EP2652045A1

EP2652045A1 - Pigment granules

Info

Publication number: EP2652045A1
Application number: EP11788047.6A
Authority: EP
Inventors: Thomas Rathschlag; Carsten Griessmann
Original assignee: Merck Patent GmbH
Current assignee: Merck Patent GmbH
Priority date: 2010-12-16
Filing date: 2011-11-17
Publication date: 2013-10-23
Also published as: JP2014511120A; CN103261332A; RU2013132616A; WO2012079677A1; DE102010054803A1; MX2013006324A; US20130264523A1; KR20130132918A

Abstract

The present invention relates to conductive pigment granules of which a feature is that they are based on a carrier material, the carrier material being coated by means of an adhesion promoter with one or more electrically conductive pigments. The pigment granules of the invention find preferred use in light-coloured surface coatings which are electrically conductive.

Description

pigment granules

The present invention relates to electrically conductive pigment granules and a process for their preparation and their use, for example, in plastic floors, surface coatings and

Powder coatings. Furthermore, the invention also relates to electrically conductive surface coatings with such pigment granules.

Conductive surfaces are typically required in areas where friction can cause static charges, the energy of which can be dissipated in the form of electrical discharges. Static charges can arise anywhere where different

Rub materials together. However, discharging the static charge may cause damage to the equipment. A common form of electrostatic charging is contact charging, for example when walking on floors. The sole of the shoe, the person and the ground surface can be electrostatically charged in such a way that subsequent contact of a conductive object can lead to a noticeable spark discharge. This can lead to the destruction of sensitive equipment and systems. For example, sensitive equipment may fail and / or be disturbed in operating theaters, resulting in incorrect results. Furthermore, the

For example, in areas where explosive gases or dusts occur, discharge will result in an explosion.

In order to counteract a possible static charge, dissipative surface coatings or materials can be used. For example, dissipative coatings or materials in plastics, fibers and fabrics can be used. Another application example is the use of dissipative

Floor surfaces in parking garages. It can by means of a

Surface covering, in which conductive pigments are embedded in a polymer matrix, resulting static charges, for example, via grounding straps or earthing grid based on copper from the

Surface to be dissipated. A measure of the ability to dissipate such static discharges is the Abieitfähigkeit. It thus denotes the property of dissipating electrical energy. How high the Abieitfähigkeit is determined by the resistance of the material, expressed in ohms. The higher the

Resistance, the lower the Abieitfähigkeit the material. Not for all applications, however, is an unlimited Abieitfähigkeit

desirable. So floors are on the one hand such a low

Resistance that just no electrostatic charges can occur, on the other hand, must not be less than a predetermined resistance to contact a voltage source, a harmful flow of current through the human body

excluded. As a guideline of Abieitfähigkeit for floor coverings is usually a resistance of <10 ⁹ Ω.

From DE 695 25 902 T2 are pigment granules of plastic

Materials are known which have at least three layers of plastic material. The intermediate layers are not visible through the surface layers, have a different color than the surface layers and are formed of an electrically conductive film. The granules are used as a floor or wall covering in the form of a film. This foil is made from the granules by thermal

Treatment and compression produced, wherein the electrically conductive intermediate layers are connected together in the form of a wire network by the film-making process. A film produced in this way can be used as a floor or wall covering which has a static discharge capability. In order for at least one intermediate layer to be electrically conductive, these intermediate layers may be interspersed with soot, wherein the

Graphite component of the carbon black contributes to the conductivity of the intermediate layer.

DE 42 12 950 A1 describes conductive pigments which consist of a component A and a component B. Component A consists of one or more conductive, platelet-shaped

Pigments, while components B consists of one or more conductive non-platelet pigments. To the training of Conductivity, the platelet-shaped and the non-platelet-shaped pigments are provided with a conductive surface layer consisting of conductive metal oxides or metal oxide mixtures. Preferably, a conductive layer of antimony-doped tin oxide is used. The platelet-shaped carrier material used are platelet-shaped effect pigments, for example natural or synthetic mica, phyllosilicates or glass platelets. As non-platelet pigments, spherical or cube-shaped carrier materials can be used. Particular preference is given to using pigments coated with antimony-doped tin oxide. Such conductive platelet-shaped pigments are commercially available under the name Minatec from Merck KGaA, Darmstadt. Conductive coatings can be produced from these conductive pigments comprising at least one component A and / or one component B. The advantage of Minatec.RTM ^® pigments is in the production of bright, static dissipative coating materials in which the use of conductive carbon black and graphite components is not suitable, due to the black, dark ground color tone of the soot and graphite components.

It would be desirable now further conductive pigments or pigment granules, which are conductive coatings, for example

Floor coverings can be produced at lower cost, but still Abieitfähigkeiten in the range of 10 ³ -10 ⁹ Ω and have a light color. As a result, the range of application of conductive pigments and pigment granules can be extended.

Surprisingly, it has now been found that the pigment granules based on a carrier material, such as polymer particles, glass beads, glass hollow sphere or the like, which are coated with one or more electrically conductive pigment, the desired

Have Abieitfähigkeit and from which more cost-effective materials for surface coating can be produced due to the reduced proportion of conductive pigment.

In one aspect of the invention, therefore, pigment granules

proposed, which are based on at least one carrier material, the is coated by at least one adhesion promoter with at least one electrically conductive pigment.

Advantageously, by coating at least one support material with at least one electrically conductive pigment, the proportion of electrically conductive pigment can be reduced in an electrically conductive dielectric material without drastically impairing the removal ability. As a result, the material with less material use and thus more economical to produce, since smaller amounts of the electrically conductive pigment can be used. Due to the reduced concentration of electrically conductive pigment can with the

granules according to the invention formulated lighter conductive materials or conductive objects are designed with attractive colors decors.

Coated is understood to be the superficial coating of the at least one carrier material with the at least one electrically conductive pigment. The at least one electrically conductive pigment is by physical forces and / or the adhesion promoter on the

Fixed surface of the substrate. In this case, a proportion of electrically conductive pigment may be loose and not fixed on the surface form.

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 0.025 to 150 mm, in particular 0.1 to 20 mm, and most preferably in the range of 0.05 to 6 mm.

The brightness of materials and thus the brightness of the

Pigment granules according to the invention and the obtainable therefrom

Materials that can also be colored, is by means of a

Color system determinable. Such color systems combine the

Information of the three elements light source, observer and object, so that with such color systems, the materials, eg. B. in terms of their Color, their color difference and their brightness can be described. For example, with the L * a * b ^* color system, the CIE

(Commission Internationale de l'Eclairage) a determination of the brightness of a material possible. In this color system, L * stands for the brightness, where a value of 100 references a white color, while a value of 0 stands for the color black. The green-red axis is indicated by the a * value, while the blue-yellow axis is indicated by the b ^* value. The respective material can now be measured with appropriate color measuring devices and in the course of which the brightness L * can be determined.

The conductive, light pigment granules according to the invention preferably themselves have a brightness or an L * value of at least 40, in particular of at least 50, very particularly preferably of at least 60 and even of at least 80. The light materials produced with these conductive pigment granules according to the invention can have a brightness or an L * value of at least 40, in particular of at least 50, for example of at least 60 and optionally even of at least 80.

As an essential ingredient, the pigment granules at least one electrically conductive pigment. Under an electrically conductive

Pigment is a pigment that can pass on the electrical current, for example when a discharge of static electricity occurs. In this case, the electrically conductive pigment has a resistance value which allows such a discharge of the electrical current at least over the surface of the pigment body. The electrical conductivity of the individual pigment bodies with one another comes about through the contact of the pigment bodies with one another in the pigment granulate or in an embodiment containing the pigment granulate. The electrically conductive pigment may consist entirely of a conductive material or of a pigment support material provided with a conductive coating. In the case of a pigment carrier material provided with an electrically conductive coating, a further cost reduction can advantageously be achieved. electrical Conductive pigments may preferably be formed platelet-shaped, or have a non-platelet-like design. In the case of the non-platelet-like formation, the electrically conductive pigments may have a needle-shaped, angular or angular shape. It is also possible to use g mixtures of different conductive pigments.

For example, at least one electrically conductive pigment can be selected from the following group:

- carrier-free or carrier-containing metal oxide-containing pigments

10 - carrier-free or carrier-containing metal-containing pigments

- conductive polymers

- graphite

- Carbon nanotubes

- Nanosilver, or

- Any mixture like.

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Become such electrically conductive pigments, together with a carrier material and optionally an adhesion promoter, to a

Processed pigment granules, the proportion of electrically conductive pigment can be significantly reduced, without undermining the Abieitfähigkeit the pigment granules, even in processed form, significantly.

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Thereby, the need for wetting agent for wetting the electrically conductive pigments can be reduced, whereby the rheological properties, such as pumpability and / or sprayability, leveling properties and leveling ability, in the processing of the pigment granules can be improved. In addition, when using pigment granules, ^ with a reduced proportion of electrically conductive pigment, the dust load during further processing can be significantly reduced, so that the use can be extended in construction sites.

As platelet-shaped pigment support materials mica, kaolin, talc, metal flakes or polymer platelets can be used. As platelet-shaped pigment support material it is also possible to use all platelet-shaped effect pigments, for example platelet-shaped iron oxide, bismuth oxychloride or with colored or colorless pigments Metal oxides coated platelet-shaped materials such. B.

natural or synthetic mica, sericite and others

Phyllosilicates such as talc or kaolin, glass flakes, A Oa flakes or Si0 ₂ flakes. It can be used as a platelet-shaped pigment carrier material coated with metal oxides mica flakes. In this case, as metal oxides both colorless high-index metal oxides such as

Example, titanium oxide or zirconium dioxide are used, as well as colored metal oxides, such as chromium oxide, nickel oxide, copper oxide,

Cobalt oxide and in particular iron oxides such. B. Fe2Ü ₃ or Fe ₃ Ü ₄ or mixtures of such metal oxides. Such metal oxide / mica pigments are (under the trade name Afflair ^® and Iriodin ^® Fa. Merck KGaA,

Darmstadt) are commercially available. Such and other support materials are known from U.S. patents. 3,087,828, U.S. Pat. 3,087,829, EP 14382, EP 6831 1, EP 265820, EP 268072 and EP 283852.

The conductive component of the pigment can consist of one or more metal oxides, metals or other conductive compounds, for example iron sulfide or polymers, such as polyacetylene. The

Applying the conductive layer is done in a conventional manner, for example according to the method described in EP-A 139557. Here are all possible conductive metal oxides or

Metal oxide mixtures can be used. A selection of such materials is known from EP-A 139557. However, it is also possible to use conductive pigments which consist entirely of a conductive material.

Preference is given to using, in particular platelet-shaped, pigment support materials coated with antimony-doped tin oxide. These are commercially available under the name Minatec® from Merck KGaA, Darmstadt. Furthermore, pigment mixtures of platelet-shaped, conductive pigments and non-platelet, conductive pigments, such as

DE 42 12 950 A1 known, are used.

Conductive polymers which can be used are electrically self-conducting polymers, such as, for example, polyacetylenes, polyanilines, polyparaphenylenes, polypyrroles or polythiophenes. Preferably, polyethylene dioxithiophene (PEDOT), which is available, for example, under the trade name Orgacon from Kodak.

As carbon nanotubes, for example, Arkema's carbon nanotubes available under the trade name Graphistrength CW 1 -20 "can be used, which contain 20% MWCNT (" Multiwallcarbonnanotubes ") and are particularly suitable for water-based applications.

As metals, all conceivable metals which are stable in the respective application can be used. Preference is given to using nanometals and preferably nanosilver and a nanosilver dispersion.

Furthermore, bright, electrically conductive pigments can be used. Accordingly, pigment granules which have a light color can advantageously be produced with these bright, electrically conductive pigments. The color of the pigment granules is preferred

or the bright, electrically conductive pigments white or light gray. The pigment granules, or pigments, but also other shades, such as a yellow tint, a

Light green tint, a light blue tint, ocher tinge or other tints from the RAL color range. The use of light, electrically conductive pigments can advantageously shift a rather dark color, as is known when using graphite or carbon black, to lighter shades. This shift to bright shades can be specifically adjusted by the bright, electrically conductive pigments.

The proportion of electrically conductive pigment in the pigment granules is preferably 1 to 20% by weight, preferably 1 to 15% by weight and

in particular 5-10% by weight, based on the granules.

Consequently, the proportion of electrically conductive pigment can advantageously be significantly reduced by the use of support materials which are coated with the electrically conductive pigments, compared to a pigment granulate without such support materials, wherein Compared to pigment granules without support materials an equal or comparable Abieitfähigkeit the pigment granules occurs.

As a further essential constituent, the pigment granules also contain at least one in addition to the electrically conductive pigments

Support material. The term "carrier material" is understood as meaning that component of the pigment granules to which the electrically conductive pigment has been coated by means of the adhesion promoter. A suitable one

Support material can have a high transparency and a smaller size compared to the electrically conductive pigment. The

Support materials can be present as individual particles.

In this case, at least one carrier material may be non-platelet-shaped, in particular spherical.

Advantageously, thereby the ingestion of a larger volume by the carrier material is possible, wherein the Abieitfähigkeit of the pigment granules is further given by the coating of the carrier material with the at least one electrically conductive pigment. It can do that

Support material may be spherical or non-circular, such as fracture split, and thus have corners and edges.

Also, at least one carrier material may also be designed to be electrically conductive. In addition, the carrier material may be more conductive than the coating comprising the electrically conductive pigments.

Advantageously, this can take place a forwarding of the electrical current through the carrier material.

Furthermore, at least one carrier material may be a polymer particle, a glass bead, a glass hollow sphere, an amorphous or crystalline

Silica, a ceramic grinding granules and / or a ceramic solid ball, z. B. steatite Mahlvollkugel, be. The can

Polymer particles also be hollow or fully formed. As a result, Polymer hollow spheres or polymer solid spheres can be used.

Advantageously, such cheaper materials can be used in comparison to the electrically conductive pigments and so the

Material costs of the pigment granules are reduced. In the case of ceramic substrates, there is also a resistance to corrosive effects of the atmosphere in the presence of salt, acid and alkaline media, gases, vapors and precipitates.

So can be used as a carrier material full glass balls and / or glass hollow spheres. Preference is given to full glass beads and particularly preferably hollow glass beads.

In addition, transparent supports, such as e.g. Full glass spheres and hollow glass spheres, with their light transmission, the optical properties, eg. As the pearlescent or metallic luster, the pigment granules support.

The glass beads should be chemically resistant depending on the application. Preferably, glass solid or hollow glass spheres of soda lime glass (main components: Si0 ₂ / CaO / Na ₂ 0), ECR glass, C glass borosilicate glass or quartz glass are used.

It is also possible to use mixtures of full glass beads and hollow glass beads. 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.

Full glass beads are commercially available, for example from the company Sovitec GmbH under the name Vialux or Microperl. The particle sizes according to DIN 66165 Part 2, Edition 1987-04, can be determined. For smaller particle sizes, the determination may also preferably be made by means of static laser light scattering, as described in ISO 13320, Edition 2009/10, respectively. As a rule, the Mie theory according to ISO 13320, edition 2009/10 is used as the measuring principle. The present in the present

Patent application for the application of carrier particles are determined by dry measurement using a particle analyzer from Retsch, type "Horiba LA-950." Glass hollow spheres are, for example, at 3M Germany GmbH under the trade name "3M Glass

Bubbles "or at the company Omega Minerals Norderstedt under the trade name" Sphericel "acquirable or at the company Trelleborg

Offshore Ltd. under the name "Fillite" and at the company Dennert Proaver under the name "Proaver" available.

The glass beads should be chemically resistant depending on the application. Preferably, glass solid or hollow glass spheres of soda-lime glass with the main components Si0 ₂ / CaO / Na ₂ 0, ECR glass, C glass borosilicate glass or quartz glass can be used.

This glass hollow spheres of 3M Germany GmbH following

Have characteristic values:

Oil absorption: 0.2-0.6 g oil / cm ³ (determined according to ASTM 0281-95).

Grain size: 9-120 pm (determined according to DIN 66165-2)

It is also possible to use glass hollow spheres or glass full spheres made of soda-lime glass with the main constituents Si0 ₂ / CaO / Na ₂ O, ECR glass, C glass,

Borosilicate glass or quartz glass can be used with a

organic or inorganic pigment coated or colored.

In principle, all organic and inorganic pigments can be used for coloring or coating glass hollow spheres or glass solid spheres.

For example, organic pigments, as in "Industrielle

Organic pigments "of the authors Hunger / Herbst, published by VCH-Verlag 1995, described on pages 633-640.

Furthermore, organic and inorganic pigments, as in the "Pigment + Füllstofftabellen" by the author Lückert, published in Vincentz- Verlag 2002, 6th edition, described, can be used. On the pages 407-434 black pigments, 72-94 white pigments, 216-299 red pigments and 326-361 blue pigments are described.

Subsequently, the colored or coated glass hollow spheres or glass solid spheres can be coated with electrically conductive pigments on the surface.

It is also possible to use colored hollow glass spheres from Quadra Industries. These glass hollow spheres used can have the following characteristic value:

Grain size: 5-65 m (determined according to DIN 66165-2).

The full glass beads from Quadra Industries are either with

enveloped organic and / or inorganic pigments.

It can also be ceramic support materials such. As steatite grinding granules and / or steatite solid balls are used. In this case, ground granules comprise non-round particles produced by means of a granulation process, while solid spheres with pressed edges produced by the solid spheres are produced by the dry-pressing process. Such steatite ground granules and / or steatite solid spheres are commercially available from Mühlmeier, Bärnau, Germany.

As polymer particles are preferably those of plastics), such as. As thermoplastics or thermosets, are used. The polymer particles are preferably composed of polyolefins, in particular of 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, e.g. B. polylactic acid (polyactide = (PLA)).

Particularly preferred carrier materials consist of PVC, in particular of spherical granules, for example in the company Geerkens

Raw materials, Willich, Germany, available. The commercially available plastic powders or plastic granules often have particle sizes of 1 to 5 mm. These polymer particles can be previously melted in the preparation of the pigment granules according to the invention and then, for example, by granulation, for. B. underwater granulation, and optionally setting the

Grain size, z. B. by means of a perforated disc to the desired

Particle size and shape can be adjusted.

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 possible 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, with aesthetic effects and economic considerations, correlate.

Carrier material mixtures are preferably mixtures of two-component mixtures which can be mixed with one another in any ratio. The ratio is preferably 1: 1 to 1:10 or 10: 1.

It is also possible to use unstructured particles of the same particle size distribution. The support materials can be used in any combination for the pigment granules. At least one carrier material may have a particle size of 0.01-100 mm, in particular 0.01-50 mm and optionally 0.1-10 mm. Preferred is a particle size of 0.025 - 5 mm.

The larger the particle sizes, the more advantageously more volume can be occupied by the carrier material in the pigment granules. Thus, the material costs of the pigment granules are significantly reduced.

The proportion of carrier material based on the pigment granules may be 80-99 wt.%. In particular, a proportion of 90-99 wt.% Is possible. Preferably, a proportion of 80-90 wt.%.

Advantageously, the wetting agent requirement can thereby be reduced and the theological properties during processing are improved. If sufficient support material is used, the desired properties of the pigment granules of the invention, e.g.

reduced dust behavior and / or improved flowability, guaranteed. For this purpose, the polymer particles must not only be coated with the electrically conductive pigment, but they must also be glued together to form a free-flowing coarse "powder".

In the pigment granules, the weight ratio of carrier material to electrically conductive pigment may be from 1: 5 to 50: 1.

For example, a weight ratio of 10: 1 to 20: 1 is preferred.

Advantageously, the pigment concentration is reduced, but nevertheless a sufficiently high conductivity is present. The weight ratio of carrier material to electrically conductive pigment can also be used to control the conductivity.

Pigment granules may preferably have at least one adhesion promoter. In this case, the adhesion promoter may preferably be selected from the group: Ethylene acrylic acid emulsion (EAA)

chlorinated or non-chlorinated polypropylene dispersion,

chlorinated or non-chlorinated polyethylene dispersion,

- Polyurethane dispersions,

- wax emulsions.

Advantageously, by using the adhesion promoter, the conductive pigment can be fixed on the support material, which does not

it is excluded that a part of the electrically conductive pigment is not fixed in the granules. The fixation can also reduce the dust emission during the processing of the pigment granulate.

Other suitable adhesion promoters are especially those which dry physically. Particularly preferred as adhesion promoter aqueous

Emulsions are used, preferably EAA emulsions (ethylene acrylic acid copolymer), commercially available, for example, from the company Michel- man under the name "Michem Prime 4983 R", as well as emulsions and dispersions based on acrylated polypropylenes or low-chlorinated polypropylenes. Such emulsions and dispersions are commercially available, for example from Tramaco under the name "Trapylen 9310 W and" Trapylene 6700 W '.

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

The size of acrylated polypropylene or low chlorinated

Polypropylene emulsion particles or dispersion particles is preferably 50-5000 nm.

Suitable adhesion promoters are also wax emulsions, commercially available, for example, from the company KEIM ADDITEC Surface GmbH. Suitable wax emulsions are z. B. LD-PE wax emulsions (LD-PE = low density polyethylene), eg Ultralube V-06070480 Fa. KEIM ADDITEC Surface GmbH. The wax emulsions preferably contain The suitable wax emulsions preferably have a melting range of 50-160 ° C., in particular of 90-140 ° C. and very particularly preferably of 90-130 ° C.

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Below further suitable adhesion promoters are called, which are based on aqueous dispersions, such as. B. such

1) based on copolymers or based on terpolymers:

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

10 - vinyl acetate (VAC / (ethylene) [E] / vinyl chloride (VC) = VAC / E VC

Vinyl chloride (VC) / ethylene [E] / acrylic 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 / E / VC

2) based on acrylate dispersions

Ί5 - styrene acrylic ester (S-AY)

Acrylic acid ester (AY)

- self-crosslinking acrylate

- Polyacrylates and their copolymers

- PMMA and their copolymers

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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

"_ - water-dilutable urea resins

zo

- water-thinnable polyester

- Water-dilutable alkyd resins

- water-dilutable rosin resins and rosin resin esters

- water-dilutable shellac

- water-dilutable polyvinyl acetals

30 - water-dilutable polyvinyl ethers

- water-dilutable soy proteins

Polyvinyl alcohols = PVOH 4) Polyurethane dispersions

4a) aliphatic polyurethanes

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

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

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

Polyester (PES) / Polycarbonate (PC) / Polyurethane (PU) logo CNRS logo INIST

PES / PC / PU

4b) aliphatic oil-based polyurethane hybrids

- based on castor oil (CO)

- based on castor oil and linseed oil (LO).

Adhesives based on resins and polymers which are dilutable with organic solvents or soluble in them are also suitable as adhesion promoters. Usually, these adhesion promoters are not water-soluble or water-dilutable. Examples of suitable raw materials can be found, for. B. in the Lackrohstofftabellen, Vincentz-Verlag, 10th edition, edition 2000, pages 62-622.

Examples of possible adhesives which can be used as adhesion promoters are generally based on the following resins and polymers:

- saturated polyesters

- unsaturated polyester

Epoxides

- Polyacrylates and copolymers

- PMMA and u. -Copolymerisate

- polyamides

- ketone resins and aldehyde resins

- polystyrenes

- polyurethanes (PU)

Polyurethanes (PU) / acrylates (AY) = (PU / AY)

- moisture-curable polyurethanes

, p c

- 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 resin 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)

- anaerobic curing 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 based on the pigment granules may be 0.05-20% by weight. For example, a proportion of 0.1-20 wt.%, in particular from 0.1 to 15% by weight and optionally from 0.1 to 10% by weight. A proportion of 0.5-10% by weight is preferred.

Advantageously, a good adhesion of the electrically conductive pigment to the carrier material can be achieved by the specified proportions of adhesion promoter in the pigment granules, so that only slightly unbound, electrically conductive pigment is present in the pigment granules.

In this case, the at least one carrier material, the at least one electrically conductive pigment and the at least one adhesion promoter can be coordinated with one another in such a way that the pigment granulate or the use form which can be produced therefrom, as described below, has a light color.

Pigment granules may additionally contain at least one additive, as they are customary for use in application media from the fields of paints, coatings, powder coatings, plastics or the like. Such additives and / or auxiliaries may include lubricants, release agents, stabilizers, antistatic agents, flame retardants, antioxidants, colorants, flexibilizers, plasticizers, such as. As diisononyl phthalate, blowing agents, antioxidants, UV absorbers, inorganic fillers and / or surfactants, organic

polymer-compatible solvents and / or surfactants, phenol derivatives, mineral oils. An overview of the applicable additives and

Excipients can be found in Saechtling, Plastic Paperback, 27th Edition, Carl Hanser Verlag or R. Wolf in "Plastics, Additives" in Ullmann's, Encyclopedia of Industrial Chemistry, Internet Edition, 7th Edition, 2003.

By using additives, the properties of the

Pigment granules are favorably influenced, so that the

Field of application for the pigment granules can be extended.

Particularly preferably, the pigment granules contain wetting agents, for. As silicones, silanes and / or fluorosurfactants.

The proportion of additive in the pigment granules can be 0.05-10% by weight, based on the granules. For example, a proportion of 0.1-10 % By weight, in particular from 0.1 to 5% by weight and optionally from 0.1 to 5% by weight. Preferably, a proportion of 0.5-5 wt.%.

In pigment granules, carrier material, adhesion promoter and electrically conductive pigment may be present in a weight ratio of 8: 1: 1 to 9.5: 0.25 0.25. Preferably, the weight ratio of 8.5: 0.5: 1.

Furthermore, pigment granules may preferably contain

1 - 20% by weight of one or more electrically conductive pigments

80-90% by weight of one or more carrier materials

1 to 5% by weight of adhesion promoter

0-5% by weight of additive (s), preferably 1-5% by weight of additive (s), based on the total formulation of the pigment granules, wherein the total amount of all components in the pigment granules is 100% by weight.

Pigment granules may also contain at least one filler, at least one dye and / or at least one color pigment, in particular those which are customary in the field of plastics and / or paints. Based on the pigment granules, the total proportion of all components being 100% by weight, the proportion of dye, color pigment and / or filler may be up to 10% by weight.

Such fillers are described in the "Pigment + Füllstofftabellen" by the author Lückert, published in Vincentz-Verlag 2002, 6th edition, on pages 596-768.

Through the use of at least one filler, at least one

Dye and / or at least one color pigment are desired

Properties, such. B. a color tint, the pigment granules specifically adjustable. Thus, the conductive granules can be color matched to the requirements of the application. It is advantageous z. As the addition of white pigments or fillers, if a light color in the application is needed. In a further aspect of the invention, a process for the production of pigment granules is proposed in which at least one electrically conductive pigment and at least one support material with at least one adhesion promoter and optionally at least one additive, filler, dye and / or color pigment are mixed simultaneously or successively ,

Pigment granules are relatively easy to produce. As a possible manufacturing process are the gentle mixture of the individual

Components comprising an electrically conductive pigment,

Carrier material, adhesion promoter, optionally colorant and / or other additives, and to call a subsequent rotogranulation. In this case, the components to be mixed are mixed with a mixer in which the carrier material, the adhesion promoter and optionally additives and the electrically conductive pigment or the mixture of electrically conductive pigments and optionally further organic and / or inorganic pigments. 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 in a fluidized bed, z. B. 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 electrically conductive pigment,

Adhesive and carrier material is variable and can for example also take place in such a way that the electrically conductive pigment is initially charged and subsequently with the adhesion promoter, the carrier material and, if appropriate,

Additives and / or colorants, is mixed. This embodiment is particularly preferred.

It is also possible that one submits the electrically conductive pigment, the carrier material and optionally additives, and then with the

Adhesive adds.

In the pigment granules according to the invention, the electrically conductive pigments, the support material and the adhesion promoter and, if appropriate, additives are mixed with one another. Preferably, the carrier material at least partially or completely coated or coated with the electrically conductive pigment by the adhesion promoter. A complete

Enclosing and "gluing" of the carrier material with the electrically conductive pigment is very particularly preferred.

As a further aspect of the invention, the use of the pigment granules in printing inks, paints, lacquers, powder coatings, surface coatings, plastic applications and / or plastics is proposed. Particularly preferred is the use of the pigment granules according to the invention in floors and / or as a PVC coating.

As a further aspect of the invention, a surface coating is proposed with a pigment granules, wherein the pigment granules comprises a carrier material which is coated by means of an adhesion promoter with at least one electrically conductive pigment.

Advantageously, a bright surface coating can be formed by the pigment granules according to the invention. This bright surface coating is also conductive, abrasion resistant and therefore cost-effective due to the use of only a small proportion of electrically conductive pigment. Such a surface coating may preferably be applied to one of the following elements: a floor, a garage floor, a floor in the medical

Area, a floor in laboratories, a floor in workshops or assembly halls, a floor in chip production or the like.

Preferably, the surface coating is white to light gray and optionally tinted in color, according to the RAL color range.

The surface coating may have a conductivity value of 10 ³ to 10 ⁹ ohms.

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

Example 1 Production of Conductive Pigment Granules Containing PVC

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.

For this purpose, 1,000 g of spherical, 1 mm PVC granulate (Fa. Geerkens raw material GmbH, Willich, Germany) and 110 g Minatec.RTM ^® 60 CM

(Mica platelets coated with antimony oxide + tin oxide, from Merck KGaA) are introduced into the mixing container and mixed for 3 min in regulator position 1 for plates and turbines of the Eirich R02 mixer. Thereafter, slowly with stirring, 65 g of an aqueous polycarbonate / polyurethane dispersion (Alberdingk & Boley, Krefeld, Germany, solids content: 37-39%, pH 7.5-9, elongation at break = 200%) are the previously produced

Plastic / pigment mixture added and homogeneous in the

Regulator position 1 of the Eirich R02 mixer Eirich R02-Mixer 1 for plate and vortex mixed for 1 min.

The moist plastic / pigment / polymer 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 at 200-350 U / min and a tilt angle of 30-40 ° the

Target grain size set. If the nominal grain size is set, is added with the portionwise entry of the total amount of water-moist

Pigment / primer / plastic batches, started.

The nominal size is particularly controlled by the dimension (size expansion in mm) of the plastic granules used and is intended in the

given experiment 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 pelleting arising "material flow kidney". 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, 10-30 min. dried. The granules thus produced are passed through a sieve of mesh size 3.55 mm

protection classified.

The pigment granules thus obtained are abrasion-resistant and dimensionally stable.

Example 2: Production of soft PVC compacts

The produced compacts A, B, C, D have the following dimensions:

Length: 20 cm; Width: 15 cm; Thickness: 5 mm.

Production Presslinq A:

90 g of PVC granules Decelith 76000 (PCW, Eilenburg, Germany) + 90 g of granules from Example 1 are pressed at 145 ° C for 2.5 min on a Collin-Thermo press at 80 bar pressure and then cooled for 2 min.

Production of Pressling B:

95 g of PVC granules Decelith 76000 (PCW, Eilenburg, Germany) + 95 g of granules from Example 1 are pressed at 145 ° C for 2.5 min on a Collin Thermo press at 80 bar pressure and then cooled for 2 min.

Production of Pressling C:

150 g of PVC granules Decelith 76000 (PCW, Eilenburg, Germany) + 50 g granules from Example 1 are pressed at 145 ° C for 2.5 min on a Collin Thermo press at 80 bar pressure and then cooled for 2 min. Production Presslinq D (comparative experiment):

150 g of PVC granules Decelith 76000 (PCW, Eilenburg, Germany) + 50 g Minatec.RTM ^® 60CM (Fa. Merck KGaA) are min at 145 ° C for 2.5, compressed on a Collin thermal press at 80 bar pressure and

then cooled for 2 min.

Example 3: Measurement of the soft PVC compacts A, B, C, D.

The surface resistances are determined in accordance with DIN-EN-61340-2-3, "Electrostatic" of December 2000. The visual color impression of the coating is determined.

Pressling Color Application concentration Surface resistance R

[%] [kQ]

A light gray 4.50 20.0

B light gray 4.50 15.0

C light gray 2.25 5.7

D light gray 25.00 5.3

Here, the use concentration [%] is the percentage of conductive pigment in 100 g of total composition of conductive PVC floor mass.

The test series shows that pigment granules according to the invention can be used to reduce the percentage of electrically conductive pigment by a factor of> 10 with an approximately constant surface resistance. In addition, the color of the compact increases with increasing pigment content, so that Pressling C has the brightest hue, followed by A and B. Pressling D has the comparatively darkest hue on.

Claims

claims

Pigment granules, characterized in that they are based on at least one carrier material, by means of at least one

Adhesive is coated with at least one electrically conductive pigment.

Pigment granules according to claim 1, characterized in that at least one electrically conductive pigment is selected from the group:

- carrier-free or carrier-containing metal oxide-containing pigments

- carrier-free or carrier-containing metal-containing pigments

- conductive polymers

- graphite

- Carbon nanotubes

- Nanosilver, or

- Any mixture like.

Pigment granules according to claim 1 or 2, characterized in that at least one carrier-free or carrier-containing metal oxide-containing pigment is a tin oxide-containing pigment.

Pigment granules according to one or more of claims 1 to 3, characterized in that the proportion of electrically conductive pigment in the pigment granules 0.1 to 20 wt.% Is.

Pigment granules according to one or more of claims 1 to 4, characterized in that at least one support material is non-platelet-shaped, in particular spherical, is formed.

6. pigment granules according to one or more of claims 1 to 5, characterized in that at least one carrier material is formed electrically conductive.

7. Pigment granules according to one or more of claims 1 to 6, characterized in that at least one carrier material is a polymer particle, a glass bead, a glass hollow sphere, an amorphous or crystalline silicon dioxide, a ceramic

Grind granules and / or a full ceramic ball, a steatite grinding granules and / or a steatite grinding solid ball is.

8. Pigment granules according to one or more of claims 1 to 7, characterized in that at least one carrier material

Particle sizes of 0.01 - 100 mm.

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 80 - 99 wt.% Is.

10. Pigment granules according to one or more of claims 1 to 9, characterized in that in the pigment granules

Weight ratio of carrier material to electrically conductive pigment of 1: 5 to 50: 1.

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

Ethylene acrylic acid emulsion (EAA)

- Chlorinated or non-chlorinated polypropylene dispersion

- Chlorinated or non-chlorinated polyethylene dispersion

- Wax emulsion

- Polyurethane dispersion.

12. pigment granules according to one or more of claims 1 to 11, characterized in that the proportion of adhesion promoter based on the pigment granules 0.05-20 wt.% Is.

13. Pigment granules according to one or more of claims 1 to 12, characterized in that the pigment granules 1 to 20% by weight of one or more electrically conductive pigments 80 to 90% by weight of one or more support materials

1 to 5% by weight of adhesion promoter

0 - 5 wt.% Additive (s) based on the total formulation of the pigment granules, wherein the total amount of all components in the pigment granules <100 wt.% Is.

14. A process for the production of pigment granules according to claim 1, characterized in that at least one electrically conductive pigment and at least one carrier material having at least one adhesion promoter and optionally

at least one additive, filler, dye and / or color pigment are mixed simultaneously or successively with each other.

15. Use of the pigment granules according to one or more of claims 1 to 13 in printing inks, paints, varnishes, powder coatings, surface coatings, plastic applications and / or plastics.

16. surface coating with a pigment granules, in particular according to one or more of claims 1 to 13, wherein the pigment granules comprises a carrier material which is coated by means of an adhesion promoter with at least one electrically conductive pigment.

17. Surface coating according to claim 16, characterized

characterized in that the surface coating has a Abieitwert of 10 ³ to 10 ⁹ ohms.