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
• • 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

Definitions

• 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 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 to the use of such moldings.
• 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 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”.
• EP-A 663 418 describes a polypropylene molding composition reinforced with glass fibers.
• 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.
• 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.
• 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 composition according to the invention preferably has a melt index M I (230/2.16) 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. 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.
• the soft material used can comprise crosslinked or uncrosslinked ethylene-propylene copolymers whose ethylene content is greater 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) 1 or 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.
• the glass material can be spun glass fibers or can be chopped spun glass fibers whose average length is from about 100 ⁇ m to 10 mm, or can be glass particles in the form of ground glass or milled glass fibers whose average particle size is in the range from 3 ⁇ m to 5 mm, or glass beads whose average bead diameter is in the range from 3 ⁇ m to 2 mm, the average length of the glass fibers in the inventive molding composition being in the range from 200 ⁇ m 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 being in the range from 5 ⁇ m to 2 mm, or the average bead diameter of the glass beads in the inventive molding composition being in the range from 5 ⁇ m to 2 mm.
• 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 described above and/or other mineral fillers is possible.
• thermoplastic polymer in the inventive molding composition, based on the total weight of the molding composition, preferably 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 copolymer.
• the particularly preferred amounts used of this copolymer being from 10 to 40 % by weight.
• propylene polymer in particular use is made here of a propylene homopolymer or a propylene random copolymer having up to 20 % by weight of copolymerized other 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.
• an isotactic polypropylene whose fraction insoluble in xylene is above 95 %, preferably above 97 %.
• the MFR ( 230 ° c / 2.16 k g) of the polyolefin is generally from 0.1 to 2500 g/10 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 also preferred.
• a polar-functionalized compatibilizer To couple the glassy fillers to the polymer matrix, it can be advantageous to use a polar-functionalized compatibilizer.
• a polar-functionalized compatibilizer To this end, use can be made of low- molecular-weight compounds which serve to make the glass component less hydrophilic and therefore more compatible with the polymer.
• suitable compounds are peroxides, such as tert.-butyl peroxide, or silanes, such as aminosilanes, epoxysilanes, amidosilanes, acrylic silanes, or maleic-anhydride- grafted polyolefins.
• 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 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 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.
• a pleasant "soft-touch feel” is found on the moldings composed of the inventive molding composition, and is 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”.
• Another entirely surprising feature is improved scratch resistance of the surface of the moldings composed of the inventive molding composition, expressed qualitatively in dl_* values of at most
• the inventive molding compositions are obtainable via melting and mixing of the individual components, the mixing process using a mixing apparatus at temperatures of from 120 to 400 0 C, preferably from 180 to 280 0 C, particularly preferably from 200 to 260 0 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 premix the soft material with the thermoplastic polymers and, if appropriate, with other additives at room temperature in a mixing apparatus.
• 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 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 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.
• 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 should, however, not exceed 10 % by weight, based on the total amount of the material, preferably 5 % by weight.
• 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 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.
• 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 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.
• 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 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.
• Soft mat 69. 5 % 59. 5 % 70 % 60 % 68.5 % 58.5 %
• test specimens were used to produce test specimens in accordance with the standard DIN EN ISO 294-1.
• test specimens were used to determine the following features:
• Soft-touch feel measured by the comparison method explained at the outset, in which the meanings of the symbols are as follows: (+) means good soft-touch feel, ( ⁇ ) means moderate soft-touch feel, and (-) means poor soft-touch feel.
• 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.
• 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 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.

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Compositions Of Macromolecular Compounds (AREA)

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Citations (5)

• 2006
  • 2006-08-23 JP JP2008528384A patent/JP2009506177A/ja not_active Withdrawn
  • 2006-08-23 AU AU2006286869A patent/AU2006286869A1/en not_active Abandoned
  • 2006-08-23 KR KR1020087005093A patent/KR20080048473A/ko not_active Application Discontinuation
  • 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 WO PCT/EP2006/008268 patent/WO2007025663A1/en active Application Filing
  • 2006-08-23 RU RU2008112217/04A patent/RU2008112217A/ru not_active Application Discontinuation

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