DE10229256A1 - Interference pigments with five or more layers including rutile titania and tin chloride are used in dyes, lacquers, inks, laser markings and cosmetics - Google Patents

Abstract

A 5-layered pigment has the following plate layers in sequence: (a) 0.1-50 Micro thick SnO 2; (b) 10-800 mu rutile TiO 2; (c) a colorless 20-800 mu layer with refractive index =1.8; (d) a layer as per (A); and (e) a layer as per (B); and optionally also (f) an external protective layer. An independent claim is also included for preparation of the pigment.

Description

The present invention relates to Five-layer pigments based on multi-coated platelet-shaped substrates.

Gloss or effect pigments used in many areas of technology, especially in the area car paints, decorative coatings, plastics, colors, Printing inks and in cosmetic formulations.

Shine pigments that change color depending on the angle between multiple interference colors are due to your Color play of particular interest for car paints and forgery-proof securities.

Processes for producing pearlescent pigments are known from the prior art, with the aid of which alternating layers with high and low refractive indices can be applied to finely divided substrates. Pigments of this type based on multi-coated platelet-shaped substrates are known, for example, from US Pat. No. 4,434,010, JP N7-759, US Pat. No. 3,438,796, US Pat. No. 5,135,812, DE 44 05 494 , DE 44 37 753, DE 195 16 181 and DE 195 15 988, DE 196 18 565, DE 197 46 067 and from the literature, for example from EURO COSMETICS, 1999, No. 8, p. 284.

Of particular importance Pearlescent pigments on a mineral basis. Pearlescent pigments by coating an inorganic, platelet-shaped carrier with a highly refractive, mostly made of oxide layer. The color of these pigments is through wavelength selective Partial reflection and interference of the reflected or transmitted Light caused at the medium / oxide or oxide / substrate interfaces.

The interference color of these pigments is determined by the thickness of the oxide layer. The hue of an interference silver pigment is due to a single high refractive index layer in the optical sense generated, the optical thickness of a reflection maximum (1st order) in the visible wavelength range conditional at approx. 500 nm. The human eye takes this wavelength than the color green true. The intensity course this maximum on their wavelength axis is so wide that so much light reflects in the whole range of visible light is that the human eye has a very bright but colorless Perceives impression.

According to the - especially from the compensation optical Components - known Rules of optics thinner In comparison to the single-layer system, layers increase the intensity at the interference maximum by more than 60. As a result, the profile of the interference reflected light much more pronounced, so for such multilayer system a green Reflection color is to be expected.

Surprisingly became five-layer pigments found that regarding their coloristic but also their application properties show significantly improved properties than the multilayer pigments from the state of the art. This could be done through an internal structuring of the high refractive index layers.

• (A) einer Schicht aus SnO₂ mit einer Schichtdicke von 0,1–50 nm,
• (B) einer Schicht aus TiO₂ in der Rutilmodifikation mit einer Schichtdicke von 10–800 nm,
• (C) einer farblosen Beschichtung mit einem Brechungsindex n < 1,8 mit einer Schichtdicke von 20–-800 nm,
• (D) einer Schicht aus SnO₂ mit einer Schichtdicke von 0,1-50 nm
• (E) einer Schicht aus TiOz in der Rutilmodifikation mit einer Schichtdicke von 10-800 nm, und optional
• (F) einer äußeren Schutzschicht

enthalten.The invention therefore relates to five-layer pigments based on multi-coated platelet-shaped substrates which comprise at least one layer sequence

• (A) a layer of SnO ₂ with a layer thickness of 0.1-50 nm,
• (B) a layer of TiO ₂ in the rutile modification with a layer thickness of 10-800 nm,
• (C) a colorless coating with a refractive index n <1.8 with a layer thickness of 20-800 nm,
• (D) a layer of SnO ₂ with a layer thickness of 0.1-50 nm
• (E) a layer of TiOz in the rutile modification with a layer thickness of 10-800 nm, and optional
• (F) an outer protective layer

contain.

• – eine deutlich erhöhte Helligkeit
• – einen stärkeren Glanz und
• – einen stärker ausgeprägten Farbflop

aufweisenThe multilayer pigments according to the invention are interference pigments compared to the known multilayer pigments with three layers

• - a significantly increased brightness
• - a stronger shine and
• - a more pronounced color flop

exhibit

The subject of the invention is furthermore the use of the multilayer pigments according to the invention in paints, varnishes, powder coatings, printing inks, plastics, ceramic Materials, glasses and cosmetic formulations, especially in the decorative Cosmetics. Furthermore, the pigments according to the invention are also for production of pigment preparations as well as for the production of dry preparations, e.g. granules, Chips, pellets, briquettes, etc. are suitable. The dry preparations are especially for Suitable for printing inks.

Suitable base substrates for the multilayer pigments according to the invention are colorless or selective tively or non-selectively absorbent platelet-shaped substrates. Layered silicates are preferred substrates. Natural and / or synthetic mica, talc, kaolin, platelet-shaped iron or aluminum oxides, glass, SiO ₂ -, TiO ₂ -, graphite platelets, synthetic carrier-free platelets, titanium nitride, titanium silicide, liquid crystal polymers (LCPs), holographic pigments are particularly suitable , BiOCl, platelet-shaped mixed oxides, such as FeTiO ₃ , Fe ₂ TiOs or other comparable materials.

The size of the base substrates is on is not critical and can be tailored to the respective application become. As a rule, the platelet-shaped substrates have a thickness between 0.005 and 10 μm, in particular between 0.05 and 5 μm. The expansion in the other two areas is usually between 1 and 500 μm, preferably between 2 and 200 μm and in particular between 5 and 60 μm.

The thickness of the layer (A) or (D) is 0.1-50 nm, preferably 0.3-30 nm, in particular 0.5-20 nm. The SnO ₂ layers (A) and (D) can be the same or have different layer thicknesses.

The thickness of each layer (B) and (C) and (E) with high and low refractive index on the Base substrate is essential for the optical properties of the pigment. For the multi-layer pigment according to the invention have to the thicknesses of the individual layers are precisely adjusted to each other become.

The thickness of the layer (B) or (E) is 10-800 nm, preferably 20-500 nm, in particular 30-400 nm. The TiO ₂ layers (B) and (E) can have the same or different layer thicknesses. The thickness of the layer (C) is 20-800 nm, preferably 30-600 nm, in particular 40-500 nm.

The colorless, low-index materials suitable for coating (C) are preferably metal oxides or the corresponding oxide hydrates, such as SiO ₂ , Al ₂ O ₃ , AlO (OH), B ₂ O ₃ , MgF ₂ , MgSiO ₃ or a mixture of the above Metal oxides, suitable. Layer (C) is in particular an SiO ₂ layer.

The five-layer pigments according to the invention can be manufacture by producing several high and low refractive indexes Interference layers with precisely defined thickness and smooth surface the finely divided, platelet-shaped substrates.

The metal oxide layers are preferably applied wet-chemically, it being possible to use the wet-chemical coating processes developed for the production of pearlescent pigments. Such methods are described, for example, in DE 14 67 468 , DE 19 59 988, DE 20 09 566, DE 22 14 545, DE 22 15 191, DE 22 44, 298, DE 23 13 331, DE 15 22 572, DE 31 37 808, DE 31 37 809, DE 31 51 343, DE 31 51 354, DE 31 51 355, DE 32 11 602, DE 32 35 017 or in other patent documents and other publications known to the person skilled in the art.

With wet coating, the Substrate particles suspended in water and with one or more hydrolyzable metal salts or a water glass solution one for the hydrolysis is shifted to a suitable pH value, which is selected in such a way that the metal oxides or metal oxide hydrates are precipitated directly on the platelets, without causing co-precipitation comes. The pH is usually constant by simultaneously adding a base and / or acid held. Subsequently the pigments are separated, washed and dried at 50-150 ° C for 6-18 h and optionally 0.5-3 h annealed, being the annealing temperature be optimized with regard to the respective coating can. As a rule, the annealing temperatures are between 250 and 1000 ° C, preferably between 350 and 900 ° C. If desired, the pigments can be applied after application individual coatings are separated off, dried and optionally annealed, then to fill up of the other layers to be resuspended.

Furthermore, the coating can also be carried out in a fluidized bed reactor by means of gas phase coating, the example in FIG EP 0 045 851 and EP 0 106 235 proposed methods for the production of pearlescent pigments can be applied accordingly.

The color of the interference pigments can be done within very wide limits by different choice of occupancy or the resulting layer thicknesses can be varied. The Fine tuning for a certain shade can over the pure choice of quantity through visually or metrologically controlled Approach the desired Color can be achieved.

To increase light, water and weather stability, it is often advisable, depending on the area of application, to subject the finished pigment to a post-coating or post-treatment. Post-coatings or post-treatments include, for example, those in DE-PS 22 15 191, DE-OS 31 51 354 , DE-OS 32 35 017 or DE-OS 33 34 598 methods described in question. This post-coating (layer F) further increases the chemical stability or facilitates the handling of the pigment, in particular the incorporation into different media.

The pigments according to the invention are compatible with a large number of color systems, preferably from the field of lacquers, paints and printing inks. A large number of binders, in particular water-soluble types, such as those from the companies BASF, Marabu, Pröll, Sericol, Hartmann, Gebr. Schmidt, Sicpa, are suitable for the production of printing inks for, for example, gravure printing, flexographic printing, offset printing, offset overprint coating , Aarberg, Siegberg, GSB-Wahl, Follmann, Ruco or Coates Screen INKS GmbH. The printing inks can be water-based or solvent-based. Furthermore, the Pig elements are also suitable for laser marking of paper and plastics as well as for applications in the agricultural sector, for example for greenhouse films and for coloring tent tarpaulins.

Since the multilayer pigments according to the invention strong shine with high brightness, transparency and strong color flop combine, they can be particularly effective effects in the different application media, e.g. in cosmetic formulations such as. Nail polishes, lipsticks, press powders, gels, lotions, Soaps, toothpastes, in paints such as Car paints, industrial paints and powder coatings as well as in plastics and ceramics.

Because of the good skin feeling and the very good skin adhesion are the pigments according to the invention especially for decorative cosmetics are suitable.

It goes without saying that, for the various applications, the multilayer pigments according to the invention are also advantageously mixed with organic dyes, organic pigments or other pigments, such as transparent and opaque white, colored and black pigments, and with platelet-shaped iron oxides, organic pigments, holographic pigments, LCPs (Liquid Crystal Polymers) and conventional transparent, colored and black gloss pigments based on metal oxide coated mica and SiO ₂ flakes etc. can be used. The five-layer pigments according to the invention can be mixed in any ratio with commercially available pigments and fillers.

As fillers e.g. to call naturally and synthetic mica, nylon powder, pure or filled melanin resins, Talcum, glasses, Kaolin, oxides or hydroxides of aluminum, magnesium, calcium, Zinc, BiOCI, barium sulfate, calcium sulfate, calcium carbonate, magnesium carbonate, Carbon, as well as physical or chemical combinations of these Substances.

Regarding the particle shape of the filler there are no restrictions. According to e.g. platy, spherical or acicular his.

Of course, the pigments of the invention in the formulations also with every kind of cosmetic raw and Auxiliaries can be combined. These include Oils, fats, waxes, film formers, Preservatives and general application properties determining auxiliary substances, e.g. Thickeners and rheological additives such as bentonites, hectorites, silicas, calcium silicates, gelatins, high molecular carbohydrates and / or surface-active aids etc.

The pigments according to the invention containing formulations belong to the lipophilic, hydrophilic or hydrophobic type. at heterogeneous formulations with discrete aqueous and non-aqueous Phases the pigments of the invention contained in only one of the two phases or over both Phases.

The pH values of the formulations can vary between 1 and 14, preferably between 2 and 11 and particularly preferably between 5 and 8 lie.

The concentrations of the pigments according to the invention there are no limits to the wording. You can - depending on Use case - between 0.001 (rinse-off products, e.g. shower gels) - 100% (e.g. gloss effect items for special Applications).

The pigments of the invention can also can also be combined with cosmetic ingredients. Suitable active ingredients are e.g. Insect repellents, UV A / BC protection filters (e.g. OMC, B3, MBC), anti-aging ingredients, Vitamins and their derivatives (e.g. vitamins A, C, E etc.), self-tanners (e.g. DNA, erytrolose etc.) and other cosmetic active ingredients such as Bisabolol, LPO, Ectoin, Emblica, Allantoin, Bioflavanoids and their Derivatives.

The pigments according to the invention are also suitable for the production of flowable pigment preparations and dry preparations, especially for Printing inks containing one or more pigments according to the invention, Binder and optionally one or more additives.

The subject of the ending is therefore also the use of pigments in formulations such as paints, printing inks, Security printing inks, varnishes, plastics, ceramic materials, glass and in cosmetic formulations.

The following examples are intended the invention closer explain but without limiting it.

Examples

Example 1: 5-layer pigment with distinctive color flop

100 g of mica with a particle size of 10–60 μm are heated to 80 ° C in 2 l of demineralized water with stirring. After this temperature has been reached, a solution consisting of 2.3 g of SnCl ₄ × 5 H ₂ O and 10 ml of hydrochloric acid (37%) in 70 ml of deionized water is slowly metered into the mica suspension at pH 1.8. Thereafter, 220 g of a 32% TiCl ₄ solution (400 g TiCl ₄ / l) are metered in at a pH of 1.8, the pH being kept constant with 32% sodium hydroxide solution. The pH is then raised to 7.5 and at this pH 800 ml of sodium silicate solution (13.0% by weight SiO ₂ ) are slowly added The pH is kept constant at 7.5 with 10% HCl. Finally, 2.3 g of SnCl ₄ × 5 H ₂ O and 10 ml of hydrochloric acid (32%) in 70 ml of demineralized water are added at pH = 1.8. After stirring for 0.5 h at pH = 1.8, the coated mica pigment is filtered off, washed and dried at 110 ° C. for 16 h. Finally, the pigment is annealed at 850 ° C for 0.5 h.

A blue interference pigment is obtained with a sharp color change from blue to red during the transition from steep to flat Observation angle.

Example 2

100 g of mica with a particle size of 10–60 μm are heated to 80 ° C in 2 l of demineralized water with stirring. After this temperature has been reached, a solution consisting of 3 g of SnCl ₄ × 5 H ₂ O and 10 ml of hydrochloric acid (37%) in 90 g of water is slowly metered into the mica suspension. At a pH of 1.8, 220 ml of TiCl ₄ solution (400 g TiCh / l) are metered in. Then the pH is kept constant at 7.5. The pH is then raised to 7.5 and 830 ml of sodium water glass solution (13 wt.

SiO ₂ ) slowly metered in, the pH being kept constant at 7.5 on 10% HCl. A solution of 11.5 g of SnCl ₄ × 5 H ₂ O and 10 ml of hydrochloric acid (32%) in 350 ml of deionized water is then metered in at pH = 1.8. Finally, 220 ml of TiCl ₄ solution (400 g of TiCl ₄ / l) are metered in at pH = 1.8. When the SnCl ₄ × 5 N ₂ O solutions and TiCl ₄ solutions are added, the pH is kept constant with NaOH solution (32%).

For processing, the coated Filtered off mica pigment, washed and dried at 110 ° C for 16 h. Finally, the pigment is annealed at 850 ° C for 0.5 h.

You get a bright shiny green, blue Interference pigment, the color of which is observed at a flat angle is red violet.

Example A1: Wet Lip Balm with 10% pearlescent pigment

production:

The components of phase B are with stirring to 75 ° C heated until everything has melted. Add phase A and stir well. The Then lipstick mass in the casting apparatus tempered to 65 ° C. fill, phase Add C and stir for 15 minutes. The homogeneous melt is poured into the mold, which has been preheated to 55 ° C.

Then the molds are cooled and removed the castings cold. After warming up the lipsticks to room temperature, the lipsticks become short flamed.

Sources:

• (1) Merck KGaA / Rona ^©
• (2) Natunola Health Inc.
• (3) Ross Waxes
• (4) Cognis GmbH
• (5) Henry Lamotte GmbH
• (6) Haarmann & Reimer GmbH

Example A: shower gel

production:

For Phase A becomes the five-layer pigment stir in water. Keltrol T with stirring Sprinkle in slowly and stir until it solved is. Add phases B and C one after the other, stirring slowly until everything is done is distributed homogeneously. Set the pH value to 6.0 to 6.5.

Sources:

• (1) Merck KGaA / Rona ^©
• (2) Kelco
• (3) Cognis GmbH
• (4) Haarmann & Reimer GmbH
• (5) BASF AG

Example A3: Eyeliner gel

production:

Five-layer pigment and Ronasphere ^® are dispersed in phase A water. Acidify with a few drops of citric acid to reduce the viscosity, sprinkle in Carbopol while stirring. After the solution has completely dissolved, slowly stir in the pre-dissolved phase B and adjust the pH to 7.0–7.5.

Sources:

• (1) Merck KGaA / Rona ^®
• (2) BF Goodrich
• (3) BASF AG
• (4) ISP Global Technologies

Example A4: eyeshadow

production:

Combine components of phase A. and premix. Subsequently the powder mixture with stirring Add the melted phase B dropwise. The powder become at 40-50 bar pressed.

Sources:

• (1) Merck KGaA / Rona ^®
• (2) J. M. Huber Corp.
• (3) Amerchol
• (4) Croda GmbH (5) N. Erhard Wagner GmbH
• (6) Haarmann & Reimer GmbH

Example A5: Eye Shadow gel

production:

Five-layer pigment and Ronasphere ^® are dispersed in phase A water. Acidify with a few drops of citric acid to reduce the viscosity, sprinkle in Carbopol while stirring. After the solution has completely dissolved, stir in the pre-dissolved phase B slowly.

Sources:

• (1) Merck KGaA
• (2) BF Goodrich GmbH
• (3) ISP Global Technologies

Example A6: Shimmering Foundation

production:

All components of phase C. approx. 75 ° C melt and stir, until everything has melted Put the phase B water cold, Homogenize blanose with the Turrax, sprinkle in Veegum and homogenize again. At 75 ° C heat and with stirring the remaining Dissolve components in it. Stir in phase A ingredients. At 75 ° C with stirring add phase C and homogenize for 2 min. The mass with stirring Cool 40 ° C, phase Admit D. With stirring Cool further to room temperature and to pH 6.0-6.5 adjust (e.g. with citric acid solution).

Sources:

• (1) Merck KGaA / Rona ^®
• (2) Aqualon GmbH
• (3) Vanderbilt
• (4) Cognis GmbH
• (5) Croda GmbH
• (6) Fragrance Resources
• (7) Schälke & Mayr GmbH

Example A7: Lip Gloss

production:

All components of phase B are weighed together, to 70 ° C heated and stirred well until a homogeneous mass has formed. Then the pigments are added and stirred again. The homogeneous mixture fills one at 50-60 ° C.

Sources:

• (1) Merck KGaA / Rona ^®
• (2) BP Amoco
• (3) Elementfis Specialites
• (4) Cognis GmbH
• (5) Dow Corning
• (6) Les Colorants Wackherr

Example A8: eyeshadow compact powder

production:

Components of phase A together give and premix. Subsequently the powder mixture with stirring Add the melted phase B dropwise. The powder are at 40-50 bar pressed.

Sources:

• (1) Merck KGaA
• (2) Südstark GmbH
• (3) Cognis GmbH
• (4) H. Erhard Wagner GmbH
• (5) Haarmann & Reimer GmbH

Example A9: Loose Eye Powder

production:

All components of phase B are weighed together, mixed well and sieved at 100 μm. Then phase Add A and mix again. The mass is added dropwise with stirring mixed with phase C.

Sources:

• (1) Merck KGaA / Rona ^©
• (2) ISP Global Technologies

Example A10: Cream Mascara (0 / VN)

production:

All components of phase B together at approx. 80 ° C melt, stir until everything has melted Stir in the effect pigments from phase A. Shellac phase C dissolve in water, to 75 ° C heat. Add the remaining components of phase C, dissolve. at 75 ° C slowly with stirring add phase C to phase A / B, homogenize for 2 min. The mass with stirring cool to room temperature.

Sources:

• (1) Merck KGaA / Rona ^®
• (2) Kahl & Co.
• (3) Cognis GmbH
• (4) Uniqema
• (5) Paroxite Ltd.

Example A11: PP-06-01 nail polish

production:

The five-layer pigment is put together weighed in with the lacquer base, mixed well by hand with a spatula and subsequently Stirred at 1000 rpm for 10 min.

Sources:

• (1) Merck KGaA / Rona ^®
• (2) International Lacquers S. A.

Example A12: shampoo

production:

For Phase A is the five-layer pigment stir into the water. With a few drops of citric acid (10%) acidify about viscosity to decrease and slowly sprinkle in the Carbopol while stirring. Slowly after complete solution Add phase B. One after the other the components of the phase C. added.

Sources:

• (1) Merck KGaA
• (2) BF Goodrich GmbH
• (3) Cognis GmbH
• (4) Haarmann & Reimer GmbH

Example A13: Sparkling Body Cream (O / W)

production:

The five-layer pigment in water disperse phase A. If necessary, acidify with a few drops of citric acid the viscosity to diminish. Carbopol with stirring Sprinkle. After more complete solution the pre-solved Stir in phase B slowly. Phase A / B and phase C to 80 ° C heat, stir phase C into phase A / B, homogenize, with phase Neutralize D, homogenize again and cool with stirring. at Add 40 ° C perfume oil, with stirring cool to room temperature.

Sources:

• (1) Merck KGaA
• (2) BF Goodrich GmbH
• (3) Schülke & Mayr GmbH
• (4) Chemag AG
• (5) Clariant GmbH
• (6) Cognis GmbH
• (7) Haarmann & Reimer GmbH

Claims (9)

Five-layer pigments based on multi-coated platelet-shaped substrates, which have at least one layer sequence of (A) a layer of SnO ₂ with a layer thickness of 0.1-50 nm, (B) a layer of TiO ₂ in the rutile modification with a layer thickness of 10 -800 nm, (C) a colorless coating with a refractive index n <1.8 with a layer thickness of 20-800 nm, (D) a layer of SnO ₂ with a layer thickness of 0.1-50 nm, (E) one Layer of TiO ₂ in the rutile modification with a layer thickness of 10-800 nm, and optionally (F) contains an outer protective layer. Five-layer pigments according to claim 1, characterized in that the platelet-shaped substrates are natural or synthetic mica, glass, Al ₂ O ₃ , SiO ₂ or TiO ₂ platelets. Five-layer pigments according to claim 1 or 2, characterized in that the layer (C) essentially made of silicon dioxide, aluminum oxide, magnesium fluoride or mixtures thereof. Five-layer pigments according to one of the claims 1 to 3, characterized in that they increase the light, temperature and weather stability an outer protective layer (F). Process for the preparation of the five-layer pigments according to a of claims 1 to 4, characterized in that the coating of the substrates wet chemical by hydrolytic decomposition of metal salts in aqueous Medium is done. Use of the five-layer pigments according to claim 1 in paints, varnishes, powder coatings, printing inks, security printing inks, Plastics, ceramic materials, glasses and in cosmetic formulations and for the production of pigment preparations and dry preparations. pigment preparations containing one or more binders, optionally one or more Additives and one or more five-layer pigments according to claim 1. dry preparations such as pellets, granules, chips, briquettes containing five-layer pigments according to claim 1. Containing hydrophilic or hydrophilic cosmetic formulations one or more five-layer pigments according to claim 1.