CA2145134A1 - Thermoplastic molding materials comprising a graft copolymer and an olefin copolymer - Google Patents
Thermoplastic molding materials comprising a graft copolymer and an olefin copolymerInfo
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- CA2145134A1 CA2145134A1 CA002145134A CA2145134A CA2145134A1 CA 2145134 A1 CA2145134 A1 CA 2145134A1 CA 002145134 A CA002145134 A CA 002145134A CA 2145134 A CA2145134 A CA 2145134A CA 2145134 A1 CA2145134 A1 CA 2145134A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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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
- C08L51/06—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 homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
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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
- 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
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
-
- 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
- C08L51/003—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 by reactions only involving unsaturated carbon-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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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
- 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
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0869—Acids or derivatives thereof
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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
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/12—Copolymers of styrene with unsaturated nitriles
Abstract
Thermoplastic molding materials contain essentially (A) from 20 to 99 % by weight of at least one graft copolymer, obtainable essentially from (a1) from 30 to 90 % by weight of a core obtainable by poly-merization of a monomer mixture consisting essentially of (a11) from 80 to 99.99 % by weight of at least one C1-C10-alkyl ester of acrylic acid, (a12) from 20 to 0.01 % by weight of a copolymerizable, polyfunctional crosslinking monomer and (a13) from 0 to 40 % by weight of a further copolymerizable, monoethylenically unsaturated monomer, and (a2) from 70 to 10 % by weight of a graft shell obtainable by polymerization of a monomer mixture in the presence of the core (a1), consisting essentially of (a21) from 50 to 100 % by weight of a styrene compound of the general formula (I)
Description
` 214513~
Thermoplastic-molding materials comprising a graft copolymer and an olefin copolymer 5 The prèsent invention relates to thermoplastic molding materials containing essentially (A) from 20 to 99 % by weight of at least one graft copolymer, obtainable essentially from ~al) from 30 to 90 % by weight of a core obtainable by poly-merization of a monomer mixture consisting essentially of (all) from 80 to 99.99 % by weight of at least one C1-C10-alkyl ester of acrylic acid, (al2) from 20 to 0.01 % by weight of a copolymerizable, polyfunctional crosslinking monomer and 20 ~al3) from 0 to 40 % by weight of a further copolymerizable, monoethylenically unsaturated monomer, and (a2) from 70 to 10 % by weight of a graft shell obtainable by polymerization of a monomer mixture in the presence of the core (al), consisting essentially of (a21) from 50 to 100 % by weight of a styrene compound of the general formula (I) R1C=CH2 ~ (I) where R1 and R2, independently of one another, are each hydrogen or Cl-C8-alkyl and/or of a C1-C8-alkyl ester of methacrylic or acrylic acid, 40 (a22) from 50 to 0 % by weight of a monofunctional comonomer, and (B) from 80 to 1 % by weight of a copolymer obtainable from at least one alpha-olefin and at least one polar comonomer, with the proviso that vinyl acetate or a vinylaromatic monomer are not used as monomers, and 214~13~
.
tc) from~0 to 50 ~ by weight, based on the total weight of components (A), (B) and (C), of a thermoplastic polymer obtainable by polymerization of a monomer mixture consisting essentially of cl) from 50 to 100 % by weight of a vinylaromatic monomer and/or of a Cl-C8-alkyl ester of methacrylic or acrylic acid and 10 ~c2) from 50 to 0 % by weight of a monofunctional comonomer.
The present invention furthermore relates to a process for the preparation of the novel thermoplastic molding materials, their use and moldings and films produced therefrom.
EP-A 526 813 describes polymer alloys comprising a graft polymer having a core based on a crosslinked alkyl acrylate and, if re-quired, comonomers and a shell obtainable by polymerization of a vinylaromatic monomer, an ethylenically unsaturated nitrile and/
20 or an alkyl (meth)acrylate, an ethylene~vinyl acetate copolymer and an elastomeric copolymer, and the use of these polymer alloys for the production of deep-drawable flexible films.
The disadvantage of films produced by the process described in 25 EP-A 526 813 is that the mixtures described tend to become dis-colored during processing and have a disadvantageous ratio of tensile strength to elongation at break. Furthermore, such films exhibit severe fogging when processed under conditions similar to those used in practice. In addition, four components are required 30 for producing the molding materials according to EP-A 526 813.
DE-A 3,149,358 describes thermoplastic molding materials obtain-able from a graft copolymer having a core of a crosslinked alkyl acrylate and, if required, comonomers and a shell obtainable by 35 polymerization of a vinylaromatic monomer and an ethylenically unsaturated monomer, and a copolymer obtainable by polymerization of a vinylaromatic monomer and an ethylenically unsaturated mono-mer. Films produced from these thermoplastic molding materials have the disadvantage that their elongation at break is too small 40 and at the same time their hardness is too high.
Plastics films having a leather-like appearance are also used, for example for lining the interior of motor vehicles. The plas-tic currently used is usually PVC, as a mixture with various 45 vinyl polymers and plasticizers. These films are not completely `; ` 21~Sl~
-stable to~aging and high temperatures, contain volatile compo-nents and are naturally halogen-cont~;n;ng (cf. DE-A 42 11 415).
It is an object of the present invention to provide further ther-5 moplastic molding materials which can be procesQed to give filmswhich have a balanced ratio of tensile strength, elongation at break, tear propagation strength, hardness and color stability during processing. In particular, film tear propagation strengths of at least 35 N/mm according to DIN 53515 should be achieved and lO halogen-free films which are stable to aging, have a leather-like appearance and contain less volatile components than correspond-ing prior art films should be obtained.
We have found that this object is achieved by the thermoplastic 15 molding materials defined at the outset.
We have also found a process for their preparation, their use for the production of moldings and films, and molding and films pro-duced from the novel thermoplastic molding materials.
The novel thermoplastic molding materials contain essentially (A) from 20 to 99, preferably from 30 to 98, particularly preferably from 60 to 95, % by weight of at least one graft copolymer, obtainable essentially from (al) from 30 to 90, preferably from 40 to 80, particularly preferably from 50 to 70, % by weight of a core obtainable by polymerization of a monomer mixture consisting essentially of (all) from 80 to 99.99, preferably from 90 to 99.8, particularly preferably from 97 to 99, % by weight of at least one C1-C10-alkyl ester of acrylic acid, (al2) from 20 to 0.01, preferably from 10 to 0.2, particularly preferably from 3 to 1, % by weight of a copolymerizable, polyfunctional crosslinking monomer and 90 (al3) from 0 to 40, preferably from 0 to 10, % by weight of a further copolymerizable, monoethylenically unsaturated monomer, and ` 21451~
(a2) from~70 to 10, preferably from 60 to 20, particularly preferably from 50 to 30, % by weight of a graft shell obtainable by polymerization of a monomer mixture in the presence of the core (al), consisting essentially of (a21) from 50 to 100, preferably from 55 to 95, particularly preferably from 60 to 90, % by weight of a styrene compound of the general formula (I) R1C=CH2 ~ (I) where R1 and R2, independently of one another, are each hydrogen or Cl-CB-alkyl and/or of a C1-C8-alkyl ester of methacrylic or acrylic acid, and 20 (a22) from 50 to 0, preferably from 45 to 5, particularly preferably from 40 to 10, % by weight of a monofunctional comonomer, and (B) from 80 to 1, preferably from 60 to 3, particularly preferably from 50 to 4, % by weight of a copolymer obtainable from at least one alpha-olefin and at least one polar comonomer, with the proviso that vinyl acetate or a vinylaromatic monomer are not used as monomers, and 30 (C) from 0 to 50, preferably from 0 to 45, particularly preferably from 0 to 40, % by weight, based on the total weight of components (A), (~) and (C), of a thermoplastic polymer obtainable by polymerization of a monomer mixture consisting essentially of (cl) from 50 to 100, preferably from 55 to 90, particularly preferably from 60 to 85, % by weight of a vinylaromatic monomer and/or of a C1-C8-alkyl ester of methacrylic or acrylic acid and gO
(c2) from 50 to 0, preferably from 45 to 10, particularly preferably from 40 to 15, % by weight of a monofunctional comonomer.
45 Methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acry-late, n-pentyl acrylate, n-hexyl acrylate, n-heptyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, n-nonyl acrylate and 214513~
n-decyl acrylate and mixtures thereof, preferably n-butyl acry-late, 2-ethylhexyl acrylate or mixtures thereof, particularly preferably n-butyl acrylate, may be used as Cl-C10-alkyl esters of acrylic acid (c~ ponent (all)).
Monomers which contain two, three or four, preferably two, double bonds which are capable of undergoing copolymerization and are not conjugated in the 1,3 position are used a~ copolymerizable, polyfunctional crosslinking monomers. Such monomers suitable for 10 crosslinking are, for example, vinylbenzenes, such as divinylben-zene and trivinylbenzene, diallyl maleate, diallyl fumarate, diallyl phthalate, triallyl cyanurate and triallyl isocyanurate.
The tricyclodecenyl acrylates Ia and Ib ~\ ~ 0-C-CH=CHz ~ ~ 0-C-CH=CHz Ia Ib have proven particularly suitable monomers for component (al2) (cf. DE-A 1,260,135) and can also be used in the form of their mixtures.
Examples of further copolymerizable, monoethylenically unsatu-rated monomers (component (al3)) are butadiene, isoprene 30 vinylaromatic monomers, such as styrene, substituted styrene of the general formula I;
methacrylonitrile, acrylonitrile;
35 acrylic acid, methacrylic acid;
Cl-C4-alkyl esters of methacrylic acid, such as methyl meth-acrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 40 sec-butyl methacrylate, tert-butyl methacrylate;
C1-C4-alkyl esters of methacrylic or acrylic acid, the alkyl radical~ being monosubstituted by phenyl or naphthyl, the naphthol and phenol which is unsubstituted or substituted by up 45 to two C1-C4-alkyl groups, such as phenyl acrylate, phenylethyl methacrylate, phenylethyl acrylate, benzyl methacrylate, benzyl acrylate, phenylpropyl methacrylate, phenylpropyl acrylate, 21~131 phenylbutyl methacrylate, phenylbutyl acrylate, 4-methylphenyl acrylate and naphthyl acrylate, and phenoxyethyl methacrylate and phenoxyethyl acrylate;
5 vinyl methyl ether and compatible mixtures thereof.
Styrene, a-methylstyrene and styrenes alkylated in the nucleus with C1-C8-alkyl, such as p-methylstyrene or tert-butylstyrene are preferably used as the styrene c~ ,oulld of the general formula 10 (I) (component (a21)), particularly preferably styrene and a-me-thylstyrene.
According to the invention, methyl methacrylate (MMA), ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, 15 n-butyl methacrylate, isobutyl methacrylate, sec-butyl meth-acrylate, tert-butyl methacrylate, pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methylacrylate or 2-ethylhexyl methacrylate, particularly preferably methyl methacrylate, are used as C1-C8-alkyl esters of methacrylic or 20 acrylic acid, as well as mixtures of these monomers, methyl acrylate (MA), ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate or 2-ethylhexyl acrylate, particularly preferably n-butyl 25 acrylate, and mixtures of these monomers with one another and with the methacrylates and/or styrene compounds of the general formula I.
According to the invention, monomers selected from the group con-30 sisting of methacrylonitrile, acrylonitrile, N-C1-C8-alkyl-, N-Cs-C8-cycloalkyl- and N-C6-C10-aryl-substituted maleimides, such as N-methyl-, N-phenyl-, N-dimethylphenyl- and N-cyclohexyl-maleimide and maleic anhydride, preferably acrylonitrile, are, if desired, used as monofunctional comonomers (component (a22)).
~5 In a preferred embodiment, a mixture of styrene (S) and acrylo-nitrile (AN) in a molar S/AN ratio of, usually, from 4.5:1 to 0.5:1, preferably from 2.2:1 to 0.65:1, styrene alone, a mixture of acrylonitrile and methyl methacrylate (MMA) or MMA alone is 40 used for producing the graft shell (a2).
Component (A) is prepared by conventional methods, for example by those described in DE-A 3,149,358.
45 For this purpose, the core (al) is first prepared by polymerizihg the aarylate or acrylates (all) and the polyfunctional monomers (al2) which effect crosslinking, with or without the further 214513~
comonomers~(al3), in the conventional aqueous emulsion in a man-ner known per se, at from 20 to 100 C, preferably from 50 to 80 C.
The conventional emulsifiers, such as alkali metal salts of al-kyl- or alkylarylsulfonic acids, alkylsulfate, fatty alcohol sul-5 fonates, salts of higher fatty acids of 10 to 30 carbon atoms,sulfosuccinates, such as Aerosol~ OT (Cyanamid), ether sulfonates such as Disponil~ FES61 (Henkel), or resin soaps, may be used.
Sodium salts of alkanesulfonates or fatty acids of 10 to 18 carbon atoms are preferably taken. It is advantageous to use the 10 emulsifiers in amounts of from 0.3 to 5, in particular from 1 to 2, % by weight, based on the monomers used in the preparation of the core (al). In general, the water/monomer ratio of from 2:1 to 0.7:1 is employed.
15 The polymerization initiators used are in particular the conven-tional persulfates, but redox systems are also suitable. The a~ount of initiators depends as a rule on the desired molecular weight and is usually from 0.1 to 1 % by weight, based on the monomers used in the preparation of the core (al).
The polymerization asgistants which may be used in the polymer-ization are the conventional buffer substances by means of which a pH of, preferably, from 6 to 9 is obtained, for example sodium bicarbonate and sodium pyrophosphate, and from 0 to 3 % by weight 25 of a molecular weight regulator, such as a mercaptan, a terpinol or dimeric alpha-methylstyrene.
The exact polymerization conditions, in particular the type, metering and amount of the emulsifier, are as a rule determined 30 specifically within the abov -ntioned ranges so that the result-ing latex of the crosslinked acrylate polymer (al) has a d50 value of from 60 to 1000 nm, preferably from 80 to 800 nm, particularly preferably from 100 to 600 nm. The particle size distribution of the latex should preferably be narrow.
In principle, it is also possible to prepare the grafting base by a method other than that of emulsion polymerization, for example by mass or solution polymerization, and subsequently to emulsify the polymers obtained. The processes for this purpose are known.
The graft rubber particles (A) usually have a particle size (d50) of from 60 to 1500 nm, preferably from 100 to 1200 nm.
In order to obtain a very tough molding material, graft rubber 45 particles (A) having a particle size (d50) of from 200 to 1000 nm are used in a preferred embodiment.
21gS13~
-In a further preferred embodiment, a mixture of graft rubber par-ticles (A) of different sizes and having a bimodal particle size distribution is used. Particularly preferably, from 0.5 to 99.5 %
by weight of this mixture have a particle size (d50) with a mean 5 diameter of from 200 to 1000 nm, and from 99.5 to 0.5 % by weight of the mixture have a particle size (dsO) with a mean diameter of from 60 to 190 nm.
The chemical composition of the two graft copolymers is prefer-10 ably the same, although the shell of the coarse-particled graft copolymers may in particular have a two-stage composition.
The graft shell (component (a2)) is also prepared, as a rule, by known polymerization methods, such as emulsion, mass, solution or 15 suspension polymerization, preferably an aqueous emulsion in the presence of an aqueous emulsion of the core (al) (cf. DE-A
1,260,135, DE-A 3,149,358 and German Patent 1,164,080). In a preferred embodiment, the graft copolymerization is carried out in the same system as the polymerization of the core (al), and, 20 if required, further emulsifier and initiator may be added. These need not be identical to the emulsifiers or initiators used for the preparation of the core (al). Emulsifier, initiator and polymerization assistants may each be initially taken alone or as a mixture for the emulsion of the core (al). Any possible com-25 bination or initially taken mixture and feed on the one hand andinitiator, emulsifier and polymerization assistants on the other hand is suitable. The preferred embodiments are known to a person skilled in the art. The monomer or monomer mixture to be grafted on may be added to the reaction mixture all at once, batchwise in 30 a plurality of stages or continuously during the polymerization.
C2-C8-Alpha-olefins, such as ethene, propene, but-l-ene, pent-1-ene, hex-1-ene, hept-1-ene and oct-l-ene, or mixtures thereof may be used as alpha-olefins for the preparation of component 35 (~), preferably ethene and propene.
Examples of polar comonomers which, according to the invention, should not include vinyl acetate and vinylaromatic monomers are alpha-beta-unsaturated C3-C8-carboxylic acids and available 40 anhydrides thereof, such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid and glycidyl esters thereof and esters with C1-C8-alkyl alcohols whose alkyl radicals may be monosubstituted by phenyl or naphthyl, naphthol and phenol which is unsubstituted or substituted by up 45 to two Cl-C4-alkyl groups, such as methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, pentyl acrylate, hexyl acrylate, 2-ethylhexyl 214513~
acrylate, 2-ethylhexyl methacrylate, glycidyl methacrylate, phenyl acrylate, phenylethyl methacrylate, phenylethyl acrylate, benzyl methacrylate, benzyl acrylate, phenylpropyl methacrylate, phenylpropyl acrylate, phenylbutyl methacrylate, phenylbutyl 5 acrylate, 4-methylphenyl acrylate and naphthyl acrylate, and phenoxyethyl methacrylate and phenoxyethyl acrylate;
methacrylonitrile, acrylonitrile;
10 carbon monoxide.
In a preferred embodiment, copolymers which can be prepared from (I) 40-75 % by weight of ethylene, 5-20 % by weight of carbon monoxide and 20-40 % by weight of n-butyl acrylate, for example 15 commercially available as ELVALOY~ HP-4051 (DuPont), or (II) 50-98,9 % by weight of ethylene, 1-45 % by weight of n-butyl acrylate, 0,1-20 % by weight of methacrylic and/or acrylic acid and~or maleic anhydride are used as component (B).
20 The copolymers (B) are prepared in a manner known per se (cf.
US 2,897,183 and US 5,057,593). The preparation is usually car-ried out by free radical polymerization. The initiators used are, as a rule, peroxides, such as lauryl peroxide, tert-butyl perace-tate, tert-butyl peroxypivalate, di-tert-butyl peroxide, di-(sec-25 butyl) peroxydicarbonate, tert-butyl peroctoate and tert-butyl perisononanoate, preferably tert-butyl peroxypivalate and tert-butyl perisononanoate. In general, azo-containing initiators, such as azobisisobutyronitrile, are also suitable.
30 The choice of the suitable initiator is usually made dependent on the polymerization temperature to be chosen, which as a rule is from 100 to 300 C, preferably from 130 to 280 C. The pressure dur-ing the polymerization is chosen as a rule in the range from 100 to 400, preferably from 150 to 250, MPa. The amount of initiator 35 is chosen in general to be from 1 to 50, preferably from 2 to 20 mol per 106 mol of the amount of polar copolymer used.
The polymerization is usually carried out in a continuous stirred reactor. Such a reactor is described in, for example, 40 US 2,897,183. The reaction time is as a rule from 30 to 1, pre-ferably from 5 to 2, minutes. Observations to date have shown that the use of a solvent is optional.
The vinylaromatic monomers (component (cl)) used are styrene, 45 substituted styrenes of general formula (I), which have already been stated as component (a21), or the C1-C8-alkyl esters of methacrylic or acrylic acid, stated under component (a21).
2i4513~
Styrene, alpha-methylstyrene and p-methylstyrene are preferably used.
If desired, monomers Which have already been stated as component 5 (a22) may be used as monofunctional comonomers (cG.,.ponent (c2)).
If desired, the Cl-Cg-alkyl esters of methacrylic and acrylic acid, stated under component (a21), may furthermore be mixed with the monomers stated under component (a21) and the mixture used as component (c2).
In a preferred embodiment, a mixture of styrene (S) and acryloni-trile (AN), S and a-methylstyrene, optionally mixed with methyl methacrylate or maleimides, or methyl methacrylate, if desired with methyl acrylate, is used.
The polymers of component (C) are as a rule known and are obtain-able by methods known per se (cf. Runststoff-Handbuch, Vieweg-Daumiller, Volume V (Polystyrol), Carl-Hanser-Verlag, Munich 1969, page 124, lines 12 et seq.). The polymerization i8 carried 20 out as a rule by free radical emulsions, suspension, solution or mass polymerization. In general, the polymers (C) have viscosity numbers (VN) (measured in a 0.5 % strength by weight solution in dimethylformamide at 23 C [~spec/C in cm3/g]) of from 40 to 160, which corresponds to average molecular weights Mw of from 40,000 25 to 2,000,000.
The novel thermoplastic molding materials may contain, as further component D), up to 50, in particular from 0.1 to 20, % by weight, based on the total material (A) + (B) + (C), of fibrous 30 or particulate fillers or of mixtures thereof. These are prefer-ably commercially available products. Processing assistants and stabilizers, such as UV stabilizers, lubricants and antistatic agents, are usually used in amounts of from 0.01 to 5 % by weight, but reinforcing agents, such as carbon fibers and glas~
35 fibers, in general in an amount of from 5 to 40 % by weight.
Fillers or reinforcing materials, such as glass beads, mineral fibers, whiskers, alumina fibers, mica, quartz powder and wollas-tonite, may also be added.
The novel molding materials may also contain further additives which are typical and conventionally used for styrene/acryloni-trile (SAN) polymers and graft copolymers based on acrylonitrile/
styrene/acrylates (ASA) or mixtures thereof. Examples of such ad-45 ditives are dyes, pigments, antistatic agents, antioxidants andin particular the lubricants which are required for further pro-cessing of the molding material, for example in the production of `` 214513~
moldings or shaped articles, in particular up to 10 ~ by weight of plasticizers and, if desired, polar copolymers having anti-static activity, such as ethylene oxide/propylene oxide copoly-mers.
The novel thermoplastic molding materials are usually prepared by processes known per se, by mixing the components (A), (B) and, if desired, (C) and/or (D). It may be advantageous to premix indi-vidual components. It is also possible to mix the components in lO solution and remove the solvents. However, mixing of the compo-nents is preferably carried out at from 200 to 320 C by extruding or kneading the components together or treating them in a roll mill, if necessary the c~l"~onents having been isolated beforehand from the solution obtained in the polymerization or from the 15 aqueous emulsion.
The novel thermoplastic molding materials can be processed by the known methods for processing thermoplastics, for example by ex-trusion, injection molding, calendering, blowmolding, pressing or 20 sintering.
In a further preferred embodiment, halogen-free films having a leather-like appearance, stable to aging and containing only a small amount of volatile c~ ~_nents are produced by, usually, 25 calendering and, if desired, subsequent deep drawing of the films, by using, as component (~), a copolymer prepared from 45-S5 % by weight of ethylene, 11-15 % by weight of carbon monoxide and 30 30-36 % by weight of n-butyl acrylate according to US 2,897,183 or US 5,057,593, and, as component (C), a copolymer prepared by continuous solution polymerization of 35 65 % by weight of styrene and 35 % by weight of acrylonitrile, having a viscosity number of 80 ml/g (measured in a 0.5 %
strength by weight solution in dimethylformamide at 23 C. A graft 40 copolymer having a core comprising essentially n-butyl acrylate which is crosslinked with tricyclodecenyl acrylate and a graft shell prepared from 60-90 % by weight of styrene and 40-10 % by weight of acrylonitrile, according to DE-A 3,149,358, is prefer-ably used as component (A). Such novel films are preferably used 45 for the interior trim of commercial vehicles, such as auto-mobiles, aircraft, ships and trains.
`` 214513~
~_ 12 The films~which can be prepared from the novel thermoplastic molding materials have a balanced ratio of tensile strength, elongation at break, tear propagation strength, hardness and col-or stability during processing, compared with those of the prior 5 art.
Examples The mean particle size and the particle size distribution were lO determined from the integral mass distribution. In all cases, the mean particle sizes are the weight average of the particle sizes, as determined by means of an analytical ultracentrifuge using the method of W. Scholtan and H. Lange, Kolloid-Z., and Z. Polymere 250 (1972), 782-796. The ultracentrifuge measurement gives the 15 integral mass distribution of particle diameter of a sample. From this it iQ possible to determine the percentage by weight of the particles which have a diameter equal to or smaller than a cer-tain size. The mean particle diameter, which i8 also referred to as the d50 value of the integral mass distribution, is defined as 20 the particle diameter at which 50 ~ by weight of the particles have a diameter smaller than the diameter which corresponds to the d50 value. Likewise, 50 % by weight of the particles then have a diameter larger than the d50 value. To characterize the width of the particle size distribution of the rubber particles, the dlo 25 and dgo values obtained from the integral mass distribution are used in addition to the d50 value (mean particle diameter). The dlo and dgo values of the integral mass distribution are defined similarly to the d50 value, except that they are based on 10 and 90 % by weight, respectively, of the particles. The quotient dgo - dlo = Q
d50 35 is a measure of the width of the particle size distribution.
The following components were used:
A. A coarse-particled graft polymer which was prepared as fol-lows:
1.5 g of the finely divided butyl acrylate latex prepared ac-cording to EP-~ 6503, page 12, line 55, to page 13, line 22, were initially taken, 50 g of water and 0.1 g of potassium persuflate were added and then, in the course of 3 hours, a mixture of 49 g of butyl acrylate and 1 g of tricyclodecenyl acrylate on the one hand and a solution of 0.5 g of the ` 2i4~134 _ 13 sodium~salt of a C12-C1g-paraffinsulfonic acid in 25 g of wa-ter on the other hand were introduced at 60 C. Polymerization was then continued for 2 hours. The resulting latex of the crosslinked butyl acrylate polymer had a solids content of 40 ~ by weight. The mean particle size (d50) (weight average of the latex) was determined as 430 nm, and the particle size distribution was narrow (Q = 0.1).
150 g of the latex prepared above were mixed with 20 g of styrene and 60 g of water, a further 0.03 g of potassium per-sulfate and 0.05 g of lauroyl peroxide were added and the mixture was then heated at 65 C for 3 hours while stirring.
The emulsion obtained in this graft copolymerization was then polymerized with 20 g of a mixture of styrene and acrylo-nitrile in a weight ratio of 75:25 for a further 4 hours. The reaction product was then precipitated from the emulsion by means of a calcium chloride solution at 95 C, isolated, washed with water and dried in a warm air stream. The degree of grafting of the graft copolymer was determined as 35 ~.
The mean particle size (d50) of the latex particles was 510 nm.
Bl) A copolymer prepared from ethylene, carbon monoxide and 30 %
by weight of n-butyl acrylate (Elvaloy0 HP-40Sl from DuPont prepared similarly to Example 2 in US 5,057,593).
B2) An ethylene/vinyl acetate copolymer (Luwax0 EVAl (BASF); melt viscosity at 140C 1500 mm2/sec).
30 A copolymer prepared from styrene and acrylonitrile in a weight ratio of 65:35 (S:AN) and having a viscosity number of ôO ml/g (measured in a 0.5 ~ strength by weight solution in dimethylform-amide at 23 C) was used as component C. The polymerization was carried out by continuous solution polymerization similarly to 35 Kunststoffe-Handbuch, Vieweg-Daumiller, Volume V (Polystyrol), Carl-Hanser-Verlag, Munich 1969, page 124, line 12 et seq.
The films were produced in a thickness of 0.5 mm, by mixing in a roll mill heated at 200-C. Moldings were punched out from these 40 films, and the tensile test according to DIN 53504 and the tear propagation test according to DIN 53515 were carried out.
The Shore hardness was determined according to DIN 53505.
45 The Vicat A heat distortion resistance was determined (in C) ac-cording to DIN 53460.
214513~
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o, o , , o ,~, o _, o U~ o Ul , ~ o a~ O
.. ~ o~ ' o O I I ~ ~1 a~
o 'U~ , ",, ~ o~
~ n Q ~ ~
Q J U' _~ ~ _ a~ ~ O ~ U
~ Q ~ z, ~ d~ Q~ ~ Z S ~ -~ O
m m u E~ n ~ ~ n-- rn.c ~--214513~
_ 15 In order to determine the volatile components in leather-like films, 2 g of each of the films to be tested, from Examples 2, 3 and 4, were heated in a glass cylinder for 1 hour at 280 C in a 5 stream of nitrogen. The masses used were determined before and after the experiment. The difference between the masses corre-sponded to the amounts of volatile components. The values ob-tained also provide information about the fogging behavior: the greater the loss of mass, ie. the higher the content of volatile 10 components, the greater is the fogging.
Table 2 Example Loss of mass [~ by weight]
15 2 0.67 3 0.75 4 0.82 for comparison Vl 1.08 V2 2.82 The following were used as comparative films:
Vl: Film comprising 80 parts by weight of c~ ,onent ~A), 10 parts by weight of component (C) and 10 parts by weight of a copolymer prepared from 90.5 ~ by weight of ethylene and 9.5 ~ by weight of vinyl acetate (melt viscosity at 120C:
1700 mm2/sec; Luwax~ EVA2 (BASF)), V2: Baymoflex~ A VPKU 3-2069 A (Bayer AG); polymer blend based on acrylonitrile/styrene/acrylate resin:
35 Softening temperature:above about 90C
Density: about l.0 g/cm3 at 20C (DIN 53479) Bulk density: about 250-350 kg/m3 Solubility in water: insoluble Ignition temperature: above 400C (DIN 51794)
Thermoplastic-molding materials comprising a graft copolymer and an olefin copolymer 5 The prèsent invention relates to thermoplastic molding materials containing essentially (A) from 20 to 99 % by weight of at least one graft copolymer, obtainable essentially from ~al) from 30 to 90 % by weight of a core obtainable by poly-merization of a monomer mixture consisting essentially of (all) from 80 to 99.99 % by weight of at least one C1-C10-alkyl ester of acrylic acid, (al2) from 20 to 0.01 % by weight of a copolymerizable, polyfunctional crosslinking monomer and 20 ~al3) from 0 to 40 % by weight of a further copolymerizable, monoethylenically unsaturated monomer, and (a2) from 70 to 10 % by weight of a graft shell obtainable by polymerization of a monomer mixture in the presence of the core (al), consisting essentially of (a21) from 50 to 100 % by weight of a styrene compound of the general formula (I) R1C=CH2 ~ (I) where R1 and R2, independently of one another, are each hydrogen or Cl-C8-alkyl and/or of a C1-C8-alkyl ester of methacrylic or acrylic acid, 40 (a22) from 50 to 0 % by weight of a monofunctional comonomer, and (B) from 80 to 1 % by weight of a copolymer obtainable from at least one alpha-olefin and at least one polar comonomer, with the proviso that vinyl acetate or a vinylaromatic monomer are not used as monomers, and 214~13~
.
tc) from~0 to 50 ~ by weight, based on the total weight of components (A), (B) and (C), of a thermoplastic polymer obtainable by polymerization of a monomer mixture consisting essentially of cl) from 50 to 100 % by weight of a vinylaromatic monomer and/or of a Cl-C8-alkyl ester of methacrylic or acrylic acid and 10 ~c2) from 50 to 0 % by weight of a monofunctional comonomer.
The present invention furthermore relates to a process for the preparation of the novel thermoplastic molding materials, their use and moldings and films produced therefrom.
EP-A 526 813 describes polymer alloys comprising a graft polymer having a core based on a crosslinked alkyl acrylate and, if re-quired, comonomers and a shell obtainable by polymerization of a vinylaromatic monomer, an ethylenically unsaturated nitrile and/
20 or an alkyl (meth)acrylate, an ethylene~vinyl acetate copolymer and an elastomeric copolymer, and the use of these polymer alloys for the production of deep-drawable flexible films.
The disadvantage of films produced by the process described in 25 EP-A 526 813 is that the mixtures described tend to become dis-colored during processing and have a disadvantageous ratio of tensile strength to elongation at break. Furthermore, such films exhibit severe fogging when processed under conditions similar to those used in practice. In addition, four components are required 30 for producing the molding materials according to EP-A 526 813.
DE-A 3,149,358 describes thermoplastic molding materials obtain-able from a graft copolymer having a core of a crosslinked alkyl acrylate and, if required, comonomers and a shell obtainable by 35 polymerization of a vinylaromatic monomer and an ethylenically unsaturated monomer, and a copolymer obtainable by polymerization of a vinylaromatic monomer and an ethylenically unsaturated mono-mer. Films produced from these thermoplastic molding materials have the disadvantage that their elongation at break is too small 40 and at the same time their hardness is too high.
Plastics films having a leather-like appearance are also used, for example for lining the interior of motor vehicles. The plas-tic currently used is usually PVC, as a mixture with various 45 vinyl polymers and plasticizers. These films are not completely `; ` 21~Sl~
-stable to~aging and high temperatures, contain volatile compo-nents and are naturally halogen-cont~;n;ng (cf. DE-A 42 11 415).
It is an object of the present invention to provide further ther-5 moplastic molding materials which can be procesQed to give filmswhich have a balanced ratio of tensile strength, elongation at break, tear propagation strength, hardness and color stability during processing. In particular, film tear propagation strengths of at least 35 N/mm according to DIN 53515 should be achieved and lO halogen-free films which are stable to aging, have a leather-like appearance and contain less volatile components than correspond-ing prior art films should be obtained.
We have found that this object is achieved by the thermoplastic 15 molding materials defined at the outset.
We have also found a process for their preparation, their use for the production of moldings and films, and molding and films pro-duced from the novel thermoplastic molding materials.
The novel thermoplastic molding materials contain essentially (A) from 20 to 99, preferably from 30 to 98, particularly preferably from 60 to 95, % by weight of at least one graft copolymer, obtainable essentially from (al) from 30 to 90, preferably from 40 to 80, particularly preferably from 50 to 70, % by weight of a core obtainable by polymerization of a monomer mixture consisting essentially of (all) from 80 to 99.99, preferably from 90 to 99.8, particularly preferably from 97 to 99, % by weight of at least one C1-C10-alkyl ester of acrylic acid, (al2) from 20 to 0.01, preferably from 10 to 0.2, particularly preferably from 3 to 1, % by weight of a copolymerizable, polyfunctional crosslinking monomer and 90 (al3) from 0 to 40, preferably from 0 to 10, % by weight of a further copolymerizable, monoethylenically unsaturated monomer, and ` 21451~
(a2) from~70 to 10, preferably from 60 to 20, particularly preferably from 50 to 30, % by weight of a graft shell obtainable by polymerization of a monomer mixture in the presence of the core (al), consisting essentially of (a21) from 50 to 100, preferably from 55 to 95, particularly preferably from 60 to 90, % by weight of a styrene compound of the general formula (I) R1C=CH2 ~ (I) where R1 and R2, independently of one another, are each hydrogen or Cl-CB-alkyl and/or of a C1-C8-alkyl ester of methacrylic or acrylic acid, and 20 (a22) from 50 to 0, preferably from 45 to 5, particularly preferably from 40 to 10, % by weight of a monofunctional comonomer, and (B) from 80 to 1, preferably from 60 to 3, particularly preferably from 50 to 4, % by weight of a copolymer obtainable from at least one alpha-olefin and at least one polar comonomer, with the proviso that vinyl acetate or a vinylaromatic monomer are not used as monomers, and 30 (C) from 0 to 50, preferably from 0 to 45, particularly preferably from 0 to 40, % by weight, based on the total weight of components (A), (~) and (C), of a thermoplastic polymer obtainable by polymerization of a monomer mixture consisting essentially of (cl) from 50 to 100, preferably from 55 to 90, particularly preferably from 60 to 85, % by weight of a vinylaromatic monomer and/or of a C1-C8-alkyl ester of methacrylic or acrylic acid and gO
(c2) from 50 to 0, preferably from 45 to 10, particularly preferably from 40 to 15, % by weight of a monofunctional comonomer.
45 Methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acry-late, n-pentyl acrylate, n-hexyl acrylate, n-heptyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, n-nonyl acrylate and 214513~
n-decyl acrylate and mixtures thereof, preferably n-butyl acry-late, 2-ethylhexyl acrylate or mixtures thereof, particularly preferably n-butyl acrylate, may be used as Cl-C10-alkyl esters of acrylic acid (c~ ponent (all)).
Monomers which contain two, three or four, preferably two, double bonds which are capable of undergoing copolymerization and are not conjugated in the 1,3 position are used a~ copolymerizable, polyfunctional crosslinking monomers. Such monomers suitable for 10 crosslinking are, for example, vinylbenzenes, such as divinylben-zene and trivinylbenzene, diallyl maleate, diallyl fumarate, diallyl phthalate, triallyl cyanurate and triallyl isocyanurate.
The tricyclodecenyl acrylates Ia and Ib ~\ ~ 0-C-CH=CHz ~ ~ 0-C-CH=CHz Ia Ib have proven particularly suitable monomers for component (al2) (cf. DE-A 1,260,135) and can also be used in the form of their mixtures.
Examples of further copolymerizable, monoethylenically unsatu-rated monomers (component (al3)) are butadiene, isoprene 30 vinylaromatic monomers, such as styrene, substituted styrene of the general formula I;
methacrylonitrile, acrylonitrile;
35 acrylic acid, methacrylic acid;
Cl-C4-alkyl esters of methacrylic acid, such as methyl meth-acrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 40 sec-butyl methacrylate, tert-butyl methacrylate;
C1-C4-alkyl esters of methacrylic or acrylic acid, the alkyl radical~ being monosubstituted by phenyl or naphthyl, the naphthol and phenol which is unsubstituted or substituted by up 45 to two C1-C4-alkyl groups, such as phenyl acrylate, phenylethyl methacrylate, phenylethyl acrylate, benzyl methacrylate, benzyl acrylate, phenylpropyl methacrylate, phenylpropyl acrylate, 21~131 phenylbutyl methacrylate, phenylbutyl acrylate, 4-methylphenyl acrylate and naphthyl acrylate, and phenoxyethyl methacrylate and phenoxyethyl acrylate;
5 vinyl methyl ether and compatible mixtures thereof.
Styrene, a-methylstyrene and styrenes alkylated in the nucleus with C1-C8-alkyl, such as p-methylstyrene or tert-butylstyrene are preferably used as the styrene c~ ,oulld of the general formula 10 (I) (component (a21)), particularly preferably styrene and a-me-thylstyrene.
According to the invention, methyl methacrylate (MMA), ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, 15 n-butyl methacrylate, isobutyl methacrylate, sec-butyl meth-acrylate, tert-butyl methacrylate, pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methylacrylate or 2-ethylhexyl methacrylate, particularly preferably methyl methacrylate, are used as C1-C8-alkyl esters of methacrylic or 20 acrylic acid, as well as mixtures of these monomers, methyl acrylate (MA), ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate or 2-ethylhexyl acrylate, particularly preferably n-butyl 25 acrylate, and mixtures of these monomers with one another and with the methacrylates and/or styrene compounds of the general formula I.
According to the invention, monomers selected from the group con-30 sisting of methacrylonitrile, acrylonitrile, N-C1-C8-alkyl-, N-Cs-C8-cycloalkyl- and N-C6-C10-aryl-substituted maleimides, such as N-methyl-, N-phenyl-, N-dimethylphenyl- and N-cyclohexyl-maleimide and maleic anhydride, preferably acrylonitrile, are, if desired, used as monofunctional comonomers (component (a22)).
~5 In a preferred embodiment, a mixture of styrene (S) and acrylo-nitrile (AN) in a molar S/AN ratio of, usually, from 4.5:1 to 0.5:1, preferably from 2.2:1 to 0.65:1, styrene alone, a mixture of acrylonitrile and methyl methacrylate (MMA) or MMA alone is 40 used for producing the graft shell (a2).
Component (A) is prepared by conventional methods, for example by those described in DE-A 3,149,358.
45 For this purpose, the core (al) is first prepared by polymerizihg the aarylate or acrylates (all) and the polyfunctional monomers (al2) which effect crosslinking, with or without the further 214513~
comonomers~(al3), in the conventional aqueous emulsion in a man-ner known per se, at from 20 to 100 C, preferably from 50 to 80 C.
The conventional emulsifiers, such as alkali metal salts of al-kyl- or alkylarylsulfonic acids, alkylsulfate, fatty alcohol sul-5 fonates, salts of higher fatty acids of 10 to 30 carbon atoms,sulfosuccinates, such as Aerosol~ OT (Cyanamid), ether sulfonates such as Disponil~ FES61 (Henkel), or resin soaps, may be used.
Sodium salts of alkanesulfonates or fatty acids of 10 to 18 carbon atoms are preferably taken. It is advantageous to use the 10 emulsifiers in amounts of from 0.3 to 5, in particular from 1 to 2, % by weight, based on the monomers used in the preparation of the core (al). In general, the water/monomer ratio of from 2:1 to 0.7:1 is employed.
15 The polymerization initiators used are in particular the conven-tional persulfates, but redox systems are also suitable. The a~ount of initiators depends as a rule on the desired molecular weight and is usually from 0.1 to 1 % by weight, based on the monomers used in the preparation of the core (al).
The polymerization asgistants which may be used in the polymer-ization are the conventional buffer substances by means of which a pH of, preferably, from 6 to 9 is obtained, for example sodium bicarbonate and sodium pyrophosphate, and from 0 to 3 % by weight 25 of a molecular weight regulator, such as a mercaptan, a terpinol or dimeric alpha-methylstyrene.
The exact polymerization conditions, in particular the type, metering and amount of the emulsifier, are as a rule determined 30 specifically within the abov -ntioned ranges so that the result-ing latex of the crosslinked acrylate polymer (al) has a d50 value of from 60 to 1000 nm, preferably from 80 to 800 nm, particularly preferably from 100 to 600 nm. The particle size distribution of the latex should preferably be narrow.
In principle, it is also possible to prepare the grafting base by a method other than that of emulsion polymerization, for example by mass or solution polymerization, and subsequently to emulsify the polymers obtained. The processes for this purpose are known.
The graft rubber particles (A) usually have a particle size (d50) of from 60 to 1500 nm, preferably from 100 to 1200 nm.
In order to obtain a very tough molding material, graft rubber 45 particles (A) having a particle size (d50) of from 200 to 1000 nm are used in a preferred embodiment.
21gS13~
-In a further preferred embodiment, a mixture of graft rubber par-ticles (A) of different sizes and having a bimodal particle size distribution is used. Particularly preferably, from 0.5 to 99.5 %
by weight of this mixture have a particle size (d50) with a mean 5 diameter of from 200 to 1000 nm, and from 99.5 to 0.5 % by weight of the mixture have a particle size (dsO) with a mean diameter of from 60 to 190 nm.
The chemical composition of the two graft copolymers is prefer-10 ably the same, although the shell of the coarse-particled graft copolymers may in particular have a two-stage composition.
The graft shell (component (a2)) is also prepared, as a rule, by known polymerization methods, such as emulsion, mass, solution or 15 suspension polymerization, preferably an aqueous emulsion in the presence of an aqueous emulsion of the core (al) (cf. DE-A
1,260,135, DE-A 3,149,358 and German Patent 1,164,080). In a preferred embodiment, the graft copolymerization is carried out in the same system as the polymerization of the core (al), and, 20 if required, further emulsifier and initiator may be added. These need not be identical to the emulsifiers or initiators used for the preparation of the core (al). Emulsifier, initiator and polymerization assistants may each be initially taken alone or as a mixture for the emulsion of the core (al). Any possible com-25 bination or initially taken mixture and feed on the one hand andinitiator, emulsifier and polymerization assistants on the other hand is suitable. The preferred embodiments are known to a person skilled in the art. The monomer or monomer mixture to be grafted on may be added to the reaction mixture all at once, batchwise in 30 a plurality of stages or continuously during the polymerization.
C2-C8-Alpha-olefins, such as ethene, propene, but-l-ene, pent-1-ene, hex-1-ene, hept-1-ene and oct-l-ene, or mixtures thereof may be used as alpha-olefins for the preparation of component 35 (~), preferably ethene and propene.
Examples of polar comonomers which, according to the invention, should not include vinyl acetate and vinylaromatic monomers are alpha-beta-unsaturated C3-C8-carboxylic acids and available 40 anhydrides thereof, such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid and glycidyl esters thereof and esters with C1-C8-alkyl alcohols whose alkyl radicals may be monosubstituted by phenyl or naphthyl, naphthol and phenol which is unsubstituted or substituted by up 45 to two Cl-C4-alkyl groups, such as methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, pentyl acrylate, hexyl acrylate, 2-ethylhexyl 214513~
acrylate, 2-ethylhexyl methacrylate, glycidyl methacrylate, phenyl acrylate, phenylethyl methacrylate, phenylethyl acrylate, benzyl methacrylate, benzyl acrylate, phenylpropyl methacrylate, phenylpropyl acrylate, phenylbutyl methacrylate, phenylbutyl 5 acrylate, 4-methylphenyl acrylate and naphthyl acrylate, and phenoxyethyl methacrylate and phenoxyethyl acrylate;
methacrylonitrile, acrylonitrile;
10 carbon monoxide.
In a preferred embodiment, copolymers which can be prepared from (I) 40-75 % by weight of ethylene, 5-20 % by weight of carbon monoxide and 20-40 % by weight of n-butyl acrylate, for example 15 commercially available as ELVALOY~ HP-4051 (DuPont), or (II) 50-98,9 % by weight of ethylene, 1-45 % by weight of n-butyl acrylate, 0,1-20 % by weight of methacrylic and/or acrylic acid and~or maleic anhydride are used as component (B).
20 The copolymers (B) are prepared in a manner known per se (cf.
US 2,897,183 and US 5,057,593). The preparation is usually car-ried out by free radical polymerization. The initiators used are, as a rule, peroxides, such as lauryl peroxide, tert-butyl perace-tate, tert-butyl peroxypivalate, di-tert-butyl peroxide, di-(sec-25 butyl) peroxydicarbonate, tert-butyl peroctoate and tert-butyl perisononanoate, preferably tert-butyl peroxypivalate and tert-butyl perisononanoate. In general, azo-containing initiators, such as azobisisobutyronitrile, are also suitable.
30 The choice of the suitable initiator is usually made dependent on the polymerization temperature to be chosen, which as a rule is from 100 to 300 C, preferably from 130 to 280 C. The pressure dur-ing the polymerization is chosen as a rule in the range from 100 to 400, preferably from 150 to 250, MPa. The amount of initiator 35 is chosen in general to be from 1 to 50, preferably from 2 to 20 mol per 106 mol of the amount of polar copolymer used.
The polymerization is usually carried out in a continuous stirred reactor. Such a reactor is described in, for example, 40 US 2,897,183. The reaction time is as a rule from 30 to 1, pre-ferably from 5 to 2, minutes. Observations to date have shown that the use of a solvent is optional.
The vinylaromatic monomers (component (cl)) used are styrene, 45 substituted styrenes of general formula (I), which have already been stated as component (a21), or the C1-C8-alkyl esters of methacrylic or acrylic acid, stated under component (a21).
2i4513~
Styrene, alpha-methylstyrene and p-methylstyrene are preferably used.
If desired, monomers Which have already been stated as component 5 (a22) may be used as monofunctional comonomers (cG.,.ponent (c2)).
If desired, the Cl-Cg-alkyl esters of methacrylic and acrylic acid, stated under component (a21), may furthermore be mixed with the monomers stated under component (a21) and the mixture used as component (c2).
In a preferred embodiment, a mixture of styrene (S) and acryloni-trile (AN), S and a-methylstyrene, optionally mixed with methyl methacrylate or maleimides, or methyl methacrylate, if desired with methyl acrylate, is used.
The polymers of component (C) are as a rule known and are obtain-able by methods known per se (cf. Runststoff-Handbuch, Vieweg-Daumiller, Volume V (Polystyrol), Carl-Hanser-Verlag, Munich 1969, page 124, lines 12 et seq.). The polymerization i8 carried 20 out as a rule by free radical emulsions, suspension, solution or mass polymerization. In general, the polymers (C) have viscosity numbers (VN) (measured in a 0.5 % strength by weight solution in dimethylformamide at 23 C [~spec/C in cm3/g]) of from 40 to 160, which corresponds to average molecular weights Mw of from 40,000 25 to 2,000,000.
The novel thermoplastic molding materials may contain, as further component D), up to 50, in particular from 0.1 to 20, % by weight, based on the total material (A) + (B) + (C), of fibrous 30 or particulate fillers or of mixtures thereof. These are prefer-ably commercially available products. Processing assistants and stabilizers, such as UV stabilizers, lubricants and antistatic agents, are usually used in amounts of from 0.01 to 5 % by weight, but reinforcing agents, such as carbon fibers and glas~
35 fibers, in general in an amount of from 5 to 40 % by weight.
Fillers or reinforcing materials, such as glass beads, mineral fibers, whiskers, alumina fibers, mica, quartz powder and wollas-tonite, may also be added.
The novel molding materials may also contain further additives which are typical and conventionally used for styrene/acryloni-trile (SAN) polymers and graft copolymers based on acrylonitrile/
styrene/acrylates (ASA) or mixtures thereof. Examples of such ad-45 ditives are dyes, pigments, antistatic agents, antioxidants andin particular the lubricants which are required for further pro-cessing of the molding material, for example in the production of `` 214513~
moldings or shaped articles, in particular up to 10 ~ by weight of plasticizers and, if desired, polar copolymers having anti-static activity, such as ethylene oxide/propylene oxide copoly-mers.
The novel thermoplastic molding materials are usually prepared by processes known per se, by mixing the components (A), (B) and, if desired, (C) and/or (D). It may be advantageous to premix indi-vidual components. It is also possible to mix the components in lO solution and remove the solvents. However, mixing of the compo-nents is preferably carried out at from 200 to 320 C by extruding or kneading the components together or treating them in a roll mill, if necessary the c~l"~onents having been isolated beforehand from the solution obtained in the polymerization or from the 15 aqueous emulsion.
The novel thermoplastic molding materials can be processed by the known methods for processing thermoplastics, for example by ex-trusion, injection molding, calendering, blowmolding, pressing or 20 sintering.
In a further preferred embodiment, halogen-free films having a leather-like appearance, stable to aging and containing only a small amount of volatile c~ ~_nents are produced by, usually, 25 calendering and, if desired, subsequent deep drawing of the films, by using, as component (~), a copolymer prepared from 45-S5 % by weight of ethylene, 11-15 % by weight of carbon monoxide and 30 30-36 % by weight of n-butyl acrylate according to US 2,897,183 or US 5,057,593, and, as component (C), a copolymer prepared by continuous solution polymerization of 35 65 % by weight of styrene and 35 % by weight of acrylonitrile, having a viscosity number of 80 ml/g (measured in a 0.5 %
strength by weight solution in dimethylformamide at 23 C. A graft 40 copolymer having a core comprising essentially n-butyl acrylate which is crosslinked with tricyclodecenyl acrylate and a graft shell prepared from 60-90 % by weight of styrene and 40-10 % by weight of acrylonitrile, according to DE-A 3,149,358, is prefer-ably used as component (A). Such novel films are preferably used 45 for the interior trim of commercial vehicles, such as auto-mobiles, aircraft, ships and trains.
`` 214513~
~_ 12 The films~which can be prepared from the novel thermoplastic molding materials have a balanced ratio of tensile strength, elongation at break, tear propagation strength, hardness and col-or stability during processing, compared with those of the prior 5 art.
Examples The mean particle size and the particle size distribution were lO determined from the integral mass distribution. In all cases, the mean particle sizes are the weight average of the particle sizes, as determined by means of an analytical ultracentrifuge using the method of W. Scholtan and H. Lange, Kolloid-Z., and Z. Polymere 250 (1972), 782-796. The ultracentrifuge measurement gives the 15 integral mass distribution of particle diameter of a sample. From this it iQ possible to determine the percentage by weight of the particles which have a diameter equal to or smaller than a cer-tain size. The mean particle diameter, which i8 also referred to as the d50 value of the integral mass distribution, is defined as 20 the particle diameter at which 50 ~ by weight of the particles have a diameter smaller than the diameter which corresponds to the d50 value. Likewise, 50 % by weight of the particles then have a diameter larger than the d50 value. To characterize the width of the particle size distribution of the rubber particles, the dlo 25 and dgo values obtained from the integral mass distribution are used in addition to the d50 value (mean particle diameter). The dlo and dgo values of the integral mass distribution are defined similarly to the d50 value, except that they are based on 10 and 90 % by weight, respectively, of the particles. The quotient dgo - dlo = Q
d50 35 is a measure of the width of the particle size distribution.
The following components were used:
A. A coarse-particled graft polymer which was prepared as fol-lows:
1.5 g of the finely divided butyl acrylate latex prepared ac-cording to EP-~ 6503, page 12, line 55, to page 13, line 22, were initially taken, 50 g of water and 0.1 g of potassium persuflate were added and then, in the course of 3 hours, a mixture of 49 g of butyl acrylate and 1 g of tricyclodecenyl acrylate on the one hand and a solution of 0.5 g of the ` 2i4~134 _ 13 sodium~salt of a C12-C1g-paraffinsulfonic acid in 25 g of wa-ter on the other hand were introduced at 60 C. Polymerization was then continued for 2 hours. The resulting latex of the crosslinked butyl acrylate polymer had a solids content of 40 ~ by weight. The mean particle size (d50) (weight average of the latex) was determined as 430 nm, and the particle size distribution was narrow (Q = 0.1).
150 g of the latex prepared above were mixed with 20 g of styrene and 60 g of water, a further 0.03 g of potassium per-sulfate and 0.05 g of lauroyl peroxide were added and the mixture was then heated at 65 C for 3 hours while stirring.
The emulsion obtained in this graft copolymerization was then polymerized with 20 g of a mixture of styrene and acrylo-nitrile in a weight ratio of 75:25 for a further 4 hours. The reaction product was then precipitated from the emulsion by means of a calcium chloride solution at 95 C, isolated, washed with water and dried in a warm air stream. The degree of grafting of the graft copolymer was determined as 35 ~.
The mean particle size (d50) of the latex particles was 510 nm.
Bl) A copolymer prepared from ethylene, carbon monoxide and 30 %
by weight of n-butyl acrylate (Elvaloy0 HP-40Sl from DuPont prepared similarly to Example 2 in US 5,057,593).
B2) An ethylene/vinyl acetate copolymer (Luwax0 EVAl (BASF); melt viscosity at 140C 1500 mm2/sec).
30 A copolymer prepared from styrene and acrylonitrile in a weight ratio of 65:35 (S:AN) and having a viscosity number of ôO ml/g (measured in a 0.5 ~ strength by weight solution in dimethylform-amide at 23 C) was used as component C. The polymerization was carried out by continuous solution polymerization similarly to 35 Kunststoffe-Handbuch, Vieweg-Daumiller, Volume V (Polystyrol), Carl-Hanser-Verlag, Munich 1969, page 124, line 12 et seq.
The films were produced in a thickness of 0.5 mm, by mixing in a roll mill heated at 200-C. Moldings were punched out from these 40 films, and the tensile test according to DIN 53504 and the tear propagation test according to DIN 53515 were carried out.
The Shore hardness was determined according to DIN 53505.
45 The Vicat A heat distortion resistance was determined (in C) ac-cording to DIN 53460.
214513~
-lg , _ V ., ~ ~ X X X X ", o X `
o, o , , o ,~, o _, o U~ o Ul , ~ o a~ O
.. ~ o~ ' o O I I ~ ~1 a~
o 'U~ , ",, ~ o~
~ n Q ~ ~
Q J U' _~ ~ _ a~ ~ O ~ U
~ Q ~ z, ~ d~ Q~ ~ Z S ~ -~ O
m m u E~ n ~ ~ n-- rn.c ~--214513~
_ 15 In order to determine the volatile components in leather-like films, 2 g of each of the films to be tested, from Examples 2, 3 and 4, were heated in a glass cylinder for 1 hour at 280 C in a 5 stream of nitrogen. The masses used were determined before and after the experiment. The difference between the masses corre-sponded to the amounts of volatile components. The values ob-tained also provide information about the fogging behavior: the greater the loss of mass, ie. the higher the content of volatile 10 components, the greater is the fogging.
Table 2 Example Loss of mass [~ by weight]
15 2 0.67 3 0.75 4 0.82 for comparison Vl 1.08 V2 2.82 The following were used as comparative films:
Vl: Film comprising 80 parts by weight of c~ ,onent ~A), 10 parts by weight of component (C) and 10 parts by weight of a copolymer prepared from 90.5 ~ by weight of ethylene and 9.5 ~ by weight of vinyl acetate (melt viscosity at 120C:
1700 mm2/sec; Luwax~ EVA2 (BASF)), V2: Baymoflex~ A VPKU 3-2069 A (Bayer AG); polymer blend based on acrylonitrile/styrene/acrylate resin:
35 Softening temperature:above about 90C
Density: about l.0 g/cm3 at 20C (DIN 53479) Bulk density: about 250-350 kg/m3 Solubility in water: insoluble Ignition temperature: above 400C (DIN 51794)
Claims (10)
1. A thermoplastic molding material containing essentially (A) from 20 to 99 % by weight of at least one graft copolymer obtainable essentially from (a1) from 30 to 90 % by weight of a core obtainable by poly-merization of a monomer mixture consisting essentially of (a11) from 80 to 99.99 % by weight of at least one C1-C10-alkyl ester of acrylic acid, (a12) from 20 to 0.01 % by weight of a copolymerizable, polyfunctional crosslinking monomer and (a13) from 0 to 40 % by weight of a further copolymerizable, monoethylenically unsaturated monomer, and (a2) from 70 to 10 % by weight of a graft shell obtainable by polymerization of a monomer mixture in the presence of a core (a1), consisting essentially of (a21) from 50 to 100 % by weight of a styrene compound of the formula (I) (I) where R1 and R2, independently of one another, are each hydro-gen or C1-C8-alkyl or of a C1-C8-alkyl ester of methacrylic or acrylic acid, (a22) from 50 to 0 % by weight of a monofunctional comonomer, and (B) from 80 to 1 % by weight of a copolymer obtainable from at least one alpha-olefin and at least one polar comonomer, with the proviso that vinyl acetate or a vinylaromatic monomer are not used as monomers, and (C) from 0 to 50 % by weight, based on the total weight of components (A), (B) and (C), of a thermoplastic polymer obtainable by polymerization of a monomer mixture consisting essentially of (c1) from 50 to 100 % by weight of a vinylaromatic monomer and/or of a C1-C8-alkyl ester of methacrylic or acrylic acid and (c2) from 50 to 0 % by weight of a monofunctional comonomer.
2. A thermoplastic molding material as claimed in claim 1, wherein the mean particle diameter (d50 value) of the graft copolymers (A) is from 60 to 1500 nm.
3. A thermoplastic molding material as claimed in claim 1, wherein the particle size distribution of component (A) is bimodal.
4. A thermoplastic molding material as claimed in claim 3, wherein a mixture of from 0.5 to 99.5 % by weight of a graft copolymer (A) whose mean particle diameter (d50 value) is from 200 to 1000 nm and from 99.5 to 0.5 % by weight of a graft copolymer (A) whose mean particle diameter (d50 value) is from 60 to 190 nm is used as component (A).
5. A thermoplastic molding material as claimed in claim 1, wherein the glass transition temperature of the core (a1) is chosen to be less than 0°C.
6. A process for the preparation of a thermoplastic molding ma-terial as claimed in claim 1 in a manner known per se, where-in (A) from 20 to 99 % by weight of at least one graft copolymer obtainable essentially from (a1) from 30 to 90 % by weight of a core obtainable by polymerization of a monomer mixture consisting essentially of (a11) from 80 to 99.99 % by weight of at least one C1-C10-alkyl ester of acrylic acid, (a12) from 20 to 0.01 % by weight of a copolymerizable, polyfunctional crosslinking monomer and (a13) from 0 to 40 % by weight of a further copolymerizable, monoethylenically unsaturated monomer, and (a2) from 70 to 10 % by weight of a graft shell, obtainable by polymerization of a monomer mixture in the presence of the core (a1) and consisting essentially of (a21) from 50 to 100 % by weight of a styrene compound of the formula (I) (I) where R1 and R2, independently of one another, are each hydrogen or C1-C8-alkyl, or of a C1-C8-alkyl ester of meth-acrylic or acrylic acid, and (a22) from 50 to 0 % by weight of a monofunctional comonomer, are mixed with (B) from 80 to 1 % by weight of a copolymer, obtainable from at least one alpha-olefin and at least one polar comonomer, with the proviso that vinyl acetate or a vinylaromatic monomer is not used as monomers, and with (C) from 0 to 50 % by weight, based on the total weight of components (A), (B) and (C), of a thermoplastic polymer obtainable by polymerization of a monomer mixture consisting essentially of (c1) from 50 to 100 % by weight of a vinylaromatic monomer or of a C1-C8-alkyl ester of methacrylic or acrylic acid and (c2) from 50 to 0 % by weight of a monofunctional comonomer.
7. Use of the thermoplastic molding material as claimed in of claim 1, or prepared as claimed in claim 6, for the produc-tion of moldings and films.
8. A molding or film obtainable by the use as claimed in claim 7.
9. A film having a leather-like appearance and prepared by mix-ing (A) from 20 to 99 % by weight of at least one graft copolymer obtainable essentially from (a1) from 30 to 90 % by weight of a core obtainable by poly-merization of a monomer mixture consisting essentially of (a11) from 80 to 99.99 % by weight of n-butyl acrylate and (a12) from 20 to 0.01 % by weight of a tricyclodecenyl acrylate, and (a2) from 70 to 10 % by weight of a graft shell obtainable by polymerization of a monomer mixture in the presence of the core (a1) and consisting essentially of (a21) from 60 to 90 % by weight of styrene and (a22) from 40 to 10 % by weight of acrylonitrile, and (B) from 80 to 1 % by weight of a copolymer prepared from 45 to 55 % by weight of ethylene, from 11 to 15 % by weight of carbon monoxide and from 30 to 36 % by weight of n-butyl acrylate, and (C) from 0 to 50 % by weight, based on the total weight of components (A), (B) and (C), of a copolymer prepared by continuous solution polymerization of (c1) 65 % by weight of styrene and (c2) 35 % by weight of acrylonitrile, and subsequently carrying out calendering to give films.
10. Use of a film having a leather-like appearance, as claimed in claim 9, for the interior trim of commercial vehicles, air-craft, ships and trains.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4410883A DE4410883A1 (en) | 1994-03-29 | 1994-03-29 | Thermoplastic molding compositions of a graft copolymer and an olefin copolymer |
| DEP4410883.4 | 1994-03-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2145134A1 true CA2145134A1 (en) | 1995-09-30 |
Family
ID=6514149
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002145134A Abandoned CA2145134A1 (en) | 1994-03-29 | 1995-03-21 | Thermoplastic molding materials comprising a graft copolymer and an olefin copolymer |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0675164B1 (en) |
| JP (1) | JPH0848848A (en) |
| KR (1) | KR950032445A (en) |
| AT (1) | ATE166373T1 (en) |
| CA (1) | CA2145134A1 (en) |
| DE (2) | DE4410883A1 (en) |
| ES (1) | ES2116638T3 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6649117B1 (en) | 1999-02-12 | 2003-11-18 | Basf Aktiengesellschaft | Thermoplastic molding materials |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19906064A1 (en) * | 1999-02-12 | 2000-08-17 | Basf Ag | Thermoplastic molding compounds |
| DE19906065A1 (en) * | 1999-02-12 | 2000-08-17 | Basf Ag | Thermoplastic molding compounds |
| DE19906040A1 (en) * | 1999-02-12 | 2000-08-17 | Basf Ag | Thermoplastic molding compounds |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3743489A1 (en) * | 1987-12-22 | 1989-07-13 | Bayer Ag | FLEXIBLE POLYMER BLENDS |
| DE3839856A1 (en) * | 1988-11-25 | 1990-05-31 | Bayer Ag | SOFT, FLEXIBLE POLYMER MIXTURES |
| DE4211415C2 (en) * | 1992-04-04 | 1996-05-23 | Benecke Ag J H | Foil or molded body made of a multi-phase plastic |
-
1994
- 1994-03-29 DE DE4410883A patent/DE4410883A1/en not_active Withdrawn
-
1995
- 1995-03-21 CA CA002145134A patent/CA2145134A1/en not_active Abandoned
- 1995-03-21 EP EP95104122A patent/EP0675164B1/en not_active Expired - Lifetime
- 1995-03-21 DE DE59502211T patent/DE59502211D1/en not_active Expired - Lifetime
- 1995-03-21 AT AT95104122T patent/ATE166373T1/en active
- 1995-03-21 ES ES95104122T patent/ES2116638T3/en not_active Expired - Lifetime
- 1995-03-29 KR KR1019950006878A patent/KR950032445A/en not_active Application Discontinuation
- 1995-03-29 JP JP7071858A patent/JPH0848848A/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6649117B1 (en) | 1999-02-12 | 2003-11-18 | Basf Aktiengesellschaft | Thermoplastic molding materials |
Also Published As
| Publication number | Publication date |
|---|---|
| ATE166373T1 (en) | 1998-06-15 |
| EP0675164A1 (en) | 1995-10-04 |
| KR950032445A (en) | 1995-12-20 |
| JPH0848848A (en) | 1996-02-20 |
| DE59502211D1 (en) | 1998-06-25 |
| EP0675164B1 (en) | 1998-05-20 |
| DE4410883A1 (en) | 1995-10-05 |
| ES2116638T3 (en) | 1998-07-16 |
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| Date | Code | Title | Description |
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| FZDE | Discontinued |