CA2099480A1 - Thermoplastic moulding compounds - Google Patents
Thermoplastic moulding compoundsInfo
- Publication number
- CA2099480A1 CA2099480A1 CA002099480A CA2099480A CA2099480A1 CA 2099480 A1 CA2099480 A1 CA 2099480A1 CA 002099480 A CA002099480 A CA 002099480A CA 2099480 A CA2099480 A CA 2099480A CA 2099480 A1 CA2099480 A1 CA 2099480A1
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- Prior art keywords
- resin
- component
- polymer resin
- moulding compounds
- methacrylic acid
- Prior art date
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- Abandoned
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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
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Thermoplastic moulding compounds A b s t r a c t Thermoplastic moulding compounds containing A) ABS-type resin, B) aromatic polycarbonate resin, C) polymer resin bearing carboxyl groups and optionally D) further polymer resins, characterised in that an ABS resin with at least one basically acting additive is used as component A, component C is selected from C.1) a polymer resin with a carboxyl group (-COOH) content of 40 to 62.5 wt.%, which is derived from acrylic acid polymers or methacrylic acid polymers or acrylic/methacrylic acid copolymers or C.2) a polymer resin with a carboxyl group (-COOH) content of 5 to 30 wt.% which was obtained by polymerisation of at least two monomers selected from styrene, acrylonitrile and acrylic acid esters and/or methacrylic acid esters with acrylic acid and/or methacrylic acid and the weight ratio of basically acting additive in A) : carboxyl groups in C) has a value of 5:1 to 1:1 (when using polymer resin C.1) or a value of 3:1 to 1:3 (when using polymer resin C.2).
Description
2~9(~80 Thermoplastic moulding compounds The invention relates to thermoplastic moulding compounds prepared from ABS polymers and aromatic polycarbonates, a process for their production and their use for the production of mouldings.
Mixtures of ABS and polycarbonate and their use as moulding compounds are known. They generally contain ABS resin, which is composed of, for example, a copolymer of styrene and acrylonitrile and a graft copolymer of styrene and acrylonitrile onto a diene rubber, such as for example polybutadiene, and, for example, polycarbonate based on bisphenol A. These moulding compounds are characterised by good strength both at room temperature and at low temperatures, good processability and elevated heat resistance. ~
A disadvantage of such moulding compounds is that, in order to avoid deleterious effects on the polycarbonate and therefore an accompanying deterioration of properties, ABS
polymers which are free of basically acting constituents must always be used in their production.
Previously, due to this requirement, a specially produced or worked up ABS polymer which is free of basic constituents, always had to be prepared for use in ABS/polycarbonate mixtures. ABS polymers, which are not intended from the outset for mixing with polycarbonates, often have basic additives incorporated (for example as lubricants or mould release agents). This also applies to ABS polymers which are blended with polymers other than polycarbonate. Such ABS
polymers or ABS polymers which are obtained from recycling moulding compounds containing basic additives, cannot therefore be used for the production of ABS/polycarbonate mixtures.
Le A 29 040-foreign countries , , ~0994~0 It has now been found that by using special polymer resins bearing carboxyl groups as blend components, mixtures of aromatic polycarbonate resins and ABS resins containing basically acting additives may be produced, which mixtures give mouldings with good properties; nor is there any damage caused to the polycarbonate component by the acid compounds.
Either a special polymer resin component with a relatively high carboxyl group content (i.e. high activity), but poorer miscibility, is used in a smaller quantity, or another special polymer resin component with a lower carboxyl group content (i.e. lower activity), but better miscibility, is used in a larger quantity.
The present invention provides thermoplastic moulding compounds containing A) ABS type resin, B) aromatic polycarbonate resin, C) polymer resin bearing carboxyl groups and optionally D) further polymer resins, characterised in that an ABS resin with at least one basically acting additive is used as component A, component C is selected from .
C.1 a polymer resin with a carboxyl group (-COOH) content of 40 to 62.5 wt.%, preferably 50 to 62.5 wt.%, which is derived from acrylic acid polymers or methacrylic acid polymers or acrylic acid/methacrylic acid copolymers or C.2 a polymer resin with a carboxyl group (-COOH) content of 5 to 30 wt.%, preferably 10 to 25 wt.%, which was obtained by polymerisation of at least two monomers selected from styrene, acrylonitrile and acrylic acid esters and/or methacrylic acid esters with acrylic acid Le A 29 040 2 2~99~
and/or methacrylic acid and the weight ratio of basically acting additive in A) : carboxyl groups in C
has a value from 5:1 to 1:1, preferably 4:1 to 1:1 (when using polymer resin C.1) or a value of 3:1 to 1:3, preferably 2:1 to 1:2 (when using polymer resin C.2).
The above-stated thermoplastic moulding compounds preferably contain 50 to 100 parts by weight, particularly preferably 60 to 90 parts by weight and in particular 70 to 80 parts by weight of component A, preferably 1 to 50 parts by weight, particularly preferably 5 to 50 parts by weight and in particular 10 to 45 parts by weight of component B and preferably 0.2 to 20, particularly preferably 0.2 to 15 and in particular 0.3 to 12.5 parts by weight of component C.
- Resins of the ABS type (component A) contain pursuant to the present invention 5 to 100 wt.%, preferably 5 to 80 wt.%, particularly preferably 10 to 75 wt.% of a graft polymer and 95 to 0% wt.%, preferably 95 to 20 wt.%, particularly preferably 90 to 25 wt.% of a thermoplastic copolymer resin.
Graft polymers are those polymers in which styrene or methyl methacrylate or a mixture of 95 to 50 wt.% of styrene, a-methylstyrene, ring-substituted styrene, methyl methacrylate or mixtures thereof and 5 to 50 wt.% of acrylonitrile, methacrylonitrile, maleic anhydride, N-substituted maleimides or mixtures thereof are graft polymerised onto a rubber. Suitable rubbers are practically all rubbers with glass transition temperatures ~ 10C, for example polybutadiene, styrene/butadiene copolymers, acrylonitrile/butadiene copolymers, polyisoprene, alkyl acrylate rubbers, preferably C1-C8 alkyl acrylate rubbers, such as for example poly-n-butyl acrylate.
The alkyl acrylate rubbers may optionally contain up to 30 wt.% (related to the weight of the rubber) of Le A 29 040 3 -.
2099~80 copolymerised monomers such as vinyl acetate, acrylonitrile, styrene, methyl methacrylate and/or vinyl ethers. The alkyl acrylate rubbers may also contain smaller quantities, preferably up to s wt.% (related to the weight of the rubber) of ethylenically unsaturated monomers with crosslinking action. Such crosslinking agents are, for example, alkenediol diacrylates and dimethacrylates, polyester diacrylates and dimethacrylates, divinyl benzene, trivinyl benzene, triallyl cyanurate, allyl acrylate and methacrylate, butadiene or isoprene.
The grafting base may also be acrylate rubbers with a core/skin structure with a core of crosslinked diene rubber prepared from one or more conjugated dienes, such as polybutadiene, or a copolymer of a conjugated diene with an ethylenically unsaturated monomer such as styrene and/or acrylonitrile.
Further suitable rubbers are, for example, the so-called EPDM rubbers (polymers of ethylene, propylene and an unconjugated diene such as, for example, dicyclopentadiene), EPM rubbers (ethylene/propylene rubbers) and silicone rubbers, which may also optionally have a core/shell structure. Polybutadiene and alkyl acrylate rubbers are preferred.
The graft polymers contain 10 to 9S wt.%, in particular 20 to 70 wt.% of rubber and 90 to 5 wt.%, in particular 80 to ; 30 wt.%, of graft copolymerised monomers. The rubbers are present in these graft copolymers in the form of at least partially crosslinked particles with an average particle - ^ diameter (d50) of in general 0.05 to 20.0 ~m, preferably 0.1 to 2.0 ~m and particularly preferably 0.1 to 0.8 ~m.
Such graft copolymers may be produced by free-radical graft copolymerisation of monomers from the range styrene, a-methylstyrene, ring-substituted styrene, Le A 29 040 4 2099~8Q
(meth)acrylonltrlle, methyl methacrylate, maleic anhydride, N-substituted maleimide in the presence of the rubbers to be grafted. Preferred production process for such graft copolymers are emulsion, solution, bulk or suspension polymerisation.
The thermoplastic copolymers may be built up from the graft monomers or similar monomers, in particular from at least one monomer from the range styrene, a-methylstyrene, halogen styrene, acrylonitrile, methacrylonitrile, methyl methacrylate, maleic anhydride, vinyl acetate and N-substituted maleimide. These thermoplastic copolymers are preferably copolymers of 95 to 50 wt.% of styrene, a-methylstyrene, methyl methacrylate or mixtures thereof with 5 to 50 wt.% of acrylonitrile, methacrylonitrile, methyl methacrylate, maleic anhydride or mixtures thereof.
Such copolymers also occur as by-products during graft copolymerisation. It is customary to incorporate separately produced copolymers as well as the copolymers contained in the graft polymer. These separately produced copolymers are not necessarily chemically identical to the ungrafted resin constituents present in the graft polymers.
Suitable separately produced copolymers are resinous, thermoplastic and contain no rubber; they are in particular copolymers of styrene and/or a-methylstyrene with acrylonitrile, optionally mixed with methyl methacrylate.
Particularly preferred copolymers consist of 20 to 40 wt.%
of acrylonitrile and 80 to 60 wt.% of styrene or a-methylstyrene. Such copolymers are known and may, in particular, be produced by free-radical polymerisation, in particular by emulsion, suspension, solution or bulk polymerisation. The copolymers generally have average molecular weights (Mw) of lS,000 to 200,000, preferably 50,000 to 150,000.
Le A 29 040 5 , :
` ~
~0~4~0 The ABS resins may be used individually or blended.
According to the invention, particularly suitable ABS resins (component A) with at least one basically acting additive are those products which have already been processed into mouldings as pure ABS resins and have already passed through at least one cycle of use as such mouldings. ABS resins which have been obtained by recovery (recycling) from already used mouldings may therefore, according to the present invention, be particularly preferably reused for the production of new mouldings.
As a rule, the basically acting additives contained in the ABS resin component which are involved are those compounds which were added to the ABS resin to improve its properties (for example, inter alia, as lubricant, mould release agent, antistatic agent, stabiliser, light stabiliser).
Examples of such compounds are carboxylic acid (di)amides, for example stearic acid amide or ethylenediamine bis-stearyl amide, metal salts of long-chain carboxylic acids, for example calcium stearate, ethoxylated fatty amines, fatty acid ethanolamides, sterically hindered phenols, for example 2,4-bis(n-octylthio)-6-(4-hydroxy-3,S-tert.-butylanilino)-1,3,5-triazine, sterically hindered amines, for example sebacic acid bis-2,2,4,4-tetramethyl-4-piperidyl ester, benzotriazole derivatives, for example 2-(2'-hydroxy-5'-methylphenyl)-benzotriazole.
The proportion of basically acting additives, related to the ABS resin, is generally from 0.01 to 5 wt.~, wherein the stated limits are not critical, and more or less may be contained.
Aromatic polycarbonate resins (component B) pursuant to the present invention may be both homopolycarbonates and Le A 29 040 6 ~0~4-80 copolycarbonates prepared from diphenols of the formulae (I) and (II) A ~ (I) Rl Rl H ~ ( C ) ~ H (II) R~ R4 in which A is a single bond, Cl-Cs alkene, C2-Cs alkylidene, Cs-C6 cycloalkylidene, -0-, -S-, or -S02-, Rs and R6 mutually independently stand for hydrogen, methyl . or halogen, in particular for hydrogen, methyl, chlorine or bromine, Rl and R2 mutually independently mean hydrogen, halogen, preferably chlorine or bromine, Cl-C8 alkyl, - 25 preferably methyl, ethyl, Cs-C6 cycloalkyl, preferably cyclohexyl, C6-Clo aryl, preferably phenyl, or C7-Cl2 aralkyl, preferably phenyl-C~-C4-alkyl, in particular benzyl, 30 m is an integer from 4 to 7, preferably 4 or 5, R3 and R4 are individually selectable for each X and mutually independently mean hydrogen or Cl-C6 alkyl, preferably methyl or ethyl and X means carbon.
Le A 29 040 7 .
. . .
2099~
The polycarbonates according to component s may be both linear and branched, they may contain aromatically bonded halogen, preferably bromine and/or chlorine, they may also, however, be free of aromatically bonded halogen, thus free of halogen.
The polycarbonates B may be used both individually and blended.
The diphenols of the formulae (I) and (II) are either known in the literature or may be produced according to processes known in the literature (see for example EP-A-0 359 953).
Production of the suitable polycarbonates according to the invention according to component s is known in the literature and may, for example, proceed with phosgene in accordance with the phase interface process or with phosgene in accordance with the homogeneous phase process ~the so-called pyridine process), wherein the particular molecular weight to be achieved is adjusted in a known manner with an appropriate quantity of known chain terminators.
Suitable chain terminators are, for example, phenol or p-tert.-butylphenol, but also long-chain alkyl phenols such as 4-(1,3-tetramethyl-butyl)phenol according to DE-OS 2 842 005 or monoalkyl phenols or dialkyl phenols with a total of 8 to 20 C atoms in the alkyl substituents according to DE-OS 3 506 472, such as, for example, p-nonylphenol, 2,5-di-tert.-butylphenol, p-tert.-octylphenol, p-dodecylphenol, 2-(3,5-dimethylheptyl)phenol and 4-(3,5-dimethylheptyl)phenol.
The quantity of chain terminators to be used is generally between 0.5 and 10 mol%, related to the total of the particular diphenols (I) and (II) used.
Le A 29 040 8 .
, 2~994~0 The suitable polycarbonates according to the invention according to component B may be branched in a known manner, namely, by way of example, by the incorporation of 0.05 to 2.0 mol%, related to the total of the diphenols used, of trifunctional or greater than trifunctional compounds, for example such compounds with three or more than three phenolic OH groups (trihydroxybenzene).
These compounds have average weight average molecular weights (Mw, measured, for example, by ultracentrifuging or light-scattering measurement) of 10,000 to 200,000, preferably from 20,000 to 80,000.
Suitable diphenols of the formulae (I) and (II) are, for example, hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, 2,2-bis(4-hydroxyphenyl)propane, 2,4-bis(4-hydroxyphenyl)-2-methylbutane, 20 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, . 25 1,1-bis(4-hydroxyphenyl)-3,3-dimethylcyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5,5-tetramethylcyclohexane or 1,1-bis(4-hydroxyphenyl)-2,4,4-trimethylcyclopentane.
Preferred diphenols of the formula (I) are 2,2-bis(4-hydroxyphenyl)propane and 1,1-bis(4-hydroxyphenyl)cyclohexane.
The preferred phenol of the formula (II) is 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane.
Mixtures of diphenols may also be used.
Le A 29 040 9 .. . . .
- .
~:
209~
According to the invention, particularly suitable polycarbonate resins (component B) are those products which (optionally mixed with ABS resins containing no basically acting additives) have already been processed into mouldings and have already passed through one cycle of use as such mouldings, i.e. polycarbonate resins which were obtained by recovery (recycling) from already used mouldings are preferred.
Polymer resins bearing carboxyl groups (component C) pursuant to the present compound are either polymers which have a carboxyl group (-COOH) content of 40 to 62.5 wt.% and are derived from acrylate polymers, or polymers which have a carboxyl group (-COOH) content of 5 to 30 wt.% and are special terpolymers or quaterpolymers.
Polymers which may be considered as the first-stated class are, for example, polyacrylic acid, polymethacrylic acid, acrylic acid/methacrylic acid copolymers together with partially saponified polyacrylic acid esters and partially saponified polymethacrylic acid esters; polyacrylic acid and polymethacrylic acid are preferred. Such polymers are known.
The special terpolymers or quaterpolymers are taken to be those polymers which were obtained by polymerisation of at least two monomers selected from styrene, acrylonitrile and acrylic acid esters and/or methacrylic acid esters, preferably acrylic acid esters or methacrylic acid esters of alcohols with 1 to 10 C atoms, with a monomer bearing a carboxyl group selected from acrylic acid and methacrylic acid.
In principle, small quantities of further vinyl monomers, preferably under 10 wt.%, may be incorporated into these polymers.
Le A 29 040 10 ' ., ' , . . , ' ' 2~99~
Examples of polymers according to component C, which are also known, are styrene/acrylonitrile/acrylic acid polymer, styrene-acrylonitrile/methacrylic acid polymer, styrene-methyl methacrylate/methacrylic acid polymer, methyl methacrylate/acrylonitrile/acrylic acid polymer, styrene/methyl methacrylate/acrylonitrile/methacrylic acid polymer, ethyl acrylate/styrene/methacrylic acid polymer, n-butylacrylate/styrene/methacrylic acid polymer.
Styrene/acrylonitrile/acrylic acid polymers and styrene/acrylonitrile/methacrylic acid polymers are preferred.
In principle, the stated polymers with average molecular weights (M~) between 1,000 and 500,000 are suitable as component C, those with Mw values between 1,000 and 300,000 are preferred and particularly preferred are those between 1,500 and 100,000 and in particular 1,500 and 80,000.
Optionally, the thermoplastic moulding compounds according to the invention may contain small proportions of further polymer resins, preferably below 20 wt.%, particularly preferably below 10 wt.%. Examples of further polymer resins are aromatic polyesters, for example polyethylene terephthalate or polybutylene terephthalate, thermoplastic polyurethanes, polyacrylates, for example copolymers of (meth)acrylate monomers with acrylonitrile or polyacetals, for example polyoxymethylene, together with polyamides such as, for example, polyamide-6 or polyamide-66.
Furthermore, other, preferably not basically acting, additives known for ABS resins and polycarbonate resins, such as for example stabilisers, pigments, mould release agents, flame retardants, lubricants and antistatic agents may be incorporated in customary quantities into the moulding compounds according to the invention.
Le A 29 040 11 - ' ' : ' .
- ~ .
'' .
. . .
210994~
Mixing of the polymer components to produce the thermoplastic moulding compounds according to the invention proceeds in customary mixing units, thus, for example, in kneaders, internal mixers, in roll mills, screw compounders or extruders, preferably above 200C. The constituents may be blended consecutively or simultaneously, preferably, components (A) and (C) are initially mixed and then the resultant blend is mixed with component (s) and optionally component (D).
The invention also therefore provides a process for the production of the moulding compounds according to the invention by mixing the constituents at elevated temperature.
The moulding compounds according to the invention may be used for the production of any kind of mouldings, for e~ample those produced by injection moulding or extrusion.
Examples of such mouldings are casing parts, covering plates or automotive parts. Mouldings may also be produced by thermoforming previously produced sheets or films. The invention also therefore provides the use of the described moulding compounds for the production of mouldings.
Le A 29 040 12 - ~ ' 209948~
Examples Polymers used:
5 A.1) ABS resin containing 15 parts by weight of a graft rubber prepared - from 50 wt.% of a poly-butadiene base with an average particle diameter (d50) of 0.1 ~m, onto which were grafted 36 wt.% of styrene and 14 wt.% of acrylonitrile, 15 parts by weight of a graft rubber prepared from 50 wt.% of a poly-butadiene base with an average particle diameter (d50) of 0.4 ~m, onto which were grafted 36 wt.% of styrene and 14 wt.% of acrylonitrile, 70 parts by weight of a styrene/acrylonitrile 72:28 copolymer with an Mw of approx. 80,000 with MW/Mn of -1 ~ 2 and 2 parts by weight of ethylenediamine bis-stearyl amide, produced by mixing the components in an internal kneader. :
A.2) ABS resin containing 60 parts by weight of a graft rubber prepared `-from 50 wt.% of a poly-butadiene base with an average particle diameter (d50) of 0.4 ~m, onto which were Le A 29 040 13 2099~8~
grafted 36 wt.% of styrene and 14 wt.% of acrylonitrile, 40 parts by weight of a styrene/acrylonitrile 72:28 copolymer with an M~ of approx. 80,000 with M~,/Mn of -1 < 2 and 1 part by weight of a mixture of ethoxylated lo fatty amines, produced by mixing the components in an internal kneader.
15 A.3) ABS resin containing 15 parts by weight of a graft rubber prepared from 50 wt.% of a poly-butadiene base with an average particle diameter (d50) of 0.1 ~m, onto which were grafted 36 wt.% of styrene and 14 wt.% of acrylonitrile, 15 parts by weight of a graft rubber prepared from 50 wt.% of a poly-butadiene base with an average particle diameter (d50) of 0.4 ~m, onto which were grafted 36 wt.% of styrene and 14 wt.% of acrylonitrile, 40 parts by weight of an a-methylstyrene/
acrylonitrile 72:28 copolymer with an M~ of approx. 65,000 with ~r/Mn of -1 < 2 and 30 parts by weight of a styrene/acrylonitrile 72:28 copolymer with an M~ of approx. 80,000 with M~,/Mn of -1 < 2 and 1 part by weight of magnesium stearate, Le A 29 040 14 ' ,:
~099~
produced by mixing the components in an internal kneader.
s.1) Aromatic polycarbonate prepared from 2,2-bis(4-hydroxyphenyl)propane (bisphenol A) with a relative viscosity of 1.26 (measured in CH2Cl2 at 250C as a 0.5 wt.% solution), corresponding to an Mw of approx. 2s,000.
C.1.1) Polyacrylic acid with an Mw of approx. 2,000 (Aldrich) (carboxyl group content approx.
62 wt.%).
C.1.2) Polyacrylic acid with an Mw f approx. 250,000 (Aldrich) (carboxyl group content approx.
62 wt.%).
C.2.1) Resin prepared from styrene, acrylonitrile and methacrylic acid 120 parts by weight of water, 2 parts by weight of the sodium salt of Cg-Cl8 alkylsulphonic acids as ` emulsifier and 0.3 parts by weight of potassium persulphate are heated to 70C in a reactor, whereupon a mixture of 57.6 parts by weight of styrene, 22.4 parts by weight of acrylonitrile, 20 parts by weight of methacrylic acid and 1.0 part --by weight of tert.-dodecyl mercaptan is incorporated within 4 hours. After a post-reaction period, the latex is coagulated after the addition of 1.2 parts by weight of antioxidants in an aqueous magnesium sulphate/acetic acid solution.
- The resultant powder is washed with water, an acid solution and again with water and vacuum dried at 70C.
The resin has a specific viscosity (~3pec /c at c =
5 g/l in dimethylformamide at 25C) of 41 and a Le A 29 040 15 2099~g~
carboxyl group content of approx. 10 wt.% (Mw approx. 28,000).
C.2.2) Resin prepared from methyl methacrylate, acrylonitrile and methacrylic acid Production proceeds analogously to the formulation described in C.2.1, wherein a mixture of 51 parts by weight of methyl methacrylate, 34 parts by weight of acrylonitrile, 15 parts by weight of methacrylic acid and 0.4 parts by weight of tert.-dodecyl mercaptan is incorporated within 4 hours. The resin obtained has a specific viscosity (~8~ /C at c = 5 g/l in DMF at 25C) of 78 and a carboxyl group content of approx. 10 wt.% (Mw approx. 76,000).
Production and testina of the moulding compounds Moulding compounds were produced by mixing the parts by weight stated in table 1 of the above-described components in an internal kneader at approx. 200C, which compounds were then injection moulded into test-pieces at 250C. The following parameters were measured, notched impact strength at room temperature (akRT) and at -40C (ak~40C) to ISO 180 A
(unit kJ/m2), impact strength at -40C (an~40C) to ISO 180 C
(unit kJ/m2), ball indentation hardness (Hc) to DIN s3 456 (unit N/mm ), softening temperature (Vicat B) to DIN 53 460 (unit oc).
Surface gloss was determined on a flat sheet in accordance with DIN 67 530 at a reflection angle of 60 (reflectometer value) with the assistance of the "Multi-Gloss" multi-angle reflectometer from the company Byk-Mallinckrodt (see table).
As may be seen from the examples, in comparison with the moulding compounds without component C, the moulding Le A 29 040 16 2099~80 compounds according to the invention exhibit distinctly better properties, in particular a combination of high strength (even at low temperature) and good surface finish with equally good heat resistance (Vicat B) and ball indentation hardness (Hc).
Le A 29 040 17 2~199480 _ _ _ = _ _ o = o _ +~ ~ o o c~ o c~ ,~ r~
Mixtures of ABS and polycarbonate and their use as moulding compounds are known. They generally contain ABS resin, which is composed of, for example, a copolymer of styrene and acrylonitrile and a graft copolymer of styrene and acrylonitrile onto a diene rubber, such as for example polybutadiene, and, for example, polycarbonate based on bisphenol A. These moulding compounds are characterised by good strength both at room temperature and at low temperatures, good processability and elevated heat resistance. ~
A disadvantage of such moulding compounds is that, in order to avoid deleterious effects on the polycarbonate and therefore an accompanying deterioration of properties, ABS
polymers which are free of basically acting constituents must always be used in their production.
Previously, due to this requirement, a specially produced or worked up ABS polymer which is free of basic constituents, always had to be prepared for use in ABS/polycarbonate mixtures. ABS polymers, which are not intended from the outset for mixing with polycarbonates, often have basic additives incorporated (for example as lubricants or mould release agents). This also applies to ABS polymers which are blended with polymers other than polycarbonate. Such ABS
polymers or ABS polymers which are obtained from recycling moulding compounds containing basic additives, cannot therefore be used for the production of ABS/polycarbonate mixtures.
Le A 29 040-foreign countries , , ~0994~0 It has now been found that by using special polymer resins bearing carboxyl groups as blend components, mixtures of aromatic polycarbonate resins and ABS resins containing basically acting additives may be produced, which mixtures give mouldings with good properties; nor is there any damage caused to the polycarbonate component by the acid compounds.
Either a special polymer resin component with a relatively high carboxyl group content (i.e. high activity), but poorer miscibility, is used in a smaller quantity, or another special polymer resin component with a lower carboxyl group content (i.e. lower activity), but better miscibility, is used in a larger quantity.
The present invention provides thermoplastic moulding compounds containing A) ABS type resin, B) aromatic polycarbonate resin, C) polymer resin bearing carboxyl groups and optionally D) further polymer resins, characterised in that an ABS resin with at least one basically acting additive is used as component A, component C is selected from .
C.1 a polymer resin with a carboxyl group (-COOH) content of 40 to 62.5 wt.%, preferably 50 to 62.5 wt.%, which is derived from acrylic acid polymers or methacrylic acid polymers or acrylic acid/methacrylic acid copolymers or C.2 a polymer resin with a carboxyl group (-COOH) content of 5 to 30 wt.%, preferably 10 to 25 wt.%, which was obtained by polymerisation of at least two monomers selected from styrene, acrylonitrile and acrylic acid esters and/or methacrylic acid esters with acrylic acid Le A 29 040 2 2~99~
and/or methacrylic acid and the weight ratio of basically acting additive in A) : carboxyl groups in C
has a value from 5:1 to 1:1, preferably 4:1 to 1:1 (when using polymer resin C.1) or a value of 3:1 to 1:3, preferably 2:1 to 1:2 (when using polymer resin C.2).
The above-stated thermoplastic moulding compounds preferably contain 50 to 100 parts by weight, particularly preferably 60 to 90 parts by weight and in particular 70 to 80 parts by weight of component A, preferably 1 to 50 parts by weight, particularly preferably 5 to 50 parts by weight and in particular 10 to 45 parts by weight of component B and preferably 0.2 to 20, particularly preferably 0.2 to 15 and in particular 0.3 to 12.5 parts by weight of component C.
- Resins of the ABS type (component A) contain pursuant to the present invention 5 to 100 wt.%, preferably 5 to 80 wt.%, particularly preferably 10 to 75 wt.% of a graft polymer and 95 to 0% wt.%, preferably 95 to 20 wt.%, particularly preferably 90 to 25 wt.% of a thermoplastic copolymer resin.
Graft polymers are those polymers in which styrene or methyl methacrylate or a mixture of 95 to 50 wt.% of styrene, a-methylstyrene, ring-substituted styrene, methyl methacrylate or mixtures thereof and 5 to 50 wt.% of acrylonitrile, methacrylonitrile, maleic anhydride, N-substituted maleimides or mixtures thereof are graft polymerised onto a rubber. Suitable rubbers are practically all rubbers with glass transition temperatures ~ 10C, for example polybutadiene, styrene/butadiene copolymers, acrylonitrile/butadiene copolymers, polyisoprene, alkyl acrylate rubbers, preferably C1-C8 alkyl acrylate rubbers, such as for example poly-n-butyl acrylate.
The alkyl acrylate rubbers may optionally contain up to 30 wt.% (related to the weight of the rubber) of Le A 29 040 3 -.
2099~80 copolymerised monomers such as vinyl acetate, acrylonitrile, styrene, methyl methacrylate and/or vinyl ethers. The alkyl acrylate rubbers may also contain smaller quantities, preferably up to s wt.% (related to the weight of the rubber) of ethylenically unsaturated monomers with crosslinking action. Such crosslinking agents are, for example, alkenediol diacrylates and dimethacrylates, polyester diacrylates and dimethacrylates, divinyl benzene, trivinyl benzene, triallyl cyanurate, allyl acrylate and methacrylate, butadiene or isoprene.
The grafting base may also be acrylate rubbers with a core/skin structure with a core of crosslinked diene rubber prepared from one or more conjugated dienes, such as polybutadiene, or a copolymer of a conjugated diene with an ethylenically unsaturated monomer such as styrene and/or acrylonitrile.
Further suitable rubbers are, for example, the so-called EPDM rubbers (polymers of ethylene, propylene and an unconjugated diene such as, for example, dicyclopentadiene), EPM rubbers (ethylene/propylene rubbers) and silicone rubbers, which may also optionally have a core/shell structure. Polybutadiene and alkyl acrylate rubbers are preferred.
The graft polymers contain 10 to 9S wt.%, in particular 20 to 70 wt.% of rubber and 90 to 5 wt.%, in particular 80 to ; 30 wt.%, of graft copolymerised monomers. The rubbers are present in these graft copolymers in the form of at least partially crosslinked particles with an average particle - ^ diameter (d50) of in general 0.05 to 20.0 ~m, preferably 0.1 to 2.0 ~m and particularly preferably 0.1 to 0.8 ~m.
Such graft copolymers may be produced by free-radical graft copolymerisation of monomers from the range styrene, a-methylstyrene, ring-substituted styrene, Le A 29 040 4 2099~8Q
(meth)acrylonltrlle, methyl methacrylate, maleic anhydride, N-substituted maleimide in the presence of the rubbers to be grafted. Preferred production process for such graft copolymers are emulsion, solution, bulk or suspension polymerisation.
The thermoplastic copolymers may be built up from the graft monomers or similar monomers, in particular from at least one monomer from the range styrene, a-methylstyrene, halogen styrene, acrylonitrile, methacrylonitrile, methyl methacrylate, maleic anhydride, vinyl acetate and N-substituted maleimide. These thermoplastic copolymers are preferably copolymers of 95 to 50 wt.% of styrene, a-methylstyrene, methyl methacrylate or mixtures thereof with 5 to 50 wt.% of acrylonitrile, methacrylonitrile, methyl methacrylate, maleic anhydride or mixtures thereof.
Such copolymers also occur as by-products during graft copolymerisation. It is customary to incorporate separately produced copolymers as well as the copolymers contained in the graft polymer. These separately produced copolymers are not necessarily chemically identical to the ungrafted resin constituents present in the graft polymers.
Suitable separately produced copolymers are resinous, thermoplastic and contain no rubber; they are in particular copolymers of styrene and/or a-methylstyrene with acrylonitrile, optionally mixed with methyl methacrylate.
Particularly preferred copolymers consist of 20 to 40 wt.%
of acrylonitrile and 80 to 60 wt.% of styrene or a-methylstyrene. Such copolymers are known and may, in particular, be produced by free-radical polymerisation, in particular by emulsion, suspension, solution or bulk polymerisation. The copolymers generally have average molecular weights (Mw) of lS,000 to 200,000, preferably 50,000 to 150,000.
Le A 29 040 5 , :
` ~
~0~4~0 The ABS resins may be used individually or blended.
According to the invention, particularly suitable ABS resins (component A) with at least one basically acting additive are those products which have already been processed into mouldings as pure ABS resins and have already passed through at least one cycle of use as such mouldings. ABS resins which have been obtained by recovery (recycling) from already used mouldings may therefore, according to the present invention, be particularly preferably reused for the production of new mouldings.
As a rule, the basically acting additives contained in the ABS resin component which are involved are those compounds which were added to the ABS resin to improve its properties (for example, inter alia, as lubricant, mould release agent, antistatic agent, stabiliser, light stabiliser).
Examples of such compounds are carboxylic acid (di)amides, for example stearic acid amide or ethylenediamine bis-stearyl amide, metal salts of long-chain carboxylic acids, for example calcium stearate, ethoxylated fatty amines, fatty acid ethanolamides, sterically hindered phenols, for example 2,4-bis(n-octylthio)-6-(4-hydroxy-3,S-tert.-butylanilino)-1,3,5-triazine, sterically hindered amines, for example sebacic acid bis-2,2,4,4-tetramethyl-4-piperidyl ester, benzotriazole derivatives, for example 2-(2'-hydroxy-5'-methylphenyl)-benzotriazole.
The proportion of basically acting additives, related to the ABS resin, is generally from 0.01 to 5 wt.~, wherein the stated limits are not critical, and more or less may be contained.
Aromatic polycarbonate resins (component B) pursuant to the present invention may be both homopolycarbonates and Le A 29 040 6 ~0~4-80 copolycarbonates prepared from diphenols of the formulae (I) and (II) A ~ (I) Rl Rl H ~ ( C ) ~ H (II) R~ R4 in which A is a single bond, Cl-Cs alkene, C2-Cs alkylidene, Cs-C6 cycloalkylidene, -0-, -S-, or -S02-, Rs and R6 mutually independently stand for hydrogen, methyl . or halogen, in particular for hydrogen, methyl, chlorine or bromine, Rl and R2 mutually independently mean hydrogen, halogen, preferably chlorine or bromine, Cl-C8 alkyl, - 25 preferably methyl, ethyl, Cs-C6 cycloalkyl, preferably cyclohexyl, C6-Clo aryl, preferably phenyl, or C7-Cl2 aralkyl, preferably phenyl-C~-C4-alkyl, in particular benzyl, 30 m is an integer from 4 to 7, preferably 4 or 5, R3 and R4 are individually selectable for each X and mutually independently mean hydrogen or Cl-C6 alkyl, preferably methyl or ethyl and X means carbon.
Le A 29 040 7 .
. . .
2099~
The polycarbonates according to component s may be both linear and branched, they may contain aromatically bonded halogen, preferably bromine and/or chlorine, they may also, however, be free of aromatically bonded halogen, thus free of halogen.
The polycarbonates B may be used both individually and blended.
The diphenols of the formulae (I) and (II) are either known in the literature or may be produced according to processes known in the literature (see for example EP-A-0 359 953).
Production of the suitable polycarbonates according to the invention according to component s is known in the literature and may, for example, proceed with phosgene in accordance with the phase interface process or with phosgene in accordance with the homogeneous phase process ~the so-called pyridine process), wherein the particular molecular weight to be achieved is adjusted in a known manner with an appropriate quantity of known chain terminators.
Suitable chain terminators are, for example, phenol or p-tert.-butylphenol, but also long-chain alkyl phenols such as 4-(1,3-tetramethyl-butyl)phenol according to DE-OS 2 842 005 or monoalkyl phenols or dialkyl phenols with a total of 8 to 20 C atoms in the alkyl substituents according to DE-OS 3 506 472, such as, for example, p-nonylphenol, 2,5-di-tert.-butylphenol, p-tert.-octylphenol, p-dodecylphenol, 2-(3,5-dimethylheptyl)phenol and 4-(3,5-dimethylheptyl)phenol.
The quantity of chain terminators to be used is generally between 0.5 and 10 mol%, related to the total of the particular diphenols (I) and (II) used.
Le A 29 040 8 .
, 2~994~0 The suitable polycarbonates according to the invention according to component B may be branched in a known manner, namely, by way of example, by the incorporation of 0.05 to 2.0 mol%, related to the total of the diphenols used, of trifunctional or greater than trifunctional compounds, for example such compounds with three or more than three phenolic OH groups (trihydroxybenzene).
These compounds have average weight average molecular weights (Mw, measured, for example, by ultracentrifuging or light-scattering measurement) of 10,000 to 200,000, preferably from 20,000 to 80,000.
Suitable diphenols of the formulae (I) and (II) are, for example, hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, 2,2-bis(4-hydroxyphenyl)propane, 2,4-bis(4-hydroxyphenyl)-2-methylbutane, 20 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, . 25 1,1-bis(4-hydroxyphenyl)-3,3-dimethylcyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5,5-tetramethylcyclohexane or 1,1-bis(4-hydroxyphenyl)-2,4,4-trimethylcyclopentane.
Preferred diphenols of the formula (I) are 2,2-bis(4-hydroxyphenyl)propane and 1,1-bis(4-hydroxyphenyl)cyclohexane.
The preferred phenol of the formula (II) is 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane.
Mixtures of diphenols may also be used.
Le A 29 040 9 .. . . .
- .
~:
209~
According to the invention, particularly suitable polycarbonate resins (component B) are those products which (optionally mixed with ABS resins containing no basically acting additives) have already been processed into mouldings and have already passed through one cycle of use as such mouldings, i.e. polycarbonate resins which were obtained by recovery (recycling) from already used mouldings are preferred.
Polymer resins bearing carboxyl groups (component C) pursuant to the present compound are either polymers which have a carboxyl group (-COOH) content of 40 to 62.5 wt.% and are derived from acrylate polymers, or polymers which have a carboxyl group (-COOH) content of 5 to 30 wt.% and are special terpolymers or quaterpolymers.
Polymers which may be considered as the first-stated class are, for example, polyacrylic acid, polymethacrylic acid, acrylic acid/methacrylic acid copolymers together with partially saponified polyacrylic acid esters and partially saponified polymethacrylic acid esters; polyacrylic acid and polymethacrylic acid are preferred. Such polymers are known.
The special terpolymers or quaterpolymers are taken to be those polymers which were obtained by polymerisation of at least two monomers selected from styrene, acrylonitrile and acrylic acid esters and/or methacrylic acid esters, preferably acrylic acid esters or methacrylic acid esters of alcohols with 1 to 10 C atoms, with a monomer bearing a carboxyl group selected from acrylic acid and methacrylic acid.
In principle, small quantities of further vinyl monomers, preferably under 10 wt.%, may be incorporated into these polymers.
Le A 29 040 10 ' ., ' , . . , ' ' 2~99~
Examples of polymers according to component C, which are also known, are styrene/acrylonitrile/acrylic acid polymer, styrene-acrylonitrile/methacrylic acid polymer, styrene-methyl methacrylate/methacrylic acid polymer, methyl methacrylate/acrylonitrile/acrylic acid polymer, styrene/methyl methacrylate/acrylonitrile/methacrylic acid polymer, ethyl acrylate/styrene/methacrylic acid polymer, n-butylacrylate/styrene/methacrylic acid polymer.
Styrene/acrylonitrile/acrylic acid polymers and styrene/acrylonitrile/methacrylic acid polymers are preferred.
In principle, the stated polymers with average molecular weights (M~) between 1,000 and 500,000 are suitable as component C, those with Mw values between 1,000 and 300,000 are preferred and particularly preferred are those between 1,500 and 100,000 and in particular 1,500 and 80,000.
Optionally, the thermoplastic moulding compounds according to the invention may contain small proportions of further polymer resins, preferably below 20 wt.%, particularly preferably below 10 wt.%. Examples of further polymer resins are aromatic polyesters, for example polyethylene terephthalate or polybutylene terephthalate, thermoplastic polyurethanes, polyacrylates, for example copolymers of (meth)acrylate monomers with acrylonitrile or polyacetals, for example polyoxymethylene, together with polyamides such as, for example, polyamide-6 or polyamide-66.
Furthermore, other, preferably not basically acting, additives known for ABS resins and polycarbonate resins, such as for example stabilisers, pigments, mould release agents, flame retardants, lubricants and antistatic agents may be incorporated in customary quantities into the moulding compounds according to the invention.
Le A 29 040 11 - ' ' : ' .
- ~ .
'' .
. . .
210994~
Mixing of the polymer components to produce the thermoplastic moulding compounds according to the invention proceeds in customary mixing units, thus, for example, in kneaders, internal mixers, in roll mills, screw compounders or extruders, preferably above 200C. The constituents may be blended consecutively or simultaneously, preferably, components (A) and (C) are initially mixed and then the resultant blend is mixed with component (s) and optionally component (D).
The invention also therefore provides a process for the production of the moulding compounds according to the invention by mixing the constituents at elevated temperature.
The moulding compounds according to the invention may be used for the production of any kind of mouldings, for e~ample those produced by injection moulding or extrusion.
Examples of such mouldings are casing parts, covering plates or automotive parts. Mouldings may also be produced by thermoforming previously produced sheets or films. The invention also therefore provides the use of the described moulding compounds for the production of mouldings.
Le A 29 040 12 - ~ ' 209948~
Examples Polymers used:
5 A.1) ABS resin containing 15 parts by weight of a graft rubber prepared - from 50 wt.% of a poly-butadiene base with an average particle diameter (d50) of 0.1 ~m, onto which were grafted 36 wt.% of styrene and 14 wt.% of acrylonitrile, 15 parts by weight of a graft rubber prepared from 50 wt.% of a poly-butadiene base with an average particle diameter (d50) of 0.4 ~m, onto which were grafted 36 wt.% of styrene and 14 wt.% of acrylonitrile, 70 parts by weight of a styrene/acrylonitrile 72:28 copolymer with an Mw of approx. 80,000 with MW/Mn of -1 ~ 2 and 2 parts by weight of ethylenediamine bis-stearyl amide, produced by mixing the components in an internal kneader. :
A.2) ABS resin containing 60 parts by weight of a graft rubber prepared `-from 50 wt.% of a poly-butadiene base with an average particle diameter (d50) of 0.4 ~m, onto which were Le A 29 040 13 2099~8~
grafted 36 wt.% of styrene and 14 wt.% of acrylonitrile, 40 parts by weight of a styrene/acrylonitrile 72:28 copolymer with an M~ of approx. 80,000 with M~,/Mn of -1 < 2 and 1 part by weight of a mixture of ethoxylated lo fatty amines, produced by mixing the components in an internal kneader.
15 A.3) ABS resin containing 15 parts by weight of a graft rubber prepared from 50 wt.% of a poly-butadiene base with an average particle diameter (d50) of 0.1 ~m, onto which were grafted 36 wt.% of styrene and 14 wt.% of acrylonitrile, 15 parts by weight of a graft rubber prepared from 50 wt.% of a poly-butadiene base with an average particle diameter (d50) of 0.4 ~m, onto which were grafted 36 wt.% of styrene and 14 wt.% of acrylonitrile, 40 parts by weight of an a-methylstyrene/
acrylonitrile 72:28 copolymer with an M~ of approx. 65,000 with ~r/Mn of -1 < 2 and 30 parts by weight of a styrene/acrylonitrile 72:28 copolymer with an M~ of approx. 80,000 with M~,/Mn of -1 < 2 and 1 part by weight of magnesium stearate, Le A 29 040 14 ' ,:
~099~
produced by mixing the components in an internal kneader.
s.1) Aromatic polycarbonate prepared from 2,2-bis(4-hydroxyphenyl)propane (bisphenol A) with a relative viscosity of 1.26 (measured in CH2Cl2 at 250C as a 0.5 wt.% solution), corresponding to an Mw of approx. 2s,000.
C.1.1) Polyacrylic acid with an Mw of approx. 2,000 (Aldrich) (carboxyl group content approx.
62 wt.%).
C.1.2) Polyacrylic acid with an Mw f approx. 250,000 (Aldrich) (carboxyl group content approx.
62 wt.%).
C.2.1) Resin prepared from styrene, acrylonitrile and methacrylic acid 120 parts by weight of water, 2 parts by weight of the sodium salt of Cg-Cl8 alkylsulphonic acids as ` emulsifier and 0.3 parts by weight of potassium persulphate are heated to 70C in a reactor, whereupon a mixture of 57.6 parts by weight of styrene, 22.4 parts by weight of acrylonitrile, 20 parts by weight of methacrylic acid and 1.0 part --by weight of tert.-dodecyl mercaptan is incorporated within 4 hours. After a post-reaction period, the latex is coagulated after the addition of 1.2 parts by weight of antioxidants in an aqueous magnesium sulphate/acetic acid solution.
- The resultant powder is washed with water, an acid solution and again with water and vacuum dried at 70C.
The resin has a specific viscosity (~3pec /c at c =
5 g/l in dimethylformamide at 25C) of 41 and a Le A 29 040 15 2099~g~
carboxyl group content of approx. 10 wt.% (Mw approx. 28,000).
C.2.2) Resin prepared from methyl methacrylate, acrylonitrile and methacrylic acid Production proceeds analogously to the formulation described in C.2.1, wherein a mixture of 51 parts by weight of methyl methacrylate, 34 parts by weight of acrylonitrile, 15 parts by weight of methacrylic acid and 0.4 parts by weight of tert.-dodecyl mercaptan is incorporated within 4 hours. The resin obtained has a specific viscosity (~8~ /C at c = 5 g/l in DMF at 25C) of 78 and a carboxyl group content of approx. 10 wt.% (Mw approx. 76,000).
Production and testina of the moulding compounds Moulding compounds were produced by mixing the parts by weight stated in table 1 of the above-described components in an internal kneader at approx. 200C, which compounds were then injection moulded into test-pieces at 250C. The following parameters were measured, notched impact strength at room temperature (akRT) and at -40C (ak~40C) to ISO 180 A
(unit kJ/m2), impact strength at -40C (an~40C) to ISO 180 C
(unit kJ/m2), ball indentation hardness (Hc) to DIN s3 456 (unit N/mm ), softening temperature (Vicat B) to DIN 53 460 (unit oc).
Surface gloss was determined on a flat sheet in accordance with DIN 67 530 at a reflection angle of 60 (reflectometer value) with the assistance of the "Multi-Gloss" multi-angle reflectometer from the company Byk-Mallinckrodt (see table).
As may be seen from the examples, in comparison with the moulding compounds without component C, the moulding Le A 29 040 16 2099~80 compounds according to the invention exhibit distinctly better properties, in particular a combination of high strength (even at low temperature) and good surface finish with equally good heat resistance (Vicat B) and ball indentation hardness (Hc).
Le A 29 040 17 2~199480 _ _ _ = _ _ o = o _ +~ ~ o o c~ o c~ ,~ r~
3-0 ~ ~ ~1 ~ _ ~ ~ _ O ~
~ l l l ~ 1. O ~
N ~ ~ ~ ~
~ ~ ~ l ~ ~ l l l ~ ~
,~ O ~ ~ l ,_ l l ~ 10 ~-- c~ u~ c~ ~n m C~ O O n m . .
~P~ ~:L lLL~
~o I n ~n u~ n u~ u~ u~ n C ~ ~ ~ ~
,0 ~ . ~
~ ~ a a ~+~
D ~ __ _ _ _ _ _ _ _ O
Le A 29 040 - lâ -.
: -20994~0 ~ ~ ~ ~ cr~ ~ ,~ I~ oo O ~r I c ~ o ~o~o~ ~~1~ ~
r--O O r _ o o o _ ~u ~ ~0 cn ,01 a~ o~ o o, o ~
u ~ t` oo ~ ~ I~ ~ d' ~ ~
I~
I
~5 ~1 Le A 29 040 - 19 -:
~ l l l ~ 1. O ~
N ~ ~ ~ ~
~ ~ ~ l ~ ~ l l l ~ ~
,~ O ~ ~ l ,_ l l ~ 10 ~-- c~ u~ c~ ~n m C~ O O n m . .
~P~ ~:L lLL~
~o I n ~n u~ n u~ u~ u~ n C ~ ~ ~ ~
,0 ~ . ~
~ ~ a a ~+~
D ~ __ _ _ _ _ _ _ _ O
Le A 29 040 - lâ -.
: -20994~0 ~ ~ ~ ~ cr~ ~ ,~ I~ oo O ~r I c ~ o ~o~o~ ~~1~ ~
r--O O r _ o o o _ ~u ~ ~0 cn ,01 a~ o~ o o, o ~
u ~ t` oo ~ ~ I~ ~ d' ~ ~
I~
I
~5 ~1 Le A 29 040 - 19 -:
Claims (9)
1. Thermoplastic moulding compounds containing A) ABS type resin, B) aromatic polycarbonate resin, C) polymer resin bearing carboxyl groups and optionally D) further polymer resins, characterised in that an ABS resin with at least one basically acting additive is used as component A, component C is selected from C.1 a polymer resin with a carboxyl group (-COOH) content of 40 to 62.5 wt.%, which is derived from acrylic acid polymers or methacrylic acid polymers or acrylic acid/methacrylic acid copolymers or C.2 a polymer resin with a carboxyl group (-COOH) content of 5 to 30 wt.%, which was obtained by polymerisation of at least two monomers selected from styrene, acrylonitrile and acrylic acid esters and/or methacrylic acid esters with acrylic acid and/or methacrylic acid and the weight ratio of basically acting additive in A): carboxyl groups in C) has a value from 5:1 to 1:1 (when using polymer resin C.1) or a value of 3:1 to 1:3 (when using polymer resin C.2).
2. Thermoplastic moulding compounds according to claim 1 containing A) 50 to 100 parts by weight of ABS type resin, B) 1 to 50 parts by weight of aromatic polycarbonate resin and C) 0.2 to 20 parts by weight of polymer resin bearing carboxyl groups.
3. Thermoplastic moulding compound according to claim 1 and 2, characterised in that an ABS resin with at least one basically acting additive is used as component A, component C is selected from C.1) polyacrylic acid and/or polymethacrylic acid and C.2) a polymer resin prepared from styrene, acrylonitrile and methacrylic acid and the weight ratio of basically acting additive in A) : carboxyl groups in C) has a value from 4:1 to 1:1 (when using polymer resin C.1) or a value of 2:1 to 1:2 (when using polymer resin C.2).
4. Thermoplastic moulding compounds according to claims 1 and 2 containing bisphenol A-polycarbonate as the aromatic polycarbonate resin.
5. Thermoplastic moulding compounds according to claims 1 and 2 containing as component A, s and optionally D
polymers which have already been processed into mouldings and which have already passed through at least one cycle of use as such mouldings.
polymers which have already been processed into mouldings and which have already passed through at least one cycle of use as such mouldings.
6. Thermoplastic moulding compounds which contain as component D aromatic polyesters, thermoplastic polyurethanes, polyacrylates, polyacetals and/or polyamides.
7. Thermoplastic moulding compounds according to claim 1, which additionally contain stabilisers, pigments, mould release agents, flame retardants, lubricants and/or antistatic agents.
8. Process for the production of thermoplastic moulding compounds according to claim 1, characterised in that components (A) and (C) are initially mixed and then the resultant blend is mixed with component (B) and optionally component (D), in each case at elevated temperature.
9. A method of stabilizing a thermoplastic composition containing an ABS-type resin, aromatic polycarbonate resins and optionally further polymer resins by adding a compound bearing carboxyl groups or a mixture thereof according to claim 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4221934A DE4221934A1 (en) | 1992-07-03 | 1992-07-03 | Thermoplastic molding compounds |
| DEP4221934.5 | 1992-07-03 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2099480A1 true CA2099480A1 (en) | 1994-01-04 |
Family
ID=6462444
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002099480A Abandoned CA2099480A1 (en) | 1992-07-03 | 1993-06-30 | Thermoplastic moulding compounds |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0576948B1 (en) |
| JP (1) | JPH0657091A (en) |
| CA (1) | CA2099480A1 (en) |
| DE (2) | DE4221934A1 (en) |
| ES (1) | ES2090786T3 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6423767B1 (en) | 1997-12-03 | 2002-07-23 | Basf Aktiengesellschaft | Polycarbonate moulding materials |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5369743B2 (en) * | 2009-02-13 | 2013-12-18 | 三菱電機株式会社 | Hydrolysis resistant polycarbonate / acrylonitrile alloy resin composition |
| US9624370B2 (en) | 2013-03-15 | 2017-04-18 | Sabic Global Technologies B.V. | Stablized polycarbonate blend with post consumer recycled plastics |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1256412C2 (en) * | 1966-03-05 | 1977-03-03 | Bayer Ag, 5090 Leverkusen | THERMOPLASTIC MOLDING COMPOUNDS WITH ANTISTATIC PROPERTIES |
| DE3114494A1 (en) * | 1981-04-10 | 1982-11-04 | Basf Ag, 6700 Ludwigshafen | THERMOPLASTIC MOLDS |
| US4472554A (en) * | 1982-07-26 | 1984-09-18 | Mobay Chemical Corporation | Polycarbonate ABS blends of improved impact strength |
| US4487881A (en) * | 1983-10-03 | 1984-12-11 | Mobay Chemical Corporation | Impact improvement of reinforced polycarbonate/ABS blends |
| DE3521957A1 (en) * | 1985-06-20 | 1987-01-02 | Basf Ag | REFRIGERANT IMPACT THERMOPLASTIC POLYESTER MOLDS |
| CA2089293A1 (en) * | 1992-02-28 | 1993-08-29 | Shripathy Vilasagar | Low gloss polycarbonate/abs blends obtained by using carboxy-functional styrene-acrylonitrile |
| EP0564242A1 (en) * | 1992-04-03 | 1993-10-06 | General Electric Company | PC/ABS blends exhibiting reduced gloss |
-
1992
- 1992-07-03 DE DE4221934A patent/DE4221934A1/en not_active Withdrawn
-
1993
- 1993-06-21 ES ES93109870T patent/ES2090786T3/en not_active Expired - Lifetime
- 1993-06-21 DE DE59303299T patent/DE59303299D1/en not_active Expired - Fee Related
- 1993-06-21 EP EP93109870A patent/EP0576948B1/en not_active Expired - Lifetime
- 1993-06-28 JP JP5178572A patent/JPH0657091A/en active Pending
- 1993-06-30 CA CA002099480A patent/CA2099480A1/en not_active Abandoned
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6423767B1 (en) | 1997-12-03 | 2002-07-23 | Basf Aktiengesellschaft | Polycarbonate moulding materials |
Also Published As
| Publication number | Publication date |
|---|---|
| ES2090786T3 (en) | 1996-10-16 |
| DE4221934A1 (en) | 1994-01-05 |
| DE59303299D1 (en) | 1996-08-29 |
| EP0576948B1 (en) | 1996-07-24 |
| EP0576948A2 (en) | 1994-01-05 |
| JPH0657091A (en) | 1994-03-01 |
| EP0576948A3 (en) | 1994-03-16 |
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