EP3655481A1 - Composition chargée en talc et matière à mouler thermoplastique - Google Patents

Composition chargée en talc et matière à mouler thermoplastique

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Publication number
EP3655481A1
EP3655481A1 EP18740253.2A EP18740253A EP3655481A1 EP 3655481 A1 EP3655481 A1 EP 3655481A1 EP 18740253 A EP18740253 A EP 18740253A EP 3655481 A1 EP3655481 A1 EP 3655481A1
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EP
European Patent Office
Prior art keywords
component
composition according
weight
composition
rubber
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP18740253.2A
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German (de)
English (en)
Inventor
Andreas Seidel
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Covestro Intellectual Property GmbH and Co KG
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Covestro Deutschland AG
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Publication of EP3655481A1 publication Critical patent/EP3655481A1/fr
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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • 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
    • C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
    • C08L51/085—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds on to polysiloxanes
    • 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
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such 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
    • C08L69/005—Polyester-carbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/18—Polymers of hydrocarbons having four or more carbon atoms, e.g. polymers of butylene, e.g. PB, i.e. polybutylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2069/00—Use of PC, i.e. polycarbonates or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60J—WINDOWS, WINDSCREENS, NON-FIXED ROOFS, DOORS, OR SIMILAR DEVICES FOR VEHICLES; REMOVABLE EXTERNAL PROTECTIVE COVERINGS SPECIALLY ADAPTED FOR VEHICLES
    • B60J1/00—Windows; Windscreens; Accessories therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60R—VEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
    • B60R13/00—Elements for body-finishing, identifying, or decorating; Arrangements or adaptations for advertising purposes
    • B60R13/02—Internal Trim mouldings ; Internal Ledges; Wall liners for passenger compartments; Roof liners
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/53—Core-shell polymer

Definitions

  • the present invention relates to a talc-filled composition, in particular a polycarbonate composition, for the production of a thermoplastic molding composition, a process for the preparation of the thermoplastic molding composition, the molding composition itself, the use of the composition or molding composition for the production of moldings and the moldings themselves.
  • the molding compound is particularly suitable for use in automotive body components, as well as a frame material for two-component injection-molded components consisting of an opaque frame and a transparent or translucent window preferably made of a polycarbonate composition.
  • thermoplastic molding compositions for production by injection molding of large-scale horizontal automotive body components is required, for example: a low thermal expansion coefficient for a high dimensional stability and low distortion to realize small gaps,
  • thermoplastic polycarbonate molding compositions which are suitable as a composite, frame or back-injection material for the production of two-component injection molded components consisting of an opaque frame or attachment and a consisting of a polycarbonate composition transparent or translucent window or component section.
  • Such components are used for example in the field of automotive glazing (glazing) as a replacement glass, but are for example as for the production of lighting fixtures and headlamps in the field of lighting, as illuminated decorative screens in the field of interior lighting (Ambient Lighting) and as a screened function screens or displays for the integration of the on-board electronics.
  • Such design and functional elements will become increasingly important in the automobile of the future.
  • thermoplastic polycarbonate compositions containing an impact modifier, optionally a vinyl copolymer, a mineral filler and an acid or an acid salt, which have improved mechanical properties and in which the polycarbonate has an improved thermal integrity of the molecular weight.
  • WO 2008/122359 A1 discloses polycarbonate compositions with improved ductility, heat resistance and processing stability containing talc, optionally rubber-containing vinyl (co) polymer and a Brönsted acid compound.
  • WO 2013/060687 A1 discloses a Bronsted acidic compound stabilized polycarbonate compositions with improved processing stability containing optionally rubber-modified vinyl (co) polymer and also optionally talc, which are prepared in a special process in which the Brönsted acid compound before compounding is applied to an inorganic or organic adsorber or absorber, preferably to a finely divided silica.
  • WO 2010/031513 A1 discloses stress-crack-resistant and low distortion two-component moldings comprising a molded from a transparent or translucent amorphous polycarbonate molding composition which is fully or partially back-injected with an opaque, also amorphous thermoplastic composition as a second component, which comes as a second component used Opaque composition polycarbonate, talc and optionally contains a rubber-containing vinyl (co) polymer.
  • thermoplastic molding composition which is suitable for the production by injection molding of large-area, preferably horizontal, (in the offline method) paintable automotive body components and as a frame material for the production of two-component injection molded components consisting of an opaque frame or attachment and a transparent or translucent window or component section consisting of a polycarbonate composition
  • the injection molded body due to improved processing stability of the thermoplastic molding composition by an improved surface quality (reduced Streaking under thermal stress and shear) and thus are also suitable for components with Class A surface geometry and wherein the components have a low coefficient of thermal expansion, a reduced compared to the value of pure polycarbonate, largely isotropic processing shrinkage, high rigidity, improved impact strength and reduced Bubble formation after heat-moisture storage (as it occurs, for example, in painting processes).
  • the molding composition is characterized by a high melt flowability.
  • the molding composition should preferably have good heat aging resistance.
  • thermoplastic molding composition contains the following constituents:
  • Wt .-% of rubber-modified vinyl (co) polymer having a gel content measured as acetone-insoluble fraction of 15 to 25 wt .-%, preferably from 18 to 24 wt .-%, particularly preferably from 20 to 24 wt .-%, based to component B,
  • the composition consists of at least 95% by weight, more preferably at least 98% by weight, most preferably 100% by weight, of components A to E.
  • component D zinc bis (dihydrogen phosphate) is used.
  • component D is zinc bis (dihydrogen phosphate) dihydrate Zn (H2P04) 2 .2H2O.
  • component D is used in the preparation of the compositions according to the invention in the form of a very finely divided powder.
  • component A a thermoplastic or a mixture of different thermoplastics selected from at least one polymer selected from the group consisting of polycarbonate, polyester carbonate and polyester is used.
  • component A) is selected from at least one polymer selected from the group consisting of polycarbonate and polyester carbonate, more preferably selected from at least one polymer selected from the group consisting of aromatic polycarbonate and aromatic polyester carbonate, most preferably Component A) to aromatic polycarbonate or a mixture of different aromatic polycarbonates.
  • component A) is free of polyesters, in a particularly preferred embodiment free of polyesters and polyester carbonates.
  • polycarbonate is understood as meaning both homopolycarbonates and copolycarbonates, in which case the polycarbonates may be linear or branched in a known manner. [Ein Ein] A portion of up to 80 mol%, preferably of 20 mol%, may also be used. Up to 50 mol% of the carbonate groups in the polycarbonates used 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 in the molecular chain are termed aromatic polyester carbonates ,
  • 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.
  • thermoplastic polycarbonates including the thermoplastic aromatic polyester carbonates have average molecular weights Mw determined by GPC (gel permeation chromatography in methylene chloride with polycarbonate based on Bisphenol A as standard) from 15,000 g / mol to 50,000 g / mol, preferably from 20,000 g / mol to 35,000 g / mol, more preferably from 23,000 g / mol to 33,000 g / mol.
  • the preparation of aromatic polycarbonates is e.g. by reacting diphenols with carbonyl halides, preferably phosgene, and / or with aromatic dicarboxylic acid dihalides, preferably benzenedicarboxylic acid dihalides, by the interfacial process, optionally with the use of chain terminators and optionally using trifunctional or more than trifunctional branching agents, a portion of the carbonic acid derivatives being used to prepare the polyestercarbonates is replaced by aromatic dicarboxylic acids or derivatives of dicarboxylic acids, depending on the extent to be replaced in the aromatic polycarbonates Carbonat Designtechniken by aromatic Dicarbon Anlagenreester Modelltechniken. Likewise, preparation via a melt polymerization process by reaction of diphenols with, for example, diphenyl carbonate is possible.
  • Dihydroxyaryl compounds suitable for the preparation of polycarbonates are those of the formula (1)
  • Z is an aromatic radical having 6 to 30 carbon 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 (1) preferably represents a radical of the formula (2)
  • R 6 and R 7 independently of one another are H, cis to cis-alkyl, cis to cis-alkoxy,
  • Halogen such as Cl or Br or for each optionally substituted aryl or aralkyl, preferably for H or Ci to Ci 2 alkyl, particularly preferably for
  • X is a single bond, -S0 2 -, -CO-, -O-, -S-, Ci- to Ce-alkylene, C 2 - to C 5 - alkylidene or Cs to C 6 -cycloalkylidene, which with Ci- to Cö-alkyl, preferably methyl or ethyl, may be substituted, further for Ce- to Ci 2 -arylene, which may optionally be condensed with further heteroatom-containing aromatic rings is.
  • X is a single bond until C 5 alkylene, C 2 - to C 5 alkylidene, C 5 - C 6 cycloalkylidene, -O-, -SO-, -CO-, -S-, -SO 2 - or for a radical of the formula (2a)
  • Diphenols suitable for the preparation of the polycarbonates are, for example, hydroquinone, resorcinol, dihydroxydiphenyls, bis (hydroxyphenyl) alkanes, bis (hydroxyphenyl) cycloalkanes, bis (hydroxyphenyl) sulfides, bis (hydroxyphenyl) ethers, bis ( hydroxyphenyl) ketones, bis (hydroxyphenyl) sulfones, bis (hydroxyphenyl) sulfoxides, ⁇ - ⁇ '-bis (hydroxyphenyl) diisopropylbenzenes, phthalimidines derived from isatin or phenolphthalein derivatives and their nuclear alkylated, nuclear-arylated and nuclear-halogenated compounds.
  • Preferred diphenols are 4,4'-dihydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) -propane (bisphenol A), 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 1,1-bis- (4-hydroxyphenyl) -p-diisopropylbenzene, 2,2-bis- (3-methyl-4-hydroxyphenyl) -propane, dimethyl-bisphenol A, 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, 1,1-bis- (3,5-dimethyl-4-hydroxyphenyl) -p-diisopropylbenzene and 1,1-bis- (4-hydroxyphenyl)
  • diphenols are 2,2-bis- (4-hydroxyphenyl) -propane (bisphenol A), 2,2-bis- (3,5-dimethyl-4-hydroxyphenyl) -propane, 1,1-bis- (4 -hydroxyphenyl) -cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and dimethyl-bisphenol A.
  • bisphenol A 2,2-bis- (4-hydroxyphenyl) -propane
  • bisphenol A 2,2-bis- (3,5-dimethyl-4-hydroxyphenyl) -propane
  • 1,1-bis- (4 -hydroxyphenyl) -cyclohexane 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane
  • dimethyl-bisphenol A is 2,2-bis (4-hydroxyphenyl) -propane (bisphenol A).
  • diphenols are e.g. in US-A 3,028,635, US-A 2,999,825, US-A 3,148,172, US-A 2,991,273, US-A 3,271,367, US-A 4,982,014 and US-A 2,999,846, in DE-A 1 570 703, DE-A 2063 050, DE-A 2 036 052, DE-A 2 211 956 and DE-A 3 832 396, in FR-A 1 561 518, in the monograph "H. Schnell , Chemistry and Physics of Polycarbonates,
  • Suitable carbonic acid derivatives are, for example, phosgene or diphenyl carbonate.
  • Suitable chain terminators that can be used in the preparation of the polycarbonates are monophenols.
  • Suitable monophenols are, for example, phenol itself, alkylphenols such as cresols, p-tert-butylphenol, cumylphenol and mixtures thereof.
  • Preferred chain terminators are the phenols which are mono- or polysubstituted by C 1 - to C 30 -alkyl radicals, linear or branched, preferably unsubstituted, or substituted by tert-butyl. Particularly preferred chain terminators are phenol, cumylphenol and / or p-tert-butylphenol.
  • the amount of chain terminator to be used is preferably 0.1 to 5 mol%, based on moles of diphenols used in each case.
  • the addition of the chain terminators can be carried out before, during or after the reaction with a carbonic acid derivative.
  • Suitable branching agents are the trifunctional or more than trifunctional compounds known in polycarbonate chemistry, especially those having three or more than three phenolic OH groups.
  • Suitable branching agents are, for example, 1,3,5-tri (4-hydroxyphenyl) benzene, 1,1,3-tri (4-hydroxyphenyl) ethane, tri- (4-hydroxyphenyl) -phenyl methane, 2,4- Bis (4-hydroxyphenylisopropyl) phenol, 2,6-bis (2-hydroxy-5'-methylbenzyl) -4-methylphenol, 2- (4-hydroxyphenyl) -2- (2,4-dihydroxyphenyl) propane, tetra (4-hydroxyphenyl) methane, tetra (4- (4-hydroxyphenylisopropyl) phenoxy) methane and 1,4-bis - ((4 ', 4 "-dihydroxytriphenyl) methyl) benzene and 3,3-bis (3-methyl-4-hydroxyphenyl) -2-oxo-2,3-dihydroindole.
  • the amount of optionally used branching agent is preferably 0.05 mol% to 2.00 mol%, based on moles of diphenols used in each case.
  • the branching agents may either be initially charged with the diphenols and the chain terminators in the aqueous alkaline phase or may be added dissolved in an organic solvent prior to phosgenation. In the case of the transesterification process, the branching agents are used together with the diphenols.
  • Particularly preferred polycarbonates are the homopolycarbonate based on bisphenol A, the homopolycarbonate based on 1,3-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and the copolycarbonates based on the two monomers bisphenol A and I, l Bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane.
  • Preferred methods of preparation of the polycarbonates to be used according to the invention, including the polyestercarbonates, are the known interfacial process and the known melt transesterification process (cf., for example, WO 2004/063249 A1, WO 2001/05866 A1, WO 2000/105867, US Pat. No. 5,340,905 A, US Pat. No. 5,097,002 A, US-A 5,717,057 A).
  • Eligible polyesters are aromatic in a preferred embodiment, more preferably polyalkylene terephthalates.
  • these are reaction products of aromatic dicarboxylic acids or their reactive derivatives, such as dimethyl esters or anhydrides, and aliphatic, cycloaliphatic or aliphatic diols and mixtures of these reaction products.
  • aromatic polyalkylene terephthalates contain at least 80% by weight, preferably at least 90% by weight, based on the dicarboxylic acid component of terephthalic acid residues and at least 80% by weight, preferably at least 90% by weight, based on the diol component of ethylene glycol and / or butanediol -l, 4-residues.
  • the preferred aromatic polyalkylene terephthalates may contain, in addition to terephthalic acid residues, up to 20 mole%, preferably up to 10 mole%, of other aromatic or cycloaliphatic dicarboxylic acids having 8 to 14 carbon atoms or aliphatic dicarboxylic acids having 4 to 12 carbon atoms, e.g. Residues of phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, 4,4'-diphenyldi-carboxylic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, cyclohexanediacetic acid.
  • the preferred aromatic polyalkylene terephthalates in addition to ethylene glycol or butane-idiol-l, 4-radicals up to 20 mol%, preferably up to 10 mol%, other aliphatic diols having 3 to 12 C atoms or cycloaliphatic diols having 6 to 21 C.
  • Contain atoms eg Residues of 1,3-propanediol, 2-ethylpropanediol 1, 3, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, cyclohexanedimethanol-1,4, 3-ethylpentanediol-2,4, 2-methylpentanediol 2,4,2,2,4-trimethylpentanediol-1,3,2-ethylhexanediol-1,3,2,2-diethylpropanediol-1,3-hexanediol 2,5,1,4-di- ( ⁇ -hydroxyethoxy ) benzene, 2,2-bis (4-hydroxycyclohexyl) propane, 2,4-dihydroxy-1,1,3,3-tetramethylcyclobutane, 2,2-bis (4-.beta.-hydroxyethoxy-phenyl ) -
  • the aromatic polyalkylene terephthalates may be prepared by incorporation of relatively small amounts of trihydric or trihydric alcohols or 3- or 4-basic carboxylic acids, e.g. in accordance with DE-A 1 900 270 and US Pat. No. 3,692,744.
  • preferred branching agents are trimesic acid, trimellitic acid, trimethylolethane and -propane and pentaerythritol.
  • aromatic polyalkylene terephthalates prepared from terephthalic acid alone and their reactive derivatives (e.g., their dialkyl esters) and ethylene glycol and / or butane-1,4-diol, and mixtures of these polyalkylene terephthalates.
  • Preferred mixtures of aromatic polyalkylene terephthalates contain 1 to 50% by weight, preferably 1 to 30% by weight, of polyethylene terephthalate and 50 to 99% by weight, preferably 70 to 99% by weight, of polybutylene terephthalate.
  • the aromatic polyalkylene terephthalates preferably used have a viscosity number of 0.4 to 1.5 dl / g, preferably 0.5 to 1.2 dl / g, measured in phenol / o- Dichlorobenzene (1: 1 parts by weight) in a concentration of 0.05g / ml according to ISO 307 at 25 ° C in Ubbelohde viscometer.
  • the aromatic polyalkylene terephthalates can be prepared by known methods (see, for example, Kunststoff-Handbuch, Volume VIII, page 695 et seq., Carl Hanser Verlag, Kunststoff 1973).
  • Aromatic polycarbonate based on bisphenol A is most preferably used as component A.
  • Component B Aromatic polycarbonate based on bisphenol A is most preferably used as component A.
  • Component B) is rubber-modified vinyl (co) polymer.
  • Component B) comprises one or more graft polymers as component B.l) and one or more rubber-free vinyl (co) polymers which are not chemically bonded to a rubber and are not included in such a rubber as component B.2).
  • the rubber-modified vinyl (co) polymer according to component B) has a gel content, measured at room temperature in acetone as solvent, of from 15 to 25% by weight, preferably from 18 to 24% by weight, particularly preferably from 20 to 24% by weight (based on component B) or the sum of all subcomponents that make up component B)).
  • the gel content of component B) is determined at 25 ° C. in a suitable solvent (here in acetone) as described in M. Hoffmann, H. Krömer, R. Kuhn, Polymer Analytics I and II, Georg Thieme Verlag, Stuttgart (1977) as insoluble in this solvent. As an alternative, it can also be calculated from the individual gel contents of the individual components of which component B) is determined, and the concentrations of the individual components in component B).
  • a suitable solvent here in acetone
  • Component B.l comprises one or more graft polymers of
  • the glass transition temperature is determined by means of differential scanning calorimetry (DSC) according to the standard DIN EN 61006 (2004 version) at a heating rate of 10 K / min with definition of the Tg as the midpoint temperature (tangent method).
  • particulate graft bases B.1.2 which generally have an average particle size (d 50 value) of 0.05 to 10 ⁇ m, preferably 0.1 to 2 ⁇ m, particularly preferably 0.2 to 1.5 ⁇ m.
  • the mean particle size d50 is the diameter, above and below which each 50 wt .-% of the particles are. It can be determined by ultracentrifuge measurement (W. Scholtan, H. Lange, Kolloid, Z. and Z. Polymere 250 (1972), 782-1796).
  • Monomers B.1.1 are preferably mixtures of B.1.1.1 50 to 99 wt .-%, preferably 65 to 85 wt .-%, preferably 70 to 80 wt .-%, each based on the totality of the monomers of the graft shell B. 1.1, vinylaromatics and / or ring-substituted vinylaromatics (such as styrene, ⁇ -methylstyrene, p-methylstyrene, p-chlorostyrene) and / or (meth) acrylic acid (C 1 -C 8) -alkyl esters, such as methyl methacrylate, ethyl methacrylate and butyl acrylate, and B.
  • vinylaromatics and / or ring-substituted vinylaromatics such as styrene, ⁇ -methylstyrene, p-methylstyrene, p-chlorostyrene
  • Preferred monomers B.1.1.1 are selected from at least one of the monomers styrene, ⁇ -methylstyrene and methyl methacrylate.
  • Preferred monomers B.1.1.2 are selected from at least one of the monomers acrylonitrile, n-butyl acrylate, maleic anhydride and methyl methacrylate.
  • Particularly preferred monomers are B.1.1.1 styrene and B.1.1.2 acrylonitrile.
  • suitable graft bases B.1.2) are for example diene rubbers, EP (D) M rubbers, ie those based on ethylene / propylene and optionally Diene, acrylate, polyurethane, silicone, chloroprene and ethylene / vinyl acetate rubbers, and silicone / acrylate composite rubbers.
  • Preferred graft bases B.1.2 are diene rubbers, for example based on butadiene and isoprene, or mixtures of diene rubbers or copolymers of diene rubbers or mixtures thereof with other copolymerizable monomers (for example according to B.1.1.1 and B.1.1.2).
  • graft B.1.2 is pure polybutadiene rubber.
  • grafting bases B.1.2 are silicone, acrylate and silicone / acrylate composite rubbers.
  • the graft copolymers B.l are prepared by free-radical polymerization, e.g. produced by emulsion, suspension, solution or bulk polymerization.
  • mixtures of different graft polymers Bl) are used in component B, wherein the graft polymers, for example in the manner of preparation and / or in the type of the graft base B.1.2) and / or in the nature of the graft shell Bll) can distinguish.
  • the graft monomers B.l.l) are known not necessarily completely grafted onto the graft. To this extent, products of grafting reactions often still contain significant proportions of free (i.e., not chemically bound to the grafting base and irreversibly entrapped in the grafting base) copolymer having a composition analogous to that of the grafted shell.
  • component B.l is understood to be exclusively the graft polymer as defined above, while the copolymer of component B.2) not bound chemically to the graft base and not included in this graft base is assigned to the preparation.
  • a suitable Solvents such as acetone, M. Hoffmann, H. Krömer, R. Kuhn, polymer analysis I and II, Georg Thieme Verlag, Stuttgart 1977
  • inclusion in the context of this patent application is understood to mean that the vinyl (co) polymer is enclosed in the rubber particles and can not be dissolved out by solvents such as acetone.
  • component B contains mixtures of different graft polymers B1), this mixture preferably contains a graft polymer B1) having a core-shell structure in which the core (ie the grafting base) is formed from silicone rubber, acrylate rubber or silicone acrylate composite rubber ,
  • the proportion of this graft polymer with a core of silicone rubber, acrylate rubber or silicone-acrylate composite rubber is selected so that this graft polymer contributes to the gel content measured in acetone of component B to at least 70%.
  • the composition contains as further component B.2) one or more rubber-free (co) polymers of at least one vinyl monomer, preferably selected from the group of vinyl aromatics, vinyl cyanides (unsaturated nitriles), (meth) acrylic acid (C 1 to C 8) alkyl esters, unsaturated carboxylic acids and derivatives (such as anhydrides and imides) of unsaturated carboxylic acids.
  • vinyl monomer preferably selected from the group of vinyl aromatics, vinyl cyanides (unsaturated nitriles), (meth) acrylic acid (C 1 to C 8) alkyl esters, unsaturated carboxylic acids and derivatives (such as anhydrides and imides) of unsaturated carboxylic acids.
  • Particularly suitable as component B.2) are (co) polymers from B.2.1) from 50 to 99% by weight, preferably from 65 to 85% by weight, particularly preferably from 70 to 80% by weight, based on the (co) Polymer B.2) of at least one monomer selected from the group of vinylaromatics (such as, for example, styrene, OC-methylstyrene), ring-substituted vinylaromatics (such as, for example, p-methylstyrene, p-chlorostyrene) and (meth) acrylic acid (C 1 -C 8) -alkyl esters (such as methyl methacrylate, n-butyl acrylate, tert-butyl acrylate) and B.2.2) 1 to 50 wt .-%, preferably 15 to 35 wt .-%, particularly preferably 20 to 30 wt .-% based on the (Co ) Polymer B.2) at least one monomer selected
  • These (co) polymers B.2) are resinous, thermoplastic and rubber-free.
  • the copolymer of B2.1) styrene and B2.2) acrylonitrile is particularly preferred.
  • Such (co) polymers B.2) are known and can be prepared by free-radical polymerization, in particular by emulsion, suspension, solution or bulk polymerization.
  • the (co) polymers B.2) have a weight-average molecular weight (Mw), determined by gel permeation chromatography with polystyrene as standard, of preferably 50,000 to 200,000 g / mol, more preferably from 70,000 to 170000 g / mol, most preferably from 80,000 to 130000 g / mol.
  • Mw weight-average molecular weight
  • talc As component C) naturally occurring or synthetically produced talc is used.
  • Pure talc has the chemical composition 3 MgO-4SiO 2 H 2 O and thus has an MgO content of 31.9% by weight, a SiO 2 content of 63.4% by weight and a chemically bound water content of 4.8% by weight .-%. It is a silicate with a layered structure.
  • Naturally occurring talc materials generally do not have the ideal composition given above, as they are formed by partial replacement of magnesium by other elements, by partial replacement of silicon, by e.g. Aluminum and / or by adhesions with other minerals such. Dolomite, magnesite and chlorite are contaminated.
  • talc As component C), preference is given to using those types of talc with particularly high purity. These are characterized by an MgO content of 28 to 35 wt .-%, preferably 30 to 33 wt .-%, particularly preferably 30.5 to 32 wt .-% and a SiO 2 content of 55 to 65 wt .-% , preferably 58 to 64 wt .-%, particularly preferably 60 to 62.5% by weight. Particularly preferred types of talc are further characterized by an A1203 content of less than 5 wt .-%, more preferably less than 1 wt .-%, in particular less than 0.7 wt .-%, from.
  • talc in the form of finely ground types with an average particle diameter d50 of ⁇ 10 ⁇ , preferably ⁇ 5 ⁇ , more preferably ⁇ 2 ⁇ , most preferably ⁇ 1.5 ⁇ .
  • the talc can be surface-treated, eg silanized, to ensure better compatibility with the polymer.
  • the use of compacted talc is advantageous.
  • component D) is a monophosphate, that is a dihydrogen phosphate salt, with a cation selected from the group consisting of aluminum and zinc, preferably zinc bis (dihydrogen phosphate) is used.
  • zinc bis (dihydrogen phosphate) dihydrate Zn (H2PO) 2 .2H2O is used.
  • the composition of the invention may contain one or more polymer additives, preferably selected from the group consisting of flame retardants, Antidrippingstoffn, Flammschutzsynergisten, smoke inhibitors, lubricants and mold release agents, nucleating agents, antistatic agents, conductivity additives, stabilizers (eg hydrolysis, heat aging and UV Stabilizers and transesterification inhibitors), flowability promoters, phase compatibilizers, other impact modifiers (both with and without core-shell structure) which differ from component B), other components other than components A) and B) (for example functional blend partners), of component C. ) various fillers and reinforcing materials as well as dyes and pigments.
  • polymer additives preferably selected from the group consisting of flame retardants, Antidrippingstoffn, Flammschutzsynergisten, smoke inhibitors, lubricants and mold release agents, nucleating agents, antistatic agents, conductivity additives, stabilizers (eg hydrolysis, heat aging and UV Stabilizers and transesterification inhibitors
  • the composition comprises at least one polymer additive selected from the group consisting of lubricants and mold release agents, stabilizers, flowability promoters, phase compatibility agents, other impact modifiers, other polymeric constituents, dyes and pigments.
  • the composition contains pentaerythritol tetrastearate as a mold release agent.
  • the composition contains as stabilizer at least one member selected from the group consisting of sterically hindered phenols, organic phosphites and sulfur-based co-stabilizers.
  • the composition contains as stabilizer at least one member selected from the group consisting of octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate and tris (2,4-di-tert-butylphenyl ) phosphite.
  • the composition contains as component E) at least one member selected from the group consisting of lubricants and mold release agents, stabilizers, flowability promoters and dyes and pigments and is free of further polymer additives according to component E).
  • the composition contains as component E) at least one mold release agent, at least one stabilizer and optionally at least one dye and / or pigment and is free of further polymer additives according to component E).
  • Thermoplastic molding compositions can be prepared from the compositions according to the invention.
  • thermoplastic molding compositions according to the invention can be prepared, for example, by mixing the respective constituents of the compositions in a known manner and at temperatures of preferably 200 ° C to 320 ° C, more preferably 240 to 300 ° C, most preferably 260 ° C to 300 ° C in conventional units such as internal kneaders, extruders and twin-screw and melt-extruded melt-extruded.
  • molding compound is meant the product which is obtained when the components of the composition are melt compounded and melt extruded.
  • the mixing of the individual constituents of the compositions can be carried out in a known manner both successively and simultaneously, both at about 20 ° C. (room temperature) and at a higher temperature. This means that, for example, some of the components can be metered via the main intake of an extruder and the remaining components can be fed later via a side extruder in the compounding process.
  • the invention also provides a process for the preparation of the molding compositions of the invention.
  • the molding compositions of the invention can be used for the production of moldings of any kind. These can be achieved, for example, by injection molding, extrusion and blow molding. be made method. Another form of processing is the production of moldings by deep drawing from previously prepared plates or films.
  • the novel molding compositions are particularly suitable for processing in extrusion, blow molding and deep-drawing processes.
  • Such shaped articles which can be produced from the compositions and molding compositions according to the invention are films, profiles, housing parts of any kind, e.g. for household appliances such as juice presses, coffee machines, blenders; for office machines such as monitors, flat screens, notebooks, printers, copiers; Panels, pipes, electrical installation ducts, windows, doors and other profiles for the building sector (interior and exterior applications) and electrical and electronic parts such as switches, plugs and sockets and components for commercial vehicles, in particular for the automotive sector.
  • household appliances such as juice presses, coffee machines, blenders
  • office machines such as monitors, flat screens, notebooks, printers, copiers
  • Panels, pipes, electrical installation ducts, windows, doors and other profiles for the building sector (interior and exterior applications) and electrical and electronic parts such as switches, plugs and sockets and components for commercial vehicles, in particular for the automotive sector.
  • compositions and molding compositions according to the invention are also suitable for the production of the following moldings or moldings: Interior components for rail vehicles, ships, aircraft, buses and other motor vehicles, body parts for motor vehicles, housings of electrical appliances containing small transformers, housings for information processing and transmission equipment, housings and Cladding of medical equipment, massagers and housings therefor, toy vehicles for children, flat wall elements, housings for safety devices, heat-insulated transport containers, fittings for sanitary and bath equipment, grille for ventilation openings and housings for garden tools.
  • composition for producing a thermoplastic molding composition comprising the following constituents:
  • component A is an aromatic polycarbonate.
  • composition according to embodiment 4 wherein the component A is aromatic polycarbonate based on bisphenol-A.
  • component B contains vinyl monomer-grafted polybutadiene-containing rubber particles containing inclusions of vinyl (co) polymer consisting of the vinyl monomers.
  • composition according to one of the preceding embodiments wherein the component B graft polymer with core-shell structure having a core selected from the group consisting of silicone rubber, acrylate rubber and silicone-acrylate composite rubber.
  • component D is a zinc bis (dihydrogen phosphate).
  • composition according to one of the preceding embodiments consisting of at least 95 wt .-% of the components A-E.
  • composition according to one of the preceding embodiments consisting of at least 98 wt .-% of the components A-E.
  • composition according to one of the preceding embodiments consisting of 100 wt .-% of the components A-E. 16. A process for the preparation of a molding composition, wherein the components of a
  • Composition according to one of embodiments 1 to 15 at a temperature of 200 to 320 ° C are mixed together.
  • a composition according to any one of embodiments 1 to 15 or a molding composition according to embodiment 19 for the production of moldings.
  • Molded body preferably an automobile body component, containing a composition according to one of embodiments 1 to 15 or a molding compound according to embodiment 19.
  • Automotive body component containing thermoplastic molding compositions having a modulus of elasticity according to ISO 527 at 23 ° C of at least 4500 MPa, a CLTEm ng s according to DIN 53752 in the temperature range of 23-55 ° C of at most 40 ppm / K, a longitudinal shrinkage according to IS0294-4 of at most 0.4% and an impact strength according to ISO 180 / U at 23 ° C of at least 60 kJ / m 2 .
  • a two-component injection-molded component comprising (i) an opaque frame or attachment made of a composition according to any one of claims 1 to 15 or a molding compound according to embodiment 19 and (ii) a transparent or translucent window or component portion directly in contact with (i) ,
  • Component A is a compound having Component A:
  • Bisphenol A-based linear polycarbonate having a weight-average molecular weight Mw of 28,000 g / mol (determined by GPC in methylene chloride against a bisphenol A polycarbonate standard).
  • Component B is a compound having Component B:
  • B-1) a styrene-acrylonitrile copolymer having an acrylonitrile content of 23% by weight and having a weight-average molecular weight M w of 100,000 Da measured by GPC in tetrahydrofuran with polystyrene as standard,
  • an ABS polymer prepared in bulk polymerization having an A: B: S weight ratio of 24%: 10%: 66% with a gel content measured in acetone at room temperature of 19% by weight, in acetone soluble sol proportion of the component B-2 has a weight-average molecular weight M w of 125,000 Da measured by GPC in tetrahydrofuran with polystyrene as a standard, and
  • a graft polymer having a core-shell structure prepared by emulsion polymerization and consisting of 75% by weight of a silicone acrylate composite rubber as core and 25% by weight of a polymethyl methacrylate shell having a gel content measured in acetone at room temperature of 90% by weight.
  • Component B has as a mixture of these three constituents a gel content measured as in acetone at room temperature insoluble fraction of 23 wt .-%. This gel component of component B is attributed to the wt .-% of the bulk ABS component B-2 and to 78 wt .-% of the graft polymer with core-shell structure B-3. The proportion of component B-1 is 53% by weight, based on B.
  • Jetfine TM 3CA talc (Imerys S.A., France)
  • Fabutit TM 289 ortho-phosphoric acid absorbed on silica gel (Chemische Fabrik Budenheim KG, Germany).
  • the component Dl has within 4 h at 23 ° C and at a relative humidity of 50%, a water absorption of 14% of the starting material.
  • the component D2 has within 4 h at 23 ° C and at a relative humidity of 50%, a water absorption of 1% of the starting material.
  • the component D3 has within 4 h at 23 ° C and at a relative humidity of 50%, a water absorption of 1% of the starting material.
  • Irganox TM B900 (BASF, Germany): stabilizer
  • Black Pearls TM 800 (Cabot Corp., Belgium): carbon black pigment
  • the components were mixed on a twin-screw extruder ZSK 25 from Coperion (Stuttgart, Germany) at a melt temperature of 260.degree. Unless stated otherwise, the moldings were produced at a melt temperature of 260 ° C. and a mold temperature of 80 ° C. on an Arburg 270 E injection molding machine.
  • the IZOD impact strength was determined at 23 ° C on test bars of the dimension of 80 mm x 10 mm x 4 mm according to ISO 180 / U (version of 2013).
  • the total energy absorbed in the puncture test is in accordance with ISO 6603-2 (version of 2002). This is carried out at 23 ° C on test specimens dimension of 60 mm x 60 mm x 2 mm.
  • Elastic modulus E and elongation at break were determined on shoulder bars measuring 170 mm ⁇ 10 mm ⁇ 4 mm at 23 ° C. according to ISO 527 (1996 version) with a strain rate of 1 mm / min (modulus of elasticity) and 5 mm / min, respectively (elongation at break).
  • the melt viscosity was determined at a temperature of 260 ° C and a shear rate of 1000 s -1 according to ISO 11443 (version of 2014).
  • the thermal expansion coefficient (CLTE) was determined longitudinally (CLTEm ng s) and transversely (CLTE que r) to the melt flow direction in the temperature interval from 23 ° C to 55 ° C on test specimens of dimension 80 mm ⁇ 10 mm ⁇ 4 mm according to DIN 53752 ( Version from 1980) with a heating rate of 3 K / min.
  • the processing shrinkage was determined longitudinally and transversely to the melt flow direction in accordance with IS0294-4 (2003 version) on test specimens of dimension 60 mm ⁇ 60 mm ⁇ 2 mm, which were produced at a pressure of 500 bar.
  • the processing stability was determined by a so-called thermal spray.
  • this test specimens of dimension of 60 mm x 40 mm x 2 mm at melt temperatures of 260 ° C, 280 ° C and 300 ° C (mold temperature in each case at 80 ° C) are sprayed and judged whether occur on the plate surface streaks as an indication of thermal decomposition ,
  • the plates produced at 260 ° C also serve to assess the surface quality.
  • Class A surfaces only those components are considered which show a faultless and homogeneous surface quality.
  • composition 3 of the invention achieves an advantageous combination of good mechanical and rheological properties, low CLTE, low and isotropic shrinkage, and good resistance to heat-moisture stress. If the composition contains component D3, the processing stability is improved and the surface quality is suitable for Class A. In addition, the impact resistance and the resistance to heat-moisture stress is particularly good.

Abstract

La présente invention concerne une composition pour produire une matière à mouler thermoplastique, ladite composition contenant les composants suivants, à savoir A) 35 à 85 % en poids de polycarbonate, polyester carbonate et/ou polyester aromatiques, B) 5 à 45 % en poids de (co)polymère de vinyle modifié par un caoutchouc ayant une teneur en gel mesurée sous forme de fraction non soluble dans l'acétone allant de 15 à 25 % en poids, rapporté aux composants B, C) 7 à 30 % en poids de talc, D) 0,01 à 1 % en poids d'au moins un sel dihydrogénophosphate ayant un cation choisi dans le groupe constitué de l'aluminium et du zinc, E) 0 à 10 % en poids d'additifs polymères, un procédé pour fabriquer une matière à mouler à partir de la composition, la matière à mouler proprement dite, l'utilisation de la composition ou de la matière à mouler pour fabriquer des corps moulés ainsi que des corps moulés contenant la composition ou la matière à mouler.
EP18740253.2A 2017-07-21 2018-07-20 Composition chargée en talc et matière à mouler thermoplastique Withdrawn EP3655481A1 (fr)

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