AU2006286869A1 - Molding-compositions composed of filler-reinforced thermoplastic material with very good scratch resistance and soft-touch feel - Google Patents
Molding-compositions composed of filler-reinforced thermoplastic material with very good scratch resistance and soft-touch feel Download PDFInfo
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- AU2006286869A1 AU2006286869A1 AU2006286869A AU2006286869A AU2006286869A1 AU 2006286869 A1 AU2006286869 A1 AU 2006286869A1 AU 2006286869 A AU2006286869 A AU 2006286869A AU 2006286869 A AU2006286869 A AU 2006286869A AU 2006286869 A1 AU2006286869 A1 AU 2006286869A1
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- 239000000203 mixture Substances 0.000 title claims description 54
- 239000012815 thermoplastic material Substances 0.000 title description 2
- 238000000465 moulding Methods 0.000 claims description 59
- 239000011521 glass Substances 0.000 claims description 21
- 239000003365 glass fiber Substances 0.000 claims description 17
- 229920001169 thermoplastic Polymers 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 13
- -1 polybutylene Polymers 0.000 claims description 13
- 229920001577 copolymer Polymers 0.000 claims description 12
- 239000007779 soft material Substances 0.000 claims description 12
- 239000000945 filler Substances 0.000 claims description 10
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 8
- 239000005977 Ethylene Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 239000011324 bead Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 239000003381 stabilizer Substances 0.000 claims description 7
- 239000000654 additive Substances 0.000 claims description 5
- 150000002978 peroxides Chemical class 0.000 claims description 5
- 239000000049 pigment Substances 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000012764 mineral filler Substances 0.000 claims description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 4
- 239000002216 antistatic agent Substances 0.000 claims description 3
- 239000005337 ground glass Substances 0.000 claims description 3
- 244000043261 Hevea brasiliensis Species 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 claims description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims description 2
- 239000003063 flame retardant Substances 0.000 claims description 2
- 229920001910 maleic anhydride grafted polyolefin Polymers 0.000 claims description 2
- 239000000155 melt Substances 0.000 claims description 2
- 229920003052 natural elastomer Polymers 0.000 claims description 2
- 229920001194 natural rubber Polymers 0.000 claims description 2
- 238000010525 oxidative degradation reaction Methods 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920001748 polybutylene Polymers 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 229920005653 propylene-ethylene copolymer Polymers 0.000 claims description 2
- 230000005855 radiation Effects 0.000 claims description 2
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical class [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 2
- 150000004756 silanes Chemical class 0.000 claims description 2
- 229920003051 synthetic elastomer Polymers 0.000 claims description 2
- 229920001897 terpolymer Polymers 0.000 claims description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims 2
- 229920001519 homopolymer Polymers 0.000 claims 1
- 229920001155 polypropylene Polymers 0.000 description 7
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 229920000098 polyolefin Polymers 0.000 description 5
- 238000007792 addition Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000000454 talc Substances 0.000 description 4
- 229910052623 talc Inorganic materials 0.000 description 4
- 239000004416 thermosoftening plastic Substances 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229920001384 propylene homopolymer Polymers 0.000 description 3
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000010456 wollastonite Substances 0.000 description 2
- 229910052882 wollastonite Inorganic materials 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000011990 phillips catalyst Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000009757 thermoplastic moulding Methods 0.000 description 1
- 229920002397 thermoplastic olefin Polymers 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
-
- 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
- C08K3/40—Glass
-
- 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
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
-
- 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
- C08L23/10—Homopolymers or copolymers of propene
-
- 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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- 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
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
WO 2007/025663 PCT/EP2006/008268 1 Molding compositions composed of filler-reinforced thermoplastic material with very good scratch resistance and soft-touch feel The invention relates to polymeric molding compositions composed of a soft 5 material, of a filler, and of a thermoplastic polymer, preferably an olefin polymer. The invention relates further to a process for the preparation of such molding composition by bringing the components together and mixing them, and to the use of such molding composition for the production of moldings with low to high stiffness, with good scratch resistance, and with pleasant soft-touch feel, and also 10 to the use of such moldings. For the purposes of the present application, "soft-touch feel" is a property of the moldings which can be described as a softness perceived as pleasant on contact of the human hand with the surface of the moldings. "Soft-touch feel" is 15 qualitatively determined via a panel composed of five persons of which at least three have to assess the contacted surface as having typical "soft-touch feel" in comparison with an internal sample catalog composed of five different surfaces with and without "soft-touch feel". 20 The reinforcement of plastic by means of glass fibers has been known for a long time period. By way of example, EP-A 663 418 describes a polypropylene molding composition reinforced with glass fibers. However, achievement of good mechanical properties is attended by an unpleasant hardness of the material, felt by the hand on touching the surface of moldings produced therefrom. 25 An object underlying the present invention was therefore to provide a thermoplastic molding composition which exhibits good mechanical properties and at the same time has a pleasant soft-touch feel and in addition thereto maintains a high scratch resistance. 30 Surprisingly, it was found that this object is achieved by the molding composition as mentioned at the outset, which comprises at least a combination of from 5 to 90 % by weight of soft material with from 5 to 60 % by weight of glass material as filler and with from 3 to 70 % by weight of a thermoplastic polymer. The molding 35 composition according to the invention preferably has a melt index MI( 23 0/ 2
.
1 6 ) in the range of from 0.1 to 100 g/10 min and a tensile modulus in the range of from 10 to 4500 MPa preferably from 100 to 4000 MPa more preferred from 130 to 2500 MPa. 40 WO 2007/025663 PCT/EP2006/008268 2 It is an essential feature of the invention that the molding composition comprises from 5 to 90 % by weight, preferably from 10 to 80 % by weight, of soft material. According to the invention, the soft material used can comprise crosslinked or uncrosslinked ethylene-propylene copolymers whose ethylene content is greater 5 than 20 % by weight, or else crosslinked or uncrosslinked ethylene-butene copolymers, or else crosslinked or uncrosslinked ethylene-hexene copolymers, or else crosslinked or uncrosslinked ethylene-propylene-diene-copolymer (EPDM), or else crosslinked or uncrosslinked synthetic or natural rubbers, or else crosslinked or uncrosslinked styrene-ethylene-butadiene terpolymers (SEBS), or 10 else crosslinked or uncrosslinked polybutylene, or else PVC. The particularly preferred amount of soft material of the above type in the molding composition of this invention is in the range of from 10 to 70 % by weight, based on the total weight of the molding composition. 15 Another essential feature of the inventive polyolefin molding composition is a content of from 5 to 60 % by weight of glass material as filler, based on the total weight of the molding composition. The glass material can be spun glass fibers or can be chopped spun glass fibers whose average length is from about 100 pm to 10 mm, or can be glass particles in the form of ground glass or milled glass fibers 20 whose average particle size is in the range from 3 pm to 5 mm, or glass beads whose average bead diameter is in the range from 3 pm to 2 mm, the average length of the glass fibers in the inventive molding composition being in the range from 200 pm to 5 mm, or the average particle size of the glass particles in the inventive molding composition in the form of ground glass or milled glass fibers 25 being in the range from 5 pm to 2 mm, or the average bead diameter of the glass beads in the inventive molding composition being in the range from 5 pm to 2 mm. According to the invention a further preference is that from 5 to 50 % by weight of spun glass fibers are used, particularly preferably from 10 to 40 % by weight. If appropriate, also a combination with other manifestations of glass as 30 described above and/or other mineral fillers is possible. Another essential feature of the molding composition is the content of an amount of from 3 to 70 % by weight of thermoplastic polymer in the inventive molding composition, based on the total weight of the molding composition, preferably 35 from 5 to 50 % by weight. The thermoplastic polymer used may be propylene homopolymer or propylene-ethylene copolymer whose ethylene content is smaller than 20 % by weight, or else polyamide, polyester, polystyrene, polycarbonate, or acrylonitrile-butadiene-styrene terpolymer (ABS), PVC, or the like. According to the invention, preference is given to propylene homo- or 40 WO 2007/025663 PCT/EP2006/008268 3 copolymer. The particularly preferred amounts used of this copolymer being from 10 to 40 % by weight. Very particular preference is given to the use of propylene polymer and in particular use is made here of a propylene homopolymer or a propylene random copolymer having up to 20 % by weight of copolymerized other 5 olefins having up to 10 carbon atoms. These other olefins are in particular C 2
-C
10 1-alkenes, such as ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene or 1 octene, preference being given to use of ethylene, 1-butene, or ethylene and 1 butene. The use of propylene homopolymer is particularly preferred. 10 It is preferable to use an isotactic polypropylene whose fraction insoluble in xylene is above 95 %, preferably above 97 %. The MFR (230 -c / 2.16 kg) of the polyolefin is generally from 0.1 to 2500 g/1 0 min to ISO 1133, preferably from 0.2 to 100 g/10 min, and particularly preferably from 0.3 to 30 g/10 min. Polypropylene molding compositions with monomodal molar mass distribution are 15 also preferred. To couple the glassy fillers to the polymer matrix, it can be advantageous to use a polar-functionalized compatibilizer. To this end, use can be made of low molecular-weight compounds which serve to make the glass component less 20 hydrophilic and therefore more compatible with the polymer. Examples of suitable compounds are peroxides, such as tert.-butyl peroxide, or silanes, such as aminosilanes, epoxysilanes, amidosilanes, acrylic silanes, or maleic-anhyd ride grafted polyolefins. 25 In practice it can also be advantageous for the inventive molding composition also to receive additions of stabilizers with respect to heat, stabilizers with respect to UV radiation, or stabilizers with respect to oxidative degradation, or of pigments, or of antistatic agents, or of flame retardants, or of other known additives, each in amounts respectively usual for these additions. The usual 30 amounts of additions of this type are somewhere in the range from 0.1 to 10 % by weight. The combination of soft material, glassy filler, and thermoplastic gives a molding composition improved over the prior art in relation to the scratch resistance of the 35 moldings produced therefrom. The stiffness of the moldings is expressed in a modulus of elasticity measured to DIN EN ISO 527 or DIN EN ISO 178 in the preferred range from 10 to 4500 MPa. Surprisingly, furthermore, despite the presence of glass as filler, a pleasant "soft-touch feel" is found on the moldings composed of the inventive molding composition, and is qualitatively determined 40 WO 2007/025663 PCT/EP2006/008268 4 via a panel composed of five persons of which at least three have to assess the contacted surface as having typical "soft-touch feel" in comparison with an internal sample catalog composed of five different surfaces with and without "soft touch feel". Another entirely surprising feature is improved scratch resistance of 5 the surface of the moldings composed of the inventive molding composition, expressed qualitatively in dL* values of at most 11.01 using a force of 10 N, measured along to the Volkswagen AG test specification PV 3952. The inventive molding compositions are obtainable via melting and mixing of the 10 individual components, the mixing process using a mixing apparatus at temperatures of from 120 to 400 0C, preferably from 180 to 280 *C, particularly preferably from 200 to 260 C, in the presence or absence of peroxides. Mixing apparatus which can be used here are in particular extruders or kneaders, particularly preferably twin-screw extruders. It can also be advantageous to 15 premix the soft material with the thermoplastic polymers and, if appropriate, with other additives at room temperature in a mixing apparatus. If the glassy fillers used comprise long spun glass fibers, this permits advantageous use of the known pultrusion technique in which the spun glass fibers are coated with the soft material and with the thermoplastic polymer in molten form and extruded through 20 dies. Finally, it is also possible to mix the components in suitable premixes in the machines for production of the finished parts or semifinished products (e.g. injection molding machines). The inventive molding compositions can moreover comprise conventional 25 additives and auxiliaries, such as stabilizers with respect to harmful effects of processing, with respect to thermal oxidation, ageing, effects of UV, neutralizing agents, antistatic agents, waxes or specific low-molecular-weight lubricants, or organic and inorganic pigments and, respectively, pigment preparations, such as carbon black dispersions in polyolefins. The amount of additives and auxiliaries 30 should, however, not exceed 10 % by weight, based on the total amount of the material, preferably 5 % by weight. For optical reasons it can also be advisable to use addition of appropriate suitable colored pigments to the inventive molding compositions to pigment these to give a different, preferably darker, color. 35 The thermoplastic polyolefins used in the inventive molding compositions may be obtained using any of the familiar processes and catalysts. Preference is given to polymerization of the appropriate monomers by means of a Ziegler-Natta catalyst, of a Phillips catalyst based on chromium oxide, or of a metallocene catalyst. Metallocenes here are intended to mean complexes composed of metals of 40 WO 2007/025663 PCT/EP2006/008268 5 groups 3 to 12 of the Periodic Table of the Elements using organic ligands, where these together with metallocenium-ion-forming compounds give effective catalyst systems. 5 To prepare the olefin polymers, use may be made of the conventional reactors used for polymerization of C 2
-C
1 0 olefins. Suitable reactors are inter alia continuously operated horizontal or vertical stirred tanks, circulating reactors, loop reactors, multistage reactors, or fluidized-bed reactors. The size of the reactors is not significant for preparation of the inventive molding compositions. It depends 10 on the output intended to be achieved in the reaction zone or in the individual reaction zones. The polymerization process may be conducted in one or more stages. The polymerization can be carried out in the gas phase, in bulk or suspension, or in a combination thereof. 15 The inventive molding composition is particularly suitable for the production of automotive vehicle parts which are subject to stringent requirements for the surface quality of the material. Use in dark-pigmented motor vehicle parts or those provided with a decorative layer is particularly advantageous, examples being center consoles or dashboard cladding. The surface softness of moldings 20 produced from the inventive molding composition makes them suitable, even when chopped spun glass fibers are used, for high-quality applications which were previously accessible only to other molding compositions. Working examples 1 to 6 25 Various mixtures composed of the soft material SOFTELL CA 02 A, a rubbery C 2 C3 copolymer having a C 2 content of about 40 % and a C3 content of about 60 %, obtainable from Basell in Italy, with chopped glass fibers whose average length is 4.5 mm, obtainable as ECS 03T 480 from Nippon Electric Glass Co., Ltd., and 30 with thermoplastic polypropylene obtainable as MOPLEN HF501 N from Basell in Italy and having an MI( 23 0/ 2
.
1 6 ) of 12 g/10 min are prepared in a ZSK 53 twin-screw extruder from Coperion-Werner&Pfleiderer at a temperature of 230 *C. Di-tert butyl peroxide and finally ground talc whose average grain size was 1.4 pm were also added in some inventive examples, the grain size of the talc being 35 determined by the Sedigraph method. Table 1 below gives the precise constitution of the mixtures. 40 WO 2007/025663 PCT/EP2006/008268 6 Table 1 Working 1 2 3 4 5 6 example 5 Soft mat. 69.5 % 59.5 % 70 % 60 % 68.5 % 58.5 % Glass 20 % 20% --- --- --- particles 10 Glass fibers --- ---- 20% 20% 20% 20% Thermoplastic 10% 20% 10% 20% 10% 20% Polypropylene 15 Peroxide 0.5 % 0.5 % --- --- 0.5 % 0.5 % Talc --- --- --- --- 1 % 1 % 20 The mixtures pursuant to the working examples 1 through 6 were used to produce test specimens in accordance with the standard DIN EN ISO 294-1. The test specimens were used to determine the following features: 25 + M1 230
/
2
.
16 in [g/10 min] to DIN EN ISO 1133 + Tensile modulus in [MPa] to DIN EN ISO 527/1+2 30 + Shore hardness A 3s to DIN EN ISO 868 + Shore hardness D 3s to DIN EN ISO 868 + Scratch resistance dL* to the Volkswagen AG test specification VW 35 PV 3952 on sample sheets with "K-85" surface grain using a loading weight of 10 N. + Soft-touch feel measured by the comparison method explained at the outset, in which the meanings of the symbols are as follows: (+) means 40 WO 2007/025663 PCT/EP2006/008268 7 good soft-touch feel, (±) means moderate soft-touch feel, and (-) means poor soft-touch feel. The results of the inventive examples 1 to 6 are illustrated in table 2 below 5 Table 2 10 Working 1 2 3 4 5 6 example M1 230
/
2
.
1 6 5.98 7.55 0.51 0.83 6.32 9.16 15 Tensile 139 188 561 1089 668 1555 modulus Shore 85 88 82 89 88 90 hardness 20 A 3s Shore 30 36 37 45 37 48 hardness D3s 25 Scratch -0.4 0.1 -0.3 -0.1 -0.1 0.03 resistance Soft-touch (+) (+) (+) (+) (+) (+) 30 feel Comparative examples 1 to 6 35 For comparison, other mixtures in which one of the inventively used components was omitted were prepared in the ZSK 53 twin-screw extruder used in working examples 1 to 6 under the same conditions, their precise constitutions being identified in table 3 below. 40 WO 2007/025663 PCT/EP2006/008268 8 Table 3 Comparison CE 1 CE 2 CE 3 CE 4 CE 5 CE 6 5 Soft mat. 80% 70% 60% 70% 89.5% 79% Glass --- --- --- --- 10% 20% particles 10 Wollastonite 20 % 20 % 20 % 29% --- -- Thermoplastic --- 10 % 20% --- --- -- Polypropylene 15 Peroxide --- --- --- --- 0.5 % 1 % Talc --- --- --- 1% --- -- 20 Specimens were then produced as in working examples 1 to 6 from the mixtures of comparative examples CE 1 to CE 6. The test specimens were then used with the same test methods to determine features which were the same as those determined in working examples 1 to 6. 25 The results of the measurements are illustrated in table 4 below. 30 35 40 WO 2007/025663 PCT/EP2006/008268 9 Table 4 Comparison CE 1 CE 2 CE 3 CE4 CE5 CE 6 5 M1 230
/
2
.
1 6 5.9 6.64 7.62 8.72 6.41 5.6 Tensile 50 123 269 58 32 49 modulus 10 Shore 75 82 86 77 75 78 hardness A3s Shore 19 27 36 21 20 22 15 hardness D3s Scratch 1.9 3 2.3 3.4 -2 -1.4 resistance 20 Soft-touch (+) () (-) (±) (+) (+) feel 25 From the inventive examples in comparison with the comparative examples, it becomes clear that the inventive combination of a soft material with a glassy filler and with a thermoplastic polymer achieves very good scratch resistance and a pleasant soft-touch feel. If, by way of example, the molding composition does not 30 comprise the thermoplastic polymer, or if, by way of example, a mineral filler, such as Wollastonite, is used to replace the glass material, the scratch resistance of the sample sheets is poor. 35 * * * * * 40
Claims (12)
1. A polymeric molding composition for production of self-supporting moldings with good stiffness, with high scratch resistance, and with pleasant soft-touch feel, which polymeric molding composition comprises 10 at least a combination of from 5 to 90 % by weight of soft material with from 5 to 60 % by weight of glass material as filler and with from 3 to 70 % by weight of a thermoplastic polymer.
2. The polymeric molding composition according to claim 1, which has a melt 15 index MI( 23 0/ 2 . 1 6 ) in the range of from 0.1 to 100 g/10 min and a tensile modulus in the range of from 10 to 4500 MPa.
3. The polymeric molding composition according to claim 1 or 2, which comprises from 10 to 80 % by weight of soft material selected from the 20 group of crosslinked or uncrosslinked ethylene-propylene copolymers whose ethylene content is greater than 20 % by weight, crosslinked or uncrosslinked ethylene-butene copolymers, crosslinked or uncrosslinked ethylene-hexene copolymers, crosslinked or uncrosslinked ethylene propylene-diene-copolymer (EPDM), or else crosslinked or uncrosslinked 25 synthetic or natural rubbers, crosslinked or uncrosslinked styrene ethylene-butadiene terpolymers (SEBS), crosslinked or uncrosslinked polybutylene, or PVC.
4. The polymeric molding composition according to one or more of claims 1 30 to 3, which comprises from 5 to 50 % by weight of glass material as filler, based on the total weight of the molding composition, where the glass material is spun glass fibers or is chopped spun glass fibers whose average length is in the range of from 100 pm to 10 mm or is glass particles in the form of ground glass or milled glass fibers whose average 35 particle size is in the range of from 3 pm to 5 mm, or glass beads or hollow glass beads whose average bead diameter is in the range of from 3 pm to 2 mm. 40 WO 2007/025663 PCT/EP2006/008268 11
5. The polymeric molding composition according to one or more of claims 1 to 4, which comprises, if appropriate in combination with the soft material with the glass material and with the thermoplastic polymer also mineral fillers. 5
6. The polymeric molding composition according to claim 4 or 5, which comprises from 10 to 40 % by weight of chopped spun glass fibers, if appropriate in combination with other manifestations of glass material or with mineral fillers. 10
7. The polymeric molding composition according to one or more of claims 1 to 6, which comprises an amount of from 5 to 50 % by weight of thermoplastic polymer, based on the total weight of the molding composition, the thermoplastic polymer used comprising propylene 15 homopolymer or polypropylene-ethylene copolymer whose ethylene content is smaller than 20 % by weight, or polyamide, polyester, polystyrene, polycarbonate, or acrylonitrile-butadiene-styrene terpolymer (ABS), or PVC or the like. 20
8. The polymeric molding composition according to claim 7, which comprises, as thermoplastic polymer, an amount of from 10 to 40 % by weight of propylene homo- or copolymers.
9. The polymeric molding composition according to one or more of claims 1 25 to 8, which also comprises a polar-functionalized compatibilizer selected from the group comprising peroxides or silanes, such as aminosilanes, epoxysilanes, amidosilanes, acrylic silanes, or maleic anhydride-grafted polyolefins. 30
10. The polymeric molding composition according to one or more of claims 1 to 9, which also comprises stabilizers with respect to heat, stabilizers with respect to UV radiation, or stabilizers with respect to oxidative degradation, or pigments, or antistatic agents, or flame retardants, or other additives, each of them in advantageous amounts. 35
11. A process for the preparation of a molding composition according to one or more of claims 1 to 10, in which the individual components are brought together and are mixed and/or kneaded at temperatures in the range of from 120 to 400 *C and are cooled subsequently. 40 WO 2007/025663 PCT/EP2006/008268 12
12. The use of a polymeric molding composition according to one or more of claims 1 to 10 for the preparation of moldings for the automotive industry or for household devices. 5 10 15 20 25 30 35 40
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102005041423.0 | 2005-08-31 | ||
| DE200510041423 DE102005041423A1 (en) | 2005-08-31 | 2005-08-31 | Polymer molding material, useful e.g. to manufacture automatic basic shaped parts for automobile industry, comprises combination of soft material with glass as filler and with thermoplastic plastic, optionally together with additives |
| US72002305P | 2005-09-23 | 2005-09-23 | |
| US60/720,023 | 2005-09-23 | ||
| PCT/EP2006/008268 WO2007025663A1 (en) | 2005-08-31 | 2006-08-23 | Molding-compositions composed of filler-reinforced thermoplastic material with very good scratch resistance and soft-touch feel |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| AU2006286869A1 true AU2006286869A1 (en) | 2007-03-08 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU2006286869A Abandoned AU2006286869A1 (en) | 2005-08-31 | 2006-08-23 | Molding-compositions composed of filler-reinforced thermoplastic material with very good scratch resistance and soft-touch feel |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP1920001A1 (en) |
| JP (1) | JP2009506177A (en) |
| KR (1) | KR20080048473A (en) |
| AU (1) | AU2006286869A1 (en) |
| CA (1) | CA2618846A1 (en) |
| RU (1) | RU2008112217A (en) |
| WO (1) | WO2007025663A1 (en) |
Families Citing this family (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2442535B (en) | 2006-10-05 | 2011-07-13 | Ngf Europ Ltd | Method and articles |
| WO2008100331A1 (en) | 2007-02-15 | 2008-08-21 | Dow Global Technologies, Inc. | Thermoplastic fiber concentrate methods and articles |
| WO2009055482A1 (en) * | 2007-10-22 | 2009-04-30 | Dow Global Technologies, Inc. | Polymeric compositions and processes for molding articles |
| ES2433216T3 (en) * | 2008-05-15 | 2013-12-10 | Saudi Basic Industries Corporation | Scratch resistant molded article made from a loaded polypropylene composition |
| CN102918099B (en) | 2010-05-21 | 2015-12-16 | 博瑞立斯有限公司 | Composition |
| GB201012554D0 (en) * | 2010-07-27 | 2010-09-08 | Thompson Gary | Process for manufacturing a building material |
| CN103717659B (en) | 2011-08-08 | 2017-06-23 | 科思创德国股份有限公司 | The polymer composition that is filled through and can co-extrusion ejecting plate therefrom |
| EP2754691B1 (en) | 2011-09-08 | 2016-02-10 | Japan Polypropylene Corporation | Fiber-reinforced polypropylene resin composition and molded article thereof |
| EP3181637B1 (en) * | 2011-09-21 | 2017-11-29 | Borealis AG | Moulding composition |
| KR101397076B1 (en) * | 2012-09-28 | 2014-05-19 | 롯데케미칼 주식회사 | Polymer resin composition and resin molded aritcle |
| US20150315365A1 (en) | 2012-12-07 | 2015-11-05 | Japan Polypropylene Corporation | Fiber-reinforced polypropylene resin composition and molded article of same |
| US9580586B2 (en) | 2012-12-12 | 2017-02-28 | Asahi Kasei Plastics North America, Inc. | Polypropylene compounds with enhanced haptics |
| KR101325584B1 (en) * | 2013-06-25 | 2013-11-06 | 현대이피 주식회사 | A thermoplastic resin composite composition for long fiber reinforced thermoplastic |
| CN105492527B (en) | 2013-08-28 | 2018-09-18 | Sabic环球技术有限责任公司 | Flexible touch composition and its product |
| KR101646398B1 (en) | 2014-12-05 | 2016-08-05 | 현대자동차주식회사 | Rubber Composition for Weather Strip Glass Run Channel |
| US10233316B2 (en) | 2015-04-13 | 2019-03-19 | Sabic Global Technologies B.V. | Thermoplastic composition and article |
| JP6770796B2 (en) | 2015-09-24 | 2020-10-21 | 日本ポリプロ株式会社 | Fiber reinforced polypropylene resin composition |
| US10759923B2 (en) | 2015-10-05 | 2020-09-01 | Albany International Corp. | Compositions and methods for improved abrasion resistance of polymeric components |
| KR101812894B1 (en) | 2016-09-19 | 2018-01-30 | 롯데케미칼 주식회사 | Glass fiber-reinforced high impact polypropylene resin |
| CN111138757A (en) * | 2019-12-27 | 2020-05-12 | 上海普利特复合材料股份有限公司 | Soft touch polypropylene composite material capable of realizing fast-beat injection molding and high rigidity-toughness balance performance and preparation method thereof |
| KR20240017933A (en) | 2021-06-10 | 2024-02-08 | 바셀 폴리올레핀 이탈리아 에스.알.엘 | Polypropylene composition and light source coating material made therefrom |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59226041A (en) * | 1983-06-08 | 1984-12-19 | Mitsubishi Petrochem Co Ltd | Filler-containing propylene polymer composition |
| JPH05154962A (en) * | 1991-12-03 | 1993-06-22 | Sekisui Chem Co Ltd | Fiber reinforced thermoplastic resin laminated sheet for thermoforming, fiber reinforced thermoplastic resin laminated profile molded product and production thereof |
| WO1997033941A1 (en) * | 1996-03-15 | 1997-09-18 | Amoco Corporation | Stiff, strong, tough glass-filled olefin polymer |
| JP3492847B2 (en) * | 1996-04-26 | 2004-02-03 | 日本プラスト株式会社 | Polyolefin automotive interior parts |
| TW200521164A (en) * | 2003-10-21 | 2005-07-01 | Basell Polyolefine Gmbh | Molding compositions composed of a glass fiber-reinforced olefin polymer |
-
2006
- 2006-08-23 WO PCT/EP2006/008268 patent/WO2007025663A1/en active Application Filing
- 2006-08-23 EP EP06777025A patent/EP1920001A1/en not_active Withdrawn
- 2006-08-23 CA CA002618846A patent/CA2618846A1/en not_active Abandoned
- 2006-08-23 RU RU2008112217/04A patent/RU2008112217A/en not_active Application Discontinuation
- 2006-08-23 JP JP2008528384A patent/JP2009506177A/en not_active Withdrawn
- 2006-08-23 KR KR1020087005093A patent/KR20080048473A/en not_active Application Discontinuation
- 2006-08-23 AU AU2006286869A patent/AU2006286869A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| EP1920001A1 (en) | 2008-05-14 |
| KR20080048473A (en) | 2008-06-02 |
| WO2007025663A1 (en) | 2007-03-08 |
| JP2009506177A (en) | 2009-02-12 |
| RU2008112217A (en) | 2009-10-10 |
| CA2618846A1 (en) | 2007-03-08 |
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