CA2715204A1 - Flame-proof impact resistant-modified polycarbonate compositions - Google Patents
Flame-proof impact resistant-modified polycarbonate compositions Download PDFInfo
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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
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
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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
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
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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
- 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
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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
- 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
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Abstract
The invention relates to impact resistant-modified polycarbonate compositions containing A) 50 to 99.4 parts by weight of aromatic polycarbonate and/or aromatic polyester carbonate, B) 0.5 to 20 parts by weight of rubber-modified graft polymer produced in an emulsion polymerization process, C) 0.1 to 30 parts by weight of a salt of a phosphinic acid, the parts by weight of each of components A, B, and C being relative to the total parts by weight of components A+B+C. Said polycarbonate compositions are characterized by an optimal combination of great thermostability, good resistance to chemicals, and good resistance to flames, especially in a glow-wire flammability test according to IEC 60695-2-12. The invention also relates to the use of said polycarbonate compositions for producing molded articles as well as said molded articles.
Description
BMS 071168-WO-nat CA 02715204 2010-06-17 FLAME-PROOF IMPACT RESISTANT-MODIFIED POLYCARBONATE COMPOSITIONS
The present invention relates to impact-modified polycarbonate compositions which comprise a graft polymer prepared in the emulsion polymerization process and a salt of a phosphinic acid, the use of the polycarbonate compositions for the production of shaped articles and the shaped articles themselves.
WO-A 2005/044906 discloses thermoplastic moulding compositions comprising at least one metal salt of hypophosphoric acid and at least one aromatic polycarbonate resin and a mixture thereof with a styrene-containing graft copolymer resin having a rubber content of 5-15 %. The contents of the styrene-containing graft copolymer are 10-40 wt.%.
The moulding compositions obtained are distinguished by good flame resistance, high heat stability under processing conditions and good weather resistance. Because of the low rubber content, other properties, in particular mechanical properties, are at a low level.
WO-A 1999/57192 describes thermoplastic moulding compositions comprising 5-96 wt.%
of a polyester or polycarbonate, 1-30 wt.% of a phosphinic acid salt and/or of a diphosphinic acid salt and/or polymers thereof, 1-30 wt.% of at least one organic phosphorus-containing flameproofing agent, and possible further additives.
DE-A 102004049342 discloses thermoplastic moulding compositions comprising 10-wt.% of thermoplastic polymer, 0.01-50 wt.% of highly branched polycarbonate or highly branched polyester or mixtures thereof, 1-40 wt.% of halogen-free flameproofing agent chosen from the group of P-containing or N-containing compounds or of P-N
condensates or mixtures thereof, and possible further additives.
JP-A 2001-335699 describes flameproofed resin compositions comprising two or more thermoplastic resins chosen from styrene resin, aromatic polyester resin, polyamide resin, polycarbonate resin and polyphenylene ether resin and one or more (in)organic phosphinic acid salts, and possible further additives.
JP-A 2001-261973 (Daicel Chemical Industries Ltd.) describes compositions of thermoplastic resins and (in)organic phosphinic acid salts. A combination of PBT, calcium phosphinate and PTFE is given as an example.
BMS 071168-WO-nat CA 02715204 2010-06-17 JP-A 2002-161211 discloses compositions of thermoplastic resins and flameproofing agents, such as salts of phosphinic and phosphoric acid and derivatives thereof. A
combination of PBT, ABS, polyoxyphenylene, calcium phosphinate, an organophosphate and glass fibres is given as an example.
Flameproofing agents which are conventional according to the prior art for polycarbonate/ABS blends are organic aromatic phosphates. These compounds can be in a low molecular weight form, in the form of a mixture of various oligomers or in the form of a mixture of oligomers with low molecular weight compounds (e.g. WO-A 99/16828 and WO-A 00/31173). The good activity as flameproofing agents is counteracted adversely by the highly plasticizing action of these compounds on the polymeric constituents, so that the heat distortion point of these moulding compositions is not satisfactory for many uses.
The object of the present invention is to provide impact-modified polycarbonate moulding compositions having an optimum combination of high heat distortion point, good resistance to chemicals and good flameproofing, in particular in the glow wire test according to IEC 60695-2-12.
It has now been found, surprisingly, that moulding compositions or compositions comprising A) polycarbonate, B) rubber-modified graft polymer prepared in the emulsion polymerization process and C) a salt of a phosphinic acid have the desired profile of properties.
It has thus been found, surprisingly, that compositions comprising A) 50 to 99.4 parts by wt., preferably 73 to 98 parts by wt., particularly preferably 82 to 91 parts by wt. (in each case based on the sum of the parts by weight of components A+B+C) of aromatic polycarbonate and/or aromatic polyester carbonate, B) 0.5 to 20 parts by wt., preferably 1 to 12 parts by wt., particularly preferably 2 to 6 parts by wt. (in each case based on the sum of the parts by weight of components A+B+C) of rubber-modified graft polymer prepared in the emulsion polymerization process, BMS 071168-WO-nat CA 02715204 2010-06-17 C) 0.1 to 30 parts by wt., preferably 1 to 15 parts by wt., particularly preferably 7 to 12 parts by wt. (in each case based on the sum of the parts by weight of components A+B+C) of a salt of a phosphinic acid, D) 0 to 20 parts by wt. (based on the sum of the parts by weight of components A+B+C = 100) of rubber-free vinyl (co)polymer and/or polyalkylene terephthalate, preferably the composition is free from rubber-free vinyl (co)polymer and/or polyalkylene terephthalate, E) 0 to 50 parts by wt., preferably 0.5 to 25 parts by wt. (in each case based on the sum of the parts by weight of components A+B+C= 100) of additives, wherein all the parts by weight stated in the present application are standardized such that the sum of the parts by weight of components A+B+C in the composition is 100, achieve the abovementioned technical object.
Component A
Aromatic polycarbonates and/or aromatic polyester carbonates according to component A
which are suitable according to the invention are known from the literature or can be prepared by processes known from the literature (for the preparation of aromatic polycarbonates see, for example, Schnell, "Chemistry and Physics of Polycarbonates", In-terscience Publishers, 1964 and DE-AS 1 495 626, DE-A 2 232 877, DE-A 2 703 376, DE-A 2 714 544, DE-A 3 000 610 and DE-A 3 832 396; for the preparation of aromatic polyester carbonates e.g. DE-A 3 077 934).
Aromatic polycarbonates are prepared e.g. by reaction of diphenols with carbonic acid halides, preferably phosgene, and/or with aromatic dicarboxylic acid dihalides, preferably benzenedicarboxylic acid dihalides, by the interfacial process, optionally using chain terminators, for example monophenols, and optionally using branching agents which are trifunctional or more than trifunctional, for example triphenols or tetraphenols. A
preparation via a melt polymerization process by reaction of diphenols with, for example, diphenyl carbonate is likewise possible.
Diphenols for the preparation of the aromatic polycarbonates and/or aromatic polyester carbonates are preferably those of the formula (I) BMS 071168-WO-nat CA 02715204 2010-06-17 (B)X (B)X OH
HO
p (I) wherein A is a single bond, C1 to C5-alkylene, C2 to C5-alkylidene, C5 to C6-cycloalkylidene, -0-, -SO-, -CO-, -5-, -SO2-, C6 to C12-arylene, on to which further aromatic rings optionally containing hetero atoms can be fused, or a radical of the formula (II) or (III) -Cl -X
\ 6 R R (II) CH
CH
CH3 (III) B is in each case C1 to C12-alkyl, preferably methyl, or halogen, preferably chlorine and/or bromine, x is in each case independently of one another 0, 1 or 2, p is 1 or 0, and R5 and R6 can be chosen individually for each X1 and independently of one another denote hydrogen or C1 to C6-alkyl, preferably hydrogen, methyl or ethyl, X1 denotes carbon and in denotes an integer from 4 to 7, preferably 4 or 5, with the proviso that on at least one atom X1 R5 and R6 are simultaneously alkyl.
Preferred diphenols are hydroquinone, resorcinol, dihydroxydiphenols, bis-(hydroxyphenyl)-C1-C5-alkanes, bis-(hydroxyphenyl)-C5-C6-cycloalkanes, bis-(hydroxy-phenyl) ethers, bis-(hydroxyphenyl) sulfoxides, bis-(hydroxyphenyl) ketones, bis-(hydroxyphenyl) sulfones and a,a-bis-(hydroxyphenyl)-diisopropyl-benzenes and derivatives thereof brominated on the nucleus and/or chlorinated on the nucleus.
BMS 071168-WO-nat CA 02715204 2010-06-17 Particularly preferred diphenols are 4,4'-dihydroxydiphenyl, bisphenol A, 2,4-bis(4-hydroxyphenyl)-2-methylbutane, 1, 1 -bis-(4-hydroxyphenyl)-cyclohexane, 1,1-bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfone and di- and tetrabrominated or chlorinated derivatives thereof, such as, for example, 2,2-bis(3-chloro-4-hydroxyphenyl)-propane, 2,2-bis-(3,5-dichloro-4-hydroxyphenyl)-propane or 2,2-bis-(3,5-dibromo-4-hydroxyphenyl)-propane. 2,2-Bis-(4-hydroxyphenyl)-propane (bisphenol A) is particularly preferred.
The diphenols can be employed individually or as any desired mixtures. The diphenols are known from the literature or obtainable by processes known from the literature.
Chain terminators which are suitable for the preparation of the thermoplastic aromatic polycarbonates are, for example, phenol, p-chlorophenol, p-tert-butylphenol or 2,4,6-tribromophenol, but also long-chain alkylphenols, such as 4-[2-(2,4,4-trimethylpentyl)]-phenol, 4-(1,3-tetramethylbutyl)-phenol according to DE-A 2 842 005 or monoalkylphenols or dialkylphenols having a total of 8 to 20 carbon atoms in the alkyl substituents, such as 3,5-di-tert-butylphenol, p-iso-octylphenol, p-tert-octylphenol, p-dodecylphenol and 2-(3,5-dimethylheptyl)-phenol and 4-(3,5-dimethylheptyl)-phenol. The amount of chain terminators to be employed is in general between 0.5 mol% and 10 mol%, based on the sum of the moles of the particular diphenols employed.
The thermoplastic aromatic polycarbonates have average weight-average molecular weights (Mw, measured e.g. by GPC, ultracentrifuge or scattered light measurement) of from 10,000 to 200,000 g/mol, preferably 15,000 to 80,000 g/mol, particularly preferably 24,000 to 32,000 g/mol.
The thermoplastic aromatic polycarbonates can be branched in a known manner, and in particular preferably by incorporation of from 0.05 to 2.0 mol%, based on the sum of the diphenols employed, of compounds which are trifunctional or more than trifunctional, for example those having three and more phenolic groups.
Both homopolycarbonates and copolycarbonates are suitable. 1 to 25 wt.%, preferably 2.5 to 25 wt.%, based on the total amount of diphenols to be employed, of BMS 071168-WO-nat CA 02715204 2010-06-17 polydiorganosiloxanes having hydroxyaryloxy end groups can also be employed for the preparation of the copolycarbonates according to the invention according to component A.
These are known (US 3 419 634) and can be prepared by processes known from the literature. The preparation of copolycarbonates containing polydiorganosiloxane is described in DE-A 3 334 782.
Preferred polycarbonates are, in addition to bisphenol A homopolycarbonates, copolycarbonates of bisphenol A with up to 15 mol%, based on the sum of the moles of diphenols, of other diphenols mentioned as preferred or particularly preferred, in particular 2,2-bis(3,5-dibromo-4-hydroxyphenyl)-propane.
Aromatic dicarboxylic acid dihalides for the preparation of aromatic polyester carbonates are preferably the diacid dichlorides of isophthalic acid, terephthalic acid, diphenyl ether 4,4'-dicarboxylic acid and of naphthalene-2,6-dicarboxylic acid.
Mixtures of the diacid dichlorides of isophthalic acid and of terephthalic acid in a ratio of between 1:20 and 20:1 are particularly preferred.
A carbonic acid halide, preferably phosgene, is additionally co-used as a bifunctional acid derivative in the preparation of polyester carbonates.
Possible chain terminators for the preparation of the aromatic polyester carbonates are, in addition to the monophenols already mentioned, also chlorocarbonic acid esters thereof and the acid chlorides of aromatic monocarboxylic acids, which can optionally be substituted by C 1 to C22-alkyl groups or by halogen atoms, and aliphatic C2 to C22-monocarboxylic acid chlorides.
The amount of chain terminators is in each case 0.1 to 10 mol%, based on the moles of diphenol in the case of the phenolic chain terminators and on the moles of dicarboxylic acid dichloride in the case of monocarboxylic acid chloride chain terminators.
The aromatic polyesters carbonates can also contain incorporated aromatic hydroxycarboxylic acids.
BMS 071168-WO-nat CA 02715204 2010-06-17 The aromatic polyester carbonates can be either linear or branched in a known manner (in this context see DE-A 2 940 024 and DE-A 3 007 934).
Branching agents which can be used are, for example, carboxylic acid chlorides which are trifunctional or more than trifunctional, such as trimesic acid trichloride, cyanuric acid trichloride, 3,3',4,4'-benzophenone-tetracarboxylic acid tetrachloride, 1,4,5,8-naphthalenetetracarboxylic acid tetrachloride or pyromellitic acid tetrachloride, in amounts of from 0.01 to 1.0 mol-% (based on the dicarboxylic acid dichlorides employed), or phenols which are trifunctional or more than trifunctional, such as phloroglucinol, 4,6-dimethyl-2,4,6-tri-(4-hydroxyphenyl)-hept-2-ene, 4,6-dimethyl-2,4-6-tri-(4-hydroxyphenyl)-heptane, 1,3,5-tri-(4-hydroxyphenyl)-benzene, 1, 1, 1 -tri-(4-hydroxy-phenyl)-ethane, tri-(4-hydroxyphenyl)-phenylmethane, 2,2-bis[4,4-bis(4-hydroxy-phenyl)-cyclohexyl] -propane, 2,4-bis(4-hydroxyphenyl-isopropyl)-phenol, tetra-(4-hydroxyphenyl)-methane, 2,6-bis(2-hydroxy-5-methyl-benzyl)-4-methyl-phenol, 2-(4-hydroxyphenyl)-2-(2,4-dihydroxyphenyl)-propane, tetra-(4-[4-hydroxyphenyl-isopropyl]-phenoxy)-methane or 1,4-bis [4,4'-dihydroxytriphenyl)-methyl] -benzene, in amounts of from 0.01 to 1.0 mol%, based on the diphenols employed. Phenolic branching agents can be initially introduced with the diphenols, and acid chloride branching agents can be introduced together with the acid dichlorides.
The content of carbonate structural units in the thermoplastic aromatic polyester carbonates can vary as desired. The content of carbonate groups is preferably up to 100 mol%, in particular up to 80 mol%, particularly preferably up to 50 mol%, based on the sum of ester groups and carbonate groups. Both the ester and the carbonate content of the aromatic polyester carbonates can be present in the polycondensate in the form of blocks or randomly distributed.
The relative solution viscosity (rlrel) of the aromatic polycarbonates and polyester carbonates is in the range of 1.18 to 1.4, preferably 1.20 to 1.32 (measured on solutions of 0.5 g of polycarbonate or polyester carbonate in 100 ml of methylene chloride solution at 25 C).
The thermoplastic aromatic polycarbonates and polyester carbonates can be employed by themselves or in any desired mixture.
BMS 071168-WO-nat CA 02715204 2010-06-17 Component B
Component B includes one or more graft polymers of B.1 5 to 95 wt.%, preferably 30 to 90 wt.% of at least one vinyl monomer on B.2 95 to 5 wt.%, preferably 70 to 10 wt.% of at least one graft base chosen from the group consisting of diene rubbers, EP(D)M rubbers (i.e. those based on ethylene/propylene and optionally diene) and acrylate, polyurethane, silicone, silicone/acrylate, chloroprene and ethylene/vinyl acetate rubbers.
The graft base B.2 in general has an average particle size (d50 value) of from 0.05 to 5 m, preferably 0.1 to 0.8 m, particularly preferably 0.2 to 0.4 m.
Monomers B.1 are preferably mixtures of B. 1.1 50 to 99 parts by wt. of vinylaromatics and/or vinylaromatics substituted on the nucleus (such as styrene, a-methylstyrene, p-methylstyrene and p-chlorostyrene) and/or (meth)acrylic acid (C1-C8)-alkyl esters (such as methyl methacrylate and ethyl methacrylate) and B. 1.2 1 to 50 parts by wt. of vinyl cyanides (unsaturated nitriles, such as acrylonitrile and methacrylonitrile) and/or (meth)acrylic acid C,-C8-alkyl esters, such as methyl methacrylate, n-butyl acrylate and t-butyl acrylate, and/or derivatives (such as anhydrides and imides) of unsaturated carboxylic acids, for example maleic anhydride and N-phenyl-maleimide.
Preferred monomers B. 1.1 are chosen from at least one of the monomers styrene, a-methylstyrene and methyl methacrylate, and preferred monomers B.1.2 are chosen from at least one of the monomers acrylonitrile, maleic anhydride and methyl methacrylate.
Particularly preferred monomers are B. 1.1 styrene and B. 1.2 acrylonitrile.
Preferred graft bases B.2 are diene rubbers (for example based on butadiene and isoprene) or mixtures of diene rubbers. Diene rubbers in the context according to the invention are also to be understood as meaning copolymers of diene rubbers or mixtures thereof with further copolymerizable monomers (e.g. according to B.1.1 and B.l .2). The graft bases B.2 BMS 071168-WO-nat CA 02715204 2010-06-17 in general have a glass transition temperature of < 10 C, preferably < 0 C, particularly preferably < -10 C.
Preferably, the graft polymer of components B.1 and B.2 has a core-shell structure, wherein component B.1 forms the shell (also called casing) and component B.2 forms the core (see e.g. Ullmann's Encyclopedia of Industrial Chemistry, VCH-Verlag, vol. A21, 1992, page 635 and page 656).
The graft copolymers B are prepared by free-radical polymerization by emulsion polymerization. The emulsion polymerization process is preferably carried out by redox initiation with an initiator system of organic hydroperoxide and ascorbic acid, as is described, for example, in US 4 937 285.
The gel content of the graft base B.2 is at least 40 wt.%, preferably at least 70 wt.%
(measured in toluene).
Particularly preferred graft polymers B are ABS polymers (emulsion ABS), which preferably have a core-shell structure, the shell being built up from the components styrene (B.1.1) and acrylonitrile (B.2.1), with a core of polybutadiene. Such ABS
polymers are known to the person skilled in the art and are described e.g. in Ullmanns Enzyklopadie der Technischen Chemie, vol. 19 (1980), p. 280 et seq.
Since as is known the grafting monomers are not necessarily grafted completely on to the graft base during the grafting reaction, according to the invention graft polymers B are also understood as meaning those products which are produced by (co)polymerization of the grafting monomers in the presence of the graft base and are also obtained during the working up.
Suitable acrylate rubbers according to B.2 of the polymers B are preferably polymers of acrylic acid alkyl esters, optionally with up to 40 wt.%, based on B.2, of other polymerizable ethylenically unsaturated monomers. The preferred polymerizable acrylic acid esters include C1 to C8-alkyl esters, for example methyl, ethyl, butyl, n-octyl and 2-ethylhexyl esters, haloalkyl esters, preferably halo-Ci-Cg-alkyl esters, such as chloroethyl acrylate, and mixtures of these monomers.
BMS 071168-WO-nat CA 02715204 2010-06-17 For crosslinking, monomers having more than one polymerizable double bond can be copolymerized. Preferred examples of crosslinking monomers are esters of unsaturated monocarboxylic acids having 3 to 8 C atoms and unsaturated monohydric alcohols having 3 to 12 C atoms, or of saturated polyols having 2 to 4 OH groups and 2 to 20 C
atoms, such as ethylene glycol dimethacrylate and allyl methacrylate; polyunsaturated heterocyclic compounds, such as trivinyl and triallyl cyanurate; polyfunctional vinyl compounds, such as di- and trivinylbenzenes; but also triallyl phosphate and diallyl phthalate. Preferred crosslinking monomers are allyl methacrylate, ethylene glycol dimethacrylate, diallyl phthalate and heterocyclic compounds which contain at least three ethylenically unsaturated groups. Particularly preferred crosslinking monomers are the cyclic monomers triallyl cyanurate, triallyl isocyanurate, triacryloylhexahydro-s-triazine and triallylbenzenes. The amount of the crosslinking monomers is preferably 0.02 to 5 wt.%, in particular 0.05 to 2 wt.%, based on the graft base B.2. In the case of cyclic crosslinking monomers having at least three ethylenically unsaturated groups, it is advantageous to limit the amount to less than 1 wt.% of the graft base B.2.
Preferred "other" polymerizable ethylenically unsaturated monomers which can optionally serve for preparation of the graft base B.2 in addition to the acrylic acid esters are e.g.
acrylonitrile, styrene, a-methylstyrene, acrylamides, vinyl C l -C6-alkyl ethers, methyl methacrylate and butadiene. Preferred acrylate rubbers as the graft base B.2 are emulsion polymers which have a gel content of at least 60 wt.%.
Suitable silicone rubbers according to B.2 can be prepared by emulsion polymerization, as described, for example, in US 2891920 and US 3294725. Further suitable graft bases according to B.2 are silicone rubbers having grafting-active sites, such as are described in DE-OS 3 704 657, DE-OS 3 704 655, DE-OS 3 631 540 and DE-OS 3 631 539.
According to the invention, silicone/acrylate rubbers are also suitable as graft bases B.2.
These silicone/acrylate rubbers are composite rubbers having grafting-active sites containing a silicone rubber content of 10 - 90 wt.% and a polyalkyl (meth)acrylate rubber content of 90 to 10 wt.%, the two rubber components mentioned penetrating each other in the composite rubber, so that they cannot be separated substantially from one another. If the content of the silicone rubber component in the composite rubber is too high, the BMS 071168-WO-nat CA 02715204 2010-06-17 finished resin compositions have adverse surface properties and cannot be coloured so readily. On the other hand, if the content of the polyalkyl (meth)acrylate rubber component in the composite rubber is too high, the impact strength of the finished resin composition is adversely influenced. Silicone/acrylate rubbers are known and are described, for example, in US 5,807,914, EP 430134 and US 4888388. A graft polymer prepared in emulsion polymerization with B.1 methyl methacrylate and B.2 silicone/acrylate composite rubber is preferably employed.
The gel content of the graft base B.2 is determined at 25 C in a suitable solvent (M.
Hoffmann, H. Kromer, R. Kuhn, Polymeranalytik I and II, Georg Thieme-Verlag, Stuttgart 1977).
The average particle size d50 is the diameter above and below which in each case 50 wt.%
of the particles lie. It can be determined by means of ultracentrifuge measurement (W.
Scholtan, H. Lange, Kolloid, Z. and Z. Polymere 250 (1972), 782-1796).
Component C
The salt of a phosphinic acid (component C) in the context according to the invention is to be understood as meaning the salt of a phosphinic acid with any desired metal cation.
Mixtures of salts which differ in their metal cation can also be employed. The metal cations are the cations of metals of main group 1 (alkali metals, preferably Li+, Na+, K+), of main group 2 (alkaline earth metals; preferably Mgt+, Cat+, Sr2+, Bat+, particularly preferably Cat+) or of main group 3 (elements of the boron group; preferably A13) and/or of subgroup 2, 7 or 8 (preferably Zn2+, Mn2+, Fee+, Fe3+) of the periodic table.
A salt or a mixture of salts of a phosphinic acid of the formula (IV) is preferably employed 11 _ M m+
H-P-O
I
H
m (IV) BMS 071168-WO-nat CA 02715204 2010-06-17 wherein Mm+ is a metal cation of main group 1 (alkali metals; in = 1), main group 2 (alkaline earth metals; in = 2) or of main group 3 (m = 3) or of subgroup 2, 7 or 8 (wherein in denotes an integer from 1 to 6, preferably 1 to 3 and particularly preferably 2 or 3) of the periodic table.
Particularly preferably, in formula (IV) for in = 1 the metal cations M+ = Li+, Na+, K+, for in = 2 the metal cations M2+ = Mgt+, Cat+, Sr2+, Ba2+ and for in = 3 the metal cations M3+ = A13+, Ca2+ (m = 2) and A13+ (m = 3) are very preferred.
In a preferred embodiment, the average particle size d50 of the phosphinic acid salt (component C) is less than 80 m, preferably less than 60 m, and d50 is particularly preferably between 10 m and 55 m. The average particle size d50 is the diameter above and below which in each case 50 wt.% of the particles lie. Mixtures of salts which differ in their average particle size d50 can also be employed.
These requirements of the particle size d50 of the phosphinic acid salt are in each case associated with the technical effect that the flameproofing efficiency of the phosphinic acid salt is increased.
The phosphinic acid salt can be employed either by itself or in combination with other phosphorus-containing flameproofing agents. The compositions according to the invention are preferably free from phosphorus-containing flameproofing agents chosen from the group of mono- and oligomeric phosphoric and phosphonic acid esters, phosphonate-amines and phosphazenes. These other phosphorus-containing flameproofing agents, such as, for example, the mono- and oligomeric phosphoric and phosphonic acid esters, have the disadvantage compared with the phosphinic acid salts that they lower the heat distortion point of the moulding compositions.
Component D
Component D includes one or more thermoplastic vinyl (co)polymers D.1 and/or polyalkylene terephthalates D.2.
BMS 071168-WO-nat CA 02715204 2010-06-17 Suitable vinyl (co)polymers DA are polymers of at least one monomer from the group of vinylaromatics, vinyl cyanides (unsaturated nitrites), (meth)acrylic acid (C1-C8)-alkyl esters, unsaturated carboxylic acids and derivatives (such as anhydrides and imides) of unsaturated carboxylic acids. (Co)polymers which are suitable in particular are those of D.1.1 50 to 99 parts by wt., preferably 60 to 80 parts by wt. of vinylaromatics and/or vinylaromatics substituted on the nucleus, such as styrene, a-methylstyrene, p-methylstyrene and p-chlorostyrene, and/or (meth)acrylic acid (Cl-Cg)-alkyl esters, such as methyl methacrylate and ethyl methacrylate, and D.1.2 1 to 50 parts by wt., preferably 20 to 40 parts by wt. of vinyl cyanides (unsaturated nitrites), such as acrylonitrile and methacrylonitrile, and/or (meth)acrylic acid (C1-Cg)-alkyl esters, such as methyl methacrylate, n-butyl acrylate and t-butyl acrylate, and/or unsaturated carboxylic acids, such as maleic acid, and/or derivatives, such as anhydrides and imides, of unsaturated carboxylic acids, for example maleic anhydride and N-phenylmaleimide.
The vinyl (co)polymers D.1 are resinous, thermoplastic and rubber-free. The copolymer of D. 1.1 styrene and D. 1.2 acrylonitrile is particularly preferred.
The (co)polymers according to D.1 are known and can be prepared by free-radical polymerization, in particular by emulsion, suspension, solution or bulk polymerization.
The (co)polymers preferably have average molecular weights Mw (weight-average, determined by light scattering or sedimentation) of between 15,000 and 200,000.
The polyalkylene terephthalates of component D.2 are reaction products of aromatic dicarboxylic acids or their reactive derivatives, such as dimethyl esters or anhydrides, and aliphatic, cycloaliphatic or araliphatic diols, and mixtures of these reaction products.
Preferred polyalkylene terephthalates contain at least 80 wt.%, preferably at least 90 wt.%, based on the dicarboxylic acid component, of terephthalic acid radicals and at least 80 wt.%, preferably at least 90 mot%, based on the diol component, of radicals of ethylene glycol and/or butane-l,4-diol.
BMS 071168-WO-nat CA 02715204 2010-06-17 The preferred polyalkylene terephthalates can contain, in addition to terephthalic acid radicals, up to 20 mol%, preferably up to 10 mol% of radicals of other aromatic or cycloaliphatic dicarboxylic acids having 8 to 14 C atoms or aliphatic dicarboxylic acids having 4 to 12 C atoms, such as e.g. radicals of phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, 4,4'-diphenyldicarboxylic acid, succinic acid, adipic acid, sebacic acid, azelaic acid and cyclohexanediacetic acid.
The preferred polyalkylene terephthalates can contain, in addition to radicals of ethylene glycol or butane-l,4-diol, up to 20 mol%, preferably up to 10 mol% of other aliphatic diols having 3 to 12 C atoms or cycloaliphatic diols having 6 to 21 C atoms, e.g. radicals of propane- 1,3-diol, 2-ethylpropane-1,3-diol, neopentyl glycol, pentane-1,5-diol, hexane-1,6-diol, cyclohexane-1,4-dimethanol, 3-ethylpentane-2,4-diol, 2-methylpentane-2,4-diol, 2,2,4-trimethylpentane-1,3-diol, 2-ethylhexane-1,3-diol, 2,2-diethylpropane-1,3-diol, hexane-2,5-diol, 1,4-di-((3-hydroxyethoxy)-benzene, 2,2-bis-(4-hydroxycyclohexyl)-propane, 2,4-dihydroxy- 1, 1,3,3 -tetramethyl-cyclobutane, 2,2-bis-(4-j3-hydroxyethoxy-phenyl)-propane and 2,2-bis-(4-hydroxypropoxyphenyl)-propane (DE-A 2 407 674, 2 407 776 and 2 715 932).
The polyalkylene terephthalates can be branched by incorporation of relatively small amounts of 3- or 4-hydric alcohols or 3- or 4-basic carboxylic acids, e.g. in accordance with DE-A 1 900 270 and US 3 692 744. Examples of preferred branching agents are trimesic acid, trimellitic acid, trimethylolethane and -propane and pentaerythritol.
Polyalkylene terephthalates which have been prepared solely from terephthalic acid and reactive derivatives thereof (e.g. dialkyl esters thereof) and ethylene glycol and/or butane-1,4-diol and mixtures of these polyalkylene terephthalates are particularly preferred.
Mixtures of polyalkylene terephthalates contain I to 50 wt.%, preferably I to 30 wt.% of polyethylene terephthalate and 50 to 99 wt.%, preferably 70 to 99 wt.% of polybutylene terephthalate.
The polyalkylene terephthalates preferably used in general have a limiting viscosity of from 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) at 25 C in an Ubbelohde viscometer.
BMS 071168-WO-nat CA 02715204 2010-06-17 The polyalkylene terephthalates can be prepared by known methods (see e.g.
Kunststoff-Handbuch, volume VIII, p. 695 et seq., Carl-Hanser-Verlag, Munich 1973).
Component E
The composition can comprise further commercially available additives according to component E), such as flameproofing synergists, rubber-modified graft polymers E* which differ from component B), antidripping agents (for example compounds of the substance classes of fluorinated polyolefins, of silicones and aramid fibres), lubricants and mould release agents (for example pentaerythritol tetrastearate), nucleating agents, stabilizers, antistatics (for example conductive carbon blacks, carbon fibres, carbon nanotubes and organic antistatics, such as polyalkylene ethers, alkylsulfonates or polyamide-containing polymers), acids, fillers and reinforcing substances (for example glass fibres or carbon fibres, mica, kaolin, talc, CaCO3 glass flakes) and dyestuffs and pigments.
The graft polymers E* which differ from component B are prepared by bulk, suspension or solution polymerization. The compositions according to the invention are preferably free from graft polymers E* which differ from component B.
Preparation of the moulding compositions and shaped articles The thermoplastic moulding compositions according to the invention are prepared by mixing the particular constituents in a known manner and subjecting the mixture to melt compounding and melt extrusion at temperatures of from 240 C to 300 C in conventional units, such as internal kneaders, extruders and twin-screw extruders.
The mixing of the individual constituents can be carried out in a known manner either successively or simultaneously, and in particular either at about 20 C (room temperature) or at a higher temperature.
The invention likewise provides processes for the preparation of the moulding compositions and the use of the moulding compositions for the production of shaped articles and the mouldings themselves.
BMS 071168-WO-nat CA 02715204 2010-06-17 The moulding compositions according to the invention can be used for the production of all types of shaped articles. These can be produced by injection moulding, extrusion and blow moulding processes. A further form of processing is the production of shaped articles by thermoforming from previously produced sheets or films.
Examples of such shaped articles are films, profiles, housing components of all types, e.g.
for domestic appliances, such as televisions, juice presses, coffee machines and mixers; for office machines, such as monitors, flatscreens, notebooks, printers and copiers; sheets, tubes, electrical installation conduits, windows, doors and further profiles for the building sector (interior finishing and exterior uses) and electrical and electronic components, such as switches, plugs and sockets, and vehicle body or interior components for utility vehicles, in particular for the automobile sector.
The moulding compositions according to the invention can also be used in particular, for example, for the production of the following shaped articles or mouldings:
interior finishing components for rail vehicles, ships, aircraft, buses and other motor vehicles, housing of electrical equipment containing small transformers, housing for equipment for processing and transmission of information, housing and lining of medical equipment, massage equipment and housing therefor, toy vehicles for children, planar wall elements, housing for safety equipment and for televisions, thermally insulated transportation containers, mouldings for sanitary and bath fittings, cover grids for ventilator openings and housing for garden equipment.
The following examples serve to explain the invention further.
BMS 071168-WO-nat CA 02715204 2010-06-17 Examples Component A-1 Linear polycarbonate based on bisphenol A having a relative solution viscosity of rite! _ 1.28, measured in CH2C12 as the solvent at 25 C and a concentration of 0.5 g/100 ml.
Component A-2 Linear polycarbonate based on bisphenol A having a relative solution viscosity of lire! _ 1.20, measured in CH2Cl2 as the solvent at 25 C and a concentration of 0.5 g/100 ml.
Component B
ABS graft polymer having a core-shell structure prepared by emulsion polymerization of 43 wt.%, based on the ABS polymer, of a mixture of 27 wt.% of acrylonitrile and 73 wt.%
of styrene in the presence of 57 wt.%, based on the ABS polymer, of a polybutadiene rubber crosslinked in particle form (average particle diameter d50 = 0.35 m).
Component C
Component C-1 (comparison) Oligophosphate based on bisphenol A
O-P O / \ i O-P O
q=1.1 Component C-2 Calcium phosphinate, average particle size d50 = 50 m.
Component E
Component E- 1: polytetrafluoroethylene (PTFE) Component E-2: pentaerythritol tetrastearate Component E-3: Irganox B900 (manufacturer: Ciba Specialty Chemicals Inc., Basle, Switzerland) BMS 071168-WO-nat CA 02715204 2010-06-17 Preparation and testing of the moulding compositions The starting substances listed in Table 1 are compounded and granulated on a twin-screw extruder (ZSK-25) (Werner and Pfleiderer) at a speed of rotation of 225 rpm and a throughput of 20 kg/h at a machine temperature of 260 C.
The finished granules are processed on an injection moulding machine to give the corresponding test specimens (melt temperature 260 C, mould temperature 80 C, melt front speed 240 mm/s).
Characterization is carried out in accordance with DIN ISO 306 (Vicat softening temperature, method B with a load of 50 N and a heating rate of 120 K/h), ISO
(environmental stress cracking (ESC) test against toluene:isopropanol 60:40, at 2.4 % and 0.8 % edge fibre elongation, in the table the time until break is stated) UL
94 V (measured on bars of dimensions 127 x 12.7 x 1.5 mm) and IEC 60695-2-12 (glow wire test;
the glow wire flammability index GWFI at a thickness of 2.0 mm is stated).
It can be seen from Table 1 that only the composition in Example 2 with the combination of polycarbonate, emulsion ABS and calcium phosphinate achieves the object according to the invention, i.e. a combination of high heat distortion point, good resistance to chemicals and good performance in the UL94V test and in the test according to JEC 60695-2-12.
BMS 071168-WO-nat CA 02715204 2010-06-17 Table 1: Compositions and their properties Composition 1 2 (comp.) A-1 pt. by wt. 70.2 70.2 A-2 pt. by wt. 24.5 24.5 B pt. by wt. 3.0 3.0 C-1 pt. by wt. 2.3 C-2 pt. by wt. 2.3 E-1 pt. by wt. 0.4 0.4 E-2 pt. by wt. 0.4 0.4 E-3 pt. by wt. 0.1 0.1 Properties Vicat B 120 (DIN ISO 306) C 100 102 ESC properties / [2.4 %] min:sec 10 19 ESC properties / [0.8%] min:sec 220 265 UL 94 V 1.5 mm / 2 d [rating] vi v o UL 94 V 1.5 mm / 2 d [total ABT] s 33 6 Glow wire flammability index 800 960 GWFI at a thickness of 2.0 mm ABT = after-burn time
The present invention relates to impact-modified polycarbonate compositions which comprise a graft polymer prepared in the emulsion polymerization process and a salt of a phosphinic acid, the use of the polycarbonate compositions for the production of shaped articles and the shaped articles themselves.
WO-A 2005/044906 discloses thermoplastic moulding compositions comprising at least one metal salt of hypophosphoric acid and at least one aromatic polycarbonate resin and a mixture thereof with a styrene-containing graft copolymer resin having a rubber content of 5-15 %. The contents of the styrene-containing graft copolymer are 10-40 wt.%.
The moulding compositions obtained are distinguished by good flame resistance, high heat stability under processing conditions and good weather resistance. Because of the low rubber content, other properties, in particular mechanical properties, are at a low level.
WO-A 1999/57192 describes thermoplastic moulding compositions comprising 5-96 wt.%
of a polyester or polycarbonate, 1-30 wt.% of a phosphinic acid salt and/or of a diphosphinic acid salt and/or polymers thereof, 1-30 wt.% of at least one organic phosphorus-containing flameproofing agent, and possible further additives.
DE-A 102004049342 discloses thermoplastic moulding compositions comprising 10-wt.% of thermoplastic polymer, 0.01-50 wt.% of highly branched polycarbonate or highly branched polyester or mixtures thereof, 1-40 wt.% of halogen-free flameproofing agent chosen from the group of P-containing or N-containing compounds or of P-N
condensates or mixtures thereof, and possible further additives.
JP-A 2001-335699 describes flameproofed resin compositions comprising two or more thermoplastic resins chosen from styrene resin, aromatic polyester resin, polyamide resin, polycarbonate resin and polyphenylene ether resin and one or more (in)organic phosphinic acid salts, and possible further additives.
JP-A 2001-261973 (Daicel Chemical Industries Ltd.) describes compositions of thermoplastic resins and (in)organic phosphinic acid salts. A combination of PBT, calcium phosphinate and PTFE is given as an example.
BMS 071168-WO-nat CA 02715204 2010-06-17 JP-A 2002-161211 discloses compositions of thermoplastic resins and flameproofing agents, such as salts of phosphinic and phosphoric acid and derivatives thereof. A
combination of PBT, ABS, polyoxyphenylene, calcium phosphinate, an organophosphate and glass fibres is given as an example.
Flameproofing agents which are conventional according to the prior art for polycarbonate/ABS blends are organic aromatic phosphates. These compounds can be in a low molecular weight form, in the form of a mixture of various oligomers or in the form of a mixture of oligomers with low molecular weight compounds (e.g. WO-A 99/16828 and WO-A 00/31173). The good activity as flameproofing agents is counteracted adversely by the highly plasticizing action of these compounds on the polymeric constituents, so that the heat distortion point of these moulding compositions is not satisfactory for many uses.
The object of the present invention is to provide impact-modified polycarbonate moulding compositions having an optimum combination of high heat distortion point, good resistance to chemicals and good flameproofing, in particular in the glow wire test according to IEC 60695-2-12.
It has now been found, surprisingly, that moulding compositions or compositions comprising A) polycarbonate, B) rubber-modified graft polymer prepared in the emulsion polymerization process and C) a salt of a phosphinic acid have the desired profile of properties.
It has thus been found, surprisingly, that compositions comprising A) 50 to 99.4 parts by wt., preferably 73 to 98 parts by wt., particularly preferably 82 to 91 parts by wt. (in each case based on the sum of the parts by weight of components A+B+C) of aromatic polycarbonate and/or aromatic polyester carbonate, B) 0.5 to 20 parts by wt., preferably 1 to 12 parts by wt., particularly preferably 2 to 6 parts by wt. (in each case based on the sum of the parts by weight of components A+B+C) of rubber-modified graft polymer prepared in the emulsion polymerization process, BMS 071168-WO-nat CA 02715204 2010-06-17 C) 0.1 to 30 parts by wt., preferably 1 to 15 parts by wt., particularly preferably 7 to 12 parts by wt. (in each case based on the sum of the parts by weight of components A+B+C) of a salt of a phosphinic acid, D) 0 to 20 parts by wt. (based on the sum of the parts by weight of components A+B+C = 100) of rubber-free vinyl (co)polymer and/or polyalkylene terephthalate, preferably the composition is free from rubber-free vinyl (co)polymer and/or polyalkylene terephthalate, E) 0 to 50 parts by wt., preferably 0.5 to 25 parts by wt. (in each case based on the sum of the parts by weight of components A+B+C= 100) of additives, wherein all the parts by weight stated in the present application are standardized such that the sum of the parts by weight of components A+B+C in the composition is 100, achieve the abovementioned technical object.
Component A
Aromatic polycarbonates and/or aromatic polyester carbonates according to component A
which are suitable according to the invention are known from the literature or can be prepared by processes known from the literature (for the preparation of aromatic polycarbonates see, for example, Schnell, "Chemistry and Physics of Polycarbonates", In-terscience Publishers, 1964 and DE-AS 1 495 626, DE-A 2 232 877, DE-A 2 703 376, DE-A 2 714 544, DE-A 3 000 610 and DE-A 3 832 396; for the preparation of aromatic polyester carbonates e.g. DE-A 3 077 934).
Aromatic polycarbonates are prepared e.g. by reaction of diphenols with carbonic acid halides, preferably phosgene, and/or with aromatic dicarboxylic acid dihalides, preferably benzenedicarboxylic acid dihalides, by the interfacial process, optionally using chain terminators, for example monophenols, and optionally using branching agents which are trifunctional or more than trifunctional, for example triphenols or tetraphenols. A
preparation via a melt polymerization process by reaction of diphenols with, for example, diphenyl carbonate is likewise possible.
Diphenols for the preparation of the aromatic polycarbonates and/or aromatic polyester carbonates are preferably those of the formula (I) BMS 071168-WO-nat CA 02715204 2010-06-17 (B)X (B)X OH
HO
p (I) wherein A is a single bond, C1 to C5-alkylene, C2 to C5-alkylidene, C5 to C6-cycloalkylidene, -0-, -SO-, -CO-, -5-, -SO2-, C6 to C12-arylene, on to which further aromatic rings optionally containing hetero atoms can be fused, or a radical of the formula (II) or (III) -Cl -X
\ 6 R R (II) CH
CH
CH3 (III) B is in each case C1 to C12-alkyl, preferably methyl, or halogen, preferably chlorine and/or bromine, x is in each case independently of one another 0, 1 or 2, p is 1 or 0, and R5 and R6 can be chosen individually for each X1 and independently of one another denote hydrogen or C1 to C6-alkyl, preferably hydrogen, methyl or ethyl, X1 denotes carbon and in denotes an integer from 4 to 7, preferably 4 or 5, with the proviso that on at least one atom X1 R5 and R6 are simultaneously alkyl.
Preferred diphenols are hydroquinone, resorcinol, dihydroxydiphenols, bis-(hydroxyphenyl)-C1-C5-alkanes, bis-(hydroxyphenyl)-C5-C6-cycloalkanes, bis-(hydroxy-phenyl) ethers, bis-(hydroxyphenyl) sulfoxides, bis-(hydroxyphenyl) ketones, bis-(hydroxyphenyl) sulfones and a,a-bis-(hydroxyphenyl)-diisopropyl-benzenes and derivatives thereof brominated on the nucleus and/or chlorinated on the nucleus.
BMS 071168-WO-nat CA 02715204 2010-06-17 Particularly preferred diphenols are 4,4'-dihydroxydiphenyl, bisphenol A, 2,4-bis(4-hydroxyphenyl)-2-methylbutane, 1, 1 -bis-(4-hydroxyphenyl)-cyclohexane, 1,1-bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfone and di- and tetrabrominated or chlorinated derivatives thereof, such as, for example, 2,2-bis(3-chloro-4-hydroxyphenyl)-propane, 2,2-bis-(3,5-dichloro-4-hydroxyphenyl)-propane or 2,2-bis-(3,5-dibromo-4-hydroxyphenyl)-propane. 2,2-Bis-(4-hydroxyphenyl)-propane (bisphenol A) is particularly preferred.
The diphenols can be employed individually or as any desired mixtures. The diphenols are known from the literature or obtainable by processes known from the literature.
Chain terminators which are suitable for the preparation of the thermoplastic aromatic polycarbonates are, for example, phenol, p-chlorophenol, p-tert-butylphenol or 2,4,6-tribromophenol, but also long-chain alkylphenols, such as 4-[2-(2,4,4-trimethylpentyl)]-phenol, 4-(1,3-tetramethylbutyl)-phenol according to DE-A 2 842 005 or monoalkylphenols or dialkylphenols having a total of 8 to 20 carbon atoms in the alkyl substituents, such as 3,5-di-tert-butylphenol, p-iso-octylphenol, p-tert-octylphenol, p-dodecylphenol and 2-(3,5-dimethylheptyl)-phenol and 4-(3,5-dimethylheptyl)-phenol. The amount of chain terminators to be employed is in general between 0.5 mol% and 10 mol%, based on the sum of the moles of the particular diphenols employed.
The thermoplastic aromatic polycarbonates have average weight-average molecular weights (Mw, measured e.g. by GPC, ultracentrifuge or scattered light measurement) of from 10,000 to 200,000 g/mol, preferably 15,000 to 80,000 g/mol, particularly preferably 24,000 to 32,000 g/mol.
The thermoplastic aromatic polycarbonates can be branched in a known manner, and in particular preferably by incorporation of from 0.05 to 2.0 mol%, based on the sum of the diphenols employed, of compounds which are trifunctional or more than trifunctional, for example those having three and more phenolic groups.
Both homopolycarbonates and copolycarbonates are suitable. 1 to 25 wt.%, preferably 2.5 to 25 wt.%, based on the total amount of diphenols to be employed, of BMS 071168-WO-nat CA 02715204 2010-06-17 polydiorganosiloxanes having hydroxyaryloxy end groups can also be employed for the preparation of the copolycarbonates according to the invention according to component A.
These are known (US 3 419 634) and can be prepared by processes known from the literature. The preparation of copolycarbonates containing polydiorganosiloxane is described in DE-A 3 334 782.
Preferred polycarbonates are, in addition to bisphenol A homopolycarbonates, copolycarbonates of bisphenol A with up to 15 mol%, based on the sum of the moles of diphenols, of other diphenols mentioned as preferred or particularly preferred, in particular 2,2-bis(3,5-dibromo-4-hydroxyphenyl)-propane.
Aromatic dicarboxylic acid dihalides for the preparation of aromatic polyester carbonates are preferably the diacid dichlorides of isophthalic acid, terephthalic acid, diphenyl ether 4,4'-dicarboxylic acid and of naphthalene-2,6-dicarboxylic acid.
Mixtures of the diacid dichlorides of isophthalic acid and of terephthalic acid in a ratio of between 1:20 and 20:1 are particularly preferred.
A carbonic acid halide, preferably phosgene, is additionally co-used as a bifunctional acid derivative in the preparation of polyester carbonates.
Possible chain terminators for the preparation of the aromatic polyester carbonates are, in addition to the monophenols already mentioned, also chlorocarbonic acid esters thereof and the acid chlorides of aromatic monocarboxylic acids, which can optionally be substituted by C 1 to C22-alkyl groups or by halogen atoms, and aliphatic C2 to C22-monocarboxylic acid chlorides.
The amount of chain terminators is in each case 0.1 to 10 mol%, based on the moles of diphenol in the case of the phenolic chain terminators and on the moles of dicarboxylic acid dichloride in the case of monocarboxylic acid chloride chain terminators.
The aromatic polyesters carbonates can also contain incorporated aromatic hydroxycarboxylic acids.
BMS 071168-WO-nat CA 02715204 2010-06-17 The aromatic polyester carbonates can be either linear or branched in a known manner (in this context see DE-A 2 940 024 and DE-A 3 007 934).
Branching agents which can be used are, for example, carboxylic acid chlorides which are trifunctional or more than trifunctional, such as trimesic acid trichloride, cyanuric acid trichloride, 3,3',4,4'-benzophenone-tetracarboxylic acid tetrachloride, 1,4,5,8-naphthalenetetracarboxylic acid tetrachloride or pyromellitic acid tetrachloride, in amounts of from 0.01 to 1.0 mol-% (based on the dicarboxylic acid dichlorides employed), or phenols which are trifunctional or more than trifunctional, such as phloroglucinol, 4,6-dimethyl-2,4,6-tri-(4-hydroxyphenyl)-hept-2-ene, 4,6-dimethyl-2,4-6-tri-(4-hydroxyphenyl)-heptane, 1,3,5-tri-(4-hydroxyphenyl)-benzene, 1, 1, 1 -tri-(4-hydroxy-phenyl)-ethane, tri-(4-hydroxyphenyl)-phenylmethane, 2,2-bis[4,4-bis(4-hydroxy-phenyl)-cyclohexyl] -propane, 2,4-bis(4-hydroxyphenyl-isopropyl)-phenol, tetra-(4-hydroxyphenyl)-methane, 2,6-bis(2-hydroxy-5-methyl-benzyl)-4-methyl-phenol, 2-(4-hydroxyphenyl)-2-(2,4-dihydroxyphenyl)-propane, tetra-(4-[4-hydroxyphenyl-isopropyl]-phenoxy)-methane or 1,4-bis [4,4'-dihydroxytriphenyl)-methyl] -benzene, in amounts of from 0.01 to 1.0 mol%, based on the diphenols employed. Phenolic branching agents can be initially introduced with the diphenols, and acid chloride branching agents can be introduced together with the acid dichlorides.
The content of carbonate structural units in the thermoplastic aromatic polyester carbonates can vary as desired. The content of carbonate groups is preferably up to 100 mol%, in particular up to 80 mol%, particularly preferably up to 50 mol%, based on the sum of ester groups and carbonate groups. Both the ester and the carbonate content of the aromatic polyester carbonates can be present in the polycondensate in the form of blocks or randomly distributed.
The relative solution viscosity (rlrel) of the aromatic polycarbonates and polyester carbonates is in the range of 1.18 to 1.4, preferably 1.20 to 1.32 (measured on solutions of 0.5 g of polycarbonate or polyester carbonate in 100 ml of methylene chloride solution at 25 C).
The thermoplastic aromatic polycarbonates and polyester carbonates can be employed by themselves or in any desired mixture.
BMS 071168-WO-nat CA 02715204 2010-06-17 Component B
Component B includes one or more graft polymers of B.1 5 to 95 wt.%, preferably 30 to 90 wt.% of at least one vinyl monomer on B.2 95 to 5 wt.%, preferably 70 to 10 wt.% of at least one graft base chosen from the group consisting of diene rubbers, EP(D)M rubbers (i.e. those based on ethylene/propylene and optionally diene) and acrylate, polyurethane, silicone, silicone/acrylate, chloroprene and ethylene/vinyl acetate rubbers.
The graft base B.2 in general has an average particle size (d50 value) of from 0.05 to 5 m, preferably 0.1 to 0.8 m, particularly preferably 0.2 to 0.4 m.
Monomers B.1 are preferably mixtures of B. 1.1 50 to 99 parts by wt. of vinylaromatics and/or vinylaromatics substituted on the nucleus (such as styrene, a-methylstyrene, p-methylstyrene and p-chlorostyrene) and/or (meth)acrylic acid (C1-C8)-alkyl esters (such as methyl methacrylate and ethyl methacrylate) and B. 1.2 1 to 50 parts by wt. of vinyl cyanides (unsaturated nitriles, such as acrylonitrile and methacrylonitrile) and/or (meth)acrylic acid C,-C8-alkyl esters, such as methyl methacrylate, n-butyl acrylate and t-butyl acrylate, and/or derivatives (such as anhydrides and imides) of unsaturated carboxylic acids, for example maleic anhydride and N-phenyl-maleimide.
Preferred monomers B. 1.1 are chosen from at least one of the monomers styrene, a-methylstyrene and methyl methacrylate, and preferred monomers B.1.2 are chosen from at least one of the monomers acrylonitrile, maleic anhydride and methyl methacrylate.
Particularly preferred monomers are B. 1.1 styrene and B. 1.2 acrylonitrile.
Preferred graft bases B.2 are diene rubbers (for example based on butadiene and isoprene) or mixtures of diene rubbers. Diene rubbers in the context according to the invention are also to be understood as meaning copolymers of diene rubbers or mixtures thereof with further copolymerizable monomers (e.g. according to B.1.1 and B.l .2). The graft bases B.2 BMS 071168-WO-nat CA 02715204 2010-06-17 in general have a glass transition temperature of < 10 C, preferably < 0 C, particularly preferably < -10 C.
Preferably, the graft polymer of components B.1 and B.2 has a core-shell structure, wherein component B.1 forms the shell (also called casing) and component B.2 forms the core (see e.g. Ullmann's Encyclopedia of Industrial Chemistry, VCH-Verlag, vol. A21, 1992, page 635 and page 656).
The graft copolymers B are prepared by free-radical polymerization by emulsion polymerization. The emulsion polymerization process is preferably carried out by redox initiation with an initiator system of organic hydroperoxide and ascorbic acid, as is described, for example, in US 4 937 285.
The gel content of the graft base B.2 is at least 40 wt.%, preferably at least 70 wt.%
(measured in toluene).
Particularly preferred graft polymers B are ABS polymers (emulsion ABS), which preferably have a core-shell structure, the shell being built up from the components styrene (B.1.1) and acrylonitrile (B.2.1), with a core of polybutadiene. Such ABS
polymers are known to the person skilled in the art and are described e.g. in Ullmanns Enzyklopadie der Technischen Chemie, vol. 19 (1980), p. 280 et seq.
Since as is known the grafting monomers are not necessarily grafted completely on to the graft base during the grafting reaction, according to the invention graft polymers B are also understood as meaning those products which are produced by (co)polymerization of the grafting monomers in the presence of the graft base and are also obtained during the working up.
Suitable acrylate rubbers according to B.2 of the polymers B are preferably polymers of acrylic acid alkyl esters, optionally with up to 40 wt.%, based on B.2, of other polymerizable ethylenically unsaturated monomers. The preferred polymerizable acrylic acid esters include C1 to C8-alkyl esters, for example methyl, ethyl, butyl, n-octyl and 2-ethylhexyl esters, haloalkyl esters, preferably halo-Ci-Cg-alkyl esters, such as chloroethyl acrylate, and mixtures of these monomers.
BMS 071168-WO-nat CA 02715204 2010-06-17 For crosslinking, monomers having more than one polymerizable double bond can be copolymerized. Preferred examples of crosslinking monomers are esters of unsaturated monocarboxylic acids having 3 to 8 C atoms and unsaturated monohydric alcohols having 3 to 12 C atoms, or of saturated polyols having 2 to 4 OH groups and 2 to 20 C
atoms, such as ethylene glycol dimethacrylate and allyl methacrylate; polyunsaturated heterocyclic compounds, such as trivinyl and triallyl cyanurate; polyfunctional vinyl compounds, such as di- and trivinylbenzenes; but also triallyl phosphate and diallyl phthalate. Preferred crosslinking monomers are allyl methacrylate, ethylene glycol dimethacrylate, diallyl phthalate and heterocyclic compounds which contain at least three ethylenically unsaturated groups. Particularly preferred crosslinking monomers are the cyclic monomers triallyl cyanurate, triallyl isocyanurate, triacryloylhexahydro-s-triazine and triallylbenzenes. The amount of the crosslinking monomers is preferably 0.02 to 5 wt.%, in particular 0.05 to 2 wt.%, based on the graft base B.2. In the case of cyclic crosslinking monomers having at least three ethylenically unsaturated groups, it is advantageous to limit the amount to less than 1 wt.% of the graft base B.2.
Preferred "other" polymerizable ethylenically unsaturated monomers which can optionally serve for preparation of the graft base B.2 in addition to the acrylic acid esters are e.g.
acrylonitrile, styrene, a-methylstyrene, acrylamides, vinyl C l -C6-alkyl ethers, methyl methacrylate and butadiene. Preferred acrylate rubbers as the graft base B.2 are emulsion polymers which have a gel content of at least 60 wt.%.
Suitable silicone rubbers according to B.2 can be prepared by emulsion polymerization, as described, for example, in US 2891920 and US 3294725. Further suitable graft bases according to B.2 are silicone rubbers having grafting-active sites, such as are described in DE-OS 3 704 657, DE-OS 3 704 655, DE-OS 3 631 540 and DE-OS 3 631 539.
According to the invention, silicone/acrylate rubbers are also suitable as graft bases B.2.
These silicone/acrylate rubbers are composite rubbers having grafting-active sites containing a silicone rubber content of 10 - 90 wt.% and a polyalkyl (meth)acrylate rubber content of 90 to 10 wt.%, the two rubber components mentioned penetrating each other in the composite rubber, so that they cannot be separated substantially from one another. If the content of the silicone rubber component in the composite rubber is too high, the BMS 071168-WO-nat CA 02715204 2010-06-17 finished resin compositions have adverse surface properties and cannot be coloured so readily. On the other hand, if the content of the polyalkyl (meth)acrylate rubber component in the composite rubber is too high, the impact strength of the finished resin composition is adversely influenced. Silicone/acrylate rubbers are known and are described, for example, in US 5,807,914, EP 430134 and US 4888388. A graft polymer prepared in emulsion polymerization with B.1 methyl methacrylate and B.2 silicone/acrylate composite rubber is preferably employed.
The gel content of the graft base B.2 is determined at 25 C in a suitable solvent (M.
Hoffmann, H. Kromer, R. Kuhn, Polymeranalytik I and II, Georg Thieme-Verlag, Stuttgart 1977).
The average particle size d50 is the diameter above and below which in each case 50 wt.%
of the particles lie. It can be determined by means of ultracentrifuge measurement (W.
Scholtan, H. Lange, Kolloid, Z. and Z. Polymere 250 (1972), 782-1796).
Component C
The salt of a phosphinic acid (component C) in the context according to the invention is to be understood as meaning the salt of a phosphinic acid with any desired metal cation.
Mixtures of salts which differ in their metal cation can also be employed. The metal cations are the cations of metals of main group 1 (alkali metals, preferably Li+, Na+, K+), of main group 2 (alkaline earth metals; preferably Mgt+, Cat+, Sr2+, Bat+, particularly preferably Cat+) or of main group 3 (elements of the boron group; preferably A13) and/or of subgroup 2, 7 or 8 (preferably Zn2+, Mn2+, Fee+, Fe3+) of the periodic table.
A salt or a mixture of salts of a phosphinic acid of the formula (IV) is preferably employed 11 _ M m+
H-P-O
I
H
m (IV) BMS 071168-WO-nat CA 02715204 2010-06-17 wherein Mm+ is a metal cation of main group 1 (alkali metals; in = 1), main group 2 (alkaline earth metals; in = 2) or of main group 3 (m = 3) or of subgroup 2, 7 or 8 (wherein in denotes an integer from 1 to 6, preferably 1 to 3 and particularly preferably 2 or 3) of the periodic table.
Particularly preferably, in formula (IV) for in = 1 the metal cations M+ = Li+, Na+, K+, for in = 2 the metal cations M2+ = Mgt+, Cat+, Sr2+, Ba2+ and for in = 3 the metal cations M3+ = A13+, Ca2+ (m = 2) and A13+ (m = 3) are very preferred.
In a preferred embodiment, the average particle size d50 of the phosphinic acid salt (component C) is less than 80 m, preferably less than 60 m, and d50 is particularly preferably between 10 m and 55 m. The average particle size d50 is the diameter above and below which in each case 50 wt.% of the particles lie. Mixtures of salts which differ in their average particle size d50 can also be employed.
These requirements of the particle size d50 of the phosphinic acid salt are in each case associated with the technical effect that the flameproofing efficiency of the phosphinic acid salt is increased.
The phosphinic acid salt can be employed either by itself or in combination with other phosphorus-containing flameproofing agents. The compositions according to the invention are preferably free from phosphorus-containing flameproofing agents chosen from the group of mono- and oligomeric phosphoric and phosphonic acid esters, phosphonate-amines and phosphazenes. These other phosphorus-containing flameproofing agents, such as, for example, the mono- and oligomeric phosphoric and phosphonic acid esters, have the disadvantage compared with the phosphinic acid salts that they lower the heat distortion point of the moulding compositions.
Component D
Component D includes one or more thermoplastic vinyl (co)polymers D.1 and/or polyalkylene terephthalates D.2.
BMS 071168-WO-nat CA 02715204 2010-06-17 Suitable vinyl (co)polymers DA are polymers of at least one monomer from the group of vinylaromatics, vinyl cyanides (unsaturated nitrites), (meth)acrylic acid (C1-C8)-alkyl esters, unsaturated carboxylic acids and derivatives (such as anhydrides and imides) of unsaturated carboxylic acids. (Co)polymers which are suitable in particular are those of D.1.1 50 to 99 parts by wt., preferably 60 to 80 parts by wt. of vinylaromatics and/or vinylaromatics substituted on the nucleus, such as styrene, a-methylstyrene, p-methylstyrene and p-chlorostyrene, and/or (meth)acrylic acid (Cl-Cg)-alkyl esters, such as methyl methacrylate and ethyl methacrylate, and D.1.2 1 to 50 parts by wt., preferably 20 to 40 parts by wt. of vinyl cyanides (unsaturated nitrites), such as acrylonitrile and methacrylonitrile, and/or (meth)acrylic acid (C1-Cg)-alkyl esters, such as methyl methacrylate, n-butyl acrylate and t-butyl acrylate, and/or unsaturated carboxylic acids, such as maleic acid, and/or derivatives, such as anhydrides and imides, of unsaturated carboxylic acids, for example maleic anhydride and N-phenylmaleimide.
The vinyl (co)polymers D.1 are resinous, thermoplastic and rubber-free. The copolymer of D. 1.1 styrene and D. 1.2 acrylonitrile is particularly preferred.
The (co)polymers according to D.1 are known and can be prepared by free-radical polymerization, in particular by emulsion, suspension, solution or bulk polymerization.
The (co)polymers preferably have average molecular weights Mw (weight-average, determined by light scattering or sedimentation) of between 15,000 and 200,000.
The polyalkylene terephthalates of component D.2 are reaction products of aromatic dicarboxylic acids or their reactive derivatives, such as dimethyl esters or anhydrides, and aliphatic, cycloaliphatic or araliphatic diols, and mixtures of these reaction products.
Preferred polyalkylene terephthalates contain at least 80 wt.%, preferably at least 90 wt.%, based on the dicarboxylic acid component, of terephthalic acid radicals and at least 80 wt.%, preferably at least 90 mot%, based on the diol component, of radicals of ethylene glycol and/or butane-l,4-diol.
BMS 071168-WO-nat CA 02715204 2010-06-17 The preferred polyalkylene terephthalates can contain, in addition to terephthalic acid radicals, up to 20 mol%, preferably up to 10 mol% of radicals of other aromatic or cycloaliphatic dicarboxylic acids having 8 to 14 C atoms or aliphatic dicarboxylic acids having 4 to 12 C atoms, such as e.g. radicals of phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, 4,4'-diphenyldicarboxylic acid, succinic acid, adipic acid, sebacic acid, azelaic acid and cyclohexanediacetic acid.
The preferred polyalkylene terephthalates can contain, in addition to radicals of ethylene glycol or butane-l,4-diol, up to 20 mol%, preferably up to 10 mol% of other aliphatic diols having 3 to 12 C atoms or cycloaliphatic diols having 6 to 21 C atoms, e.g. radicals of propane- 1,3-diol, 2-ethylpropane-1,3-diol, neopentyl glycol, pentane-1,5-diol, hexane-1,6-diol, cyclohexane-1,4-dimethanol, 3-ethylpentane-2,4-diol, 2-methylpentane-2,4-diol, 2,2,4-trimethylpentane-1,3-diol, 2-ethylhexane-1,3-diol, 2,2-diethylpropane-1,3-diol, hexane-2,5-diol, 1,4-di-((3-hydroxyethoxy)-benzene, 2,2-bis-(4-hydroxycyclohexyl)-propane, 2,4-dihydroxy- 1, 1,3,3 -tetramethyl-cyclobutane, 2,2-bis-(4-j3-hydroxyethoxy-phenyl)-propane and 2,2-bis-(4-hydroxypropoxyphenyl)-propane (DE-A 2 407 674, 2 407 776 and 2 715 932).
The polyalkylene terephthalates can be branched by incorporation of relatively small amounts of 3- or 4-hydric alcohols or 3- or 4-basic carboxylic acids, e.g. in accordance with DE-A 1 900 270 and US 3 692 744. Examples of preferred branching agents are trimesic acid, trimellitic acid, trimethylolethane and -propane and pentaerythritol.
Polyalkylene terephthalates which have been prepared solely from terephthalic acid and reactive derivatives thereof (e.g. dialkyl esters thereof) and ethylene glycol and/or butane-1,4-diol and mixtures of these polyalkylene terephthalates are particularly preferred.
Mixtures of polyalkylene terephthalates contain I to 50 wt.%, preferably I to 30 wt.% of polyethylene terephthalate and 50 to 99 wt.%, preferably 70 to 99 wt.% of polybutylene terephthalate.
The polyalkylene terephthalates preferably used in general have a limiting viscosity of from 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) at 25 C in an Ubbelohde viscometer.
BMS 071168-WO-nat CA 02715204 2010-06-17 The polyalkylene terephthalates can be prepared by known methods (see e.g.
Kunststoff-Handbuch, volume VIII, p. 695 et seq., Carl-Hanser-Verlag, Munich 1973).
Component E
The composition can comprise further commercially available additives according to component E), such as flameproofing synergists, rubber-modified graft polymers E* which differ from component B), antidripping agents (for example compounds of the substance classes of fluorinated polyolefins, of silicones and aramid fibres), lubricants and mould release agents (for example pentaerythritol tetrastearate), nucleating agents, stabilizers, antistatics (for example conductive carbon blacks, carbon fibres, carbon nanotubes and organic antistatics, such as polyalkylene ethers, alkylsulfonates or polyamide-containing polymers), acids, fillers and reinforcing substances (for example glass fibres or carbon fibres, mica, kaolin, talc, CaCO3 glass flakes) and dyestuffs and pigments.
The graft polymers E* which differ from component B are prepared by bulk, suspension or solution polymerization. The compositions according to the invention are preferably free from graft polymers E* which differ from component B.
Preparation of the moulding compositions and shaped articles The thermoplastic moulding compositions according to the invention are prepared by mixing the particular constituents in a known manner and subjecting the mixture to melt compounding and melt extrusion at temperatures of from 240 C to 300 C in conventional units, such as internal kneaders, extruders and twin-screw extruders.
The mixing of the individual constituents can be carried out in a known manner either successively or simultaneously, and in particular either at about 20 C (room temperature) or at a higher temperature.
The invention likewise provides processes for the preparation of the moulding compositions and the use of the moulding compositions for the production of shaped articles and the mouldings themselves.
BMS 071168-WO-nat CA 02715204 2010-06-17 The moulding compositions according to the invention can be used for the production of all types of shaped articles. These can be produced by injection moulding, extrusion and blow moulding processes. A further form of processing is the production of shaped articles by thermoforming from previously produced sheets or films.
Examples of such shaped articles are films, profiles, housing components of all types, e.g.
for domestic appliances, such as televisions, juice presses, coffee machines and mixers; for office machines, such as monitors, flatscreens, notebooks, printers and copiers; sheets, tubes, electrical installation conduits, windows, doors and further profiles for the building sector (interior finishing and exterior uses) and electrical and electronic components, such as switches, plugs and sockets, and vehicle body or interior components for utility vehicles, in particular for the automobile sector.
The moulding compositions according to the invention can also be used in particular, for example, for the production of the following shaped articles or mouldings:
interior finishing components for rail vehicles, ships, aircraft, buses and other motor vehicles, housing of electrical equipment containing small transformers, housing for equipment for processing and transmission of information, housing and lining of medical equipment, massage equipment and housing therefor, toy vehicles for children, planar wall elements, housing for safety equipment and for televisions, thermally insulated transportation containers, mouldings for sanitary and bath fittings, cover grids for ventilator openings and housing for garden equipment.
The following examples serve to explain the invention further.
BMS 071168-WO-nat CA 02715204 2010-06-17 Examples Component A-1 Linear polycarbonate based on bisphenol A having a relative solution viscosity of rite! _ 1.28, measured in CH2C12 as the solvent at 25 C and a concentration of 0.5 g/100 ml.
Component A-2 Linear polycarbonate based on bisphenol A having a relative solution viscosity of lire! _ 1.20, measured in CH2Cl2 as the solvent at 25 C and a concentration of 0.5 g/100 ml.
Component B
ABS graft polymer having a core-shell structure prepared by emulsion polymerization of 43 wt.%, based on the ABS polymer, of a mixture of 27 wt.% of acrylonitrile and 73 wt.%
of styrene in the presence of 57 wt.%, based on the ABS polymer, of a polybutadiene rubber crosslinked in particle form (average particle diameter d50 = 0.35 m).
Component C
Component C-1 (comparison) Oligophosphate based on bisphenol A
O-P O / \ i O-P O
q=1.1 Component C-2 Calcium phosphinate, average particle size d50 = 50 m.
Component E
Component E- 1: polytetrafluoroethylene (PTFE) Component E-2: pentaerythritol tetrastearate Component E-3: Irganox B900 (manufacturer: Ciba Specialty Chemicals Inc., Basle, Switzerland) BMS 071168-WO-nat CA 02715204 2010-06-17 Preparation and testing of the moulding compositions The starting substances listed in Table 1 are compounded and granulated on a twin-screw extruder (ZSK-25) (Werner and Pfleiderer) at a speed of rotation of 225 rpm and a throughput of 20 kg/h at a machine temperature of 260 C.
The finished granules are processed on an injection moulding machine to give the corresponding test specimens (melt temperature 260 C, mould temperature 80 C, melt front speed 240 mm/s).
Characterization is carried out in accordance with DIN ISO 306 (Vicat softening temperature, method B with a load of 50 N and a heating rate of 120 K/h), ISO
(environmental stress cracking (ESC) test against toluene:isopropanol 60:40, at 2.4 % and 0.8 % edge fibre elongation, in the table the time until break is stated) UL
94 V (measured on bars of dimensions 127 x 12.7 x 1.5 mm) and IEC 60695-2-12 (glow wire test;
the glow wire flammability index GWFI at a thickness of 2.0 mm is stated).
It can be seen from Table 1 that only the composition in Example 2 with the combination of polycarbonate, emulsion ABS and calcium phosphinate achieves the object according to the invention, i.e. a combination of high heat distortion point, good resistance to chemicals and good performance in the UL94V test and in the test according to JEC 60695-2-12.
BMS 071168-WO-nat CA 02715204 2010-06-17 Table 1: Compositions and their properties Composition 1 2 (comp.) A-1 pt. by wt. 70.2 70.2 A-2 pt. by wt. 24.5 24.5 B pt. by wt. 3.0 3.0 C-1 pt. by wt. 2.3 C-2 pt. by wt. 2.3 E-1 pt. by wt. 0.4 0.4 E-2 pt. by wt. 0.4 0.4 E-3 pt. by wt. 0.1 0.1 Properties Vicat B 120 (DIN ISO 306) C 100 102 ESC properties / [2.4 %] min:sec 10 19 ESC properties / [0.8%] min:sec 220 265 UL 94 V 1.5 mm / 2 d [rating] vi v o UL 94 V 1.5 mm / 2 d [total ABT] s 33 6 Glow wire flammability index 800 960 GWFI at a thickness of 2.0 mm ABT = after-burn time
Claims (20)
1. Compositions comprising A) 50 to 99.4 parts by wt. (in each case based on the sum of the parts by weight of components A+B+C) of aromatic polycarbonate and/or aromatic polyester carbonate, B) 0.5 to 20 parts by wt. (in each case based on the sum of the parts by weight of components A+B+C) of rubber-modified graft polymer prepared in the emulsion polymerization process, C) 0.1 to 30 parts by wt. (in each case based on the sum of the parts by weight of components A+B+C) of a salt of a phosphinic acid.
2. Composition according to claim 1, comprising 2 to 6 parts by wt. (in each case based on the sum of the parts by weight of components A+B+C) of rubber-modified graft polymer according to component B).
3. Composition according to claim 1 or 2, comprising 7 to 12 parts by wt. (in each case based on the sum of the parts by weight of components A+B+C) of a salt of a phosphinic acid.
4. Composition according to one of claims 1 to 3, comprising 0 to 20 parts by wt.
(based on the sum of the parts by weight of components A+B+C = 100) of rubber-free vinyl (co)polymer and/or polyalkylene terephthalate as component D).
(based on the sum of the parts by weight of components A+B+C = 100) of rubber-free vinyl (co)polymer and/or polyalkylene terephthalate as component D).
5. Composition according to one of claims 1 to 3 which is free from rubber-free vinyl (co)polymer and/or polyalkylene terephthalate.
6. Composition according to one of claims 1 to 5, comprising as component B) one or more graft polymers of B.1 5 to 95 wt.% of at least one vinyl monomer on B.2 95 to 5 wt.% of at least one graft base chosen from the group consisting of diene rubbers, EP(D)M rubbers (i.e. those based on ethylene/propylene and optionally diene) and acrylate, polyurethane, silicone, silicone/acrylate, chloroprene and ethylene/vinyl acetate rubbers.
7. Composition according to claim 6, comprising as B.1 mixtures of B.1.1 50 to 99 parts by wt. of vinylaromatics and/or vinylaromatics substituted on the nucleus and/or (meth)acrylic acid (C1-C8)-alkyl esters and B.1.2 1 to 50 parts by wt. of vinyl cyanides and/or (meth)acrylic acid (C1-C8)-alkyl esters and/or derivatives of unsaturated carboxylic acids.
8. Composition according to one of claims 1 to 7, comprising a graft polymer according to component B) prepared in the emulsion polymerization process by redox initiation with an initiator system of organic hydroperoxide and ascorbic acid.
9. Composition according to claim 6, wherein the graft polymer B) has a graft base B.2 having an average particle size (d50 value) of from 0.2 to 0.4 µm.
10. Composition according to one of claims 1 to 9, comprising as component C) a salt or a mixture of salts of a phosphinic acid, wherein the metal cation is Li+, Na+, K+, Mg2+, Ca2+, Sr2+, Ba2+, Al3+, Zn2+, Mn2+, Fe2+ and/or Fe3+.
11. Composition according to claim 10, comprising as the salt or a mixture of salts a phosphinic acid of the formula (IV) wherein M'+ is a metal cation of main group 1(alkali metals; m = 1), main group 2 (alkaline earth metals; m = 2) or of main group 3 (m = 3) or of subgroup 2, 7 or 8 (wherein m denotes an integer from 1 to 6) of the periodic table.
12. Composition according to claim 11, wherein M m+ = Ca2+ and m = 2 or M m+ =
Al3+
and m = 3.
Al3+
and m = 3.
13. Composition according to one of claims 1 to 12, wherein the average particle size d50 of the phosphinic acid salt (component C) is less than 80 µm.
14. Composition according to one of claims 1 to 13, wherein the composition is free from phosphorus-containing flameproofing agents chosen from the group of mono-and oligomeric phosphoric and phosphonic acid esters, phosphonate-amines and phosphazenes.
15. Composition according to one of claims 1 to 14, comprising 0 to 50 parts by wt. (in each case based on the sum of the parts by weight of components A+B+C = 100) of additives as component E.
16. Composition according to one of claims 1 to 15, wherein the commercially available additives according to component E) are flameproofing synergists, rubber-modified graft polymers E* which differ from component B), antidripping agents, lubricants and mould release agents, nucleating agents, stabilizers, antistatics, acids, fillers and reinforcing substances and dyestuffs and pigments.
17. Composition according to one of claims 1 to 16 which are free from graft polymers E* which differ from component B.
18. Use of the compositions according to claim 1 to 17 for the production of shaped articles.
19. Shaped articles comprising a composition according to one of claims 1 to 18.
20. Shaped article according to claim 19, characterized in that the shaped article is a part of a motor vehicle, rail vehicle, aircraft or aquatic vehicle or a film, a profile or housing components of all types.
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| DE102007061759A DE102007061759A1 (en) | 2007-12-20 | 2007-12-20 | Flame-retardant toughened polycarbonate compositions |
| DE102007061759.5 | 2007-12-20 | ||
| PCT/EP2008/010695 WO2009080245A1 (en) | 2007-12-20 | 2008-12-16 | Flame-proof impact resistant-modified polycarbonate compositions |
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| CA2715204A1 true CA2715204A1 (en) | 2009-07-02 |
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| EP (1) | EP2225316B1 (en) |
| JP (1) | JP2011506705A (en) |
| KR (1) | KR20100096186A (en) |
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| DE102007061758A1 (en) * | 2007-12-20 | 2009-06-25 | Bayer Materialscience Ag | Flame-retardant toughened polycarbonate compositions |
| CN104277443A (en) * | 2014-10-29 | 2015-01-14 | 南通日之升高分子新材料科技有限公司 | Preparation method of heat-resistant halogen-free flame-retardant PC (polycarbonate)/ABS |
| CN110358278A (en) * | 2019-07-01 | 2019-10-22 | 武汉市太行冶金材料有限公司 | A kind of packaging steel coils flame retardant type plastic sheet PP Pipe Compound and preparation method thereof |
| CN114621573B (en) * | 2022-03-15 | 2023-06-23 | 金发科技股份有限公司 | Halogen-free flame-retardant carbon fiber reinforced polycarbonate composition and preparation method and application thereof |
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| DE19820398A1 (en) * | 1998-05-07 | 1999-11-11 | Basf Ag | Flame-retardant polyester molding compounds |
| DE19820399A1 (en) | 1998-05-07 | 1999-11-11 | Basf Ag | Flame retardant polyester molding compounds |
| WO2000012614A1 (en) * | 1998-08-31 | 2000-03-09 | General Electric Company | Flame retardant resin compositions containing phosphoramides, and method for making |
| DE19853105A1 (en) | 1998-11-18 | 2000-05-25 | Bayer Ag | Polycarbonate composition useful for production of molded articles contains graft polymer, phosphorous compound and fluorinated polyolefin |
| JP2001261973A (en) | 2000-03-16 | 2001-09-26 | Daicel Chem Ind Ltd | Thermoplastic resin composition |
| JP2001335699A (en) | 2000-05-30 | 2001-12-04 | Daicel Chem Ind Ltd | Flame-retardant resin composition |
| JP5255169B2 (en) | 2000-11-24 | 2013-08-07 | 株式会社ダイセル | Flame retardant resin composition |
| DE10234420A1 (en) * | 2002-07-29 | 2004-02-12 | Bayer Ag | Impact-modified polycarbonate blends |
| DE10309622A1 (en) * | 2003-03-04 | 2004-09-23 | Clariant Gmbh | Meltable zinc phosphinates |
| US7608654B2 (en) * | 2003-11-07 | 2009-10-27 | Italamatch Chemicals S.P.A. | Halogen-free flame retardant polycarbonate compositions |
| DE102004035508A1 (en) * | 2004-07-22 | 2006-02-16 | Clariant Gmbh | Flame-retardant polymer molding compounds |
| DE102004049342A1 (en) | 2004-10-08 | 2006-04-13 | Basf Ag | Flowable thermoplastics with halogen-free flame retardance |
| DE102005058836A1 (en) * | 2005-12-09 | 2007-06-14 | Bayer Materialscience Ag | Polycarbonate molding compositions |
| JP5309355B2 (en) * | 2006-05-02 | 2013-10-09 | 大和化学工業株式会社 | Textile processing method |
| DE102007061761A1 (en) * | 2007-12-20 | 2009-06-25 | Bayer Materialscience Ag | Flame-retardant toughened polycarbonate compositions |
-
2007
- 2007-12-20 DE DE102007061759A patent/DE102007061759A1/en not_active Withdrawn
-
2008
- 2008-12-16 WO PCT/EP2008/010695 patent/WO2009080245A1/en active Application Filing
- 2008-12-16 CN CN200880121451.3A patent/CN101903444B/en not_active Expired - Fee Related
- 2008-12-16 RU RU2010129709/05A patent/RU2010129709A/en not_active Application Discontinuation
- 2008-12-16 CA CA2715204A patent/CA2715204A1/en not_active Abandoned
- 2008-12-16 JP JP2010538436A patent/JP2011506705A/en active Pending
- 2008-12-16 KR KR1020107013519A patent/KR20100096186A/en not_active Application Discontinuation
- 2008-12-16 EP EP08864111A patent/EP2225316B1/en not_active Not-in-force
- 2008-12-16 MX MX2010005721A patent/MX2010005721A/en unknown
- 2008-12-16 BR BRPI0821403-4A patent/BRPI0821403A2/en not_active IP Right Cessation
- 2008-12-19 TW TW097149555A patent/TW200946590A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| JP2011506705A (en) | 2011-03-03 |
| RU2010129709A (en) | 2012-01-27 |
| MX2010005721A (en) | 2010-08-04 |
| EP2225316B1 (en) | 2013-03-13 |
| WO2009080245A1 (en) | 2009-07-02 |
| TW200946590A (en) | 2009-11-16 |
| EP2225316A1 (en) | 2010-09-08 |
| BRPI0821403A2 (en) | 2015-06-16 |
| CN101903444B (en) | 2013-03-27 |
| KR20100096186A (en) | 2010-09-01 |
| CN101903444A (en) | 2010-12-01 |
| DE102007061759A1 (en) | 2009-06-25 |
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| Date | Code | Title | Description |
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| FZDE | Discontinued |
Effective date: 20121217 |