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WO2010089241A1 - Matières à mouler thermoplastiques noires et stables aux uv - Google Patents

Matières à mouler thermoplastiques noires et stables aux uv Download PDF

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Publication number
WO2010089241A1
WO2010089241A1 PCT/EP2010/051003 EP2010051003W WO2010089241A1 WO 2010089241 A1 WO2010089241 A1 WO 2010089241A1 EP 2010051003 W EP2010051003 W EP 2010051003W WO 2010089241 A1 WO2010089241 A1 WO 2010089241A1
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Prior art keywords
black
molding compositions
weight
glass
fibers
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German (de)
English (en)
Inventor
Rainer Anderlik
Rebekka Von Benten
Mark VÖLKEL
Martin Weber
Kurt HÖFLI
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0041—Optical brightening agents, organic pigments

Definitions

  • the invention relates to thermoplastic molding compositions containing
  • thermoplastic polymer A) 20 to 99.99 wt .-% of a thermoplastic polymer
  • the invention relates to the use of such molding compositions for the production of fibers, films moldings and foams, as well as the fibers, films, foams and moldings obtainable in this case.
  • Colored polymer-glass fiber composites, as well as undyed polymer-glass fiber composites tend to change color of the visible surface under UV irradiation.
  • two effects occur due to the radiation-related degradation of the polymer matrix.
  • the degradation products of the polymer itself may have a different color than the composite.
  • erosion of the top polymer layer of the component exposes subsurface glass fibers.
  • undyed glass fibers are used for this type of composite, which then makes the surface appear duller and less intensely colored.
  • black glass fiber reinforced polyester molding compounds show a pronounced graying after UV irradiation.
  • harmful UV radiation in particular, is conducted through undyed glass fibers into deeper layers of the component, as a result of which the polymer matrix is also damaged below the visible surface.
  • Glass fibers are used as standard as reinforcing fillers for polymer molding compounds. Such composites are generally e.g. in Handbook of Polymeric Fiber Composites, F.R. Jones (Ed.), Longman Scientific + Technical, UK 1994, Chapters 1, 3-5 ".
  • UV-stabilizing additives may be added to the molding composition, for example organic substances which have a UV-absorbing or radical-scavenging effect.
  • Other UV-absorbing substances for example carbon black, are also used for this purpose.
  • JP-A 09/124346 describes the preparation of colored glass fibers by coating with a leuco dye and subsequent incorporation by kneading into a polypropylene matrix.
  • JP-A 2000/239517 discloses a curable polyphenylene ether composition containing black glass fibers for coloring which are said to have high flame retardancy, chemical resistance and heat aging resistance.
  • JP-A 10/92685 teaches a red masterbatch-colored plastic molding composition containing red-colored glass fibers which is said to exhibit improved surfaces after molding.
  • JP-A 60/40757 dyed glass fibers are blended in a curable unsaturated polyester composition to prepare fine-grained artificial marble. Similar articles are also described in JP-A 61/21 1003A2 where colored inorganic fibers are used.
  • the use of dyed fibers can reduce the damage to the component surface due to UV radiation. Since the glass fiber has the same color as the colored polymer composite, no other component is visible despite degradation of the upper polymer layer, whereby the overall color impression of the component remains unchanged. Damage to the deeper layers by the above-described optical fiber effect of the fibers is also reduced by absorbing colorants contained in or on the glass fibers. Ideally, the fiber is opaque to the damaging wavelength.
  • Another advantage of the molding compositions according to the invention is that by combining the two functions of reinforcement and coloring in only one filler - the colored glass fiber - the concentration of coloring additives in the polymer matrix can be reduced. As a result, the material cost of the composite are lower. In addition, coloring additives in the polymer matrix often have a negative effect on the mechanical properties, in particular the impact resistance, of the composites. A lower concentration of coloring additive by using colored glass fibers in this case causes an improvement in the mechanical properties of the composite.
  • the molding compositions according to the invention contain from 29 to 99.99% by weight, of at least one thermoplastic polymer.
  • the proportion of A) is preferably from 25 to 98.99 and in particular from 30 to 94.99 wt .-%. These details are based on the molding compositions A) to D).
  • thermoplastics of any kind.
  • An enumeration of suitable thermoplastics can be found for example in the plastic paperback (Hrsg. Saechtling), edition 1989, where sources are also called. Processes for the production of such thermoplastics are known per se to the person skilled in the art. Below some preferred types of plastic are explained in more detail.
  • polyesters A) based on aromatic dicarboxylic acids and an aliphatic or aromatic dihydroxy compound are used.
  • a first group of preferred polyesters are polyalkylene terephthalates, which in particular have 2 to 10 carbon atoms in the alcohol part.
  • Such polyalkylene terephthalates are known per se and described in the literature. They contain an aromatic ring in the main chain derived from the aromatic dicarboxylic acid. The aromatic ring may also be substituted, for. Example by halogen such as chlorine and bromine or by Ci-C4-alkyl groups such as methyl, ethyl, i- or n-propyl and n-, i- or t-butyl groups.
  • polyalkylene terephthalates can be prepared by reacting aromatic dicarboxylic acids, their esters or other ester-forming derivatives with aliphatic dihydroxy compounds in a manner known per se.
  • Preferred dicarboxylic acids are 2,6-naphthalenedicarboxylic acid, terephthalic acid and isophthalic acid or mixtures thereof. Up to 30 mol%, preferably Not more than 10 mol% of the aromatic dicarboxylic acids can be replaced by aliphatic or cycloaliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, dodecanedioic acids and cyclohexanedicarboxylic acids.
  • aliphatic dihydroxy compounds are diols having 2 to 6 carbon atoms, in particular 1, 2-ethanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 6-hexanediol, 1, 4-hexanediol, 1, 4-cyclohexanediol, 1 , 4-cyclohexanedimethanol and neopentyl glycol or mixtures thereof.
  • polyesters (A) are polyalkylene terephthalates which are derived from alkanediols having 2 to 6 C atoms. Of these, particularly preferred are polyethylene terephthalate, polypropylene terephthalate and polybutylene terephthalate or mixtures thereof. Preference is furthermore given to PET and / or PBT which contain up to 1% by weight, preferably up to 0.75% by weight, of 1,6-hexanediol and / or 2-methyl-1,5-pentanediol as further monomer units.
  • the viscosity number of the polyesters (A) is generally in the range from 50 to 220, preferably from 80 to 160 (measured in a 0.5% strength by weight solution in a phenol / o-dichlorobenzene mixture (wt. 1 at 25 ° C) according to ISO 1628).
  • polyesters whose carboxyl end group content is up to 100 meq / kg, preferably up to 50 meq / kg and in particular up to 40 meq / kg of polyester.
  • Such polyesters can be prepared, for example, by the process of DE-A 44 01 055.
  • the carboxyl end group content is usually determined by titration methods (e.g., potentiometry).
  • Particularly preferred molding compositions contain as component A) a mixture of polyesters which are different from PBT, such as, for example, polyethylene terephthalate (PET) and / or polycarbonate.
  • PBT polyethylene terephthalate
  • the proportion e.g. of the polyethylene terephthalate and / or the polycarbonate is preferably in the mixture up to 50, in particular 10 to 30 wt .-%, based on 100 wt .-% A).
  • PET recyclates also termed scrap PET
  • PBT polyalkylene terephthalates
  • post-industrial recyclate these are production waste during polycondensation or during processing, for example, sprues in the injection molding process, start-up goods in injection molding or extrusion or edge sections of extruded sheets or foils.
  • Post Consumer Recyclate These are plastic items that are collected and processed after use by the end user. By far the dominating items in terms of volume are blow-molded PET bottles for mineral water, soft drinks and juices.
  • Both types of recycled material can be present either as regrind or in the form of granules. In the latter case, the slag cyclates after separation and purification are melted in an extruder and granulated. This usually facilitates the handling, the flowability and the metering for further processing steps.
  • the maximum edge length should be 6 mm, preferably less than 5 mm.
  • the residual moisture content after drying is preferably 0.01 to 0.7, in particular 0.2 to 0.6%.
  • Suitable aromatic dicarboxylic acids are the compounds already described for the polyalkylene terephthalates. Preference is given to mixtures of 5 to
  • isophthalic acid 100 mol% isophthalic acid and 0 to 95 mol% terephthalic acid, in particular mixtures of about 80% terephthalic acid with 20% isophthalic acid to about equivalent mixtures of these two acids used.
  • the aromatic dihydroxy compounds preferably have the general formula
  • Z represents an alkylene or cycloalkylene group having up to 8 C atoms, an arylene group having up to 12 C atoms, a carbonyl group, a sulfonyl group, an oxygen or sulfur atom or a chemical bond and in the m the value 0 to 2 has.
  • the compounds may also carry C 1 -C 6 -alkyl or alkoxy groups and fluorine, chlorine or bromine as substituents on the phenylene groups.
  • these compounds are, for example
  • Dihydroxydiphenyl di (hydroxyphenyl) alkane, di (hydroxyphenyl) cycloalkane, di (hydroxyphenyl) sulfide, di (hydroxyphenyl) ether, di (hydroxyphenyl) ketone, di (hydroxyphenyl) sulfoxide, a, ⁇ -di- (hydroxyphenyl) -dialkylbenzol,
  • polyalkylene terephthalates and wholly aromatic polyesters and / or polycarbonates generally contain from 20 to 98% by weight, preferably from 50 to 96% by weight, of the polyalkylene terephthalate and from 2 to 80% by weight, preferably from 4 to 50% by weight, of the wholly aromatic polyester and / or of the polycarbonate.
  • polyester block copolymers such as copolyetheresters may also be used.
  • Such products are known per se and described in the literature, for example in US Pat. No. 3,651,014. Also in the trade, corresponding products are For example, Hytrel® (DuPont).
  • Suitable halogenated polycarbonates are, for example, those based on diphenols of the general formula
  • Q is a single bond, a C 1 to C 8 alkylene, a C 2 to C 3 alkylidene, a C 3 to C 6 cycloalkylidene group, a C 6 to C 12 arylene group and also -O-, -S- or -SO 2 - and m is an integer from 0 to 2.
  • the diphenols may also have substituents on the phenylene radicals, such as C 1 -C 6 -alkyl or C 1 -C 6 -alkoxy.
  • Preferred diphenols of the formula are, for example, hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) propane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 1, 1 bis (4-hydroxyphenyl) -cyclohexane.
  • Particularly preferred are 2,2-bis (4-hydroxyphenyl) propane and 1, 1-bis (4-hydroxyphenyl) cyclohexane, and 1, 1-bis (4-hydroxyphenyl) -3,3,5- trimethylcyclohexane.
  • both homopolycarbonates and copolycarbonates are suitable as component A, and in addition to the bisphenol A homopolymer, the copolycarbonates of bisphenol A are preferred.
  • the suitable polycarbonates may be branched in a known manner, preferably by the incorporation of from 0.05 to 2.0 mol%, based on the sum of the diphenols used, of at least trifunctional compounds, for example those having three or more than three phenolic compounds OH groups.
  • Polycarbonates which have proved to be particularly suitable have the relative viscosities hrel of from 1.10 to 1.50, in particular from 1.25 to 1.40. This corresponds to average molecular weights Mw (weight average) of 10,000 to 200,000, preferably 20,000 to 80,000.
  • the diphenols of the general formula are known per se or can be prepared by known processes.
  • the polycarbonates can be prepared, for example, by reacting the diphenols with phosgene by the phase boundary process or with phosgene by the homogeneous phase process (the so-called pyridine process), the molecular weight to be set in each case being determined in a known manner by a corresponding amount of known chain terminators is achieved.
  • phosgene by the phase boundary process or with phosgene by the homogeneous phase process (the so-called pyridine process)
  • Suitable chain terminators are, for example, phenol, p-t-butylphenol but also long-chain alkylphenols such as 4- (1, 3-tetramethyl-butyl) -phenol, according to DE-OS 28 42 005 or monoalkylphenols or dialkylphenols with a total of 8 to
  • Halogen-free polycarbonates in the context of the present invention means that the polycarbonates are composed of halogen-free diphenols, halogen-free chain terminators and optionally halogen-free branching agents, the content of minor ppm amounts of saponifiable chlorine, resulting, for example, from the preparation of the polycarbonates with phosgene by the interfacial process, is not to be regarded as halogen-containing in the context of the invention.
  • Such polycarbonates with ppm contents of saponifiable chlorine are halogen-free polycarbonates in the context of the present invention.
  • suitable components A) may be mentioned amorphous polyester carbonates, wherein phosgene was replaced by aromatic dicarboxylic acid units such as isophthalic acid and / or terephthalic acid units in the preparation.
  • aromatic dicarboxylic acid units such as isophthalic acid and / or terephthalic acid units in the preparation.
  • bisphenol A can be replaced by bisphenol TMC.
  • polycarbonates are available under the trademark APEC HT® from Bayer.
  • the polyamides of the molding compositions according to the invention generally have a viscosity number of 90 to 350, preferably 110 to 240 ml / g, determined in a 0.5% strength by weight solution in 96% strength by weight sulfuric acid at 25 ° C. ISO 307.
  • polyamides which are derived from lactams having 7 to 13 ring members, such as polycaprolactam, polycapryllactam and polylaurolactam, and also polyamides which are obtained by reacting dicarboxylic acids with diamines.
  • alkanedicarboxylic acids having 6 to 12, in particular 6 to 10 carbon atoms and aromatic dicarboxylic acids can be used.
  • adipic acid, azelaic acid, sebacic acid, dodecanedioic acid and terephthalic and / or isophthalic acid are mentioned as acids.
  • Suitable diamines are in particular alkanediamines having 6 to 12, in particular 6 to 8 carbon atoms and m-xylylenediamine, di (4-aminophenyl) methane, di (4-aminocyclohexyl) methane, 2,2-di- (4-aminophenyl ) -propane or 2,2-di- (4-aminocyclohexyl) -propane.
  • Preferred polyamides are polyhexamethylene adipamide, polyhexamethylene sebacamide and polycaprolactam and also copolyamides 6/66, in particular with a content of 5 to 95% by weight of caprolactam units.
  • polyamides which are e.g. are obtainable by condensation of 1,4-diaminobutane with adipic acid at elevated temperature (polyamide-4,6). Manufacturing processes for polyamides of this structure are known e.g. in EP-A 38 094, EP-A 38 582 and EP-A 39 524 described.
  • polyamides which are obtainable by copolymerization of two or more of the abovementioned monomers or mixtures of a plurality of polyamides are suitable, the mixing ratio being arbitrary.
  • the triamine content is less than 0.5, preferably less than 0.3 wt .-% (see EP-A 299 444).
  • the production of the preferred partly aromatic copolyamides with a low triamine content can be carried out by the processes described in EP-A 129 195 and 129 196.
  • Suitable polyphenylene ethers generally have a weight average molecular weight in the range of from 10,000 to 80,000, preferably from 20,000 to 60 000 and in particular from 40 000 to 55 000 on.
  • the molecular weight distribution is generally determined by gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • PPE samples are dissolved in THF under pressure at 110 ° C.
  • THF as eluent, is used to inject 0.16 ml of a 0.25% solution onto suitable separation columns.
  • the detection is generally carried out with a UV detector.
  • the separation columns are suitably calibrated with PPE samples of known molecular weight distribution.
  • the unmodified polyphenylene ethers a1) are known per se and are preferably prepared by oxidative coupling of phenols disubstituted in the o-position.
  • halogen atoms such as chlorine or bromine and alkyl groups having 1 to 4 carbon atoms which preferably do not have an ⁇ -terminal tertiary hydrogen atom, e.g. Methyl, ethyl, propyl or butyl radicals.
  • the alkyl radicals may in turn be substituted by halogen atoms, such as chlorine or bromine, or by a hydroxyl group.
  • alkoxy radicals preferably having up to 4 carbon atoms or phenyl radicals optionally substituted by halogen atoms and / or alkyl groups.
  • copolymers of various phenols e.g. Copolymers of 2,6-dimethylphenol and 2,3,6-trimethylphenol. Of course, mixtures of different polyphenylene ethers can be used.
  • the polyphenylene ethers used as component a1) may optionally contain process-related defects, which are described, for example, in White et al., Macromolecules 23, 1318-1329 (1990).
  • polyphenylene ethers are used which are compatible with vinyl aromatic polymers, i. wholly or largely soluble in these polymers (see A. Noshay, Block Copolymers, pp. 8-10, Academic Press, 1977 and O. Olabisi, Polymer-Polymer Miscibility, 1979, p.117-189).
  • polyphenylene ethers examples include poly (2,6-dilauryl-1,4-phenylene) ether, poly (2,6-diphenyl-1,4-phenylene) ether, poly (2,6-dimethoxy-1,4-phenylene) ether, poly (2,6-diethoxy-1,4-phenylene) ether, poly (2-methoxy-6-ethoxy-1,4-phenylene) ether, poly (2-ethyl-6-stearyloxy-1,4) phenylene) ether, poly (2,6-dichloro-1,4-phenylene) ether, poly (2-methyl-6-phenyl-1, 4-phenylene) ether, poly (2,6-dibenzyl-1, 4- phenylene) ether, poly (2-ethoxy-1,4-phenylene) ether, poly (2-chloro-1, 4-phenylene) ether, poly (2,5-dibromo-1, 4- phenylene) ether.
  • Polyphenylene ethers are preferably used in which the substituents are alkyl radicals having 1 to 4 carbon atoms, such as poly (2,6-dimethyl-1, 4-phenylene) ether, poly (2,6-diethyl-1, 4-phenylene) ether, poly (2-methyl-6-ethyl-1, 4-phenylene) ether, poly (2-methyl-6-propyl-1, 4-phenylene) ether, poly (2,6-dipropyl-1, 4- phenylene) ether and poly (2-ethyl-6-propyl-1,4-phenylene) ether.
  • the substituents are alkyl radicals having 1 to 4 carbon atoms, such as poly (2,6-dimethyl-1, 4-phenylene) ether, poly (2,6-diethyl-1, 4-phenylene) ether, poly (2-methyl-6-ethyl-1, 4-phenylene) ether, poly (2-methyl-6-propyl-1, 4-phenylene) ether, poly
  • graft copolymers of polyphenylene ether and vinyl aromatic polymers such as styrene, ⁇ -methylstyrene, vinyltoluene and chlorostyrene are suitable.
  • Functionalized or modified polyphenylene ethers are known per se, e.g. from WO-A 86/02086, WO-A 87/00540, EP-A-222 246, EP-A-223 1 16 and EP-A-254 048 and are preferably used for mixtures with PA or polyester.
  • an unmodified polyphenylene ether a1) is prepared by incorporation of at least one carbonyl, carboxylic acid, acid anhydride, acid amide, acid imide, carboxylic ester, carboxylate, amino, hydroxyl, epoxy, oxazoline, urethane, urea, Lactam or halobenzyl modified so that a sufficient compatibility, eg with the polyamide, guaranteed.
  • the modification is generally carried out by reacting an unmodified polyphenylene ether a1) with a modifier containing at least one of the abovementioned groups and at least one C-C double or C-C triple bond in solution (WO-A 86/2086) aqueous dispersion, in a gas phase process (EP-A-25 200) or in the melt optionally in the presence of suitable vinyl aromatic polymers or Schlagzähmodifiern carried out, wherein optional radical initiator may be present.
  • Suitable modifiers (a3) are, for example, maleic acid, methylmaleic acid, itaconic acid, tetrahydrophthalic acid, their anhydrides and imides, fumaric acid, the mono- and diesters of these acids, e.g. of Ci- and C2- to Cs-alkanols (a3i), the mono- or diamides of these acids, such as N-phenylmaleimide (monomers 832), maleic hydrazide.
  • a modified polyphenylene ether is preferably used as component A) in the molding compositions according to the invention, which is prepared by reacting
  • a-i from 70 to 99.95, preferably from 76.5 to 99.94% by weight of an unmodified polyphenylene ether,
  • percentages by weight refer to the sum of ai) to a 4 ), in the course of 0.5 to 15 minutes at 240 to 375 ° C in suitable mixing and kneading aggregates such as twin-screw extruders.
  • the vinylaromatic polymer 82 should preferably be compatible with the polyphenylene ether used, as described above under 2.
  • Radical starters a 4 may be mentioned:
  • organic hydroperoxides such as di-isopropylbenzene monohydroperoxide, cumene hydroperoxide, tert-butyl hydroperoxide, p-methyl hydroperoxide and pinane hydroperoxide and highly branched alkanes of the general structure
  • R 6 R 3 where R 1 to R 6 are alkyl groups having 1 to 8 C atoms, alkoxy groups having 1 to 8 C atoms, aryl groups such as phenyl, naphthyl or 5- or 6-membered heterocycles having a ⁇ -electron system and nitrogen, oxygen or sulfur as heteroatoms represent.
  • the substituents R 1 to R 6 may in turn contain functional groups as substituents, such as carboxyl, carboxyl derivative, hydroxyl, amino, thiol or epoxide groups. Examples are 2,3-dimethyl-2,3-diphenylbutane, 3,4-dimethyl-3,4-diphenylhexane and 2,2,3,3-tetraphenylbutane.
  • Particularly preferred polyphenylene ethers A) in the molding compositions according to the invention are obtained by modification with maleic acid, maleic anhydride and fumaric acid.
  • Such polyphenylene ethers preferably have an acid number of from 1.8 to 3.2, in particular from 2.0 to 3.0.
  • the acid number is a measure of the degree of modification of the polyphenylene ether and is generally determined by titration with bases under inert gas conditions.
  • the acid number generally corresponds to the amount of base in mg, which is required for the neutralization of 1 g of such an acid-modified polyphenylene ether A) (according to DIN 53 402).
  • these polymers have at least 50 mole percent of repeating units -CH 2 O- in the polymer backbone.
  • the homopolymers are generally prepared by polymerization of formaldehyde or trioxane, preferably in the presence of suitable catalysts.
  • polyoxymethylene copolymers as component A, in particular those which, in addition to the repeating units -CH 2 O-, also contain up to 50, preferably 0.1 to 20, in particular 0.3 to 10, mol% and very particularly preferably 2 to 6 mol% of recurring units
  • R 1 to R 4 independently of one another are a hydrogen atom, a C 1 - to C 4 -alkyl group or a halogen-substituted alkyl group having 1 to 4 C atoms and R 5 is a -CH 2 -, -CH 2 O-, a C 1 - to C 4 -alkyl- or Ci to C4 haloalkyl substituted methylene group or a corresponding oxymethylene group and n has a value in the range of 0 to 3.
  • these groups can be introduced into the copolymers by ring opening of cyclic ethers.
  • Preferred cyclic ethers are those of the formula
  • R 1 to R 5 and n have the abovementioned meaning.
  • ethylene oxide, 1, 2-propylene oxide, 1, 2-butylene oxide, 1, 3-butylene oxide, 1, 3-dioxane, 1, 3-dioxolane and 1, 3-dioxepane called cyclic ethers and linear oligo- or polyformals such as polydioxolane or polydioxepan called comonomers.
  • component A) oxymethylene terpolymers which are obtained, for example, by reacting trioxane, one of the cyclic ethers described above, with a third monomer, preferably bifunctional compounds of the formula
  • Preferred monomers of this type are ethylene diglycide, diglycidyl ether and diether from glycidylene and formaldehyde, dioxane or trioxane in the molar ratio 2: 1 and diether from 2 mol glycidyl compound and 1 mol of an aliphatic diol having 2 to 8 carbon atoms such as the diglycidyl ethers of ethylene glycol, 1 , 4-butanediol, 1, 3-butanediol, cyclobutane-1, 3-diol, 1, 2-propanediol and cyclohexane-1, 4-diol, to name just a few examples to call.
  • the preferred polyoxymethylene copolymers have melting points of at least 150oC and weight average molecular weights M w in the range of 5,000 to 200,000, preferably 7,000 to 150,000.
  • End-group stabilized polyoxymethylene polymers having C-C bonds at the chain ends are particularly preferred.
  • components C) and D) when premixed with the polyoxymethylene prior to blending, stabilize such crude polyoxymethylenes very well.
  • thermoplastic polyurethanes TPU
  • TPU thermoplastic polyurethanes
  • suitable polymers include vinylaromatic polymers, polyimides, polyolefins such as polyethylene and / or polypropylene homopolymers or copolymers, and also polyketones, polyarylene ethers (so-called HT thermoplastics), in particular polyether sulfones, polyvinyl chlorides, poly (meth) acrylates and mixtures (blends) from all the thermoplastics listed above.
  • HT thermoplastics polyarylene ethers
  • polyether sulfones polyvinyl chlorides
  • poly (meth) acrylates mixtures (blends) from all the thermoplastics listed above.
  • the black or gray-colored fibrous fillers B) are present in the molding compositions according to the invention in amounts of from 0.1 to 60, preferably from 1 to 50, and in particular from 5 to 40,% by weight.
  • Preferred fibrous fillers are carbon fibers, carbon nanotubes, long glass fibers, carbon nanofibers, aramid fibers and potassium titanate fibers, wherein glass fibers are particularly preferred as E glass. These can be used as rovings or cut glass in the commercial forms.
  • glass fibers of the same or approximately the same color as the polymer matrix are used in the present invention in particular.
  • the color of the glass and the resulting composite is gray to black.
  • Glass is an amorphous solid.
  • the basic elements that make up glass are usually silicon dioxide, sodium dioxide and calcium dioxide.
  • the fabrics generally give transparent glasses.
  • the hardness or color of the glass can be changed.
  • Glass has no arrangements such.
  • the simplest glass is the quartz glass. It consists only of silicon dioxide. Each silicon atom is surrounded by four oxygen atoms. This constellation yields a tetrahedron.
  • To produce the quartz glass particularly high temperatures of more than 1600 ° C. are required.
  • the melting point can be increased and the strength can be improved.
  • Each supplied ion separates the grid of silicon dioxide. Emerging chains can become very long. However, there is no ordered structure.
  • An essential feature is the chemical composition, resulting in three main groups: soda lime glass, lead glass, borosilicate glass. At least 95% of the total glass production is attributed to these 3 groups, the remaining 5% are special glasses.
  • Glass products can also be distinguished by product form, manufacturing method and application. Essentially, there are the following main groups: flat glass, hollow glass and glass tube, pressed glass (glass bricks, concrete glass blocks, glass roof tiles), glass fiber, insulating materials made of glass, special glass, optical glass.
  • glass allows light to pass through, because there are no interfaces inside that can reflect the light, and further, the atomic structure of glass does not absorb the visible light. Light is absorbed in a matter when the energy of light in matter excites to vibrate. Metal has many free electrons and is therefore impermeable to light. Even black-colored glass does not allow light to pass through, because this black glass contains the coloring ions of cobalt, iron or manganese and their electrons absorb the energy of visible light.
  • lead glass can be used as a further type of glass. In this type of glass, calcium oxide is replaced by lead oxide. Leaded glass impresses with its high refractive index, lack of color, shine and a beautiful sound.
  • Glass fibers are long, thin fibers made of o. Glass types exist. To produce glass fibers, molten glass is drawn into thin threads. Glass fibers are used in glass fiber cables for data transmission, or as roving or textile fabric, for thermal and acoustic insulation, and for glass fiber reinforced plastics.
  • the coloring of glass fibers can be achieved either by coloring the glass matrix itself, e.g. by addition of C) or by applying a dye to the exterior of the fiber.
  • the latter methods of coloring are described, for example, in US Pat. No. 2,932,587, US Pat. No. 2,824,828, US Pat. No. 2,593,818.
  • the introduction of colorants into the glass fiber size is also known to the person skilled in the art as a common coloring method for glass fibers.
  • the fibrous fillers B) can be surface-pretreated for better compatibility with the thermoplastic with a silane compound.
  • Suitable silane compounds are those of the general formula
  • X is NH 2 -, CH 2 -CH-, HO-,
  • O n is an integer from 2 to 10, preferably 3 to 4 m, an integer from 1 to 5, preferably 1 to 2 k, an integer from 1 to 3, preferably 1
  • Preferred silane compounds are aminopropyltrimethoxysilane, aminobutyltrimethoxysilane, aminopropyltriethoxysilane, aminobutyltriethoxysilane and the corresponding silanes which contain a glycidyl group as substituent X.
  • the silane compounds are generally used in amounts of from 0.01 to 2, preferably from 0.025 to 1, 0 and in particular from 0.05 to 0.5% by weight (based on C) of the surface coating.
  • carbon fibers also called carbon fiber, graphite fiber, carbon fiber. As a rule, these have a diameter of 5 to 15 microns and a carbon content of> 95%.
  • Carbon fibers for the production of reinforced plastics (CFRP) are generally subjected to an (oxidative) surface treatment in order to improve the adhesion between fiber and fiber. To obtain polymer matrix.
  • CFRP reinforced plastics
  • carbon fibers have a very high tensile strength (up to 6000 MPa) or a very high tensile modulus (up to 450 GPa).
  • C-fibers are temperature resistant up to 2500 0 C, corrosion resistant, good heat and electrical conductors.
  • CNF carbon nanofibers
  • Such fibers are synthetically accessible via catalyzed CVD (Chemical Vapor Deposition).
  • carbon nanotube B is understood as meaning carbonaceous macromolecules in which the carbon has (mainly) graphene structure and the individual graphene layers are arranged in a tubular manner.
  • Na- noubes and their synthesis are already known in the literature (for example J. Hu et al., Acc. Chem. Res. 32 (1999), 435-445).
  • any type of nanotube can be used within the scope of the present invention.
  • the diameter of the individual tubular graphene layers is 4 to 12 nm, in particular 5 to 10 nm.
  • Nanotubes can be divided into so-called single-walled nanotubes (SWNTs) and multiwalled nanotubes (MWNTs; Nanotubes) differ. In the MWNTs several graphene hoses are thus stacked one above the other.
  • the outer shape of the tubes may vary, this may have uniform diameter inside and outside, but there are also knot-shaped tubes and worm-like structures (vermiculär) produced.
  • the aspect ratio (length of the respective graphene tube to its diameter) is at least> 10, preferably> 50.
  • the nanotubes have a length of at least 10 nm.
  • MWNTs are preferred as component B).
  • the MWNTs have an aspect ratio of about 1000: 1 and an average length of about 10,000 nm.
  • the BET specific surface area is generally from 50 to 2000 m 2 / g, preferably from 200 to 1200 m 2 / g.
  • the resulting in the catalytic preparation impurities are generally according to HRTEM from 0.1 to 12%, preferably from 0.2 to 10%.
  • Suitable nanotubes can be obtained under the name "multiwall" from the company Hyperion Catalysis Int., Cambridge MA (USA) (see also EP 205 556, EP 969 128, EP 270 666, US 6,844,061) or Nanocyl® 7000, Sambrevil-Ie , Belgium.
  • the molding compositions according to the invention contain 0.01 to 20, preferably 0.01 to 10 and in particular 0.01 to 8 wt .-% of a gray or black colorant.
  • a colorant is generally understood to mean all colorants according to DIN 55944, which can be classified into inorganic and organic colorants as well as natural and synthetic (see Rompps Chemie Lexikon, 1981, 8th edition, page 1237).
  • the DBP adsorption rate is generally determined according to DIN 53601 or ASTM-D 2414 and represents a measure of the structure of the particular carbon black. Structurally is understood to mean the linking of carbon black primary particles to aggregates.
  • dibutyl phthalate is added dropwise to 10 g of soot, which is initially introduced in a kneader with measurable force transmission (plastographs), until the maximum torque (net point of the soot) is exceeded.
  • Component C) preferably has a BET specific surface area (according to ISO 4652 of at least 20 to 1000, preferably 30 to 300 m 2 / g.
  • the average primary particle size is usually 5 to 50, preferably 10 to 35 nm.
  • Such types of carbon black are e.g. available under the trademarks Printex® XE2 (Evonik GmbH) or Ketjen Black EC DJ 600 (Akzo) as well as furnace carbon blacks such as Printex® 90, 75, 80, 85, 95 and 60-A.
  • graphite can also be used as component C.
  • Graphite is a modification of carbon as described, for example, in AF Hollemann, E. Wieberg, N. Wieberg, "Lehrbuch der anorganischen Chemie", 91. - 100. ed., Pp. 701 - 702.
  • Graphite consists of planar Graphite can be comminuted by grinding The particle size is in the range of 0.01 ⁇ m to 1 mm, preferably in the range of 1 to 250 ⁇ m.
  • Graphites are very soft (Mohs hardness 1) and have a greyish to black intrinsic color. Their density is usually from 2.1 to 2.3 g / cm 3 .
  • graphene monoatomic layers of honeycombed arranged as sp 2 -hybridized called carbon atoms.
  • the condensed carbon six-membered rings have double bonds.
  • Graphenes are the basic building blocks of z. As graphite or carbon blacks, in which they are ordered and flat or disordered and bent superimposed layered. Accordingly, one way to make graphene is to break up graphite in its basal planes. Another possibility of the synthesis consists of heating hexagonal silicon carbide surfaces, wherein the silicon atoms evaporate and thin layers of monocrystalline graphite are left over from a few graphene monolayers. Graphenes are also electron conductors parallel to the surface. Commercially available graphenes are e.g. For example, the Vor x (R) products (Vorbeck Materials).
  • the thickness is usually from 1 to 5 nm, the diameter from 20 to 1000 nm and the BET from 500 to 1000 m 2 / g (N 2 ).
  • the molding compositions according to the invention contain nigrosine.
  • Nigrosines are generally understood to mean a group of black or gray indulene-related phenazine dyes (azine dyes) in various embodiments (water-soluble, fat-soluble, gas-soluble) which are useful in wool dyeing and printing, blackening of silks, for dyeing leather, shoe creams, varnishes, plastics, stoving lacquers, inks and the like, as well as being used as microscope dyes.
  • azine dyes in various embodiments (water-soluble, fat-soluble, gas-soluble) which are useful in wool dyeing and printing, blackening of silks, for dyeing leather, shoe creams, varnishes, plastics, stoving lacquers, inks and the like, as well as being used as microscope dyes.
  • Nigrosine as component C can be used as free base or else as salt (for example, hydochloride).
  • nigrosines can be found, for example, in the electronic lexicon Rompp Online, Version 2.8, Thieme-Verlag Stuttgart, 2006, keyword "nigrosine".
  • bone charcoal is suitable as colorant C.
  • the organic substance mainly Ossein
  • results from 100 kg of bone
  • Bone charcoal is used as well as activated carbon due to their strong adsorption capacity for decoloring and odor-free. From a mixture of bone charcoal and sugar or syrup, the so-called bone black or Cologne black is produced on charring with concentrated sulfuric acid.
  • Finely ground bone charcoal is also used as a painter's paint (leg black) and is suitable for coloring thermoplastic molding compounds. If the mineral constituents are dissolved out with the help of hydrochloric acid, a blacker, "more concentrated” bone charcoal remains, which is mixed with a little bit of Berlin blue as a patent black or Parisian black and is also used as Carbo medicinalis vegetabilis.
  • Suitable pigments C) are generally classified according to the Color Index (Cl.), In addition to systematic or trivial names, a unique classification enabling C.I. designation is added.
  • Black color pigments which can be used in the present invention are iron oxide black (Fe.sub.3 U.sub.4), spinel black (Cu, (Cr, Fe.sub.3 Cu), manganese black (mixture of manganese dioxide, silica and iron oxide), cobalt black and antimony black.
  • pigments C) lead to different matte shades of black color to gray and are well known, see, for. BR Gumbleter and H. Müller, Taschenbuch der Kunststoffadditive, Carl Hanser Verlag, 1983, p. 494 to 510.
  • the first preferred group of pigments are white pigments such as zinc oxide, zinc sulfide, lead white (2 PbCOs) Pb (OH) 2), Lithopone, antimony white and titanium dioxide.
  • white pigments such as zinc oxide, zinc sulfide, lead white (2 PbCOs) Pb (OH) 2
  • Lithopone antimony white and titanium dioxide.
  • titanium dioxide Of the two most common crystal modifications (rutile and anatase-type) of the titanium dioxide, in particular the rutile form is used for shading the molding compositions according to the invention.
  • thermoplastic Furthermore, it is possible to achieve the black to gray color of the thermoplastic using complementary colored pigments.
  • red to yellow pigments C) are used with correspondingly complementary pigments C) (green, blue or violet pigments) or mixtures thereof, as desired, to achieve a black to gray color of the molding compositions.
  • Preferred pigments are copper phthalocyanine pigments which have a green or blue color. The green color is generally achieved by substitution of hydrogen by chlorine atoms on macrocyclic tetraamine.
  • pigments are manganese violet pigments (pyrophosphates of ammonium and manganese (III) of the formula MnNH 4 P 2 O 7, which give bluer or redder shades by varying the stoichiometric composition), ultramarine pigments (sodium silicates, aluminum silicates), blue and green pigments based on, for example, For example, chromium oxides or cobalt oxides with spinel structure.
  • Such pigments are commercially available under the trade names Heliogen® blue, Heliogen® green, Sicopal® green, Sicopal® blue (registered trademark of BASF SE) and as ultramarine, chromium oxide or manganese violet pigments ,
  • Preferred pigments are in accordance with CI Part 1 Pigment blue 15, Pigment blue 15: 2, Pigment blue 15: 4, Pigment blue 16, Pigment blue 28, Pigment blue 29, Pigment blue 36, Pigment green 17, Pigment green 24, Pigment green 50 , Pigment violet 15 and pigment violet 16, wherein pigment blue 15: 1 and 15: 3 and pigment green 7 and 36 are particularly preferred.
  • the molding compositions of the invention may contain 0 to 40, in particular up to 30 wt .-% of other additives and processing aids.
  • customary additives D are, for example, in amounts of up to 25, preferably up to 20 wt .-% rubber-elastic polymers (often also referred to as impact modifiers, elastomers or rubbers).
  • these are copolymers which are preferably composed of at least two of the following monomers: ethylene, propylene, butadiene, isobutene, isoprene, chloroprene, vinyl acetate, styrene, acrylonitrile and acrylic or methacrylic acid esters having 1 to 18 C Atoms in the alcohol component.
  • elastomers In the following some preferred types of such elastomers are presented. Preferred types of such elastomers are the so-called ethylene-propylene (EPM) or ethylene-propylene-diene (EPDM) rubbers.
  • EPM ethylene-propylene
  • EPDM ethylene-propylene-diene
  • EPM rubbers generally have practically no double bonds, while EPDM rubbers can have 1 to 20 double bonds / 100 carbon atoms.
  • diene monomers for EPDM rubbers for example, conjugated dienes such as isoprene and butadiene, non-conjugated dienes having 5 to 25 carbon atoms such as penta-1, 4-diene, hexa-1, 4-diene, hexa-1, 5 -diene, 2,5-dimethylhexa-1,5-diene and octa-1,4-diene, cyclic dienes such as cyclopentadiene, cyclohexadienes, cyclooctadienes and dicyclopentadienes and also alkenylnorbornenes such as 5-ethylidene-2-norbornene, 5- Butylidene-2-norbornene, 2-methallyl-5-norbornene, 2-isopropenyl-5-norbornene and tricyclodienes such as 3-methyltricyclo (5.2.1.0.2.6) -3,8-decadiene or mixtures thereof.
  • the diene content of the EPDM rubbers is preferably 0.5 to 50, in particular 1 to 8 wt .-%, based on the total weight of the rubber.
  • EPM or EPDM rubbers may preferably also be grafted with reactive carboxylic acids or their derivatives.
  • reactive carboxylic acids or their derivatives e.g. Acrylic acid, methacrylic acid and its derivatives, e.g. Glycidyl (meth) acrylate, and called maleic anhydride.
  • Another group of preferred rubbers are copolymers of ethylene with acrylic acid and / or methacrylic acid and / or the esters of these acids.
  • the rubbers may still contain dicarboxylic acids such as maleic acid and fumaric acid or derivatives of these acids, e.g. Esters and anhydrides, and / or monomers containing epoxy groups.
  • dicarboxylic acid derivatives or monomers containing epoxy groups are preferably incorporated into the rubber by addition of monomers containing dicarboxylic acid or epoxy groups of the general formulas I or II or III or IV to the monomer mixture
  • R1 to R9 are hydrogen or alkyl groups having 1 to 6 carbon atoms and m is an integer of 0 to 20, g is an integer of 0 to 10 and p is an integer of 0 to 5.
  • the radicals R1 to R9 are hydrogen, where m is 0 or 1 and g is 1.
  • the corresponding compounds are maleic acid, fumaric acid, maleic anhydride, allyl glycidyl ether and vinyl glycidyl ether.
  • Preferred compounds of the formulas I, II and IV are maleic acid, maleic anhydride and epoxy group-containing esters of acrylic acid and / or methacrylic acid, such as glycidyl acrylate, glycidyl methacrylate and the esters with tertiary alcohols, such as t-butyl acrylate. Although the latter have no free carboxyl groups, their behavior is close to the free acids and are therefore termed monomers with latent carboxyl groups.
  • the copolymers consist of 50 to 98 wt .-% of ethylene, 0.1 to 20 wt .-% of monomers containing epoxy groups and / or methacrylic acid and / or acid-anhydride-containing monomers and the remaining amount of (meth) acrylic acid esters.
  • 0.1 to 40 in particular 0.3 to 20 wt .-% glycidyl acrylate and / or glycidyl methacrylate, (meth) acrylic acid and / or maleic anhydride, and
  • esters of acrylic and / or methacrylic acid are the methyl, ethyl, propyl and i- or t-butyl esters.
  • vinyl esters and vinyl ethers can also be used as comonomers.
  • the ethylene copolymers described above can be prepared by methods known per se, preferably by random copolymerization under high pressure and elevated temperature. Corresponding methods are generally known.
  • Preferred elastomers are also emulsion polymers, their preparation e.g. at Blackley in the monograph "Emulsion Polymerization".
  • the emulsifiers and catalysts which can be used are known per se.
  • homogeneously constructed elastomers or those with a shell structure can be used.
  • the shell-like structure is determined by the order of addition of the individual monomers; the morphology of the polymers is also influenced by this order of addition.
  • acrylates such as e.g. N-butyl acrylate and 2-ethylhexyl acrylate, corresponding methacrylates, butadiene and isoprene and their mixtures called.
  • monomers for the preparation of the rubber portion of the elastomers acrylates such as e.g. N-butyl acrylate and 2-ethylhexyl acrylate, corresponding methacrylates, butadiene and isoprene and their mixtures called.
  • monomers may be reacted with other monomers such as e.g. Styrene, acrylonitrile, vinyl ethers and other acrylates or methacrylates such as methyl methacrylate, methyl acrylate, ethyl acrylate and propyl acrylate are copolymerized.
  • the soft or rubber phase (with a glass transition temperature below 0 ° C.) of the elastomers can be the core, the outer shell or a middle shell (in the case of elastomers with more than two-shelled construction); in the case of multi-shell elastomers, it is also possible for a plurality of shells to consist of a rubber phase.
  • one or more hard components (with glass transition temperatures of more than 20 0 C) to the structure of the elastomer, so these are generally prepared by polymerization of styrene, acrylonitrile, methacrylonitrile, ⁇ -methylstyrene, p-methylstyrene, Acrylklareestern and methacrylic acid esters such as methyl acrylate, ethyl acrylate and methyl methacrylate as the main monomers.
  • methacrylic acid esters such as methyl acrylate, ethyl acrylate and methyl methacrylate as the main monomers.
  • smaller proportions of other comonomers can also be used here.
  • emulsion polymers which have reactive groups on the surface.
  • groups are, for example, epoxy, carboxyl, latent carboxyl, amino or amide groups and functional groups obtained by concomitant use of monomers of the general formula can be introduced
  • R 10 is hydrogen or a C 1 to C 4 alkyl group
  • R 11 is hydrogen, a C 1 to C 8 alkyl group or an aryl group, in particular
  • R 12 is hydrogen, a C 1 to C 10 alkyl, a C 6 to C 12 aryl group or -OR 13
  • R 13 is a C 1 to C 1 alkyl or C 6 to C 12 aryl group, which is optionally substituted by O or
  • X is a chemical bond, a C 1 -C 10 -alkylene or C 6 -C 12 -arylene group
  • Z is a C 1 -C 10 -alkylene or C 6 -C 12 -arylene group.
  • the graft monomers described in EP-A 208 187 are also suitable for introducing reactive groups on the surface.
  • acrylamide methacrylamide and substituted esters of acrylic acid or methacrylic acid, such as (Nt-butylamino) -ethyl methacrylate, (N, N-dimethylamino) ethyl acrylate, (N, N-dimethylamino) -methyl acrylate and (N, N-) Diethylamino) ethyl acrylate.
  • the particles of the rubber phase can also be crosslinked.
  • monomers acting as crosslinkers are buta-1,3-diene, divinylbenzene, diallyl phthalate and dihydrodicyclopentadienyl acrylate, and also the compounds described in EP-A 50 265.
  • graft-linking monomers ie monomers having two or more polymerizable double bonds which react at different rates during the polymerization. Preference is given to using those compounds in which at least one reactive group polymerizes at about the same rate as the other monomers, while the other reactive group (or reactive groups), for example, polymerizes (polymerizes) much more slowly.
  • the different polymerization rates bring a certain proportion of unsaturated double bonds in the rubber with it. If a further phase is subsequently grafted onto such a rubber, the double bonds present in the rubber react at least partially with the grafting monomers to form chemical bonds, ie the grafted-on phase is at least partially linked to the grafting base via chemical bonds.
  • graft-crosslinking monomers examples include allyl-containing monomers, in particular allyl esters of ethylenically unsaturated carboxylic acids, such as allyl acrylate, allyl methacrylate, diallyl maleate, diallyl fumarate, diallyl itaconate or the corresponding monoallyl compounds of these dicarboxylic acids.
  • allyl-containing monomers such as allyl acrylate, allyl methacrylate, diallyl maleate, diallyl fumarate, diallyl itaconate or the corresponding monoallyl compounds of these dicarboxylic acids.
  • allyl-containing monomers in particular allyl esters of ethylenically unsaturated carboxylic acids, such as allyl acrylate, allyl methacrylate, diallyl maleate, diallyl fumarate, diallyl itaconate or the corresponding monoallyl compounds of these dicarboxylic acids.
  • the proportion of these crosslinking monomers in the impact-modifying polymer is up to 5% by weight, preferably not more than 3% by weight, based on the impact-modifying polymer.
  • graft polymers having a core and at least one outer shell, which have the following structure:
  • graft polymers having a multi-shell structure instead of graft polymers having a multi-shell structure, homogeneous, i. single-shell elastomers of buta-1, 3-diene, isoprene and n-butyl acrylate or copolymers thereof are used. These products can also be prepared by concomitant use of crosslinking monomers or monomers having reactive groups.
  • emulsion polymers examples include n-butyl acrylate / (meth) acrylic acid copolymers, n-butyl acrylate / glycidyl acrylate or n-butyl acrylate / glycidyl methacrylate copolymers, graft polymers having an inner core of n-butyl acrylate or butadiene-based and an outer shell of the above copolymers and copolymers of ethylene with comonomers which provide reactive groups.
  • the novel molding materials may contain 0 to 5, preferably 0.05 to 3 and in particular 0.1 to 2 wt .-% of at least one ester or amide of saturated or unsaturated aliphatic carboxylic acids having 10 to 44, preferably 16 to 22 C Atoms containing aliphatic saturated alcohols or amines having 2 to 40, preferably 2 to 6 carbon atoms.
  • the carboxylic acids can be 1- or 2-valent.
  • alcohols are n-butanol, n-octanol, stearyl alcohol, ethylene glycol, propylene glycol, neopentyl glycol, pentaerythritol, with glycerol and pentaerythritol being preferred.
  • the aliphatic amines can be monohydric to trihydric. Examples of these are stearylamine, ethylenediamine, propylenediamine, hexamethylenediamine, di (6-aminohexyl) amine, with ethylenediamine and hexamethylenediamine being particularly preferred.
  • Preferred esters or amides are correspondingly glyceryl distearate, glycerol tristearate, ethylenediamine sistearate, glycerol monopalmitate, glycerol trillaurate, glycerol monobehenate and pentaerythritol tetrastearate.
  • fibrous or particulate fillers D) - without staining - carbon fibers long glass fibers, glass fibers, glass beads, amorphous silica, asbestos, calcium silicate, calcium metasilicate, magnesium carbonate, kaolin, chalk, powdered quartz, mica, barium sulfate and feldspar called in amounts to be used to 50 wt .-%, in particular up to 40%.
  • Preferred fibrous fillers are carbon fibers, aramid fibers and potassium titanate fibers, glass fibers being particularly preferred as E glass. These can be used as rovings or cut glass in the commercial forms.
  • the fibrous fillers can be surface-pretreated with a silane compound.
  • acicular mineral fillers are also suitable.
  • needle-shaped mineral fillers are understood to mean a mineral filler with a pronounced, needle-like character.
  • An example is acicular wollastonite.
  • the mineral has a UD (length diameter) ratio of 8: 1 to 35: 1, preferably 8: 1 to 1: 1: 1.
  • the mineral filler may optionally be pretreated with the abovementioned silane compounds; however, pretreatment is not essential.
  • Kaolin, calcined kaolin, wollastonite, talc and chalk are mentioned as further fillers.
  • thermoplastic molding compositions according to the invention can be prepared by processes known per se, in which mixing the starting components in conventional mixing devices such as screw extruders, Brabender mills or Banbury mills and then extruded. After extrusion, the extrudate can be cooled and comminuted. It is also possible to premix individual components and then to add the remaining starting materials individually and / or likewise mixed.
  • the mixing temperatures are usually 230 to 320 0 C.
  • the components B) to C) and optionally D) can be mixed with a prepolymer, formulated and granulated. Become Neil. The resulting granules are then condensed in solid phase under inert gas continuously or discontinuously at a temperature below the melting point of component A) to the desired viscosity.
  • thermoplastic molding compositions of the invention are characterized by good mechanics, in particular a good toughness and good damage work with good stiffness (low drop in moisture absorption), as well as a significantly improved UV stability and color consistency and color depth.
  • Exterior parts on automobiles including trucks (for example, mirror mount, windscreen wiper arms, roof rails, etc.) - Furniture for indoors and outdoors (garden chairs, etc.) Generally visible components / objects that do not become ugly with age
  • Vehicle interior speaker grille, covers
  • Polybutylene terephathalate with a viscosity number VZ of 130 ml / g and a carboxyl end group content of 34 meq / kg (Ultradur® B 4520 from BASF SE) (VZ measured in 0.5% strength by weight solution of phenol / o-dichlorobenzene, 1 : 1 mixture) at 25 ° C, containing 0.65 wt .-% pentaerythritol tetrastearate.
  • Component B is a compound having Component B:
  • the glass fiber bundles contain 0.5-0.8% by weight of a size functionalized with an epoxy silane.
  • Colorless glass fiber made of E-glass with a diameter of 10 ⁇ m, which was added for packaging in bundles of approx. 4.5 mm in length.
  • the glass fiber bundles contain 0.5-0.8% by weight of a size functionalized with an epoxy silane.
  • the plastic molding compositions of Examples 1-2 were prepared by Schmelzecompoundie- tion with a twin-screw extruder (at 280 0 C). Subsequently, in an injection molding die having 60 * 60 * 2 mm 3 were manufactured, which were weathered. The weathering took place in the Weather-O-Mat (Atlas Material Testing Technology LLC) under the conditions of the SAE J 1960 standard. These conditions were
  • the impact resistance was measured on unnotched specimens with 80 * 10 * 4 mm 3 edgewise according to ISO 179/1 eil.
  • compositions of the molding compositions and the results of the measurements are shown in the table.

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Abstract

La présente invention a pour objet des matières à mouler thermoplastiques comprenant A) de 20 à 99,99 % en poids d'un polymère thermoplastique B) de 0,1 à 60 % en poids d'une charge fibreuse de couleur noire ou grise C) de 0,01 à 20 % en poids d'un colorant noir ou gris D) de 0 à 40 % en poids d'autres additifs, la somme des pourcentages en poids des composants A) à D) étant égale à 100 %.
PCT/EP2010/051003 2009-02-04 2010-01-28 Matières à mouler thermoplastiques noires et stables aux uv Ceased WO2010089241A1 (fr)

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CN108841152A (zh) * 2018-06-30 2018-11-20 杭州高烯科技有限公司 一种石墨烯-发泡聚乳酸复合材料及其制备方法
WO2019011789A1 (fr) 2017-07-14 2019-01-17 Clariant Plastics & Coatings Ltd Compositions de polyamide ignifuges de couleur grise et leur utilisation
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