt><dd>Ronasphere® (silica) (1)</dd><dt>0.40%</dt><dd>Carbopol ETD 2001 (Carbomer) (2)</dd><dt>qs</dt><dd>Citric acid (1)</dd><dt>60.00%</dt><dd>water</dd></dl>

phase B

<dl tsize="12" compact="compact"><dt>4.0%</dt><dd>Glycerine (1)</dd><dt>0.90%</dt><dd>Triethanolamine (1)</dd><dt>2.00%</dt><dd>Luviskol.RTM VA 64 powder (PVP / VA Copolymer) (3) </dd><dt>0.20%</dt><dd>Germaben II (Propylene Glycol, Diazolidinyl Urea, Methyl paraben, propyl paraben) (4)</dd><dt>100.00%</dt><dd>water</dd></dl>

Sources:

<sl><li>(1) Merck KGaA</li><li>(2) BF Goodrich</li><li>(3) BASF</li><li>(4) ISP Europe</li></sl>

The pigments and Ronasphere® be in the water of phase A dispersed. With a few drops of citric acid solution of pH 3.8 is adjusted to reduce the viscosity. Carbopol is added with stirring interspersed. After complete dissolution of the pre-dissolved phase B slowly stirred.

The product obtained is characterized by high gloss and intense Interference color.