HK1178490A

HK1178490A - Composite components from polycarbonate / polyester compositions and polyurethane, having improved interlayer adhesion

Info

Publication number: HK1178490A
Application number: HK13105251.8A
Authority: HK
Inventors: Thomas Eckel; Andreas Seidel; Uli Franz
Original assignee: Bayer Intellectual Property Gmbh
Priority date: 2009-12-08
Filing date: 2010-12-08
Publication date: 2013-09-13

Description

Composite component from polycarbonate/polyester compositions and polyurethane with improved adhesion

The invention provides a composite component having high toughness and stable bond adhesion, comprising a structure-imparting polycarbonate and/or polyester composition support having good processability and at least one polyurethane layer, and the use thereof and a method for producing the same.

WO 2006/072366 a1 describes a method for shaping and coating a substrate in a mould having at least two cavities. The method comprises the following steps:

a) shaping the substrate in a first cavity of a mold,

b) introducing the substrate produced in the preceding step into a second cavity of the mould, and

c) coating the substrate with a lacquer in the second cavity, wherein the coating is performed under increased pressure.

Polyurethane lacquers and PC + ABS substrates (polycarbonate + acrylonitrile-butadiene-styrene substrates) are mentioned as examples and are preferred. No description is given in this application of the influence of the support material composition on the adhesion properties of the composite material.

DE 102006048252B 3 discloses a method for producing a composite component, which comprises in particular an injection-molded part and a polyurethane element, with the following steps:

a) the support member is manufactured so that the support member,

b) the support member is introduced or transferred into the open mould cavity,

c) closing the mold to a predetermined position, wherein an enlarged cavity is created having a first size,

d) a reduced pressure is created in the enlarged cavity of the first size,

e) filling the enlarged cavity with a casting material, and

f) simultaneously and/or after filling with the casting material, an embossing step is carried out, in which the size of the cavity is at least slightly reduced.

In order to improve the bonding adhesion, it is described here that the surface of the thermoplastic is activated by baking, plasma impact (Plasmabeaufschlagung) or by gas. No description is given in this application of the influence of the support material composition on the adhesion properties of the composite material.

DE 102006033059 a1 discloses a method for producing plastic interior parts. In the method, the support is shaped in a first step in a first mold, wherein the first mold is then at least partially replaced by a second mold, and subsequently the cover layer is shaped on the support in a second step. In this method, a hard component, for example a PA + ABS blend (polyamide + acrylonitrile-butadiene-styrene) or a PC + ABS blend (polycarbonate + acrylonitrile-butadiene-styrene), is used as the support material, and a soft component, preferably a polyurethane foam, is used as the cover layer. No description is given in this application of the influence of the composition of the support material on the bonding properties of components produced in this way. In contrast, it is likewise proposed in DE 10206033059 a1 to prepare the surface by primer or laser-, corona-or plasma treatment in order to improve the adhesion.

WO 99/20464 discloses composites of at least two different plastic materials bonded directly to one another, wherein a) is a thermoplastic polymer or a thermoplastic mixture of polymers comprising at least one polar compound of at least one metal of main groups 1 to 5 or sub-groups 1 to 8 of the periodic table as an extremely finely distributed inorganic powder, and b) is a polyurethane, which is present as a foam, a lacquer or as a compact material. The composite does not require an adhesion promoter layer. No indication is given in this publication about the influence of the composition of the ABS-and rubber-containing support material on the adhesion properties of the composite.

DE 10109226 a1 discloses a polycarbonate composition comprising: a) aromatic polycarbonates and/or polyester carbonates, b) graft polymers and c) copolymers of styrene and carboxyl-containing monomers, wherein the copolymers have an average molecular weight Mw of > = 10500 g/mol, and wherein the copolymers may comprise one or more vinyl monomers. Component C is preferably a copolymer of styrene and maleic anhydride. DE 10109226 a1 further discloses composite components comprising at least one first layer (1) and one second layer (2), wherein layer (1) has at least a polycarbonate composition (as described under a, b and c) and layer (2) comprises at least polyurethane. The composite is characterized in that the foam adhesion between the layers (1, 2) is reduced by at most 35% after two alternating climate tests (KWT). No indication is given in this publication as to the effect of ABS and rubber content of the support material composition on the adhesion properties of the composite.

The object of the present invention is to provide alternative composite components having high toughness and improved bond adhesion, the use thereof and a method for producing said composite components, wherein the components comprise a support of a structure-imparting polycarbonate and/or polyester composition having good processability and at least one polyurethane layer.

In this context, the polyurethane layer may serve, for example, to improve the surface properties, tactile properties, visual properties, and to insulate noise and heat of the composite component.

The object of the invention is achieved by a composite component comprising:

a) a thermoplastic composition support comprising:

A) at least one polymer selected from the group consisting of aromatic polycarbonates, aromatic polyester carbonates and aromatic polyesters, the proportion of [ A ] being from 20.0 to 85.0 parts by weight, based on the sum of components A and B,

B) at least one rubber-modified vinyl (co) polymer, [ B ] based on the sum of components A and B]In an amount of 15.0 to 80.0 parts by weight, based on component B, of a rubber content [ K_B]Is at least 25.0 parts by weight, and

C) at least one polymer additive, the proportion of [ C ] being from 0 to 30.0 parts by weight, based on the sum of components A to C, and

b) at least one layer of polyurethane is applied to the substrate,

wherein the thermoplastic composition is characterized by a total rubber content of at least 12 parts by weight, based on the sum of components A and B.

The object of the invention is furthermore and preferably achieved by a composite component comprising:

a) a thermoplastic composition support comprising:

B) at least one rubber-modified vinyl (co) polymer, [ B ] based on the sum of components A and B]Based on component B, the rubber content [ K ] is 15.0 to 80.0 parts by weight_B]Is at least 25.0 parts by weight, and

b) at least one layer of polyurethane is applied to the substrate,

wherein the thermoplastic composition is characterized by

Quotient Q = [ B =]/[K_B] <2 and

rubber content [ K ] based on the sum of components A and B]=[K_B]∙[B]A/100 of at least 12 parts by weight.

Rubber content [ K ] of component B_B]Preferably from 25.0 to 80.0 parts by weight, more preferably from 25.0 to 50.0 parts by weight, in particular from 30.0 to 45.0 parts by weight.

The total rubber content and rubber content [ K ] is in each case at least 12 parts by weight, preferably at least 13 parts by weight, and particularly preferably at least 14 parts by weight, based in each case on the sum of components A and B.

The total rubber content and rubber content [ K ] is preferably up to 35 parts by weight, more preferably up to 30 parts by weight, particularly preferably 25 parts by weight, based in each case on the sum of components A and B, where the ranges can be freely combined from the upper and lower limits stated above.

The total rubber content and rubber content [ R ] is preferably from 12 to 35 parts by weight, more preferably from 13 to 30 parts by weight, and particularly preferably from 14 to 25 parts by weight, based in each case on the sum of components A and B.

In this context, the polyurethane layer can be, for example, a PU lacquer, a PU foam or a compact PU skin with a polyurethane layer thickness of, for example, 1 μm to 20 cm.

In a preferred embodiment, the polyurethane layer is a lacquer having a layer thickness of 1 to 1000 μm.

In another preferred embodiment, the polyurethane layer is a solid skin having a layer thickness of 1 mm to 10 mm.

In another preferred embodiment, the polyurethane layer is a foam having a layer thickness of 4 mm to 20 cm.

The composite component can in principle be manufactured in any known manner.

Preferably, the polyurethane layer is completely polymerized by a reactive polyurethane raw material mixture comprising:

-at least one polyisocyanate component,

at least one polyfunctional H-active compound, and

optionally at least one polyurethane additive and/or processing aid,

is prepared in direct contact with a support previously shaped and cured from the thermoplastic composition.

The support member may be prefabricated, for example, from a thermoplastic PC + ABS composition, and a reactive polyurethane raw material mixture may be applied thereon and fully reacted. Depending on the reactivity of the polyurethane reaction components, they can already be premixed or mixed in a known manner during application. The application can be carried out in particular by spraying, knife coating or calendering.

However, the composite according to the invention can also be produced by coextrusion by known methods.

In the case of foamed composites to be produced, the reaction mixture can be introduced in a manner known per se into a mold containing a preformed and cured support member. The mold may optionally contain an additional decorative layer (commonly referred to as a "skin") such as a polyvinyl chloride (PVC), Thermoplastic Polyolefin (TPO), Thermoplastic Polyurethane (TPU), or polyurethane spray skin. In the mold, the foamable reactive mixture expands into contact with the support member and optional decorative layer and forms a composite member. Here, the forming foaming may be performed such that the composite member has a honeycomb structure on the surface thereof. However, it is also possible to carry out this so that the composite component has a solid skin and a cellular core (integral foam). The polyurethane component can be introduced into the mold using a high or low pressure machine.

Polyurethane foams may also be made into slabstock foams.

The preparation of the polyurethane complex can also be carried out in a sandwich structure. In this context, the method can be arranged as a deposition build method (Depotverfahren) or an envelope build method (Hullbauferfahren). Deposition build-up methods and cladding build-up methods are known per se. In the deposition method (filling build-up), two half-shells (e.g. plastic cover layers) are prefabricated and placed in a mold and foamed with PU foam in the hollow space between the shells. In the cladding construction, a core of PU foam is placed in advance in a mold and then covered with a suitable cladding material, for example with one of the mentioned thermoplastics. The sandwich composite is preferably made in a jacket construction.

In a preferred embodiment of the invention, the composite component is produced by a method in which

(i) In a first method step a melt of the thermoplastic composition is injected into a first mold cavity and subsequently cooled,

(ii) in a second method step the cavity of the injection mold is enlarged and a gap space is thereby created,

(iii) in a third process step, a reactive polyurethane starting mixture comprising

-at least one polyisocyanate component,

at least one polyfunctional H-active compound, and

optionally at least one polyurethane additive and/or processing aid,

into the gap space between the thermoplastic component thus obtained and the mould surface of the enlarged cavity, wherein the polyurethane raw material mixture in direct contact with the surface of the thermoplastic support is completely polymerized to a compact polyurethane layer or to a polyurethane foam layer, and

(iv) in a fourth method step, the composite component is demolded from the mold cavity.

In a further preferred embodiment of the invention, the method steps (i) to (iv) in the production of the composite component are carried out immediately after one another.

The temperature of the workpiece is prevented from cooling to room temperature during processing by the process immediately following the run. Thereby achieving a reduction in production time and higher energy efficiency of the overall process.

In the case of a modification of the polyurethane system, the process steps (ii) and (iii) can be repeated at least once, wherein one or more polyurethane layers are applied only on one or both sides of the support, so that a composite component is obtained which is composed of a thermoplastic support and at least two identical or different PU assemblies having optionally also more than two-layer structures.

In method steps (ii) and (iv), the workpiece is cooled until the shape is stable before it is demolded.

In order to produce the gap in method step (ii), the injection mold can be opened and then one half of the injection mold cavity can be exchanged for a new half with a larger cavity size, or the component can be transferred from the first mold cavity into a cavity of the same mold with a larger cavity size or into a second mold, or the first cavity can be opened to the gap size.

The transfer of the substrate in process step (ii) can be carried out according to known methods, for example those used in multicolour injection moulding. Typical methods are, on the one hand, transfer by means of rotary feeders, turntables, sliding cavities (Schiebekavir ä t) or graduated disks or comparable methods in which the substrate is left in the center. If the substrate remains in the transfer center, this has the advantage that the position is also precisely defined after the transfer. Another aspect is a method of transferring a substrate known from the prior art, wherein the substrate is removed from one cavity and placed in another cavity, for example by means of an handling system. The transfer of the extraction substrate provides a greater design latitude in coating, for example, creating folds or coating in masked areas.

Composite components are preferred in which the quotient Q is less than 1.7, in particular less than 1.5.

The thermoplastic composition used for the manufacture of the composite member according to the invention preferably comprises:

A) from 30.0 to 64.9 parts by weight, in particular from 40.0 to 64.9 parts by weight, particularly preferably from 40.0 to 55.0 parts by weight, based on the sum of components A and B, of at least one polymer selected from the group consisting of aromatic polycarbonates, aromatic polyester carbonates and aromatic polyesters,

B) from 35.1 to 70.0 parts by weight, in particular from 35.1 to 60.0 parts by weight, particularly preferably from 45.0 to 60.0 parts by weight, based on the sum of components A and B, of at least one rubber-modified vinyl (co) polymer.

Component C) is preferably used in a portion of 0 to 20.0 parts by weight, in particular 0.1 to 10.0 parts by weight, based on the sum of components A to C.

The thermoplastic composition used for the production of the composite component according to the invention preferably comprises, as component a, a mixture of at least one aromatic polycarbonate and/or polyester carbonate and at least one aromatic polyester.

In a preferred embodiment, a thermoplastic polymer composition is used in the first process step which comprises: the composition exhibits a characteristic of more than 30 kJ/m in a notched impact test according to ISO 180-1A at room temperature and particularly preferably also at-30 DEG C²The notched impact toughness value of (a), and/or the fracture pattern of toughness (no fracture) in the impact penetration test according to ISO 6603.

The reactive polyurethane starting mixture used for producing the composite component according to the invention preferably has characteristic parameters of from > 80 to < 125, more preferably from > 100 to < 120, and particularly preferably from 105 to 115.

The characteristic parameter is defined as the percentage of the amount of isocyanate actually used to the calculated stoichiometric amount in the case of complete reaction of the polyol, i.e. the characteristic parameter = (amount of isocyanate used/amount of isocyanate stoichiometrically calculated) = 100.

In an alternative embodiment, thermoplastic polyurethanes can also be used instead of the reactive polyurethane raw material mixture.

In another preferred embodiment, in process step (iii), the surface of the injection mold which is brought into contact with the thermoplastic polymer composition is brought to a temperature in the range from 50 to 95 ℃, preferably from 60 to 85 ℃ and particularly preferably from 60 to 80 ℃.

In a further preferred embodiment, in process step (iii), the surface of the injection mold which is brought into contact with the reactive polyurethane mixture is brought to a temperature in the range from 50 to 160 ℃, preferably from 70 to 120 ℃, more preferably from 80 to 110 ℃ and particularly preferably from 90 to 100 ℃.

In a more preferred embodiment, in process step (iii), the surface of the injection mold which is in contact with the thermoplastic polymer composition is adjusted to a temperature in the range from 50 to 95 ℃, preferably from 60 to 85 ℃, and particularly preferably from 60 to 80 ℃, and the surface of the injection mold which is in contact with the reactive polyurethane mixture is adjusted to a temperature in the range from 50 to 160 ℃, preferably from 70 to 120 ℃, more preferably from 80 to 110 ℃, and particularly preferably from 90 to 100 ℃.

In the case of a foamed polyurethane system with a decorative layer, the surface of the foaming mold which is in contact with the thermoplastic polymer composition or with the decorative skin can in an alternative embodiment be adjusted to a temperature in the range from 20 to 80 ℃, preferably from 30 to 60 ℃.

The composite component according to the invention is particularly suitable as an interior or exterior component of a rail vehicle, aircraft or motor vehicle.

In a particularly preferred embodiment, the composite component exhibits a tough (non-brittle) fracture behaviour on a fracture image measured at-30 ℃ under multiaxial impact stress in an impact penetration test according to ISO 6603.

In a preferred embodiment, the bond adhesion between the polycarbonate composition support and the polyurethane coating in the composite component according to the invention is measured in a roller peeling test according to DIN 53357A at a test speed of 100 mm/min on a strip sample taken from the component and having a width of 20 mm at least 1N/mm.

The polymer composition used in the process according to the invention comprises:

component A

Suitable aromatic Polycarbonates and polyester carbonates according to the invention which are suitable for component A are known In the literature or can be prepared according to methods known In the literature (for the preparation of aromatic Polycarbonates see, for example, Schnell, "Chemistry and Physics of Polycarbonates", In-terscience Publishers, 1964 and DE-AS 1495626, DE-A2232877, DE-A2703376, DE-A2714544, DE-A3000610, DE-A3832396; for the preparation of aromatic polyester carbonates see, for example, DE-A3077934).

Aromatic polycarbonates and polyester carbonates are produced, for example, according to the phase interface process, optionally using chain terminators, for example monophenols, and optionally using trifunctional or more than trifunctional branching agents, for example triphenols or tetraphenols, by reaction of diphenols with carbonic acid halides, preferably phosgene, and/or with aromatic dicarboxylic acid dihalides, preferably benzenedicarboxylic acid dihalides. The preparation by the melt polymerization process by reaction of diphenols with, for example, diphenyl carbonate is also possible.

Diphenols for the preparation of the aromatic polycarbonates and/or aromatic polyester carbonates are preferably those of the formula (I)

(I)

Wherein

A is a single bond, C₁-C₅Alkylene group, C₂-C₅Alkylidene group, C₅-C₆Cycloalkylidene, -O-, -SO-, -CO-, -S-, -SO₂-、C₆-C₁₂Arylene which may be fused to other aromatic rings optionally containing heteroatoms,

or is a residue of formula (II) or (III)

(II)

(III)

B is in each case C₁-C₁₂Alkyl, preferably methyl, halogen, preferably chlorine and/or bromine

x is in each case independently of one another 0, 1 or 2,

p is 1 or 0, and

R⁵and R⁶For each X¹Can be selected independently of one another and represent hydrogen or C independently of one another₁-C₆Alkyl, preferably hydrogen, methyl or ethyl,

X¹represents carbon, and

m represents an integer from 4 to 7, preferably 4 or 5, with the proviso that at least one atom X¹Above, R⁵And R⁶And is an alkyl group.

Preferred diphenols are hydroquinone, resorcinol, dihydroxydiphenols, bis (hydroxyphenyl) -C₁-C₅Alkane, bis (hydroxyphenyl) C₅-C₆Cycloalkanes, bis (hydroxyphenyl) ethers, bis (hydroxyphenyl) sulfoxides, bis (hydroxyphenyl) ketones, bis (hydroxyphenyl) sulfones and α, α -bis (hydroxyphenyl) diisopropylbenzenes, and also their derivatives brominated and/or chlorinated on aromatic rings.

Particularly preferred diphenols are 4,4' -dihydroxydiphenyl, bisphenol A, 2, 4-bis (4-hydroxyphenyl) -2-methylbutane, 1-bis (4-hydroxyphenyl) cyclohexane, 1-bis (4-hydroxyphenyl) -3,3, 5-trimethylcyclohexane, 4' -dihydroxydiphenyl sulfide, 4' -dihydroxydiphenyl sulfone and their di-and tetrabrominated or chlorinated derivatives, such as, for example, 2-bis (3-chloro-4-hydroxyphenyl) propane, 2-bis (3, 5-dichloro-4-hydroxyphenyl) propane or 2, 2-bis (3, 5-dibromo-4-hydroxyphenyl) propane. 2, 2-bis (4-hydroxyphenyl) propane (bisphenol A) is particularly preferred.

The diphenols may be used individually or as arbitrary mixtures. The diphenols are known from the literature or obtainable by processes known from the literature.

Suitable chain terminators for the preparation of the thermoplastic, aromatic polycarbonates are, for example, phenol, p-chlorophenol, p-tert-butylphenol or 2,4, 6-tribromophenol, but also long-chain alkylphenols, such as 4- [2- (2,4, 4-trimethylpentyl) ] phenol, 4- (1, 3-tetramethylbutyl) phenol according to DE-A2842005, or monoalkylphenols or dialkylphenols having a total of from 8 to 20 carbon atoms in the alkyl substituents, such as 3, 5-di-tert-butylphenol, p-isooctylphenol, p-tert-octylphenol, p-dodecylphenol and 2- (3, 5-dimethylheptyl) phenol and 4- (3, 5-dimethylheptyl) phenol. The amount of chain terminators to be used is generally from 0.5mol% to 10mol%, based on the molar sum of the diphenols used in each case.

The thermoplastic aromatic polycarbonates may be branched in a known manner, and particularly preferably by the incorporation of 0.05 to 2.0mol%, based on the sum of the diphenols used, of trifunctional or more than trifunctional compounds, for example those having 3 or more phenolic groups.

Both homopolycarbonates and copolycarbonates are suitable. For the preparation of copolycarbonates according to the invention which are suitable as component A, it is also possible to use 1 to 25 wt.%, preferably 2.5 to 25 wt.%, based on the sum of diphenols to be used, of polydiorganosiloxanes with hydroxyaryloxy terminal groups. These are known (US 3419634) and can be prepared according to methods known in the literature. The preparation of copolycarbonates comprising polydiorganosiloxanes is described in DE-A3334782.

Preferred polycarbonates, in addition to the bisphenol A homopolycarbonates, are the copolycarbonates of bisphenol A with up to 15mol%, based on the molar sum of diphenols, of other diphenols mentioned as preferred or particularly preferred, in particular 2, 2-bis (3, 5-dibromo-4-hydroxyphenyl) propane.

Aromatic dicarboxylic acid dihalides for the preparation of aromatic polyester carbonates are preferably the diacid dichlorides of isophthalic acid, terephthalic acid, diphenyl ether-4, 4' -dicarboxylic acid and naphthalene-2, 6-dicarboxylic acid.

Mixtures of diacid dichlorides of isophthalic acid and terephthalic acid in a ratio between 1:20 and 20:1 are particularly preferred.

In the preparation of polyester carbonates, a carbonic acid halide, preferably phosgene, is additionally co-used as bifunctional acid derivative.

As chain terminators for the preparation of the aromatic polyester carbonates, it is also possible to use, in addition to the monophenols already mentioned, the chlorocarbonic esters of monophenols and optionally C₁－C₂₂Acid chlorides of alkyl or halogen-substituted aromatic monocarboxylic acids and aliphatic C₂－C₂₂A monocarboxylic acid chloride.

The amount of chain terminators is in each case from 0.1 to 10mol%, based in the case of phenolic chain terminators on moles of diphenols and in the case of monocarboxylic acid chloride chain terminators on moles of dicarboxylic acid dichlorides.

The aromatic polyester carbonates may also contain embedded aromatic hydroxycarboxylic acids.

The aromatic polyester carbonates may be linear or branched in a known manner (see DE-A2940024 and DE-A3007934 in this connection).

Branching agents which may be used are, for example, trifunctional or more than trifunctional carboxylic acid chlorides, such as trimesoyl chloride, cyanuric chloride, 3',4,4' -benzophenone tetracarbonyl chloride, 1,4,5, 8-naphthalenetetracarbonyl chloride or pyromellitic chloride, in amounts of from 0.01 to 1.0mol%, based on the dicarboxylic acid dichloride used, or trifunctional or more than trifunctional phenols, such as phloroglucinol, 4, 6-dimethyl-2, 4, 6-tris (4-hydroxyphenyl) hept-2-ene, 4, 6-dimethyl-2, 4, 6-tris (4-hydroxyphenyl) heptane, 1,3, 5-tris (4-hydroxyphenyl) benzene, 1,1, 1-tris (4-hydroxyphenyl) ethane, in amounts of from 0.01 to 1.0mol%, based on the diphenols used, Tris (4-hydroxyphenyl) phenylmethane, 2-bis [4, 4-bis (4-hydroxyphenyl) cyclohexyl ] propane, 2, 4-bis (4-hydroxyphenyl isopropyl) phenol, tetrakis (4-hydroxyphenyl) methane, 2, 6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, 2- (4-hydroxyphenyl) -2- (2, 4-dihydroxyphenyl) propane, tetrakis- (4- [ 4-hydroxyphenyl isopropyl ] phenoxy) methane, 1, 4-bis [4,4' - (dihydroxytriphenyl) methyl ] benzene. Phenolic branching agents may be introduced beforehand together with the diphenols, acid chloride branching agents may be introduced together with the acid dichlorides.

In the thermoplastic, aromatic polyester carbonates the proportion of carbonate structural units can be varied at will. The proportion of carbonate groups is preferably up to 100mol%, in particular up to 80mol%, particularly preferably up to 50mol%, based on the sum of ester groups and carbonate groups. The ester and carbonate constituents of the aromatic polyester carbonates may be present in the form of blocks or randomly distributed in the polycondensate.

Relative solution viscosity (. eta.) of aromatic polycarbonates and polyester carbonates_{Relative to each other}) Preferably in the range from 1.18 to 1.4, particularly preferably in the range from 1.20 to 1.32 (measured on solutions of 0.5g of polycarbonate or polyester carbonate in 100ml of methylene chloride solution at 25 ℃). The weight average molecular weights Mw of the aromatic polycarbonates and polyester carbonates, as measured by GPC (gel permeation chromatography with polycarbonate as standard in methylene chloride), are preferably in the range from 15000-35000, more preferably in the range from 20000-33000, and particularly preferably in the range from 23000-30000.

In a preferred embodiment, the aromatic polycarbonate suitable as component A according to the invention is a polyalkylene terephthalate. In a particularly preferred embodiment, these are reaction products of aromatic dicarboxylic acids or their reactive derivatives, such as dimethyl esters or anhydrides, and aliphatic, cycloaliphatic or araliphatic diols, and also mixtures of these reaction products.

Particularly preferred polyalkylene terephthalates contain at least 80 wt.%, preferably at least 90 wt.%, based on the dicarboxylic acid component, of terephthalic acid residues and at least 80 wt.%, preferably at least 90 mol.%, based on the diol component, of ethylene glycol and/or butane-1, 4-diol residues.

In addition to terephthalic acid residues, preferred polyalkylene terephthalates may contain up to 20 mol%, preferably up to 10mol%, of residues of other aromatic or cycloaliphatic dicarboxylic acids having 8 to 14C atoms or aliphatic dicarboxylic acids having 4 to 12C atoms, such as, for example, residues of phthalic acid, isophthalic acid, naphthalene-2, 6-dicarboxylic acid, 4' -diphenyldicarboxylic acid, succinic acid, adipic acid, sebacic acid, azelaic acid and cyclohexanediacetic acid.

In addition to ethylene glycol or butane-1, 4-diol residues, the preferred polyalkylene terephthalates may contain up to 20 mol%, preferably up to 10mol%, of other aliphatic diols having 3 to 12C atoms or cycloaliphatic diols having 6 to 21C atoms, such as propane-1, 3-diol, 2-ethylpropane-1, 3-diol, neopentyl glycol, pentane-1, 5-diol, hexane-1, 6-diol, cyclohexane-1, 4-dimethanol, 3-ethylpentane-2, 4-diol, 2-methylpentane-2, 4-diol, 2, 4-trimethylpentane-1, 3-diol, 2-ethylhexane-1, 3-diol, 2-diethylpropane-1, residues of 3-diol, hexane-2, 5-diol, 1, 4-di- (. beta. -hydroxyethoxy) benzene, 2-bis- (4-hydroxycyclohexyl) propane, 2, 4-dihydroxy-1, 1,3, 3-tetramethylcyclobutane, 2-bis- (4-. beta. -hydroxyethoxyphenyl) propane and 2, 2-bis- (4-hydroxypropoxyphenyl) propane (DE-A2407674, 2407776, 2715932).

The polyalkylene terephthalates may be branched, for example, according to DE-A1900270 and U.S. Pat. No. 3,692,744 by inserting relatively small amounts of 3-or 4-membered alcohols or 3-or 4-membered carboxylic acids. Examples of preferred branching agents are trimesic acid, trimellitic acid, trimethylolethane and-propane, and pentaerythritol.

Polyalkylene terephthalates which have been prepared solely from terephthalic acid and its reactive derivatives (e.g.its dialkyl esters) and ethylene glycol and/or butane-1, 4-diol, and mixtures of these polyalkylene terephthalates are particularly preferred.

The mixture of polyalkylene terephthalates contains 1 to 50 wt.%, preferably 1 to 30 wt.%, polyethylene terephthalate and 50 to 99 wt.%, preferably 70 to 99 wt.%, polybutylene terephthalate.

The polyalkylene terephthalates preferably used generally have an intrinsic viscosity of 0.4 to 1.5 dl/g, preferably 0.5 to 1.2 dl/g, measured in phenol/o-dichlorobenzene (1:1 parts by weight) at 25 ℃ in an Ubbelohde viscometer.

The polyalkylene terephthalates may be prepared according to known methods (see, for example, Kunststoff-Handbuch, volume VIII, p.695 et seq., Carl-Hanser-Verlag, Munich 1973).

Component B

Component B is a rubber-based graft polymer B.1 or a mixture of a rubber-based graft polymer B.1 and a rubber-free vinyl (co) polymer B.2, wherein the rubber content of component B is at least 25.0 parts by weight, relative to the sum of the components.

The rubber-based graft polymer B.1 used in component B comprises

B.1.1 from 5 to 95, preferably from 15 to 92, in particular from 25 to 60,% by weight, based on component B.1, of at least one vinyl monomer

B.1.2 based on component B.1, 95 to 5, preferably 85 to 8, in particular 75 to 40% by weight of one or more graft bases having a glass transition temperature of <10 ℃, preferably <0 ℃, particularly preferably < -20 ℃.

The glass transition temperature is measured by dynamic differential thermal analysis (DSC) according to standard DIN EN 61006 at a heating rate of 10K/min, Tg being defined as the midpoint temperature (tangent method).

The graft base B.1.2 generally has a mean particle diameter (d) of 0.05 to 10.00. mu.m, preferably 0.1 to 5.0. mu.m, particularly preferably 0.2 to 1.0. mu.m₅₀Value).

Average particle diameter d₅₀Is present in an amount of 50% by weight or more and lessThe diameter of the particles of (a). It can be determined by means of ultracentrifuge measurements (W. Scholtan, H. Lange, Kolloid, Z. und Z. Polymer 250 (1972), 782-1796).

The monomers B.1.1 are preferably mixtures of the following components:

b.1.1.1 parts, based on B.1.1, of from 50 to 99, preferably from 65 to 85, in particular from 75 to 80 parts by weight of vinylaromatic and/or vinylaromatic substituted on the aromatic ring (e.g.styrene,. alpha. -methylstyrene, p-chlorostyrene) and/or methacrylic acid- (C)₁-C₈) Alkyl esters (e.g. methyl methacrylate, ethyl methacrylate), and

b.1.1.2 based on B.1.1, 1 to 50, preferably 15 to 35, in particular 20 to 25 parts by weight of vinyl cyanides (unsaturated nitriles, such as acrylonitrile and methacrylonitrile) and/or (meth) acrylic acid- (C)₁-C₈) Alkyl esters, such as methyl methacrylate, N-butyl acrylate, t-butyl acrylate, and/or derivatives (such as anhydrides and imides) of unsaturated carboxylic acids, such as maleic anhydride and N-phenylmaleimide.

Preferred monomers B.1.1.1 are at least one selected from the group consisting of styrene, alpha-methylstyrene and methyl methacrylate, and preferred monomers B.1.1.2 are at least one selected from the group consisting of acrylonitrile, maleic anhydride and methyl methacrylate. Particularly preferred monomers are B.1.1.1 styrene and B.1.1.2 acrylonitrile.

Suitable graft bases B.1.2 for the graft polymers B.1 are, for example, diene rubbers, EP (D) M rubbers, i.e.those based on ethylene/propylene and optionally diene, acrylate-, polyurethane-, silicone-, chloroprene-and ethylene/vinyl acetate rubbers and silicone/acrylate composite rubbers.

Preferred grafting bases B.1.2 are, for example, diene rubbers based on butadiene and isoprene, or mixtures of diene rubbers or copolymers of diene rubbers or mixtures thereof with further copolymerizable monomers (for example according to B.1.1.1 and B.1.1.2), with the proviso that the glass transition temperature of component B.1.2 is below <10 ℃, preferably <0 ℃, particularly preferably < -20 ℃.

Pure polybutadiene rubber is particularly preferred as graft base B.1.2.

Particularly preferred polymers B.1 are, for example, ABS or MBS polymers, as described, for example, in DE-OS 2035390 (= US-PS 3644574) or in DE-OS 2248242 (= GB-PS 1409275) and in Ullmanns, Enzyklop ä die der Technischen Chemie, Vol.19 (1980), p.280 and the following pages.

The graft copolymers B.1 are prepared by free-radical polymerization, for example by emulsion, suspension, solution or bulk polymerization, preferably by emulsion or bulk polymerization, in particular by emulsion polymerization.

The graft base B.1.2 is preferably contained in the graft polymer B.1 prepared by the emulsion polymerization process in an amount of from 20 to 95% by weight, particularly preferably from 40 to 85% by weight, in particular from 50 to 75% by weight, based in each case on B.1.

The graft base B.1.2 is preferably contained in the graft polymer B.1 prepared in bulk in an amount of from 5 to 50% by weight, particularly preferably from 8 to 25% by weight, in particular from 10 to 20% by weight, based in each case on B.1.

The gel fraction of the graft base B.1.2 is at least 30% by weight, preferably at least 40% by weight, in particular at least 60% by weight, based in each case on B.1.2 and measured as the proportion of insolubles in toluene.

Particularly suitable graft rubbers are also ABS polymers which have been prepared by redox initiation with an initiator system of organic hydroperoxides and ascorbic acid according to U.S. Pat. No. 4,493,85.

Since it is known that the graft monomers are not necessarily grafted completely onto the graft base during the grafting reaction, graft polymers B.1 according to the invention are also understood to be those products which are prepared by (co) polymerization of the graft monomers in the presence of the graft base and which are produced together during processing. These products may therefore also comprise (co) polymers of free, i.e. not chemically bound, graft monomers to the rubber.

Suitable acrylate rubbers according to B.1.2 are preferably polymers of alkyl acrylates, optionally with up to 40% by weight, based on B.1.2, of further polymerizable ethylenically unsaturated monomers. Preferred polymerizable acrylates include C₁-C₈Alkyl esters, such as methyl, ethyl, butyl, n-octyl and 2-ethylhexyl esters; haloalkyl esters, preferably halo-C₁-C₈Alkyl esters, such as chloroethyl acrylate, and mixtures of these monomers.

Monomers having more than one polymerizable double bond may be copolymerized for crosslinking. Preferred examples of crosslinking monomers are esters of unsaturated monocarboxylic acids having 3 to 8C atoms with unsaturated monohydric alcohols having 3 to 12C atoms, or saturated polyols having 2 to 4 OH groups and 2 to 20C atoms, such as ethylene glycol dimethacrylate, allyl methacrylate; polyunsaturated heterocyclic compounds, such as trivinyl cyanurate and triallyl cyanurate; polyfunctional vinyl compounds, such as di-and trivinylbenzenes; and triallyl phosphate and diallyl phthalate. Preferred crosslinking monomers are allyl methacrylate, ethylene glycol dimethacrylate, diallyl phthalate and heterocyclic compounds containing at least three ethylenically unsaturated groups. Particularly preferred crosslinking monomers are the cyclic monomers triallyl cyanurate, triallyl isocyanurate, triacryloylhexahydro-s-triazine, triallylbenzenes. The amount of crosslinking monomers is preferably from 0.02 to 5.00, in particular from 0.05 to 2.00,% by weight, based on the graft base B.1.2. In the case of cyclic crosslinking monomers having at least three ethylenically unsaturated groups, it is advantageous to limit the amount to less than 1.00% by weight of the graft base B.1.2.

The preferred "other" polymerizable ethylenically unsaturated monomers which may optionally be used in addition to the acrylates for preparing the graft base B.1.2 are, for example, acrylonitrile, styrene, alpha-methylstyrene, acrylamide, vinyl-C₁-C₆Alkyl ethers, methyl methacrylate, butyleneAn alkene. Preferred acrylate rubbers as graft base B.1.2 are emulsion polymers having a gel content of at least 60% by weight.

Further suitable graft bases according to B.1.2 are silicone rubbers having graft-active sites, as described in DE-OS 3704657, DE-OS 3704655, DE-OS 3631540 and DE-OS 3631539.

The gel contents of the grafting base B.1.2 and of the graft polymer B.1 were determined as the content of insolubles in suitable solvents at 25 ℃ in these solvents (M. Hoffmann, H. Kr. nano-mer, R. Kuhn, Polymeranalytik I und II, Georg Thieme-Verlag, Stuttgart 1977).

Rubber-free vinyl (co) polymers suitable for component B.2 are preferably rubber-free homo-and/or copolymers selected from at least one of the following monomers: vinyl aromatic compound, vinyl cyanide (unsaturated nitrile), and (meth) acrylic acid (C)₁-C₈) Alkyl esters, unsaturated carboxylic acids and unsaturated carboxylic acid derivatives (such as anhydrides and imides).

Particularly suitable (co) polymers B.2 are obtained from:

b.2.1 from 50 to 99% by weight, preferably from 60 to 80% by weight, in particular from 70 to 80% by weight, based in each case on the total weight of the (co) polymer B.2, of at least one monomer selected from the group consisting of: vinylaromatic compounds, e.g. styrene,. alpha. -methylstyrene, vinylaromatic compounds substituted on the aromatic ring, e.g. p-methylstyrene, p-chlorostyrene, and (meth) acrylic acid- (C)₁-C₈) Alkyl esters, such as methyl methacrylate, n-butyl acrylate, t-butyl acrylate, and

b.2.2 from 1 to 50% by weight, preferably from 20 to 40% by weight, in particular from 20 to 30% by weight, based in each case on the total weight of the (co) polymer B.2, of at least one monomer selected from the group consisting of: vinyl cyanides, e.g. unsaturated nitriles, such as acrylonitrile and methacrylonitrile, (meth) acrylic acid- (C)₁-C₈) Alkyl esters, e.g. methyl methacrylate, n-butyl acrylate, propylTert-butyl alkenoates, unsaturated carboxylic acids and derivatives of unsaturated carboxylic acids, such as maleic anhydride and N-phenylmaleimide.

These (co) polymers B.2 are resinous, thermoplastic and rubber-free. Copolymers from B.2.1 styrene and B.2.2 acrylonitrile are particularly preferred.

Such (co) polymers B.2 are known and can be prepared by free-radical polymerization, in particular by emulsion, suspension, solution or bulk polymerization. The (co) polymers preferably have an average molecular weight Mw (weight average, measured by GPC) of between 15000 g/mol and 250000 g/mol, preferably in the range 80000-150000 g/mol.

Component C

The present compositions may comprise as component C a commercially available polymer additive. Suitable as commercially customary polymer additives for component C are additives such as flame retardants (for example phosphorus compounds, such as phosphoric or phosphonic esters, phosphonic acid amides and phosphazenes, or halogen compounds), flame-retardant synergists (for example nanoscale metal oxides), smoke-inhibiting additives (for example boric acid or borates), anti-drip agents (compounds of the substance class, for example fluorinated polyolefins, silicones and aramid fibers), internal and external lubricants and mold-release agents (for example pentaerythritol tetrastearate, stearyl stearate, montan wax or polyethylene wax), flow aids (for example low-molecular-weight vinyl (co) polymers), antistatic agents (for example block copolymers from ethylene oxide and propylene oxide, other polyethers or polyhydroxyethers, polyether amides, polyester amides or sulfonates), flame retardants, flame, Conductive additives (e.g. conductive carbon black or carbon nanotubes), nucleating agents, stabilizers (e.g. UV/light stabilizers, heat stabilizers, antioxidants, transesterification inhibitors, hydrolysis protectors), additives which act antibacterial (e.g. silver or silver salts), additives which improve scratch resistance (e.g. silicone oils or hard fillers, e.g. ceramic (hollow) spheres), IR absorbers, optical brighteners, fluorescent additives, fillers and reinforcing substances (e.g. talc, optionally ground glass or carbon fibers, glass or ceramic (hollow) spheres, mica, glass, carbon nanotubes,Kaolin, CaCO₃And glass flakes) as well as dyes and pigments (for example carbon black, titanium dioxide or iron oxide), impact modifiers which do not fall under the definition of B.1, and brensted acid compounds as alkali scavengers, or mixtures of a plurality of said additives.

Polyurethane

Preferably, polyurethane foams or compact polyurethane layers are used as coating materials.

The polyurethanes used according to the invention are obtained by reacting polyisocyanates with H-reactive polyfunctional compounds, preferably polyols.

The term "polyurethane" is also understood in the context of the present invention as a polyurethaneurea, in which those compounds having an N-H functionality are used as H-reactive polyfunctional compounds, optionally in admixture with polyols.

Suitable polyisocyanates are the aromatic, araliphatic, aliphatic or cycloaliphatic polyisocyanates known per se to the person skilled in the art with an NCO functionality of preferably 2 or more, which may also have iminooxadiazinedione-, isocyanurate-, uretdione-, urethane-, allophanate-, biuret-, urea-, oxadiazinetrione-, oxazolidinone-, acylurea-and/or carbodiimide structures. These may be used individually or in any proportion to each other.

The polyisocyanates mentioned are based here on di-or triisocyanates known per se to the person skilled in the art having aliphatically, cycloaliphatically, araliphatically and/or aromatically attached isocyanate groups, it being immaterial whether phosgene is used or else the preparation takes place according to a phosgene-free process. Examples of such di-or triisocyanates are 1, 4-diisocyanatobutane, 1, 5-diisocyanatopentane, 1, 6-diisocyanatohexane (HDI), 2-methyl-1, 5-diisocyanatopentane, 1, 5-diisocyanato-2, 2-dimethylpentane, 2, 4-or 2,4, 4-trimethyl-1, 6-diisocyanatohexane, 1, 10-diisocyanatodecane, 1, 3-and 1, 4-diisocyanatocyclohexane, 1, 3-and 1, 4-bis (isocyanatomethyl) cyclohexane, 1-diisocyanatomethylCyanate-3, 3, 5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 4' -diisocyanatodicyclohexylmethane (Desmodur)^®W, Bayer AG, levirkusen, germany), 4-isocyanatomethyl-1, 8-octane-diisocyanate (triisocyanatononane, TIN), ω' -diisocyanato-1, 3-dimethylcyclohexane (H)₆XDI), 1-isocyanato-1-methyl-3-isocyanatomethylcyclohexane, 1-isocyanato-1-methyl-4-isocyanatomethylcyclohexane, bis- (isocyanatomethyl) -norbornane, 1, 5-naphthalene-diisocyanate, 1, 3-and 1, 4-bis- (2-isocyanato-prop-2-yl) benzene (TMXDI), 2, 4-and 2, 6-diisocyanatotoluene (TDI), in particular the 2, 4-and 2, 6-isomers and technical-grade mixtures of these two isomers, 2,4 '-and 4,4' -diisocyanatodiphenylmethane (MDI), polymeric MDI (pMDI), 1, 5-diisocyanatonaphthalene, toluene, xylene, 1, 3-bis (isocyanatomethyl) benzene (XDI) and any mixture of said compounds.

The polyisocyanates here preferably have an average NCO functionality of 2.0 to 5.0, preferably 2.2 to 4.5, particularly preferably 2.2 to 2.7, and an isocyanate group content of 5.0 to 37.0% by weight, preferably 14.0 to 34.0% by weight.

In a preferred embodiment, polyisocyanates or polyisocyanate mixtures of the above-mentioned type having exclusively aliphatically and/or cycloaliphatically bound isocyanate groups are used.

Polyisocyanates of the above-mentioned type are most particularly preferably based on hexamethylene diisocyanate, isophorone diisocyanate, the isomeric bis- (4,4' -isocyanatocyclohexyl) methanes and mixtures thereof.

Among the higher molecular weight modified polyisocyanates, prepolymers with terminal isocyanate groups known from polyurethane chemistry in the molecular weight range 400-15000, preferably 600-12000, are of particular interest. These compounds are prepared in a manner known per se by reacting an excess of simple polyisocyanates of the type mentioned by way of example with organic compounds having at least two isocyanate-group-reactive groups, in particular organic polyhydroxyl compounds. Suitable polyols of this type are simple polyols having a molecular weight in the range from 62 to 599, preferably from 62 to 200, such as ethylene glycol, trimethylolpropane, propane-1, 2-diol or butane-1, 4-diol or butane-2, 3-diol, but in particular higher molecular weight polyether polyols and/or polyester polyols of the type known per se from polyurethane chemistry having a molecular weight of 600-12000, preferably 800-4000, and having at least two, usually 2 to 8, but preferably 2 to 6 primary and/or secondary hydroxyl groups. It is of course also possible to use, for example, those NCO prepolymers which result from low molecular weight polyisocyanates of the type mentioned by way of example with less preferred compounds having isocyanate-group-reactive groups, such as polythioether polyols, hydroxyl-containing polyacetals, polyhydroxy polycarbonates, polyester amides having hydroxyl groups, or hydroxyl-containing copolymers of ethylenically unsaturated compounds.

Compounds suitable for preparing NCO prepolymers having isocyanate-reactive groups, in particular hydroxyl groups, are, for example, the compounds disclosed in U.S. Pat. No. 3, 4218543. In the preparation of NCO prepolymers, these compounds having isocyanate group-reactive groups are reacted with simple polyisocyanates of the type mentioned by way of example above, under conditions such that an NCO excess is maintained. NCO prepolymers generally have an NCO content of from 10 to 26, preferably from 15 to 26,% by weight. It has been shown that, within the scope of the present invention, "NCO prepolymers" or "prepolymers having terminal isocyanate groups" are to be understood as meaning both reaction products and mixtures having an excess of unreacted starting polyisocyanates, which are also often referred to as "semiprepolymers".

As aliphatic diols having an OH number of > 500 mg KOH/g, chain extenders which are customarily used in polyurethane chemistry, such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butane-1, 4-diol, propane-1, 3-diol, can be considered. Diols such as 2-butane-1, 4-diol, butene-1, 3-diol, butane-2, 3-diol and/or 2-methylpropane-1, 3-diol are preferred. It is of course also possible to use aliphatic diols which are optionally mixed with one another.

Suitable as H-active components are polyols having an average OH number of from 5 to 600 mg KOH/g and an average functionality of from 2 to 6. Preference is given to polyols having an average OH number of from 10 to 50 mg KOH/g. Suitable polyols according to the invention are, for example, polyhydroxypolyethers which are obtainable by alkoxylation of suitable starter molecules, such as ethylene glycol, diethylene glycol, 1, 4-dihydroxybutane, 1, 6-dihydroxyhexane, dimethylolpropane, glycerol, pentaerythritol, sorbitol or sucrose. Ammonia or amines such as ethylenediamine, hexamethylenediamine, 2, 4-diaminotoluene, aniline or aminoalcohols, or phenols such as bisphenol a can likewise serve as starters. The alkoxylation is carried out using propylene oxide and/or ethylene oxide in any order or as a mixture.

In addition to the polyol, at least one further crosslinker and/or chain extender selected from the group comprising: amines and amino alcohols, such as ethanolamine, diethanolamine, diisopropanolamine, ethylenediamine, triethanolamine, isophoronediamine, N' -dimethyl (diethyl) -ethylenediamine, 2-amino-2-methyl (or ethyl) -1-propanol, 2-amino-1-butanol, 3-amino-1, 2-propanediol, 2-amino-2-methyl (ethyl) -1, 3-propanediol, and alcohols, such as ethylene glycol, diethylene glycol, 1, 4-dihydroxybutane, 1, 6-dihydroxyhexane, dimethylolpropane, glycerol and pentaerythritol, and sorbitol and sucrose, or mixtures of these compounds.

Suitable are, furthermore, polyester polyols, such as are obtainable by reacting low molecular weight alcohols with polycarboxylic acids, such as adipic acid, phthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid or the anhydrides of these acids, in a manner known per se, provided that the viscosity of the H-active component does not become too high. A preferred polyol having an ester group is castor oil. In addition, formulations with castor oil, which can be obtained, for example, by dissolving resins such as aldehyde-ketone resins, and also modifications of castor oil and polyols based on other natural oils are also suitable.

Higher molecular weight polyhydroxypolyethers in which the high molecular weight addition or condensation polymers or polymers are present in homogeneously dispersed, dissolved or grafted form are likewise suitable. Such modified polyhydroxyl compounds are obtained in a manner known per se, for example by carrying out a polyaddition reaction (for example between a polyisocyanate and an amino-functional compound) or a polycondensation reaction (for example between formaldehyde and a phenol and/or an amine) in situ of the compound having hydroxyl groups. However, it is also possible to mix the aqueous polymer dispersion produced with the polyol and subsequently remove the water from the mixture.

Polyols modified by vinyl polymers, such as are obtained, for example, by polymerization of styrene and acrylonitrile in the presence of polyether or polycarbonate polyols, are also suitable for the preparation of polyurethanes. In the case of the use of polyether polyols modified by graft polymerization with vinylphosphonates and optionally (meth) acrylonitrile, (meth) acrylamides or OH-functional (meth) acrylates according to DE-A2442101, DE-A2844922 and DE-A2646141, plastics having special flame retardancy are obtained.

Representative of the compounds mentioned as H-active compounds are described, for example, in High Polymers, volume XVI, "Polyurethanes Chemistry and Technology", Saunders-Friech (eds.) Interscience Publishers, New York, London, volumes 1, 32-42, 44, 54 and volumes II, 1984, pages 5-6 and 198-199.

Mixtures of the compounds listed may also be used.

The increased brittleness of the resulting polyurethanes in particular imposes limitations on the average OH number and average functionality of the H-reactive components. However, the possibilities of influencing the polymer physical properties of polyurethanes are known in principle to the person skilled in the art, and therefore the NCO component, the aliphatic diols and the polyols can be coordinated with one another in an advantageous manner.

The polyurethane layer (b) may be foamed or solid, for example present as a lacquer or coating.

All auxiliaries and additives known per se, such as mold release agents, blowing agents, fillers, catalysts and flame retardants, can be used for their preparation.

The auxiliaries and additives which may optionally be used here are:

a) water and/or volatile inorganic or organic substances as blowing agents

Suitable as organic blowing agents are, for example, acetone, ethyl acetate, halogen-substituted alkanes, such as methylene chloride, chloroform, dichloroethane, vinylidene chloride, trichlorofluoromethane, chlorodifluoromethane, dichlorodifluoromethane, furthermore butane, hexane, heptane or diethyl ether, suitable as inorganic blowing agents are air, CO₂Or N₂And O. Foaming may also be achieved by the addition of compounds which decompose at temperatures above room temperature, separating off gases such as nitrogen, for example azo compounds, such as azodicarbonamide or azobisisobutyronitrile.

b) Catalyst and process for preparing same

The catalyst is for example

Tertiary amines (e.g. triethylamine, tributylamine, N-methylmorpholine, N-ethylmorpholine, N, N, N ', N ' -tetramethylethylenediamine, pentamethyldiethylenetriamine and higher homologues, 1, 4-diazabicyclo- (2,2,2) octane, N-methyl-N ' -dimethylaminoethylpiperazine, bis- (dimethylaminoalkyl) piperazine, N, N-dimethylbenzylamine, N, N-dimethylcyclohexylamine, N, N-diethylbenzylamine, bis- (N, N-diethylaminoethyl) adipate, N, N, N ', N ' -tetramethyl-1, 3-butanediamine, N, N-dimethyl- β -phenylethylamine, 1, 2-dimethylimidazole, 2-methylimidazole),

mono-and bicyclic amides, bis- (dialkylamino) alkyl ethers,

tertiary amines having an amide group (preferably a carboxamide group),

mannich bases from secondary amines, such as dimethylamine, and aldehydes, preferably formaldehyde, or ketones, such as acetone, methyl ethyl ketone or cyclohexanone, and phenols, such as phenol, nonylphenol or bisphenol,

tertiary amines having hydrogen atoms reactive toward isocyanate groups, such as triethanolamine, triisopropanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-dimethylethanolamine and reaction products thereof with alkylene oxides, such as propylene oxide and/or ethylene oxide,

a secondary tertiary amine, a tertiary amine,

silamines having carbon-silicon bonds (2,2, 4-trimethyl-2-silamorpholine and 1, 3-diethylaminomethyl tetramethyldisiloxane),

a nitrogenous base (such as a tetraalkylammonium hydroxide),

alkali metal hydroxides (e.g., sodium hydroxide), alkali metal phenolates (e.g., sodium phenolate),

alkali metal alkoxides (e.g. sodium methoxide) and/or

Hexahydrotriazine.

The reaction between the NCO groups and the Zerewitinoff-active hydrogen atoms is also strongly accelerated in a manner known per se by lactams and azalactams, in which firstly an association is formed between lactam and compound having an acidic hydrogen.

Organometallic compounds, in particular organotin and/or bismuth compounds, can also be used as catalysts. In addition to sulfur-containing compounds, there come into consideration, for example, di-n-octyltin mercaptide, preferably tin (II) salts of carboxylic acids, such as tin (II) acetate, tin (II) octanoate, tin (II) ethylhexanoate and tin (II) laurate, and tin (IV) compounds, such as dibutyltin oxide, dibutyltin dichloride, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate or dioctyltin diacetate, as organotin compounds. Organobismuth catalysts are described, for example, in patent application WO 2004/000905.

Of course, all of the above-mentioned catalysts can be used as mixtures. Of particular interest herein are combinations of organometallic compounds and amidines, aminopyridines or hydrazinopyridines.

The catalysts are generally used in amounts of about 0.001 to 10% by weight, based on the total amount of compounds having at least two isocyanate-reactive hydrogen atoms.

c) Surface-active additives, such as emulsifiers and foam stabilizers.

Suitable emulsifiers are, for example, the sodium salt of castor oil sulfonate or the salts of fatty acids with amines, such as oleic acid diethylamine or stearic acid diethanolamine. It is also possible to use sulfonic acids such as dodecylbenzenesulfonic acid or dinaphthylmethanedisulfonic acid, or alkali metal-or ammonium salts of fatty acids such as ricinoleic acid or polymerized fatty acids together as surface-active additives.

Suitable foam stabilizers are, in particular, polyether siloxanes, in particular water-soluble representatives. These compounds are generally constructed such that a copolymer of ethylene oxide and propylene oxide is bonded to the polydimethylsiloxane residue. Of particular interest are polysiloxane/polyoxyalkylene copolymers which are multiply branched via allophanate groups.

d) Reaction retarder

Suitable reaction retarders are, for example, acidic reactive substances (e.g. hydrochloric acid or organic acid halides).

e) Additive agent

Suitable PU additives are, for example, cell regulators of a type known per se (e.g.paraffins or fatty alcohols) or dimethylpolysiloxanes and pigments or dyes and flame retardants of a type known per se (e.g.trichloroethyl phosphate, tricresyl phosphate or phosphoric acid-and ammonium polyphosphates), stabilizers against ageing and weathering, plasticizers and substances which inhibit fungi and bacteria, and also fillers (e.g.barium sulfate, diatomaceous earth, carbon black or chalk powder).

Further examples of surface-active additives and foam stabilizers and cell regulators, reaction retarders, stabilizers, flame-retardant substances, plasticizers, dyes and fillers and fungistatically and bacteriostatic active substances which are optionally used together according to the invention are known to the person skilled in the art and are described in the literature.

Examples

Polycarbonate compositions

Components A

Components A-1

Having a weight-average molecular weight M of 28000 g/mol_wA bisphenol A-based linear polycarbonate.

Components B

Components B-1

An ABS polymer having a acrylonitrile to butadiene to styrene weight ratio of 20:18:62 parts by weight.

Components B-2

An ABS polymer having a acrylonitrile to butadiene to styrene weight ratio of 20:26:54 parts by weight.

Components C

C-1: Pentaerythritol tetrastearate (PETS) as a lubricant/mold release agent

C-2: Irganox B900A mixture of 80 wt% Irgafos 168 (tris- (2, 4-di-tert-butyl) phenyl phosphite) and 20 wt% Irganox 1076 (octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate) (BASF, Germany)

C-3: Irganox 1076 octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (BASF, Germany)

C4 carbon black as pigment.

Reactive polyurethane raw material mixture

A mixture of Bayflex VP 47IF01A (polyol component) and Desmodur VP 48IF30 (diisocyanate component), both from Bayer MaterialScience AG, Leverkusen, Germany, having a characteristic value of 95 was used as polyurethane coating system.

Bayflex VP. PU 47IF01A is a polyol based on a long-chain polyether, comprising ethylene glycol, diethanolamine, isophoronediamine, having a viscosity of 1600 mPas at 20 ℃ according to DIN 53019 and 1.04 g/cm at 20 ℃ according to DIN 51757³And a hydroxyl number of 166 mg KOH/g.

Desmodur VP. PU 48IF30 is an aliphatic isocyanate based on isophorone diisocyanate (IPDI) having an NCO content of 30.5% by weight according to DIN EN ISO 11909, a viscosity of 200 mPas at 23 ℃ according to DIN EN ISO 3219/A.3 and 1.1 g/cm at 20 ℃ according to DIN EN ISO 2811³The density of (c).

Preparation and characterization of polycarbonate Molding materials

The raw materials listed in Table 1 were compounded on a twin-screw extruder (ZSK-25) (Werner und Pfleiderer) at a rotational speed of 220 revolutions per minute and with a throughput of 20 kg/h at a melt temperature in the range of 260 ℃ and 280 ℃ and granulated after the melt of the compound had cooled and solidified.

The pellets, each resulting from compounding, were processed on an injection molding machine (Arburg) at a melt temperature of 260 ℃ and a mold temperature of 80 ℃ into test specimens of dimensions 80 mm x 10 mm x 4 mm.

The sizes mentioned in the present application are measured by the following method, if not otherwise stated.

Ductility of the moulding compositions by means of notched impact strength values a measured at 23 ℃ and-30 ℃ according to ISO 180-1A on these test specimens_kTo evaluate.

The heat distortion temperature is evaluated by means of the Vicat B120 value determined according to ISO 306 on these test specimens.

Melt flowProperties were determined by means of the method according to ISO 11443 at 260 ℃ and 1000 s^-1Is evaluated by the melt viscosity measured at the shear rate.

The bond adhesion between the polycarbonate composition substrate and the polyurethane skin was measured by the roller peeling test according to DIN 53357A at a test speed of 100 mm/min on a strip sample of 20 mm width sawn from a partially PU-coated 2-component composite sheet produced in this manner.

Production of composite components

A412 cm section was made on an injection molding machine with two cavities (one substrate side cavity and one polyurethane side coating cavity attached to the RIM apparatus)²A molded article having a projected area with a surface portion coated. The composite member is a flat plate-like thermoplastic plastic member (support) whose surface is partially coated with a polyurethane skin. The wall thickness supporting the molded article was about 4 mm. The polyurethane layer thickness is likewise 4 mm.

The method according to the invention for producing a composite component according to the invention, described in the examples, is shown in fig. 1 for better illustration.

In a first method step, a supporting molded part is produced. For this purpose, thermoplastic pellets of the composition as described in table 1 were melted in an injection molding barrel and injected at a temperature of 270 ℃ into a first mold cavity of a closed mold (steps 1 and 2 in fig. 1). The mold cavity temperature was controlled to a temperature of 80 ℃. After the dwell time and the cooling time leading to the solidification of the support have ended, the mold is opened in a second method step (step 3 in fig. 1). Here, the produced support member is held on the casting ejector side of the injection mold and is completely advanced from the support position (step 3 in fig. 1) together with the mold core via the sliding element into the coating position (step 4 in fig. 1). Subsequently, the injection mold is closed again (step 5 in fig. 1), a closing force of a maximum pressure of 200 bar is established, and the solvent-free reactive polyurethane system (see above) is injected into the coating cavity at a pressure of about 30 bar in a third process step (step 6 in fig. 1). Here, the two reactive components of the polyurethane coating system are conveyed by the RIM unit into a high-pressure counter-current mixing head and mixed there before injection. Here, the cavity temperature of the PU side was controlled to a temperature of 80 ℃. After the end of the injection, the injection nozzle of the polyurethane mixing head is sealed by means of a hydraulic cylinder at an initial pressure of 50 bar to prevent backflow of the coating material. After the end of the reaction and cooling time, the mold is opened again in a fourth method step (step 7 in fig. 1) and the coated mold is removed from the mold (step 8 in fig. 1).

Table 1 shows the effect of the support composition on the adhesion between the layers of the composite member. This example shows the rubber content [ K ] in component B based on the sum of A and B_B]And the positive surprising effect of an increase in the rubber content of the composition on supporting adhesion to the PU skin.

Table 1:

	1(V)	2
			A1	50	50
B1	50
			B2		50
C1	0.75	0.75
			C2	0.10	0.10
C3	0.20	0.20
			C4	0.2	0.2
[K_B]	18	26
			[K]	9	13
quotient Q	2.8	1.9
			Supporting adhesion to PU skin [ N/mm ]]	0.38	1.1
ak (23℃)－260℃[KJ/m²]	48	41
			ak (-30℃)－260℃[KJ/m²]	27	56
Vicat B 120 [℃]	110.3	115.6
			Melt viscosity (260 ℃/1,000) s^-1( [Pa·s]	186	236

The claims (modification according to treaty clause 19)

1. A composite member comprising:

a) a thermoplastic composition support comprising:

B) at least one rubber-modified vinyl (co) polymer, [ B ] based on the sum of components A and B]Has a rubber content [ K ] of 15.0 to 80.0 parts by weight, based on component B_B]Is at least 25.0 parts by weight, and

b) at least one layer of polyurethane is applied to the substrate,

wherein the thermoplastic composition is characterized by a total rubber content of at least 12 parts by weight, based on the sum of components A and B, and in that the supported thermoplastic composition comprises:

A) from 30.0 to 64.9 parts by weight, based on the sum of components A and B, of at least one polymer selected from the group consisting of aromatic polycarbonates, aromatic polyester carbonates and aromatic polyesters, and

B) 35.1 to 70.0 parts by weight, based on the sum of components A and B, of at least one rubber-modified vinyl (co) polymer.

2. A composite member comprising:

a) a thermoplastic composition support comprising:

A) at least one polymer selected from the group consisting of aromatic polycarbonates, aromatic polyester carbonates and aromatic polyesters, the proportion of [ A ] being from 30.0 to 64.9 parts by weight, based on the sum of components A and B,

B) at least one rubber-modified vinyl (co) polymer, [ B ] based on the sum of components A and B]Has a rubber content [ K ] of 35.1 to 70.0 parts by weight, based on component B_B]Is at least 25.0 parts by weight, and

C) at least one polymer additive, based on the sum of components A to C, the content of [ C ] being from 0 to 30.0 parts by weight, and

b) at least one layer of polyurethane is applied to the substrate,

wherein the thermoplastic composition is characterized by

<Quotient Q = [ B ] of 2]/[K_B]And

3. Composite component according to one of claims 1 or 2, characterized in that the supported thermoplastic composition comprises:

A) from 40.0 to 64.9 parts by weight, based on the sum of components A and B, of at least one polymer selected from the group consisting of aromatic polycarbonates, aromatic polyester carbonates and aromatic polyesters, and

B) from 35.1 to 60 parts by weight, based on the sum of components A and B, of at least one rubber-modified vinyl (co) polymer.

4. Composite component according to one of claims 2 to 3, characterized in that the quotient Q is less than 1.7, in particular less than 1.5.

5. Composite component according to one of claims 1 to 4, characterized in that at least one aromatic polycarbonate and/or a mixture of polyester carbonates and at least one aromatic polyester is used as component A.

6. Composite component according to one of the preceding claims, characterized in that the polyurethane layer is completely polymerized by means of a reactive polyurethane raw material mixture comprising:

-at least one polyisocyanate component,

at least one polyfunctional H-active compound, and

-optionally at least one polyurethane additive and/or processing aid,

to be prepared in direct contact with a support previously shaped and cured from the thermoplastic composition.

7. Composite component according to one of the preceding claims, characterized in that the polyurethane layer is completely polymerized by means of a reactive polyurethane raw material mixture comprising:

-at least one polyisocyanate component,

at least one polyfunctional H-active compound, and

-optionally at least one polyurethane additive and/or processing aid,

on one side, in direct contact with a support previously shaped and cured from a thermoplastic composition, and on the other side, in direct contact with a decorative skin, optionally composed of polyvinyl chloride (PVC), Thermoplastic Polyolefin (TPO), Thermoplastic Polyurethane (TPU), or a polyurethane jet skin.

8. Composite component according to claim 6 or 7, characterized in that the reactive polyurethane raw material mixture has a characteristic value of > 80 to < 125.

9. Composite component according to one of the preceding claims, characterized in that component C is represented by at least one selected from the following group: flame retardants, flame-retardant synergists, smoke-inhibiting additives, anti-dripping agents, internal and external lubricants and mold release agents, flow aids, antistatic agents, conductive additives, nucleating agents, stabilizers, additives which act as antibacterial agents, additives which improve scratch resistance, IR absorbers, optical brighteners, fluorescent additives, fillers and reinforcing substances, dyes and pigments, impact modifiers which do not fall under the definition of B.1, and Brenstedt acid compounds.

10. Composite component according to one of the preceding claims, produced by a method, wherein

-at least one polyisocyanate component,

at least one polyfunctional H-active compound, and

optionally at least one polyurethane additive and/or processing aid,

into the gap space between the thermoplastic component thus obtained and the mould surface of the enlarged cavity, wherein the polyurethane raw material mixture in direct contact with the surface of the thermoplastic support is completely polymerized to a compact polyurethane layer or a polyurethane foam layer is obtained,

(iv) in a fourth method step, the composite component is demolded from the mold cavity, wherein method steps (i) to (iv) are carried out directly after one another.

11. Method for manufacturing a composite component according to one of claims 1 to 10,

-at least one polyisocyanate component,

at least one polyfunctional H-active compound, and

optionally at least one polyurethane additive and/or processing aid,

12. The process according to claim 11, characterized in that in process step (iii) the surface temperature of the injection mold in contact with the thermoplastic composition is controlled at a temperature in the range from 50 to 95 ℃ and the surface temperature of the injection mold in contact with the reactive polyurethane mixture is controlled at a temperature in the range from 50 to 160 ℃.

13. Use of a composite component according to one of claims 1 to 10 as an interior or exterior component of a rail vehicle, aircraft or motor vehicle.

Claims

1. A composite member comprising:

a) a thermoplastic composition support comprising:

B) at least one rubber-modified vinyl (co) polymer, [ B ] based on the sum of components A and B]Has a rubber content [ K ] of 15.0 to 80.0 parts by weight, based on component B_B]Is at least25.0 parts by weight, and

b) at least one layer of polyurethane is applied to the substrate,

2. A composite member comprising:

a) a thermoplastic composition support comprising:

B) at least one rubber-modified vinyl (co) polymer, [ B ] based on the sum of components A and B]In an amount of 15.0 to 80.0 parts by weight, based on component B, having a rubber content [ K_B]Is at least 25.0 parts by weight, and

b) at least one layer of polyurethane is applied to the substrate,

wherein the thermoplastic composition is characterized by

<Quotient Q = [ B ] of 2]/[K_B]And

4. Composite component according to one of claims 1 or 2, characterized in that the supported thermoplastic composition comprises:

5. Composite component according to one of claims 2 to 4, characterized in that the quotient Q is less than 1.7, in particular less than 1.5.

6. Composite component according to one of claims 1 to 5, characterized in that at least one aromatic polycarbonate and/or a mixture of polyester carbonates and at least one aromatic polyester is used as component A.

-at least one polyisocyanate component,

at least one polyfunctional H-active compound, and

-optionally at least one polyurethane additive and/or processing aid,

8. Composite component according to one of the preceding claims, characterized in that the polyurethane layer is completely polymerized by means of a reactive polyurethane raw material mixture comprising:

-at least one polyisocyanate component,

at least one polyfunctional H-active compound, and

optionally at least one polyurethane additive and/or processing aid,

9. Composite component according to claim 7 or 8, characterized in that the reactive polyurethane raw material mixture has a characteristic value of > 80 to < 125.

10. Composite component according to one of the preceding claims, characterized in that component C is represented by at least one selected from the following group: flame retardants, flame-retardant synergists, smoke-inhibiting additives, anti-dripping agents, internal and external lubricants and mold release agents, flow aids, antistatic agents, conductive additives, nucleating agents, stabilizers, additives which act as antibacterial agents, additives which improve scratch resistance, IR absorbers, optical brighteners, fluorescent additives, fillers and reinforcing substances, dyes and pigments, impact modifiers which do not fall under the definition of B.1, and Brenstedt acid compounds.

11. Composite component according to one of the preceding claims, produced by a method, wherein

-at least one polyisocyanate component,

at least one polyfunctional H-active compound, and

optionally at least one polyurethane additive and/or processing aid,

12. Method for manufacturing a composite component according to one of claims 1 to 11,

-at least one polyisocyanate component,

at least one polyfunctional H-active compound, and

optionally at least one polyurethane additive and/or processing aid,

injecting the gap space between the thermoplastic component thus obtained and the mould surface of the enlarged cavity, wherein the polyurethane raw material mixture in direct contact with the surface of the thermoplastic support is completely polymerized into a compact polyurethane layer or a polyurethane foam layer is obtained,

13. The process according to claim 12, characterized in that in process step (iii) the surface temperature of the injection mold in contact with the thermoplastic composition is controlled at a temperature in the range from 50 to 95 ℃ and the surface temperature of the injection mold in contact with the reactive polyurethane mixture is controlled at a temperature in the range from 50 to 160 ℃.

14. Use of a composite component according to one of claims 1 to 11 as an interior or exterior component of a rail vehicle, aircraft or motor vehicle.