CA2110502C - Foil or moulded body made of a thermoplastic material based on a polypropylene block copolymer - Google Patents
Foil or moulded body made of a thermoplastic material based on a polypropylene block copolymer Download PDFInfo
- Publication number
- CA2110502C CA2110502C CA002110502A CA2110502A CA2110502C CA 2110502 C CA2110502 C CA 2110502C CA 002110502 A CA002110502 A CA 002110502A CA 2110502 A CA2110502 A CA 2110502A CA 2110502 C CA2110502 C CA 2110502C
- Authority
- CA
- Canada
- Prior art keywords
- ethylene
- copolymer
- weight
- sheet
- block copolymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
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
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/02—Heterophasic composition
-
- 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
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
Abstract
A foil or moulded body made of a thermoplastic material based on at least one partially crystalline polyalkene elastomer and/or elastomer mixture is composed of a multiphase alkene block copolymer with a determined proportion of a heterophase elastomer copolymer of a homopolymer and/or copolymer of an alkene, as well as a polymer modifier. The plastic material con-tains if required stabilisers, fillers, parting agents, colorants and other usual additives. This foil or moulded body is characterised in that the thermoplastic material contains a multiphase polypropylene block copolymer with about 51 to 85 % by weight ethylene propylene copolymer, with respect to 100 parts by weight polypropylene block copolymer. The thermoplastic material represents a thermoplastic elastomer and from about 70 to 30 parts by weight polypropylene block copolymer, about 30 to 70 parts by weight are constituted by a polymer modifier represented by a homopolymer and/or copolymer of ethylene. These moulded bodies and foils are weather resistant. This foil has improved properties when it is shaped into moulded parts, such as in particular an im-proved pitting resistance.
Description
21 ~ 0502 FOIL OR MOLDED BODY OF THERMOPLASTIC PLASTIC
BASED ON A POLYPROPYLENE BLOCK COPOLYMER
The invention is directed to a sheet or molded body of thermoplastic plastic based tin at least one semicrystalline polyalkene elastomer and/or a mixture of polyalkene elastomers having a multiple-phase alkene block copolymer with a determined hetero-phase elastomer copolymer component and a homopolymer and/or copolymer of an alkene and of a polymeric modifier, which plastic may contain stabilizers, fillers, slipping or parting agents, dyes and other conventional additives.
Plastic sheets of this type and molded or composite articles produced with such plastic are known from DE-A-40 13 748 published on October 31, 1991. The plastic component of such a sheet contains ay 55 to 95 parts by weight of at least one thermoplastic polyolefin elastomer or a mixture of polyolefin elastomers having a hetero-phase polypropylene block copolymer with an ethylene/propylene copolymer component of 15 to 50 percent by weight (with respect to 100 parts by weight of the ethylene/propylene block copolymer) and b) 45 to 5 parts by weight of other polymers, particularly in the form of olefins and styrene-containing polymers. The total amount of ethylene and propylene in the block copolymer must be 10 to 50 percent by weight. The block copolymer cannot be replaced in its entirety by a random or statistical copolymer. However, the block ~1 1 0502 copolymer can be replaced up to 80 percent by weight, preferably to 35 percent by weight, by an ethylene/propylene random copolymer or a block copolymer with an ethylene content of 2 to 10 percent by weight. The known plastic sheet achieves improved properties, particularly an improved deep-drawing quality and improved resistance to pitting or scarring. Moreover, it is flexible and satisfies the specification requirements of the automobile industry, e.g.
with respect to aging and fogging properties. Tests have shown that this sheet is in need of improvement with respect to the deep-drawing quality and resistance to scarring.
Therefore, the present invention has the object of further developing the material mentioned above in such a way that is shows an improved deep-drawing quality and resistance to scarring, as well as a good dimensional stability at high temperatures when subjected to further processing by deep-drawing.
This object is met according to the invention in that the thermoplastic plastic contains a multiple-phase polypropylene block copolymer with an ethylene/propylene elastomer copolymer proportion of approximately 51 to 85 percent by weight with respect to 100 parts by weight of the propylene block copolymer, the thermoplastic plastic is a thermoplastic elastomer, and approximately 30 to 70 parts by weight of a polymeric modifier in the form of a homopolymer and/or copolymer of ethylene are allotted to approximately 70 to 30 parts by weight of the propylene block copolymer.
2a According to one aspect of the present invention there is provided a sheet or molded body of thermoplastic material based on at least onf~ semicrystalline polyalkene elastomer and/or a mixture of polyalkene elastomers having a multiple-phase alkene block copolymer with a determined hetero-phase elastomer copolymer component, a homopolymer and/or copolymer of an alkene and of a polymeric modifier, which comprises an elastomer comprising:
1) a multiple-phase polypropylene block copolymer having an ethylene/propylene copolymer proportion of approximately 51 to 85~ by weight based on the weight of the polypropylene block copolymer, and a degree of crosslinking of approximately 30 to 75~; and 2) a polymeric modifier selected from the group consisting of an ethylene copolymer, an ethylene homopolymer, an ethylene/propylene copolymer comprising 5 to 20°s by weight ethylene and having a narrow molecular mass distribution with a heterogeneity or non-uniformity U of less than 6 and a melt-flow index MFI (230/2.16) of 0.5 to 10 g/10 min when calendering a melt-flow index of at least approximately 0.8 g/10 min when extruding, an ethylene/propylene/diene terpolymer, an ethylene/acrylic acid copolymer, an ethylene/acrylic acid ester copolymer, an ethylene/vinyl acetate copolymer, and ethylene/glycidyl methacrylate copolymer, a styrene/ethylene/propylene copolymer (SEP), a styrene/ethylene/butadiene/styrene block copolymer (SEBS), an acrylonitrile/ethylene/propylene/diene/styrene copolymer (A-2b EPDM-S) and a high-molecular amorphous EPM rubber;
BASED ON A POLYPROPYLENE BLOCK COPOLYMER
The invention is directed to a sheet or molded body of thermoplastic plastic based tin at least one semicrystalline polyalkene elastomer and/or a mixture of polyalkene elastomers having a multiple-phase alkene block copolymer with a determined hetero-phase elastomer copolymer component and a homopolymer and/or copolymer of an alkene and of a polymeric modifier, which plastic may contain stabilizers, fillers, slipping or parting agents, dyes and other conventional additives.
Plastic sheets of this type and molded or composite articles produced with such plastic are known from DE-A-40 13 748 published on October 31, 1991. The plastic component of such a sheet contains ay 55 to 95 parts by weight of at least one thermoplastic polyolefin elastomer or a mixture of polyolefin elastomers having a hetero-phase polypropylene block copolymer with an ethylene/propylene copolymer component of 15 to 50 percent by weight (with respect to 100 parts by weight of the ethylene/propylene block copolymer) and b) 45 to 5 parts by weight of other polymers, particularly in the form of olefins and styrene-containing polymers. The total amount of ethylene and propylene in the block copolymer must be 10 to 50 percent by weight. The block copolymer cannot be replaced in its entirety by a random or statistical copolymer. However, the block ~1 1 0502 copolymer can be replaced up to 80 percent by weight, preferably to 35 percent by weight, by an ethylene/propylene random copolymer or a block copolymer with an ethylene content of 2 to 10 percent by weight. The known plastic sheet achieves improved properties, particularly an improved deep-drawing quality and improved resistance to pitting or scarring. Moreover, it is flexible and satisfies the specification requirements of the automobile industry, e.g.
with respect to aging and fogging properties. Tests have shown that this sheet is in need of improvement with respect to the deep-drawing quality and resistance to scarring.
Therefore, the present invention has the object of further developing the material mentioned above in such a way that is shows an improved deep-drawing quality and resistance to scarring, as well as a good dimensional stability at high temperatures when subjected to further processing by deep-drawing.
This object is met according to the invention in that the thermoplastic plastic contains a multiple-phase polypropylene block copolymer with an ethylene/propylene elastomer copolymer proportion of approximately 51 to 85 percent by weight with respect to 100 parts by weight of the propylene block copolymer, the thermoplastic plastic is a thermoplastic elastomer, and approximately 30 to 70 parts by weight of a polymeric modifier in the form of a homopolymer and/or copolymer of ethylene are allotted to approximately 70 to 30 parts by weight of the propylene block copolymer.
2a According to one aspect of the present invention there is provided a sheet or molded body of thermoplastic material based on at least onf~ semicrystalline polyalkene elastomer and/or a mixture of polyalkene elastomers having a multiple-phase alkene block copolymer with a determined hetero-phase elastomer copolymer component, a homopolymer and/or copolymer of an alkene and of a polymeric modifier, which comprises an elastomer comprising:
1) a multiple-phase polypropylene block copolymer having an ethylene/propylene copolymer proportion of approximately 51 to 85~ by weight based on the weight of the polypropylene block copolymer, and a degree of crosslinking of approximately 30 to 75~; and 2) a polymeric modifier selected from the group consisting of an ethylene copolymer, an ethylene homopolymer, an ethylene/propylene copolymer comprising 5 to 20°s by weight ethylene and having a narrow molecular mass distribution with a heterogeneity or non-uniformity U of less than 6 and a melt-flow index MFI (230/2.16) of 0.5 to 10 g/10 min when calendering a melt-flow index of at least approximately 0.8 g/10 min when extruding, an ethylene/propylene/diene terpolymer, an ethylene/acrylic acid copolymer, an ethylene/acrylic acid ester copolymer, an ethylene/vinyl acetate copolymer, and ethylene/glycidyl methacrylate copolymer, a styrene/ethylene/propylene copolymer (SEP), a styrene/ethylene/butadiene/styrene block copolymer (SEBS), an acrylonitrile/ethylene/propylene/diene/styrene copolymer (A-2b EPDM-S) and a high-molecular amorphous EPM rubber;
3) and wherein approximately 70 to 30 parts by weight of the propylene block copolymer are allotted to 30 to 70 parts by weight of the polymeric modifier.
The term "thermoplast.ic plastic" is understood in the broadest sense within the framework of the present invention. For example, it includes thermoplastic mixtures, polymer blends, polymer alloys, graft polymers and the like.
Consequently, the essence of the present invention, in contrast to the prior art mentioned above, consists in the use of a multiple-phase or hetero-phase polypropylene block copolymer with an increased proportion of ethylene/propylene copolymer, i.e. of more than 50 percent by weight. To achieve the effects aimed at by the invention, this proportion must be at least approximately 51 percent by weight, preferably approximately 55 to 80 percent by weight, in particular approximately 60 to 75 percent by weight. In this regard, it must be considered surprising that contrary to the strict specifications of the prior art, the proportion in percent by weight of the ethylene/propylene copolymer in the block copolymer in question is more or less far more than 50 percent by weight and that, in so doing, particularly advantageous properties of the plastic result, e.g. an improved resistance to scarring of the sheet produced with this plastic, an improved deep-drawing quality and deformability.
The thermoplastic plastic representing the essence of the invention can be cross-linked to a greater or lesser extent. In specific cases, it is advantageous to effect a certain cross-linking. A cross-linking of roughly 20 to 80%, in particular 50 to 75%, may be used as a guideline in this respect.
The extent of cross-linking can be determined, for example, by treating the thermoplastic elastomer with solvents so that the remaining cross-linked polymer is in the form of a gel and conclusions may be drawn regarding the extent of cross linking from the amount of this gel. The degree of cross linking may also be determined according to DIN 16892. The cross-linking of the thermoplastic plastic is advisably effected when it is already mixed with all other constituents, including conventional additives. This may be effected, for example, in a conventional mixing apparatus such as a kneader, a screw type extruder, and the like under appropriate conditions with respect to temperature, shear, mixing and pressure.
In order to create the desired effects it is necessary within the framework of the present invention to make use of a semicrystalline and/or amorphous polymeric modifier.
The modifier is used to regulate the melting point and melting viscosity, strength, calendering properties, extruding properties and the like characteristics. It can also impair or prevent the tendency of the sheets or molded articles to crystallize, which has a positive effect on the deep-drawing qualities and resistance to scarring. The modifiers can also positively affect the mixing properties and compatibility of the individual components of the mixture and improve the wetting properties and adhesive or bonding properties. In some cases, they can also cause internal and external softening or stiffening of the matrix polymers or influence the latter in the desired manner. Depending on the objective, the person skilled in the art can easily find the appropriate modifier from those described in the following.
According to the invention, a homopolymer and/or copolymer of ethylene is used as a polymeric modifier. In so doing, a homopolymer of propylene is not taken into consideration with respect to the marginal conditions for the propylene block copolymer. When an ethylene/propylene copolymer is used, it preferably contains approximately 5 to 20 percent by weight of ethylene. In particular, the ethylene/propylene copolymer preferably has a narrow molecular mass distribution with a heterogeneity or nonuniformity U of less than 6, particularly less than approximately 4. The use of an ethylene copolymer containing approximately 5 to 20 percent by weight octane and/or butene as comonomer is also particularly advantageous. It is also especially advantageous when the homopolymer and/or copolymer of the ethylene or propylene has a melt-flow index MFI (230/2.16) of roughly 0.5 to 10 g/10 min, in particular approximately 0.8 to 2.5 g/10 min, when calendering and a melt-flow index of at least approximately 0.8 g/10 min, particularly approximately 2.5 to 25 g/10 min, when extruding.
Other preferred polymeric modifiers which can be used according to the invention are: an ethylene/propylene copolymer, ethylene/propylene/diene terpolymer, an ethylene/acrylic acid copolymer, an ethylene/acrylic acid ester copolymer, a low-density polyethylene, an ethylene/vinyl acetate copolymer, an ethylene/glycidyl methacrylate copolymer, a styrene/ethylene/propylene block copolymer (SEP), a styrene/ethylene/butadiene/styrene block copolymer (SEBS) (hydrogenated), a styrene/ethylene/butadiene block copolymer (SEB), an acrylonitrile/ethylene/propylene/diene/styrene copolymer (A-EPDM-S) and/or a high-molecular amorphous EPM
rubber.
A particularly suitable modifier within the framework of the invention is a semicrystalline statistical ethylene/propylene/diene terpolymer (EPDM), that is, not a block terpolymer. This makes it possible to subject the finished mixture to a cross-linking via the dime component with the use of conventional cross-linking agents such as peroxide, epoxide and silane compounds and the like. The dime component in this terpolymer can be, in particular, a dicyclopentadiene, 1,4-hexadiene and/or 5-ethylidene-2-norbornene. The total proportion of the ethylene and propylene in the statistical terpolymer in percent by weight is preferably approximately 52 to 91 percent by weight, and the minimum content of ethylene is preferably approximately 65 percent by weight.
In the majority of cases of practical application, the thermoplastic plastic which can be used to produce sheets and molded bodies according to the invention preferably contains fillers. The proportion of filler is preferably approximately 8 to 28 percent by weight. All conventional fillers can be used, particularly those of potassium aluminum silicate, talc, chalk, kaolin, metal oxides, particularly titanium dioxide, and/or soot. Finally, other conventional additives can be used, particularly stabilizers such as antioxidants and heat stablizers, e.g. sterically hindered phenols, hydroquinones, substituted representatives of this group, phosphites, phosphonites and/or mixtures thereof, UV
stabilizers, e.g. various low-molecular, high-molecular, substituted resorcinols, salicylates, benzotriazoles, and benzophenones and/or mixtures thereof and the like, parting agents such as C1z- to C26-fatty acids, fatty alcohols, fatty acid esters and fatty acid amides and/or mixtures thereof and the like, dyes such as organic dyestuffs and pigments, e.g.
titanium dioxide, phthalocyanines or soot, flame retardants such as ammonium polyphosphate, zinc borate, magnesium, hydroxide, and aluminum hydroxide and the like.
The characteristics of the polypropylene block copolymer (abbreviation: PP) contained in the thermoplastic plastic are determined by the functional interaction of the polypropylene contained therein as well as that of the polymeric modifiers which are copolymerized with the latter, e.g. particularly ethylene/propylene copolymer. The latter represents the rubber component (abbreviation: EPM or EPR).
The PP component may also be regarded as a "hard" component, whereas the EPM component is considered a "soft" component.
Accordingly, the elastic and thermoplastic properties of the finished plastic mixture are substantially influenced by the PP/EPM ratio. Further possible influences are provided by incorporating the modifiers mentioned above.
The thermoplastic plastic which can be used to produce sheets and molded bodies according to the invention is characterized by desirable resistance to weathering. A sheet according to the invention which is produced with this material has superior resistance to scarring, good melting strength and a particularly good deep-drawing quality. This is demonstrated in the various deep-drawing processes, e.g. in the air pressing process, diaphragm pressing process, and the like. Deep-drawn -7- ~1 ~ p502 molded articles or composite formations produced from the sheet according to the invention can be used in particular advantage, for example, in aircraft and motor vehicles, interior paneling or panel parts in motor vehicles, preferably control panels or dashboards, pillars, side paneling, door paneling, shelves and exterior trim in motor vehicles. The sheet according to the invention can also be glued with or without deformation to a wide range of flat or three-dimensional substrates by conventional techniques. It may be provided with additional l0 layers or coats, e.g. protective coats. Finally, adhesive layers may also be affixed to the back of the sheets, possibly also with appropriate foam layer lining or bonding.
The invention is explained in more detail in the following examples:
Examples 1 to 5 A base sheet with a thickness of 1.1 mm was produced by means of a 4-roll calender using the recipes indicated in the following table. This sheet was measured for various characteristics which are likewise compiled in the following table.
Raw materials from Examples 1 to 5:
A-1: hetero-phase polypropylene block copolymer (cross-1 inked ) melt-flow index (230°C/2.18 kg) (DIN 53 735): 0.8 g/10 min elongation at failure (DIN 53 455): 620%
ethylene/propylene copolymer . 52% by weight proportion f . 27998-21 _g_ Table Cont'd extent of cross-linking (gel (DIN 16 892): 55%
content) elastic modulus in tension (DIN 53 457): 800 MPa density (DIN 53 479) : 0.87 g/cm3 crystallinity :22%
A-2: hetero-phase polypropylene block copolymer (not cross-linked) melt-flow index (230C/2.16 kg) (DIN 53 735): 2 g/10 min elongation at failure (DIN 53 455): 560%
ethylene/propylene copolymer . 52% by weight proportion elastic modulus in tension (DIN 53 457): 550 MPa density (DIN 53 479) 0.88 g/cm3 :
crystallinity . 28%
A-3: hetero-phase polypropyleneblock copolymer (not cross-1 inked ) melt-flow index(230C/2.16 kg) (DIN 53 735): 0.6 g/10 min elongation at failure (DIN 52 910): 596%
-9- ~1 ~ 0502 Table Cont'd ethylene/propylene copolymer . 58% by weight proportion elastic modulus in tension (DIN 52 910): 86 MPa density (DIN 53 479) : 0.89 g/cm3 crystallinity :25%
B-1: thermoplastic elastomer based on the ethylene/propylene/dicyclopentadiene terpolymer (cross-linked) melt-flow index (230°C/2.16 kg) (DIN 53 735): 8 g/10 min elongation at failure (DIN 52 910): 600%
rubber content (E=65% by . 52% by weight weight, P=23% by weight) extent of cross-linking (gel (DIN 16 892): 53% by weight content) density (DIN 53 479) : 0.88 g/cm3 B-2: LLDPE copolymer (with 8% octene-1) melt-flow index(230C/2.16 kg) (DIN 53 735) : 2.3 g/10 min elongation at failure (DIN 52 910): 650%
x .. -10- ~1 ~ 0502 Table Cont'd density (DIN 53 479): 0.92 g/cm3 crystallinity . 35%
B-3: VLDPE copolymer (with 12% octene-1) melt-flow index (230C/2.16 kg) (DIN 53 735): 2.8 g/10 min elongation at failure (DIN 52 910): 850%
density (DIN 53 479): 0.905 g/cm3 crystallinity :17%
B-4: A/EPDM/S copolymer (with 70% EPDM rubber) density (DIN 53 479): 1.03 g/cm3 elongation at failure (DIN 52 910): 490%
elastic modulus in tension (DIN 52 910): 310 MPa amorphous B-5: Block polymer with polystyrene end blocks and ethylene/butadiene center block (SEBS) (hydrogenated center block) density (DIN 53 479): 0.91 g/cm styrene content . 29% by weight ,.
Table Cont'd elongation at failure (DIN 52 910): 510%
B-6: EVACO (ethylene/vinyl acetate/carbon monoxide terpolymer) density (DIN 53 479): 1.00 g/cm3 carbon monoxide content :12% by weight B-7: High-molecular amorphous EPM rubber (not cross-linked/thermoplastic elastomer) melt-flow index (230C/2.16 kg) (DIN 53 735): 1.3 g/10 min elongation at failure (DIN 52 910): 620%
elastic modulus in tension (DIN 52 910): 140 MPa density (DIN 53 479): 0.94 g/cm3 Rubber proportion . 34% by weight ( amorphous ) Note: A = semicrystalline polyalkene elastomer B = polymeric modifier r f Examples Recipes 1 2 3 4 5 A1 hetero-phase polypropylene 30 - 70 - 60 block copolymer (cross-linked) A2 hetero-phase polypropylene - 70 - - -block copolymer (not cross-linked) A3 hetero-phase polypropylene - - 10 70 -block copolymer (not cross-linked) B1 thermoplastic elastomer - 10 - - -based on EPDM (cross-1 inked ) B2 LLDPE (with 8% octene-1) - - - - 20 B3 VLDPE (with 12% octene-1) 30 - - - -B4 A/EPDM/S (with 70% EPDM) 25 - - 30 20 B5 SEBS block copolymer (with - 20 - - -29% styrene) B6 EVACO (ethylene/vinyl - - 20 - -acetate/carbon monoxide terpolymer) B7 thermoplastic elastomer 15 - - - -based on EPM- not cross-linked filler (potassium aluminum 8 10 10 10 10 silicate) x -12a- 2 1 1 0 5 0 2 Table Cont'd filler (soot) ~ 1.5 1.5 1.5 1.5 1.5 parting agent (ethylene 0.3 0.3 0.3 0.3 0.3 montanic acid ester) antioxidant (Irganox 0.12 0.12 0.12 0.12 0.12 1010/Irgaphos 168) light stabilizer (Tinuvin 0.12 0.12 0.12 0.12 0.12 770) Examples Recipe characteristics 1 2 3 4 5 hardness (Shore D-15 sec) 31 41 39 35 39 initial elongation at failure 675 617 749 580 734 ( a ) DIN 52 910 Residual elongation at failure (%) a) thermal a in g g (500 h/120C) b) UV radiation 472 430 528 392 514 (480 h according to DIN 75 220)
The term "thermoplast.ic plastic" is understood in the broadest sense within the framework of the present invention. For example, it includes thermoplastic mixtures, polymer blends, polymer alloys, graft polymers and the like.
Consequently, the essence of the present invention, in contrast to the prior art mentioned above, consists in the use of a multiple-phase or hetero-phase polypropylene block copolymer with an increased proportion of ethylene/propylene copolymer, i.e. of more than 50 percent by weight. To achieve the effects aimed at by the invention, this proportion must be at least approximately 51 percent by weight, preferably approximately 55 to 80 percent by weight, in particular approximately 60 to 75 percent by weight. In this regard, it must be considered surprising that contrary to the strict specifications of the prior art, the proportion in percent by weight of the ethylene/propylene copolymer in the block copolymer in question is more or less far more than 50 percent by weight and that, in so doing, particularly advantageous properties of the plastic result, e.g. an improved resistance to scarring of the sheet produced with this plastic, an improved deep-drawing quality and deformability.
The thermoplastic plastic representing the essence of the invention can be cross-linked to a greater or lesser extent. In specific cases, it is advantageous to effect a certain cross-linking. A cross-linking of roughly 20 to 80%, in particular 50 to 75%, may be used as a guideline in this respect.
The extent of cross-linking can be determined, for example, by treating the thermoplastic elastomer with solvents so that the remaining cross-linked polymer is in the form of a gel and conclusions may be drawn regarding the extent of cross linking from the amount of this gel. The degree of cross linking may also be determined according to DIN 16892. The cross-linking of the thermoplastic plastic is advisably effected when it is already mixed with all other constituents, including conventional additives. This may be effected, for example, in a conventional mixing apparatus such as a kneader, a screw type extruder, and the like under appropriate conditions with respect to temperature, shear, mixing and pressure.
In order to create the desired effects it is necessary within the framework of the present invention to make use of a semicrystalline and/or amorphous polymeric modifier.
The modifier is used to regulate the melting point and melting viscosity, strength, calendering properties, extruding properties and the like characteristics. It can also impair or prevent the tendency of the sheets or molded articles to crystallize, which has a positive effect on the deep-drawing qualities and resistance to scarring. The modifiers can also positively affect the mixing properties and compatibility of the individual components of the mixture and improve the wetting properties and adhesive or bonding properties. In some cases, they can also cause internal and external softening or stiffening of the matrix polymers or influence the latter in the desired manner. Depending on the objective, the person skilled in the art can easily find the appropriate modifier from those described in the following.
According to the invention, a homopolymer and/or copolymer of ethylene is used as a polymeric modifier. In so doing, a homopolymer of propylene is not taken into consideration with respect to the marginal conditions for the propylene block copolymer. When an ethylene/propylene copolymer is used, it preferably contains approximately 5 to 20 percent by weight of ethylene. In particular, the ethylene/propylene copolymer preferably has a narrow molecular mass distribution with a heterogeneity or nonuniformity U of less than 6, particularly less than approximately 4. The use of an ethylene copolymer containing approximately 5 to 20 percent by weight octane and/or butene as comonomer is also particularly advantageous. It is also especially advantageous when the homopolymer and/or copolymer of the ethylene or propylene has a melt-flow index MFI (230/2.16) of roughly 0.5 to 10 g/10 min, in particular approximately 0.8 to 2.5 g/10 min, when calendering and a melt-flow index of at least approximately 0.8 g/10 min, particularly approximately 2.5 to 25 g/10 min, when extruding.
Other preferred polymeric modifiers which can be used according to the invention are: an ethylene/propylene copolymer, ethylene/propylene/diene terpolymer, an ethylene/acrylic acid copolymer, an ethylene/acrylic acid ester copolymer, a low-density polyethylene, an ethylene/vinyl acetate copolymer, an ethylene/glycidyl methacrylate copolymer, a styrene/ethylene/propylene block copolymer (SEP), a styrene/ethylene/butadiene/styrene block copolymer (SEBS) (hydrogenated), a styrene/ethylene/butadiene block copolymer (SEB), an acrylonitrile/ethylene/propylene/diene/styrene copolymer (A-EPDM-S) and/or a high-molecular amorphous EPM
rubber.
A particularly suitable modifier within the framework of the invention is a semicrystalline statistical ethylene/propylene/diene terpolymer (EPDM), that is, not a block terpolymer. This makes it possible to subject the finished mixture to a cross-linking via the dime component with the use of conventional cross-linking agents such as peroxide, epoxide and silane compounds and the like. The dime component in this terpolymer can be, in particular, a dicyclopentadiene, 1,4-hexadiene and/or 5-ethylidene-2-norbornene. The total proportion of the ethylene and propylene in the statistical terpolymer in percent by weight is preferably approximately 52 to 91 percent by weight, and the minimum content of ethylene is preferably approximately 65 percent by weight.
In the majority of cases of practical application, the thermoplastic plastic which can be used to produce sheets and molded bodies according to the invention preferably contains fillers. The proportion of filler is preferably approximately 8 to 28 percent by weight. All conventional fillers can be used, particularly those of potassium aluminum silicate, talc, chalk, kaolin, metal oxides, particularly titanium dioxide, and/or soot. Finally, other conventional additives can be used, particularly stabilizers such as antioxidants and heat stablizers, e.g. sterically hindered phenols, hydroquinones, substituted representatives of this group, phosphites, phosphonites and/or mixtures thereof, UV
stabilizers, e.g. various low-molecular, high-molecular, substituted resorcinols, salicylates, benzotriazoles, and benzophenones and/or mixtures thereof and the like, parting agents such as C1z- to C26-fatty acids, fatty alcohols, fatty acid esters and fatty acid amides and/or mixtures thereof and the like, dyes such as organic dyestuffs and pigments, e.g.
titanium dioxide, phthalocyanines or soot, flame retardants such as ammonium polyphosphate, zinc borate, magnesium, hydroxide, and aluminum hydroxide and the like.
The characteristics of the polypropylene block copolymer (abbreviation: PP) contained in the thermoplastic plastic are determined by the functional interaction of the polypropylene contained therein as well as that of the polymeric modifiers which are copolymerized with the latter, e.g. particularly ethylene/propylene copolymer. The latter represents the rubber component (abbreviation: EPM or EPR).
The PP component may also be regarded as a "hard" component, whereas the EPM component is considered a "soft" component.
Accordingly, the elastic and thermoplastic properties of the finished plastic mixture are substantially influenced by the PP/EPM ratio. Further possible influences are provided by incorporating the modifiers mentioned above.
The thermoplastic plastic which can be used to produce sheets and molded bodies according to the invention is characterized by desirable resistance to weathering. A sheet according to the invention which is produced with this material has superior resistance to scarring, good melting strength and a particularly good deep-drawing quality. This is demonstrated in the various deep-drawing processes, e.g. in the air pressing process, diaphragm pressing process, and the like. Deep-drawn -7- ~1 ~ p502 molded articles or composite formations produced from the sheet according to the invention can be used in particular advantage, for example, in aircraft and motor vehicles, interior paneling or panel parts in motor vehicles, preferably control panels or dashboards, pillars, side paneling, door paneling, shelves and exterior trim in motor vehicles. The sheet according to the invention can also be glued with or without deformation to a wide range of flat or three-dimensional substrates by conventional techniques. It may be provided with additional l0 layers or coats, e.g. protective coats. Finally, adhesive layers may also be affixed to the back of the sheets, possibly also with appropriate foam layer lining or bonding.
The invention is explained in more detail in the following examples:
Examples 1 to 5 A base sheet with a thickness of 1.1 mm was produced by means of a 4-roll calender using the recipes indicated in the following table. This sheet was measured for various characteristics which are likewise compiled in the following table.
Raw materials from Examples 1 to 5:
A-1: hetero-phase polypropylene block copolymer (cross-1 inked ) melt-flow index (230°C/2.18 kg) (DIN 53 735): 0.8 g/10 min elongation at failure (DIN 53 455): 620%
ethylene/propylene copolymer . 52% by weight proportion f . 27998-21 _g_ Table Cont'd extent of cross-linking (gel (DIN 16 892): 55%
content) elastic modulus in tension (DIN 53 457): 800 MPa density (DIN 53 479) : 0.87 g/cm3 crystallinity :22%
A-2: hetero-phase polypropylene block copolymer (not cross-linked) melt-flow index (230C/2.16 kg) (DIN 53 735): 2 g/10 min elongation at failure (DIN 53 455): 560%
ethylene/propylene copolymer . 52% by weight proportion elastic modulus in tension (DIN 53 457): 550 MPa density (DIN 53 479) 0.88 g/cm3 :
crystallinity . 28%
A-3: hetero-phase polypropyleneblock copolymer (not cross-1 inked ) melt-flow index(230C/2.16 kg) (DIN 53 735): 0.6 g/10 min elongation at failure (DIN 52 910): 596%
-9- ~1 ~ 0502 Table Cont'd ethylene/propylene copolymer . 58% by weight proportion elastic modulus in tension (DIN 52 910): 86 MPa density (DIN 53 479) : 0.89 g/cm3 crystallinity :25%
B-1: thermoplastic elastomer based on the ethylene/propylene/dicyclopentadiene terpolymer (cross-linked) melt-flow index (230°C/2.16 kg) (DIN 53 735): 8 g/10 min elongation at failure (DIN 52 910): 600%
rubber content (E=65% by . 52% by weight weight, P=23% by weight) extent of cross-linking (gel (DIN 16 892): 53% by weight content) density (DIN 53 479) : 0.88 g/cm3 B-2: LLDPE copolymer (with 8% octene-1) melt-flow index(230C/2.16 kg) (DIN 53 735) : 2.3 g/10 min elongation at failure (DIN 52 910): 650%
x .. -10- ~1 ~ 0502 Table Cont'd density (DIN 53 479): 0.92 g/cm3 crystallinity . 35%
B-3: VLDPE copolymer (with 12% octene-1) melt-flow index (230C/2.16 kg) (DIN 53 735): 2.8 g/10 min elongation at failure (DIN 52 910): 850%
density (DIN 53 479): 0.905 g/cm3 crystallinity :17%
B-4: A/EPDM/S copolymer (with 70% EPDM rubber) density (DIN 53 479): 1.03 g/cm3 elongation at failure (DIN 52 910): 490%
elastic modulus in tension (DIN 52 910): 310 MPa amorphous B-5: Block polymer with polystyrene end blocks and ethylene/butadiene center block (SEBS) (hydrogenated center block) density (DIN 53 479): 0.91 g/cm styrene content . 29% by weight ,.
Table Cont'd elongation at failure (DIN 52 910): 510%
B-6: EVACO (ethylene/vinyl acetate/carbon monoxide terpolymer) density (DIN 53 479): 1.00 g/cm3 carbon monoxide content :12% by weight B-7: High-molecular amorphous EPM rubber (not cross-linked/thermoplastic elastomer) melt-flow index (230C/2.16 kg) (DIN 53 735): 1.3 g/10 min elongation at failure (DIN 52 910): 620%
elastic modulus in tension (DIN 52 910): 140 MPa density (DIN 53 479): 0.94 g/cm3 Rubber proportion . 34% by weight ( amorphous ) Note: A = semicrystalline polyalkene elastomer B = polymeric modifier r f Examples Recipes 1 2 3 4 5 A1 hetero-phase polypropylene 30 - 70 - 60 block copolymer (cross-linked) A2 hetero-phase polypropylene - 70 - - -block copolymer (not cross-linked) A3 hetero-phase polypropylene - - 10 70 -block copolymer (not cross-linked) B1 thermoplastic elastomer - 10 - - -based on EPDM (cross-1 inked ) B2 LLDPE (with 8% octene-1) - - - - 20 B3 VLDPE (with 12% octene-1) 30 - - - -B4 A/EPDM/S (with 70% EPDM) 25 - - 30 20 B5 SEBS block copolymer (with - 20 - - -29% styrene) B6 EVACO (ethylene/vinyl - - 20 - -acetate/carbon monoxide terpolymer) B7 thermoplastic elastomer 15 - - - -based on EPM- not cross-linked filler (potassium aluminum 8 10 10 10 10 silicate) x -12a- 2 1 1 0 5 0 2 Table Cont'd filler (soot) ~ 1.5 1.5 1.5 1.5 1.5 parting agent (ethylene 0.3 0.3 0.3 0.3 0.3 montanic acid ester) antioxidant (Irganox 0.12 0.12 0.12 0.12 0.12 1010/Irgaphos 168) light stabilizer (Tinuvin 0.12 0.12 0.12 0.12 0.12 770) Examples Recipe characteristics 1 2 3 4 5 hardness (Shore D-15 sec) 31 41 39 35 39 initial elongation at failure 675 617 749 580 734 ( a ) DIN 52 910 Residual elongation at failure (%) a) thermal a in g g (500 h/120C) b) UV radiation 472 430 528 392 514 (480 h according to DIN 75 220)
Claims (13)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A sheet or molded body of thermoplastic material based on at least one semicrystalline polyalkene elastomer and/or a mixture of polyalkene elastomers having a multiple-phase alkene block copolymer with a determined hetero-phase elastomer copolymer component, a homopolymer and/or copolymer of an alkene and of a polymeric modifier, which comprises an elastomer comprising:
1) a multiple-phase polypropylene block copolymer having an ethylene/propylene copolymer proportion of approximately 51 to 85% by weight based on the weight of the polypropylene block copolymer, and a degree of crosslinking of approximately 30 to 75%; and 2) a polymeric modifier selected from the group consisting of an ethylene copolymer, an ethylene homopolymer, an ethylene/propylene copolymer comprising 5 to 20% by weight ethylene and having a narrow molecular mass distribution with a heterogeneity or non-uniformity U of less than 6 and a melt-flow index MFI (230/2.16) of 0.5 to 10 g/10 min when calendering, a melt-flow index of at least approximately 0.8 g/10 min when extruding, an ethylene/propylene/diene terpolymer, an ethylene/acrylic acid copolymer, an ethylene/acrylic acid ester copolymer, an ethylene/vinyl acetate copolymer, an ethylene/glycidyl methacrylate copolymer, a styrene/ethylene/propylene copolymer (SEP), a styrene/ethylene/butadiene/styrene block copolymer (SEBS), an acrylonitrile/ethylene/propylene/diene/styrene copolymer (A-EPDM-S) and a high-molecular amorphous EPM rubber;
3) and wherein approximately 70 to 30 parts by weight of the propylene block copolymer are allotted to 30 to 70 parts by weight of the polymeric modifier.
1) a multiple-phase polypropylene block copolymer having an ethylene/propylene copolymer proportion of approximately 51 to 85% by weight based on the weight of the polypropylene block copolymer, and a degree of crosslinking of approximately 30 to 75%; and 2) a polymeric modifier selected from the group consisting of an ethylene copolymer, an ethylene homopolymer, an ethylene/propylene copolymer comprising 5 to 20% by weight ethylene and having a narrow molecular mass distribution with a heterogeneity or non-uniformity U of less than 6 and a melt-flow index MFI (230/2.16) of 0.5 to 10 g/10 min when calendering, a melt-flow index of at least approximately 0.8 g/10 min when extruding, an ethylene/propylene/diene terpolymer, an ethylene/acrylic acid copolymer, an ethylene/acrylic acid ester copolymer, an ethylene/vinyl acetate copolymer, an ethylene/glycidyl methacrylate copolymer, a styrene/ethylene/propylene copolymer (SEP), a styrene/ethylene/butadiene/styrene block copolymer (SEBS), an acrylonitrile/ethylene/propylene/diene/styrene copolymer (A-EPDM-S) and a high-molecular amorphous EPM rubber;
3) and wherein approximately 70 to 30 parts by weight of the propylene block copolymer are allotted to 30 to 70 parts by weight of the polymeric modifier.
2. The sheet or molded body of claim 1 wherein the proportion of ethylene/propylene copolymer in the polypropylene block copolymer is approximately 55 to 80 percent by weight.
3. The sheet or molded body of claim 1 or 2 wherein the degree of crosslinking of the polypropylene block copolymer is from 50 to 75%.
4. The sheet or molded body of claim 1, 2 or 3 wherein the ethylene/propylene copolymer has a heterogeneity U of less than 4.
5. The sheet or molded body of any one of claims 1 to 4 wherein the ethylene copolymer comprises approximately 5 to 20%
by weight octene and/or butene as a comonomer.
by weight octene and/or butene as a comonomer.
6. The sheet or molded body of any one of claims 1 to 5 wherein the ethylene/propylene/diene terpolymer is a statistical terpolymer.
7. The sheet or molded body of claim 6 wherein the total proportion of the ethylene and propylene in the statistical terpolymer is approximately 52 to 91% by weight.
8. The sheet or molded body of claim 7 wherein the statistical terpolymer contains at least approximately 65% by weight ethylene.
9. The sheet or molded body of any one of claims 1 to 8 wherein the thermoplastic material contains a filler.
10. The sheet or molded body of claim 9 wherein the thermoplastic material contains approximately 8 to 28% by weight of a filler.
11. The sheet of molded body of claim 9 wherein the filler is selected from the group consisting of potassium aluminum silicate, talc, chalk, kaolin, metal oxides and soot.
12. The sheet or molded body of claim 11 wherein the filler is titanium dioxide or soot.
13. A deep-drawn molded article produced from a sheet of any one of claims 1 to 12 in the form of a control panel, dashboard, pillar, side paneling, door paneling, shelf or exterior trim in a motor vehicle.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4211413A DE4211413C2 (en) | 1992-04-04 | 1992-04-04 | Film or molded body made of a thermoplastic based on a polypropylene block copolymer and use of the film for the production of deep-drawn molded parts |
| DEP4211413.6 | 1992-04-04 | ||
| PCT/EP1993/000821 WO1993020146A1 (en) | 1992-04-04 | 1993-04-02 | Foil or moulded body made of a thermoplastic material based on a polypropylene block copolymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2110502A1 CA2110502A1 (en) | 1993-10-14 |
| CA2110502C true CA2110502C (en) | 2001-07-03 |
Family
ID=6456130
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002110502A Expired - Fee Related CA2110502C (en) | 1992-04-04 | 1993-04-02 | Foil or moulded body made of a thermoplastic material based on a polypropylene block copolymer |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0587871B1 (en) |
| CA (1) | CA2110502C (en) |
| DE (2) | DE4211413C2 (en) |
| ES (1) | ES2092297T3 (en) |
| MX (1) | MX9301912A (en) |
| WO (1) | WO1993020146A1 (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4427376A1 (en) | 1994-08-03 | 1996-02-08 | Hoechst Ag | Oriented polyolefin film with alkene block copolymer, process for its production and use |
| DE19521632C2 (en) * | 1995-06-14 | 1998-10-22 | Porsche Ag | Cladding part for the underside of a motor vehicle, in particular a passenger car |
| AUPN714295A0 (en) * | 1995-12-14 | 1996-01-11 | Photonic Technologies Pty Ltd | Fibre optic circulator |
| TW509707B (en) * | 1997-02-21 | 2002-11-11 | Montell Technology Company Bv | Soft elastomeric thermoplastic polyolefin compositions |
| JP3476355B2 (en) * | 1998-01-21 | 2003-12-10 | 日本プラスト株式会社 | Airbag storage case |
| AT408757B (en) * | 1999-06-29 | 2002-03-25 | Constantia Verpackungen Ag | RIGID DEAD FOLD FILMS |
| BR0305246B1 (en) | 2002-06-26 | 2012-12-11 | impact resistant polyolefin compositions, their preparation process, as well as injection molded articles comprising them. | |
| RU2308470C2 (en) | 2002-06-26 | 2007-10-20 | Базелль Полиолефин Италия С.П.А. | Shock-resistant polyolefin compositions |
| DE10332280A1 (en) * | 2003-07-10 | 2005-01-27 | Basell Poliolefine Italia S.P.A. | Covering part, in particular interior trim part of a motor vehicle |
| CN1997704B (en) | 2003-11-06 | 2011-07-13 | 巴赛尔聚烯烃意大利有限公司 | Polypropylene composition |
| AU2005252325A1 (en) | 2004-06-08 | 2005-12-22 | Basell Poliolefine Italia S.R.L. | Polyolefin composition having a high balance of stiffness, impact strength and elongation at break and low thermal shrinkage |
| DE102014226349A1 (en) * | 2014-12-18 | 2016-06-23 | Benecke-Kaliko Aktiengesellschaft | Thermoforming and scoring composite film, a process for their preparation and their use |
| RU2726661C2 (en) | 2015-12-22 | 2020-07-15 | Нора Системз Гмбх | Self-adhesive floor coating and method of its manufacturing |
| SI3394363T1 (en) * | 2015-12-22 | 2021-08-31 | Nora Systems Gmbh | Floor covering containing thermoplastic elastomer and method for producing same |
| CN112391023B (en) * | 2020-11-12 | 2022-04-29 | 杭州星点包装材料有限公司 | Heat-sealing film based on propylene copolymer and preparation method thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL278595A (en) * | 1961-05-18 | |||
| US3689595A (en) * | 1970-04-28 | 1972-09-05 | Phillips Petroleum Co | High impact polypropylenes |
| US4194155A (en) * | 1978-06-14 | 1980-03-18 | Honda Giken Kogyo Kabushiki Kaisha | Radio receiving device for automotive use |
| JPS6236428A (en) * | 1985-08-10 | 1987-02-17 | Nissan Motor Co Ltd | Glass fiber-reinforced instrument panel |
| JPH0618951B2 (en) * | 1989-07-17 | 1994-03-16 | チッソ株式会社 | Method for producing polyolefin-based thermoplastic elastomer composition |
| DE4015748A1 (en) * | 1990-05-16 | 1991-11-21 | Alkor Gmbh | Single or multi-layered plastic, plastic liner or molded part thereof |
-
1992
- 1992-04-04 DE DE4211413A patent/DE4211413C2/en not_active Expired - Fee Related
-
1993
- 1993-04-02 EP EP93908894A patent/EP0587871B1/en not_active Expired - Lifetime
- 1993-04-02 DE DE59303844T patent/DE59303844D1/en not_active Expired - Fee Related
- 1993-04-02 ES ES93908894T patent/ES2092297T3/en not_active Expired - Lifetime
- 1993-04-02 WO PCT/EP1993/000821 patent/WO1993020146A1/en active IP Right Grant
- 1993-04-02 MX MX9301912A patent/MX9301912A/en not_active IP Right Cessation
- 1993-04-02 CA CA002110502A patent/CA2110502C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| DE4211413A1 (en) | 1993-10-07 |
| EP0587871A1 (en) | 1994-03-23 |
| DE59303844D1 (en) | 1996-10-24 |
| MX9301912A (en) | 1994-08-31 |
| CA2110502A1 (en) | 1993-10-14 |
| EP0587871B1 (en) | 1996-09-18 |
| DE4211413C2 (en) | 1997-04-24 |
| ES2092297T3 (en) | 1996-11-16 |
| WO1993020146A1 (en) | 1993-10-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5482766A (en) | Deep-drawable film | |
| CA2110502C (en) | Foil or moulded body made of a thermoplastic material based on a polypropylene block copolymer | |
| US4917944A (en) | Multi-ply weatherable plasticizer-free sheet | |
| US6153680A (en) | Thermoplastic polymer alloy compositions and in-line compounding process for direct sheet extrusion of sheets prepared from the thermoplastic polymer alloy compositions | |
| CA2093295C (en) | Film or molded article of a thermolastic with a terpolymer component | |
| CA2235096A1 (en) | Co-extruded laminate comprising at least one propylene graft copolymer layer | |
| US5948867A (en) | Polyolefin compositions used for making embossed sheets with improved gain retention | |
| JP2001220472A (en) | Low-linear expansion polyolefin-based composite resin composition, and part item for automotive sheathing material | |
| EP0635360B1 (en) | Deep-drawable film, method for its manufacture and its use | |
| US6162872A (en) | Polyolefin compositions used for making embossed sheets with improved grain retention | |
| US6777476B2 (en) | Polypropylene resin composition | |
| US20140288223A1 (en) | Bio resin compositions, bio molded article and method of manufacturing the same | |
| US6020046A (en) | Embossed sheets of polyolefin compositions with improved grain retention | |
| US6284355B1 (en) | Film, laminated film and laminated structure | |
| GB2161490A (en) | Propylene-ethylene copolymer base resin composition for molding purposes | |
| CZ181494A3 (en) | Deep-drawing foil, process of its production and its use | |
| US6906144B2 (en) | Polypropylene-based resin composition for powder slush molding | |
| JP2925982B2 (en) | Composite molded article and method for producing the same | |
| JP4732749B2 (en) | Thermoplastic resin composition, molded article and use thereof | |
| JP2920837B2 (en) | Laminate | |
| JPH10330578A (en) | Thermoplastic elastomer composition and laminate prepared therefrom | |
| KR100633656B1 (en) | Polypropylene resin composite for high paint adhesive and low temperature impact resistance | |
| KR19980067272A (en) | Composite elastomeric composition for automotive exterior | |
| KR20050123255A (en) | Composition of thermoplastic | |
| KR100810052B1 (en) | Thermoplastic elastomer mat |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKLA | Lapsed |