CA2270715A1 - Thermoplastic polymer compositions - Google Patents
Thermoplastic polymer compositions Download PDFInfo
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- CA2270715A1 CA2270715A1 CA002270715A CA2270715A CA2270715A1 CA 2270715 A1 CA2270715 A1 CA 2270715A1 CA 002270715 A CA002270715 A CA 002270715A CA 2270715 A CA2270715 A CA 2270715A CA 2270715 A1 CA2270715 A1 CA 2270715A1
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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
- C08L23/10—Homopolymers or copolymers of propene
-
- 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
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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
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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
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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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
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
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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
-
- 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
- C08L23/0876—Neutralised polymers, i.e. ionomers
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Abstract
A thermoplastic polymer composition contains polypropylene, uncrosslinked ethylene propylene copolymer rubber, an ionomeric copolymer, a copolymer of ethylene and glycidyl acrylate or glycidyl methacrylate, inorganic filler and optionally an uncrosslinked ethylene propylene copolymer rubber grafted with an .alpha.,.beta.-unsaturated carboxylic acid or an anhydride thereof is disclosed. These compositions are, in particular, suitable for forming automobile instrument panel skins, and can be calendered at elevated temperatures without sticking to the calender rolls.
Description
Title Thermoplastic Polymer Compositions Backeround of the Invention This invention relates to thermoplastic polymer compositions which are thermoformable, and to thermoformed articles made from such compositions.
io The compositions of the present invention, which are halogen-free, are useful for making laminates, sheets and films, and for replacing polyvinyl chloride (PVC) resins in many of their tradition uses. In particular, compositions of the present invention, and thermoformed articles made therefrom, are suitable as PVC
replacements in the automotive field. They may be used in the fabrication of interior sheathing of automobiles, for example, in the instrument panel skins, door panels, roof liners and seat covers.
Automotive applications require certain properties in the resins, including good 2o flexibility, low temperature properties, capability of providing a soft surface texture and grain retention: as well as good high temperature properties and low emissions associated with it in view of the extreme temperatures the interior of automobiles can reach on hot. sunny days.
Non-halogenated thermoplastic compositions having good high temperature properties are known in the art, for example the polyolefin/ionomer blends disclosed in U.S. Patent No. 4.871,810, or the blends of partially crosslinked ethylene/a-olefin copolymers with reaction products of ethylene copolymer ionomers and olefin/epoxy copolymers, disclosed in U.S. Patent No. 4,968,75?.
3o Such compositions, however, are deficient in softness.
SUBSTITUTE SHEET (RULE 26) WO 99/11698 ,~ PCTlUS98117159 The deficiencies of the prior art compositions have been largely overcome ~y a composition comprising a blend of polypropylene. ethylene copolymer ionomer resin, ethylenelglycidyl acrylate or methacrylate copolymer, and uncrosslinked ethylene propylene rubber as described in U.S. Patent No. S, 206,294. Such a blend has been proven suitable for most applications and it is characterized by good thermoformability and grain retention. These blends, however. are not calenderable. The presence of ionomer resin and ethylene/glycidyl acrylate or methacrylate copolymer leads to excessive sticking of the blend on metal rolls of the processing equipment. As certain processors are equipped only with 1 o calendering equipment (not with extrusion equipment) there is a commercial need for thermoplastic polymer blends suitable for making thermoformed articles by calendering; which articles demonstrate the requisite flexibility. temperature properties) capability of providing a soft surface texture and grain retention for automotive applications.
Summary of the Invention In accordance with the present invention. thermoplastic polymer compositions are provided comprising (a) 50-90 «~t. % of a polymer blend comprising (i) 10-40 wt. % polypropylene (ii) 1 S-SO wt. % uncrosslinked ethylene propylene copolymer rubber having an ethylene content of 60-80 wt. %, (iii) 20-60 wt. % of an ionomeric copolymer of ethylene and an a,(3-unsaturated C3-Ca carboxylic acid, and (iv) 0.1-S wt. % of a copolymer of ethylene and giycidyl acrylate or glycidyl methacrylate, (b) 10-40 wt. % inorganic filler and (c) 0-15 w. % of an uncrosslinked ethylene propylene copolymer rubber having an ethylene content of 60-80 wt. % grafted with 0.01-S wt. °,~o of an a,p-unsaturated carboxylic acid or an anhydride thereof.
SUBSTITUTE SHEET (RULE 26) _.....___.~____. 1.....__._..._~....._ _ WO 99/11698 PCT'US98/17159 These compositions exhibit excellent flexibility, temperature properties.
capability of providing a soft surface texture and good grain retention. The present invention is also directed to thermoformed articles from such compositions, particularly instrument panel skins.
Detailed Description of the Invention The polymer blend component (component (a)) of the thermoplastic polymer t0 composition of the present invention is present in amounts of 50-90 wt. %, preferably 55-85 wt. %.
The polypropylene component of the polymer blend (component (a)(i)) consists of crystalline polypropylene and is intended to include in addition to the homopolymer those polymers that also contain minor amounts, usually not greater than 1 S weight percent, of higher or lower a-olefins, e.g. those containing 3-carbon atoms, such as ethylene, butene, octene, etc. The polypropylene polymers useful in this invention have melt indices in the range of from about 0.07-30 dg/minute at 230 °C/2.16 g, and are present in the blend in amounts of 10-40 wt.
%, preferably 15 to 30 wt. %.
The uncrosslinked ethvleneipropylene copolymer rubber (component (a)(ii) and which serves as the base of component (c)) may be an ethylene/propylene/nonconjugated diene copolymer (EPDM) or an ethylene/propylene copolymer (EPM). EPDMs are preferred as component (a)(iii); EPMs are preferred as the base of component (c). The uncrosslinked ethylene/propylene copolymer rubber contains about 60-80 wt. %, usually about 65-75 wt % ethylene.
3o The nonconjugated dienes can contain from 6-22 carbon atoms having at least one readily polymerizable double bond. The amount of nonconjugated diene is generally from about 1-7 wt. %, usually 2-S wt. %. EPDM copolymers that are SUBSTITUTE SHEET (RULE 26) especially prefe:red are ethylene/propylene/l.4-hexadiene, ethylene/propyiene/
dicyclopentadiene, ethvlenelpropyleneinorbornene, ethylenelpropylene/methylene-2-norbornene and ethylene/propylene/l,4-hexadiene/norbornadiene. It is preferred that the ethylene/propylene copolymer rubber are non-crosslinked. The ethylene/propylene copolymer rubber present as component (a)(ii) in the blend is present in amounts of 15-50 wt. %, preferably 15-40 wt. %.
The ionic copolymer of ethylene and an a,(3-unsaturated C3 -C8 carboxylic acid l0 (component (a)(iii)) optionally contains at least one softening comonomer that is copolymerizable with ethylene. Acrylic and methacrylic acids are preferred acid comonomers. The softening comonomer can be an alkyl acrylate selected from the group consisting of n-propyl-, n-butyl, n-octyh 2-ethylhexyl-, and 2=methoxyethyl-acrylates. The preferred alkyl acrylates are n-butyl-. 2-t 5 ethyihexyl-, and 2-methoxyethyl-acrylates. The softening comonomer can also be an alkyl vinyl ether selected from the group consisting of n-butyl, n-hexyl, 2-ethylhexyl-, and 2-methoxyethyl-vinyl ether. The preferred alkyl vinyl ethers are n-butyl vinyl ether and n-hexyl vinyl ether. The coplymer is about 10 to 70%
neutralized with metal ions selected from groups Ia, Ib, IIa, IIIa, IVa, VIb, and 2o VIII of the Periodic Table of Elements such as sodium. potassium zinc.
calcium, maenesium, lithium, aluminum. nickel, and chrominum. Preferably the copolymer has from about 35 to about 70% of the carboxylic acid groups ionized by neutralization with metal ions selected from the group consisting of sodium, potassium, zinc. calcium, and magnesium. The ionomeric copolymer is present in 25 the blend in amounts of 20-60 wt. %, preferably 30-50 wt. %.
The copolymer of ethylene and glycidyl acrylate or ethylene and glycidyl methacrylate (component (a)(iv)) preferably contains copolymerized units of an alkyl acrylate or an alkyl methacrylate having I -6 carbon atoms. The 3o ethylene/glycidvl acrylate or ethylene/-glycidyl methacrylate copolymer contains 60-88 weight percent ethylene and I-12 weight percent glycidyl acrviate or glycidvl methacrylate. Representative alkyl acrylates and alkyl methacrylates that SUBSTITUTE SHEET (RULE 26) __.__~__ _ ..r .~~.___..
WO 99/11698 PCT'US98/17159 are used in the copolymer include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobut5~l acrylate, hexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, and hexyl methacrylate.
Ethyl acrylate is preferred and n-butyl acrylate is especially preferred.
The ethylene/glycidyl (meth)acrylate copolymer can be prepared by direct polymerization, for example, copolymerizing ethylene, an alkyl acrylate, and glycidyl methacrylate or glycidyl acrylate in the presence of a free-radical polymerization initiator at elevated temperatures, generally 100°-230° C., and at to elevated pressures. i.e. 140-350 MPa. The most preferred ethylene/glycidyl(methacrylate copolymers that are used in this invention are copolymers of ethylene. ethyl acrylate, glycidyl methacrylate, and, especially, ethylene. n-butyl acrylate, and glycidyl methacrylate. The copolymer of ethylene and glycidyl acn~late or ethylene and glycidyl methacryiate is present in the blend in amounts of 0.1-5 weight %. preferably 2-5 weight %.
A wide range of particulate inorganic fillers (component (b)) may be used depending on the intended use of the composition and, if desired, a mixture of particulate inorganic fillers may be used. The particulate inorganic fillers is 2o suitably a basic filler for example an oxide, a hydrated oxide, a hydroxide, a carbonate or a mixture thereof, and especially is predominantly an oxide. a hydrated oxide, a hydroxide or carbonate of a metal of group II or III. such as magnesium, calcium or aluminium or a mixture thereof. The particulate inorganic filler is typically a material of the type which is used as an intumescent filler for a plastic material. The inorganic filler may a hydroxycarbonate such as hydrated magnesium hydroxy caronate which occurs naturally as hydromagnesite, a mixed carbonate such as magnesium-calcium carbonate or may be a mixture of two or more such materials. Preferred inorganic fillers are calcium carbonate, talc, mica and gypsum, more preferably calcium carbonate or talc. The inorganic filler will 3o be present in the polymer blend in an amount of 10-40 wt. %. In cases where there is no component (c) present, there is preferably 20-40 wt. % inorganic filler SUBSTITUTE SHEET (RULE 26) WO 99/11698 PCT;LS98/17159 present. In cases where component (c) is present. there is preferably 10-30°ro inorganic filler present.
The grafting monomer suitable for grafting the uncrosslinked ethylene propylene copolymer rubber (the resulting grafted rubber being component (c)) is at least one of a, (3-ethylenically unsaturated carboxylic acids and anhydrides thereof, including derivatives of such acids and anhydrides, which may be mono-, di- or polycarboxylic acids, are acrylic acid, methacrylic acid, malefic acid, fumaric acid.
itaconic acid, crotonic acid, itaconic anhyddride, malefic anhydride and substituted to malefic anhydride e.g. dimethyl malefic anhydride. Examples of derivates of the unsaturated acids are salts, amides, imides and esters e.g. mono- and disodium maieate, acrylamide. maleimide and diethyl fumarate. Malefic anhydride is preferred. The amount of grafting will be 0.01-5 wt. %, preferably 0.1-3 wt.
%, based upon the weight of the uncrosslinked ethylene propylene copolymer rubber in component (c). Grafting processes are known in the art. The melt viscosity of the grafted uncrosslinked ethylene propylene copolymer rubber is not restricted, however, most preferred is found if the meld index, measured at 2.16 kg and 190°
is between 50 and I SOg/10 min. or if the melt flow index, measured at 2.16 kg and 280° C is 5-30 g110 min. The grafted uncrosslinked ethylene/propylene 2o copolymer rubber will be present in the polymer composition in an amount of 0-15 wt. %, preferably 2 to 10 wt. %.
The thermoplastic polymer compositions of the present invention are generally prepared by melt blending the polymeric components under high shear conditions.
for example in an extruder. The various ingredients may first be combined with one another e.g., in a pellet blend, or they may be combined with one another via simultaneous or separate metering of the various components. They may also be divided and blended in on or more passes into separate sections of the mixing equipment.
The resultant compositions may be thermoformed into a variety of articles, including sheets, or they may be molded into any desired shape. In particular.
SUBSTITUTE SHEET (RULE 26) they may be thermoformed at high deep-draw ratios for use as instrument panel skins for automobiles. Excellent iow temperature flexibility and high temperature resistance enables these compositions to be useful in applications wherein a wide range of temperature and abrasive conditions are encountered. In addition, as these compositions resist sticking to metal at elevated temperatures, e.g. 150-200 °C, they can be used in processes in which hot polymer comes into pressure contact with hot metal rolls.
The invention can be further understood by the following examples in which parts 1o and percentages are by weight unless otherwise indicated.
Examples Sheets of thermoplastic polymer compositions are formed by blending a ''salt and pepper" mixture of granules of polymers and fillers on a laboratory two mill for 3 min. at 170-190 °C. The releasability of the sheets from the calender rolls of the mill are judged subjectively:
1 = very good release - can be drawn off by hand 2 = good release - similar to 1 but higher force required 3 = poor release - doctor knife required for removal 4 = very poor release - sticks entirely to the rolls and cannot be released at all as a continuous sheet Milled sheets removed from the rolls are pressed in a hydraulic press at 220 °C in order to prepare a 12 mm x 12 mm x 2 mm plaque on which tensile strength, elongation, secant moduius and hardness are determined according to DIN 57504 In addition, compositions are compounded in a 25 mm PRISM twin screw 3o extruder. All ingredients are prepared as a "salt and pepper'' blend and granulated after exiting the extruder. The granulate so obtained is melted on a two roll mill SUBSTITUTE SHEET (RULE 26) and blended at 190 °C to give a feedstock for a lab calender which is run at 180 °C.
Ali -compositions are based on the following thermoplastic polyolefin (TPO) composition (amounts given in wt. %) Polypropylene ' 20 EPDM z 44 Zn Ionomer' 32 ENBAGMA ° 2 1 o Carbon black 2 I melt index 4 g/10 min., ASTM D-1238, Condition L
2 70 wt. % ethylene/26 .wt. % propylene/4 wt. % 1,4-hexadiene 3 29.5 wt. % ethylene/22 wt. % n-butyl acrylate/8.5 wt. % methacrylic acid.
45% neutralized with zinc 4 66.7 wt. % ethylene/28 wt. % n-butyl acrylate/5.3 wt. % glycidyl methacrylate To this formulation is added the following processing aids. iorganic fillers and other additives.
2o Ingredient Obtained from Zinc stearate Merck. Germany MICROLINE A3 talc Naintsch, Austria EXTRA PUR CaCOj Merck, Germany Fusabond MF416D 5 DuPont 2s Fusabond MD353D 6 DuPont MB50-002 ' Dow-Coming 5 EPM grafted with malefic anhydride 6 polypropylene grafted with malefic anhydride 7 A masterbatch of 50 wt % silicone ene in polyethyl SUBSTITUTE SHEET (RULE 26) .._..~....._ ____ . __ ._~ __._ ___.r_ _ __.._.~.__ 8 9 PCT.~IJS98/17159 Compositions in wt % ('C' = comparative example; 'E' = inventive example) -rp0 100 95 98 90 80 70 90 s MB50-002 Zn Stearate 2 Talc A3 10 20 30 C
, a Rating 4 4 4 3 3 2 3 to TPO 70 75 75 65 75 70 ~6 Zinc stearate Talc A3 10 10 20 15 15 25 15 t s CaCO, 15 15 15 22 Fusabond MF416D 5 5 10 5 7 Fusabond MD353D
Rating 1 2 2 4 3 3 1 2o We have found that common processing aids such as silicons, and fluoropolymer processing aids such as PTFE micro-powder sold as ZONYL MP 1 SOO (available from DuPont) do not enhance calenderability in these formulations, although thev have been proven to be effective in reducing sticking to metal and many other substances.
As is indicated by the test results, the inorganic fillers interact with the ionomer and ENBAGMA to reduce the adhesion to the metal rolls of the calender and the roll mill. Comparative Example C4 shows that grafted polypropylene does not lead to any improvement in terms of sticking to metal, and in fact, reverses the 3o positive effect of the filler.
SUBSTITUTE SHEET (RULE 26)
io The compositions of the present invention, which are halogen-free, are useful for making laminates, sheets and films, and for replacing polyvinyl chloride (PVC) resins in many of their tradition uses. In particular, compositions of the present invention, and thermoformed articles made therefrom, are suitable as PVC
replacements in the automotive field. They may be used in the fabrication of interior sheathing of automobiles, for example, in the instrument panel skins, door panels, roof liners and seat covers.
Automotive applications require certain properties in the resins, including good 2o flexibility, low temperature properties, capability of providing a soft surface texture and grain retention: as well as good high temperature properties and low emissions associated with it in view of the extreme temperatures the interior of automobiles can reach on hot. sunny days.
Non-halogenated thermoplastic compositions having good high temperature properties are known in the art, for example the polyolefin/ionomer blends disclosed in U.S. Patent No. 4.871,810, or the blends of partially crosslinked ethylene/a-olefin copolymers with reaction products of ethylene copolymer ionomers and olefin/epoxy copolymers, disclosed in U.S. Patent No. 4,968,75?.
3o Such compositions, however, are deficient in softness.
SUBSTITUTE SHEET (RULE 26) WO 99/11698 ,~ PCTlUS98117159 The deficiencies of the prior art compositions have been largely overcome ~y a composition comprising a blend of polypropylene. ethylene copolymer ionomer resin, ethylenelglycidyl acrylate or methacrylate copolymer, and uncrosslinked ethylene propylene rubber as described in U.S. Patent No. S, 206,294. Such a blend has been proven suitable for most applications and it is characterized by good thermoformability and grain retention. These blends, however. are not calenderable. The presence of ionomer resin and ethylene/glycidyl acrylate or methacrylate copolymer leads to excessive sticking of the blend on metal rolls of the processing equipment. As certain processors are equipped only with 1 o calendering equipment (not with extrusion equipment) there is a commercial need for thermoplastic polymer blends suitable for making thermoformed articles by calendering; which articles demonstrate the requisite flexibility. temperature properties) capability of providing a soft surface texture and grain retention for automotive applications.
Summary of the Invention In accordance with the present invention. thermoplastic polymer compositions are provided comprising (a) 50-90 «~t. % of a polymer blend comprising (i) 10-40 wt. % polypropylene (ii) 1 S-SO wt. % uncrosslinked ethylene propylene copolymer rubber having an ethylene content of 60-80 wt. %, (iii) 20-60 wt. % of an ionomeric copolymer of ethylene and an a,(3-unsaturated C3-Ca carboxylic acid, and (iv) 0.1-S wt. % of a copolymer of ethylene and giycidyl acrylate or glycidyl methacrylate, (b) 10-40 wt. % inorganic filler and (c) 0-15 w. % of an uncrosslinked ethylene propylene copolymer rubber having an ethylene content of 60-80 wt. % grafted with 0.01-S wt. °,~o of an a,p-unsaturated carboxylic acid or an anhydride thereof.
SUBSTITUTE SHEET (RULE 26) _.....___.~____. 1.....__._..._~....._ _ WO 99/11698 PCT'US98/17159 These compositions exhibit excellent flexibility, temperature properties.
capability of providing a soft surface texture and good grain retention. The present invention is also directed to thermoformed articles from such compositions, particularly instrument panel skins.
Detailed Description of the Invention The polymer blend component (component (a)) of the thermoplastic polymer t0 composition of the present invention is present in amounts of 50-90 wt. %, preferably 55-85 wt. %.
The polypropylene component of the polymer blend (component (a)(i)) consists of crystalline polypropylene and is intended to include in addition to the homopolymer those polymers that also contain minor amounts, usually not greater than 1 S weight percent, of higher or lower a-olefins, e.g. those containing 3-carbon atoms, such as ethylene, butene, octene, etc. The polypropylene polymers useful in this invention have melt indices in the range of from about 0.07-30 dg/minute at 230 °C/2.16 g, and are present in the blend in amounts of 10-40 wt.
%, preferably 15 to 30 wt. %.
The uncrosslinked ethvleneipropylene copolymer rubber (component (a)(ii) and which serves as the base of component (c)) may be an ethylene/propylene/nonconjugated diene copolymer (EPDM) or an ethylene/propylene copolymer (EPM). EPDMs are preferred as component (a)(iii); EPMs are preferred as the base of component (c). The uncrosslinked ethylene/propylene copolymer rubber contains about 60-80 wt. %, usually about 65-75 wt % ethylene.
3o The nonconjugated dienes can contain from 6-22 carbon atoms having at least one readily polymerizable double bond. The amount of nonconjugated diene is generally from about 1-7 wt. %, usually 2-S wt. %. EPDM copolymers that are SUBSTITUTE SHEET (RULE 26) especially prefe:red are ethylene/propylene/l.4-hexadiene, ethylene/propyiene/
dicyclopentadiene, ethvlenelpropyleneinorbornene, ethylenelpropylene/methylene-2-norbornene and ethylene/propylene/l,4-hexadiene/norbornadiene. It is preferred that the ethylene/propylene copolymer rubber are non-crosslinked. The ethylene/propylene copolymer rubber present as component (a)(ii) in the blend is present in amounts of 15-50 wt. %, preferably 15-40 wt. %.
The ionic copolymer of ethylene and an a,(3-unsaturated C3 -C8 carboxylic acid l0 (component (a)(iii)) optionally contains at least one softening comonomer that is copolymerizable with ethylene. Acrylic and methacrylic acids are preferred acid comonomers. The softening comonomer can be an alkyl acrylate selected from the group consisting of n-propyl-, n-butyl, n-octyh 2-ethylhexyl-, and 2=methoxyethyl-acrylates. The preferred alkyl acrylates are n-butyl-. 2-t 5 ethyihexyl-, and 2-methoxyethyl-acrylates. The softening comonomer can also be an alkyl vinyl ether selected from the group consisting of n-butyl, n-hexyl, 2-ethylhexyl-, and 2-methoxyethyl-vinyl ether. The preferred alkyl vinyl ethers are n-butyl vinyl ether and n-hexyl vinyl ether. The coplymer is about 10 to 70%
neutralized with metal ions selected from groups Ia, Ib, IIa, IIIa, IVa, VIb, and 2o VIII of the Periodic Table of Elements such as sodium. potassium zinc.
calcium, maenesium, lithium, aluminum. nickel, and chrominum. Preferably the copolymer has from about 35 to about 70% of the carboxylic acid groups ionized by neutralization with metal ions selected from the group consisting of sodium, potassium, zinc. calcium, and magnesium. The ionomeric copolymer is present in 25 the blend in amounts of 20-60 wt. %, preferably 30-50 wt. %.
The copolymer of ethylene and glycidyl acrylate or ethylene and glycidyl methacrylate (component (a)(iv)) preferably contains copolymerized units of an alkyl acrylate or an alkyl methacrylate having I -6 carbon atoms. The 3o ethylene/glycidvl acrylate or ethylene/-glycidyl methacrylate copolymer contains 60-88 weight percent ethylene and I-12 weight percent glycidyl acrviate or glycidvl methacrylate. Representative alkyl acrylates and alkyl methacrylates that SUBSTITUTE SHEET (RULE 26) __.__~__ _ ..r .~~.___..
WO 99/11698 PCT'US98/17159 are used in the copolymer include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobut5~l acrylate, hexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, and hexyl methacrylate.
Ethyl acrylate is preferred and n-butyl acrylate is especially preferred.
The ethylene/glycidyl (meth)acrylate copolymer can be prepared by direct polymerization, for example, copolymerizing ethylene, an alkyl acrylate, and glycidyl methacrylate or glycidyl acrylate in the presence of a free-radical polymerization initiator at elevated temperatures, generally 100°-230° C., and at to elevated pressures. i.e. 140-350 MPa. The most preferred ethylene/glycidyl(methacrylate copolymers that are used in this invention are copolymers of ethylene. ethyl acrylate, glycidyl methacrylate, and, especially, ethylene. n-butyl acrylate, and glycidyl methacrylate. The copolymer of ethylene and glycidyl acn~late or ethylene and glycidyl methacryiate is present in the blend in amounts of 0.1-5 weight %. preferably 2-5 weight %.
A wide range of particulate inorganic fillers (component (b)) may be used depending on the intended use of the composition and, if desired, a mixture of particulate inorganic fillers may be used. The particulate inorganic fillers is 2o suitably a basic filler for example an oxide, a hydrated oxide, a hydroxide, a carbonate or a mixture thereof, and especially is predominantly an oxide. a hydrated oxide, a hydroxide or carbonate of a metal of group II or III. such as magnesium, calcium or aluminium or a mixture thereof. The particulate inorganic filler is typically a material of the type which is used as an intumescent filler for a plastic material. The inorganic filler may a hydroxycarbonate such as hydrated magnesium hydroxy caronate which occurs naturally as hydromagnesite, a mixed carbonate such as magnesium-calcium carbonate or may be a mixture of two or more such materials. Preferred inorganic fillers are calcium carbonate, talc, mica and gypsum, more preferably calcium carbonate or talc. The inorganic filler will 3o be present in the polymer blend in an amount of 10-40 wt. %. In cases where there is no component (c) present, there is preferably 20-40 wt. % inorganic filler SUBSTITUTE SHEET (RULE 26) WO 99/11698 PCT;LS98/17159 present. In cases where component (c) is present. there is preferably 10-30°ro inorganic filler present.
The grafting monomer suitable for grafting the uncrosslinked ethylene propylene copolymer rubber (the resulting grafted rubber being component (c)) is at least one of a, (3-ethylenically unsaturated carboxylic acids and anhydrides thereof, including derivatives of such acids and anhydrides, which may be mono-, di- or polycarboxylic acids, are acrylic acid, methacrylic acid, malefic acid, fumaric acid.
itaconic acid, crotonic acid, itaconic anhyddride, malefic anhydride and substituted to malefic anhydride e.g. dimethyl malefic anhydride. Examples of derivates of the unsaturated acids are salts, amides, imides and esters e.g. mono- and disodium maieate, acrylamide. maleimide and diethyl fumarate. Malefic anhydride is preferred. The amount of grafting will be 0.01-5 wt. %, preferably 0.1-3 wt.
%, based upon the weight of the uncrosslinked ethylene propylene copolymer rubber in component (c). Grafting processes are known in the art. The melt viscosity of the grafted uncrosslinked ethylene propylene copolymer rubber is not restricted, however, most preferred is found if the meld index, measured at 2.16 kg and 190°
is between 50 and I SOg/10 min. or if the melt flow index, measured at 2.16 kg and 280° C is 5-30 g110 min. The grafted uncrosslinked ethylene/propylene 2o copolymer rubber will be present in the polymer composition in an amount of 0-15 wt. %, preferably 2 to 10 wt. %.
The thermoplastic polymer compositions of the present invention are generally prepared by melt blending the polymeric components under high shear conditions.
for example in an extruder. The various ingredients may first be combined with one another e.g., in a pellet blend, or they may be combined with one another via simultaneous or separate metering of the various components. They may also be divided and blended in on or more passes into separate sections of the mixing equipment.
The resultant compositions may be thermoformed into a variety of articles, including sheets, or they may be molded into any desired shape. In particular.
SUBSTITUTE SHEET (RULE 26) they may be thermoformed at high deep-draw ratios for use as instrument panel skins for automobiles. Excellent iow temperature flexibility and high temperature resistance enables these compositions to be useful in applications wherein a wide range of temperature and abrasive conditions are encountered. In addition, as these compositions resist sticking to metal at elevated temperatures, e.g. 150-200 °C, they can be used in processes in which hot polymer comes into pressure contact with hot metal rolls.
The invention can be further understood by the following examples in which parts 1o and percentages are by weight unless otherwise indicated.
Examples Sheets of thermoplastic polymer compositions are formed by blending a ''salt and pepper" mixture of granules of polymers and fillers on a laboratory two mill for 3 min. at 170-190 °C. The releasability of the sheets from the calender rolls of the mill are judged subjectively:
1 = very good release - can be drawn off by hand 2 = good release - similar to 1 but higher force required 3 = poor release - doctor knife required for removal 4 = very poor release - sticks entirely to the rolls and cannot be released at all as a continuous sheet Milled sheets removed from the rolls are pressed in a hydraulic press at 220 °C in order to prepare a 12 mm x 12 mm x 2 mm plaque on which tensile strength, elongation, secant moduius and hardness are determined according to DIN 57504 In addition, compositions are compounded in a 25 mm PRISM twin screw 3o extruder. All ingredients are prepared as a "salt and pepper'' blend and granulated after exiting the extruder. The granulate so obtained is melted on a two roll mill SUBSTITUTE SHEET (RULE 26) and blended at 190 °C to give a feedstock for a lab calender which is run at 180 °C.
Ali -compositions are based on the following thermoplastic polyolefin (TPO) composition (amounts given in wt. %) Polypropylene ' 20 EPDM z 44 Zn Ionomer' 32 ENBAGMA ° 2 1 o Carbon black 2 I melt index 4 g/10 min., ASTM D-1238, Condition L
2 70 wt. % ethylene/26 .wt. % propylene/4 wt. % 1,4-hexadiene 3 29.5 wt. % ethylene/22 wt. % n-butyl acrylate/8.5 wt. % methacrylic acid.
45% neutralized with zinc 4 66.7 wt. % ethylene/28 wt. % n-butyl acrylate/5.3 wt. % glycidyl methacrylate To this formulation is added the following processing aids. iorganic fillers and other additives.
2o Ingredient Obtained from Zinc stearate Merck. Germany MICROLINE A3 talc Naintsch, Austria EXTRA PUR CaCOj Merck, Germany Fusabond MF416D 5 DuPont 2s Fusabond MD353D 6 DuPont MB50-002 ' Dow-Coming 5 EPM grafted with malefic anhydride 6 polypropylene grafted with malefic anhydride 7 A masterbatch of 50 wt % silicone ene in polyethyl SUBSTITUTE SHEET (RULE 26) .._..~....._ ____ . __ ._~ __._ ___.r_ _ __.._.~.__ 8 9 PCT.~IJS98/17159 Compositions in wt % ('C' = comparative example; 'E' = inventive example) -rp0 100 95 98 90 80 70 90 s MB50-002 Zn Stearate 2 Talc A3 10 20 30 C
, a Rating 4 4 4 3 3 2 3 to TPO 70 75 75 65 75 70 ~6 Zinc stearate Talc A3 10 10 20 15 15 25 15 t s CaCO, 15 15 15 22 Fusabond MF416D 5 5 10 5 7 Fusabond MD353D
Rating 1 2 2 4 3 3 1 2o We have found that common processing aids such as silicons, and fluoropolymer processing aids such as PTFE micro-powder sold as ZONYL MP 1 SOO (available from DuPont) do not enhance calenderability in these formulations, although thev have been proven to be effective in reducing sticking to metal and many other substances.
As is indicated by the test results, the inorganic fillers interact with the ionomer and ENBAGMA to reduce the adhesion to the metal rolls of the calender and the roll mill. Comparative Example C4 shows that grafted polypropylene does not lead to any improvement in terms of sticking to metal, and in fact, reverses the 3o positive effect of the filler.
SUBSTITUTE SHEET (RULE 26)
Claims (6)
1. A thermoplastic polymer composition comprising (a) 50-90 wt. % of a polymer blend comprising (i) 10-40 wt. % polypropylene (ii) 15-50 wt. % uncrosslinked ethylene propylene copolymer rubber having an ethylene content of 60-80 wt. %, (iii) 20-60 wt. % of an ionomeric copolymer of ethylene and an .alpha.,.beta.-unsaturated C3-C8 carboxylic acid. and (iv) 0.1-5 wt. % of a copolymer of ethylene and glycidyl acrylate or glycidyl methacrylate, (b) 10-40 wt. % inorganic filler and (c) 0-15 wt. % of an uncrosslinked ethylene propylene copolymer rubber having an ethylene content of 60-80 wt. % grafted with 0.01-5 wt. % of an .alpha.,.beta.-unsaturated carboxylic acid or an anhydride thereof.
2. A thermoplastic polymer composition according to claim 1 wherein component (b) is selected from calcium carbonate, talc, mica and gypsum.
3. A thermoplastic polymer composition according to claim 1 wherein component (c) comprises 2 to 10 wt. % of the composition and is an ethylene/propylene/nonconjugated diene copolymer grafted with 0.1-3 wt. %
malefic anhydride and has a melt flow index at 280 °C/2.16 kg of 5-30 g/10 min.
malefic anhydride and has a melt flow index at 280 °C/2.16 kg of 5-30 g/10 min.
4. A thermoplastic polymer composition according to claim 3 wherein component (b) comprises 10-30 wt. % calcium carbonate or talc.
5. A thermoformed article made from a composition according to any one of claims 1 to 4.
6. A thermoformed article according to claim 5 wherein the article is an instrument panel skin.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP97202670.2 | 1997-09-01 | ||
| EP97202670 | 1997-09-01 | ||
| PCT/US1998/017159 WO1999011698A1 (en) | 1997-09-01 | 1998-08-19 | Thermoplastic polymer compositions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2270715A1 true CA2270715A1 (en) | 1999-03-11 |
Family
ID=8228686
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002270715A Abandoned CA2270715A1 (en) | 1997-09-01 | 1998-08-19 | Thermoplastic polymer compositions |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0941279A4 (en) |
| JP (1) | JP2001505616A (en) |
| KR (1) | KR20000068883A (en) |
| AU (1) | AU8914498A (en) |
| BR (1) | BR9806140C1 (en) |
| CA (1) | CA2270715A1 (en) |
| WO (1) | WO1999011698A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4289898A3 (en) * | 2022-06-09 | 2024-03-06 | EcoPals GmbH | Additive for asphalt and method for producing an additive and an asphalt using such an additive |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6217982B1 (en) * | 1997-10-10 | 2001-04-17 | E. I. Du Pont De Nemours And Company | Thermoplastic polymer alloy composition |
| KR100379223B1 (en) * | 2000-12-22 | 2003-04-08 | 삼성종합화학주식회사 | Thermoplastic Olefin Elastomer Resin Composition Having Good Adhesive Property And Method Of Preparing The Same |
| EP1642709A1 (en) * | 2004-10-01 | 2006-04-05 | Centro Tecnologico de Grupo Copo, S.L. | Thermoformable layered sheet and manufacturing process |
| JP4931384B2 (en) * | 2005-08-02 | 2012-05-16 | 三井・デュポンポリケミカル株式会社 | Thermoplastic resin composition, production method thereof and use thereof |
| JP5229065B2 (en) * | 2009-03-31 | 2013-07-03 | 三菱化学株式会社 | Polyolefin resin composite material and method for producing the same |
| JP6148483B2 (en) * | 2013-02-04 | 2017-06-14 | 三井・デュポンポリケミカル株式会社 | Cross-linked product, film, and adhesive film |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4871810A (en) * | 1987-11-13 | 1989-10-03 | E. I. Du Pont De Nemours And Company | Composition comprising melt blended product of thermoplastic resin and two ethylene copolymers containing coreactive groups |
| EP0382849B1 (en) * | 1988-02-22 | 1994-12-14 | Du Pont-Mitsui Polychemicals Co., Ltd. | Polymer composition |
| JP2521807B2 (en) * | 1989-01-31 | 1996-08-07 | 三井・デュポンポリケミカル株式会社 | Ionomer composition |
| US5206294A (en) * | 1991-11-06 | 1993-04-27 | E. I. Du Pont De Nemours And Company | Thermoplastic polymer alloy composition |
| US5395881A (en) * | 1994-03-04 | 1995-03-07 | E. I. Du Pont De Nemours And Company | Flexible polar thermoplastic polyolefin compositions |
| US6217982B1 (en) * | 1997-10-10 | 2001-04-17 | E. I. Du Pont De Nemours And Company | Thermoplastic polymer alloy composition |
| EP0922729B1 (en) * | 1997-12-10 | 2001-06-06 | E.I. Du Pont De Nemours And Company | Thermoformable thermoplastic polymer alloy compositions |
-
1998
- 1998-08-19 WO PCT/US1998/017159 patent/WO1999011698A1/en not_active Application Discontinuation
- 1998-08-19 CA CA002270715A patent/CA2270715A1/en not_active Abandoned
- 1998-08-19 AU AU89144/98A patent/AU8914498A/en not_active Abandoned
- 1998-08-19 JP JP51684599A patent/JP2001505616A/en active Pending
- 1998-08-19 BR BR9806140-2A patent/BR9806140C1/en unknown
- 1998-08-19 EP EP98940989A patent/EP0941279A4/en not_active Withdrawn
- 1998-08-19 KR KR1019997003889A patent/KR20000068883A/en not_active Application Discontinuation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4289898A3 (en) * | 2022-06-09 | 2024-03-06 | EcoPals GmbH | Additive for asphalt and method for producing an additive and an asphalt using such an additive |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0941279A4 (en) | 2000-11-15 |
| JP2001505616A (en) | 2001-04-24 |
| BR9806140C1 (en) | 2000-05-23 |
| WO1999011698A1 (en) | 1999-03-11 |
| KR20000068883A (en) | 2000-11-25 |
| AU8914498A (en) | 1999-03-22 |
| EP0941279A1 (en) | 1999-09-15 |
| BR9806140A (en) | 1999-10-26 |
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