WO2015086562A1 - Composite component with an improved feel and the production and use thereof - Google Patents

Abstract

The invention relates to a composite component made of a foamed, light-fast polyurethane layer and a plastics support, and to the production and use thereof.

Description

 Composite component with improved feel and its manufacture and use

The invention relates to a composite component of a foamed, lightfast polyurethane layer and a plastic carrier, its preparation and use.

Polyurethanes (PUR) based on isocyanates with aromatic-bonded NCO groups are known to discolor under the action of light. This is a problem in outdoor or under light exposed interior parts. For the production of light-resistant moldings therefore a surface with appropriate properties is required.

For the production of polyurethanes (PUR) with high light resistance usually aliphatically bound isocyanates are used. A use of such isocyanates for producing foamed, light-resistant PUR is described in WO 2012/031990.

In times of automation, particularly components are preferred in whose production time and personnel can be saved. If, for example, a three-layer structure can be replaced by a two-layer structure, or if individual parts can be produced and bonded directly in one work step, this is economically preferable. In the case of e.g. By default, PVC sheets are first contoured into an instrument panel of a car, then a carrier component, e.g. made of polypropylene. Both components are placed in a tool and then foamed with polyurethane foam, wherein the same also the bonding of the layer structure takes place. In contrast, for example, The so-called "direct skinning" method has the advantage that it is possible to work with a turning tool or a sliding table, whereby the two-layer component can be produced on a machine and removed directly as a finished component (WO2010 / 083959) One mold half is removed, leaving the carrier in the other mold half and replaced with a new, larger mold half, and then the resulting cavity is filled with polyurethane, at the same time adhering to the carrier This procedure represents a cost-effective alternative, although the materials used are slightly more expensive than the standard materials currently used.

In addition to an efficient process and a lightfast, foamed topcoat, a certain haptic is also expected, especially in the automotive sector. Each car manufacturer has its own wishes and ideas as to how a component should feel when you sweep your fingers over its surface. Since this requirement is a kind of sliding feel, the measurement of the friction coefficient can serve as an evaluation criterion. Here, it has been shown that for components with a KA3A leather graining low values (<0.6) as pleasant whereas components with a coefficient of friction> 0.6 are perceived to be too slippery, rubbery and dull.

It is known that silicone-containing and / or siloxane-containing reagents can be used as surface additives in polyurethanes. Such substances are described for example in "auxiliaries and additives" in "Kunststoffhandbuch 7 -Polyurethanes", Becker / Braun, Carl Hanser Verlag, Müchen / Vienna, 1993, pages 104ff. By enrichment at the surface, properties such as e.g. Demoulding or sliding feel (friction coefficient) can be influenced. It is advantageous if as much reagent accumulates on the surface, since then either less substance used or a higher effect can be achieved. The substances used are described for example in US 20120101175 AI. In this document, attention is drawn to a better emulsifiability of polyurethane foam starting mixtures by the use of siloxane-polyalkylene oxide copolymers, in contrast to organofunctional polydimethylsiloxanes. It is shown that siloxane-polyalkylene oxide copolymers, in contrast to organofunctional polydimethylsiloxanes, lead to more stable, more emulsified mixtures. This means that the siloxane-polyalkylene oxide copolymers used are more emulsifiable than the organofunctional polydimethylsiloxanes. Surprisingly, however, when using the more emulsifiable siloxane-polyalkylene oxide copolymers, a better effect with respect to the sliding feel (friction coefficients) is observed than with the less emulsifiable organofunctional polydimethylsiloxanes, which should be easier to accumulate on the surface. US 20120101175 AI describes a component made of polyurethane foam. In the examples, aromatic isocyanates are used. The use of silicone copolymers as surface-active additives is described which, unlike pure siloxanes, have a better emulsifying ability.

It was therefore an object of the present invention to provide a cost-effectively producible composite component with a grained, light-fast polyurethane cover layer with a pleasant feel and a plastic support, which is e.g. can be used for the production of dashboards, door linings, armrests and consoles, and a method for its production.

Surprisingly, this object could be achieved by a composite component made of a polyurethane cover layer I) and a plastic support II), wherein the plastic of the support of I) is different, which is preferably produced in the direct-skinning process, wherein for the layer A) used lightfast polyurethane containing a siloxane-polyalkylene oxide copolymer. The present invention relates to composite components made of a lightfast polyurethane top layer I) and a plastic backing II) different from I), characterized in that the polyurethane cover layer I) is obtainable from

A) organic modified cycloaliphatic and / or aliphatic polyisocyanate compounds

B) polyols having an average molecular weight of from 1,000 to 15,000 g / mol and a functionality of from 2 to 8, preferably from 2 to 6,

C) Polyols and / or polyamines having a molecular weight of 62-500 g / mol and a functionality of 2 to 8, preferably 2 to 4, as chain extenders or crosslinkers,

D) blowing agents,

E) siloxane-polyalkylene oxide copolymers as haptic improvers,

F) optionally further auxiliaries and / or additives.

A further subject of the present invention is a process for the production of the composite components according to the invention from a light-fast polyurethane cover layer I) and a plastic backing II) different from I) by the DirectSkinning method by application of the lightfast polyurethane cover layer I) to the plastic support II), characterized the polyurethane cover layer I) is obtainable from

A) organic modified cycloaliphatic and / or aliphatic polyisocyanate compounds

B) polyols having an average molecular weight of from 1,000 to 15,000 g / mol and a functionality of from 2 to 8, preferably from 2 to 6,

C) Polyols and / or polyamines having a molecular weight of 62-500 g / mol and a functionality of 2 to 8, preferably 2 to 4, as chain extenders or crosslinkers,

D) blowing agents,

E) siloxane-polyalkylene oxide copolymers as haptic improvers,

F) optionally further auxiliaries and / or additives. The outer skin of the composite component is defined for the measurement of the density as the outer layer of the composite component with a thickness of 1.5 mm on the side of the polyurethane cover layer I).

To prepare the modified polyisocyanate compounds A), (cyclo) aliphatic polyisocyanates are used as starting compounds. Suitable (cyclo) aliphatic polyisocyanates are preferably any by phosgenation or by phosgene-free processes, for example by thermal urethane cleavage, accessible diisocyanates of the molecular weight range 140 to 400 with aliphatically or cycloaliphatically bound isocyanate groups. As (cyclo) aliphatic compounds are suitable for. B. 1, 4-diisocyanatobutane, 1,5-diisocyanatopentane, 1,6-diisocyanatohexane (HDI), 2-methyl-l, 5-diisocyanatopentane, l, 5-diisocyanato-2,2-dimethylpentane, 2.2 , 4- or 2,4,4-trimethyl-l, 6-diisocyanatohexane, 1, 10-diisocyanatodecane, 1,3- and 1,4-diisocyanatocyclohexane, 1,3- and 1,4-bis- (isocyanatomethyl) -cyclohexane, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 4,4'-diisocyanatodicyclohexylmethane (H12-MDI), optionally in a mixture with 2, 4'-isomer, 1-isocyanato-1-methyl-4 (3) isocyanato-methylcyclohexane (IMCI), bis (isocyanatomethyl) -norbornane (NBDI) or any mixtures of such diisocyanates. The modified compounds A) prepared from the monomeric (cyclo) aliphatic polyisocyanates are prepared by customary known processes. They contain as modification, for example, uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and / or oxadiazinetrione structures, as described, for example, in J. Prakt. Chem. 336 (1994), pages 185-200, in DE-A 1670666 and EP-A 0798299 are described by way of example. As modified polyisocyanates A) it is also possible to use reaction products containing urethane and isocyanate groups, so-called isocyanate prepolymers and carbodiimide-modified polyisocyanates. The polyisocyanates A) preferably have an isocyanate content of 10 to 30 wt .-%. Preferred modified polyisocyanates A) are low-viscosity products based on HDI with a monomer content of <0.5% by weight. Particular preference is given to using polyisocyanates based on HDI, which contain uretdione groups, and / or prepolymers based on HDI. Very particular preference is given to using polyisocyanates based on HDI, which contain uretdione groups, and / or prepolymers based on HDI, where component A contains less than 5 percent by weight of cycloalipatic polyisocyanates since cycloaliphatic polyisocyanates are significantly more expensive than polyisocyanates based on HDI.

Component B) has an average hydroxyl functionality of 2 to 8 and preferably consists of at least one polyhydroxy polyether having an average molecular weight of from 1,000 to 15,000 g / mol, preferably from 2,000 to 13,000 g / mol and / or at least one polyhydroxy polyester having an average molecular weight Molecular weight of 2,000 to 10,000 g / mol, preferably 2,000 to 8,000 g / mol and / or at least one oligocarbonate polyol having an average molecular weight of 1,000 - 5,000 g / mol. Suitable polyhydroxypolyethers are the alkoxylation products known per se from polyurethane chemistry of preferably di- or trifunctional starter molecules or mixtures of such starter molecules. Examples of suitable starter molecules are water, ethylene glycol, diethylene glycol, propylene glycol, trimethylolpropane, glycerol and sorbitol. Alkylene oxides used for the alkoxylation are in particular propylene oxide and ethylene oxide, these alkylene oxides being able to be used in any order and / or as a mixture. Furthermore, as component B) it is also possible to use aliphatic oligocarbonate polyols having an average molecular weight of from 1,000 to 5,000 g / mol, preferably from 1,000 to 2,000 g / mol. Suitable aliphatic oligocarbonate polyols are the per se known transesterification products of monomeric dialkyl carbonates such as dimethyl carbonate, diethyl carbonate etc. with polyols or mixtures of polyols having an OH functionality> 2.0 such as 1, 4-butanediol, 1,3-butanediol, 1, 5- pentanediol, 1,6-hexanediol, 3-methyl-l, 5-pentanediol, 1,12-dodecanediol, cyclohexanedimethanol, trimethylolpropane and / or mixtures of said polyols with lactones, as described by way of example in EP-A 1 404 740 and EP-A 1 518 879 A2. Suitable polyester polyols are the esterification products of preferably dihydric alcohols which are known per se, such as, for example, ethylene glycol, propylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, with lower amounts of preferably difunctional carboxylic acids, for example succinic acid, adipic acid, Phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid or mixtures of such acids. Component C) is a chain extender having a functionality of 2 to 8 and a molecular weight of 62 to 500 g / mol, preferably 62 to 400 g / mol. Preferred chain extenders C) include dihydric alcohols such as ethylene glycol, diethylene glycol, 1,4-butanediol, 1,6-hexanediol, or mixtures of such diols. Also suitable as component C) or as part of component C) are diols containing ether groups with molecular weights of less than 400 g / mol, as obtainable by propoxylation and / or ethoxylation of divalent starter molecules of the type already mentioned above by way of example. Also suitable as chain extenders C) are diamines having arylalkyl-containing amino groups, for example 1,3-xylyenediamine. Furthermore, it is also possible to use polycarbonate diols, provided that their molecular weight is below 500 g / mol. Any mixtures of the exemplified chain extenders may also be used. The chain extenders C) are used in amounts of 2 to 15, preferably 4 to 12 wt .-%, based on the weight of the sum of components B), C), D) and E).

The blowing agents D) which are essential to the invention are physical blowing agents from the group of (cyclo) aliphatic hydrocarbons having up to 5 carbon atoms, partially halogenated hydrocarbons having up to 5 carbon atoms or partially halogenated olefins having up to 5 carbon atoms or ethers, ketones or acetates each having up to 5 carbon atoms or nitrogen-containing hydrocarbons having up to 5 carbon atoms. Examples of cyclic hydrocarbons are cyclopropane and cyclopentane. Non-cyclic hydrocarbons include butane, n-pentane and isopentane. Halogen-containing hydrocarbons include hydrogen-containing fluorochlorohydrocarbons or fluorohydrocarbons or perfluoro compounds, for. As perfluoroalkanes understood. As chlorofluorocarbons z. For example, chlorodifluoromethane (R22), 1,1-dichloro-1-fluoroethane (R141b), 1-chloro-1, 1 -difluoroethane (R142b) or l, 3-dichloro-l, l, 2,3,3, hexafluoropropane (R216a) can be used. Examples of fluorohydrocarbons are pentafluoroethane (R125), 1,1,1-trifluoroethane (R143a), 1,1,1,2-tetrafluoroethane (R134a), 1,1,2-trifluoroethane (R143), 1,1-difluoroethane ( R152a), 1,1,1,3,3-pentafluoropropane (R245fa), octafluoropropane (R218) or 1,1,1,3,3-pentafluorobutane (R365 mfc). Halogen-containing ethers include hydrogen-containing fluorochloro or fluoro ethers, such as. B. difluoro-methoxy-2,2,2-trifluoroethane (E245) understood. Examples of usable ethers are dimethyl ether or diethyl ether. Preferred nitrogen-containing hydrocarbon is nitromethane. Examples of partially halogenated olefins are trans-1,3,3,3-tetrafluoroprop-1-ene (HFO-1234ze), 2,3,3,3-tetrafluoroprop-1-ene (HFO-1234yf), FEA 1100 (1, 1 , l, 4,4,4-hexafluoro-2-butene) and FEA 1200 understood. With a focus on safety, preference is to be given to the propellants which are not flammable. Propellant mixtures can also be used.

In the preparation of the polyurethane cover layer I), the physical blowing agent D) in an amount of 0.1 to 15 wt .-%, preferably 1 to 10 wt .-%, particularly preferably 2 to 8 wt .-% based on the weight of Sum of components B), C), D) E) and F).

Preferred siloxane-polyalkylene oxide copolymers used are compounds having the following formula:

M * D _x D * _y D ** _z M * where

M * [R ¹ O (CH (CH ₃ ) CH ₂ O) _m (CH ₂ CH ₂ O) _n R ² ] _a [CH ₃ ] ₃ - _{a is} S1O1 2, D (CH ₃ ) ₂ Si0 _2/2 is, D * [R ³ O (CH ₂ CH ₂ O) _Q R ⁴ ] [CH ₃ ] Si0 _2/2 ,

D ** [R ⁵ O (CH (CH ₃ ) CH ₂ O) _P (CH ₂ CH ₂ O) _q R ⁶ ] [CH ₃ ] SiO _2/2 R ¹ , R ³ and R ^{5 are} each independently selected from the group consisting of hydrogen, monovalent hydrocarbon groups of 1 to 12 carbon atoms, (R ⁷ ) 3Si and R ⁷ C (0) groups, wherein R ^{7 is} a monovalent hydrogen group with 1 to 18 carbon atoms, R ² , R ⁴ and R ^{6 are} each independently a divalent hydrocarbon group of 1 to 12

Carbon atoms; a, m, n, o, p, q, x, y and z are each independently and a is 0 to 1; m is 0 to 200; n is 0 to 200; o is 1 to 200; p is 1 to 200; q is 1 to 200; x is 1 to 100; y is 1 to 50 and z is 1 to 50; at least one of R ³ or R ^{5 is} preferably hydrogen and most preferably both R ³ and R ^{5 are} hydrogen.

In the preparation of the cover layer of polyurethane (PUR), the siloxane-polyalkylene oxide copolymers (Haptikverbesserer E)) are preferably in an amount of 0.1 to 5 wt .-%, particularly preferably from 0.2 to 4% by weight, most preferably from> 0.2 to 2% by weight, based on the weight of the sum of components B), C), D) E) and F). Optionally with auxiliary and additive F) to be used are compounds of the type known per se. These are the usual and known in the preparation of polyurethane foams compounds such. Catalysts, stabilizers, pigments, fillers or water, which may optionally be used in an amount of up to 0.3 wt .-%, based on the weight of component B). However, the preparation of the PUR cover layer is preferably carried out without added water.

Catalysts which can be used are the known catalysts customary for polyurethanes, which are listed, for example, in WO 2008/034884 or EP-A 0929586. These include salts and chelates of tin, zinc, bismuth, iron, mercury as well as tertiary amine compounds. Organotin compounds such as, for example, dimethyltin (IV) didodecylmercaptide, dimethyltin (IV) bis (2-ethylhexylthioglycolate), dimethyltin (rV) dimethyleneisooctyl ester mercaptide, dimethyltin (IV) didecylmercaptide, dimethyltin (IV) butenyldicarboxylate, dimethyltin dilaurate and Dimethyltin (IV) di (neo-decylcarboxylate) are preferably used. Preferably non-fungicidal catalysts should be used.

Stabilizers are understood to mean both UV absorbers, antioxidants, free-radical scavengers and foam stabilizers. UV absorbers may contain both inorganic compounds, such as, for example, titanium dioxide, zinc oxide or cerium dioxide, and also organic compounds, such as 2-hydroxybenzophenones, 2- (2-hydroxyphenyl) benzotriazoles, 2- (2-hydroxyphenyl) -1,3- tri-azines, 2-cyanoacrylates and oxalanilides. Radical scavengers are known to include HALS systems (Hindered Amine Light Stabilizer), and as hindered phenols and / or secondary aromatic amines can be used as antioxidants. Foam stabilizers usually consist of polyether siloxanes or block copolymers of polyoxyalkylenes.

Among pigments and fillers, e.g. Calcium carbonate, graphite, carbon black, titanium dioxide, titanium dioxide, iron oxide, wollastonite, glass fibers, carbon fibers and organic dyes or

Fillers understood.

Further examples of component E) "auxiliaries and additives" are listed in "Kunststoffhandbuch 7 -Polyurethanes", Becker / Braun, Carl Hanser Verlag, Munich, 1993, pages 104ff. Incidentally, the starting components are used in amounts such that preferably one

Isocyanate index of 80 to 120, preferably 95 to 105, is obtained. Isocyanate index is the ratio of the number of NCO groups divided by the number of NCO-reactive groups multiplied by 100.

For the production of the cover layer of polyurethane, the components B) to F) are generally combined to form a so-called "polyol component", which is then combined with the polyisocyanate component

A) is mixed and reacted in closed molds. Here one uses conventional measuring and metering devices. Optionally, an external release agent can be used to avoid adhesion of the polyurethane topcoat to the mold.

The temperature of the reaction components (polyisocyanate component A) or "polyol component" consisting of components B), C), D), E) and F) is generally within the temperature range from 20 to 60 ° C. The temperature of the molding tools is generally from 20 to 100 ° C, for aliphatic PUR preferably at 50 to 90 ° C.

The amount of the foamable material introduced into the mold is such that the bulk densities of the moldings result from 200 to 700 kg / m ³ . Examples of suitable thermoplastic materials include polycarbonate, copolycarbonate, polyestercarbonate, polystyrene, styrene copolymers, aromatic polyesters such as polyethylene terephthalate (PET), PET-cyclohexanedimethanol copolymer (PETG), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), cyclic polyolefin , Poly- or copolyacrylates and poly- or copolymer methacrylate such as poly- or copolymethyl methacrylates (such as PMMA) and copolymers with styrene such as transparent polystyrene acrylonitrile (PSAN), thermoplastic

Polyurethanes, polymers based on cyclic olefins (eg TOPAS®, a commercial product of Ticona) and polyamides (PA). Thermoplastic, aromatic polycarbonates suitable as carrier material are both homopolycarbonates and copolycarbonates; The polycarbonates may be linear or branched in a known manner.

The thermoplastic polycarbonates including the thermoplastic aromatic polyester carbonates have average molecular weights M _w (determined by measuring the relative viscosity at 25 ° C in CH ₂ Cl ₂ and a concentration of 0.5 g per 100 ml of CH ₂ Cl ₂ ) of 20,000 g / mol to 32,000 g / mol, preferably from 23,000 g / mol to 28,000 g / mol.

A portion, up to 80 mole%, preferably from 20 mole% to 50 mole%, of the carbonate groups in the appropriate polycarbonates may be replaced by aromatic dicarboxylic acid ester groups. Such polycarbonates, which contain both acid residues of carbonic acid and acid residues of aromatic dicarboxylic acids incorporated into the molecular chain, are referred to as aromatic polyester carbonates. They are subsumed for simplicity in the present application under the generic term of the thermoplastic, aromatic polycarbonates.

The preparation of the polycarbonates is carried out in a known manner from diphenols, carbonic acid derivatives, optionally chain terminators and optionally branching agents, wherein for the production of polyester carbonates, a part of the carbonic acid derivatives is replaced by aromatic dicarboxylic acids or derivatives of dicarboxylic acids, depending on the extent to be replaced in the aromatic polycarbonates Carbonate structural units by aromatic dicarboxylic ester structural units. Dihydroxyaryl compounds suitable for the preparation of polycarbonates are those of the formula (2)

HO-Z-OH (2) in which

Z is an aromatic radical having 6 to 30 carbon atoms, which may contain one or more aromatic nuclei, may be substituted and aliphatic or cycloaliphatic radicals or

Alkylaryl or heteroatoms may contain as bridge members.

Z in formula (2) preferably represents a radical of the formula (3)

in the

R ⁶ and R ⁷ are each independently H, Ci-Ci8-alkyl, Ci-Ci8-alkoxy, halogen such as Cl or Br or each optionally substituted aryl or aralkyl, preferably H or Ci-Ci2-alkyl, particularly preferably are H or Ci-Cs-alkyl and most preferably H or methyl, and

X is a single bond, -SO 2 -, -CO-, -O-, -S-, Ci- to Ce-alkylene, C ₂ - to C ₅ -alkylidene or C ₅ - to C 6 -cycloalkylidene which is substituted by C 1 - to C 6 -cycloalkyl- Alkyl, preferably methyl or ethyl may be substituted, further for Ce to Ci2-arylene, which may optionally be condensed with further heteroatom-containing aromatic rings is.

X is preferably a single bond, C ₁ to C ₅ -alkylene, C ₂ to C ₅ -alkylidene, C ₅ to C ₈ -cycloalkylidene, -O-, -SO-, -CO-, -S-, - SO 2 -, or one for a radical of the formula (3a) or (3b)

in which

R ⁸ and R ^{9 are} individually selectable for each X ¹ , independently of one another denote hydrogen or C ₁ to C ₆ -alkyl, preferably hydrogen, methyl or ethyl, and

X ^{1 is} carbon and n is an integer from 4 to 7, preferably 4 or 5, with the proviso that on at least one atom X ¹ , R ⁸ and R ^{9 are} simultaneously alkyl.

Examples of Dihydroxyarylverbmdungen (diphenols) are: dihydroxybenzenes, Dihydroxydiphenyle, bis (hydroxyphenyl) alkanes, bis (hydroxyphenyl) cycloalkanes, bis (hydroxyphenyl) -aryl, bis (hydroxyphenyl) ether, bis (hydroxyphenyl ) ketones, bis (hydroxyphenyl) sulfides, bis (hydroxyphenyl) - sulfones, bis (hydroxyphenyl) sulfoxides, l, l 'bis- (hydroxyphenyl) -diisopropylbenzenes, and their ring-alkylated and ring-halogenated compounds.

Diphenols suitable for the preparation of the polycarbonates to be used are, for example, hydroquinone, resorcinol, dihydroxydiphenyl, bis (hydroxyphenyl) alkanes, bis (hydroxyphenyl) -cycloalkanes, bis (hydroxyphenyl) sulfides, bis (hydroxyphenyl) ethers, Bis (hydroxyphenyl) ketones, bis (hydroxyphenyl) sulfones, bis (hydroxyphenyl) sulfoxides, α, α'-bis (hydroxyphenyl) diisopropylbenzenes, and their alkylated, nuclear alkylated and nuclear halogenated compounds.

Preferred diphenols are 4,4'-dihydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) -l-phenyl-propane, 1,1-bis (4-hydroxyphenyl) -phenyl-ethane, 2,2-bis- (4-hydroxyphenyl) propane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 1,3-bis [2- (4-hydroxyphenyl) -2-propyl] benzene (bisphenol M), 2,2-bis- (3-methyl-4-hydroxyphenyl) -propane, bis (3,5-dimethyl-4-hydroxyphenyl) -methane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl ) -propane, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, 2,4-bis (3,5-dimethyl-4-hydroxyphenyl) -2-methylbutane, 1,3-bis- [2 - (3,5-dimethyl-4-hydroxyphenyl) -2-propyl] benzene and 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (bisphenol TMC). Particularly preferred diphenols are 4,4'-dihydroxydiphenyl, 1, 1-bis (4-hydroxyphenyl) phenyl ethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3,5 -dimethyl-4-hydroxyphenyl) -propane, 1,1-bis (4-hydroxyphenyl) -cyclohexane and 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (bisphenol TMC).

These and other suitable diphenols are described, for example, in US Pat. Nos. 2,999,835, 3,148,172, 2,991,273, 3,271,367, 4,982,014 and 2,999,846, in German Offenlegungsschriften 1,570,703, 2,063,050, 2,036 052, 2 211 956 and 3 832 396, French Patent Specification 1 561 518, in the monograph "H. Schnell, Chemistry and Physics of Polycarbonates, Interscience Publishers, New York 1964, p. 28 et seq., P.102ff, and in" In the case of homopolycarbonates, only one diphenol is used, in the case of copolycarbonates two or more diphenols are used Like all other chemicals and auxiliaries added to the synthesis may be contaminated with the impurities resulting from their own synthesis, handling and storage, it is desirable to use as pure raw materials as possible monofunctional chain terminators, such as phenol or alkylphenols, in particular phenol, p-tert. Butylphenol, iso-octylphenol, cumylphenol, their chlorocarbonic acid esters or acid chlorides of monocarboxylic acids or mixtures of these chain terminators, either with the bisphenolate or the bisphenolates of the reaction added or added at any point in the synthesis, as long as in the reaction mixture phosgene or Chlorkohlensäureendgruppen are present or in the case of acid chlorides and chloroformate as chain terminators as long as sufficient phenolic end groups of the forming polymer are available. Preferably, however, the chain terminator (s) are added after phosgenation at one point or at a time when phosgene is no longer present but the catalyst has not yet been metered, or before the catalyst, with the catalyst together or in parallel.

In the same way, any branching or debranching compounds to be used are added to the synthesis, but usually before the chain terminators. Usually trisphenols, quarterphenols or acid chlorides of tri- or tetracarboxylic acids are used, or mixtures of polyphenols or acid chlorides.

Some of the branching compounds having three or more than three phenolic hydroxyl groups include, for example, phloroglucinol, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptene-2, 4,6-dimethyl-2, 4,6-tri- (4-hydroxyphenyl) -heptane, 1, 3,5-tri- (4-hydroxyphenyl) -benzene, 1,1,1-tri- (4-hydroxyphenyl) -ethane, tri- (4 -hydroxyphenyl) phenylmethane, 2,2-bis (4,4-bis (4-hydroxyphenyl) cyclohexyl] propane, 2,4-bis- (4-hydroxyphenyl-isopropyl) -phenol, tetra- (4-hydroxyphenyl) methane.

Some of the other trifunctional compounds are 2,4-dihydroxybenzoic acid, trimesic acid, cyanuric chloride and 3,3-bis- (3-methyl-4-hydroxyphenyl) -2-oxo-2,3-dihydroindole. Preferred branching agents are 3,3-bis- (3-methyl-4-hydroxyphenyl) -2-oxo-2,3-dihydroindole and 1,1,1-

Tri- (4-hydroxyphenyl) ethane.

The amount of optionally used branching agent is 0.05 mol% to 2 mol%, based in turn on moles of diphenols used in each case.

The branching agents may be presented either with the diphenols and the chain terminators in the aqueous alkaline phase, or dissolved in an organic solvent before

Phosgenation can be added.

All these measures for the preparation of the polycarbonates are familiar to the expert.

Suitable aromatic dicarboxylic acids for the preparation of the polyester carbonates are, for example, orthophthalic acid, terephthalic acid, isophthalic acid, tert-butyl isophthalic acid, 3,3'-diphenyl dicarboxylic acid, 4,4'-diphenyl dicarboxylic acid, 4,4-benzophenone dicarboxylic acid, 3,4'-benzophenone dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 4,4'-diphenylsulfonedicarboxylic acid, 2,2-bis (4-carboxyphenyl) -propane, trimethyl-3-phenylindane-4,5'-dicarboxylic acid.

Of the aromatic dicarboxylic acids, terephthalic acid and / or isophthalic acid are particularly preferably used. Derivatives of the dicarboxylic acids are the dicarboxylic acid dihalides and the dicarboxylic acid dialkyl esters, in particular the dicarboxylic acid dichlorides and the dimethyl dicarboxylates.

Substitution of the carbonate groups by the aromatic dicarboxylic ester groups is essentially stoichiometric and also quantitative, so that the molar ratio of the reactants is also found in the finished polyester carbonate. The incorporation of the aromatic dicarboxylic acid ester groups can be carried out both statistically and in blocks.

Preferred methods of preparation of the polycarbonates to be used, including the polyester carbonates, are the known interfacial method and the known melt transesterification method (cf., for example, WO 2004/063249 A1, WO 2001/05866 A1, WO 2000/105867, US Pat. No. 5,340,905, US Pat. No. 5,097,002, US-A 5,717,057). In the first case, preferably acid derivatives are phosgene and optionally dicarboxylic acid dichlorides, in the latter case preferably diphenyl carbonate and optionally dicarboxylic acid diester. Catalysts, solvents, work-up, reaction conditions, etc. for the production of polycarbonate or production of polyester carbonate are adequately described and known in both cases. The polycarbonates, polyester carbonates and polyesters can be worked up in a known manner and processed to form any shaped articles, for example by extrusion or injection molding.

The polycarbonate compositions may also contain the customary for the thermoplastics mentioned additives such as fillers, UV stabilizers, heat stabilizers, antistatic agents, dyes and pigments, mold release agents, IR absorbers and flame retardants in the usual amounts of generally up to 5 wt .-%, preferably 0 , 01 to 3 wt .-% based on the total composition can be added.

Suitable additives are described, for example, in "Additives for Plastics Handbook, John Murphy, Elsevier, Oxford 1999", in the "Plastics Additives Handbook, Hans Zweifel, Hanser, Munich 2001". Further thermoplastic polymers which are suitable as carrier material may be homopolymers or copolymers of ethylenically unsaturated monomers or polymers of bifunctional reactive Be connections. Suitable thermoplastic polymers may also be mixtures of different polymers.

Suitable thermoplastic polymers include homopolymers or copolymers of one or more ethylenically unsaturated monomers (vinyl monomers) such as vinyl acetate, styrene, α-methylstyrene, nucleus-substituted styrenes, acrylonitrile, methacrylonitrile, methyl methacrylate, maleic anhydride, N-substituted-maleimides, chloroprene, butadiene-1, 3, isoprene and C 1 -C 8 -alkyl acrylates and alkyl methacrylates.

Suitable vinyl polymers are:

Rubber-free vinyl polymers (hereinafter referred to as VP.1)

Rubber-containing vinyl polymers, such as graft polymers of vinyl monomers, on a rubber (hereinafter referred to as VP.2)

• Mixtures of rubber-free and rubber-containing vinyl polymers. The Copolymeriste VP.l are resinous, thermoplastic and rubber-free. Preferred vinyl copolymers VP.l are those from

VP.1.1

50 to 98 wt .-% of styrene, α-methylstyrene, ring-substituted styrene, methyl methacrylate or mixtures thereof and

VP.1.2

50 to 2 wt .-% of acrylonitrile, methacrylonitrile, methyl methacrylate, maleic anhydride, N-substituted maleimide or mixtures thereof.

Particularly preferred copolymers VP. l are those of styrene, acrylonitrile and optionally methyl methacrylate, of α-methyl styrene, acrylonitrile and optionally methyl methacrylate and of styrene, α-methyl styrene, acrylonitrile and optionally methyl methacrylate.

The styrene-acrylonitrile copolymers VP. l are known and can be prepared by free-radical polymerization, in particular by emulsion, suspension, solution or bulk polymerization. The copolymers VP.l preferably have molecular weights Mw (weight average, determined by light scattering or sedimentation) of 15,000 to 200,000. Further particularly preferred copolymers VP. l are random copolymers of styrene and maleic anhydride, which are preferably prepared by a continuous bulk or solution polymerization in incomplete conversions from the corresponding monomer. Their composition can be varied within wide limits. Preferably, they contain 5 to 25 wt .-% maleic anhydride units.

Instead of styrene, the polymers may also contain ring-substituted styrenes such as p-methylstyrene, vinyltoluene, 2,4-dimethylstyrene and other substituted styrenes such as α-methylstyrene.

Their molecular weights (number average R _n ) are preferably 60,000 to 200,000. They preferably have an intrinsic viscosity of from 0.3 to 0.9 (measured in dimethylformamide at 25 ° C., see Hoffmann, Krömer, Kuhn, Polymeranalytik I, Stuttgart, 1977, page 316 et seq.).

The vinyl polymers VP.2 are thermoplastic and rubber-containing.

Preferred vinyl polymers VP.2 are graft polymers. These include, e.g. Graft copolymers having rubbery elastic properties which are essentially obtainable from at least two of the following monomers: chloroprene, 1,3-butadiene, isoprene, styrene, acrylonitrile, ethylene, propylene, vinyl acetate and C 1 -C 8 -alkyl acrylates and methacrylates. Such polymers are e.g. in "Methods of Organic Chemistry" (Houben-Weyl), Vol. 14/1, Georg Thieme-Verlag, Stuttgart, 1961, pp. 393-406 and in C.B. Bucknall, "Toughened Plastics", Appl. Science Publishers, London 1977. Preferred polymers VP.2 are partially crosslinked and have gel contents of more than 20% by weight, preferably more than 40% by weight, in particular more than 60% by weight.

Graft polymers VP.2 are e.g. polybutadienes grafted with styrene and / or acrylonitrile and / or alkyl acrylates or methacrylates, butadiene / styrene copolymers and acrylate rubbers; i.e. Copolymers of the type described in DE-OS 1 694 173 (= US Pat. No. 3,564,077); polybutadienes grafted with acrylic or methacrylic acid alkyl esters, vinyl acetate, acrylonitrile, styrene and / or alkylstyrenes, butadiene / styrene or butadiene / acrylonitrile copolymers, polyisobutenes or polyisoprenes, e.g. in DE-OS 2 348 377 (= US Pat. No. 3,919,353), and also ABS polymers, as described, for example, in US Pat. in DE-OS 2 035 390 (= US-PS 3,644,574) or in DE-OS 2,248,242 (= GB-PS 1 409 275) are described.

Preferred vinyl polymers VP.2 are graft polymers of: VP.2.1

5 to 95, preferably 30 to 80 parts by weight, of a mixture of VP.2.1.1

50 to 95 wt. Parts of styrene, α-methylstyrene, alkylkemsubstituierten, preferably methylene-substituted styrenes, C 1 -C 8 -alkyl methacrylates, preferably methyl methacrylate, C 1 -C 8 -alkyl acrylates, preferably methacrylate or mixtures of these compounds and VP.2.1.2

5 to 50 parts by weight of acrylonitrile, methacrylonitrile, C 1 -C 8 -alkyl methacrylates, preferably methyl methacrylate, C 1 -C 8 -alkyl acrylate, preferably methacrylate, maleic anhydride, C 1 -C 4 -alkyl- or phenyl-N-substituted maleimides or mixtures of these compounds

VP.2.2 5 to 95, preferably 20 to 70, parts by wt. Of rubber polymer having a glass transition temperature below -10 ° C, preferably a diene, acrylate, silicone or ethylene-propylene-diene rubber, in particular polybutadiene.

Particularly preferred graft polymers VP.2 are obtainable by graft polymerization of a. 10 to 70, preferably 15 to 50, in particular 20 to 40 wt .-%, based on graft polymer A.2, of acrylic acid esters or methacrylic acid esters or from 10 to 70, preferably 15 to 50, especially 20 to 40 wt .-% of a mixture from 10 to 50, preferably 20 to 35 wt .-%; based on mixture, acrylonitrile, acrylic ester or methacrylic acid ester and 50 to 90, preferably 65 to 80 wt .-%, based on the mixture, styrene (as grafting VP.2.1) on ß. From 30 to 90, preferably from 50 to 85, in particular from 60 to 80,% by weight, based on graft polymer VP.2, of a butadiene polymer having at least 50% by weight, based on β, butadiene radicals (as grafting base VP.2.2), wherein preferably the gel content of the graft base ß at least 70 wt .-% (measured in toluene), the graft G 0.15 to 0.55 and the average particle diameter dso of the graft polymer VP.2 0.05 to 2 m, preferably 0.1 to 0.6 m.

Acrylic esters or methacrylic esters are esters of acrylic acid or methacrylic acid and monohydric alcohols having 1 to 8 carbon atoms. Particularly preferred are methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl acrylate, t-butyl acrylate and t-butyl methacrylate.

The butadiene polymer β can, in addition to butadiene radicals, contain up to 50% by weight, based on β, of radicals of other ethylenically unsaturated monomers, such as styrene, acrylonitrile, C 1 -C 4 -alkyl ester or acrylonitrile. or methacrylic acid (such as methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate), vinyl esters and / or vinyl ethers. Preference is given to polybutadiene.

In the graft polymerization, it is known that the graft monomers are not completely polymerized onto the graft base; why graft polymers VP.2 include products obtained by polymerization of the graft monomers in the presence of the grafting base.

The degree of graft G is the weight ratio of graft grafted gomomers to the graft base (dimensionless number).

The mean particle diameter dso is the diameter, above and below which each 50 wt .-% of the particles are. It can be determined by means of ultracentrifuge measurement (for example Scholtan, H. Lange, Kolloid, Z. and Z. Polymere 250 (1972), 782-796).

Further particularly preferred polymers VP.2 are graft polymers of x. 20 to 90 wt .-%, based on VP.2, acrylate rubber having a glass transition temperature below -20 ° C as a grafting base VP.2.2 and δ. From 10 to 80% by weight, based on VP.2, of at least one polymerisable, ethylenically unsaturated monomer, the or thereof in the absence of x. resulting homo- or

Copolymers would have a glass transition temperature above 25 ° C, as graft monomers VP.2.1.

The acrylate rubbers of the polymers VP.2 are preferably polymers of alkyl acrylates, optionally with up to 40% by weight, based on x, of other polymerizable, ethylenically unsaturated monomers. Preferred polymerizable acrylic acid esters include C 1 -C 8 alkyl esters, for example, methyl, ethyl, butyl, n-octyl and 2-ethylhexyl esters; Haloalkyl esters, preferably halo-C 1 -C 8 -alkyl esters, such as chloroethyl acrylate, and mixtures of these monomers.

For crosslinking, monomers having more than one polymerizable double bond can be copolymerized. Preferred examples of crosslinking monomers are esters of unsaturated monocarboxylic acids having 3 to 8 C atoms and unsaturated monohydric alcohols having 3 to 12 C atoms or saturated polyols having 2 to 4 OH groups and 2 to 20 C atoms, such as, for example, ethylene glycol dimethacrylate Allyl methacrylate; polyunsaturated heterocyclic compounds, such as trivinyl and triallyl cyanurate; polyfunctional vinyl compounds such as di- and trivinylbenzenes; but also triallyl phosphate and diallyl phthalate. Preferred crosslinking monomers are allyl methacrylate, ethylene glycol dimethacrylate, diallyl phthalate and heterocyclic compounds having at least 3 ethylenically unsaturated groups.

Particularly preferred crosslinking monomers are the cyclic monomers triallylcyanurate, triallylisocyanurate, trivinylcyanurate, triacryloylhexahydro-s-triazine, triallylbenzenes.

The amount of crosslinking monomers is preferably 0.02 to 5, in particular 0.05 to 2 wt .-%, based on the graft base x. In the case of cyclic crosslinking monomers having at least 3 ethylenically unsaturated groups, it is advantageous to limit the amount to less than 1% by weight of the graft base x. Preferred "other" polymerisable, ethylenically unsaturated monomers which, in addition to the acrylic acid esters, may optionally be used for the preparation of the graft base are e.g. Acrylonitrile, styrene, α-methylstyrene, acrylamides, vinyl C1-C6 alkyl ethers, methyl methacrylate, butadiene. Preferred acrylate rubbers as graft base x are emulsion polymers which have a gel content of at least 60% by weight. Further suitable graft bases according to VP.2.2 are silicone rubbers with graft-active sites, as described in DE-OS 37 04 657, DE-OS 37 04 655, DE-OS 36 31 540 and DE-OS 36 31 539.

The gel content of the grafting base VP.2.2 is determined at 25 ° C. in dimethylformamide (M. Hoffmann, H. Krömer, R. Kuhn, Polymeranalytik I and II, Georg Thieme Verlag, Stuttgart 1977). The graft polymers VP.2 can be prepared by known processes, such as mass, suspension, emulsion or bulk suspension processes.

Further thermoplastic polymers which are suitable as carrier material may be polyesters, preferably polyalkylene terephthalates. These are reaction products of aromatic dicarboxylic acids (or their reactive derivatives, e.g., dimethyl esters or anhydrides) and aliphatic, cycloaliphatic or arylaliphatic diols and mixtures of such reaction products.

Preferred polyalkylene terephthalates can be prepared from terephthalic acids (or their reactive derivatives) and aliphatic and cycloaliphatic diols having 2 to 10 carbon atoms by known methods (Kunststoff-Handbuch), Vol. VIII, p. 695 ff, Carl Hanser Verlag, Munich 1973). Preferred polyalkylene terephthalates contain from 80 to 100, preferably from 90 to 100, mol%, based on the dicarboxylic acid component, of terephthalic acid residues and from 80 to 100, preferably from 90 to 100 Mol%, based on the diol component, ethylene glycol and / or butanediol-l, 4 radicals. In addition to terephthalic acid radicals, 0 to 20 mol% of radicals of other aromatic dicarboxylic acids having 8 to 14 C atoms or aliphatic dicarboxylic acids having 4 to 12 C atoms, such as radicals of phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, 4.4 'Diphenyl dicarboxylic acid, succinic, adipic, sebacic, azelaic or cyclohexanediacetic acid. In addition to ethylene glycol and / or butanediol

1,4-radicals are 0 to 20 mole% of other aliphatic diols having 3 to 12 carbon atoms or cycloaliphatic diols having 6 to 12 carbon atoms, e.g. Residues of pentanediol-1,5, hexanediol-1,6, cyclohexanedimethanol-1,4, 3-methylpentanediol-1,3,3 and 1,6,2-ethylhexanediol-1,3,2,2-diethylpropanediol-1,3, Hexanediol 2,5, 1-4-di (β-hydroxyethoxyphenyl) -propane, 2,4-dihydroxy-1,1,3,3-tetramethylcyclobutane, 2,2-bis (3-β-hydroxyethoxyphenyl) -propane and 2,2-bis (4-hydroxypropoxyphenyl) propane (DE-OS 2,407,647, 2,407,776, 2,715,932).

The polyalkylene terephthalates can be branched by incorporation of relatively small amounts of dihydric or trihydric alcohols or of tri- or tetrabasic carboxylic acids, as described in DE-OS 1 900 270 and US Pat. No. 3,692,744. Examples of preferred branching agents are trimesic acid, trimellitic acid, trimethylolethane and propane, and pentaerythritol. It is advisable not more than 1

Mol%) of the branching agent, based on the acid component.

Particular preference is given to polyalkylene terephthalates which have been prepared solely from terephthalic acid (or its reactive derivatives, for example their dialkyl esters) and ethanediol and / or butanediol-1,4, and mixtures thereof. Preferred polyalkylene terephthalates are also copolyesters prepared from at least two of the above diols; Particularly preferred copolyesters are poly (ethylene glycol / butanediol-1,4-terephthalates). In the copolyesters, the various diol residues may be in the form of blocks or randomly distributed.

The polyalkylene terephthalates generally have an intrinsic viscosity of 0.4 to 1.4 dl / g, preferably 0.5 to 1.3 dl / g, in particular 0.6 to 1.2 dl / g, each measured in phenol / o-Dichlorobenzene (1: 1 wt. -Tl.) At 25 ° C.

Further preferred embodiments of mixtures of polycarbonates and vinyl polymers are described in EP 10787136.

Further preferred embodiments of mixtures of polycarbonates, vinyl polymers and polyesters are described in WO 2013098176.

Further thermoplastic polymers suitable as carrier material may be polyolefins

Be polyethylene or polypropylene. Polyethylene can be of high and low density, ie densities from 0.91 g / cm ³ to 0.97 g / cm ³ , which are prepared by known methods, Ullmann (4.), 19, page 167 et seq., Winnacker-Kückler (4th ed.). ), 6, 353-367, Elias et al. Vohwinkel, New Polymeric Materials for Industrial Application, Munich, Hanser 1983, can be used. Also suitable are polypropylenes having molecular weights of from 10,000 g / mol to 1,000,000 g / mol, which are prepared by known processes, Ullmann (5.) A10, page 615 et seq., Houben-Weyl E20 / 2, page 722 et seq., Ullmann (4. ) 19, page 195 ff, Kirk Othmer (3rd) 16, page 357 ff, can be produced.

But there are also copolymers of said olefins or with other α-olefins possible, such as polymers of ethylene with butene, hexene and / or octene and EVA (ethylene vinyl acetate copolymers), EEA (ethylene ethyl acrylate), EBA (ethylene-butyl acrylate), EAS (Acrylsäureethylenacrylatcopolymerisate ), EVK (ethylene-vinylcarbazole copolymers), EPB (ethylene-propylene block copolymers), EPDM (ethylene-propylene-diene copolymers), PB (polybutylenes), PMP (polymethylpentenes), PIB (polyisobutylenes), NBR (acrylonitrile-butadiene copolymers), polyisoprenes , Methyl butylene copolymers, isoprene isobutylene copolymers.

The preparation processes of such polymers are e.g. in Plastics Handbook, Volume IV, Munich, Hanser Verlag, Ullmann (4th), 19, page 167 ff, Winnacker-Kückler (4) 6, 353-367, Elias u. Vohwinkel, New Polymer Materials, Munich, Hanser 1983, Franck u. Biederbick, Kunststoff Kompendium Würzburg, Vogel 1984, discloses. Further thermoplastic polymers which are suitable as carrier material may be poly (meth) acrylates.

The term (meth) acrylates include methacrylates and acrylates as well as mixtures of both.

Poly (meth) acrylates are polymers which are obtainable by polymerization of a monomer mixture which has at least 60% by weight, preferably at least 80% by weight of (meth) acrylates, based on the weight of the monomers. These monomers are well known in the art and commercially available.

These include, among others

^■ (meth) acrylic acid and (meth) acrylates derived from saturated alcohols, such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, Hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate;

■ (meth) acrylates derived from unsaturated alcohols, such as. B. 01eyl (meth) acrylate, 2-

Propynyl (meth) acrylate, allyl (meth) acrylate, vinyl (meth) acrylate, etc .; ^■ amides and nitriles of (meth) acrylic acid, such as N- (3-dimethylaminopropyl) (meth) acrylamide, N- (diethylphosphono) (meth) acrylamide, 1-methacryloylamido-2-methyl-2-propanol;

^■ cycloalkyl (meth) acrylates, such as 3-vinylcyclohexyl (meth) acrylate, bornyl (meth) acrylates;

^■ hydroxyalkyl (meth) acrylates such as 3-hydroxypropyl (meth) acrylate, 3,4-dihydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate;

^■ glycol di (meth) acrylates such as l, 4-butanediol (meth) acrylates;

^■ (meth) acrylates of ether alcohols, such as tetrahydrofurfuryl (meth) acrylate, vinyloxyethoxyethyl (meth) acrylate; and

^■ polyvalent (meth) acrylates, such as trimethyloylpropane tri (meth) acrylate. In addition to the (meth) acrylates set out above, it is also possible to use for the preparation of the poly (meth) acrylates other unsaturated monomers which are copolymerizable with the abovementioned methacrylates. In general, these compounds are used in an amount of 0 to 40 wt .-%, preferably 0 to 20 wt .-%, based on the weight of the monomers, wherein the comonomers can be used individually or as a mixture. These include, inter alia, 1-alkenes, such as hexene-1, heptene-1; branched alkenes such as vinylcyclohexane, 3,3-dimethyl-1-propene, 3-methyl-1-diisobutylene, 4-methylpentene-1; Vinyl esters, such as vinyl acetate; Styrene, substituted styrenes having an alkyl substituent in the side chain, such as. [Alpha] - methylstyrene and [alpha] -ethylstyrene, substituted styrenes having an alkyl substituent on the ring such as vinyltoluene and p-methylstyrene, halogenated styrenes such as monochlorostyrenes, dichlorostyrenes, tribromostyrenes and tetrabromostyrenes; Heterocyclic vinyl compounds, such as 2-vinylpyridine, 3-vinylpyridine, 2-methyl-5-vinylpyridine, 3-ethyl-4-vinylpyridine, 2,3-dimethyl-5-vinylpyridine, vinylpyrimidine, vinylpiperidine, 9-vinylcarbazole, 3-vinylcarbazole, 4-vinylcarbazole, 1-vinylimidazole, 2-methyl-1-vinylimidazole, N-vinylpyrrolidone, 2-vinylpyrrolidone, N-vinylpyrrolidine, 3-vinylpyrrolidine, N-vinylcaprolactam, N-vinylbutyrolactam, vinyloxolane, vinylfuran, vinylthiophene, vinylthiolane, vinylthiazoles and hydrogenated vinylthiazoles, vinyloxazoles and hydrogenated vinyloxazoles; Vinyl and isoprenyl ethers; Maleic acid derivatives such as maleic anhydride, methylmaleic anhydride, maleimide, methylmaleimide; and dienes, such as divinylbenzene.

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 called polymethyl methacrylates. Preferred thermoplastics may contain various poly (meth) acrylates, which differ, for example, in molecular weight or in the monomer composition. Further preferred embodiments are mixtures of polymethyl methacrylate copolymers, in particular polymethylmethacrylate-poly (meth) acrylimide copolymers.

The preparation of the (meth) acrylate homopolymers and / or copolymers from the monomers set forth above according to the various processes of radical polymerization is known per se. Thus, the polymers can be prepared in bulk, solution, suspension or emulsion polymerization. The bulk polymerization is exemplified in Houben-Weyl, Vol. E20, Part 2 (1987), pp. 1145ff. described. Valuable information regarding solution polymerization can be found on p. 1156ff. Explanations of the suspension polymerization technique can be found on p. 1149ff, while the emulsion polymerization can be found on p. 1150ff. is executed and explained.

Further thermoplastic polymers suitable as carrier material may be polyamides. Preferred polyamides include aliphatic polyamides such as PA-6, PA-11, PA-12, PA-4,6, PA-4,8, PA-4,10, PA-4,12, PA-6,6 , PA-6,9, PA-6, 10, PA-6, 12, PA-10, 10, PA-12, 12, PA-6 / 6,6 copolyamide, PA-6/12 copolyamide, PA -6/11 copolyamide, PA-6,6 / 11 copolyamide, PA-6,6 / 12 copolyamide, PA-6/6, 10-copolyamide, PA-6,6 / 6,10-copolyamide, PA -4,6 / 6-copolyamide, PA

6 / 6,6 / 6, 10-terpolyamide, and copolyamides of 1,4-cyclohexanedicarboxylic acid and 2,2,4- and 2,4,4-trimethylhexamethylenediamine; aromatic polyamides, such as PA-6,1, PA-6, 1 / 6,6-copolyamide, PA-6, T, PA-6, T / 6-copolyamide, PA-6, T / 6,6-copolyamide, PA-6, l / 6, T-copolyamide, PA-6,6 / 6, T / 6, l-copolyamide, PA-6, T / 2-MPMDT copolyamide (2-MPMDT = 2-methylpentamethylenediamine), PA - 9, T, copolyamides of terephthalic acid, 2,2,4- and 2,4,4-trimethylhexamethylenediamine, copolyamide of isophthalic acid, laurolactam and 3,5-dimethyl-4,4-diaminodicyclohexylmethan, copolyamides of isophthalic acid, azelaic acid and / or Sebacic acid and 4,4-diaminodicyclohexylmethane, copolyamides of caprolactam, isophthalic acid and / or terephthalic acid and 4,4-diaminodicyclohexylmethane, copolyamides of caprolactam, isophthalic acid and / or terephthalic acid and isophoronediamine, copolyamides of isophthalic acid and / or terephthalic acid and / or other aromatic or aliphatic Dicarboxylic acids, optionally alkyl-substituted hexamethylenediamine and alkyl-substituted 4,4-diaminodicyclohexylamine, and also copolyamides and mixtures of the foregoing n polyamides. Further preferred are semi-crystalline polyamides selected from the group comprising PA-6, PA-6,6, PA-6,10, PA-4,6, PA-11, PA-12, PA-12,12, PA- 6.1, PA-6, T, PA-6, T / 6,6-copolyamide, PA-6, T / 6-copolyamide, PA-6 / 6,6-copolyamide, PA-6,6 / 6, T / 6, 1-copolyamide, PA-6, T / 2-MPMDT copolyamide, PA-9, T, PA-4,6 / 6-copolyamide and mixtures of the aforementioned polyamides. Particularly preferred as support material are polyamides based on polyamide 66 (polyhexamethylene adipamide) or polyamides of cyclic lactams having 5 to 12 carbon atoms, preferably of laurolactam and more preferably ε-caprolactam = polyamide 6 (polycaprolactam) or copolymers with main components 6 or 66 or blends used with main component of said polyamides. Preference is given to copolyamide prepared by activated anionic polymerization and having the main constituent polycaprolactam.

The activated anionic polymerization of lactams to polyamides is carried out on an industrial scale by preparing on the one hand a solution of catalyst in lactam, optionally with impact modifier, and on the other hand a solution of activator in lactam, usually both solutions are composed so that a combination in the same ratio gives the desired total formulation. That is not necessary. It is also possible to choose other compositions, for example to meter a concentrated activator and catalyst melt into a lactam melt. Depending on the compatibility, further additives can be added to the activator, catalyst or optionally lactam melt.

The polymerization is carried out by mixing the individual solutions to the total formulation at 80 ° C to 200 ° C, preferably 100 ° C to 140 ° C.

In PU foam production, foaming is usually carried out in closed molds.

The components according to the invention are preferably produced by the so-called DirectSkinning technology, which combines the injection molding of thermoplastics with the reaction injection molding (RIM) process of PUR processing. Similar to multi-component injection molding, the composite component can be manufactured directly on an injection molding machine in just one tool (multiple tools are also possible). In this case, the reaction mixture is introduced into a mold in which the plastic support II) is already located. As a molding material is metal, such as aluminum, or plastic, such as epoxy resin, in question. In the mold, the foamable reaction mixture foams and forms the composite component. When using a turntable or insert tool, for example, both manufacturing steps can be performed in parallel, which ensures short cycle times and thus high productivity. The foaming of the mold can be carried out in such a way that the component has cell structure on its surface, but it can also be carried out in such a way that the molded part has a compact skin and a cellular core. In this context, one can proceed in such a way that so much foamable reaction mixture is introduced into the mold that the foam formed just fills the mold. But you can also work so that one enters more foamable reaction mixture into the mold, as is necessary for filling the mold interior with foam. In the latter case, it is thus worked under "over-charging"; such a procedure is well known.

The post-processing effort for the composite components thus produced is very low. The thickness of the polyurethane layer can be varied within wide ranges. Since the composite component is produced in just one tool, DirectSkinning does not require a separate coating system, unlike conventional processes. The transport and intermediate storage of the pure injection molded parts (plastic carrier) is eliminated, which simplifies the logistical processes and minimizes the risk of contamination and damage.

 The composite components according to the invention are used for example for the production of steering wheels, door side panels, instrument panel covers, consoles, protective pads and shelves in the vehicle interior.

The invention will be explained in more detail with reference to the following examples.

Examples

The percentages in the following examples and Tables 1 and 2 are by weight.

Preparation of the Polyisocyanate AI): HDI containing isocyanurate and uretdione groups was catalyzed by tributylphosphine

Oligomerization of HDI based on Example la) of EP-A 0 377 177 prepared, but no 2,2,4-trimethyl-l, 3-pentanediol was used. The reaction was stopped at an NCO content of the crude solution of 42% and unreacted HDI removed by thin film distillation at a temperature of 130 ° C and a pressure of 0.2 mbar. NCO content: 22.7%

 NCO functionality: 2.2

monomeric HDI: 0.3%

 Viscosity (23 ° C): 90 mPas

 Preparation of polyisocyanate A2): 7 moles of 1,6-diisocyanatohexane (HDI) and 1 mole of a polypropylene oxide diol having a weight-average molecular weight of 400 (OH number = 280) were reacted at 80 ° C until a constant NCO content was reached. Subsequently, the excess of monomeric HDI was removed by thin film distillation at a temperature of 130 ° C and a pressure of about 0.5 mbar. NCO content: 12.6%

monomeric HDI: 0.2%

 Viscosity (23 ° C): 4250 mPas

 Polyisocyanate I:

Mixture of 1 part by weight of polyisocyanate A2) and 1 part by weight of polyisocyanate AI). Polvol B):

Polyether polyol having an OH number of 28; prepared by alkoxylation of sorbitol with propylene oxide / ethylene oxide (PO / EO) in the weight ratio 82 PO: 18 EO and predominantly PRE OH end groups. Propellant D:

40 parts by weight of HFC 245 fa [1, 1, 1,3,3-pentafluoropropane from Honeywell] and 60 parts by wt. Of R 365 mfc [1,1,3,3-pentafluorobutane from the company Honeywell] used. Depending on the haptic improver, the blowing agent mixture is added in such a way that the blowing agent content is in each case about 7.5% by weight, based on all starting materials.

Table 1 :

inventively IPDA: isophorone diamine

Irganox ^® 1135: Antioxidant phenolic-based BASF SE

Tinuvin ^® B75: mixture of Irganox ^® 1135 (Antioxidant), Tinuvin ^® 765 (HALS), and Tinuvin ^® 571 (UV stabilizer), BASF SE.

 ISOPUR-SA-17244/9211: black paste: carbon black with long-chain polyether as pasting agent, from ISL Chemie

Fomrez ^® UL22: dimethyl tin mercaptide (activator), from Momentive.

Fomrez ^® UL28: dimethyl tin di-neodecanoate (activator), from Momentive.

Niax ^® Silicone 1160: organo-functional polydimethylsiloxane, company Momentive

Niax Silicone ^® 1162: Siloxane polyalkylene oxide copolymer, from Momentive.

Niax Silicone ^® 1166: Siloxane polyalkylene oxide copolymer, from Momentive.

PUR sheets were produced in the laboratory. The mold temperature in the experiments was 70 ° C. and the mold size was 100 mm × 100 mm × 20 mm. The surface of the samples was made with a KA3A leather grain. To prevent adhesion between the tool surface and the polyurethane plate, "Eckert und Wölk VP 84151" was used as the external release agent.

The temperature of the components used was 25 ° C for both the isocyanate and the polyol formulation.

The amount that was poured into the mold was sized to give the stated mold density.

rehearse

1 without HV (haptic improvers)

 2 with 0.2% HV Niax Silicone L-1162

 3 with 0.5% HV Niax Silicone L-1162

 4 with 1.0% HV Niax Silicone L-1162

 5 with 2.0% HV Niax Silicone L-1162

 6 with 1.0% HV Niax Silicone L-1160

 7 with 2.0% HV Niax Silicone L-1160

 8 with 1.0% HV Niax Silicone L-1166

 9 with 2.0% HV Niax Silicone L-1166

The friction behavior was determined using the friction slide method according to DIN EN ISO 8295 and a Zwicki 2.5KN tensile testing machine with attached mirror table. The friction slide is 200g heavy and occupied on one side with open needle felt (The felt covering was not changed in the course of the measurements). The sample was fixed once parallel to the longer side of the sample ("longitudinal") and once across it ("across") on the mirror table, and the friction slide was pulled over the surface at a constant speed of 500 mm / min. Traction and friction were measured and graphically displayed. The samples were previously one day in standard atmosphere at 23 ° C and 50% rel. Moisture stored and measured under these conditions.

Six laterally offset measuring runs were made, overlapping the rub marks. The frictional forces at 20mm and 70mm glideslope, the dynamic frictional force FD [N] as an average of the frictional force values at 20 and 70mm and the dynamic friction coefficient μθ as the quotient of frictional force FD and normal force FP (carriage mass) were evaluated from the traction force along the friction path.

Unweighted averages were generated from all individual curves in the longitudinal and transverse directions.

In the following table, the mean values of the friction measurements in the longitudinal and transverse direction are respectively listed for the grained samples.

Table 2:

Samples Friction force average dynamic friction at 20mnn at 70mnn friction force coefficient

 FD MD

 1 (without HV) 1, 35 N 1, 35 N 1, 35 N 0.68

2 (0.2% 1, 41 N 1, 53 N 1, 47 N 0.74

 1 162)

 3 (0.5% 0.90 N 0.98 N 0.95 N 0.48

 1 162)

 4 (1, 0% 0.85 N 0.85 N 0.85 N 0.43

 1 162)

 5 (2.0% 0.80 N 0.87 N 0.82 N 0.41

 1 162)

 6 (1, 0% 1, 06 N 1, 14 N 1, 07 N 0.54

1 160) 7 (2.0% 0.83 N 0.92 N 0.85 N 0.43

 1 160)

 8 (1, 0% 1, 40 N 1, 53 N 1, 48 N 0.74

 1 166)

 9 (2.0% 1, 18 N 1, 30 N 1, 23 N 0.62

 1 166)

As already mentioned, it has been found that in components with a KA3A leather graining, low values (<0.6) are perceived as pleasant to the touch, whereas components with a friction coefficient> 0.6 are perceived as too slippery, rubbery and dull , It can be seen clearly from the table that the Niax ^® Silicone L-1162 and L-1160 the coefficient of friction even in small concentrations (0.5% and 1%) to lower than 0.6, whereas when Niax Silicone L-1166 ^® Also significantly higher concentrations (2%), the lubricity (low coefficient of friction) can not lower in this perceived as pleasant area. Haptikverbesserer be used for cost reasons only in low concentrations. The use of Niax silicones L ^® 1162 and L-1160 is therefore advantageous.

Claims

Claims:

1. Composite components of a lightfast polyurethane top layer I) and a plastic support II), wherein the plastic in the support II) of I) is different, characterized in that the polyurethane cover layer I) is available from

A) organically modified cycloaliphatic and / or aliphatic polyisocyanate compounds

B) polyols having a number average molecular weight of from 1,000 to 15,000 g / mol and a functionality of from 2 to 8, preferably from 2 to 6,

C) Polyols and / or polyamines having a molecular weight of 62-500 g / mol and a functionality of 2 to 8, preferably 2 to 4, as chain extenders or crosslinkers,

D) blowing agents,

E) siloxane-polyalkylene oxide copolymers as haptic improvers,

F) optionally further auxiliaries and / or additives.

2. A method for producing the composite components according to claim 1, characterized in that after the DirectSkinning- method, the lightfast polyurethane topcoat I) according to claim 1 on the plastic substrate II) according to claim 1 is applied.

3. Use of the composite components according to claim 1 for the production of steering wheels, door side panels, instrument panel covers, consoles, protective pads and shelves in the vehicle interior.