EP2188333A1

EP2188333A1 - Molded parts having improved surfaces

Info

Publication number: EP2188333A1
Application number: EP08785612A
Authority: EP
Inventors: Rolf Wehrmann; Michael Erkelenz; Gesa Dern; Berit Krauter
Original assignee: Bayer MaterialScience AG
Current assignee: Covestro Deutschland AG
Priority date: 2007-08-30
Filing date: 2008-08-19
Publication date: 2010-05-26
Also published as: CN101784600A; WO2009030357A1; US20110269896A1; KR20100058513A; JP2010537012A

Abstract

The invention relates to molded parts, obtained from compositions containing A) 99.91 to 85 wt.-% thermoplastic, and B) 0.09 to 15 wt.-% multi-wall carbon nanotubes, having a 20° gloss from 104 to 20 and a 60° gloss from 103 to 50, measured in accordance with ISO 2813, utilizing a Byk/Gardner haze gloss, and to the use of the compositions for the production of molded parts having said degrees of gloss.

Description

Moldings with improved surfaces

Polycarbonates belong to the group of engineering thermoplastics. Technical thermoplastics find versatile applications in the electrical and electronics sector, as housing material of luminaires and in applications where special mechanical properties are required. These applications almost always require good thermal and mechanical properties such as Vicat temperature, glass transition temperature and impact strength. This u. a. Blacks used for dark or opaque coloring. A disadvantage of such compositions is often the shiny surface of the articles / moldings made therefrom. To prevent this disadvantage, the tool surfaces must be roughened

It was therefore an object to provide moldings that do not have the disadvantages mentioned above.

Thermoplastics and Multi Wall Carbon Nanotubes (MWCNT) have not been found to have these disadvantages.

EP-A 1770126 describes polycarbonate compositions containing a fluorine-containing organic metal salt, at least one further component selected from the group consisting of a flame retardant, a fatty acid ester, a UV absorber, PTFE fibers, a filler, a silicate mineral and a titanium dioxide pigment. As fillers a variety of different fillers are mentioned, among others, so-called MWCNT (mulitwall carbon nanotubes) are mentioned. Concrete examples containing MWCNT are not described.

JP 2006-291081 A, JP 2006-193649 A, JP 2006-016553A and WO 2008/078850 A describe the use of MWCNT in polycarbonate. However, the cited patent applications do not describe molded parts made of polycarbonate and MWCNT with a certain degree of gloss.

The invention therefore relates to moldings obtainable from compositions containing

A) 99.91 to 85% by weight, preferably 99.90 to 88, particularly preferably 99.88 to 93% by weight.

%, very particularly preferably 99.70 to 93% by weight, in particular 98 to 94% by weight, of thermoplastic and

B) 0.09 to 15 wt .-%, preferably 0.1 to 12 wt .-%, particularly preferably 0.12 to 7 wt .-%, most preferably 0.3 to 7 wt.%, In particular 2 to 6 wt.% Multi Wall Carbon Nanotubes, a degree of gloss 20 ° of 104 to 20, preferably 100 to 20, particularly preferably 40 to 22 and a gloss level 60 ° of 103 to 50, preferably 100 to 50, particularly preferably 80 to 55, measured according to ISO 2813 with a Byk-Gardner Haze gloss exhibit.

The subject of the present invention is furthermore the use of compositions containing

A) 99.91 to 85 wt.%, Preferably 99.90 to 88, particularly preferably 99.88 to 93 wt.%, Very particularly preferably 99.70 to 93 wt.%, In particular 98 to 94 wt.% Thermoplastic and

B) 0.09 to 15 wt .-%, preferably 0.1 to 12 wt .-%, particularly preferably 0.12 to 7 wt .-%, most preferably 0.3 to 7 wt.%, In particular 2 to 6% by weight ^' Multi Wall Carbon Nanotubes,

for the production of molded parts which have a degree of gloss 20 ° of 104 to 20, preferably 100 to 20, particularly preferably 40 to 22 and a degree of gloss 60 ° of 103 to 50, preferably 100 to 50, particularly preferably 80 to 55, measured according to ISO 2813 with a Byk-Gardner haze gloss.

As thermoplastics are particularly transparent thermoplastics such as polycarbonate, polyester, z. As polyethylene terephthalate and Polybutylenterephtalat, polysulfones, polyethers, polyolefins, cycloolefin copolymers, polystyrenes and polyacrylates. Preferred thermoplastic is polycarbonate. But also opaque compositions such as polycarbonate-based blends such. B. with polyesters, SAN, ABS and / or polylactate are suitable.

Multiwall carbon nanotubes (MWNTs) are preferably understood as meaning cylindrical carbon tubes with a carbon content of> 95%, which contain no amorphous carbon. The carbon nanotubes preferably have an outer diameter between 3 and 80 nm, more preferably 5 to 20 nm. The mean value of the outer diameter is preferably 13 to 16 nm. The length of the cylindrical carbon nanotubes is preferably 0.1 to 20 .mu.m, more preferably 1 to 10 .mu.m. The carbon nanotubes preferably consist of 2 to 50, more preferably 3 to 15 graphitic layers (also referred to as "layers" or "walls") having a minimum inside diameter of 2 to 6 nm. These carbon nanotubes are also referred to as "carbon fibrils" or "hollow carbon fibers", for example. The preparation of the MWNT used according to the invention is generally known (cf., for example, US Pat. No. 5,643,502 and DE 10 2006 017 695 A1, preferably the preparation is carried out according to the method described in DE 10 2006 017 695 Al, particularly preferably according to the method disclosed in Example 3 of DE 10 2006 017 695 A1).

Thermoplastic, aromatic polycarbonates in the context of the present invention are both homopolycarbonates and copolycarbonates; The polycarbonates may be linear or branched in a known manner.

The thermoplastic polycarbonates, including the thermoplastic, aromatic polyester carbonates, have average molecular weights M _w (determined by gel permeation chromatography with polycarbonate calibration) of 12,000 to 120,000, preferably of 15,000 to 80,000, in particular of 18,000 to 60,000. most preferably from 18,000 to 40,000 g / mol.

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

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

Dihydroxyaryl compounds suitable for the preparation of polycarbonates are those of the formula (2)

HO-Z-OH (2)

in which

Z is an aromatic radical having 6 to 30 C atoms which may contain one or more aromatic nuclei, may be substituted and may contain aliphatic or cycloaliphatic radicals or alkylaryls or heteroatoms as bridge members.

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

in the

R ⁶ and R ⁷ independently of one another are H, C 1 -C 6 -alkyl-, C 1 -C 6 -alkoxy, halogen, such as Cl or Br, or each optionally substituted aryl or aralkyl, preferably H or C 1 -C ₂ -alkyl, particularly preferably H or Q-Cg-alkyl and very particularly preferably H or methyl, and

X is a single bond, -SO ₂ -, -CO-, -O-, -S-, C _r to Cβ-alkylene, C ₂ - to C ₅ -alkylidene or

C ₅ - to C (, - cycloalkylidene which may be substituted by Q- to C _ό -alkyl, preferably methyl or ethyl, furthermore C ₆ - to C ^ -arylene which optionally condenses with further heteroatome-containing aromatic rings can be, stands.

X is preferably a single bond, C ₁ to C ₅ -alkylene, C ₂ to C ₅ -alkylidene, C ₅ to C ₆ -cycloalkylidene, -O-, -SO-, -CO-, -S-, - SO ₂ -,

or one for a radical of the formula (3a) or (3b)

in which

R ⁸ and R ^{9 are} individually selectable for each X ¹ , independently of one another are hydrogen or C ¹ -C 4 -alkyl, preferably hydrogen, methyl or ethyl, and

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

Examples of dihydroxyaryl compounds (diphenols) are dihydroxybenzenes, dihydroxydiphenyls, bis (hydroxyphenyl) alkanes, bis (hydroxyphenyl) -cycloalkanes, bis (hydroxyphenyl) -aryls, bis (hydroxyphenyl) ethers, bis (hydroxyphenyl) ketones, bis (hydroxyphenyl) sulfides, bis (hydroxyphenyl) sulfones, bis (hydroxyphenyl) sulfoxides, l, r-bis (hydroxyphenyl) -dnsopropylbenzenes, and their ring-alkylated and ring-halogenated compounds

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

Preferred diphenols are 4,4'-dihydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) -1-phenyl-propane, 1,1-bis (4-hydroxyphenyl) -phenyl-ethane, 2,2-bis- (4-hydroxyphenyl) propane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 1,3-bis [2- (4-hydroxyphenyl) -2-propyl] benzene (bisphenol M), 2, 2-bis- (3-methyl-4-hydroxyphenyl) -propane, bis (3,5-dimethyl-4-hydroxyphenyl) -methane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) - propane, bis- (3,5-dimethyl-4-hydroxyphenyl) sulfone, 2,4-bis- (3,5-dimethyl-4-hydroxyphenyl) -2-methylbutane, 1,3-bis- [2- (2- 3,5-dimethyl-4-hydroxyphenyl) -2-propyl] -benzene and 1, 1-bis (4-hydroxyphenyl) -3,3,5-t-methylcyclohexane (bisphenol TMC)

Particularly preferred diphenols are 4,4'-dihydroxydiphenyl, 1, 1-bis (4-hydroxyphenyl) phenyl ethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3,5 -dimethyl-4-hydroxyphenyl) -propane, 1,1-bis (4-hydroxyphenyl) -cyclohexane and 1,1-bis (4-hydroxyphenyl) -3,3,5-t-methylcyclohexane (Bisphenol TMC)

These and other suitable diphenols are described, for example, in US Pat. Nos. 2,999,835, 3,148,172, 2,991,273, 3,271,367, 4,982,014 and 2,999,846, in German Offenlegungsschπften 1 570 703, 2 063 050, 2 036,052, 2,121,1956 and 3,832,396, French Patent 1,561,518, in the monograph "H Fast, Chemistry and Physics of Polycarbonates, Interscience Pubhshers, New York 1964, pp. 28ff, p. 102ff", and in "DG Legrand, JT Bendler, Handbook of Polycarbonates Science and Technology, Marcel Dekker New York 2000, p. 72ff "

In the case of homopolycarbonates, only one diphenol is used, in the case of copolycarbonates, two or more diphenols are used. The diphenols used, as well as all others of the Synthesis added chemicals and adjuvants may be contaminated with the impurities derived from their own synthesis, handling and storage. However, it is desirable to work with as pure as possible raw materials.

The monofunctional chain terminators needed to control the molecular weight, such as phenol or alkylphenols, in particular phenol, p-tert. Butylphenol, iso-octylphenol, cumylphenol, their chlorocarbonic acid esters or acid chlorides of monocarboxylic acids or mixtures of these chain terminators are fed either with the bisphenolate or the bisphenolates of the reaction or added at any time during the synthesis, as long as phosgene or Chlorkohlensäureendgruppen in the reaction mixture are present or in the case of acid chlorides and chloroformate as chain terminators as long as enough phenolic end groups of the forming polymer are available. Preferably, however, the chain terminator (s) are added after phosgenation at one point or at a time when phosgene is no longer present but the catalyst has not yet been metered, or before the catalyst, with the catalyst together or in parallel.

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

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

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

Preferred branching agents are 3,3-bis (3-methyl-4-hydroxyphenyl) -2-oxo-2,3-dihydroindole and 1,1,1-tri- (4-hydroxyphenyl) -ethane.

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

The branching agents can be presented either with the diphenols and the chain terminators in the aqueous alkaline phase, or dissolved in an organic solvent prior to phosgenation be added.

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

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

Of the aromatic dicarboxylic acids, terephthalic acid and / or isophthalic acid are particularly preferably used.

Derivatives of the dicarboxylic acids are the dicarboxylic acid dihalides and the dicarboxylic acid dialkyl esters, in particular the dicarboxylic acid dichlorides and the dimethyl dicarboxylates.

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

Preferred methods of preparation of the polycarbonates to be used according to the invention, including the polyester carbonates, are the known interfacial process and the known melt remover process (cf., for example, WO 2004/063249 A1, WO 2001/05866 A1, WO 2000/105867, US Pat. No. 5,340,905, US 5,097,002, US-A 5,717,057).

In the first case, the acid derivatives used are preferably phosgene and optionally dicarboxylic acid dichlorides, in the latter case preferably diphenyl carbonate and optionally dicarboxylic acid diester. Catalysts, solvents, workup, reaction conditions, etc., for polycarbonate production or polyester carbonate production are sufficiently described and known in both cases.

The polycarbonates, polyester carbonates and polyesters can be worked up in a known manner and processed to form any shaped articles, for example by extrusion or injection molding.

The polycarbonate compositions may be added to the conventional additives for the thermoplastics mentioned additives such as fillers, UV stabilizers, heat stabilizers, antistatic agents, dyes and pigments, mold release agents, ER absorbers and flame retardants in the usual amounts become. It is particularly preferred to use only those that do not affect the transparency of the material.

Suitable additives are described, for example, in "Additives for Plastics Handbook, John Murphy, Elsevier, Oxford 1999", in the "Plastics Additives Handbook, Hans Zweifel, Hanser, Munich 2001".

Suitable antioxidants or thermal stabilizers are, for example:

Alkylated monophenols, alkylthiomethylphenols, hydroquinones and alkylated hydroquinones, tocopherols, hydroxylated thiodiphenyl ethers, alkylidenebisphenols, O-, N- and S-benzyl compounds, hydroxybenzylated malonates, aromatic hydroxybenzyl compounds, triazine compounds, acyl laminophenols, esters of β- (3,5-) Di-tert-butyl-4-hydroxyphenyl) propionic acid, esters of β- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid, esters of β- (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid, Esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid, amides of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid, suitable thiosynergists, secondary antioxidants, phosphites and phosphonites, benzofuranones and indolinones ,

Preference is given to organic phosphites, phosphonates and phosphanes, usually those in which the organic radicals completely or partially consist of optionally substituted aromatic radicals.

As thermostabilizer is very particularly preferred (2,4,6-tri-t-butylphenyl) - (2-butyl-2-ethyl-propane-1, 3-diyl) phosphite:

The phosphites can be used alone, but also in combination with other phosphorus compounds, wherein the other phosphorus compounds can also be those which have a different oxidation number of the phosphorus. Accordingly, for example, combinations of the phosphites according to the invention with other phosphites, with phosphines, for example triphenylphosphine, with phosphonites, with phosphates, with phosphonates, etc. can be used. Phosphines can also be used alone, for example triphenylphosphine or tritoluylphosphine. The phosphites used are generally known or prepared analogously to known phosphites, (2,4,6-tri-t-butylphenyl) - (2-butyl-2-ethyl-propane-l, 3-diyl) phosphite is described for example in the EP-A 702 018 and EP 635 514.

The polymer mixtures generally contain the phosphorus compound in a proportion of 10 to 5000 ppm, preferably 10 to 1000 ppm, particularly preferably 20 to 700 ppm, very particularly preferably between 50 and 500 ppm.

The addition of the mold release agents, the phosphorus compound and the formals to the thermoplastic molding compositions is carried out by way of example and preferably by adding them after the preparation and during the work-up of the polycarbonates, e.g. added by addition to the polycarbonate polymer solution, or a melt of the thermoplastic molding compositions. Furthermore, it is also possible to meter in the components independently of one another in different work steps, e.g. one of the components during the processing of the polymer solution and the other (s) component (s) in the melt, as long as it is ensured that all components in the production of the end products (moldings) are included.

Very particularly suitable additives are IRGANOX 1076 ^®, and so the group of benzotriazoles 2.1 (so-called. Tinuvins), in particular in mixture with one another as well as triphenylphosphine (TPP).

Suitable flame retardants C) are: alkali metal or alkaline earth metal salts of aliphatic or aromatic sulfonic acid sulfonamide and sulfonimide derivatives, e.g. Potassium perfluorobutanesulfonate, potassium diphenyl sulfone sulfonate, N- (p-tolylsulfonyl) -p-toluenesulfimide potassium salt, N- (N'-benzylamino-cabonyl) -sulfanylimide potassium salt.

Salts which can optionally be used in the molding compositions are, for example:

Sodium or potassium perfluorobutanesulfate, sodium or potassium perfluoromethanesulfonate, sodium or potassium perfluorooctane sulfate, sodium or potassium 2,5-dichlorobenzene sulfate, sodium or potassium 2,4,5-trichlorobenzene sulfate, sodium or potassium methylphosphonate, sodium or potassium - (2-phenyl-ethylene) -phosphonate, sodium or potassium pentachlorobenzoate, sodium or potassium 2,4,6-trichlorobenzoate, sodium or potassium 2,4-dichlorobenzoate, lithium phenylphosphonate, sodium or potassium diphenylsulfone sulfonate, sodium or potassium 2-formylbenzenesulfonate, sodium or potassium (N-benzenesulfonyl) benzenesulfonamide. Trisodium or tripotassium hexafluoroaluminate, disodium or dipotassium hexafluorotitanate, disodium or dipotassium hexafluorosilicate, disodium or dipotassium hexafluorozirconate, sodium or potassium pyrophosphate, sodium or potassium metaphosphate, sodium or potassium tetrafluoroborate , Sodium or potassium hexafluorophosphate, Sodium or potassium or lithium phosphate, N- (p-tolylsulfonyl) -p-toluenesulfimide potassium salt, N- (N'-benzylaminocarbonyl) -sulfanylimide potassium salt.

Preference is given to sodium or potassium perfluorobutane sulfate, sodium or potassium perfluorooctane sulfate, sodium or potassium diphenylsulfone sulfonate and sodium or potassium 2,4,6-trichlorobenzoate and N- (p-tolylsulfonyl) -p-toluenesulfimide Potassium salt, N- (N'-benzylaminocarbonyl) sulfanylimide potassium salt most particularly preferred are potassium perfluorobutane sulfate and sodium or potassium diphenylsulfone sulfonate.

Likewise suitable are mixtures of the salts mentioned.

These organic flame retardant salts are preferably used in amounts of from 0.01 to 0.1 part by weight, preferably from 0.01 to 0.08 part by weight, more preferably from 0.01 to 0.06 part by weight, and more preferably 0.01 to 0.03 parts by weight (based on the polymer composition) used in the molding compositions.

In addition, the compositions may contain suitable PTFE blends. These are all physical mixtures of PTFE (polytetrafluoroethylene) with a layer substance which is compatible with polycarbonate or polyester carbonate and PTFE and obtains the fibril structure of the PTFE chains. Suitable substances are, for example, styrene-acrylonitrile copolymers (SAN) and polyacrylates. In these blends, PTFE is present in proportions of 20-80% by weight, preferably 20-70% by weight and most preferably 30-60% by weight. Such blends are commercially available for example under the trade name Blendex ^® B449 of GE Specialty Chemicals or Metablen A ^® series from Mitsubishi Rayon. The blends are prepared by mixing a PTFE emulsion with an emulsion of the suitable blend partner. From the resulting mixture, the blend is recovered by a suitable method such as coagulation, freeze drying, spray drying, etc.

Alkali or alkaline earth salts for the production of flame-retardant polycarbonate are known, see, for example: US Pat. Nos. 3,775,367, 3,836,490, 3,933,734, 3,940,366, 3,953,399, 3,926,908, 4,104,246, 4,469,833 , 4,626,563, 4,254,015, 4,626,563 and 4,649,168.

These substances are found in many publications, such as Additives for Plastics Handbook, John Murphy, 1999, and are commercially available.

1. Suitable antioxidants are, for example:

1.1. Alkylated monophenols, for example 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl 4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2- (α-methylcyclohexyl) -4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6- Di-tert-butyl-4-methoxymethylphenol, nonylphenols which are linear or branched in the side chain, for example, 2,6-dinonyl-4-methylphenol, 2,4-dimethyl-6- (1 '- methylundec-r-yl) phenol, 2,4-dimethyl-6- (1'-methylheptadec-1'-yl) phenol, 2,4-dimethyl-6- (1 '-methyltridec-r-yl) phenol ,

1.2. Alkylthiomethylphenols

1.3. Hydroquinones and alkylated hydroquinones

1.4. tocopherols

1.5. Hydroxylated thiodiphenyl ethers

1.6. alkylidene

1.7. O, N and S benzyl compounds

1.8. Hydroxybenzylated malonates.

1.9. Aromatic hydroxybenzyl compounds

1.10. triazine

1.1 1. Acylaminophenols

1.12. Esters of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid with monohydric or polyhydric alcohols, very particular preference is given to the ester with octadecanol (IRGANOX 1076® from Ciba Spec.)

1.13. Esters of ß- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid with mono- or polyhydric alcohols

1.14. Esters of β- (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid with monohydric or polyhydric alcohols

1.15. Esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid with monohydric or polyhydric alcohols,

16.1. Amides of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid

1.17. Ascorbic acid (vitamin C) 1.18. Amine antioxidants

1.19 Suitable thiosynergists are, for example, dilauryl thiodipropionate and / or distearyl thiodipropionate.

2. UV absorbers and light stabilizers can be used in the compositions according to the invention in amounts of from 0.1 to 15% by weight, preferably from 3 to 8% by weight, based on the mass of the composition. Suitable UV absorbers and light stabilizers are, for example:

2.1. 2- (2'-Hydroxyphenyl) benzotriazoles, for example 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (3 ', 5'-di-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2 - (5'-tert-butyl-2'-hydroxyphenylbenzotriazole, 2- (2'-hydroxy-5 '- (1, l, 3,3-tetramethylbutyl) phenyl) benzo-triazole, 2- (3', 5 '-Di-tert-butyl-2'-hydroxyphenyl) -5-chlorobenzo-triazole, 2- (3'-tert-butyl-2'-hydroxy-5'-methylphenyl) -5-chlorobenzotriazole, 2- (3 '- sec -butyl-5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-4'-octyloxyphenyl) benzotriazole, 2- (3', 5'-di-tert-amyl- 2'-hydroxyphenyl) benzotriazole, 2- (3 ', 5'-bis (α, α-dimethylbenzyl) -2'-hydroxyphenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'- (2-octyloxycarbonyl-ethyl) -phenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-5 '- [2- (2-ethyl-hexyloxy) -carbonyl-ethyl] -2'-hydroxyphenyl) -5- chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-meth-oxycarbonylethyl) phenyl) -5-chlorobenzotriazole, 2- (3 ^{1-tert-butyl-2'-hydroxy} -5 ^I - (2-methoxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydrox y-5 '- (2-octyloxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert-Butyl-5' - [2- (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) benzotriazole, 2- 3'-Dodecyl-2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-isooctyl-oxycarbonylethyl) phenylbenzotriazole, 2,2' -Methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-benzotriazol-2-ylphenol]; the transesterification product of 2- [3'-tert-butyl-5 '- (2-methoxycarbonylethyl) -2'-hydroxyphenyl] -2H-benzotriazole with polyethylene glycol 300; [R-CH ₂ CH ₂ -COO-CH ₂ CH ₂ I _2, where R = 3'-tert-butyl-4'-hydroxy-5'-2H-benzo- triazol-2-ylphenyl, 2- [2 ' -Hydroxy-3 '- (α, α-dimethylbenzyl) -5' - (1, 1, 3,3-tetra-methyl-butyl) -phenyl] -benzotriazole, 2- [2'-hydroxy-3 '- (l, 1,3,3-tetramethylbutyl) -5 '- (α, α-dimethylbenzyl) phenyl] benzotriazole.

2.2. 2-hydroxybenzophenones

2.3. Esters of substituted and unsubstituted benzoic acids

2.4. acrylates

2.5. nickel compounds

2.6. Sterically hindered amines 2.7. oxamide,

2.8. 2- (2-hydroxyphenyl) -1, 3,5-triazines

It is possible to use individual ones of these compounds or mixtures thereof.

For the compound classes 1 and 2 examples are z. As mentioned in WO 06/012993.

3. Suitable metal deactivators are, for example, N, N'-diphenyloxamide, N-salicylal-N'-salicyloylhydrazine, N, N'-bis (salicyloyl) hydrazine, N, N'-bis (3,5-di-tert-butyl 4-hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1, 2,4-triazole, bis (benzylidene) oxalyldihydrazide, oxanilide, iso-sophoyldihydrazide, sebacoylbisphenylhydrazide, N, N'-diacetyladipoyldihydrazide, N, N'-bis (salicyl - oyl) oxalyldihydrazide, N, N'-bis (salicyloyl) thiopropionyldihydrazide. It is possible to use individual ones of these compounds or mixtures thereof.

4. Suitable peroxide scavengers are, for example, esters of β-thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl ester, mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis (dodecylmercapto) propionate. It is possible to use individual ones of these compounds or mixtures thereof.

5. Suitable basic costabilizers are, for example, melamine, polyvinyl pyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids, for example calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palmitate, antimony pyrocatechol. lat or zinc pyrocatecholate. It is possible to use individual ones of these compounds or mixtures thereof.

6. Suitable nucleating agents are, for example, inorganic substances, such as talc, metal oxides, such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates, preferably of alkaline earth metals; organic compounds such as mono- or polycarboxylic acids and their salts, e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; polymeric compounds, such as ionic copolymers (ionomers). Particularly preferred are 1, 3: 2,4-bis (3 ', 4'-dimethylbenzylidene) sorbitol, 1, 3: 2,4-di (paramethyldibenzyliden) sorbitol and 1, 3: 2,4-di (benzyliden ) sorbitol. It is possible to use individual ones of these compounds or mixtures thereof.

7. Suitable fillers and reinforcing agents are, for example, calcium carbonate, silicates, glass fibers, glass balloons, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, Graphite, wollastonite, wood flour and flours or fibers of other natural products, synthetic fibers. It is possible to use individual ones of these compounds or mixtures thereof.

8. Suitable other additives are, for example, plasticizers, lubricants, emulsifiers, pigments, viscosity modifiers, catalysts, leveling agents, optical brighteners, flame retardants, antistatic agents and blowing agents.

9. Suitable benzofuranones and indolinones are, for example, those described in U.S. Pat. 4,325,863; U.S. 4,338,244; U.S. 5,175,312; U.S. 5,216,052; U.S. 5,252,643; DE-A-4316611; DE-A-4316622; DE-A-4316876; EP-A-0589839 or EP-A-0591 102, or 3- [4- (2-acetoxyethoxy) phenyl] -5,7-di-tert-butylbenzofuran-2-one, 5,7-di tert -butyl-3- [4- (2-stearoyloxyethoxy) phenyl] benzofuran-2-one, 3,3'-bis [5,7-di-tert-butyl-3- (4- [2-hydroxyethoxy] phenyl) benzofuran-2-one], 5,7-di-tert-butyl-3- (4-ethoxyphenyl) benzofuran-2-one, 3- (4-acetoxy-3,5-dimethylphenyl) -5,7- di-tert-butylbenzofuran-2-one, 3- (3,5-dimethyl-4-pivaloyloxyphenyl) -5,7-di-tert-butylbenzo-furan-2-one, 3- (3,4-dimethylphenyl) - 5,7-di-tert-butylbenzofuran-2-one, 3- (2,3-dimethylphenyl) -5,7-di-tert-butylbenzofuran-2-one, lactone antioxidants such as

These compounds, for example, act as antioxidants. It is possible to use individual ones of these compounds or mixtures thereof.

10. Suitable fluorescent plasticizers are those listed in "Plastics Additives Handbook", ed. R. Gächter and H. Müller, Hanser Verlag, 3rd ed., 1990, pages 775-789.

1 1. Suitable flame retardant additives are Phosphatester, ie triphenyl phosphate, resorcinol diphosphoric acid esters, gocarbonate bromine-containing compounds such as brominated organophosphate, brominated olive and polycarbonates, as well as salts such as C ₄ F ₉ SG ^ -Na ^+.

12. Suitable tougheners are butadiene rubber grafted with styrene-acrylonitrile or methyl methacrylate, ethylene-propylene rubbers grafted with maleic anhydride, ethyl and butyl acrylate rubbers grafted with methyl methacrylate or styrene-acrylonitrile, interpenetrable rubber. siloxane and acrylate networks with grafted methyl methacrylate or styrene-acrylonitrile.

13. Suitable antistatic agents are sulfonate salts, for example tetraethylammonium salts or phosphonium salts of C ₁₂ H ₂₅ SO ^{3 "} or C ₈ Fi ₇ SO ^3" .

14. Suitable colorants are pigments as well as organic and inorganic dyes.

15. Compounds containing epoxy groups, such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, copolymers of glycidyl methacrylate and epoxysilanes.

16. Compounds, the anhydride groups, such as maleic anhydride, succinic anhydride, benzoic anhydride and phthalic anhydride.

17. Suitable phosphites and phosphonites as stabilizers It is possible to use some of these compounds or mixtures thereof.

Particularly preferred are tris (2,4-di-tert-butylphenyl) phosphite (Irgafos® 168, Ciba-Geigy), or triphenylphosphine.

The moldings according to the invention can be processed from the compositions on conventional machines, for example on extruders or injection molding machines, to any desired shaped bodies or shaped parts, to films or sheets, in the usual way.

Possible molded parts are safety discs, which are known to be required in many areas of buildings, vehicles and aircraft, as well as shields of helmets. Production of extrusion and dissolution films for displays, blister packs or electric motors, blown bodies (see, for example, US Pat. No. 2,964,794), translucent panels, in particular hollow panel panels, for example for covering buildings such as railway stations, greenhouses and lighting installations, traffic light housings, traffic signs, molded parts for lighting purposes ( see, for example, DE-A 1 554 020), goggles. As electrical insulating materials for electrical conductors and for connector housings and connectors. As carrier material for organic photoconductors, luminaires or diffusers or lamp covers, housing parts, such as electrical distribution cabinets, electrical appliances, household appliances. Components of household articles, electrical and electronic equipment, motorcycle and protective helmets, automotive parts, such as glazings, sunroofs, dashboards, body parts, transport racks and storage containers for electronic components. Particularly preferred moldings are:

Safety windows, translucent panels or moldings for the building sector, in particular hollow panel panels, safety windows, diffused light panels and lamp covers, sun roofs, automotive parts, housing parts and packaging materials for the electrical industry.

Examples

As a multi-wall carbon nanotubes (MWNT) is Baytubes ^® DP HP, Bayer MaterialScience AG, 51368 Leverkusen, Germany, is used. They consist of 3-15 graphitic layers, which have a smallest inner diameter of 2-6 nm, the lengths of the tubes are 1 to 10 microns and their outer diameter is between 5 and 20 nm (mean 13-16 nm).

The carbon blacks used were from Degussa AG (Dusseldorf, Germany) (Flammruß 101) and the Cabot Corp. (Boston MA, USA) (Black Pearls 800).

Bisphenol A-based polycarbonate (Makrolon ^® 2805 Bayer Material Science AG, 51368 Leverkusen, Germany) having an MVR of 9.5 cm ³ / (10 min.) (Measured according to ISO 1133 (300 ⁰ C, 1, 2 kg) ) was provided by compounding with a ZSK 25 (Paul Beier KG, Kassel, Germany) with different levels of the MWNTs and carbon blacks described above. The compositions are listed in Tables 1 and 2 together with the values for the degree of gloss of the test specimens.

The test specimens (60 x 40 x 4 mm) were produced by injection molding in an Allrounder 370C 800-250 (Arburg GmbH & Co. KG, Lossburg, Germany) using a tool with polished surfaces.

The gloss values were measured on a Byk-Gardner Haze-Gloss according to ISO 2813 (ASTM D 523) in the angles 20 ° and 60 °.

The results are summarized in the following tables (amounts in% by weight):

Table 1: Gloss values of Baytubes DP-HP in PC

Table 2: Gloss values of carbon black in PC

Table 1 clearly shows a decrease in the degree of gloss (ie an increasingly matte surface) with increasing filling level of Baytubes DP-HP. Compared to the data from Table 2 (Example 4) it is clear that the addition of Black Pearls 800 leads to a much lower decrease in the gloss value.

Claims

claims

1. moldings, obtainable from compositions containing

A) 99.91 to 85 wt .-% thermoplastic and

B) 0.09 to 15 wt% Multi Wall Carbon Nanotubes,

which have a degree of gloss 20 ° of 104 to 20 and a gloss level 60 ° of 103 to 50, measured according to ISO 2813 with a Byk-Gardner Haze Gloss.

2. Moldings according to claim 1 containing 99.90 to 88 wt. % Thermoplastic and 0.1 to 12 wt% Multi Wall Carbon Nanotubes.

3. Moldings according to claim 2 containing 98 to 94 wt.% Thermoplastic and 2 to 6 wt.% Multi Wall Carbon Nanotubes.

4. Molding parts according to claim 1 to 3, which have a gloss level 20 ° of 100 to 20 and a gloss level 60 ° of 100 to 50.

5. Molding parts according to claim 1 to 3, which have a degree of gloss 20 ° of 40 to 22 and a gloss level 60 ° of 80 to 55.

6. Molding according to claim 1, wherein the thermoplastic is selected from at least one of the group of polycarbonates, polyesters, polysulfones, polyolefins, polystyrenes and polyacrylates te.

7. Safety Discs, Panels, Moldings for the Construction Sector, Scatter Lenses, Lamp Covers, Sunroofs, Casing Parts, Packaging Materials for E / E Industry and Automotive Parts according to claim 1.

8. Use of compositions containing

A) 99.91 to 85 wt .-% thermoplastic and

B) 0.09 to 15 wt .-% Multi Wall Carbon Nanotubes, for the production of moldings, the degree of gloss 20 ° from 104 to 20 and a gloss level

60 ° from 103 to 50, measured according to ISO 2813 with a Byk-Gardner haze gloss.