DE19822248A1 - Polyalkylene terephthalate-based molding materials with improved mechanical and thermal properties - Google Patents

Abstract

UV-stabilizers for thermoplastic molding materials based on polyalkylene terephthalate and/or polyamide comprise aryl esters of 4-hydroxy-benzoic acid with at least 2 branched alkyl substituents and/or (meth)acrylate copolymers with units containing optionally 2,2,6,6-tetra-alkyl-substituted piperidin-4-yl ester groups. Thermoplastic molding materials containing polyalkylene terephthalate and/or polyamide and (B) at least one UV-stabilizer selected from (B1) compound(s) of formula (I) and (B2) (meth)acrylate copolymers with repeating units of formula (II): in which: R<1>-R<3> = H or 1-10C alkyl, provided that at least two of these groups are branched 3-10C alkyl; R<4>-R<7> = H or 1-6C alkyl. An Independent claim is also included for molded products obtained from these materials.

Description

The present invention relates to thermoplastic molding compositions Polyalkylene terephthalate, the UV stabilizers based on z. B. of 2,4-di-tert-butyl-4- hydroxibenzoate (CAS # 4221-80-1) and / or based on a polymer, steric hindered amine (CAS # 115340-81-3) included.

The use of the above-mentioned UV stabilizers in polymeric molding compositions for UV stabilization is known and in the brochure "UV Check, Light Stabilizers for Polymers "from Bedford Chemical Division, Ferro Corporation, Krick Road, Wal ton Hills, OH 44146 U.S.A., U.S. Patent No. 3,189,615, U.S. Patent No. 3,004,896, EP-A 416 404.

However, it is not known that the addition of the UV stabilizers mentioned Thermoplastics surprisingly in addition to the desired improvement in UV Stabilization also better toughness, ductility and stabilization at thermi shear stress with a simultaneous increase in flow behavior (Processing behavior) can be achieved.

The molding compositions according to the invention can be used to produce moldings be used, the good elongation and toughness behavior and a good flow ratio hold have.

The molding compositions according to the invention also have good thermostable behavior with aging.

The invention relates to thermoplastic molding compositions containing

• A) polyalkylene terephthalate and / or polyamide and
• B) at least one UV stabilizer selected from
  • B1) one or more compounds of the formula (I)
    wherein
    R ¹ , R ² and R ³ independently of one another are hydrogen or C ₁ -C ₁₀ alkyl, at least two of the radicals R ¹ , R ² and R ³ being iso-branched C ₃ -C ₁₀ alkyl, preferably isopropyl Butyl, tert-butyl,
  • B2) an acrylate / methyl methacrylate copolymer based on the repeating unit (II)
    wherein
    R ^{4 represents} hydrogen or C ₁ -C ₆ alkyl, preferably hydrogen,
    R ⁵ and R ⁶ each independently represent hydrogen or C ₁ -C ₆ alkyl, preferably C ₁ -C ₄ alkyl, in particular methyl and / or ethyl,
    R ^{7 represents} C ₁ -C ₆ alkyl, preferably C ₁ -C ₄ alkyl, in particular methyl.

The content of component A) is generally 97.5 to 99.99, preferably 99.98 to 99, in particular 99.97 to 99.6 parts by weight. The UV stabilizer content is generally 0.01 to 2.5, preferably 0.02 to 1, in particular 0.03 to 0.4 parts by weight, both individually (B1, B2) or as a combination of the individual components B1 and B2 (based on the total mixture).

Polyalkylene terephthalates (component A) in the context of the invention are reaction products made from aromatic dicarboxylic acid or its reactive derivatives (e.g. dimethyl esters or anhydrides) and aliphatic, cycloaliphatic or araliphatic diols and mixtures of these reaction products.

Preferred polyalkylene terephthalates can be derived from terephthalic acid (or its reactive derivatives) and aliphatic or cycloaliphatic diols with 2 Manufacture up to 10 carbon atoms using known methods (Kunststoff-Handbuch, Vol. VIII, p. 695 FF, Karl-Hanser-Verlag, Munich 1973).

Preferred polyalkylene terephthalates contain at least 80, preferably 90 mol%, based on the dicarboxylic acid, terephthalic acid residues and at least 80, preferably at least 90 mol%, based on the diol component, ethyl lenglycol and / or 1,4-butanediol residues.

The preferred polyalkylene terephthalates can besides terephthalic acid residues 20 mol% of residues of other aromatic dicarboxylic acids with 8 to 14 carbon atoms or contain aliphatic dicarboxylic acids with 4 to 12 carbon atoms, such as residues of  Phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, 4,4'-diphenyldicarbon acid, succinic, adipic, sebacic, azelaic, cyclohexanediacetic acid.

In addition to ethylene or butanediol, the preferred polyalkylene terephthalates can 1,4-glycol residues up to 20 mol% of other aliphatic diols with 3 to 12 C- Contain atoms or cycloaliphatic diols with 6 to 21 carbon atoms, for. B. Leftovers 1,3-propanediol, 2-1,3-propanediol, neopentylglycol, 1,5-pentanediol, Hexanediol-1,6, cyclohexane-dimethanol-1,4, 3-methylpentanediol-2, 4,2-methyl pentanediol-2,4, 2,2,4-trimethylpentanediol-1,3 and -1,6,2-ethylhexanediol-1,3 2,2- 1,3-diethyl propanediol, 2,5-hexanediol, 1,4-di (β-hydroxyethoxy) benzene, 2,2-bis (4-hydroxycyclohexyl) propane, 2,4-dihydroxy-1,1,3,3-tetramethyl-cyclobutane, 2,2-bis (3-β-hydroxyethoxyphenyl) propane and 2,2-bis (4-hydroxypropoxyphenyl) - propane (DE-OS 24 07 674, 24 07 776, 27 15 932).

The polyalkylene terephthalates can be 3- or by incorporating relatively small amounts 4-valent alcohols or 3- or 4-basic carboxylic acid, such as z. B. in the DE-OS 19 00 270 and US Pat. No. 3,692,744 are described. At games preferred branching agent are trimesic acid, trimellitic acid, trime ethylethane and propane and pentaerythritol.

It is advisable to use no more than 1 mole% of the branching agent, based on the Acid component to use.

Polyalkylene terephthalates which consist solely of terephthalic acid are particularly preferred and their reactive derivatives (e.g. their dialkyl esters) and ethylene glycol and / or 1,4-butanediol (polyethylene and polybutylene therephthalate), and mixtures of these polyalkylene terephthalates.

Preferred polyalkylene terephthalates are also copolyesters which consist of at least two of the above acid components and / or from at least two of the  above alcohol components are produced, particularly preferred Co polyesters are poly (ethylene glycol / 1,4-butanediol) terephthalates.

The polyalkylene terephthalates preferably used as component A have zen generally an intrisic viscosity of about 0.4 to 1.5 dl / g, preferably 0.5 to 1.3 dl / g, each measured in phenol / o-dichlorobenzene (1: 1 parts by weight) 25 ° C.

In general, aliphatic polyamides or polyamides with a predominantly aliphatic content are used as polyamides in the thermoplastic polyamide molding compositions. Polyamide 6 or polyamide 66 or copolyamides of polyamide 6 with diamines (preferably C ₄ -C ₁₆ -, in particular C ₄ -C ₈ alkylene diamines) and dicarboxylic acids (preferably C ₄ -C ₁₂ -, in particular C ₄ -C ₈ ) are preferred -Alkylene dicarboxylic acids) or polyamides 66 with a comonomer content of at most 20% by weight. The polyamides are generally known or can be prepared by known processes (for example US Pat. No. 5,218,080, US Pat. No. 4,053,457).

Component B1 is particularly preferably 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate (CA Reg. No. 4221-80-1).

2,2,6,6-Tetramethylene piperidin-4-yl is particularly preferred as component B2 Repeat acrylate / methyl methacrylate copolymer (CAS 115340-81-3) Ness.  

The two products are under the name UV Chek AM-340 and 806 from Bed Ford Chemical Division, Ferro Corporation, Bedford, Ohio USA.

The copolymer according to component B2 is generally medium Molecular weights (weight average) greater than 1000, preferably 1500, especially preferably greater than 2000.

The compounds according to component B are generally known compounds or can be produced according to generally known methods.

Part of the polyalkylene terephthalate can be replaced by other polymers or mixtures of Polymers to be replaced. As a rule, up to 60, preferably up to 40, in particular special 20 parts by weight can be replaced by other polymers.

Examples include polycarbonates, polyolefins, styrene polymers, ABS polymers, Copolymers based on ethylenically unsaturated monomers, such as. B. styrene and / or acrylonitrile, alkyl methacrylate polymers, polyphenylene sulfides, thermo plastic polyurethanes.

Aromatic polycarbonates are understood to mean homopolycarbonates and mixtures of these polycarbonates, which z. B. is based on at least one of the following diphenols:
Hydroquinone,
Resorcinol,
Dihydroxydiphenyls,
Bis (hydroxyphenyl) alkanes,
Bis (hydroxyphenyl) cycloalkanes,
Bis (hydroxyphenyl) sulfides,
Bis (hydroxyphenyl) ether,
Bis (hydroxyphenyl) ketones,
Bis (hydroxyphenyl) sulfones,
Bis (hydroxyphenyl) sulfoxides,
α, α'-bis (hydroxyphenyl) diisopropylbenzenes
as well as their nuclear alkylated and nuclear halogenated derivatives.

These and other suitable diphenols are e.g. B. in U.S. Patent 3,028,365, 29 99 835, 31 48 172, 22 75 601, 29 91 283, 32 71 367, 30 62 781, 29 70 131 and 2,999,846, in German Offenlegungsschriften 15 70 703, 20 63 050, 20 63 052, 22 11 956, 22 11 957 of French patent 1,561,518 and in the monograph "H. Schnell, Chemistry and Physics of Polycarbonates, Inter science Publishers, New York 1964 ".

Examples of preferred diphenols are:
2,2-bis (4-hydroxyphenyl) propane,
1,1-bis (4-hydroxyphenyl) cyclohexane,
2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane
2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane,
2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane,
Bis (3,5-dimethyl-4-hydroxyphenyl) methane,
Bis (4-hydroxyphenyl) sulfide,
1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane.

The diphenols can be used both individually and in a mixture. Be particularly preferred aromatic polycarbonates are polycarbonates based on of 2,2-bis (4-hydroxyphenyl) propane or one of the others as preferred called diphenols. Those based on 2,2-bis are very particularly preferred. (4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane or 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane or mixtures of 2,2-bis (4-hydroxyphenyl) propane and 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclo hexane.

The aromatic polycarbonates can be produced by known processes the, e.g. B. by melt transesterification of a corresponding bisphenol Diphenyl carbonate and in solution from bisphenols and phosgene. The solution can be homogeneous (pyridine process) or heterogeneous (two-phase interface process ren) (see H. Schnell, "Chemistry and Physics of Polycarbonates", Polymer Reviews, Vol. IX, S 33ff, Intersciencs Publ. 1964).

The aromatic polycarbonates generally have average molecular weights M _w of approximately 10,000 to 200,000, preferably 20,000 to 80,000 (determined by gel chromatography after prior calibration).

Copolycarbonates in the sense of the invention are in particular polydiorganosiloxane-polycarbonate block copolymers with an average molecular weight M _w of approximately 10,000 to 200,000, preferably 20,000 to 80,000 (determined by gel chromatography after prior calibration) and with a content of aromatic carbonate structural units of about 75 to 97.5% by weight, preferably 85 to 97% by weight and a content of polydiorganosiloxane structural units of about 25 to 2.5% by weight, preferably 15 to 3% by weight, the block copolymers starting from α, ω-Bishydroxyaryloxy end group-containing polydiorganosiloxanes with a degree of polymerization P _n of 5 to 100, preferably 20 to 80, are prepared.

The polydiorganosiloxane-polycarbonate block polymers can also be a Mixture of polydiorganosiloxane-polycarbonate block copolymers with conventional ones be polysiloxane-free, thermoplastic polycarbonates, the total content 2.5 to 25% by weight of polydiorganosiloxane structural units in this mixture is.

Such polydiorganosiloxane-polycarbonate block copolymers are characterized in that they contain aromatic carbonate structure units (1) on the one hand and polydiorganosiloxanes (2) containing aryloxy end groups on the other in the polymer chain,

wherein
Ar are identical or different aryl residues from diphenols and
R and R ^{1 are} identical or different and are linear alkyl, branched alkyl, alkenyl, halogenated linear alkyl, halogenated branched alkyl, aryl or halogenated aryl, but preferably methyl,
and
the number of diorganosiloxy units is n = a + b + c = 5 to 100, preferably 20 to 80.

Alkyl in the above formula (2) is, for example, C ₁ -C ₂₀ alkyl, alkenyl in the above formula (2) is, for example, C ₂ -C ₆ alkenyl; Aryl in the above formula (2) is C ₆ -C ₁₄ aryl. Halogenated in the above formula means partially or completely chlorinated, brominated or fluorinated.

Examples of alkyls, alkenyls, aryls, halogenated alkyls and halogenated aryls are methyl, ethyl, propyl, n-butyl, tert-butyl, vinyl, phenyl, naphthyl, chlorine methyl, perfluorobutyl, perfluorooctyl and chlorophenyl.

Such polydiorganosiloxane-polycarbonate block copolymers are e.g. B. from U.S. Patent 3,189,662, U.S. Patent 3,821,325 and U.S. Patent 3,832,419 are known.

Preferred polydiorganosiloxane-polycarbonate block copolymers are available by using α, ω-bishydroxyaryloxy end group-containing polydiorganosiloxanes together with other diphenols, optionally with the use of Ver branch in the usual amounts, e.g. B. after the two-phase interface ren (see also H. Schnell, Chemistry and Physics of Polycarbonates Polymer Rev. Vol. IX, page 27 ff, Interscience Publishers New York 1964) each selected the ratio of the bifunctional phenolic reactants is that the content of aromatic carbonate structure according to the invention units and diorganosiloxy units results.

Such α, ω-bishydroxyaryloxy end group-containing polydiorganosiloxanes are e.g. B. from US 3,419,634.

ABS graft polymers in the sense of the invention are graft polymers from

• A.1) 5 to 95, preferably 30 to 80 parts by weight of a mixture of
  • A.1.1) 50 to 95 parts by weight of styrene, o: -methylstyrene, halogen-substituted or methyl-substituted styrene, C ₁ -C ₈ -alkyl methacrylate, in particular methyl methacrylate, C ₁ -C ₈ -alkyl acrylate, in particular methyl acrylate or mixtures thereof Connections and
  • A.1.2) 5 to 50 parts by weight of acrylonitrile, methyl acrylonitrile, C ₁ -C ₈ alkyl methacrylates, in particular methyl methacrylate, C ₁ -C ₈ alkyl acrylate, in particular methyl acrylate, maleic anhydride, C ₁ -C ₄ alkyl or phenyl-N-substituted maleimides or mixtures of these compounds
• A.2) 5 to 95, preferably 20 to 70 parts by weight of butadiene, polybutadiene or Butadiene / styrene copolymer with a glass transition temperature below -10 ° C.

Such graft polymers are e.g. B. in DE-OS 20 35 390 (= US-PS 3 644 574) or described in DE-OS 22 48 242 (= GB-PS 1 409 275).

As is known, the graft monomers in the grafting reaction are not necessarily full are constantly grafted onto the graft base, arise from the graft monomeric copolymers. The term ABS graft polymers are also to understand such products, which, due to polymerization, are precisely these copo contain polymers.

The average particle diameter d _{50 of} the ABS graft polymer is generally 0.5 to 5 nm, preferably 0.1 to 2 nm. The average particle diameter d ₅₀ is the diameter above and below which 50% by weight of the particles lie. It can be determined by means of ultracentrifuge measurements (W. Scholtan, H. Lange, Kolloid, Z. Polymer 250 (1972), 782-796).

Polyolefins are polyethylene, polypropylene, poly-1-butene and polymethylpentene, which may still contain small amounts of non-conjugated dienes in copolymerized form nen. These polymers are known and in Roempp's chemistry dictionary, 8th edition  1987, vol. 5, page 3307 and in the literature cited therein. Prefers is polypropylene.

For the purposes of the invention, styrene polymers are homopolymers of styrene (Polystyrene) or copolymers with preferably acrylonitrile and / or malein acid esters, e.g. B. by suspension polymerization in the presence of catalyst ren be prepared from the monomers or the mixture of monomers. The Styrene polymers generally have weight average molecular weights of 10,000 to 600,000 (measured in DMF at a concentration of 5 g / l and 20 ° C).

C ₁ -C ₄ -Alkyl methacrylate polymers suitable according to the invention are known polymers of the methyl, ethyl, propyl and butyl methacrylic acid esters, preferably the methyl and ethyl methacrylic acid esters. Both homopolymers and copolymers of these methacrylic acid esters are to be understood. In addition, up to a maximum of 9.5% by weight of other ethylenically unsaturated, copolymerizable monomers, based in each case on the total weight of these unsaturated monomers and the methacrylic acid esters, can be copolymerized, so that the C ₁ -C ₄ -alkyl methacrylate polymers suitable according to the invention are composed of 90 5 wt .-% to 100 wt .-% of alkyl methacrylate units and from 9.5 wt .-% to 0 wt .-% of other ethylenically unsaturated monomer units are built up.

Other ethylenically unsaturated copolymerizable monomers are, for example, (meth) acrylonitrile, (α-methyl) styrene, bromostyrene, vinyl acetate, acrylic acid. C ₁ -C ₈ alkyl esters, (meth) acrylic acid aryl esters, (meth) acrylic acid, ethylene, propylene, N-vinyl pyrrolidone, vinyl sulfonic acid (salts) or styrene sulfonic acid (salts).

The C ₁ -C ₄ alkyl methacrylate polymers are substances which are soluble in certain organic solvents and thus have a linear or branched structure; Gel-containing polymers, as such with cross-linked structures, are not polymers (b) in the sense of the invention.

The polyalkyl methacrylates can be produced by certain polymerization processes are provided, but preferably by radical or thermal polymerization. Suitable polymerization processes are processes in emulsion, mass, suspension, Dispersion, especially the emulsion, but preferably the mass or Solution polymerization. The molecular weights can be determined by known methods contingent measures, for example by using mercaptans from Reg learn to be varied in a wide range. They usually have according to the invention usable polyalkyl methacrylates of such molecular weights (or Staudinger Indices, or melt viscosities), the thermoplastic injection molding or Make extrusion processing useful.

Polyphenylene sulfides in the sense of the invention are, for example, in EP-A 171 021 described.

Thermoplastic polyurethanes in the sense of the invention are reaction products Diisocyanates, with wholly or predominantly aliphatic oligo- and / or polyesters and / or ethers and one or more chain extenders.

These thermoplastic polyurethanes are essentially linear and possess thermoplastic processing characteristics.

The thermoplastic polyurethanes are either known or can be known methods (see, for example, U.S. Patent 3,214,411, J.H. Saunders and K.C. Frisch, "Polyurethanes, Chemistry and Technology", Vol. II, pages 299 to 451, Interscience Publishers, New York, 1964 and Mobay Chemical Corporation, "A Processing Handbook for Texin Urethane Elastoplastic Materials ", Pittsburgh, PA) getting produced.

Starting materials for the production of the oligoesters and polyesters are, for example Adipic acid, succinic acid, subecic acid, sebacic acid, oxalic acid, methyl adipine acid, glutaric acid, pimelic acid, azelaic acid, phthalic acid, terephthalic acid and Isophthalic acid.  

Adipic acid is preferred here.

As glycols for the production of the oligoesters and polyesters are, for example Ethylene glycol, 1,2- and 1,3-propylene glycol, 1,2-, 1,3-, 1,4-, 2,3-, 2,4-butanediol, Hexanediol, bishydroxymethylcyclohexane, diethylene glycol and 2,2-dimethyl-propy lenglycol. In addition, small together with the glycols Amounts up to 1 mol%, tri- or higher functional alcohols, e.g. B. Trimethylolpro pan, glycerin, hexanetriol etc. are used.

The resulting hydroxyl oligo- or polyesters have a molecular weight of at least 600, a hydroxyl number of about 25 to 190, preferably about 40 to 150, an acid number of approx. 0.5 to 2 and a water content of approx. 0.01 to 0.2%.

Oligoesters or polyesters are also oligomeric or polymeric lactones, such as as oligo-caprolactone or poly-caprolactone, and aliphatic polycarbonates, such as for example poly-butanediol (1,4) carbonate or poly-hexanediol (1,6) carbonate.

A particularly suitable oligo residue that is used as a starting material for the thermoplastic Polyurethane can be used is made from adipic acid and a glycol provides that has at least one primary hydroxyl group. The condensation will terminated when an acid number of 10, preferably about 0.5 to 2 is reached. The Water which is formed during the reaction is thus removed at the same time or afterwards separated so that the water content in the end ranges from about 0.01 to 0.05%, preferably 0.01 to 0.02%.

Oligo- or polyethers for the production of thermoplastic polyurethanes are included for example, those based on tetramethylene glycol, propylene glycol and ethyl lenglycol.

Polyacetals are also to be understood and used as polyethers.  

The oligoethers or polyethers should have average molecular weights M _n (number average, determined via the OH number of the products) from 600 to 2000, preferably from 1000 to 2000.

Organic diisocyanate is used to produce the polyurethanes according to Kompo nente A preferably 4,4'-diphenylmethane diisocyanate used. It should be less than 5% 2,4'-diphenylmethane diisocyanate and less than 2% of the dimer of Contain diphenyl diisocyanate. It is also desirable that acidity, calculated as HCl is in the range of 0.005 to 0.2%.

The acidity, calculated as HCl, is determined by extracting the chloride from the Isocya nat in hot, aqueous methanol solution or by releasing the chloride Hydrolysis with water and titration of the extract with standard silver nitrate solution determined in order to obtain the chloride ion concentration contained therein.

Other diisocyanates can also be used to make the thermoplastic polyurethane can be used, for example the diisocyanates of ethylene, ethyl lidens, Propylene, butylene, cyclopentylene-1,3, cyclohexylene-1,4, cyclohexylene-1,2, des 2,4-tolylene, 2,6-tolylene, p-phenylene, n-phenylene, xylene, des 1,4-naphthylene, 1,5-naphthylene, 4,4'-diphenylene, 2,2-diphenylpropane 4,4'-diisocyanate, the azobenzene-4,4'-diisocyanate, the diphenyl-sulfone-4,4'-diisocya nat, the dichlorohexane methylene diisocyanate, the pentamethylene diisocyanate, the Hexamethylene diisocyanate, 1-chlorobenzene-2,4-diisocyanate, furfuryl diisocya nat, the dicyclohexylmethane diisocyanate, the isophorone diisocyanate, the diphe nylethane diisocyanate and bis (isocyanatophenyl) ether of ethylene glycol, butanediol Etc.

Organic difunctional compounds can be used as chain extenders are the active, reactive with isocyanates, contain hydrogen, for. B. diols, Hydroxycarboxylic acids, dicarboxylic acids, diamines and alkanolamines and water.  

Examples include ethylene, propylene, butylene glycol, 1,4-butanediol, Butanediol, butynediol, xylylene glycol, amylene glycol, 1,4-phenylene-bis-β-hydroxyethyl ether, 1,3-phenylene-bis-β-hydroxyl ether, bis (hydroxymethyl-cyclohexane), hexanediol, Adipic acid, ω-hydroxycaproic acid, thiodiglycol, ethylenediamine, propylene, buty len-, hexamethylene, cyclohexylene, phenylene, tolylene, xylylenediamine, di aminodicyclohexylmethane, isophoronediamine, 3,3'-dichlorobenzidine, 3,3'-dinitrobene zidin, ethanolamine, aminopropyl alcohol, 2,2-dimethylpropanolamine, 3-aminocyclo To name hexyl alcohol and p-aminobenzyl alcohol. The molar ratio of oligo or Polyester to bifunctional chain extenders ranges from 1: 1 to 1: 50, preferably 1: 2 to 1:30.

In addition to bifunctional chain extenders can also be used in minor quantities up to about 5 mol%, based on moles of bifunctional chain extensions used rer, trifunctional or more than trifunctional chain extenders can be used.

Such trifunctional or more than trifunctional chain extenders are in for example glycerol, trimethylolpropane, hexanetriol, pentaerythritol and triethanol amine.

Monofunctional components, for example butanol, can also be used for the manufacture thermoplastic polyurethanes according to component A are used.

The diisocyanates mentioned as building blocks for the thermoplastic polyurethanes, Oligoester, polyester, polyether, chain extender and monofunctional compo Nenten are either known from the literature or obtained by processes known from the literature Lich.

The known production of the thermoplastic polyurethane component is in described for example in DE-OS 43 09 981.

Glass fibers, glass balls, mica, silicates, Quartz, talc, titanium dioxide, wollastonite, etc. a. are used, which also surface  can be treated. Preferred reinforcing materials are commercially available glass fibers. The glass fibers, which generally have a fiber diameter between 8 and 14 µm, can be used as continuous fibers or as cut or ground glass fa be used, the fibers with a suitable sizing system and can be equipped with an adhesion promoter or adhesion promoter system based on silane nen. The mixture can preferably contain up to 45, in particular 10 to 40 Parts by weight of fillers and reinforcing materials are added.

Commercially available organic compounds or Halogen compounds with synergists or commercially available organic nitrogen compounds or organic / inorganic phosphorus compounds added the. Mineral flame retardant additives such as Mg hydroxide or Ca-Mg carbonate hydrate can be mixed either individually or with one another be set. The flame retardant additives are usually used in an amount up to 60 parts by weight, depending on the type of flame retardant added.

The molding compositions according to the invention can up to 20, preferably 3 to 18, in particular in particular 6 to 15 parts by weight of halogenated compounds and up to 8, preferably 2 up to 6 parts by weight of antimony compounds, in particular antimony trioxide or antimony contain pentoxide.

Examples of halogen-containing, in particular brominated and chlorinated, organic compounds are:
Ethylene-1,2-bistetrabromophthalimide,
Epoxidized tetrabromobisphenol A resin,
Tetrabromobisphenol A oligocarbonate,
Tetrachlorobisphenol A oligocarbonate,
Pentabromobenzyl polyacrylate,
brominated polystyrene.

Pentabromobenzyl polyacrylate generally has average molecular weights M _w (weight average) of 10,000 to 200,000, brominated polystyrene generally 10,000 to 500,000.

Epoxidized tetrabromobisphenol-A and tetrabromobisphenol-A- are preferred. Oligocarbonate and pentabromobenzyl polyacrylate are used.

Epoxidized tetrabromobisphenol-A is a known diepoxide resin with a molecular weight of about 350 to about 2100, preferably 360 to 1000, particularly preferably 370 to 400, and consists essentially of at least one condensation product of bisphenol A and epihalohydrin and is described by the formula (I )

where X represents hydrogen or bromine and n is an average number between Is zero and less than 2.3 (see, for example, EP-A 180 471).

Tetrabromobisphenol A oligocarbonate or tetrachlorobisphenol A oligocarbonate is described by formula (II), the oligomers being terminated either with phenol or with tribromophenol or trichlorophenol:

where X represents hydrogen, bromine or chlorine, n is an average number between 4 and 7.

Tetrabromo (chloro) bisphenol A oligocarbonate is known and according to known ver drive producible.

As organic phosphorus compounds, the phosphorus compounds are in accordance with EP-A 345 522 (US-PS 061.745) or DE-OS 43 28 656.9 in those described there Suitable amounts, e.g. B. triphenyl phosphate, oligomeric phosphates, resorcinol phosphate or a mixture thereof.

Antimony trioxide is well known and can e.g. B. purchased from Campine be.

The molding compositions according to the invention can be conventional additives, such as lubricants and ent shaping agents, nucleating agents, antistatic agents, stabilizers, dyes, Pigments.

The molding compositions according to the invention from the respective components and given if necessary, other known additives such as stabilizers, sliding and demolding agents, reinforcing materials, nucleating agents and antistatic agents can be produced be made by countering the respective components in a known manner  optionally in the form of masterbatches, admixed with the thermoplastic polymer and at temperatures from 180 ° C to 330 ° C in common units such as internal knees terns, extruders, twin-shaft screws melt-compounded or melt-x trudged.

The invention furthermore relates to the use of the molding compositions for Production of moldings and the moldings themselves.

The subject is also the use of the UV Stabilizers selected to improve physical properties Toughness, elasticity, the stabilization of thermal stress in the form body of any kind.  

Examples

The components and additives specified in the examples are mixed and processed to test specimens in an injection molding machine under customary PBT processing conditions (melt temperature approx. 260 ° C.).
PBT: polybutylene terephthalate (PBT) (relative solution viscosity 1.834 to 1.875, measured at T = 25 ° C in a 0.5% solution of phenol and o-dichlorobenzene, mixing ratio 1: 1 parts by weight)
TBBOC: Tetrabromobisphenol-A Oligocarbonate BC 52 HP® Great Lakes Chemicals, Belgium
Antimony trioxide
glass fiber
Polyamide B 30 S, Bayer AG, Leverkusen, Germany
Tinuvin 328/770 DF 1: 1, Ciba Geigy, Basel, Switzerland
Component B (UV Check AM 340 and 806) have already been described above.
The Izod impact strength is measured according to ISO 180 1U.

Examples and results

Table 1

Table 2

Table 3

Table 4

Table 5

Table 6

The molding compositions according to the invention are characterized by better toughness, one higher fluidity and less yellowing behavior and toughness loss due to temperature aging.

Claims (10)

1. Thermoplastic molding compositions containing polyalkylene terephthalate or polyamide or a mixture thereof and

• B) at least one UV stabilizer selected from
  • B1) one or more compounds of the formula (I)
    wherein
    R ¹ , R ² and R ³ independently of one another are hydrogen or C ₁ -C ₁₀ alkyl, where at least two of the radicals R ¹ , R ² and R ^{3 are} branched C ₃ -C ₁₀ alkyl,
  • B2) an acrylate / methyl methacrylate copolymer based on the repeating unit (II)
    wherein
    R ^{4 represents} hydrogen or C ₁ -C ₆ alkyl,
    R ⁵ and R ⁶ each independently represent hydrogen or C ₁ -C ₆ alkyl, and
    R _{7 represents} C ₁ -C ₆ alkyl.

2. Molding compositions according to claim 1, containing as component B1 a compound of the formula
3. Molding compositions according to claim 1, containing as component B2 a copolymer with the repeating unit
4. Molding compositions according to claims 1 to 3, containing 97.5 to 99.99 Parts by weight of component A and 0.01 to 25 parts by weight of component B, the Sum of A + B results in 100.   5. Molding compositions according to claims 1 to 3, containing 99.98 to 99 Parts by weight of A) and 0.02 to 1 part by weight of B). 6. Molding compositions according to claims 1 to 5, wherein polyalkylene terephthalate by up to 60 parts by weight of another polymer or a mixture of Polymers can be replaced. 7. Molding compositions according to claims 1 to 6, containing additives selected from the group of fillers and reinforcing materials, flame retardants, lubricants and Mold release agents, nucleating agents, antistatic agents, stabilizers, colors substances, pigments. 8. Use of the molding compositions according to the preceding claims Manufacture of molded articles. 9. Shaped body, produced from molding compositions according to claims 1 to 7. 10. Use of the UV stabilizers according to component B) of claims 1 to 3 in terms of improving physical properties Toughness, ductility and / or stabilization with a thermal bean saying.