DE102011088149A1 - A coated composite comprising a composite material - Google Patents

Abstract

The present invention describes a composite body comprising a composite material comprising at least one cellulosic material and at least one poly (alkyl) (meth) acrylate, the molding having at least one coating associated with the composite material.

Description

The present invention relates to a composite comprising a composite material containing at least one cellulosic material and at least one poly (alkyl) (meth) acrylate and at least one coating associated with the composite material. Furthermore, the present invention describes a method for producing such a composite body.

Composite body referred to in the context of the present invention, a three-dimensional body comprising preferably at least one molded body and / or a casting of the composite material according to the invention and at least one coating.

Composite material in the context of the present invention denotes a composition comprising at least one cellulosic material and at least one poly (alkyl) (meth) acrylate. This is preferably a molding compound or a reactive solution or a syrup, which can be used for casting processes.

Shaped body in the context of the present invention, a three-dimensional body which has been prepared by a thermoplastic deformation process, preferably extrusion or injection molding, of a composite material according to the invention. Casting in the context of the present invention, a three-dimensional body, which was prepared by a casting process of a composite material according to the invention.

Composite bodies of at least one cellulosic material and at least one plastic are nowadays produced industrially, in particular in the form of wood-plastic composites, so-called WPCs "wood plastic composites". In the context of the invention described below, the terms "wood-plastic composite (s)", "wood-plastic composite (s)" and "WPC (s)" are used interchangeably. The terms "composite", "WPC material" and "composite" are also used interchangeably.

Historically, solid wood and traditional wood-based materials are typically used as building and furniture materials. The WPC materials have expanded these classic applications to include significant new uses due to improved molding techniques.

WPC materials are usually a combination of wood particles (such as wood chips, sawdust, wood fibers or wood flour) with a plastic matrix. As a plastic matrix usually serve thermoplastics.

In the original development of WPCs in North America, wood was primarily used as a cheap filler. The cost of wood shavings is a fraction of the alternative plastics used, making the share of wood cheaper in the product. Compared to the plastics used, wood has a higher modulus of elasticity, so that better mechanical properties result from an optimized wood-plastic combination compared to pure plastic.

Three plastics dominate the world in almost all commercially produced WPC materials. While predominantly polyethylene (PE) is used in America, mainly polypropylene (PP) is used in Europe. In Asia polyvinyl chloride (PVC) is often used as WPC plastic. All three plastics have in common that they represent mass plastics and therefore are relatively inexpensive to have. This commercial aspect is one of the reasons why WPC research was only concerned with the mentioned thermoplastics.

On the other hand, it is still a challenge to permanently bind natural fibers (such as cellulose) to polymers. In the case of the plastics PE, PP and PVC mentioned above, the connection to wood fibers by means of adhesion promoters has been solved sufficiently well as a result of decades of development.

The current development of WPC materials is, in addition to the optimization of process technology, very much concerned with the improvement of product properties or properties tailored to specific applications.

WPC materials are currently used primarily in outdoor applications. A large application for WPC are patio panels, so-called "deckings". Here, WPC materials mainly compete against Precious woods from subtropical regions. In construction applications, WPC materials are expected to have the highest durability in addition to material strength, but at least comparable to resistant natural woods.

Due to the raw materials used, WPC materials are generally subject to changes in the outdoor area due to the effects of weathering. The degree of aging depends on the one hand on the resistance of the wood fibers used, on the other hand also on the long-term behavior of the plastic used.

It is well known that plastics have very broad product characteristics. This applies to both thermal and mechanical and long-term properties. With the development of durable outdoor WPC materials, there is still a need for composites with better weatherability compared to polyolefin based WPCs.

The production of WPC composites is often done by injection molding or extrusion process and thus takes place by plasticizing at melt temperature of the plastic component. Also, but rather less common, are wet-chemical polymerisation processes with wood particles.

Polymethyl methacrylate, PMMA for short, is known for extreme weather resistance and high mechanical strength. It is therefore well suited in the property spectrum for construction applications. For WPC applications, however, this material has not yet gained acceptance, since extruded molded articles made of this material show a relatively high water absorption. Such moldings are for example in FR 1 575 752 A shown. Shaped bodies obtainable from (meth) acrylate reactive resins, such as those described in, for example, US Pat EP 0 982 110 A are also very expensive to manufacture. Accordingly, WPC materials based on PMMA have not been commercially sold.

Commercially available WPC materials that have been exposed to weathering for a long time are difficult to recycle. It should be noted that on the commonly used polymers coatings such. B. primers, paints or glazes difficult to adhere. Accordingly, these WPC composite bodies can not be worked up and are replaced after a relatively short time. WPC materials based on PVC also have relatively large problems with regard to their environmental compatibility.

In view of the prior art, it was therefore an object of the present invention to provide a composite body comprising a composite material containing at least one cellulosic material and at least one polymer having an improved property profile.

In particular, the composite should have a very high weather resistance, wherein the composite should be able to be easily worked after weathering. Accordingly, weathered composites should show a similar property profile to wood so that they could be refurbished and restored without special knowledge and expensive tools.

Furthermore, it was an object of the present invention to provide a composite whose color is easily adjustable to specific customer requirements, without this would be a costly adaptation in the manufacture of the composite body as such would be necessary. Here, the color of already built composite bodies should be customizable.

Another object can be seen to provide a composite based on WPC materials that can be manufactured and processed easily, inexpensively, and in an environmentally friendly manner. In particular, the moldings used should be obtainable by extrusion and processed by conventional standard methods, which are used in particular in the treatment and processing of wood. Here, the composite body should be able to be recycled relatively well, without environmental damage would be feared.

One particular task was to provide composites with excellent mechanical properties.

Other tasks that are not explicitly mentioned emerge from the overall context of the following description, examples and claims.

These and other objects which are not explicitly mentioned but which are readily derivable or deducible from the contexts discussed hereinbelow, are solved by means of a molded article having all the features of patent claim 1.

The present invention accordingly provides a composite comprising a composite material comprising at least one cellulosic material and at least one poly (alkyl) (meth) acrylate, characterized in that the composite has at least one coating associated with the composite material, having.

The composite has a very high weather resistance, wherein the composite body can be easily worked after weathering. Accordingly, weathered composites show a similar property profile to wood, so that they can be worked up and restored without special knowledge and expensive tools.

Furthermore, the color of a composite body according to the invention can be easily adjusted to specific customer requirements, without this necessitating a costly adaptation in the production of the composite body as such. Here, the color of already installed composite bodies can be adapted to changed wishes of the consumer.

Furthermore, a composite body according to the invention based on WPC materials can be produced and processed in a simple, cost-effective and environmentally friendly manner. In particular, preferred moldings are obtainable by extrusion and can be processed by conventional standard methods, which are used in particular in the treatment and processing of wood. Here, the composite body can be recycled relatively well, without environmental damage to be feared.

In addition, composites of the present invention exhibit excellent mechanical properties that match or exceed the characteristics of structural wood.

The composite bodies of the invention are ideally suited for outdoor use, since they have a low water absorption, high dimensional stability due to low swelling behavior and high mechanical strength.

Further advantages of the composite according to the invention z. B. in comparison to similar bodies of pure wood can be seen in the fact that the composite bodies according to the invention do not rot. In contrast to z. B. wood, the WPC composite body according to the invention can thus be used outdoors or in wet rooms or greenhouses. The paintability of the protection can be improved again.

In comparison to wood components, the composite bodies according to the invention have the advantage that they are not attacked by parasites and thus remain stable in the long term or can be used in areas in which conventional wood components can not be used. Thus, the import of wood into certain countries is limited because of possible parasite infestation. This restriction is omitted in the composites of the invention.

The composite bodies according to the invention may have hollow chambers. These can be filled with insulating materials to improve the thermal insulation properties or soundproofing properties, but these can also be filled with reinforcements to improve the carrying capacity of the composite materials according to the invention. These can be highly resilient parts z. B. iron or carbon, etc. act. Thus, with the composite materials according to the invention, e.g. Structural parts are manufactured, which are far superior to those made of pure wood or metal in terms of load or weather protection. In this case, in comparison with these materials, particular attention must be drawn to the low cost of renovation and maintenance required by the composite materials according to the invention.

In contrast to wood, the color of the composite body according to the invention changes significantly less and slower and can be refreshed by painting again. A composite according to the invention comprises at least one composite material containing at least one cellulosic material and at least one poly (alkyl) (meth) acrylate.

In the context of the present invention, poly (alkyl) (meth) acrylate matrix material is understood as meaning a matrix material which contains exclusively poly (alkyl) (meth) acrylate as the polymer component but also a matrix material which comprises a blend of different poly (alkyl) (meth ) acrylates or poly (alkyl) (meth) acrylate (s) and other polymers but also contains a matrix material which is a copolymer of at least one poly (alkyl) (meth) acrylate and other comonomers, preferably styrene, α- Methylstyrene, (meth) acrylic acid and / or (alkyl) acrylates, cyclic carboxylic anhydride derivatives, especially preferably maleic anhydride, itaconic anhydride, citraconic anhydride, glutaconic anhydride, glutaric anhydride, (alkyl) (meth) acrylamides, (alkyl) (meth) acrylimides, N-vinylpyrolidone, vinyl acetate, ethylene or propylene.

The composites may be comprised of the composite. Poly (alkyl) (meth) acrylates may be obtained by casting from reactive resins, thereby providing sufficient adhesion between the cellulosic material and the polymer. However, the composite bodies thus produced are relatively expensive, so that preferred composite materials can preferably be processed by thermoplastic methods. When using a thermoplastic composite material has in poly (alkyl) (meth) acrylate as the matrix material whose flow behavior has proven to be an important criterion. The poly (alkyl) (meth) acrylate used according to the invention as the matrix material therefore preferably has a melt index MVR [230 ° C., 3.8 kg] in the range of 0.5-30 ml / 10 min, preferably 1-20 ml / 10 min and particularly preferably in Range of 1-10 ml / 10 min, measured according to ISO 1133 , In the case where the poly (alkyl) (meth) acrylate is present as a copolymer with a cellulose-compatible adhesion promoter, the MVR [230 ° C., 3.8 kg] is preferably in the range of 1-30 ml / 10 min and more preferably 3-15 ml / 10min.

Experiments with various poly (alkyl) (meth) acrylate grades have shown that when the poly (alkyl) (meth) acrylate melts are too high in molecular weight, they can be mixed with, for example, sodium chloride. B. wood particles is very difficult, since the necessary temperature increase an incipient damage of the wood particles was found. Too low molecular weight poly (alkyl) (meth) acrylate may cause problems with the "floating" of the wood fibers in the plasticizer and thus difficulties with the mixing of the components. Particular preference is given to using polymethyl (meth) acrylate, polyethyl (meth) acrylate or polybutyl (meth) acrylate.

"Alkyl" in the poly (alkyl) (meth) acrylate is a branched or unbranched, cyclic or linear alkyl radical having 1 to 20, preferably 1 to 8, particularly preferably 1 to 4 carbon atoms which are substituted by functional groups or heteroatoms such as O. , S or N. It is preferably a methyl, ethyl, butyl or cyclohexyl radical. Polymethyl (meth) acrylate, polyethyl (meth) acrylate or polybutyl (meth) acrylate is particularly preferably used, with polymethyl methacrylate (PMMA) being particularly preferred.

The term "(meth) acrylate" in the context of the present invention is generally and generally applicable to both methacrylates and acrylates, as well as mixtures of both. Poly (alkyl) (meth) acrylates are polymers which are obtainable by polymerization of a monomer mixture which preferably has at least 60% by weight, particularly preferably at least 80% by weight of (meth) acrylates, based on the total weight of the monomers to be polymerized. Preferred poly (meth) acrylates are obtainable by polymerization of mixtures which have at least 20% by weight, in particular at least 60% by weight and particularly preferably at least 80% by weight, based in each case on the total weight of the monomers to be polymerized, of methyl methacrylate. These polymers are referred to in the context of the present invention as polymethyl methacrylates.

The proportion of poly (alkyl) (meth) acrylate in the preferably used composite material can vary within wide ranges. Preferably, between 0.5 and 70% by weight, preferably between 1% by weight and 50% by weight, particularly preferably between 2% by weight and 40% by weight, very particularly preferably between 3% by weight and 30% by weight. , particularly preferably in the range 5 wt.% To 25 wt.% Poly (alkyl) (meth) acrylate, based on the weight of the composite material used.

In addition to the poly (alkyl) (meth) acrylate matrix material, the composite of the present invention may preferably comprise at least one cellulosic adhesive. A "cellulose-compatible adhesion promoter" is understood to mean a coupling agent which contains functional groups which can form hydrogen bonds, ionic bonds or chemical compounds with the OH groups of the cellulose.

In a first preferred embodiment of the present invention, the adhesion promoter is added as a separate component in addition to the matrix material (component a) in the formulation of the composite material. Although the matrix material may indeed be a copolymer, in this embodiment the adhesion promoter does not form a copolymer with the matrix polymer or is not part of a matrix copolymer. The adhesion promoter which is preferably used here is preferably a copolymer comprising one or more monomers (e) selected from the group consisting of cyclic carboxylic anhydride derivatives, such as, for example, Example, maleic anhydride, itaconic anhydride, citraconic anhydride and Glutaconsäureanhydrid, (meth) acrylic acid derivatives such as methacrylic acid or acrylic acid, amino, imide monomers and monomers containing epoxy groups, preferably (alkyl) (meth) acrylamides, (alkyl) (meth) acrylimides, N-vinylpyrolidone. Furthermore, one or more monomers selected from the group consisting of styrene, α-methylstyrene, α-ethylstyrene, acrylates, methacrylates, vinyl acetate, ethylene or propylene may be included.

The copolymers of the coupling agent can be used with random distribution of the monomer units but also as a graft copolymer or block copolymer. As the cyclic carboxylic acid anhydride derivatives, those having a 5-, 6- or 7-membered ring, particularly preferably maleic anhydride, itaconic anhydride, citraconic anhydride and glutaconic anhydride are preferably used.

"Alkyl" in the coupling agent copolymer stands for a branched or unbranched, cyclic or linear alkyl radical having 1 to 20, preferably 1 to 8, particularly preferably 1 to 4, carbon atoms which may be substituted by functional groups or heteroatoms such as O, S or N. It is preferably a methyl, ethyl, butyl or cyclohexyl radical.

The adhesion promoter which is preferably to be used according to the invention may, according to a first embodiment, preferably be a low molecular weight copolymer. Particularly preferred is a styrene-maleic anhydride copolymer, most preferably a commercially available under the brand name XIRAN ^® SMA the Dutch company Polyscope Polymers BV polymer.

The melt index MVR [230 ° C., 3.8 kg] of the adhesion promoter copolymer is preferably in the range of 1-30 ml / 10 min, more preferably 2-20 ml / 10 min and most preferably in the range of 3-15 ml / 10 min. The proportion of the adhesion promoter based on the total weight of the composite material to be used according to the invention in this embodiment depends on the concentration of the cellulose-forming bridge-forming functional groups within the adhesion promoter. The proportion of the adhesion promoter may vary between 0.5 and 70% by weight, preferably 1% by weight and 50% by weight, particularly preferably 1% by weight and 40% by weight, very particularly preferably 2% by weight and 30% by weight. %, more preferably in the range of 3% by weight to 25% by weight and most preferably in the range of 3% by weight to 15% by weight. In a very particularly preferred embodiment, a styrene-maleic anhydride copolymer - namely Xiran ^® SZ 22065 - with about 20-22 wt.% Effective maleic anhydride groups used.

This first preferred embodiment allows maximum flexibility in the manufacture and composition of the composite material.

In a second preferred embodiment of the present invention, the adhesion promoter (component b) and the monomers forming the matrix polymer (component a) are "fused" together, i. a copolymer of the primer and the matrix polymer is formed so that the "adhesion promoter-modified" matrix polymer can be used directly to make the composite. In this case, it is not necessary to add a coupling agent as an isolated further component, but this is quite possible.

In this embodiment, a copolymer of the monomers of the poly (alkyl) (meth) acrylate and the monomers of the adhesion promoter is preferably used. Here, the copolymer may be, for example, a random copolymer, a block copolymer or a graft copolymer.

Accordingly, preferred copolymers include moieties which are preferably selected from the group consisting of cyclic carboxylic acid anhydride derivatives, preferably maleic anhydride and glutaconic anhydride, and derived (meth) acrylic acid derivatives, preferably (meth) acrylic acid, amino, imide monomers and epoxy group-containing monomers wherein cyclic carboxylic anhydride derivatives are particularly preferred. The copolymers may further preferably comprise units derived from styrenic monomers, in particular styrene, α-methylstyrene, (meth) acrylic acid, (alkyl) methacrylates and (alkyl) acrylates, (alkyl) (meth) acrylamides, (alkyl) (meth) acrylimides , vinyl acetate, ethylene or propylene derived N-vinyl pyrrolidone, as represented, for example, the Altuglas ^® HT121. Particularly preferably, the composite material to be used comprises a copolymer comprising at least one poly (alkyl) (meth) acrylate and at least one cyclic carboxylic acid anhydride derivative which, for example, with random distribution of the monomer units but also as a graft copolymer in which a cyclic carboxylic anhydride derivative on a Poly (alkyl) (meth) acrylate is grafted, may be present. As the cyclic carboxylic anhydride derivatives, particularly preferred are those having a 5-, 6- or 7-membered ring, most preferably maleic anhydride and glutaric anhydride.

A further preferred adhesion-promoting copolymer comprises poly (alkyl) (meth) acrylate and (meth) acrylic acid and preferably has an MVR [230 ° C., 3.8 kg] in the range of 0.5-30 ml / 10 min, particularly preferably 1-6. 20 ml / 10min and most preferably in the range of 1-10 ml / 10min and thus ensures a sufficiently low processing temperature and sufficiently good incorporation ability of the cellulose component.

Particularly preferred is a copolymer as in the WO 2005/108486 as "copolymer (I)" is used. The content of the publication WO 2005/108486 , filed on 07.04.2005 at the European Patent Office with the application number PCT / EP2005 / 003652 , is hereby explicitly included in the description of the present application.

This second preferred embodiment has the particular advantage that the components a) and b) need not be added separately in the production of the composite material and thus the cost of producing the composite material is lower.

In a particularly preferred embodiment of the present invention, which also comprises the two preferred embodiments described above, the adhesion promoter comprises a cyclic carboxylic acid anhydride derivative, the proportion of which is preferably in the range of 0.1-5 wt.%, And more preferably in the range of 0 , 4-3 wt.% Based on the total weight of the composite material according to the invention.

The proportion of the total copolymer comprising at least one poly (alkyl) (meth) acrylate and at least one cyclic carboxylic anhydride derivative based on the total weight of the composite material to be used according to the invention is preferably in the range from 0.5% by weight to (100% of cellulosic material Percentage of other constituents of the composite material)% by weight and more preferably in the range from 2% by weight to (100% fraction of cellulosic material - proportion of other constituents of the composite material)% by weight.

In addition to the adhesion promoter and the poly (alkyl) (meth) acrylate matrix polymer, the composite material according to the invention also comprises a cellulosic component, in particular wood particles. The proportion of the cellulosic component in the composite material has a great influence on the product properties. Thus, on the one hand, the flexibility and mechanical properties are improved and an economic advantage is achieved. On the other hand, a high proportion leads to increased moisture absorption, so that it is difficult to realize a very high proportion of cellulosic component. With preferred composite materials comprising a coupling agent, in particular wood filler contents of up to 80 wt.%, Preferably 40 to 80 wt.%, Particularly preferably 50 to 80 wt.% And most preferably 60 to 75 wt.%, Respectively be realized based on the total weight of the composite material.

The cellulose-containing component used according to the invention is preferably wood or paper or cardboard or other cellulosic materials. The cellulose-containing component preferably has a cellulose content of at least 20% by weight, particularly preferably at least 30% by weight, very particularly preferably at least 40% by weight. Wood is particularly preferably used. With regard to the wood particles, there are no particular limitations in the composite materials according to the invention. For example, wood chips, sawdust, wood fibers or wood flour can be used.

It has been found in the context of the present invention that it is advantageous if the composite material comprises a lubricant. By using a lubricant, the processability of the composite material can be improved, for example, a relatively low processing temperature can be realized. In particular, polyolefins, polar ester waxes, polyethylene waxes, carboxylic and fatty acids and their esters (for example stearates), and long-chain fatty alcohols and fatty alcohol esters may be used as lubricants. The proportion of the lubricant based on the total mass of the composite material is preferably 0 to 5% by weight, more preferably 0.1 to 4% by weight, very preferably 0.5 to 4% by weight and especially preferably 1 to 3% by weight. ,

Especially in the first preferred embodiment of the present invention, i. with separate addition of the coupling agent, it is preferred that a lubricant is used, wherein the proportion of the lubricant based on the total mass of the composite material is particularly preferably at least 0.1 wt.%.

The composite materials according to the invention may contain other customary auxiliaries and / or additives such. As dyes, light stabilizers, IR absorbers, antimicrobial agents, flame retardants, thermal stabilizers, antioxidants, crosslinking polymers, fiber-reinforcing additives of organic or inorganic nature, polysiloxanes, Polysiloxanamine and / or Polysiloxanimine included.

Because the composites according to the invention have a coating and this coating can likewise contain dyes, IR absorbers, light stabilizers, etc., the present invention also encompasses preferred embodiments in which the WPC composite material contains no or only reduced amounts of dyes, IR absorbers , Light stabilizers, etc. contains. This has the advantage that the required amount of these excipients can be significantly reduced because now no longer the entire composite body must be colored, but only the thin coating is colored. This saves resources, reduces costs and facilitates recyclability.

In a particularly preferred embodiment, the composite materials according to the invention in the plastic contain an impact modifier, in particular in a proportion of 0.1 to 15 wt.%, Preferably 0.5 to 10 wt.% And most preferably 1 to 6 wt.%, In each case on the mass of the plastic components contained in the composite material. It is possible to use all commercially available impact modifiers, in particular elastomer particles having an average particle diameter of from 10 to 300 nm (measurements using, for example, the ultracentrifuge method). The elastomer particles preferably have a core with a soft elastomer phase and at least one hard phase bound thereto.

Wood-plastic composite materials which have up to 80% by weight of cellulose-containing material, preferably wood particles and at least 15% by weight of poly (alkyl) (meth) acrylate, in each case based on the total weight of the composite material, have proven to be particularly advantageous. Poly (alkyl) (meth) acrylates here are polymers which have at least 60% by weight, preferably at least 80% by weight, of units derived from (meth) acrylates, as stated above. The polymer fraction is most preferably either a) a copolymer comprising at least one poly (alkyl) (meth) acrylate and at least one cyclic carboxylic acid anhydride derivative or b) a blend of at least one poly (alkyl) (meth) acrylate matrix polymer and at least one copolymer comprising at least one poly (alkyl) (meth) acrylate and at least one cyclic carboxylic acid anhydride derivative.

In a first particularly preferred embodiment of the present invention, the composite material according to the invention comprises the following components: a) poly (alkyl) (meth) acrylate matrix polymer: 0-59% by weight, preferably 1-57.5% by weight; b) adhesion promoter: 1-50% by weight; c) cellulosic component, preferably wood fibers: 40-80% by weight; d) Lubricant: 0-5% by weight, preferably 0.1-4% by weight, particularly preferably 0.5-3% by weight; e) Colorants: 0-5% by weight; f) Light stabilizers: 0-0.5% by weight, preferably 0.01-0.2% by weight. wherein the components a) and b) together constitute 9.5 to 59.9% by weight of the total weight of the six components mentioned above and the sum of the proportions of the six components mentioned above adds up to 100% by weight. With regard to components a) and b), it should be noted that the adhesion promoter can be a poly (alkyl) (meth) acrylate, so that in this case the components a) and b) are to be taken together and the proportions together in the range of 9 , 5% to 59.9% by weight of the total weight of the six components mentioned above.

In a second particularly preferred embodiment of the present invention, the composite material according to the invention comprises the following components: a) poly (alkyl) (meth) acrylate matrix polymer: 0-59% by weight, preferably 1-57.5% by weight; b) copolymer comprising at least one poly (alkyl) (meth) acrylate and at least one cyclic carboxylic anhydride derivative: 1-50% by weight; c) cellulosic component, preferably wood fibers: 40-80% by weight; d) Lubricant: 0-5% by weight, preferably 0.5-4% by weight, e) Colorants: 0-5% by weight; f) Light stabilizers: 0-0.5% by weight, preferably 0.01-0.2% by weight. wherein components a) and b) together make up 9.5 to 60% by weight of the total weight of the six components mentioned above and the sum of the proportions of the six components mentioned above adds up to 100% by weight.

In the most preferred embodiments, 100% by weight refers to the total weight of the o.g. Components. This may be identical to the total weight of the composite, but may also be less than 100% by weight of the composite if the composite is other than the aforementioned. includes six components. Components a) and b) may be combined as one component as above in the preferred embodiment.

Details of composite materials in which the coupling agent is in a copolymer mentioned above, can be found in the PCT / EP2011 / 059008 and the DE 10 2010 030 927. Details of above-mentioned composite materials, in which a bonding agent is added separately to the matrix material, can be found in the PCT / EP2011 / 059006 and the 102010030926 , To avoid mere repetition, the contents of all intellectual property rights mentioned in this paragraph are included in full in the content of the present application.

According to a first embodiment, the composite body can be produced by casting from a reactive resin and then coated. However, this variant has the disadvantage that the production and processing of the molding obtained therefrom is expensive, for example, a formability is only very limited.

Preferably, however, the composite is made by using thermoplastically processable polymeric composites. Here, polymethyl methacrylates can be used with a high processing temperature, which have no coupling agent. By using a coating, the composite material can be protected from moisture. However, the durability of these materials is not optimal because the protection afforded by the coating decreases over time, so that the relatively high water absorption limits the durability of the composite materials obtainable thereby. Here are holes are relatively critical, as a result, the composite material is directly exposed to moisture.

Accordingly, composite materials are particularly preferably used which have at least one of the adhesion promoters set out above. This makes it possible to reduce the water absorption of the WPCs compared to WPCs made of pure PMMA from about 30 wt.% To less than 6 wt.%, So that the reduced values in the corresponding requirement range for outdoor WPC products are. As a result, the coating can serve a purely decorative purpose, so that the products last very long and minor damage to the coating does not lead to peeling thereof. It should be remembered that a high water absorption of WPCs without adhesion promoter leads to a volume expansion.

The quality of WPC composites is highly dependent on compliance with various parameters. Thus, the inventors have found that the flow properties of the polymer are just as important as the compliance with certain upper temperature limits from which wood particles begin to be damaged. It has been found that this temperature in the production of WPC composites should be below 225 ° C, preferably below 220 ° C in order to largely exclude the charring of the wood particles. At the same time, the polymer should be melted at this temperature and have sufficient flowability. In particular, in composite materials according to preferred embodiments 1 and 2 of the present invention, this requirement is met.

It is also crucial for the use of WPC materials that practical product characteristics have minimum sizes or do not exceed maximum limits. These are, for example, the increase in weight due to water, the swelling behavior due to moisture, and material strengths, such as bending and breaking strength.

Materials, eg. As wood fibers, with cellulose as the main ingredient are extremely polar and hydrophilic. Moisture absorption up to large material depths is mainly caused by the hydrophilicity of the cellulosic material.

By the preferred use of a cellulose-compatible adhesion promoter together with a poly (alkyl) (meth) acrylate it can be achieved that the wood particles are very well "completely" or "sheathed" with the polymer. This can significantly reduce water absorption.

The preferred composite material may preferably be prepared by subjecting at least one cellulosic material to at least one of the above-described plastics and optionally one and / or another of the above-mentioned. Adjuvants and / or additives, preferably at least one lubricant mixed and processed into a composite material. The further processing of the composite material is preferably carried out by extrusion or injection molding. In this case, preferably at a melting temperature below 230 ° C, more preferably below 225 ° C, most preferably from 170 to 220 ° C, more preferably from 190 to 215 ° C and most preferably from 190 to 210 ° C plasticized. In particular, said processing temperatures can be achieved by the use of the copolymers set forth above with units derived from cyclic carboxylic acid anhydrides. Furthermore, for example, lubricants can be used to achieve low processing temperatures. This is particularly preferred in the case of the separate addition of adhesion promoters, according to preferred embodiment 1.

Due to the possibility of processing at temperatures less than or equal to 225 ° C., preferably less than or equal to 220 ° C., damage to the cellulose-containing material, in particular when using wood, can be avoided and energy costs can be reduced.

In particular, when using one of the plastics set out above, together with a lubricant, it is possible to produce a composite material which, surprisingly, can be extruded well at about 205 ° C. with a wood content of 70% by weight. Furthermore, even WPCs with a wood content of up to 80% by weight can be obtained in this way.

A composite body according to the invention has a coating. In this case, the coating can completely cover the surface of the composite body. According to a further embodiment, however, the coating can only be applied partially. Preferably, at least the visible surfaces of the composite body are provided with a coating. Consequently, preferably at least 10% of the surface of the shaped body, in particular at least 20%, particularly preferably at least 40%, can be coated. The upper limit arises for economic reasons, in many cases a coating of less than 90%, preferably less than 80%, and more preferably less than 60%, of the surface of the composite may suffice. For example, the coating may also be constructed of a composite material set forth above. This can be done, for example, by coextrusion, wherein this coextruded layer has a thickness in the range of 0.05 to 10 mm, preferably 0.5 to 5 mm. As a result, for example, only the surface layer can be provided with a pigment.

The coating preferably represents a primer and / or lacquer and / or a glaze. The term glaze here refers to a coating which has no color components or pigment components. Accordingly, a "clear coat" is a glaze. In this case, the glaze may be a thin-layer glaze, which penetrates into the composite material and has a protective effect. Preferably, however, the layer is for decorative purposes and accordingly has a layer thickness in the range of 5 to 1000 .mu.m, preferably 30 to 250 .mu.m. Clearcoats or lacquers may be used here, it also being possible for the lacquers to have high contents of pigments, for example above 40% by weight, preferably above 60% by weight, so that the term lacquer herein also refers to colors which have a high covering effect exhibit.

These lacquers and / or glazes include, inter alia, acrylate lacquers, polyurethane lacquers, epoxy lacquers, alkyd resins, radiation-curable lacquers, dispersion lacquers based on polymer dispersions, in particular acrylate dispersions and pure acrylate dispersions; Silicone resins, cellulose acetobutyrate, cellulose nitrate, polyvinyl esters, polyvinyl ethers, polystyrene, copolymers, melamine resin paints. These are weather-resistant Systems preferred, in particular polyurethane coatings, acrylate, epoxy coatings, but also for the home improvement important aqueous systems such as paints based on polymer dispersions.

Here, lacquers and / or glazes are preferred which have sufficient elasticity, so that the WPC cyclic expansions and shrinking processes that occur due to temperature changes or swelling and drying processes can be intercepted. In particular, not too highly crosslinked paint systems with a wide-meshed network and elastic components are preferred. Although non-crosslinking, physically drying lacquers are suitable, they have lower chemical resistance than crosslinked systems. Examples of suitable lacquers are the solvent-based or water-based wood lacquers available in professional or home improvement stores for craftsmen and end users, such as e.g. commercial polymer dispersions. Examples are products from the company Clou on 1K or 2K basis for outdoor use or paints from the company Adler for outdoor use (commercially available under the product name Pullex Aqua-Color and Pullex Color). Suitable primers are e.g. Brillux Wood Impregnation Primer 550, Aidol Primer and Aidol Impregnation Stain for long-term durability from Remmers. Suitable glazes are e.g. Aidol HK-Lasur and Aidol Langzeitlasur, by Remmers. An example of a resurfacing glaze after a long service life is Aidol Renovierlasur. An example of a water-based glaze is Aidol Weather Protection Glaze UV and an example of a high-quality water-based PU acrylic thick-layer glaze is Aidol Compact-Glaze PU from Remmers. Furthermore, a glaze from Remmers can be used which is available under the trade name Induline, preferably Induline LW-720/40. Also suitable, but primarily intended for industrial use, are radiation-curable coating systems, e.g. solvent-free or low-solvent monomer oligomer-based systems, optionally with dyes or fillers, pigments, UV protectants and the required photoinitiators. These systems are characterized by fast curing, low energy and space requirements with an in-line coating and environmental friendliness by dispensing with solvents.

Paints and / or glazes usually comprise a binder, which binder is not subject to any particular restrictions. Preferably, however, these binders have high adhesion to poly (alkyl) (meth) acrylates and / or cellulosic materials, especially wood. Accordingly, in particular binders can be used, which are used for the production of paints, lacquers and glazes, which are used for the protection or refinement of wood.

As a binder, the paint and / or the glaze may preferably be a cellulose or a cellulose derivative, for example nitrocellulose or cellulose acetobutyrate, a polyurethane, a polyester, a polycarbonate, a hydrocarbon resin, a polyamide, a polyvinyl ester, a polyvinyl ether, a polyvinyl halide, in particular Polyvinyl chloride, an epoxy resin, a polystyrene or a poly (meth) acrylate. These polymers can be used singly or as a mixture.

Preferred binders may contain functional groups which may form hydrogen bonds, ionic bonds or chemical compounds with the OH groups of the cellulose. Here, in particular, chemical bonds can also be obtained by crosslinkers or other components of the coatings. Furthermore, preferred binders exhibit high compatibility with the poly (alkyl) (meth) acrylates used in the composite material, this compatibility being given for example by good miscibility or good adhesion. Accordingly, particular preference is given to coatings which comprise poly (meth) acrylates or form these polymers from corresponding monomers or oligomers. Furthermore, lacquers with cellulose derivatives, for example nitrocellulose or cellulose acetobutyrate, polyurethane, polyester or polycarbonate are preferred.

The binder used in the paint and / or the glaze may preferably have a weight average molecular weight in the range from 1000 to 5,000,000 g / mol, more preferably in the range from 2,000 to 2,000,000 g / mol. The number average molecular weight of the binder used is preferably in the range of 1,000 to 5,000,000 g / mol, more preferably in the range of 2,000 to 2,000,000 g / mol. The number average and weight average molecular weights can be determined by known methods, for example, gel permeation chromatography (GPC), preferably using a PMMA standard.

These binders can be non-crosslinking physical systems as set forth above. High molecular weight binders are used in these systems. According to a further embodiment, binders are used which can be crosslinked by polymerization, polycondensation or polyaddition. In these embodiments, the binders preferably have a lower molecular weight before curing.

It is preferred to use lacquers and / or glazes which have a certain elasticity, accordingly comprising a wide-meshed crosslinking. For this purpose, the binders of the paints and / or glazes may have reactive groups which can be reacted with a crosslinked. For example, binders which have hydroxyl groups which can be crosslinked with isocyanates or isocyanate derivatives to give polyurethanes can preferably be used. Surprising advantages can be achieved, in particular, with binders which before crosslinking have a hydroxyl number in the range from 0.1 to 50 mg KOH / g, particularly preferably from 0.5 to 30 mg KOH / g. The hydroxyl number can, for example, according to DIN EN ISO 4629 be determined. Similar properties can also be achieved with other crosslinking systems, including unsaturated groups, wherein the number of reactive groups is preferably selected to achieve similar crosslinking. For example, a lacquer and / or a glaze based on an oil or an alkyd resin can be used, which crosslinks under the action of atmospheric oxygen. Further, other monomers, oligomeric or polymeric compounds can be used which cure by crosslinking to a lacquer. These include in particular paints based on epoxides or urethanes.

According to a preferred embodiment, dispersion lacquers or lacquers based on solvents, including reactive diluents, are used, which are used predominantly for coloring or decorative purposes. These coating compositions are particularly suitable for compensating age-related visual impairments.

Accordingly, for example, preferred are alkyd resins which are relatively inexpensive to obtain. Alkyd resins have long been known, and are generally understood to mean resins obtained by condensation of polybasic carboxylic acids and polyhydric alcohols, these compounds generally having long-chain alcohols (fatty alcohols), fatty acids or fatty acid-containing compounds, for example fats or oils are modified ( DIN 55945 ; 1968). Alkyd resins are set forth, for example, in Ullmann's Encyclopedia of Industrial Chemistry 5th Edition on CD-ROM. In addition to these classic alkyd resins and resins can be used, which have similar properties. These resins are also characterized by a high content of groups derived from the long-chain alcohols (fatty alcohols), fatty acids or fatty acid-containing compounds described above, for example, fats or oils. However, these derivatives do not necessarily have polybasic carboxylic acids but can be obtained, for example, by reacting polyols with isocyanates. The usable alkyd resins may preferably be mixed or diluted with water.

Furthermore, it is also possible to use modified alkyd resins which have been modified with resins, in particular rosin, with styrene polymers, with acrylic polymers, with epoxides, with urethanes, with polyamides and / or with silicones. These modifications are set forth, inter alia, in the patent literature set forth above and in Ullmann's Encyclopedia of Industrial Chemistry 5th Edition on CD-ROM. By these embodiments, in particular, the drying, the adhesive strength, the weatherability, the storability, the chemical resistance, the curing, the wet film strength, and the abrasion resistance can be changed.

For example, it is preferable to use alkyd resins modified with polymers obtainable by radical polymerization. Such resins are inter alia from the publications US 5,538,760 . US 6,369,135 and DE-A-199 57 161 known. The in the publication US 5,538,760 filed on May 22, 1995 with the United States Patent Office (USPTO) No. 446,130, are incorporated in the present application for the purposes of disclosure. The in the publication US 6,369,135 B1 filed on 13.08.96 with the United States Patent Office (USPTO), application number 08 / 696,361, are incorporated herein for purposes of disclosure. The in the publication DE-A-199 57 161 submitted on 27.11.99 to the German Patent and Trademark Office with the application number DE 19957161.9 The resins set forth above are incorporated in the present application for the purposes of disclosure.

Furthermore, alkyd resins are preferred, which according to the document US 5,096,959 are available. The in the publication US 5,096,959 B1 filed 30/10/90 with the United States Patent Office (USPTO) No. 609,024 are incorporated in the present application for the purposes of disclosure. These alkyd resins are modified by cycloaliphatic polycarboxylic acid, with cyclohexanedicarboxylic acids and cyclopentanedicarboxylic acids in particular being suitable for the modification.

In addition, alkyd resins modified with polyethylene glycol can be used. A large number of patents describe the preparation of water-emulsifiable alkyd resins by modification with polyethylene glycol (PEG). In most processes, about 10 to 30% PEG are incorporated directly into the alkyd resin by transesterification or esterification (see, inter alia, US Pat U.S. Patent No. 2,634,245 ; 2,853,459 ; 3,133,032 ; 3,223,659 ; 3,379,548 ; 3,437,615 ; 3,437,618 ; 10 3,442,835 ; 3,457,206 ; 3,639,315 ; the German patent application 14 95 032 or British Pat. 1,038,696 and no. 1,044,821 ).

Preferred alkyd resins which have been modified with polyethylene glycol are inter alia from the document EP-A-0 029 145 known. The in the publication EP-A-0 029 145 submitted on 30.10.80 to the European Patent Office with the application number EP 80106672.1 The resins set forth above are incorporated in the present application for the purposes of disclosure. According to this document, a polyethylene glycol can first be reacted with epoxide-containing carboxylic acid. The reaction product thus obtained can then be used in the reaction mixture for the preparation of the alkyd resin. Preferred polyethylene glycols for modifying the alkyd resins have, for example, a number average molecular weight of 500 to 5000 g / mol.

Particularly preferred alkyd resin modified with polyethylene glycol can be further modified with copolymers obtainable by polymerization of methacrylic acid, unsaturated fatty acids and vinyl and / or vinylidene compounds.

Also useful are alkyd resins modified with urethane groups. Such alkyd resins are inter alia in WO 2006/092211 and EP-A-1 533 342 explained.

The in the publication EP-A-1 533 342 submitted on 09.11.04 to the European Patent Office with the application number EP 04026511.8 The resins set forth above are incorporated in the present application for the purposes of disclosure.

In addition to the classic alkyd resins set out above, for the preparation of which polycarboxylic acids are generally used, it is also possible to use further alkyd resins, as already stated above. These include in particular alkyd resins based on urethanes. These urethane-alkyd resins can be obtained, for example, by reacting polyhydric alcohols with polyfunctional isocyanates. Preferred urethane resins are for example EP-A-1 129 147 known. These can be obtained, for example, by reacting amide ester diols with polyols and polyfunctional isocyanates. The according to EP-A-1 129 147 Amide ester diols to be used can be obtained by reacting vegetable oils with N, N-dialkanolamines.

According to a preferred aspect of the present invention, the alkyd resin may be an iodine number after DIN 53241 of at least 1 g of iodine / 100 g, preferably of at least 10 g of iodine / 100 g, more preferably of at least 15 g of iodine / 100 g. According to a particular aspect of the present invention, the iodine value of the alkyd resin may range from 2 to 100 g iodine per 100 g alkyd resin, more preferably 15 to 50 g iodine per 100 g alkyd resin. The iodine value can be determined by means of a dispersion, the value relating to the solids content.

Suitably, the alkyd resin may have an acid number in the range of 0.1 to 100 mg KOH / g, preferably 1 to 40 mg KOH / g and most preferably in the range of 2 to 10 mg KOH / g. The acid number can according to DIN EN ISO 2114 be determined by a dispersion, wherein the value refers to the solids content.

The hydroxyl number of an alkyd resin may preferably be in the range of 0 to 400 mg KOH / g, more preferably 1 to 200 mg KOH / g and most preferably in the range of 3 to 150 mg KOH / g. The hydroxyl number can according to DIN EN ISO 4629 be determined by a dispersion, wherein the value refers to the solids content.

According to a further embodiment, a lacquer and / or a glaze based on poly (meth) acrylates can be used. These paints comprise as binders (meth) acrylates which can be polymerized or are already present in polymeric form. In this case, for example, aqueous dispersions can be used, such as those in the publications DE-A-41 05 134 . DE-A-25 13 516 . DE-A-26 38 544 . JP 59011376 . US 5,750,751 . EP-A-1 044 993 . US 6,599,972 and WO 2006/013061 The teachings of these documents are incorporated by reference into the present application.

Preferred paints and / or glazes based on poly (meth) acrylates, optionally in admixture with alkyd resins, inter alia in the publications WO 2009/047237 A1 , filed on 6/10/2008 with the European Patent Office, with the application number PCT / EP2008 / 063362 ; WO 2009/047234 A2 , filed on 6/10/2008 with the European Patent Office, with the application number PCT / EP2008 / 063356 ; WO 2009/146995 A1 , filed on 08.05.2009 with the European Patent Office, with the application number PCT / EP2009 / 055573 ; WO 2009/146977 A1 , submitted on 23.04.2009 to the European Patent Office with the application number PCT / EP2009 / 054862 ; WO 2010/026204 A1 , submitted on 04.09.2009 to the European Patent Office with the application number PCT / EP2009 / 061429 ; WO 2010/026119 A1 , submitted on 31.08.2009 to the European Patent Office with the application number PCT / EP2009 / 061178 ; WO 2010/112285 A1 , submitted on 02.03.2010 to the European Patent Office with the application number PCT / EP2010 / 052585 ; WO 2010/108762 A1 , submitted on 02.03.2010 to the European Patent Office with the application number PCT / EP2010 / 052575 ; WO 2010/112474 A1 , filed on 30.03.2010 with the European Patent Office, with the application number PCT / EP2010 / 054139 ; These references are incorporated by reference into the present application for purposes of disclosure.

The iodine number preferred for the production of paints / glazes polymers to be used, preferably poly (alkyl) (meth) acrylates, is preferably in the range of 1 to 150 g of iodine per 100 g of polymer, more preferably in the range of 2 to 100 g of iodine per 100 g Polymer and most preferably 5 to 40 g of iodine per 100 g of polymer, measured according to DIN 53241-1 , In particular, the iodine value can also be measured by means of a dispersion according to the invention.

Suitably, the preferably used for the production of paints / glazes polymer, preferably the poly (alkyl) (meth) acrylate, an acid number in the range of 0.1 to 40 mg KOH / g, preferably 1 to 20 mg KOH / g and very particularly preferably in the range of 2 to 10 mg KOH / g. The acid number can according to DIN EN ISO 2114 also be determined by means of a dispersion.

The hydroxyl number of the polymers preferably used for the preparation of paints / glazes may preferably be in the range from 0 to 200 mg KOH / g, more preferably 1 to 100 mg KOH / g and most preferably in the range from 3 to 50 mg KOH / g. The hydroxyl number can according to DIN EN ISO 4629 also be determined by means of a dispersion.

The preferred binders further include by polymerization, polycondensation or polyaddition self-crosslinking one-component binder or by polymerization, polycondensation or polyaddition crosslinkable multicomponent preferably two-component systems. These systems generally require specific knowledge of the paints to be applied and are often used commercially or commercially, for example in industrial plants. Suitable for these preferred systems are, in particular, optionally urethane-modified, free-radically curable, olefinically unsaturated polyester resins which are suitable as binders for coating compositions, fillers and sealants,
oxidatively drying binders, in particular alkyd resins, which are used in particular for the production of paints,
Two-component polyurethane binder based on hydroxyl-containing polyester and / or polyacrylate resins in combination with the usual paint polyisocyanates, which are used in particular for the production of high-quality two-component polyurethane coatings, the known, in particular amine curable epoxy resins, which are also both for the production of coating compositions as well as for the production of filling and sealing compounds are suitable,
Aminoplast and Phenoplastharze, which can be used either as self-crosslinking paint binders or as a hardener for other film-forming, in particular hydroxyl or carboxyl groups having binder components in paints for a variety of applications, or
Silicone resins that can be cured by polycondensation to high quality paint films.

Among the preferred binders which can be crosslinked and optionally used in combination with reactive diluents are, inter alia, optionally urethane-modified, unsaturated polyester resins including air-drying alkyd resins and / or unsaturated acrylate resins, which generally with the addition of suitable photoinitiators under the action of high-energy radiation (UV radiation). Light, electron beams) or under the action of atmospheric oxygen with the concomitant use of siccatives (alkyd resins) are cured.

Construction principle, production process and applications of the unsaturated polyester and unsaturated acrylate resins are in H. Wagner, HF Sarx "Lackkunstharze", 5th edition, Carl Hanser Verlag, Munich (1971), p. 129 ff. , in Houben-Weyl "Methods of Organic Chemistry", Volume 4, Georg Thieme Verlag Stuttgart New York (1987), Volume 2, Macromolecular Substances, p. 1405 et seq. , in Ullmann's Encyclopedia of Industrial Chemistry, Volume 11 (1960), p. 345 ff. And Volume 14 (1963), p. 87 ff. , furthermore from SE Young in Progress in Organic Coatings, 4 (1976), p. 225 ff. , from H.-J. Rosary in color and lacquer 18, (1975), p. 608 ff. , from W. Brushwell in color and lacquer 91, Issue 9 (1985), p. 812 ff. , from CB Rybuy et al., Journal of Paint Technology 46, No. 596 (1974), p. 60 et seq. and from KJ O'Hara in "A Review of the Chemistry and Formulation of Todays Radiation Curable Coatings and Inks" beta-gamma 1/91, p 13 ff. , detailed at the "Rad Tech. Europe Radiation Curing Seminar" in Barcelona (1990).

In the case of crosslinking by means of UV irradiation, it is necessary to add photoinitiators to the coating compositions.

Suitable photoinitiators are the compounds customarily used, as described, for example, in Houben-Weyl, "Methods of Organic Chemistry", Volume E 20, page 80 ff., Georg Thieme Verlag Stuttgart 1987 , are described.

Well suited, e.g. Benzoin ethers, such as benzoin isopropyl ether, benzil ketals, e.g. Benzil dimethyl ketal and hydroxyalkyl phenones, e.g. 2-hydroxy-2-methyl-1-phenyl-1-propan-1-one.

The photoinitiators mentioned, which are used depending on the intended use of the products in amounts between 0.1 to 10 wt .-%, preferably 0.1 to 5 wt .-%, based on the total weight of all binder components, can be used as a single substance or, because of more favorable synergistic effects, also be used in combination.

Two-component polyurethane coatings which can likewise be used are, in particular, those based on hydroxyl-containing resins, in particular hydroxyl-containing polyester and / or polyacrylate resins, and the customary coating polyisocyanates. With regard to the known chemistry of the two-component polyurethane coatings, which may be modified by the concomitant use of the reactive diluents, be, for example U.S. Patent 3,124,605 . 3,358,010 . 3 903 126 . 3 903 127 . 3,976,622 . 3 183 112 . 3 394 111 . 3,645,979 . 3,919,218 . GB-PS 1 060 430 . 1 234 972 . 1 506 373 and 1 458 564 directed.

The polyisocyanate component consists in all these two-component systems in general from the usual, biuret, isocyanurate or uretdione or urethane-containing lacquer polyisocyanates based on simple diisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate or 2,4- and / or 2,6-diisocyanatotoluene, where the corresponding lacquer polyisocyanates with aliphatically bound isocyanate groups are preferred. Epoxy resins, which can also be used, are the usual, with hydroxyl, carboxyl and especially amino groups reacting with addition epoxy resins, such as in H. Wagner, HF Sarx "Lackkunstharze", Carl Hanser Verlag, Munich, 5th edition (1971), p. 174 et seq. , in "Methods of Organic Chemistry", Houben-Weyl, 4th Edition, Georg Thieme Verlag, Stuttgart - New York (1987), Volume 3, Macromolecular substances, p. 1891 et seq. and the one made from it Paints in Ullmann's Encyclopedia of Industrial Chemistry, Verlag Chemie Weinheim (1978), 4th Edition, Volume 15, p. 637 ff. , are described. Aminoplastharze, which can be further used for coating, in particular with hydroxyl and carboxyl-containing compounds to condensation reactions capable of aminoplast resins, such as melamine, urea and / or guanamine-formaldehyde condensation products described in the French patent FR-PS 943 411 , in DH Solomon, "The Chemistry of Organic Film Formers," John Wiley & Sons, Inc. New York (1974), pp. 235-240 , in "Methods of Organic Chemistry", Houben-Weyl, 4th Edition, Georg Thieme Verlag, Stuttgart - New York (1987), Volume 3, Macromolecular Materials, p. 1811 et seq. and in H. Wagner and HF Sarx "Lackkunstharze", Carl Hanser Verlag, Munich, 5th edition (1971), p. 61 ff. , and the one made from it Paints in Ullmann's Encyclopedia of Industrial Chemistry, Verlag Chemie Weinheim (1978), 4th Edition, Volume 15, pp. 643 ff. Phenol-formaldehyde resins are, in particular, phenol-formaldehyde resins capable of condensation reactions with hydroxyl and carboxyl groups, such as, for example, novolak and / or resole resins, described in US Pat "Methods of Organic Chemistry", Houben-Weyl, 4th Edition, Georg Thieme Verlag, Stuttgart - New York (1987) Volume 3, Macromolecular Materials, p. 1794 et seq. and H. Wagner, HF Sarx "Lackkunstharze", Carl Hanser Verlag, Munich, 5th edition (1971), p. 45 ff.

Furthermore, it is possible to use coating compositions based on fluoropolymers.

Such paints and / or glazes are among other things in the documents WO 2004/088422 , filed on 19.11.2003 with the Japanese Patent Office with the application number PCT / JP2003 / 014743 ; JP 10324843 , filed on 26.05.1997 with the Japanese Patent Office with the application number JP19970149868 ; and WO 02/34849 , filed on 16.10.2001 with the Japanese Patent Office with the application number PCT / JP01 / 09059 the contents of which are incorporated herein by reference for purposes of disclosure.

Furthermore, these coating compositions can for example be obtained by AGC Chemicals under the trade designation Lumiflon ^®. Here, lacquers and / or glazes are available for different requirements. The coating materials sold under the name Lumiflon ^® can be obtained in the form of a dispersion or as a solvent-based system, this also systems available that cure at room temperature.

The different binder types can be used singly or as a mixture, although mixed types can also be used, for example epoxy acrylates, polyester acrylates, polyether acrylates, polyurethane acrylates, silicone acrylates. Examples include Laromer® ^® products.. Fa. BASF, Ebecryl ^® products of Cytec, Genomer® ^® products of the company Rahn, Sartomer ^® products of the company. Sartomer.

Epoxy acrylates are formed from the reaction of aromatic or aliphatic epoxy resins with free acrylic acid. Coatings are characterized by high reactivity, high hardness and good chemical resistance.

Polyester acrylates are reaction products of hydroxyl-terminated polyesters and acrylic acid. The coatings are characterized by good hardness and weather resistance.

Polyether acrylates are products of esterification of mostly linear polyethers with free hydroxyl groups and acrylic acid.

Polyurethane acrylates are obtained in the reaction of polyurethane prepolymers having terminal isocyanate groups and hydroxyalkyl acrylates. The simplest Urethanacrylate arise by reacting a diisocyanate with a hydroxyl-containing monomer. The coatings are characterized by very good weather resistance, chemical resistance and hardness with good flexibility.

Silicone acrylates are formed either by reaction of polydialkylsilanes with terminal silanol groups and hydroxyalkyl acrylates or by addition of acrylic acid to polydialkylsilanes containing terminal epoxide groups.

The paints and / or glazes set out above may be in the form of aqueous dispersions. These dispersions, preferably (meth) acrylate dispersions, generally have a water content in the range from 30 to 90% by weight, preferably 40 to 80% by weight. The aqueous dispersions preferably have a solids content in the range from 10 to 70% by weight, particularly preferably from 20 to 60% by weight. Aqueous dispersions may contain a low to moderate level of organic solvents to aid film formation; in particular if the binders used have such a high glass transition temperature that they no longer film at the coating temperature. The solvent content in these cases is set between zero and 20%, preferably zero and 10%, based on the total formulation. The solvents used are preferably water-soluble or water-miscible solvents, e.g. Alcohols, (poly) glycol ethers or water-soluble nitrogen-containing heterocycles. In the selection of solvents, in addition to the support of the film formation in particular to pay attention to the health hazards of consumers, especially home improvement products.

For the production of a coated molding, it is possible to use preferably a polymer dispersion (meth) acrylate dispersion which has a dynamic viscosity in the range from 0.1 to 180 mPas, preferably from 1 to 80 mPas and very particularly preferably from 10 to 50 mPas , measured according to DIN EN ISO 2555 at 25 ° C (Brookfield).

According to a further embodiment, the coating agent may contain solvent, wherein the solvent is used in larger quantities.

The term of the solvent is to be understood here broadly. The preferred solvents include in particular aromatic hydrocarbons, such as toluene, xylene; Esters, in particular acetates, preferably butyl acetate, ethyl acetate, propyl acetate; Ketones, preferably ethyl methyl ketone, acetone, methyl isobutyl ketone or cyclohexanone; Alcohols, especially isopropanol, n-butanol, isobutanol; Ethers, in particular glycol monomethyl ether, glycol monoethyl ether, glycol monobutyl ether; Aliphatic, preferably pentane, Hexane, cycloalkanes and substituted cycloalkanes, for example cyclohexane; Mixtures of aliphatics and / or aromatics, preferably naphtha; Gasoline, biodiesel; but also plasticizers such as low molecular weight polypropylene glycols or phthalates. The solvents mentioned can be used individually or as a mixture.

The proportion of solvent in preferred solvent-containing coating compositions may be in particular in the range of 0.1 to 60 wt .-%, particularly preferably in the range of 5 to 40 wt .-%, based on the total weight of the coating composition.

The dynamic viscosity of the solvent-borne coating agent is dependent on the solids content and the type of solvent and can encompass a wide range. So this can be more than 20,000 mPas at high polymer content. Expediently, a dynamic viscosity in the range from 10 to 10000 mPas, preferably 100 to 8000 mPas and very particularly preferably 1000 to 6000 mPas, measured according to DIN EN ISO 2555 at 25 ° C (Brookfield).

Of particular interest are, in particular, solvent-containing coating compositions which preferably contain from 10 to 80% by weight, particularly preferably from 25 to 65% by weight, of at least one binder, preferably a binder based on (meth) acrylates. In addition, a surprisingly good processability show solvent-containing coating compositions whose solids content is preferably at least 40% by weight, particularly preferably at least 60% by weight.

In addition to aqueous dispersions, reactive or reactive stains form another group of known coating compositions. Such coating compositions are for example made EP-0 693 507 and EP-0 546 417 These documents are incorporated into the present application for disclosure purposes. Particularly preferred are coating compositions with a binder based on (meth) acrylates, for example, in WO 2010/112288 A1 are disclosed. The content of the publication WO 2010/112288 A1 , submitted on 03.03.2010 to the European Patent Office with the application number PCT / EP2010 / 052662 , is hereby explicitly included in the description of the present application.

Reactive diluents are low viscosity liquids which, because of their low viscosity, allow the adjustment of processing viscosities while minimizing the amount of inert solvents and, on the other hand, participate in a crosslinking reaction due to reactive centers, thus being incorporated into the solid paint layer and are not released into the environment. These compounds include, among others, radically polymerizable monomers having one or more double bonds. In addition to the (meth) acrylates and the styrene monomers set out above, these preferably include compounds which comprise at least one octadienyl group, such as these in particular EP-0 546 417 are set out.

The dynamic viscosity of the reactive diluent can be in a wide range. Expediently, a dynamic viscosity in the range from 1 to 5000 mPas, preferably 10 to 1000 mPas and very particularly preferably 10 to 500 mPas, measured according to DIN EN ISO 2555 at 25 ° C (Brookfield).

Accordingly, reactive diluents having a boiling point of at least 180 ° C., preferably at least 250 ° C., particularly preferably at least 280 ° C. at atmospheric pressure (1024 mbar), are of particular interest. According to a preferred embodiment, the boiling point of the reactive diluent at atmospheric pressure in the range of 180 to 350 ° C, more preferably in the range of 250 to 300 ° C.

Preferably, a coating agent with a reactive diluent preferably comprises 0.1 to 50 wt .-%, more preferably 5 to 30 wt .-% and most preferably 15 to 25 wt .-% reactive diluent, based on the total weight of the coating composition.

A paint to be used preferably for the production of the coating has at least one colorant. A colorant is after DIN 55943 the collective name for all coloring substances. The colorants include, but are not limited to, soluble dyes and inorganic or organic pigments. These colorants may be used singly or as a mixture of two or more. Thus, in particular mixtures of organic color pigments with soluble organic dyes can be used. Furthermore, it is possible to use mixtures which comprise inorganic and organic color pigments. In addition, mixtures containing soluble organic dyes in addition to the inorganic color pigments can be used. Furthermore, mixtures comprising soluble dyes and inorganic and organic pigments are useful. The colorants set out above are inter alia in Kirk Orthmer Encyclopedia of Chemical Technology, Third Edition, vol. 19, pp. 1 to 78 and in Ullmann's Encyclopedia of Industrial Chemistry 5th edition set out on CD-ROM.

The pigments which are preferably contained in the color layer may be any pigments. For example, but not limited to, titanium dioxide, zinc sulfide, pigment black, azodiaryl yellow, isoindole yellow, diarylidane, quinacridone magenta, diketopyrrolorot, copper phthalocyanine blue, copper phthalocyanine green, dioxazine violet and diketometal oxide may be used.

A fairly comprehensive listing of other useful pigments is found in Color Index International, Fourth Edition Online, 2001, published by the Society of Dyers and Colourists in association with the American Association of Textile Chemists and Colorists.

It is also possible to use effect pigments such as, but not limited to, metal oxide-coated mica and metallic pigments. The amount of colored pigment is usually from 1 to 50% by weight, preferably from 3 to 45% by weight, based on the weight of the varnish, depending on the type of pigment, the desired opacity and the coating method chosen.

White pigment is usually used in an amount of 20 to 50% by weight, preferably 25 to 45% by weight. The colored pigments are often used in an amount of 1 to 20 wt.%, Depending on the type and color shade and the printing method used. Metal oxide-coated mica and metallic pigments are widely used in an amount of 1 to 20% by weight, depending on the type and hue and the coating method used.

In addition to pigments, the compositions used for coating may further comprise customary additives, for example fillers, siccatives, leveling agents, anti-skinning agents, anti-foaming agents, curing catalysts, UV absorbers, accelerators, catalysts, stabilizers against thermal, photochemical and oxidative degradation. Preferably, the coating agent used for coating the above-described composite body is a liquid. In this way, the coatings can be obtained without much effort. Expediently, a dynamic viscosity in the range from 0.1 to 10000 mPas, preferably from 1 to 1000 mPas and very particularly preferably from 10 to 500 mPas, measured in accordance with DIN EN ISO 2555 at 25 ° C (Brookfield).

The coating applied to the composite may comprise one or more layers. For example, a filling or primer layer can be applied, which serves, for example, as a primer. For example, a cover layer can be applied to this layer. However, this structure is relatively complicated, so that the present invention preferably provides a molded article with a single-layer coating, which preferably has a high adhesive strength without primer. This property is due to the high compatibility of many coating agents with poly (alkyl) (meth) acrylates and / or cellulosic materials. This single-layer coating can be done in one or more coating operations.

The coating composition, preferably a lacquer and / or a glaze can be applied by conventional methods, such as dipping, rolling, flooding, casting, in particular by brushing, rolling, spraying (high pressure, low pressure, airless or electrostatic (ESTA)).

The coating communicates with the composite material such that the coating agent is applied directly to the surface of the molded composite material.

Preferred coatings obtained from the coating compositions according to the invention show a high König pendulum attenuation. The pendulum hardness after seven days is preferably at least 10 s, preferably at least 20 s, more preferably at least 30 s and especially preferably at least 50 s measured according to DIN EN ISO 1522 ,

Preferred coatings exhibit excellent resistance, in particular to polar solvents, in particular alcohols, for example 2-propanol, or ketones, for example methyl ethyl ketone (MEK), non-polar solvents, for example diesel fuel (alkanes). After an exposure of 15 minutes and subsequent drying (24 hours at room temperature), preferred coatings exhibit a pendulum damping according to DIN ISO 1522 of preferably at least 10 s, preferably at least 30 s.

In addition, preferred coatings show a surprisingly good cupping. According to particular modifications of the present invention, preferred coatings may have a depth of at least 1 mm, more preferably at least 3.0 mm, measured according to DIN 53156 (Erichsen) show.

Furthermore, coatings which can preferably be used are characterized by a surprisingly high adhesive strength, which can be determined in particular according to the cross-cut test. Thus, in particular a classification of 0 to 1, particularly preferably 0 according to the Standard DIN EN ISO 2409 be achieved.

Further valuable information on the usable lacquers and / or glazes, which are preferably suitable for wood and / or plastics, especially poly (meth) acrylates, can be found inter alia in paint formulation and paint formulation of Muller and U. Poth, edited by U. Zorll, Vincentz, 2003, ISBN 3-87870-746-0 with further references, this book and the citations contained in this book being incorporated by reference into the application for purposes of disclosure.

The coated composites may be solid, semi-solid or cavitated. In the cavities serving for stabilization elements, for. B., made of metal or other very stable materials such. As carbon may be included. The cavities can also be filled with insulating materials to give the composite bodies good thermal insulation properties. The composite bodies of the invention can be used in all applications known for WPC, in particular as a material in areas with increased moisture exposure, especially in outdoor areas such. B. as floor coverings, z. B. as terrace panels, etc., as construction materials such. B. as construction timbers, boards, beams, posts, formwork panels, garden sheds, game towers, playground equipment, sand boxes, carports, gazebos, door frames, window sills, etc., as wall elements, wall coverings, sound insulation elements, balustrades, as ceiling panels, as roofing, in Shipbuilding or for the construction of port facilities, z. As boat jibs, boat deflectors, ship decks, etc., as maintenance-free furniture material indoors and outdoors, such. Chairs, loungers, shelves, counters, garden benches, kitchen furniture, countertops, bathroom furniture, etc., as containers or enclosures, such. As lawn enclosures, bed borders, Rollrabatte, flowerpots, plant troughs, etc., are used.

The soundproofing effect of the composite bodies according to the invention can be based on the reflection of the sound but also on the absorption. While smooth surfaces of the components are sufficient for reflection, components for the use as soundproofing elements with sound absorption effect are preferably produced from the shaped bodies according to the invention whose surface is structured such that a structurally sound-absorbing effect is achieved. Furthermore, hollow panels or profiles are preferred moldings of the present invention which are provided with respective apertures or bores that allow the sound waves to penetrate into the component. As a result, a significant sound absorption effect can be achieved. Combinations or modifications of the two mentioned variants of the soundproofing elements are also covered by the present invention.

measurement methods:

Melt index MVR

The MVR [230 ° C, 3.8kg] is determined after ISO 1133

Water absorption (cooking test)

The water absorption is in a Koch test based on the Standard EN 1087-1 certainly. For this purpose, a 100 mm long sample section in thickness and width of the production measure for 5 h immersed in boiling water and after about 60min cooling in cold water for swelling and gravimetric water absorption.

Breaking strength and deflection

The determination of the breaking strength and the deflection at 500 N load of the composite materials according to the invention is done on the basis of DIN EN 310 ("Wood materials - Determination of flexural modulus and flexural strength").

The following examples serve to further illustrate and better understand the present invention, however, limit these or their scope in any way.

example 1

General description:

A PMMA molding composition average molecular weight, PLEXIGLAS ^® FM 6N or PLEXIGLAS ^® FM 7N Evonik Röhm GmbH, Darmstadt, was mixed with a proportion of the 70th% wood fibers, using the polar Esterwachses Licowax E from Clariant, Sulzbach, as a lubricant and a Adhesive mixed and extruded. Experiments have shown that such a mixture with up to 75% by weight wood content in the range 210 +/- 10 ° C can be plasticized very well and produces WPC extrudates which have a very low water absorption, high dimensional stability to moisture and a high mechanical stability.

Example 1a

The experiment was carried out as in the general description. It was a styrene-maleic anhydride copolymer with about 20-22 wt.% Incorporated maleic anhydride used as a primer.

The composition of the feeds for the extrusion was as follows: Wood fibers: 320 μm 70% by weight Adhesive: XIRAN ^® SZ 22065 6.0% by weight Lubricant: LICOWAX ^® E 3.0% by weight PMMA: PLEXIGLAS ^® 7N 21% by weight

The performance tests of the WPC obtained gave the following results: Water absorption in the boiling test at 100 ° C: 4.5% by weight Breaking Strength: 3.3 kN Bend 500N: 2.3 mm

The resulting molded article was coated with Aidol-HK-Lasur. The coating showed excellent adhesion to the extruded molded article.

Example 1b

The experiment was carried out as in the general description. It was a polymethyl methacrylate-maleic anhydride copolymers corresponding to the copolymer (I) of Example A of WO 2005/108486 , used with 10 wt.% Incorporated maleic anhydride as a primer.

The composition of the feeds for the extrusion was as follows: Wood fibers: 70% by weight Primer: 10% by weight Lubricant: LICOWAX E 2.0% by weight PMMA: PLEXIGLAS ^® 7N 18% by weight

The performance tests of the WPC obtained gave the following results: Water absorption in the boiling test at 100 ° C: 4.3% by weight Breaking Strength: 4114 kN Bend 500N: 1.8 mm

The resulting molded article was coated with Induline LW-720/40 (aqueous glaze based on pure acrylates). The coating showed excellent adhesion to the extruded molded article.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

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Claims (15)

A composite comprising a composite material containing at least one cellulosic material and at least one poly (alkyl) (meth) acrylate, characterized in that the composite has at least one coating associated with the composite material. A composite according to claim 1, characterized in that the composite material comprises a poly (alkyl) (meth) acrylate having a melt index MVR [230 ° C, 3.8kg] in the range of 0.530 ml / 10min. A composite according to claim 1 or 2, characterized in that the composite material comprises a copolymer comprising units derived from a cyclic carboxylic acid anhydride and units derived from (meth) acrylates. Composite body according to at least one of the preceding claims, characterized in that the composite material contains at least one cellulosic compatible adhesion promoter. Composite body according to claim 4, characterized in that the proportion of the adhesion promoter based on the total weight of the composite material according to the invention between 0.5 and 70 wt.%, Preferably 1 and 50 wt.%, Particularly preferably 1 and 40 wt.%, Very particularly preferably 2 and 30 wt.%, Particularly preferably in the range 3 to 25 wt.% And most preferably in the range 3 to 15 wt.% Is. A composite according to claim 3 or 4, characterized in that it is the adhesion promoter to a copolymer comprising one or more monomers (s) selected from the group consisting of cyclic carboxylic anhydride derivatives such. Maleic anhydride, itaconic anhydride, citraconic anhydride and glutaconic anhydride, (meth) acrylic acid derivatives such as e.g. Methacrylic acid or acrylic acid, amino, imide monomers and monomers containing epoxy groups, preferably (alkyl) (meth) acrylamides, (alkyl) (meth) acrylimides, N-vinylpyrolidone and optionally one or more monomers selected from the group consisting of styrene , α-methylstyrene, α-ethylstyrene, acrylates, methacrylates, vinyl acetate, ethylene or propylene. Composite body according to at least one of the preceding claims, characterized the proportion of the copolymer comprising at least one poly (alkyl) (meth) acrylate and at least one cyclic carboxylic anhydride derivative based on the total weight of the composite material according to the invention 0.5 to (100 - fraction of cellulosic material - other constituents of the composite material) wt.% , Preferably 2 to (100 - content of cellulosic material - other constituents of the composite material) wt.%, Is and / or the proportion of the cyclic carboxylic acid anhydride derivative based on the total weight of the composite material according to the invention is in the range from 0.1 to 5% by weight, preferably in the range from 0.4 to 3% by weight, and / or that is the cyclic carboxylic acid anhydride derivative, a derivative having a 5-, 6- or 7-membered ring. Composite body according to at least one of the preceding claims, characterized in that it comprises the following components: a) cellulosic component, preferably wood fibers: 40-80% by weight b) copolymer comprising at least one poly (alkyl) (meth) acrylate and at least one cyclic carboxylic acid anhydride derivative: 1-50% by weight c) Lubricant: 0-5% by weight, preferably 0.5-4% by weight d) Poly (alkyl) (meth) acrylate matrix polymer: 0-59% by weight, preferably 1-57.5% by weight e) dye 0-5% by weight f) light stabilizers 0-0.5% by weight, preferably 0.01-0.2% by weight comprising, wherein the components b) and d) together from 9.5 to 60 wt.% Of the total weight of the components a) to f) and the sum of the components a) to f) to 100 wt.% Results. Composite according to at least one of the preceding claims, characterized in that the composite material comprises at least one lubricant, preferably selected from the group consisting of polyolefins, polar ester waxes, polyethylene waxes, carboxylic and fatty acids and their esters (e.g., stearates), and long chain fatty alcohols and fatty alcohol esters. Composite body according to at least one of the preceding claims, characterized in that the composite material up to 80 wt.% Wood particles and at least 15 wt.% Poly (alkyl) (meth) acrylate, each based on the total weight of the composite material having. Composite body according to at least one of the preceding claims, characterized in that the coating is a primer and / or coating and / or a glaze and / or a co-extruded layer, and / or that it is a single-layer coating. Composite body according to at least one of the preceding claims, characterized in that the coating comprises at least one polymer which is based on (meth) acrylates and / or which has functional groups which can be reacted with hydroxyl groups. Composite body according to at least one of the preceding claims 1 to 12, characterized in that the coating has a thickness in the range of 10 to 1000 microns. A method for producing a composite body according to any one of the preceding claims, characterized in that a molding and / or casting, comprising a composite material containing at least one cellulosic material and at least one poly (alkyl) (meth) acrylate, is provided with a coating agent , A method according to claim 14, characterized in that the coating agent is liquid.