EP2367888A1

EP2367888A1 - Pigment granules

Info

Publication number: EP2367888A1
Application number: EP09799537A
Authority: EP
Inventors: Thomas Rathschlag; Carsten Griessmann
Original assignee: Merck Patent GmbH
Current assignee: Merck Patent GmbH
Priority date: 2008-12-22
Filing date: 2009-12-18
Publication date: 2011-09-28
Also published as: KR101792264B1; UA107922C2; KR20110100292A; WO2010072376A1; CN102264846B; EA026672B1; EA201100972A1; US8883879B2; DE102008064201A1; CN102264846A; US20110301273A1

Abstract

The present invention relates to pigment granules which are distinctive in being based on a support material, the support material being coated, by means of an adhesion promoter, with one or more platelet-shaped effect pigments. The pigment granules of the invention find use preferably for the pigmentation of application media, more particularly inks, renders, paints, powder coatings and plastics, and particularly as scatter granules and effect granules, for the decoration of wallpaper, for example.

Description

pigment granules

The present invention relates to non-dusting pigment granules based on a carrier coated with one or more c-shaped effect pigments and their use for

Pigmentation of application media, in particular paints, plasters, lacquers, powder coatings, plastics and as scattering granules, e.g. for decoration of wallpaper.

The flow behavior of pigments based on platelet-shaped substrates, e.g. Mica platelets are often unsatisfactory. In a variety of applications, especially in the printing and color range, this does not lead to major problems. Moreover, in the processing of pearlescent pigments to a pronounced dust, resulting in an increased equipment cost

Elimination of dusts and cleaning of the machinery requires. 15

The production of pigment granules using inorganic or organic pigments is known to the person skilled in the art. Color masterbatches with pigment proportions of 20-50% by weight are used for coloring various plastic systems. This is usually a 2-stage process until the final granules are produced.

The wetting of plastics, e.g. nonpolar thermoplastics based on polyolefins, e.g. Polyethylene, polypropylene, without pretreatment methods, e.g. Corona discharge or flame,

_In a subsequent coating with aqueous adhesion promoters, this often leads to a lack of adhesion to the substrate to be coated, which is especially pronounced when coating plastic-based supports with platelet-shaped particles especially in the form of dusty abrasion and

30 loss of adhesion of the colored coating from the carrier substrate in the form of a delamination manifests.

BESTATIGUNGSKOPIE Glass-based support particles often require silanization to provide durable coatings with a platelet effect pigment with appropriate adhesion to the surface.

Object of the present invention is therefore the provision of

Pigment granules with plastic supports preferably polyolefins and / or glass, which do without additional pretreatment and do not have the disadvantages of the prior art mentioned above.

Surprisingly, it has now been found that pigment granules based on a carrier material, such as e.g. Polymer particles, glass beads or hollow glass spheres or mixtures thereof, which are coated with one or more platelet-shaped effect pigments, are very well suited for economical and sustainable permanent coating.

The present invention therefore relates to pigment granules based on a carrier material which is coated by means of an adhesion promoter with one or more platelet-shaped effect pigments. The effect pigment is preferably on the surface with the support, e.g. a polymer particle, a glass ball or glass hollow sphere, glued or partially or completely coated.

The present invention further describes a one-step process for the preparation of the pigment granules according to the invention, which is based on the direct coating of the support materials, wherein the proportion of effect pigments on the support surface is generally <50% by weight. Since the process of the invention is not bound to a thermoplastic or duroplastic carrier plastic, but is a carrier-independent process, this process is also considered to be particularly economical.

The present invention furthermore relates to a process for the preparation of the pigment granules according to the invention, wherein one or more platelet-shaped effect pigments, at least one adhesion promoter and optionally additives are mixed with the support material. The pigment granules according to the invention are particularly suitable for use as scattering granules in effect wallpapers, for structural plaster systems and textile coatings.

The pigment granules of the invention are not dusty and very free-flowing, which reduces the expenditure on equipment in their processing.

An essential constituent of the pigment granules according to the invention is, in addition to the effect pigment, the carrier material. A suitable carrier material should in particular have a high transparency.

Transparent supports, e.g. Plastic particles, glass spheres and hollow glass spheres, with their translucency, support the optical properties, e.g. the pearlescent or metallic luster, the effect pigments applied to the surface.

As a measure of the light transmittance / transparency in this application, the transmittance ζ (= Tau) = Φ _n / Φ _v x 100 (%) according to DIN 1349-1 used.

The carrier materials are present as individual particles, which are preferably spherical. The carrier material preferably has particle sizes of

0.05 - 50 mm, in particular from 0.6 to 10 mm and most preferably from 0.5 to 5 mm. The particle sizes in this patent application are determined in accordance with DIN 66165 part 2. Suitable support materials are preferably polymer particles, glass full spheres and glass hollow spheres.

As polymer particles are preferably those of plastic (e), such as. Thermoplastics or thermosets, for use. The polymer particles are preferably composed of polyolefins, in particular polyethylene (PE) and polypropylene (PP), polystyrene (PS), polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), polycarbonate (PC), polyvinyl acetate copolymer (PVAC), polyvinyl chloride ( PVC)

Ethylene acrylic acid copolymer (EAA), ethylene vinyl acetate copolymer or biodegradable polyesters, eg polylactic acid (polyactide = (PLA)). Particularly preferred support materials are composed of EAA (ethylene-acrylic acid copolymer), eg available from the Fa. ExxonMobil under the trade name Escor ™, or EVA (ethylene vinyl acetate copolymer), for example, Evatane ^® 24-03 by the company. ARKEMA, or of polyvinyl acetate (PVAC), for example Vinnaperl 10 or Vinnaperl 20 from Wacker Chemie.

The carrier material is preferably spherical. It preferably has a particle size of 0.05-50 mm, in particular 0.5-10 mm, very particularly preferably 0.5-5 mm.

The commercially available plastic powders or plastic granules often have particle sizes of 1 to 5 mm. These polymer particles must then be previously melted for use in the preparation of the pigment granules of the invention and then, for example, by granulation, e.g. Underwater granulation, and grain size adjustment, e.g. B. by means of a perforated disc, can be adjusted to the desired particle size and shape.

Particularly preferred is the use of spherical microgranules of 0.5 -1 mm, which consist of LD-PE (low density polyethylene) or HD-PE (high-density polyethylene), as this example, the Fa.

Geerkens Rohstoffe GmbH, Willich (Germany).

If the pigment granules according to the invention are used for the rotary molding process, the polymer particles are preferably spherical and have a particle size of 0.05-5 mm, in particular 0.05-2 mm, very particularly preferably 0.05-1 mm. It is also possible to use unstructured particles of the same particle size distribution.

Rotational molding is understood to mean the production of plastic hollow bodies after spin-spinning using a biaxial rotational movement.

Glass carrier beads or hollow glass beads may also be used as carrier material, preferably particle sizes of 0.3-50 mm, in particular from 0.5 to 10 mm, very particularly preferably from 0.5 to 5 mm. Such glass beads are commercially available, for example from the Fa. Sovitec GmbH.

The glass beads should be chemically resistant depending on the application. Preferably glass beads or glass hollow spheres of soda lime glass (main components: SiO ₂ / CaO / Na ₂ O), ECR glass, C glass Borosilakatglas or quartz glass are used.

Mixtures of different carrier materials may also be used, e.g.

- full glass balls + glass hollow spheres,

- glass bulbs + thermoplastics,

- glass bulbs + thermosets,

- Thermoplastics + thermosets + glass solid beads

- Glass bubbles + thermoplastics

- Glass hollow spheres + thermosets

- Thermoplastics + thermosets + hollow glass spheres

- thermoplastics + thermosets

In this case, all conceivable mixing ratios can be used, preferably the carrier materials are mixed in such a way that physical and chemical properties, such as adhesion in the application medium and chemical resistance, correlate with aesthetic effects and economic considerations.

Preferably, carrier material mixtures are binary mixtures which can be mixed with each other in any ratio. The ratio is preferably 1: 1 to 1:10 or 10: 1.

Furthermore, as a carrier material and blowing agent-additive-thermoplastic plastic particles can be used, provided that they are in the

It is possible to create three-dimensional structures. Pigment granules on Such support materials can be used in particular in the design of textured wallpaper.

Suitable adhesion promoters are preferably those which physically dry c. Particularly preferred as adhesion promoter aqueous

Emulsions are used, preferably EAA emulsions (ethylene acrylic acid copolymer), commercially available, for example, from Messrs. Michelman under the name "Michem Prime 4983 R" and emulsions and dispersions based on acrylated polypropylenes or low chlorinated polypropylenes. Such emulsions and dispersions are commercially available, for example from the Fa.

Tramaco under the designation "Trapylen 9310 W" and "Trapylen 6700 W".

The size of the EAA emulsion is preferably 20-300 nm, the EAA emulsions preferably used are preferably composed of 65-85 parts of water and ¹⁵ parts EAA 15-35..

The size of the acrylated polypropylene or low chlorinated polypropylene emulsion particles or dispersion particles is preferably 50-5000 nm.

20

Suitable adhesion promoters are also wax emulsions, commercially available, for example, from the company KEIM ADDITEC Surface GmbH. Suitable wax emulsions are, for example, LD-PE wax emulsions (LD-PE = low density polyethylene), for example Ultralube V-06070480 from KEIM ADDITEC Surface GmbH. The wax emulsions preferably _{contain? F-} emulsion of the size 20-100 nm. The appropriate wax emulsions preferably have a melting range of 50-160 ⁰ C, especially 90-140 ⁰ C and most preferably from 90-130 ⁰ C. on.

In the following, further suitable adhesion promoters are mentioned which are based on aqueous dispersions, such as for example those 1) based on copolymers or based on terpolymers:

Vinyl acetate (VAC) / (ethylene) [E] = VAC / E

- Vinyl acetate (VAC / (ethylene) [E] / vinyl chloride (VC) = VAC / EA / C ₅ - vinyl chloride (VC) / ethylene [E] / acrylic acid ester (AY) = VC / E / AY

Vinyl chloride (VC) / ethylene [E] / vinyl laurate (VL) = VC / EA / L

Vinyl acetate (VAC) / (ethylene) [E] / vinyl chloride (VC) = VAC / EA / C

2) based on acrylate dispersions

10 - Styrene acrylic acid ester (S-AY)

Acrylic acid ester (AY)

- self-crosslinking acrylate

- Polyacrylates and their copolymers

- PMMA and their copolymers

15 3) Dispersions based on the composition:

- Versatic acid vinyl ester (VeoVa) / acrylic acid ester (AY) = VeoVa / AY

Ethylene copolymer / acrylate = E-Copo./AY

- Aqueous polyvinyl butyral dispersions = PVB

- Aqueous polyvinyl propionate dispersions = PVP

20

- water-dilutable urea resins

- water-thinnable polyester

- Water-dilutable alkyd resins

- water-dilutable rosin resins and rosin resin esters

- water-dilutable shellac

_c - water-dilutable polyvinyl acetals

- water-dilutable polyvinyl ethers

- water-dilutable soy proteins

Polyvinyl alcohols = PVOH

30 4) Polyurethane dispersions

4a) aliphatic polyurethanes

₅ - Polyether (PE) / Polyurethane (PU) = PE / PU

- Polyester (PES) / Polyurethane (PU) = PES / PU

Polycarbonate (PC) / Polyurethane (PU) = PC / PU

Polyester (PES) / Polycarbonate (PC) / Polyurethane (PU) = PES / PC / PU

10 4b) aliphatic oil-based polyurethane hybrids

- based on castor oil (CO)

- based on castor oil and linseed oil (LO)

Suitable adhesion promoters are furthermore adhesives based on resins and polymers which are dilutable or soluble in organic solvents. Examples of suitable raw materials can be found e.g. in Lackrohstofftabellen, Vincentz-Verlag, 10th edition, edition 2000, pages 62-622.

Examples of possible adhesives based on resins and polymers

20 are named below:

- saturated polyesters

- unsaturated polyester

Epoxides

"- Polyacrylates and copolymers

- PMMA and u. -Copolymerizates polyamides

- ketone resins and aldehyde resins

- polystyrenes

- polyurethanes (PU)

30 - polyurethanes (PU) / acrylates (AY) = (PU / AY)

- moisture-curable polyurethanes

- PVC - Polyvinyl acetates

- polyvinyl acetals

- polyvinyl ether

- Alkyd / melamine - urea resins

Polyvinyl butyral = PVB

Polyvinylpropionate = PVP

- urea resins

- Polyester resins

- Alkyd resins - rosin resins and rosin esters

- shellac

The adhesives that can be used as adhesion promoters are subdivided according to the hardening mechanism in:

1. Polymerization adhesives, e.g.

- cyanoacrylate (CY-AY);

- MMA adhesives (MMA = methyl methacrylate);

- Anerob hardening adhesives

- Radiation-curing adhesives

2. polycondensation adhesives, e.g.

Phenol-formaldehyde adhesives

- Silicone adhesives

- Silane-crosslinking polymer adhesives

- Polyimide adhesives

3. Polyaddition adhesives, e.g.

- Epoxy adhesives

- Polyurethane adhesives

4. hot melt adhesives, e.g. Moisture-reactive amorphous poly alpha olefin hot melt adhesive

= 1 K-APAO. The proportion of adhesion promoter in the pigment granules according to the invention is preferably from 0.05 to 20% by weight, in particular from 0.1 to 10% by weight, very particularly preferably from 0.15 to 5% by weight, based on the total mass of the pigment granules.

5

In the pigment granules according to the invention, the effect pigments, the support material and the adhesion promoter and optionally additives are mixed with one another. Preferably, the carrier material with the effect pigment is at least partially or completely coated or enveloped by the emulsion. A complete coating and "gluing" of the carrier material with the platelet-shaped effect pigment is very particularly preferred.

The flake-form effect pigments are preferably pearlescent pigments, interference pigments, metallic effect pigments, multilayer pigments with transparent, semitransparent and / or opaque layers, holographic pigments, coated or uncoated BiOCl pigments and / or LCP pigments.

Pearlescent pigments, interference pigments, metallic effect pigments or multilayered pigments which can be used according to the present invention are based on transparent, semi-transparent and / or opaque layers

20 in particular on carriers, which is preferably platelet-shaped.

For example, platelet-shaped TiO ₂ , kaolin, talc, synthetic (eg fluorophlogopite) or natural mica, doped or undoped glass flakes, metal flakes, flaky SiO ₂ , flaky Al ₂ O ₃ or platelet-shaped iron oxide are suitable. The

_{? (-} metal plates may include aluminum, titanium, bronze, steel or silver, preferably aluminum and / or titanium, the metal flakes may be passivated by appropriate treatment The glass flakes can be made of all known to those skilled glass types consist, for example from A.. Glass, E glass, C glass, ECR glass, waste glass, window glass, borosilicate glass, ^Duran® glass, laboratory glassware or optical

30 glass. The refractive index of the glass flakes is preferably 1.45-1.80, in particular 1.50-1.70. Particularly preferably, the glass substrates of C glass, ECR glass or borosilicate glass. In a preferred embodiment, the support of the effect pigment may be provided with one or more transparent semitransparent and / or opaque layers comprising metal oxides, metal oxide hydrates, metal suboxides, metals, metal fluorides, metal nitrides, metal oxynitrides or

Be coated 5 mixtures of these materials. The metal oxide,

Metal oxide hydrate, metal suboxide, metal, metal fluoride, metal nitride, metal oxynitride layers or mixtures thereof may be low (refractive index <1.8) or high refractive index (refractive index> 1.8). Suitable metal oxides and metal oxide hydrates are all metal oxides or metal oxide hydrates known to the person skilled in the art, such as, for example, For example, alumina,

10 alumina hydrate, silica, silica oxide, iron oxide, tin oxide, ceria, zinc oxide, zirconia, chromia, titania, especially titania, titania hydrate and mixtures thereof, e.g. Ilmenite or pseudobrookite. As metal suboxides, for example, the titanium suboxides can be used. Suitable metals are e.g. Chromium, aluminum, nickel, silver, gold, titanium, copper or alloys, as

For example, magnesium fluoride is suitable. As metal nitrides or metal oxynitrides, for example, the nitrides or oxynitrides of the metals titanium, zirconium and / or tantalum can be used. Preference is given to metal oxide, metal, metal fluoride and / or metal oxide hydrate layers and very particularly preferably metal oxide and / or

Metal oxide hydrate layers applied to the carrier. Furthermore you can

20 also multilayer constructions of high and low refractive index metal oxide,

Metal oxide hydrate, metal or metal fluoride layers are present, preferably alternating high and low refractive layers. Particular preference is given to layer packages of a high and a low refractive index layer, one or more layers being present on the support

_{? (-.} This layer packages to be applied The sequence of high and low refractive index layers can be adapted to the carrier thereby to offset the carriers in the multi-layer structure with In another embodiment, the metal oxide, metal oxide hydrate, metal suboxide, metal can. , Metal fluoride, metal nitride, metal oxynitride layers may be mixed or doped with colorants as colorants or others

30 elements are, for example, organic or inorganic color pigments such as colored metal oxides, eg magnetite, chromium oxide or color pigments such as Berlin Blue, ultramarine, bismuth vanadate, Thenards Blue, or organic color pigments such as indigo, azo pigments, phthalocyanines or carmine red or elements such as yttrium or antimony. Effect pigments comprising these layers exhibit a wide variety of colors with respect to their body color and an angle-dependent change of color (color flop) may be due to interference in many cases, _c.

The outer layer on the support is in a preferred embodiment a high refractive index metal oxide. This outer layer may additionally be applied to the above-mentioned layer packages or to high-index carriers

10 be part of a layer package and for example of TiO ₂ , titanium suboxides, Fe ₂ O ₃ , Fe ₃ O ₄ , 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 pseudobrookite exist. TiO ₂ is particularly preferred, further Fe ₂ O ₃ , as well as mixtures of TiO ₂ and Fe ₂ O ₃ . If the support plates are coated with TiO ₂ , the TiO _{2 is} preferably present in the rutile modification, further in the

15 anatase modification.

Particularly preferred effect pigments have the following structure:

Substrate platelets + (SiO ₂ ) + TiO ₂ (rutile)

Substrate platelets + (SiO ₂ ) + Fe ₂ O ₃

? 0

Substrate platelets + (SiO ₂ ) + Fe ₃ O ₄

Substrate platelets + (SiO ₂ ) + SiO ₂ + TiO ₂ (rutile) Substrate platelets + (SiO ₂ ) + TiO ₂ (rutile) + SiO ₂ + TiO ₂ (rutile) Substrate platelets + (SiO ₂ ) + TiO ₂ (anatase) + SiO ₂ + TiO ₂ (anatase) Substrate platelets + (SiO ₂ ) + TiO ₂ / Fe ₂ O ₃ + SiO ₂ + TiO ₂ + TiO ₂ / Fe ₂ O ₃ Substrate platelets + (SiO ₂ ) + TiO ₂ / Fe ₂ O ₃ + SiO ₂ + TiO ₂ / Fe ₂ O ₃ .

Optionally, an SiO ₂ layer can be applied as a protective layer to the substrate chip. If the substrate chip is a glass plate, it is often advisable to apply an SiO ₂ layer in order to protect the glass plate against leaching in the case of the wet-chemical coating. In this patent application, "high refractive index" means a refractive index of> 1.8, while "low refractive index" means a refractive index of <1.8.

₅ The thickness of the metal oxide, metal oxide hydrate, metal suboxide, metal,

Metal fluoride, metal nitride, metal oxynitride or a mixture thereof is usually 3 to 300 nm and in the case of the metal oxide, metal oxide, metal, metal fluoride, metal nitride, metal oxynitride or a mixture thereof preferably 20 to 200 nm Metal layers is preferably 4 to 50 nm.

10

The size of the carrier and thus the effect pigments is not critical per se. Platelet-shaped supports and / or platelet-shaped supports coated with one or more transparent or semitransparent metal oxide, metal or metal fluoride layers generally have a thickness between 0.05 and 5 μm, in particular between 0.1 and

15 4.5 microns on. The extension in the length or width is usually between 1 and 250 μm, preferably between 2 and 200 μm and in particular between 2 and 100 μm.

Very particularly preferred effect pigments have the following layer structure:

20

Mica platelets + TiÜ2

Mica flakes + TiO ₂ + Fe ₂ O ₃

Mica flakes + TiO ₂ / Fe ₂ O ₃

Mica platelets + Fe ₂ O ₃ ? _(- Mica platelets + Fe ₃ O ₄

Mica platelets + titanium oxynitrides

Mica flakes + TiO ₂ + SiO ₂ + TiO ₂

Mica flakes + TiO ₂ / Fe ₂ O ₃

Mica flakes + TiO ₂ / Fe ₂ O ₃ + SiO ₂ + TiO ₂

Mica flakes + TiO ₂ / Fe ₂ O ₃ + SiO ₂ + TiO ₂ / Fe ₂ O ₃ 30 mica flakes + TiO ₂ / Fe ₂ O ₃ + SiO ₂ + TiO ₂ + TiO ₂ / Fe ₂ O ₃

Mica flakes + TiO ₂ + SiO ₂ + TiO ₂ / Fe ₂ O ₃

Mica flakes + TiFe ₂ O ₅ Al ₂ O ₃ platelets + TiO ₂

Al ₂ O ₃ platelets + Fe ₂ O ₃

Al ₂ O ₃ platelets + titanium oxynitrides

SiO ₂ platelets + TiO ₂ SiO ₂ platelets + Fe ₂ O ₃

SiO ₂ platelets + titanium oxynitrides

Glass slides + TiO ₂

Glass slides + Fe ₂ O ₃

Glass slides + TiO ₂ + Fe ₂ O ₃

Glass flakes + SiO ₂ + TiO ₂ glass flakes + SiO ₂ + Fe ₂ O ₃

Glass flakes + SiO ₂ + TiO ₂ + Fe ₂ O ₃

Glass flakes + SiO ₂ + TiO ₂ + SiO ₂

Glass slides + TiO ₂ + SiO ₂ + TiO ₂

Glass slides + TiO ₂ / Fe ₂ O ₃

Glass flakes + TiO ₂ / Fe ₂ O ₃ + SiO ₂ + TiO ₂ glass flakes + TiO ₂ / Fe ₂ O ₃ + SiO ₂ + TiO ₂ / Fe ₂ O ₃

Glass flakes + TiO ₂ / Fe ₂ O ₃ + SiO ₂ + TiO ₂ + TiO ₂ / Fe ₂ O ₃

Glass flakes + TiO ₂ + SiO ₂ + TiO ₂ / Fe ₂ O ₃

Glass slides + TiFe ₂ O ₅

Glass flakes + SiO ₂ + TiO ₂ / Fe ₂ O ₃

Glass flakes + SiO ₂ + TiO ₂ / Fe ₂ O ₃ + SiO ₂ + TiO ₂

Glass flakes + SiO ₂ + TiO ₂ / Fe ₂ O ₃ + SiO ₂ + TiO ₂ / Fe ₂ O ₃

Glass flakes + SiO ₂ + TiO ₂ / Fe ₂ O ₃ + SiO ₂ + TiO ₂ + TiO ₂ / Fe ₂ O ₃ glass flakes + SiO ₂ + TiO ₂ + SiO ₂ + TiO ₂ / Fe ₂ O ₃ glass flakes + SiO ₂ + TiFe ₂ O ₅ Fe ₂ O ₃ platelets + TiO ₂ Fe ₂ O ₃ platelets + Fe ₂ O ₃ Fe ₂ O ₃ platelets + titanium oxynitrides Metal platelets (optionally passivated) + TiO ₂ metal platelets (optionally passivated) + Fe ₂ O ₃ .

TiO ₂ / Fe ₂ O ₃ means that TiO ₂ and Fe ₂ O _{3 are present} in one layer as a mixture and / or as a mixed oxide in the form of the pseudobrookite. The

Pseudobrookite or the TiO ₂ / Fe ₂ O ₃ mixed layer may optionally also be doped with Al ₂ O ₃ . Suitable effect pigments are commercially available, for example from BASF Corp. For example, under the brand names Fire Mist ^®, ™ Rightfit, Magna Pearl ^®, from Merck KGaA under the trade name Iriodin ^®, Miraval ^®, Xirallic ^® and ColorStream ^®.

In this patent application, effect pigments are understood as those listed in claim 2.

To additionally increase the light, water and weather stability of the pigments, it is often advisable, depending on the field of application, to subject the effect pigment to a subsequent coating or after-treatment. As post-coatings or post-treatments are, for example, in DE-PS 22 15 191, DE-OS 31 51 354, DE-OS 32 35 017 or DE-OS 33 34 598 described methods in question. This postcoating further increases the chemical stability or facilitates the handling of the pigment, in particular the incorporation into different media. To improve the wettability, dispersibility and / or compatibility with the application media, functional coatings of Al ₂ O ₃ or ZrO ₂ or mixtures thereof or mixed phases can be applied to the pigment surface. Furthermore, organic or organic / inorganic combined secondary coatings are possible, for example with silanes, as described, for example, in EP 0090259, EP 0 634 459, WO

99/57204, WO 96/32446, WO 99/57204, U.S. Pat. 5,759,255, U.S. Pat. 5,571, 851, WO 01/92425 or in JJ. Ponjee, Philips Technical Review, Vol. 3, 81 ff. And P.H. Harding J.C. Berg, J. Adhesion Sci. Technol. Vol. 11 no. 4, p. 471-493.

The proportion by weight of the platelet-shaped effect pigments in the pigment granules according to the invention is generally between 0.1 and 50% by weight, preferably between 0.5 and 30% by weight, very particularly preferably between 1 and 10% by weight, based on the pigment granules. The optimum proportions are easy to determine for a person skilled in the art and depend essentially on the particle size of the effect pigments used, the form factor of the effect pigments and the type of pigment buildup. Particularly preferred pigment granules according to the invention contain

0.1-50% by weight of one or more effect pigments 50-99.5% by weight of carrier material 5 0.05-20% by weight of adhesion promoter

0.05-10% by weight of additives,

based on the total formulation of the pigment granules, wherein the total amount of all components in the pigment granules is <100% by weight.

For reasons of economy, preference is given to effect granules which contain the smallest possible proportion (<10% by weight) of the relatively expensive effect pigments and a high proportion (> 50% by weight) of inexpensive carrier material. This preferred embodiment is particularly interesting in the scatter application of the granules of effect wallpaper. 15

However, sufficient support material must be used to achieve the desired properties of the pigment granules of the invention, such as e.g. Non-dusting and / or improved flowability, to ensure. This requires the polymer particles not only with the

Effect pigment to be wrapped, but they also need to be together

20 a good free-flowing coarse "powder" glued.

In a further embodiment, the pigment granules according to the invention may contain further additives, such as are suitable for use in application media in the fields of paints, lacquers, powder coatings,

_{? £} - plastics, are common. Such additives and / or adjuvants may include lubricants, release agents, stabilizers, antistatic agents, flame retardants, antioxidants, colorants, such as dyes, inorganic color pigments and / or organic color pigments, flexibilizers, plasticizers, such as diisononyl phthalate, adhesion promoters, blowing agents, antioxidants, UV absorbers , inorganic fillers and / or surfactants, organic

30 polymer-compatible solvents and / or surfactants, phenol derivatives, mineral oils. An overview of the usable additives and auxiliaries can be found in Saechtling, Plastic Paperback, 27th edition, Carl Hanser Verlag or gives R. Wolf in "Plastics, Additives" in Ullmann ^'s , Encyclopedia of Industrial Chemistry, Internet Edition, 7th Edition, 2003.

Most preferably, the pigment granules of the invention contain wetting agents, e.g. Silicones, silanes and / or fluorosurfactants.

The pigment granules according to the invention can be produced relatively easily. Possible first 11 methods are the gentle mixture of the individual components-effect pigment (s), carrier material, adhesion promoter-and subsequent rotogranulation. In this case, the components to be mixed with a mixer, in which the

Support material, the coupling agent and optionally additives and the effect pigment or the mixture of effect pigments and optionally further organic and / or inorganic pigments mixed. In the next step, the granules are rounded to the intended particle size on a horizontally rotating pelletizing plate. Finally, the gentle drying of the raw granules takes place in a fluidized bed, e.g. in a fluidized bed or fluidized bed dryer. However, preference is given to the embodiment in a fluidized-bed dryer.

The order of addition of effect pigment, adhesion promoter and

Support material is variable and can for example also be carried out in such a way that the effect pigment is presented and subsequently with the

Adhesive, the carrier material and optionally additives is mixed. This embodiment is particularly preferred.

It is also possible to submit the effect pigment, the support material and optionally additives, and then added with the adhesion promoter.

The invention also provides a process for the preparation of the pigment granules according to the invention, which is characterized in that one or more platelet-like effect pigments, the or the support material (a) with at least one adhesion promoter and optionally one or more additives are mixed simultaneously or sequentially , The pigment granules according to the invention are characterized by being abrasion-resistant, dimensionally stable and having a uniform color effect.

By the term "granules" in this application are all solid particle shapes conceivable in the art, such as e.g. Pellets, briquettes, pearlets,

Sausages or the tableted form, to understand. The particle sizes of the granules are preferably in the range of 0.05 to 150 mm, in particular 0.1 to 20 mm, and most preferably in the range of 0.1 to 6 mm.

The granules according to the invention preferably contain

0.1-50% by weight, preferably 1-40% by weight of effect pigment 0.05-20% by weight, preferably 0.5-10% by weight adhesion promoter 50-99.5% by weight, preferably 60-95% by weight .% Support material and optionally up to 10 wt.% Of customary in the plastics and / or paint area additives, fillers, dyes and / or color pigments, based on the pigment granules, wherein the total amount of all components <100 wt.% Is.

The coating process produces such a directed structure of the employed platelet effect pigments (or mixtures) in the finished granules that the low pigment loading noted in the invention achieves similar effects that would otherwise produce the prior art granules having effect pigment levels> 50%.

The pigment granules of the invention are particularly suitable as spreading granules, e.g. for PVC plastisols, in aqueous and solvent-based PU adhesives (PU = polyurethane), in aqueous and solvent-based acrylate adhesives. There they can e.g. on wallpaper made of paper, non-woven, PVC foam or textile, firmly glued.

For wallpaper application, it is possible to submit an adhesion primer to which the effect granules are scattered. For uniform application, a metering device has proven to be advantageous. The Application of the effect granules takes place via a screen selected according to the desired particle diameters.

Due to the partial or full-surface application of the pigment granules according to the invention to PVC plastisols customary in the wallpaper industry

Primer, such. B. Folcosol K-RSD 5048 transparent, or Folcosol S-RSD 2067/9 smooth foam (manufacturer: Fa. Folmann, Munich), decorative wallpaper produced.

The present invention also relates to the use of the pigment granules of the invention in paints, lacquers, printing inks, plastics, and as scattering granules, e.g. for wallpaper, as well as the use in hydraulic curing effect plaster systems.

The present invention furthermore relates to the use of the pigment granules according to the invention in plastics applications, in particular rotary molding. By firmly anchoring the

Pigments over the bonding agent with the carrier material, it is possible that during the melting process and the rotation of the workpiece, depending on the complexity of the workpiece 20-40 min. may amount, the effect pigments migrate in the polymer matrix to the surface of the workpiece (= plastic).

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

Example 1: Support material: PVAC particles

For the preparation of the pigment granules according to the invention, a homogeneous mixing is to be ensured. The mixture is made using an Eirich R02 mixer.

1000 g Vinnaperl 10 (PVAC particles of particle size 0.5-1 mm of Fa.

Wacker-Chemie) and 60 g of Iriodin 305 ^® (multilayer pigment from Merck;. With TiO _2, Fe ₂ O ₃ and SiO ₂ coated mica flakes) are in Mixing container presented and mixed (plate / whirler). Then 55 g of Michem Prime 4990 R (35% EAA emulsion from Michelman Inc.) are added slowly. The mixture is then mixed homogeneously (plate / whirler).

The moist pigment / polymer / plastic mixture produced in this way is pelleted on an Eirich pelletizing plate TR 04. There, the size distribution is set.

For this purpose, 200 g of freshly prepared granules are placed on the plate and at 200-350 U / min and a tilt angle of 30-40 ° the

Target grain size set. If the nominal grain size is set, the batchwise entry of the total amount of the water-wet pigment / polymer / plastic batch is started.

The nominal size is particularly controlled by the dimension (size expansion in mm) of the plastic granules used and should increase in the given experiment to 2 ± 0.5 mm.

In this case, portions between 50-100 g are entered, which can be added within a short time (1 kg about 10-15 min).

Coarser aggregates accumulate in the middle of the "material flow kidney" produced during pelleting. These are picked up with a small shovel, crushed by hand and added again.

The moist, granulated mixture is at 40 - 60 ° C in a fluidized bed dryer for 10-60 min. dried. The granules produced in this way are classified as safe by a sieve of mesh size 3.55 mm.

The pigment granules obtained is resistant to abrasion, dimensionally stable and has an extraordinary purity of the pearl effect produced. Example 2: Support material: glass solid beads

For the preparation of the pigment granules according to the invention, a homogeneous mixing is to be ensured. The mixture is prepared with the aid of an Eirich R02 mixer.

985 g Vialux SB 20 (solid glass beads of particle size 0.6-1, 4 mm of Fa. Sovitec GmbH) and 10.0 g Iriodin ^® 305 are placed in the mixing container and mixed (Plates / swirler). Thereafter, 5 g of Michem Prime 4983 R (25% EAA emulsion from Michelman Inc.) are added. Subsequently, the mixture is mixed homogeneously (plate / whirler).

The moist pigment / polymer / glass bead mixture produced in this way is pelleted on an Eirich pelletizing plate TR 04. There, the size distribution is set. For this purpose, 200 g of freshly prepared granules are placed on the plate and set at 200-350 U / min and a 15 tilt angle of 30-40 °, the target grain size. Is the

Set desired grain size, is started with the portionwise entry of the total amount of the water-moist effect pigment / polymer / plastic batch.

The nominal size is especially determined by the dimension (size expansion in

20 mm) of the glass beads used and should be in the specified

Attempt to grow to 2 ± 0.5 mm. In this case, portions between 50-100 g are entered, which can be added within a short time (1 kg about 10-15 min). Coarser aggregates accumulate in the middle of the "material flow kidney" produced during pelleting. These are with _{/ -} included a small shovel, comminuted by hand and added again.

The moist, granulated mixture is at 40 - 60 ° C in a fluidized bed dryer for 10-60 min. dried. The granules produced in this way are classified by a sieve of mesh size 3.55 mm 30. The pigment granules obtained is resistant to abrasion, dimensionally stable and has an extraordinary purity of the pearl effect produced.

_c Example 3: Alkali-resistant coating - carrier material: PE particles

1 o 1000 g Escorene LL6101 XR (LLD-PE plastic / LLDPE: linear low density Fa ExxonMobil.), Particle size 3-5 mm, and 53.0 g of Iriodin 305 ^® ischbe containers are introduced and mixed (plates in M / swirly). Thereafter, 36 g of trapezium 6700 W (30% strength chlorinated PP dispersion from Tramaco) are added slowly. The mixture is then mixed homogeneously (plate / whirler). 15

For this purpose, 200 g of freshly prepared granules are placed on the plate

20 and at 200-350 rpm and an inclination angle of 30-40 ° the

Target grain size set. If the nominal grain size is set, the portion-wise entry of the total amount of the water-moist effect pigment / polymer / plastic batch is started. The nominal size is particularly controlled by the dimension (size expansion in mm) of the plastic granules used and should increase in the given experiment to 5.5 ± 0.5 mm. In this case, portions between 50-100 g are entered, which can be added within a short time (1 kg about 10-15 min). Coarser aggregates accumulate in the middle of the "material flow kidney" produced during pelleting. These are picked up with a small shovel, crushed by hand and added again. The moist, granulated mixture is at 40 - 60 ⁰ C in a fluidized bed dryer for 10-60 min. dried. The granules produced in this way are classified as safe by a sieve of mesh size 6.5 mm.

The pigment granules obtained is resistant to abrasion, dimensionally stable and has an extraordinary purity of the pearl effect produced. The produced effect granules also have an alkaline strength according to DIN EN ISO 175 (precast part test).

Example 4: Carrier material: PE particles

917 g Escorene LL6101 XR (LLD-PE plastic / LLD: linear low density from ExxonMobil) of particle size 3-5 mm, and 55.0 g Iriodin ^® 305 are placed in the mixing container and 2 min. mixed into controller position 1 (plate / whirler). Then 28 g of Michem Prime 4990 R (35% strength EAA emulsion from Michelman Inc.) are added slowly. The mixture is then mixed homogeneously (plate / whirler).

The moist pigment / polymer / plastic mixture produced in this way is pelleted on an Eirich pelletizing plate TR 04. There, the size distribution is set. For this purpose, 200 g of freshly prepared granules are placed on the plate and set at 200-350 U / min and an inclination angle of 30-40 °, the target grain size. If the nominal grain size is set, the batchwise entry of the total amount of the water-wet pigment / polymer / plastic batch is started.

The target size is particularly controlled by the dimension (size expansion in mm) of the plastic granules used and should increase in the given experiment to 5.5 ± 0.5 mm. Here, portions between 50-100 g are registered, which within a short time can be added (1 kg about 10-15 min). Coarser aggregates accumulate in the middle of the "material flow kidney" produced during pelleting. These are picked up with a small shovel, crushed by hand and added again.

The moist, granulated mixture is at 40 - 60 ⁰ C in one

Fluidized bed dryer 10-60 min. dried. The granules produced in this way are classified as safe by a sieve of mesh size 6.5 mm.

The pigment granules obtained is resistant to abrasion, dimensionally stable and has an extraordinary purity of the pearl effect produced.

Example 5: Support Material: Full Glass Beads

985 g Vialux coated SB 20 (solid glass beads of particle size 0.6-1, 4 mm of Fa. Sovitec GmbH) and 10.0 g Colorstream ^® Arcticfire (with TiO ₂

SiO ₂ platelets; Fa. Merck KGaA) are presented in the mixing vessel and mixed (plate / whirler). Then 5 g of Michem Prime 4983 R (25

% EAA emulsion from Messrs. Michelman Inc.) was added. The mixture is then mixed homogeneously (plate / whirler).

The moist pigment / polymer / glass bead mixture produced in this way is pelleted on an Eirich pelletizing plate TR 04. There will be the

Size distribution set. For this purpose, 200 g of freshly prepared granules are placed on the plate and set at 200-350 U / min and an inclination angle of 30-40 °, the target grain size. If the nominal grain size is set, the portionwise entry of the total amount of the water-moist effect pigment / polymer / plastic batch is started. The target size is particularly controlled by the dimension (size expansion in mm) of the glass beads used and should increase in the given experiment to 2 ± 0.5 mm. Here, portions between 50-100 g are added, which can be added within a short time _c (1 kg about 10-15 min). Coarser aggregates accumulate in the middle of the "material flow kidney" produced during pelleting. These are picked up with a small shovel, crushed by hand and added again.

The moist, granulated mixture is at 40 - 60 ⁰ C in a 10 fluid bed dryer for 10-60 min. dried. The granules produced in this way are classified as safe by a sieve of mesh size 3.55 mm.

The pigment granules obtained is resistant to abrasion, dimensionally stable and has an extraordinary purity of the pearl effect produced. 15

Example 6: Support Material: PE Particles

For the preparation of the pigment granules according to the invention, a homogeneous mixing is to be ensured. The mixture will help with

20 of an Eirich R02 mixer.

917 g of Escorene LL6101 XR (. LLD-PE plastic / LLDPE: linear low density Fa ExxonMobil) of particle size 3-5 mm, and 55.0 g Iriodin ^® 103 (TiO ₂ -coated mica platelets; Merck KGaA.) will be in »,. Submitted mixing vessel and 2 min. mixed in controller position 1

(Plates / swirler). Then slowly 28 g Michem Prime 4990 R

(35% EAA emulsion from Michelman Inc.) was added. The mixture is then mixed homogeneously (plate / whirler).

The moist pigment / polymer / plastic mixture prepared in this way is pelleted on an Eirich pelletizing plate TR 04. There will be the

Size distribution set. For this purpose, 200 g of freshly prepared granules are placed on the plate and at 200-350 U / min and a Inclination angle of 30-40 ° set the target grain size. If the nominal grain size is set, the batchwise entry of the total amount of the water-wet pigment / polymer / plastic batch is started.

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The target size is particularly controlled by the dimension (size expansion in mm) of the plastic granules used and should increase in the given experiment to 5.5 ± 0.5 mm. In this case, portions between 50-100 g are entered, which can be added within a short time (1 kg about 10-15 min). Coarser aggregates 10 accumulate in the middle of the "material flow kidney" produced during pelleting. These are picked up with a small shovel, crushed by hand and added again.

The moist, granulated mixture is at 40 - 60 ⁰ C in a fluidized bed dryer for 10-60 min. dried. The 15 granules produced in this way are classified as safe by a sieve of mesh size 6.5 mm.

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Example 7 Pigment Granules for Use in the Rotomoulding Process

Carrier material: PE particles

The carrier plastic powder Borecene LLD RM 7243 (LLD-PE plastic powder from Borealis) is microgranulated to the particle diameter 0.6-1 mm in an underwater granulation prior to the start of the test using an _? The measure serves to produce a uniform carrier surface for subsequent coating by means of effect pigments on the plastic carrier surface.

For the preparation of the pigment granules according to the invention a homogeneous mixing is to be ensured. The mixture is made using an Eirich R02 mixer. 901 g Borecene LLD RM 7243 microgranules (LLD-PE plastic / LLD. Linear low density Fa Borealis) the particle size of 0,5 - 1 mm and 28.50 g of Iriodin 305 ^® (. Pearlescent pigment from Merck) are used in Mixing container presented and mixed (plate / whirler). Then slowly 71, 5 g Ultralaube XP-06070480 (42% LDPE-Emulison the Fa.

Germ Additec) was added. The mixture is then mixed homogeneously (plate / whirler). The moist pigment / polymer / plastic mixture produced in this way is pelleted on an Eirich pelletizing plate TR 04. There, the size distribution is set. For this purpose, 200 g of freshly prepared granules are placed on the plate and set at 200-350 U / min and an inclination angle of 30-40 °, the target grain size. If the nominal grain size is set, the batchwise entry of the total amount of the water-wet pigment / polymer / plastic batch is started. The nominal size is particularly controlled by the dimension (size expansion in mm) of the plastic granules used and should increase in the given experiment to 1, 5-2 mm.

In this case, portions between 50-100 g are entered, which can be added within a short time (1 kg about 10-15 min). Coarser aggregates accumulate in the middle of the "material flow kidney" produced during pelleting. These are picked up with a small shovel, crushed by hand and added again.

The moist, granulated mixture is dried at 40 - 60 ⁰ C in a fluidized bed dryer for 10-60 min. The granules produced in this way are classified as safe by a sieve of mesh size 2.5 mm.

Example 8: Litter application on wallpaper

This z. As the above Plastisol - Folcsol RSD 2067/9

Smooth foam by means of flat bed screen printing with a 27/120 sieve (distribution of the company Häusler, Erzhausen, open mesh size: 250 μm, thread thickness 120 μm) was applied to a coated nonwoven fabric of the Tempera VS085xENX brand (basis weight: 85 g / m ² ) from Dresden Papier, Heidenau, Germany.

Subsequently, the thus applied plastisol Folcsol RSD 2067/9

Smooth foam partially or completely coated with the pigment granules according to the invention according to Example 1 and finally at 200 ⁰ C, 1 min., In a drying oven; Type Heraeus; Type 5050EK (nominal temperature: 300 ⁰ C) in the recirculation method, dried. The plastisol Folcosol S-RSD 2067/9 smooth foam expands to a foam and fixes the pigment granules of the invention on the non-woven wallpaper Tempera ^® VS085xENX (basis weight: 85 g / m ² ), the company Dresden paper.

To increase the adhesion immediately after the 1-minute drying / expansion process of the plastisol at 200 ⁰ C in a drying oven, by means of a smooth, structured or embossing roll, the pigment granules according to the invention in the still plastic PVC plastisol adhesive matrix under a pressure of 0 , 1-5 Pa subsequently fixed.

In the drying VExpansionstemperaturdes plastisol of 200 ⁰ C, the support materials of the granules of the invention are that a

Have melting point of <200 ⁰ C, plastic, but without that the

Loss of effect pigment coating on the substrate decreases. It is thereby possible to create relief-like structures on the surface of the effect granulate paper or nonwoven surface. An additional advantage of embossing arises in the increase of the mechanical resistances, such as the abrasion resistance of the effect granules surface produced.

Claims

claims

1. pigment granules, characterized in that they are based on a carrier material which is coated by means of an adhesion promoter with one or _c several platelet-shaped effect pigments.

2. Pigment granules according to claim 1, characterized in that the effect pigment is selected from the group pearlescent pigments, interference pigments, metallic effect pigments, multilayer pigments with transparent, semitransparent and / or opaque layers,

10 goniochromatic pigments, holographic pigments, coated or uncoated BiOCl platelets and / or LCP pigments.

3. pigment granules according to claim 1 or 2, characterized in that the proportion of effect pigments in the pigment granules

0.1 - 50 wt.% Is. 15

4. Pigment granules according to one or more of claims 1 to 3, characterized in that the carrier material is a polymer particle, a glass bead and / or a glass hollow sphere.

5. Pigment granules according to one or more of claims 1 to 4,

20 characterized in that the polymer particles of polyolefins,

Polystyrene (PS), polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), polycarbonate (PC), polyvinyl acetate copolymer (PVAC), ethylene acrylic acid copolymer (EAA), ethylene vinyl acetate copolymer (EVA) or polylactic acid (PLA).

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6. pigment granules according to one or more of claims 1 to 5, characterized in that the polymer particles of EAA or EVA or polyvinyl acetate copolymer (PVAC) exist.

7. Pigment granules according to one or more of claims 1 to 6, characterized in that the carrier material is spherical.

8. Pigment granules according to one or more of claims 1 to 7, characterized in that the carrier material particle sizes of 0.05 - 50 mm.

_c 9. Pigment granules according to one or more of claims 1 to 8, characterized in that the proportion of support material based on the pigment granules 50 - 99.5 wt.% Is.

10. Pigment granules according to one or more of claims 1 to 9, characterized in that the adhesion promoter is selected from 10 of the group

Ethylene acrylic acid emulsion (EAA)

low chlorinated polypropylene dispersion,

- Non-chlorinated polypropylene dispersion

- Wax emulsion.

15 pigment granules according to one or more of claims 1 to 10, characterized in that the proportion of adhesion promoter based on the pigment granules 0.05-20 wt.% Is.

12. Pigment granules according to one or more of claims 1 to 11, characterized in that the pigment granules additionally

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Additives selected from the group of lubricants, wetting agents,

Antioxidants, contains.

13. Pigment granules according to one or more of claims 1 to 12, characterized in that the proportion of the additives based on

"The pigment granules 0.05 to 10 wt.% Is.

14. Pigment granules according to one or more of claims 1 to 13, characterized in that the pigment granules

0.1-50% by weight of one or more effect pigments 30 50-99.5% by weight of carrier material

0.05 to 20% by weight of adhesion promoter 0.05 to 10% by weight of additives contains based on the pigment granules, wherein the total amount of all components in the pigment granules <100

% By weight.

_cc

15. Pigment granules according to claim 1, characterized in that the pigment granules additionally contain inorganic fillers, dyes and / or color pigments.

16. A process for the preparation of the pigment granules according to one or more of claims 1 to 15, characterized in that a

10 or more platelet-shaped effect pigments, the or

Support material (a) with at least one adhesion promoter and optionally one or more additives simultaneously or successively mixed together.

17. Use of the pigment granules according to one or more of 15 claims 1 to 15 in paints, varnishes, powder coatings,

Plastic applications, textile applications and effect plaster systems in the construction sector as well as litter and effect granules.

18. Use of the pigment granules according to one or more of claims 1 to 15 in Rotational Molding method.

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