Polymeric compositions and processes for molding articles

Priority claim This application claims the benefits of US Provisional Patent Application No. 60 / 981,658 (filed October 22, 2007). The entire patent application is incorporated herein by reference for all purposes. Field of invention The present invention relates to modified polyolefin compositions and methods associated therewith. More specifically, the present invention relates to blended polyolefin materials that provide high quality surface appearance and / or improved durability after molding. Specifically, the present invention has one, two, three or even all of the following properties: low gloss, good gloss uniformity, durable surface quality and soft touch. The present invention relates to a polymer composition suitable for molding a color article.

Much effort has been made to develop polymer compositions that exhibit desirable properties and are less costly or both. For some applications, it is desirable to improve one or more of the following properties: the tactile properties of polymeric articles, the low gloss surface appearance or durability. For example, since vehicle passengers come into contact with various automobile interiors, it is recommended to use materials that have a soft touch tactile sensation, are durable, and can withstand frequent contact and scratches. desirable. A method of giving a soft-touch feel, low-gloss appearance and high surface durability is a multi-step process of applying a secondary layer of functional material to the top of the part by overmolding, painting or other techniques. There is use. Another way to provide a soft-touch feel, low-gloss appearance and high surface durability is to modify the thermoplastic material to suit the properties of interest.

Examples of prior art polymer compositions and methods of forming these compositions are described in Patent Documents 1-5, which are hereby incorporated by reference in their entirety for all purposes. Incorporate into.

Patent Documents 6-10, which are incorporated herein by reference in their entirety, can be blends with soft thermoplastics and polypropropylenes with improved mechanical properties. , A block (ie, massive) copolymer of a lower α-olefin (LOA) and a second α-olefin (ie, an LOA / α-olefin interpolymer, such as an ethylene / α-olefin interpolymer).

Patent Documents 11-17 (all of which are specifically incorporated herein by reference) are linear or substantially linear ethylene polymers (S) which can be soft thermoplastics. / LEP) and polymer blends containing S / LEP are described.

Patent Documents 11, 12 and 15 (incorporated herein by reference to all of these) describe polymer blends with polypropylene elastomers and propylene elastomers, which can be soft thermoplastics.

<p><patcit num="1"><text>U.S. Pat. No. 6,300,419</text></patcit><patcit num="2"><text>U.S. Pat. No. 6,949,605</text></patcit><patcit num="3"><text>U.S. Pat. No. 6,498,214</text></patcit><patcit num="4"><text>US Patent Application Publication No. 2005/0288393</text></patcit><patcit num="5"><text>PCT International Patent Application Publication WO2007 / 025663A1</text></patcit><patcit num="6"><text>U.S. Patent Application Publication No. 2007/0010616</text></patcit><patcit num="7"><text>PCT application PCT / US2005 / 0008917 (filed on March 17, 2005)</text></patcit><patcit num="8"><text>PCT International Patent Application Publication Publication WO2006 / 102155A2 (filed on March 15, 2006)</text></patcit><patcit num="9"><text>PCT International Patent Application Publication Publication WO2006 / 101966A1 (filed on March 15, 2006)</text></patcit><patcit num="10"><text>PCT International Patent Application Publication Publication WO 2006/101932A2 (filed on March 15, 2006)</text></patcit><patcit num="11"><text>PCT International Patent Application Publication Publication WO2003 / 040201A1 (filed on May 6, 2002)</text></patcit><patcit num="12"><text>U.S. Patent Application Publication No. 2003/0204017 (filed May 5, 2002)</text></patcit><patcit num="13"><text>European Patent No. 0495099 (filed December 12, 1989)</text></patcit><patcit num="14"><text>European Patent Application No. 129368 (filed June 5, 1984)</text></patcit><patcit num="15"><text>U.S. Pat. No. 6,525,157 (issued February 25, 2003)</text></patcit><patcit num="16"><text>US Pat. No. 6,403,692 (issued June 11, 2002)</text></patcit><patcit num="17"><text>U.S. Pat. No. 5,272,236 (issued December 21, 1993)</text></patcit></p>

<p num="0008"> It can exhibit a relatively soft touch and can withstand the situations encountered in vehicle interior applications, such as substantially low gloss, scratch resistance, scratch resistance, low temperature ductility, dimensional stability or theirs. It is still desired to provide polymer compositions that can exhibit properties such as any combination, especially molded thermoplastic polyolefin compositions. Highly costly or highly treated (eg, grafted) polymers, special fillers or agents or other relatively costly additional or alternative ingredients, processes, multilayer structures while still maintaining the desired properties. It would be particularly attractive if such a composition could be provided without the use of (eg, coatings) or the like.</p>

<p num="0009"> In one aspect, the present invention relates to a first polymer component; a second polymer component (the second polymer component is relatively (or relatively) softer in thermoplasticity than the first polymer component. Selected from the group consisting of resin-containing and propylene elastomers, substantially linear or linear ethylene polymers (S / LEPs), or both; said S / LEPs are from about 40 to about 40 on a total weight basis of S / LEPs. It contains an α-olefin comonomer having 4 to 20 carbon atoms having an ethylene concentration of about 85% by weight; the propylene elastomer contains propylene and one or more α-olefin comonomer having 2 or 4 to 20 carbon atoms. It has a comonomer concentration of less than about 20% by weight based on the total weight of the propylene elastomer); and the polymer composition comprising a blend of at least one reinforcing material.</p><p num="0010"> This aspect of the invention can further be characterized by one or any combination of the following features: The polymer composition has a ratio of the first polymer component to the second polymer component greater than about 10:42, The first polymer component is present in an amount of about 3 to about 70% by weight based on the total weight of the composition; The first polymer component is present in an amount of about 3 to about 60% by weight based on the total weight of the composition; The first polymer component is present in an amount of about 10 to about 50% by weight based on the total weight of the composition; The second polymer component comprises S / LEP and the ratio of the first polymer component to the second polymer component ranges from about 10:42 to about 10: 2; The second polymer component comprises a propylene elastomer and the ratio of the first polymer component to the second polymer component ranges from about 10:42 to about 10: 2; The second polymer component is present in an amount of about 10 to about 45% by weight on a total weight basis; The second polymer component is present in an amount of about 10 to about 90% by weight (eg, about 20 to about 90% by weight) on a total weight basis; The second polymer component is present in an amount of about 20 to about 45% by weight (eg, about 20 to about 35% by weight) on a total weight basis; The soft thermoplastic resin is about 0.850 to about 0.900 g / cm.³Includes S / LEP with a density of and a melt index of about 0.2 to about 40 (measured at 190 ° C., 2.16 kg according to ASTM D-1238-04); The soft thermoplastic resin is about 0.860 to about 0.880 g / cm.³Includes S / LEP with a density of and a melt index of about 0.5 to about 10 (measured at 190 ° C., 2.16 kg according to ASTM D-1238-04); The S / LEP is present at a concentration of about 20 to about 35% by weight based on the total weight of the polymer composition; The S / LEP is the melt flow ratio I₁₀/ I₂5.63, equation M_w/ M_nI₁₀/ I₂-4.63 Molecular weight distribution defined by (M_w/ M_n) And about 4x10⁶Dyne / cm²It is characterized by a critical shear stress at the onset of the larger gloss melt fracture; The S / LEP is as follows: density 0.85 to 0.92 g / cm², Extreme viscosity number (η) (measured in decalin at 135 ° C.) 0.1-10 dl / g, weight average molecular weight (M)_w) Logarithmic mean molecular weight (M)_n) Ratio (M_w/ M_n) (Measured by GPC) 1.2-4, or the ratio of (MFR10 under load 10 kg) to (MFR2 under load 2.16 kg) measured at 190 ° C. (MFR10 / MFR2) 8-50 (MFR10 / MFR2) Is characterized by one or any combination (which can be measured, for example, by ASTM D-1238 at 190 ° C. with loads of 10 kg and 2.16 kg, respectively); The S / LEP α-olefin comonomer is a monomer having 8 carbon atoms (for example, 1-octene); The ratio of the first polymer component to the second polymer component is from about 10:27 to about 10: 2; The composition gives the composition a soft touch (i) a coefficient of friction (coefficient of static friction) in the range of about 0.2 to about 0.7 (according to ASTM D-1894); (ii) about 0.1. Coefficient of friction (coefficient of friction) in the range of ~ 0.6 (according to ASTM D-1894); or characterized by both (i) and (ii); The first component comprises polypropylene homopolymers, polypropylene random copolymers, impact resistant polypropylene copolymers or any combination thereof; The first polymer component has a melt flow rate of about 1 to about 60 g / 10 min (measured according to ASTM D-1238 (230 ° C., 2.16 kg)); The first component comprises a polypropylene homopolymer present in a concentration of about 20 to about 50% by weight based on the total weight of the polymer composition; The composition has a melt flow rate of about 50 to about 55 g / 10 min (according to ASTM D-1238 (230 ° C., 2.16 kg)) and about 1 to about 5 kJ / m.²Charpy (notched) impact strength (according to ISO 179-1 / 1eA (23 ° C.)) or polypropylene homopolymers having both; The second polymer component is an ethylene-octene copolymer containing S / LEP, wherein the S / LEP contains about 50 to about 70% by weight of ethylene based on the total weight of the ethylene-octene copolymer, and the ethylene-octene copolymer. The octene copolymer has a melt flow rate of about 1 to about 30 g / 10 min (measured according to ASTM D-1238 (190 ° C., 2.16 kg)); The second polymer component has a Shore A hardness of about 65 to about 95 (according to ASTM D-2240); The polymer composition has a total ethylene concentration of about 2 to about 10% by weight based on the total weight of the polymer composition; The second polymer component is a propylene-ethylene copolymer containing a propylene elastomer, wherein the propylene elastomer has an ethylene concentration of about 4 to about 20% by weight based on the total weight of the propylene elastomer; The second polymer component comprises a propylene elastomer, which has a propylene concentration of about 80 to about 96% by weight based on the total weight of the propylene elastomer; The propylene elastomer is a low elastic ethylene-propylene copolymer (LEEP copolymer): The LEEP copolymer has the following characteristics: the melting point ranges from less than 110 ° C to the lower limit of 25 ° C; the relationship between elasticity and 500% tensile modulus is, for example, elasticity 0.935M + 12 (elasticity is percentage). (M is a 500% tensile modulus expressed in megapascal (MPa)); the relationship between flexural modulus and 500% modulus is, for example, flexural modulus 4.2e.^0.27M+50 (bending modulus is expressed in MPa, M is 500% tensile modulus expressed in MPa); heat of fusion is more than 1.0 joule / g at the lower limit and less than 125 J / g at the upper limit; triad tacticity ) (Carbon-13 nuclear magnetic resonance (¹³(Measured by C NMR) is over 75%; tacticity index m / r ranges from lower limit 4 to upper limit 12; ratio of reverse-inserted propylene units based on 2,1-insertion of propylene monomer during total propylene insertion¹³More than 0.5% (measured by C NMR); ratio of reverse-inserted propylene units based on 1,3-insertion of propylene monomer during total propylene insertion (measured by C NMR)¹³More than 0.05% (measured by 1 NMR); at least 75% by weight of the copolymer is soluble in two adjacent temperature fractions of thermal fractionation performed by heating in hexanes by 8 ° C. Intermolecular tacticity such as; reactive ratio product r₁r₂Is less than 1.5; molecular weight distribution Mw / Mn is in the range of lower limit 1.5 to upper limit 40; molecular weight is 15,000 to 5,000,000; solid proton nuclear magnetic resonance (¹1 H NMR) relaxation time less than 18 ms (ms); elasticity less than 30% or less than 20% or less than 10% or less than 8% or less than 5%; or 500% tensile modulus greater than 0.5 MPa (or) Has one or any combination of more than 0.8 MPa or more than 1.0 MPa or more than 2.0 MPa; The propylene elastomer is a region-error ethylene-propylene copolymer (R-EPE copolymer), and the R-EPE copolymer has one or any combination of the following properties: ethylene-derived units are at least about about. Approximately equal strengths of 0.1% by weight and corresponding to region errors of about 14.6 and about 15.7 ppm.¹³Has a C NMR peak; a skewness index S of at least about 60% by weight of propylene-derived units and at least about 0.1% by weight of ethylene-derived units and greater than about -1.20_ixThe unit of propylene is at least about 60% by weight and the unit of ethylene is at least about 0.1% by weight, and the DSC curve is essentially unchanged._meAnd T which decreases as the amount of ethylene in the copolymer increases_maxPropylene / which has at least about 60% by weight of propylene-derived units and at least about 0.1% by weight of ethylene-derived units and is produced using a Ziegler-Natta catalyst but has similar weight average molecular weights. It has an X-ray diffraction pattern showing more γ-type crystals than ethylene copolymers; propylene-derived units are at least about 60% by weight or ethylene-derived units are at least about 0.1% by weight and the ethylene content of R-EPE copolymers. Has a B value greater than about 1.4 when is at least about 3% by weight; The at least one reinforcing material described above comprises glass fibers selected such that the glass fibers in the resulting composition have an average fiber length of about 1-2 mm; The at least one reinforcing material comprises glass fibers present in a concentration of about 5 to about 40% by weight (eg, about 10 to about 40% by weight) based on the total weight of the polymer composition; The polymer composition is free of inorganic fillers; The polymer composition is talc-free; or The polymer composition is free of peroxides.</p><p num="0011"> Another aspect of the invention relates to a molded article, at least in part, comprising the polymeric compositions described herein.</p><p num="0012"> The method aspect of the present invention relates to a method for producing a part in which a part of a molded product contains the polymer composition described in the present specification.</p><p num="0013"> This aspect of the invention can be further explained by one or any combination of the following features: The method prepares (eg, supplies) about 3 to about 60 parts by weight of a first material containing at least a portion of a relatively hard thermoplastic; propylene elastomer, substantially linear or linear ethylene. Approximately 10 to about 70 parts by weight of a second material containing at least a portion of a polymer (S / LEP) or a relatively soft thermoplastic resin selected from the group consisting of both is prepared (eg, supplied) (eg, S). / LEP contains an α-olefin comonomer having 4 to 20 carbon atoms having an ethylene concentration of about 40 to about 85% by weight based on the total weight of S / LEP, and the propylene elastomer contains propylene and one or more carbons. Containing α-olefin comonomer of number 2 or 4 to 20 carbon atoms and having a comonomer concentration of less than about 20% by weight based on the total weight of the propylene elastomer); Prepare (eg, supply) about 20 to about 75 parts by weight of the material of 3; blend the first material, the second material and the third material to form a blend; and mold the blend. Includes the steps of molding in to form an article; The article gives the composition a soft touch (a) coefficient of friction (coefficient of static friction) in the range of about 0.2 to about 0.7 (measured by ASTM D-1894) or about 0.1 to about 0. Coefficient of friction (coefficient of friction) in the range of .6 (measured by ASTM D-1894) or both; or (b) an ethylene content of about 5 to about 9 parts by weight of the resulting article, or (a) and (b). ) Includes materials with a combination of; The at least one reinforcing material contains glass fiber, and the at least one reinforcing material concentrate further contains polypropylene; The relatively hard thermoplastics mentioned above are polyethylene homopolymers, polyethylene copolymers, polypropylene homopolymers, impact resistant polypropylene copolymers, polypropylene random copolymers or any combination thereof; At least one of the above reinforcing materials includes glass length fibers having an average fiber length of more than about 5 mm; The at least one reinforcing material described above comprises short glass fibers having an average fiber length of less than 5 mm (preferably less than about 2 mm or even less than about 0.5 mm); The polyolefin resin is present in a concentration of about 20 to about 60% by weight based on the total weight of the reinforcing material concentrate; The at least one reinforcement is present at a concentration of about 30 to about 90% by weight (eg, about 40 to about 80% by weight) based on the total weight of the reinforcement concentrate; The at least one reinforcement is present in an amount of about 10 to about 40% by weight based on the total weight of the article; The relatively soft thermoplastic resin contains S / LEP present at a concentration of about 10 to about 45% by weight based on the total weight of the molded product, and the S / LEP is about 0.850 to about 0. It has a density of .900 and a melt index of about 0.2 to about 40 (measured according to ASTM D-1238 (190 ° C., 2.16 kg)); The relatively soft thermoplastic resin is a propylene elastomer having about 4 to about 20% by weight of ethylene and has a melting temperature of less than about 120 ° C., based on the total weight of the propylene elastomer; The propylene elastomer has a Shore A hardness of about 65 to about 85 (according to ASTM D-2240); The propylene elastomer has a crystallinity of less than about 30% by weight (eg, less than about 14% by weight); The propylene elastomer has a crystallinity lower than that of the relatively hard thermoplastic resin; The article further comprises a coupling agent (eg, a coupling agent present in a concentration of less than about 10% by weight based on the total weight of the article); The method further comprises the step of simultaneously blending two or more of the first material, the second material or the third material prior to the blending step; The method substantially does not involve blending any two of the first, second or third materials together prior to the blending step; The method prepares a first material containing polypropylene homopolymers, impact resistant polypropylene copolymers, polypropylene random copolymers or any combination thereof; S / LEP, propylene elastomers or a second material containing both; At least one reinforcing material is prepared; the first material, the second material and the reinforcing material are mixed to form a polymer composition; and the polymer composition is molded into a part. Including the process of The coefficient of friction (coefficient of static friction) (measured by ASTM D-1894) in the range of about 0.2 to about 0.7 or about 0.1 to about 0.6 where the polymer composition gives the composition a soft touch feel. It features one or both of the coefficients of friction (coefficient of dynamics) (measured by ASTM D-1894) in the range of; The molding step includes a step of injection molding the polymer composition; The part is formed by single shot molding; The mixing step includes mixing the reinforcing material with at least a part of the first material, at least a part of the second material, or both before the step of preparing the reinforcing material; The mixing step includes mixing the second material with at least a portion of the first material prior to preparing the at least one reinforcing material; The material of the component comprises glass fibers having an average fiber length of more than about 1 mm (eg, about 1-2 mm); The polymer composition does not contain inorganic fibers; The polymer composition is talc-free; The polymer composition contains no glass particles other than glass fibers; The polymer composition is free of peroxides.</p><p num="0014"> Another method aspect of the invention is to prepare a first material comprising polypropylene homopolymers, impact resistant polypropylene copolymers, polypropylene random copolymers or any combination thereof; a second comprising S / LEP, propylene elastomer or both. The materials of the above are prepared; at least one kind of reinforcing material is prepared, and the first material, the second material and the reinforcing material are mixed to form a polymer composition; and the polymer composition is pelletized. The present invention relates to a method for producing an article, which comprises forming pellets or granules that can be supplied to a thermoplastic resin molding machine; and placing at least 5 kg of the pellets or granules in a container.</p><p num="0015"> This aspect of the invention can be further characterized by one or any combination of the following features: The method further comprises the step of injection molding the polymer composition; The injection molding step includes the step of forming an article by single shot injection molding; The mixing step includes mixing the reinforcing material with at least a part of the first material, at least a part of the second material, or both before the step of preparing the reinforcing material; The mixing step includes mixing the second material with at least a part of the first material before the step of preparing the at least one kind of reinforcing material.</p><p num="0016"> Yet another aspect of the present invention is the first polymer component; the second polymer component (the second polymer component comprises an ethylene content present in an amount of about 20% by weight or less of the second polymer component. ); And for a soft-touch-feeling polymer composition comprising a blend of at least one reinforcing material, the ratio of the first polymer component to the second polymer component is about 5: 1 to about 1: 4. In the range of .2; the first polymer component is present in an amount of about 3 to about 50 parts by weight of the composition; the second polymer component has an ethylene content of about 4 to about 20% by weight. The second polymer component is present in an amount of about 10 to about 70 parts by weight of the composition and has a Shore A hardness of about 65 to about 95 (according to ASTM D-2240).</p>

In general, the present invention relates to a modified polymer composition, a method of forming the polymer composition, and an article or component formed from the polymer composition, formed by the method, or formed from the polymer composition by the method. Regarding. Advantageously, the polymer composition can be used to form parts or members with a soft-touch feel with desirable properties at a relatively low cost, so that parts for automotive applications (eg, occupants are more accessible). It is attractive to use as an automobile interior member). The polymer composition is typically selected from at least one relatively hard thermoplastic resin (eg, polypropylene homopolymers, polyethylene homopolymers, propylene copolymers, ethylene copolymers and any mixture thereof, of about 20). A first polymer component comprising at least one polymer having a degree of crystallinity greater than% by weight; at least one relatively soft thermoplastic resin (eg, one such as a thermoplastic polyolefin) or A second polymer component containing (more elastomers); at least one reinforcing material (eg, glass fiber); and optionally a coupling or cross-linking agent, cross-linking aid, flame retardant, ignition resistant additive, Stabilizers, foaming agents, foaming agent activators, colorants, antioxidants, mold release agents, antistatic agents, slip aids (ie non-slip aids), flow enhancers, nucleating agents, clarifying agents or theirs. Includes (but is not limited to) one or more additives which can include (but is not limited to) a combination of the above. In one aspect of the invention, the polymer composition may be free of coupling agents, cross-linking agents and foaming agents.

Surprisingly, by using the relatively soft thermoplastic resin at a lower concentration than the soft thermoplastic resins used so far, reinforcement having a desirable low hardness and / or low flexural modulus is achieved. It was found that the composition was obtained. In addition, the fortified compositions of the present invention show surprising improvements in their low temperature properties (eg, ductility at temperatures of about 20 ° C.). The reinforced compositions of the present invention further have the following surface properties: improved glossiness, improved scratch resistance and / or scratch resistance, more elastic soft touch feel, high surface friction or elimination of tiger stripes. It was unexpected that it was observed that one or any combination of / reductions could also be present. Furthermore, it has been observed that the composition can also have surprisingly desirable bulk properties such as sound deadening, high stiffness, high heat deflection temperature and / or high Vicat softening temperature. This combination of properties makes this reinforced composition currently available in applications that require at least two materials (eg, a first material that gives good surface properties and a second material that gives good bulk properties). It will be possible to use it to produce one-shot articles.

Further teachings applicable in the practice of the present invention are disclosed in simultaneously filed US Patent Application No. 12 / 256,301 (filed October 22, 2008; corresponding to agent reference number 1062.098 (67447A)). It has been incorporated herein by reference in its entirety. The test methods for olefinic block copolymers (eg, ethylene / α-olefin interpolymers or propylene / α-olefin interpolymers) described above are used herein by way of example, without limitation. Can be done.

First polymer component / hard thermoplastic resin Here, we look at the individual components in more detail from the entire composition. The articles described herein are typically at least one type of rigid thermoplastic resin (which can be a thermoplastic polymer) that is relatively strong, rigid, impact resistant, or any combination thereof. Contains a first polymer component comprising. For example, the thermoplastic polymer described here can be polyolefin-based, more preferably polyolefin-based homopolymer. The first polymer component typically comprises at least about 3% by weight, preferably at least about 10% by weight, more preferably at least about 15% by weight, most preferably at least about 20% by weight, based on the total weight of the polymer composition. It is present in an amount of% by weight (eg, at least about 30% by weight). The total polymer composition is also typically less than about 70% by weight, more typically less than about 60% by weight, more typically less than about 45% by weight, most typically less than about 40% by weight. Contains the first polymer component of.

Preferably, the thermoplastic polymer comprises at least one polymer selected from polypropylene homopolymers, polyethylene homopolymers, propylene copolymers, ethylene copolymers and any mixture thereof. One embodiment, but not limited to, preferred polypropylene homopolymers is disclosed in US Pat. No. 7,087,680, which is incorporated herein by reference for all purposes. ..

Polypropylene is generally an isotactic type homopolymer polypropylene, but other types of homopolymer polypropylene such as syndiotactic polypropylene or atactic polypropylene are also at low concentrations (eg less than about 15% by weight based on the total weight of the homopolymer polypropylene or. Furthermore, it can be used at less than about 5% by weight). Polypropylene is typically impact resistant polypropylene copolymers (eg, those using a secondary copolymerization step that reacts ethylene with propylene) or polypropylene random copolymers (also reaction modified and copolymerized with propylene). Can also be 2 to 20% by weight, more typically 2 to 7% by weight).

The molecular weight of the rigid thermoplastic resin (for example, polypropylene) used in the present invention, and thus the melt flow rate, may vary depending on the application. The melt flow rate of a soft thermoplastic resin such as polypropylene useful in the present invention is more than about 0.1 g / 10 minutes, preferably about 0 when measured according to ISO 1133 (tested at 230 ° C./2.16 kg). It can be more than .5 g / 10 minutes, more preferably more than about 3 g / 10 minutes, most preferably more than about 5 g / 10 minutes. The melt flow rate of a soft thermoplastic resin such as polypropylene useful in the present invention is less than about 100 g / 10 minutes, preferably about 80 g / 10 when measured according to ISO 1133 (tested at 230 ° C./2.16 kg). It can be less than a minute, more preferably less than about 60 g / 10 minutes, most preferably less than about 30 g / 10 minutes. Therefore, the melt flow rate is ISO Measured according to 1133 (tested at 230 ° C./2.16 kg load), about 0.1 g / 10 min to about 100 g / 10 min, preferably about 0.5 g / 10 min to about 80 g / 10 min, more preferably. Can be from about 3 to 60 g / 10 minutes, most preferably from about 5 g / 10 minutes to about 60 g / 10 minutes (eg, about 30 g / 10 minutes to about 60 g / 10 minutes).

As shown herein, the first polymeric component is important to help impart rigidity, strength and possibly even impact resistance to the resulting composition. Therefore, the material selected preferably exhibits attractive impact resistance. For example, the Charpy (notched) impact strength (23 ° C.) of a soft thermoplastic resin (eg polypropylene) useful in the present invention is about 0.8 kJ / m when measured according to ISO 179-1 / 1eA.²Super, preferably about 1 kJ / m²Ultra, more preferably about 1.6 kJ / m²Super, most preferably about 2 kJ / m²Super (for example, about 2.3 kJ / m²Super or even about 4kJ / m²) Can be. Suitable soft thermoplastic resins (eg suitable polypropylene) also have a polypropylene Charpy (notched) impact strength (23 ° C) of about 15 kJ / m when measured at 23 ° C according to ISO 179-1 / 1eA.²Less than, preferably about 12 kJ / m²Less than, more preferably about 8 kJ / m²Less than, most preferably about 6 kJ / m²Less than (for example, about 5 kJ / m)²It can be characterized by being less than).

In a preferred aspect of the invention, the thermoplastic polymer has a melt flow rate of about 1 to about 5 g / 10 min and ISO 179-1 / 1 eA (23 ° C) as measured according to ISO 1133 (230 ° C, 2.16 kg). Approximately 3 to 8 kJ / m when measured according to²Contains polypropylene homopolymers with Charpy (notched) impact strength. In the second preferred aspect of the invention, the thermoplastic polymer is about 40 g / 10 min to about 60 g / 10 min (eg, about 50 g / 10 min to about) as measured according to ISO 1133 (230 ° C., 2.16 kg). (55 g / 10 min) melt flow rate and about 1 to about 5 kJ / m when measured according to ISO 179-1 / 1 eA (23 ° C).²Contains polypropylene homopolymers with Charpy (notched) impact strength. In a third preferred aspect of the invention, the thermoplastic polymer is about 30 g / 10 min to about 55 g / 10 min (eg, about 37 g / 10 min) as measured according to ISO 1133 (230 ° C., 2.16 kg). About 4 to about 12 kJ / m when measured according to the melt flow rate (about 47 g / 10 minutes) and ISO 179-1 / 1 eA (23 ° C).²(For example, about 5 to about 8 kJ / m²) Charpy (notched) impact resistant polypropylene copolymer with impact strength.

The first polymer component useful in the present invention (eg, a thermoplastic polymer) typically has a flexural modulus in the range of about 1400 to about 1800 MPa, more specifically about 1500 to about 1700 MPa (measured according to ISO 178). Yield point tensile strength typically in the range of about 20 to about 50 MPa, more specifically about 30 to about 40 MPa (measured according to ISO 527-2); about 5 to about 20%, more specifically It can be seen that yield point tensile elongation (according to ISO 527-2) in the range of about 7 to about 15%, or any combination thereof can be shown. In a highly preferred embodiment, the first polymer component comprises a propylene polymer, preferably a polypropylene homopolymer, most preferably an isotactic polypropylene (eg, an isotactic polypropylene containing less than about 5% by weight of atactic polypropylene). However, the first polymer component can still contain random copolymers or even impact resistant copolymers (those already containing a rubber phase). An example of a polypropylene homopolymer particularly preferred for use in the present invention is The Dow Chemical. Examples include H705-03 and H734-52 available from the Company and / or both or others having similar properties. Examples of polypropylene impact-resistant copolymers particularly preferred for use in the present invention include C705-44NA available from The Dow Chemical Company or others with similar properties.

Second polymer component / soft thermoplastic resin The second polymer component is softer than the hard first polymer component (eg Shore). It is characterized by low A-durometer values), more flexibility (eg, lower flexural modulus), lower crystallinity, or any combination thereof. The second polymer component typically comprises one or more (relatively) soft thermoplastic resins. Suitable soft thermoplastic resins include olefinic block copolymers (eg lower α-olefins / α-olefin interpolymers such as ethylene / α-olefin interpolymers or ethylene / α-olefin interpolymers), substantially linear. Or linear ethylene polymers (S / LEPs), propylene elastomers or any combination thereof. In one aspect of the invention, the second polymer component comprises or consists essentially of an ethylene / α-olefin interpolymer. In another aspect of the invention, the second polymer component comprises or consists essentially of S / LEP. In yet another aspect of the invention, the second polymer component comprises or consists essentially of a propylene elastomer. In yet another aspect of the invention, the soft thermoplastic resin comprises two or all three of the soft polymers.

As shown herein, the compositions of the present invention may contain ethylene, preferably at least one ethylene-containing soft thermoplastic resin (eg, a semi-crystalline ethylene-containing elastomer). The polymer component of 2 is further intended. Thus, the second polymer component can include one or more soft thermoplastic resins, typically including one copolymer containing ethylene or any combination of such copolymers, at least in part. The soft thermoplastic resin of the above has a phase transition (eg, peak melting temperature or glass transition temperature, preferably peak melting temperature) above about 40 ° C. (eg, at least part of this elastomer is crystalline). ..

The second polymer component, the soft thermoplastic resin, or both, is a crystal of more than about 2%, preferably more than about 3%, more preferably more than about 5%, most preferably more than about 7% (eg, more than about 10%). Can have a degree of crystallization. The second polymer component, the soft thermoplastic resin, or both, is less than about 44%, preferably less than about 40%, more preferably less than about 35%, most preferably less than about 30% (eg, less than about 20%) crystals. Can have a degree of crystallization. For example, the second polymer component, the soft thermoplastic resin, or both, is about 2 to about 44%, preferably about 2 to about 40%, more preferably about 5 to about 35%, most preferably about 7 to about 30%. It can have a crystallinity of (eg, about 10 to about 20%).

The second polymer component, the soft thermoplastic resin, or both, is at least about 10% by weight, preferably at least about 20% by weight, more preferably at least about 25% by weight, most preferably at least about 25% by weight, based on the total weight of the total polymer composition. It can be present in an amount of at least about 30% by weight. The second polymer component, the soft thermoplastic resin, or both, is less than about 90% by weight, preferably less than about 75% by weight, more preferably less than about 70% by weight, most preferably less than about 70% by weight, based on the total weight of the total polymer composition. It can be present in an amount less than about 50% by weight.

SLEP The second polymer component described herein is one or more α-olefin soft thermoplastic resins (eg, α-olefin elastomers), such as one or more linear ethylene copolymers (also as LEPs). One or more substantially linear ethylene copolymers (also known as SLEPs) or both can be used. As used herein, "S / LEP" typically includes LEP and / or SEP. Substantially linear ethylene copolymers and linear ethylene copolymers and methods for their manufacture are detailed in US Pat. Nos. 5,272,236 and 5,278,272, which are used for all purposes. Incorporated herein by reference to the patents of.

As used herein, a "linear or substantially linear ethylene polymer" has a linear main chain and has a certain limit of long-chain branching or no long-chain branching. Means a copolymer of ethylene with one or more α-olefin comonomer, which has a narrow molecular weight distribution, a narrow composition distribution (eg, with respect to an α-olefin copolymer), or a combination thereof. Further description of such polymers is described in US Pat. No. 6,403,692 and is incorporated herein by reference in this patent for any purpose.

Examples of α-olefins are propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-hexadodecene, 4-methyl-. 1-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 3,3-dimethyl-1-butene, diethyl-1-butene, trimethyl-1-butene, 3-methyl-1-pentene, ethyl -1-Pentene, propyl-1-pentene, dimethyl-1-pentene, methylethyl-1-pentene, diethyl-1-hexene, trimethyl-1-pentene, 3-methyl-1-hexene, dimethyl-1-hexene, 3,5,5-trimethyl-1-hexene, methylethyl-1-heptene, trimethyl-1-heptene, dimethyloctene, ethyl-1-octene, methyl-1-nonene, ethylene-octene, vinylcyclopentene, vinylcyclohexene and Vinyl norbornene is mentioned, and the alkyl branching position is generally at the 3-position or higher position number of alkene and styrene, unless otherwise specified. Alpha-olefins are preferably C₃~ C₂₀Or C₃~ C₁₀It is an α-olefin. Preferred copolymers include ethylene-propylene (EP), ethylene-butene (EB), ethylene-hexene-1 (EH) and ethylene oxide (EO) polymers. Examples of terpolymers include ethylene / propylene / octene terpolymer and ethylene, C.₃~ C₂₀Examples include terpolymers of α-olefins and dienes (eg, dicyclopentadiene, 1,4-hexadiene, piperylene or 5-ethylidene-2-norbornene).

The S / LEP can include one or more higher α-olefins containing at least 4 (eg, at least 8) carbon atoms. For example, a suitable higher α-olefin is one or more α-olefins having 4 to about 20 carbon atoms (for example, 8 to about 20), more preferably one or more carbon atoms having about 8 to about 12 carbon atoms. It can contain α-olefins. The higher α-olefin can be butane, hexane, octane or any combination thereof, without limitation. Higher α-olefins can contain 1-octene or can essentially consist of 1-octene. A typical S / LEP (eg, an S / LEP that can be useful as an ethylene elastomer) is, but is not limited to, more than about 50% by weight, preferably about 55% by weight, based on the total weight of the S / LEP. It can contain more than% ethylene monomer. A typical S / LEP may contain less than about 85% by weight, preferably less than about 80% by weight, more preferably less than about 70% by weight of ethylene monomer based on the total weight of the S / LEP. The concentration of the higher α-olefin in the S / LEP can be greater than about 12% by weight, more preferably greater than 20% by weight, and most preferably greater than about 30% by weight, based on the total weight of the S / LEP. For example, S / LEP is a copolymer containing an ethylene monomer having a concentration of more than about 50% by weight and a 1-octene monomer having a concentration of more than about 12% by weight (for example, more than about 20% by weight) based on the total weight of S / LEP. be able to. Suitable S / LEPs are commercially available from The Dow Chemical Company under the name Energy®.

Representative S, but not limited to, described in US Pat. No. 5,272,236 (eg, Column 2, Rows 41-51 and Column 3, Rows 25-3, 0). / LEP has the following new characteristics: a) Melt flow ratio I₁₀/ I₂5.63 b) Equation: M_w/ M_nI₁₀/ I₂-4.63 Molecular weight distribution defined by M_w/ M_n,as well as c) 4x10⁶Dyne / cm²Critical shear stress at the start of greater gloss melt fracture It can be characterized as a substantially linear olefin polymer having.

Such polymers include ethylene and at least one C.₃~ C₂₀It can be an interpolymer with an α-olefin. Melt flow ratio I₁₀/ I₂Is I₁₀(Meltflow index measured according to ASTM D-1238 (190/10)) and I₂It is a ratio of (melt flow index measured according to ASTM D-1238 (190/2.16)). These "substantially linear" polymers are substituted or unsubstituted with no more than 3 long chain branches per 1000 carbon atoms, where one long chain branch has at least about 6 carbon atoms. Can have a polymer backbone. Preferred polymers are long chains of about 0.01 to about 3/1000 carbon atoms, more preferably about 0.01 to about 1/1000 carbon atoms, especially about 0.3 to about 1/1000 carbon atoms. It has been replaced by a branch. A method for measuring the polydispersity index of this polymer is described in US Pat. No. 5,272,236, column 5, lines 18-40 and is performed according to the following method: the polymer at a system temperature of 140 ° C. Waters equipped with three linear mixed bed columns (Polymer Laboratories (particle size 10 microns)) to be operated Analyze by gel permeation chromatography (GPC) on a 150C high temperature chromatograph unit. The solvent is 1,2,4-trichlorobenzene, which is used to prepare an approximately 0.5% by weight solution of the sample for injection. The flow rate is 1.0 ml / min and the injection size is 100 μl. Molecular weight measurements are estimated by using the narrow molecular weight distribution polystyrene standard (from Polymer Laboratories) in combination with its elution volume. Using the Mark-Howink coefficient suitable for polyethylene and polystyrene (described in Williams and Word, Journal of Polymer Science, Polymer Letters, Vol.6, (621) 1968 (incorporated herein by reference)): formula: M_polyethylene= (A) (M_polystyrene）^{b b}The converted polyethylene molecular weight is calculated by deriving. In this equation, a = 0.4316 and b = 1.0. Weight average molecular weight M_wFormula: M_w= (R) (w_i) (M_i) [During the ceremony, w_iAnd M_iIs the weight fraction and molecular weight of the i-th fraction eluted from the GPC column, respectively] Calculate according to the usual method. Critical shear stress at the start of gloss melt fracture. The critical shear stress at the start of the gloss melt fracture is measured by the gas extrusion rheometer (GER) described in US Pat. No. 5,272,236 (eg, column 4, rows 10-45). To do. The gas extrusion rheometer is from John Dealy, published by Polymer Engineering Science, Vol.17, no.11, p.770 (1977) by M. Shida, RN Schroff and LV Cancio, and Van Nostrand Reinhold Co. (1982). According to "Rheometers for Molten" It is described on page 97 of "Plastics". The whole of these two documents is incorporated herein by reference. All GER experiments are 0.0296 inches in diameter at 190 ° C. and nitrogen pressure 5250-500 psig. The melt fracture phenomenon is confirmed using a plot of apparent shear stress vs. apparent shear rate. Ramamurthy (Journal of). According to Rheology, 30 (2), 337-357,1986), the irregularities of the extruded material observed above a certain critical flow velocity can be broadly divided into two main types: surface melt fracture and gloss melt fracture. .. Surface melt fractures occur under apparently steady-state conditions, ranging in detail from loss of mirror gloss to more severe "shark skin." Gross melt fractures occur under unsteady flow conditions, ranging in detail from ordered strains (alternate rough and smooth surfaces, spirals, etc.) to random strains. For commercial acceptance (eg in inflation film products), surface defects must be as low as possible, if not zero. Here, the critical shear rate at the start of surface melt fracture (OSMF) and the critical shear rate at the start of gloss melt fracture (OGMF) are used based on the changes in surface roughness and shape of the extruded product extruded by GER. Preferably, the substantially linear ethylene polymers described herein have a critical shear stress at OGMF and a critical shear stress at OSMF of about 4 × 10, respectively.⁶Dyne / cm²Super and about 2.8x10⁶Dyne / cm²It's super.

Another example, but not limited to, a suitable S / LEP is described in European Patent No. 0495099 (filed December 12, 1989), which is incorporated herein by reference. European Patent No. 0495099 describes an S / LEP copolymer having (a) a structural unit derived from ethylene and (b) a structural unit derived from an α-olefin having 3 to 20 carbon atoms. Is (I) Density is 0.85 to 0.92 g / cm³, (Ii) The ultimate viscosity number [η] measured in decalin at 135 ° C. is 0.1 to 10 dl / g. (Iii) The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the logarithmic mean molecular weight (Mn) measured by GPC is 1.2 to 4, and (Iv) The ratio (MFR10 / MFR2) of (MFR10 under a load of 10 kg) to (MFR2 under a load of 2.16 kg) measured at 190 ° C. is 8 to 50. It is characterized by being. MFR10 and MFR2 can be measured, for example, by ASTM D-1238 at 190 ° C. with loads of 10 kg and 2.16 kg, respectively.

S / LEP can be polymerized using any suitable catalyst system. For example, the elastomer can be polymerized using a catalyst containing a Ziegler-Natta catalyst, a metallocene catalyst, an activated non-metallocene metal center to teloaryl ligand catalyst, and the like. A combination of catalysts can also be used. One of the typical catalysts, but not limited to, is a metallocene catalyst. For example, S / LEP is polymerized using a catalyst containing a metallocene catalyst as described in European Patent Application No. 129368 (filed June 5, 1984; Ewen et al.) (Incorporated herein by reference). be able to. Such metallocenes have the general formula: (C₅R'_m）_pR "₅(C₅R'_m) MeQ_3-pAnd R "_s(C₅R'_m) MeQ' [In the formula, Me is a Group 4b, Group 5b, Group 6b metal; (C₅R'_m) Is a cyclopentadienyl or a substituted cyclopentadienyl; each R'(which can be the same or different) is a hydrogen, an alkyl, alkenyl, aryl, alkylaryl or arylalkyl group having 1 to 20 carbon atoms. Or two R'substituents condensed together C₄~ C₆Form a ring; R "is two (C)₅-R'_m) C to crosslink the ring₁~ C₄An alkylene group, a dialkyl germanium or silicon, or an alkylphosphine or amine group; each Q (which can be the same or different) is an aryl, alkyl, alkenyl, alkylaryl or arylalkyl group having 1 to 20 carbon atoms. It is a halogen; Q'is an alkylidene group having 1 to 20 carbon atoms; s is 0 or 1; p is 0, 1 or 2; if p is 0, s is 0. M is 4 when s = 1; m is 5 when s is 0; at least one R'is a hydrocarbyl group when Q is an alkyl group] Can be a compound of.

The S / LEP can have a phase transition (eg, peak melting temperature) at temperatures above about 40 ° C. (eg, at least a portion of the S / LEP is crystalline). S / LEP can have a crystallinity of about 2 to about 14%, more preferably about 3 to about 11%, most preferably about 4 to about 9%.

S / LEP is typically at least about 10% by weight, more typically at least about 20% by weight, and more typically at least about 25% by weight (eg, at least about) on a total weight basis of the total polymer composition. It is present in an amount of 30% by weight). The second polymer component is also typically less than about 80% by weight, more typically less than about 75% by weight, most typically less than about 70% by weight, on a total weight basis of the total polymer composition. In some cases, it is less than about 45% by weight (eg, less than about 35% by weight).

The S / LEP selected for the second polymer component has a Shore A hardness of at least about 25, preferably at least about 45, more preferably at least about 55, even more preferably at least about 60, according to ASTM D2240-05. It can preferably be at least about 65. The Shore A hardness of S / LEP can be less than about 95, preferably less than about 90, more preferably less than about 85, and even more preferably less than about 80. For example, the hardness of S / LEP can be in the range of about 65 to about 95, more preferably about 65 to about 85, and even more preferably about 65 to about 80.

The S / LEP for the second polymer component generally has a density of about 0.8 to about 0.9 g / cm as measured according to ASTM D792-00.³(For example, about 0.855 to about 0.895 g / cm³). Suitable S / LEP is at least 0.850 g / cm³, Preferably at least 0.855 g / cm³, More preferably at least 0.860 g / cm³Most preferably at least 0.867 g / cm³Can have a density of. The density of ethylene elastomer is about 0.908 g / cm³Less than, preferably about 0.900 g / cm³Less than, more preferably about 0.890 g / cm³Less than, most preferably about 0.880 g / cm³Can be less than. Density is measured and determined by ASTM D792-00.

Suitable S / LEPs have a melt index measured according to ASTM D-1238-04 (190 ° C., 2.16 kg) of at least about 0.2 g / 10 min, preferably at least about 0.5 g / 10 min, more preferably. Can be characterized by at least about 1.0 g / 10 minutes, more preferably at least about 5 g / 10 minutes. The melt index of S / LEP can also be less than about 60 g / 10 min, preferably less than about 40 g / 10 min, more preferably less than about 30 g / 10 min, and most preferably less than about 10 g / 10 min. For example, the melt flow rate can be in the range of about 0.2 to about 60 g / 10 min, more preferably about 2 to about 40 g / 10 min, and even more preferably about 0.5 to about 10 g / 10 min.

Propylene elastomer The second polymeric component can also contain or consist essentially of polypropylene elastomers. Suitable polypropylene elastomers are propylene monomers based on the weight of the polypropylene elastomer in excess of about 50% by weight, preferably greater than about 65% by weight, more preferably greater than about 70% by weight, most preferably greater than about 80% by weight (eg, at least. It can be contained in a concentration of 85% by weight). Polypropylene elastomers also include one or more additional Cs.₂~ C₁₂Alpha-olefin comonomer (eg, ethylene-containing or ethylene-containing or butene-containing or butene-containing comonomer) is added to more than about 5% by weight, preferably more than about 7% by weight, more preferably, based on the total weight of the polypropylene elastomer. It can be contained in a concentration of more than about 9% by weight, most preferably more than about 12% by weight. For example, the comonomer content can be in the range of about 5 to about 40% by weight, more preferably about 7 to about 30% by weight, even more preferably about 9 to about 15% by weight of the polypropylene elastomer composition. The polypropylene elastomer can have some degree of crystallinity or can be amorphous. A suitable polypropylene elastomer is about 130 when measured at a heating rate of about 10 ° C./min for a sample cooled at a rate of about 10 ° C./min from about 220 ° C. to about 0 ° C. by differential scanning calorimetry. It can have a peak melting temperature of less than ° C., preferably less than about 115 ° C., most preferably less than about 100 ° C.

Propylene elastomers preferably contain α-olefins selected from ethylene, butene, hexene and octene. More preferably, the propylene elastomer comprises an α-olefin selected from ethylene, butene and octene. Most preferably, the propylene elastomer comprises an α-olefin selected from ethylene and butene.

Polypropylene elastomers can have a Shore A hardness (ie, durometer) as measured by ASTM D2240-05 of at least about 40, more preferably at least about 50, and even more preferably at least about 65. Shore A hardness can also be less than about 97, preferably less than about 95, more preferably less than about 92, even more preferably less than about 85 (eg, less than about 80). For example, polypropylene elastomers can have a Shore A hardness of about 40-about 97, more preferably about 50-about 95, even more preferably about 65-about 95.

Suitable polypropylene elastomers have a melt flow rate of at least 1 g / 10 min, preferably at least about 4 g / 10 min, more preferably at least about 7 g / 10 min, most preferably at least about 7 g / 10 min, as measured according to ASTM D1238 (230 ° C / 2.16 kg). It can be at least about 10 g / 10 minutes. Suitable propylene elastomers for polymer compositions are, but not limited to, less than about 1500 g / 10 min, preferably less than about 150 g / 10 min, more preferably less than about 100 g / 10 min, most preferably about 60 g / 10 min. It can have a melt flow rate of less than.

Polypropylene elastomers preferably exhibit at least some degree of crystallinity. For example, the crystallinity can be at least about 2% by weight, preferably at least about 5% by weight, more preferably at least about 7% by weight of the polypropylene elastomer material. Suitable polypropylene elastomers, but not limited to, can have a crystallinity of less than about 50% by weight. For example, the crystallinity of the propylene elastomer can be less than about 40% by weight, preferably less than about 35% by weight, more preferably less than about 28% by weight, still more preferably less than about 20% by weight of the polypropylene elastomer material. In general, suitable propylene elastomers can have a crystallinity of about 2 to about 50% by weight. For example, this crystallinity can be in the range of about 2 to about 40% by weight, more preferably about 5 to about 35% by weight, even more preferably about 7 to about 20% by weight of the polypropylene elastomer material.

If the propylene elastomer is a copolymer of propylene and ethylene (ie, the comonomer is ethylene), then the preferred total composition (ie, polymer composition) obtained from the above is the ethylene content (total ethylene). You will find that it has minutes). For example, on one side, the total ethylene content in the resulting final composition can be greater than about 2% by weight, preferably greater than about 3% by weight, more preferably greater than about 4% by weight of the total composition obtained. In this aspect of the invention, on the other hand, the total concentration of ethylene in the resulting total composition is less than about 35% by weight, preferably less than about 25% by weight, more preferably less than about 20% by weight. More preferably, it is generally expected to be less than about 10% by weight.

Propylene elastomers are propylene and C₄~ C₁₂In the case of a copolymer with an α-olefin (eg butene, hexane or octene), therefore, from the above, the preferred total composition (ie, polymer composition) obtained, including the propylene elastomer, is total C.₄~ C₁₂You will find that it has an α-olefin. For example, on one side, all C in the resulting final composition₄~ C₁₂The α-olefin content can be more than about 2% by weight, preferably more than about 3% by weight, more preferably more than about 4% by weight of the total composition obtained. In this aspect of the invention, on the other hand, C in the resulting total composition₄~ C₁₂It is generally expected that the total concentration of α-olefins will be less than about 35% by weight, preferably less than about 25% by weight, more preferably less than about 20% by weight, even more preferably less than about 10% by weight of the total composition. ..

Suitable propylene elastomers that can be used in accordance with the teachings of this specification include, but are not limited to, International Patent Application Publication WO 03/040201A1 (filed May 6, 2002), US Patent Application Publication No. 2003/0204017. (Filing May 5, 2002) and US Pat. No. 6,525,157 (issued February 25, 2003) include those disclosed. All of these patent documents are incorporated herein by reference.

For example, propylene elastomers are low elasticity α-olefin-propylene copolymers, eg, low elasticity as taught in US Pat. No. 6,525,157 (issued February 25, 2003), incorporated herein by reference. It can be an ethylene-propylene copolymer (ie, a LEEP copolymer). Such LEEPs described in US Pat. No. 6,525,157 (issued February 25, 2003), column 2, lines 15 to 3, line 54, are metallocene catalysts and activities in a single steady-state reactor. It can be a (LEEP) copolymer that exhibits a surprisingly unexpected balance of flexural modulus, tensile strength and elasticity when manufactured in the presence of an agent. Moreover, these and other properties of the (LEEP) copolymer show surprising differences compared to conventional polymer blends such as blends of isotactic polypropylene and ethylene-propylene copolymers.

In one embodiment, the (LEEP) copolymer has a lower limit of 5% by weight or 6% by weight or 8% by weight or 10% by weight to an upper limit of 20% by weight or 25% by weight of ethylene-derived units and a lower limit of 75% by weight or 25% by weight of propylene-derived units. 80% by weight to upper limit 95% by weight or 94% by weight, 92% by weight or 90% by weight (the weight percentage is based on the total weight of the propylene-derived unit and the ethylene-derived unit). The copolymer is substantially free of diene-derived units.

In various embodiments, the (LEEP) copolymer is characterized by some or all of the following properties (in this property, the range from any stated upper limit to any stated lower limit is conceivable): (I) The melting point is in the range of the upper limit of less than 110 ° C. or less than 90 ° C. or less than 80 ° C. or less than 70 ° C. to the lower limit of more than 25 ° C. or more than 35 ° C. (Ii) The relationship between elasticity and 500% tensile modulus is elasticity 0.935M + 12, elasticity 0.935M + 6 or elasticity 0.935M (elasticity is expressed as a percentage, and M is megapascal). It is a 500% tensile elastic modulus expressed in (MPa)); (Iii) The relationship between flexural modulus and 500% tensile modulus is flexural modulus 4.2e.^0.27M+50 or flexural modulus 4.2e^0.27M+30 or flexural modulus 4.2e^0.27M+10 or flexural modulus 4.2e^0.27M+2 (bending modulus is expressed in MPa, M is 500% tensile modulus expressed in MPa); (Iv) The lower limit of heat of fusion is more than 1.0 joule / g (J / g) or more than 1.5 J / g or more than 4.0 Jg or more than 6.0 J / g or more than 7.0 J / g to the upper limit of 125 J / g. Less than or less than 100 J / g or less than 75 J / g or less than 60 J / g or less than 50 J / g or less than 40 J / g or less than 30 J / g; (V) Triad Tacticity (Carbon-13 Nuclear Magnetic Resonance (v)¹³Measured by C NMR) is greater than 75% or greater than 80% or greater than 85% or greater than 90%; (Vi) The tacticity index m / r ranges from a lower limit of 4 or 6 to an upper limit of 8 or 10 or 12; (Vii) Ratio of reverse-inserted propylene units based on 2,1-insertion of propylene monomer in total inserted propylene (¹³(Measured by C NMR) is greater than 0.5% or greater than 0.6%; (Viii) Ratio of reverse-inserted propylene units based on 1,3-insertion of propylene monomer in total inserted propylene (¹³(Measured by C NMR) is greater than 0.05% or greater than 0.06% or greater than 0.07% or greater than 0.08% or greater than 0.085%; Intermolecular tacticity (X is 75 or 80) such that at least X% by weight of the (ix) copolymer is soluble in two adjacent temperature fractions of thermal fractionation performed by heating in hexanes by 8 ° C. Or 85 or 90 or 95 or 97 or 99); (X) Product of reactivity ratio r₁r₂Is less than 1.5 or less than 1.3 or less than 1.0 or less than 0.8; (Xi) The molecular weight distribution Mw / Mn ranges from a lower limit of 1.5 or 1.8 to an upper limit of 40 or 20 or 10 or 5 or 3; (Xii) has a molecular weight of 15,000 to 5,000,000; (Xiii) Solid Proton Nuclear Magnetic Resonance (¹1 H NMR) relaxation time is less than 18 ms (ms) or less than 16 ms or less than 14 ms or less than 12 ms or less than 10 ms; (Xiv) The elasticity defined herein is less than 30% or less than 20% or less than 10% or less than 8% or less than 5%; (Xv) The 500% tensile elastic modulus is more than 0.5 MPa, more than 0.8 MPa, more than 1.0 MPa, or more than 2.0 MPa.

The LEEP copolymer is produced in a single steady state reactor in the presence of a crosslinked metallocene catalyst.

Test methods for LEEP copolymers are described in US Pat. No. 6,525,157: Test methods for measuring the melting temperature and heat of fusion of LEEP copolymers are described in US Pat. No. 6,525,157, columns 19-12 to 29. The melting point and heat of fusion are measured by differential scanning calorimetry (DSC) as follows. Remove about 6-10 mg of the polymer sheet pressed at about 200-230 ° C. with a punch die. This is annealed at room temperature for 24 hours. At the end of this time, the sample is placed in a differential scanning calorimetry (Perkin Elmer 7 Series Thermal Analysis System) and cooled to about -50 to about -70 ° C. The sample is heated at 20 ° C./min to reach a final temperature of about 200 ° C. to about 220 ° C. The heat output is recorded as the area below the melting peak of the sample (typically peaking at about 30-about 175 ° C and taking place at about 0-about 200 ° C) and measured in joules as an indicator of heat of fusion. To do. The melting point is recorded as the maximum heat absorption temperature within the melting range of the sample.

Test methods for measuring the elasticity, 500% elastic modulus and flexural modulus of LEEP copolymers are described in US Pat. No. 6,525,157, columns 17, lines 1-18: 60: The aspect of the LEEP copolymer is elastic after tensile deformation. Elasticity, represented by a slight increase in sample length, expressed as a percentage of sample length, is measured according to the general method ASTM D790. The copolymer sample is stretched during tensile elongation and the polymer attempts to restore its original size when the stretching force is removed. This recovery is not perfect and the final length of the stress relaxation sample is slightly longer than the length of the original sample. Elasticity is represented by a slight increase in sample length, expressed as a percentage of the original unstretched sample length.

The protocol for measuring the elasticity of the sample reserves the deformable zone (the narrow part of the specimen) of the dumbbell created according to the method for measuring elongation and tensile strength up to 200% of its original length. It consists of pre-stretching the sample by stretching. This is done at a deformation rate of 10 inches (25 cm) / min. The sample is stress relaxed at the same rate to form an analytical test piece, which is a pre-stretched test piece of the original sample. This slightly oriented or pre-stretched sample is stress relaxed at room temperature for 48 hours prior to elastic measurements. The length of the deformation zone in the sample is d₁Is measured. After 48 hours, the sample is deformed again at a rate of 10 inches / minute to stretch the deformation zone of the sample by 200% and stress relaxed at the same rate. After removing the sample and relaxing the stress for 10 minutes, the sample has a new length of deformation zone d₂Is measured. The elasticity (%) of the sample is 100 * (d)₂D₁) / D₁Is calculated.

Aspects of the LEEP copolymer can have less than 30% or less than 20% or less than 10% or less than 8% or less than 5% elasticity as measured by the method described above.

These elastic values over the entire composition range of the copolymer depend on the tensile strength of the sample as measured by the 500% modulus of elasticity. Therefore, the elasticity of the copolymers of this system is (a) elongation up to 500% elongation with measurable modulus (500% tensile modulus) and (b) 200% elongation with respect to the slightly oriented sample described above. It is represented by two criteria of elasticity from elongation to. First, the copolymer in the form of a LEEP copolymer has a measurable tensile strength at 500% elongation (also known as 500% tensile modulus) greater than 0.5 MPa or greater than 0.75 MPa or greater than 1.0 MPa or It must be greater than 2.0 MPa and secondly the copolymer must have the elastic modulus.

As another method, the relationship between elasticity and 500% tensile modulus can be explained. In the embodiment of the LEEP copolymer, elasticity as a function of 500% tensile modulus (MPa) is defined by the following equation: Elasticity (%) 0.935M + 12; or Elasticity (%) 0.935M + 6; or Elasticity (%) 0.935M [In the formula, M is a 500% tensile modulus (MPa)].

Flexural modulus The softness of the copolymer in the embodiment of the LEEP copolymer can be measured by the flexural modulus. The flexural modulus is measured at a crosshead speed of 0.05 in / min (1.3 mm / min) using a type IV dogbone according to ASTM D790. The value of flexural modulus over the entire composition range of the copolymer depends on the tensile strength of the sample as measured by the 500% tensile modulus. Therefore, the flexural modulus of the copolymer of this system can be expressed by two criteria: (a) elongation up to 500% elongation according to measurable modulus (500% tensile modulus) and (b) flexural modulus. it can.

The flexural modulus (MPa) of the LEEP copolymer as a function of the 500% tensile modulus (MPa) is given by the formula: Flexural modulus 4.2e^0.27M+50; or Flexural modulus 4.2e^0.27M+30; or Flexural modulus 4.2e^0.27M+10; or Flexural modulus 4.2e^0.27M+2 Defined by.

A test method for measuring the tacticity index of a LEEP copolymer is described in US Pat. No. 6,525,157, column 6, lines 22-36: tacticity, represented herein as "m / r". The index is¹³Measured by C nuclear magnetic resonance (NMR). The tacticity index m / r is calculated as defined in HNCheng, Macromolecules, 17, 1950 (1984). "M" or "r" represents the stereochemistry of adjacent propylene group pairs, "m" means meso, and "r" means racemic. An m / r ratio of 1.0 generally represents a syndiotactic polymer, and an m / r ratio of 2.0 represents an atactic material. Isotactic materials can theoretically have ratios close to infinity, and many by-product atactic polymers have an isotactic content sufficient to yield ratios greater than 50. The LEEP copolymer can have a tacticity index m / r in the range of lower limit 4 or 6 to upper limit 8 or 10 or 12.

Test methods for measuring the molecular weight and polydispersity index of LEEP copolymers described in US Pat. No. 6,525,157, column 5, lines 1-57 include: The molecular weight distribution (MWD) is an indicator of the molecular weight range within a given polymer sample. It is well known that the width of MWD can be characterized by the ratio of various molecular weight averages, for example the weight average molecular weight logarithmic mean molecular weight ratio Mw / Mn or the Z-average molecular weight to weight average molecular weight ratio Mz / Mw.

Mz, Mw and Mn can be measured using gel permeation chromatography (GPC) (also known as size exclusion chromatography (SEC)). This method uses equipment that includes a column filled with porous beads, an elution solvent, and a detector to separate macromolecules of different particle sizes. In a typical measurement method, the GPC instrument used is a Waters chromatograph equipped with an ultra-styrogel column operated at 145 ° C. The elution solvent used is trichlorobenzene. This column is calibrated using 16 polystyrene standards with exactly known molecular weights. The polymer molecular weight is obtained by correlating the polystyrene retention capacity obtained from these standards with the retention capacity of the test polymer.

The average molecular weight M is the formula:

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[In the formula, N_iIs the molecular weight M_iIs the number of molecules that have Can be calculated by computer. When n = 0, M is the number average molecular weight M_nWhen n = 1, M is the weight average molecular weight M._wWhen n = 2, M is the Z average molecular weight M._zIs. Desirable MWD function (eg M_w/ M_nOr M_z/ M_w) Is the ratio of the corresponding M values. Methods for measuring M and MWD are well known in the industry, such as Slade, PEEd., Polymer Molecular Weights Part II, Marcel Dekker, Inc., NY, (1975) 287-368; Rodriguez, F., Patents of Polymer Systems 3rd ed., Hemisphere Pub. Corp., NY, (1989) 155-160; US Pat. No. 4,540,753; Verstrate et al., Macromolecules, vol.21, (1988) 3360. These are incorporated herein by reference.

In aspects of the LEEP copolymer, the weight average molecular weight (Mw) is 15,000 to 5,000,000 or 20,000 to 1,000,000 and the molecular weight distribution is Mw / Mn ("polydispersion index" (PDI)). Includes LEEP copolymers whose lower limit is in the range of 1.5 or 1.8 to the upper limit of 40 or 20 or 10 or 5 or 3.

The test method for measuring the triad of the LEEP copolymer described in US Pat. No. 6,525,157, column 6, lines 37 to 7, line 44 is as follows. An auxiliary means for expressing propylene unit tacticity in LEEP copolymers is the use of triad tacticity. The triad tacticity of a polymer is the relative tacticity of three adjacent propylene units, i.e., a chain sequence consisting of a head-tail bond, represented as a combination of two components, an m sequence and an r sequence. This is usually expressed as the ratio of the number of units of a particular tacticity to the total propylene triad in the copolymer for the LEEP copolymer of the present invention.

The triad tacticity (mm fraction) of the propylene copolymer is that of the propylene copolymer.¹³C NMR spectrum and the following formula: mm fraction = PPP (mm) / [PPP (mm) + PPP (mr) + PPP (rr)] [In the formula, PPP (mm), PPP (mr) and PPP (rr) are the following three propylene unit chains consisting of a head-tail bond:

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Means the peak area derived from the methyl group of the second unit in] Can be obtained from.

Of propylene copolymer¹³The C NMR spectrum is measured as described in US Pat. No. 5,504,172. The spectrum corresponding to the methyl carbon region (19 to 23 ppm) includes a first region (21.2 to 21.9 ppm), a second region (20.3 to 21.0 ppm) and a third region (19.5 ppm). It can be divided into ~ 20.3 ppm). Each peak in the spectrum was assigned with reference to the article, Journal Polymer, Volume 30 (1989), page 1350.

In the first region, the methyl group of the second unit in the 3propylene unit chain represented by PPP (mm) resonates.

In the second region, the methyl group of the second unit in the 3-propylene unit chain represented by PPP (mr) resonates, and the propylene unit methyl group (PEE-methyl) whose adjacent units are propylene and ethylene units. The group) resonates (around 20.7 ppm).

In the third region, the methyl group of the second unit in the 3-propylene unit chain represented by PPP (rr) resonates, and the adjacent unit is the ethylene unit of the propylene unit methyl group (EPE-methyl group). Resonates (around 19.8 ppm).

Calculation of Triad Tacticity and Error in Propylene Insertion: Calculation of triad tacticity is outlined in the method presented in US Pat. No. 5,504,172. 3propylene consisting of a head-tail bond by subtracting the peak area for propylene insertion (both 2, 1 and 1, 3) errors from the peak area from the total peak area of the second and third regions. A peak area based on the unit chain (PPP (mr) and PPP (rr)) can be obtained. Therefore, the peak areas of PPP (mm), PPP (mr) and PPP (rr) can be evaluated, and based on this, the triad tacticity of the propylene unit chain consisting of the head-tail bond can be obtained.

LEEP copolymer¹³Triad tacticity of 3 propylene units measured by C NMR is greater than 75% or greater than 80% or greater than 82% or greater than 85% or greater than 90%.

Test methods for measuring steric and regional errors in propylene insertion for LEEP copolymers (eg, the ratio of reverse-inserted propylene units based on 1,3-insertion and / or 2,1-insertion of propylene) are described in US Pat. No. 6,037. , 525, 157, column 7, line 45 to column 9, line 29. The ratio of 2,1-insertion to total propylene insertion in the LEEP copolymer is described by the following formula, referring to the paper of Journal Polymer, vol.30 (1989), page 1350:

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Can be calculated by.

The peaks in the equation can be named according to the method of Carman et al., Journal Rubber Chemistry and Technology, volume 44 (1971), page 781. In the above formula, I_αδIs αδ⁺It means the peak area of the second carbon peak. Due to the overlap of peaks, the peak area of labp (structure (i)) is set to I._αβIt is difficult to separate from (structure (ii)). Therefore, a carbon peak with a corresponding area is substituted.

Measurement of βγ peak is required for measurement of 1,3-insertion. Two structures can result in βγ peaks: (1) 1,3-insertion of propylene monomer; and (2) 2,1-insertion of propylene monomer followed by two ethylene monomers. This peak is described as a 1,3-insertion peak, and we used the method described in US Pat. No. 5,504,172 to describe this βγ peak and described it as four methylene units. Understand that it represents an array of. The ratio (%) of these error amounts was determined by [area of βγ peak (resonance near 27.4 ppm)] ÷ [total methyl group peak + (βγ peak area × 1/2)] × 100. When an α-olefin having 3 or more carbon atoms is polymerized using an olefin polymerization catalyst, a large number of reverse-inserted monomer units are present in the molecule of the obtained olefin polymer. In a polyolefin produced by polymerization of an α-olefin having 3 or more carbon atoms in the presence of a chiral metallocene catalyst, 2,1-insertion or 1,3-insertion occurs in addition to the usual 1,2-insertion. As a result, reverse insertion units such as 2,1-insertion or 1,3-insertion are formed in the olefin polymer molecule (Macromolecular Chemistry Rapid by K. Sogah, T. Shoono, S. Takemura and W. Kaminski). Communication, Volume 8, see page 305 (1987)).

¹³The proportion of reverse-inserted propylene units in the LEEP copolymer, based on 2,1-insertion of propylene monomer in total-inserted propylene, as measured by C NMR, is greater than 0.5% or greater than 0.6%.

¹³The proportion of reverse-inserted propylene units in aspects of the LEEP copolymers of the invention, based on 1,3-insertion of propylene monomers, as measured by C NMR, is greater than 0.05% or greater than 0.06% or greater than 0.07%. Or more than 0.08% or more than 0.085%.

The test method for measuring the reactivity ratio of the LEEP copolymer described in US Pat. No. 6,525,157, column 11, lines 10-60 uses a monomer sequence distribution. Starting with a polymer with a known average composition, the monomer sequence distribution can be measured using spectroscopic analysis. For this purpose carbon-13 nuclear magnetic resonance spectroscopy (¹³C NMR) can be used. This can be used to determine the diad and triad distributions by integrating the spectral peaks. (For this analysis¹³Without C NMR, r is usually much lower than this₁r₂The product is obtained. ) The reactive ratio is described in detail in the Textbook of Polymer Chemistry, FW Billmeyer, Jr. (Interscience Publishers, New York), p.221 et seq. (1957).

Reactive ratio product r₁r₂(R₁Is the reactivity of ethylene, r₂Is the reactivity of propylene) from the measured diad distribution (PP, EE, EP and PE in this nomenclature): r₁r₂= 4 [EE] [PP] [EP]² r₁= K₁₁/ K₁₂= 2 x [EE] / [EP] r₂= K₂₂/ K₂₁= 2 x [PP] / [EP] P = [PP] + [EP] / 2 E = [EE] + [EP] / 2 {In the formula, mol% E = [(E) / (E + P)] * 100; X = E / P (in reactor); K₁₁And K₁₂Is the kinetic insertion constant for ethylene, K₂₁And K₂₁Is the dynamic insertion constant for propylene} Can be calculated by applying.

As those skilled in the art will understand, the reactivity ratio product r₁r₂= 0 can define "alternate" copolymers and reactive ratio product = 1 can define "statistically random" copolymers. That is, the reactivity ratio product r of 0.6 to 1.5₁r₂Copolymers with are generally considered random (from a strict theoretical point of view, generally greater than 1.5 reactive ratios r).₁r₂Only copolymers with are considered to be "massive", containing relatively long homopolymer sequences). LEEP copolymers have a reactive ratio of less than 1.5 or less than 1.3 or less than 1.0 or less than 0.8 r₁r₂Will have. The substantially uniform distribution of comonomer within the polymer chains of the LEEP copolymer generally eliminates the possibility of significant amounts of propylene units or sequences being present within the molecular weight (weight average) polymer chains disclosed herein. ..

Test methods for measuring the intermolecular tacticity of LEEP copolymers are described in US Pat. No. 6,525,157, column 9, lines 42-10, lines 15. LEEP copolymers may not have statistically significant intermolecular differences in the tacticity of polymerized propylene (intermolecular) between different chains. This is measured by thermal fractionation, generally controlled by dissolution, in a single solvent over a series of slowly rising temperatures. A typical solvent is a saturated hydrocarbon such as hexane or heptane. These dissolution control methods are often used to separate similar polymers with different crystallinities due to differences in isotactic propylene sequences, as shown in the paper Macromolecules, Vol.26, p.2064 (1993). Be done. For LEEP copolymers where propylene unit tacticity determines crystallinity, we expect this fractionation method to separate molecules according to the incorporated propylene tacticity.

In the LEEP copolymer, at least 75% by weight or at least 80% by weight or at least 85% by weight or at least 90% by weight or at least 95% by weight or at least 97% by weight or at least 99% by weight of the copolymer is a single temperature fraction or two. It is soluble in the adjacent temperature fraction and the remaining copolymer is soluble in the immediately preceding or immediately following temperature fraction. These percentages are fractions starting at ° C. (eg, in hexane), with subsequent fractions raised by about 8 ° C from 23 ° C. Meeting such fractionation requirements means that the polymer has intermolecular differences that are not statistically significant in the tacticity of the polymerized propylene.

Separation was carried out using boiling pentane, hexane, heptane and even diethyl ether. In such boiling solvent separation, the LEEP copolymer is completely soluble in any solvent, so no analytical information is available. For this reason, fractionation is carried out as described above and as detailed herein, to more detail the characteristics of the copolymer and within such conventional fractionation range and to the surprise of the polymerized propylene copolymer. We must find a place that shows in more detail the unexpected and insignificant intermolecular tacticity difference that should be.

Test methods for measuring the relaxation time of solid proton nuclear magnetic resonance in LEEP copolymers are described in US Pat. No. 6,525,157, column 12, lines 10-60 and Table I.

Solid proton NMR relaxation time (¹1 NMR T_1p) And its relationship to polymer morphology are described in Macromolecule 32 (1999), 1611. T of LEEP copolymer and polypropylene (PP) homopolymer (control sample)_1pExperimental data for mitigation is shown in Figure 1 of US Pat. No. 6,525,157 (the natural logarithm of crystal strength is plotted against time), and the experimental procedure for collecting these data. Is described below. To fit the data to a single exponential function, linear regression was performed on the ln (I) vs. t data (I is the intensity of the crystal signal). Then the fit quality R²To calculate. R of perfect linear correlation²Is 1.0. R of polypropylene (control) and typical LEEP copolymer²Are 0.9945 and 0.9967, respectively. Therefore, the T of both polypropylene homopolymers and typical LEEP copolymers._1pRelaxation can fit well with a single exponential function. From this fit, polypropylene and LEEP copolymer T_1pAre calculated to be 25 milliseconds (ms) and 8.7 ms, respectively. T_1pThe large difference in morphology reflects the difference in their morphology.

The virtual polypropylene-like region has a T similar to polypropylene homopolymers._1pWill have relaxation time. As a result, if such a region exists in the form of a LEEP copolymer, then T_1pRelaxation time is T, which is characteristic of polypropylene homopolymers._1pRelaxation time (ie T_1p= 25 ms) will be included. As can be seen in Figure 1 of US Pat. No. 6,525,157, the relaxation of the LEEP copolymer fits well only in a single exponential function. T_1pIncorporating a component with = 25 ms would result in a poor fit. This indicates that the LEEP copolymer does not contain long continuous isotactic propylene units. In some LEEP copolymers, T_1pThe relaxation time can be less than 18 ms or less than 16 ms or less than 14 ms or less than 12 ms or less than 10 ms.

T_1pMeasurements: Experiments with a Bruker DSX-500 Nuclear Magnetic Resonance (NMR) spectrometer¹H frequency 500.13MHz and¹³It is carried out using a C frequency of 125.75 MHz. The pulse sequence is 90 ° (¹H) Pulse, followed by spinlock and tolerance pole (CP; time = 0.1 ms). Spinlock magnetic field strength γ₁= 2Π * 60kHz is used. Magnetization by CP after spinlock¹³Move to C and then detect the signal. A 26.7 ppm crystalline methine signal is recorded, normalized and its natural logarithm (Ln) is plotted against the spinlock time.

The ethylene concentration of the LEEP copolymer can be measured as ethylene weight% as described in US Pat. No. 6,525,157, column 18, lines 61 to 19, line 12 according to ASTM D3900. A thin uniform film of copolymer components pressed at a temperature of 150 ° C. or higher is attached to a PerkinElmer PE 1760 infrared spectrophotometer. 600-4000 cm^-1The entire spectrum of the sample was recorded and the ethylene weight% of the copolymer component was calculated by the following formula: Ethylene weight% = 82.585-111.98X + 30.045X²{In the formula, X is [1155 cm^-1Peak height] vs. [772 cm^-1Or 732 cm^-1Peak height (whichever is higher)] Calculate from.

Another example of a propylene elastomer that can be used is a propylene-ethylene copolymer (ie, R-EPE copolymer) containing a region error described in US Patent Application Publication No. 2003/2004017 (published October 30, 2003). is there.

As disclosed in paragraph [0006] of US Patent Application Publication No. 2003/2004017 (published October 30, 2003), R-EPE copolymers contain at least about 60% by weight of propylene-derived units and ethylene-derived units. Includes from about 0.1 to 35% by weight and from 0 to about 35% by weight of units derived from one or more unsaturated comonomer (provided that the total weight% of units derived from ethylene and unsaturated comonomer is about 40%. It can be characterized as less than% by weight). These copolymers also correspond to the following properties: (i) region errors of about 14.6 ppm and about 15.7 ppm and have approximately equal intensities.¹³C NMR peaks; (ii) copolymer content, i.e. B value greater than about 1.4 when the unit derived from ethylene and / or unsaturated comonomer is at least about 3% by weight; (iii) about -1.20. Super skewness index S_ix(Iv) T that remains essentially the same_meAnd decrease with increasing amount of comonomer in copolymer, i.e. units derived from ethylene and / or unsaturated comonomer T_maxDSC curve with; and (v) characterized as having at least one of an X-ray diffraction image showing more γ-ray crystals than an equivalent copolymer made with a Ziegler-Natta (ZN) catalyst. .. Typically, the copolymer of this embodiment is characterized by at least two, preferably at least three, more preferably at least four, and even more preferably all five of these properties.

Corresponds to region errors of about 14.6 ppm and about 15.7 ppm¹³A method for measuring a C NMR peak is described in paragraph 128 of US Patent Application Publication No. 2003/0204017 (published October 30, 2003): ¹³This data corresponding to the C resonance frequency of 100.4 MHz is collected using a Varian UNITY Plus 400 MHz NMR spectrometer. Acquired parameters quantitatively in the presence of palliatives¹³C Select to guarantee data acquisition. Data are shown using a probe head heated to 130 ° C. with gated decoupling, 4000 transients per data file, 7 second pulse repetition delay time, 24,200 Hz spectral width. And get using the file size of 32K data points. Samples are prepared by adding about 3 mL of 0.025 M tetrachloroethane-d2 / ortodichlorobenzene 50/50 mixture in chromium acetylacetoneate (relaxant) to 0.4 g of sample in a 10 mm NMR tube. Oxygen is expelled from the tube headspace by substituting with pure nitrogen. The sample is melted and homogenized by heating the tube and its contents to 150 ° C. with regular reflux (started with a heat gun).

The skewness index of the R-EPE copolymer is associated with the shape of the curve for the thermal elution fractionation test and is described in paragraphs 112-116 of US Patent Application Publication No. 2003/2004017 (published October 30, 2003). Can be determined using the method: The length distribution of the crystalline sequence can be measured on an experimental scale by thermal elution fractionation (TREF). The relative mass of the individual fractions can be used as a basis for estimating a more continuous distribution. L. Wild et al., Journal of Polymer Science: Polymer.Physics Ed., 20,441 (1982) scaled down the sample size and added a mass detector to continuously display this distribution as a function of elution temperature. This scaled-down type of analytical temperature-increasing elution fractionation (ATREF) is not related to the actual isolation of the fraction, but to a more accurate determination of the weight distribution of the fraction.

TREF was originally applied to copolymers of ethylene and higher α-olefins, but can also be used to analyze copolymers of propylene and ethylene (or higher α-olefins). Analysis of propylene copolymers requires higher temperatures for dissolution and crystallization of pure isotactic polypropylene, but most of the copolymer products are at similar temperatures as seen for ethylene copolymers. Is eluted in. The table below summarizes the conditions used in the analysis of propylene copolymers. Except as described, the conditions of TREF are consistent with those of Wild et al. (Supra) and Hazlitt, Journal of Applided Polymer Science: Appl. Polymer Symp., 45, 25 (1990).

A parameter used to describe the TREF parameter. Column Type and Dimensions-Stainless Steel Shot with Gap Capacity 1.5cc; Mass Detector-Single Beam Infrared Detector, 2920cm^-1Injection temperature-150 ° C; Temperature controller-GC oven; Solvent-1,2,4-trichlorobenzene; Concentration-0.1.0.3% (weight / weight); Cooling rate 1- (140-120 ° C) ) At -6.0 ° C / min; Cooling rate 2- (120-44.5 ° C) at -0.1 ° C / min; Cooling rate 3- (44.5-20 ° C) at -0.3 ° C / min Minutes; 1.8 ° C./min at heating rate- (20-140 ° C.); Data acquisition rate-12 pieces / minute.

The data obtained from the TREF is represented as a normalized plot of weight fraction as a function of elution temperature. The separation mechanism is similar to that of ethylene copolymers, where the molar content of the crystalline component (ethylene) is a major factor in determining the elution temperature. In the case of propylene copolymers, it is the molar content of isotactic propylene units that primarily determines the elution temperature. FIG. 5 of US Patent Application Publication No. 2003/0204017 (published October 30, 2003) represents the expected distribution of an example of a propylene / ethylene copolymer and an R-EPE copolymer prepared using a metallocene polymer. The type is illustrated.

The shape of the metallocene curve in FIG. 5 is typical of uniform copolymers. This shape results from the original random incorporation of comonomer. A striking feature of this shape of the curve is that tailing is seen at relatively low elution temperatures, compared to sharp or steep curves at higher elution temperatures. Skewness is a statistic that reflects this type of asymmetry. Equation 1 below is the skewness index S._ixIs mathematically expressed as an index of this asymmetry.

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T_maxThe value is defined as the temperature of the maximum weight fraction that elutes at 50-90 ° C. in the TREF curve. T_iAnd w_iIs the elution temperature and weight fraction of any i-th fraction in the TREF distribution, respectively. The distribution is normalized with respect to the total area of the curve elution above 30 ° C (w)._iThe sum of is 100%). Therefore, the exponent reflects only the shape of the crystallized polymer and excludes all uncrystallized polymers (polymers still in solution at 30 ° C. or below) from the calculations shown in Equation 1 above. There is.

R-EPE copolymer T_meAnd T_maxIs described in paragraphs [0998]-[0100] of US Patent Application Publication No. 2003/2004017 (published October 30, 2003): Differential scanning calorimetry (DSC) is a common method that can be used to examine the melting and crystallization of semicrystalline polymers. The general principles of DSC measurement and the application of DSC to the study of semi-crystalline polymers are described in standard textbooks (eg, EATuri, ed., Thermal characterization of Polymeric Materials, Academic Press, 1981). Some R-EPE copolymers remain essentially identical T_meAnd T which decreases as the amount of unsaturated comonomer in the copolymer increases_maxIt is characterized by a DSC curve having. T_meMeans the temperature at which melting ends, T_maxMeans the peak melting temperature.

Differential scanning calorimetry (DSC) analysis is performed using a model Q1000 DSC manufactured by TA Instruments, Inc. The DSC is calibrated as follows. First, a baseline is obtained by performing DSC from 90 ° C. to 290 ° C. without placing any sample in an aluminum DSC pan. Analysis of 7 g of fresh indium sample was then performed by heating the sample to 180 ° C., cooling the sample to 140 ° C. at a cooling rate of 10 ° C./min, and then holding the sample isothermally at 140 ° C. for 1 minute. Subsequently, the sample is heated from 140 ° C. to 180 ° C. at a heating rate of 110 ° C./min. The heat of fusion and the start of melting of the indium sample are measured and confirmed to be 156.6 ° C. ± 0.5 ° C. for the start of melting and 28.71 ± 0.5 J / g for the heat of fusion. Analysis of deionized water is then performed by cooling small droplets of fresh sample in a DSC pan from 25 ° C. to 30 ° C. at a cooling rate of 10 ° C./min. The sample is held isothermal at 30 ° C. for 2 minutes and heated to 30 ° C. at a heating rate of 10 ° C./min. Measure the start of melting and confirm that it is 0 ± 0.5 ° C.

The polypropylene sample is pressed onto a thin film at a temperature of 190 ° C. Approximately 5-8 mg of sample is weighed and placed in a DSC pan. A lid is crimped onto the pan to create a closed atmosphere. The sample pan is placed in the DSC cell and then heated at a high speed of about 100 ° C./min to a temperature about 30 ° C. above the melting temperature. Hold the sample at the same temperature for about 3 minutes. The sample is then cooled to 40 ° C. at a rate of 10 ° C./min and isothermally maintained at the same temperature for 3 minutes. The sample is heated at a rate of 10 ° C./min until it is completely melted. The obtained enthalpy curve is shown as peak melting temperature, start and peak crystallization temperature, heat of fusion and heat of crystallization, T._meAlso analyze all other DSC analyzes of interest.

R-EPE copolymer T_meAnd T_maxIs described in paragraphs [0102]-[0105] of US Patent Application Publication No. 2003/2004017 (published October 30, 2003): "High B value" and similar terms mean that the ethylene units of a copolymer of propylene and ethylene or a copolymer of propylene, ethylene and at least one unsaturated comonomer are distributed in the polymer chain in a non-random manner. means. The B value ranges from 0 to 2, where 1 indicates a completely random distribution of comonomer units. The higher the B value, the more the comonomer distribution in the copolymer alternates. The lower the B value, the more massive or more clustered the comonomer distribution in the copolymer. The high B value of the R-EPE copolymer is typically at least about 1.3, preferably at least about 1.4, more preferably at least about 1.5, and most preferably at least about 1.7. The B value is calculated as follows.

B is for propylene / ethylene copolymer

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[In the formula, f (EP + PE) is the sum of the EP and PE diad fractions, and F_EAnd F_PAre the mole fractions of ethylene and propylene in the copolymer, respectively] Is defined as. The B value can be similarly calculated for other copolymers by assigning their respective copolymer diads. For example, the calculation of the B value for the propylene / 1-octene copolymer is calculated by the following formula:

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Is used.

For propylene polymers made with metallocene catalysts, the B value is typically 1.1-1.3. For propylene polymers made with restricted geometric catalysts, the B value is typically 0.9-1.0. In contrast, R-EPE copolymers typically produced using activated non-metallocene metal center heteroaryl ligand catalysts have a B value of greater than about 1.4, typically about 1.5. ~ About 1.85. In other words, for any R-EPE copolymer, not only is the propylene block length relatively short relative to a given ethylene percentage, but a long sequence of three or more continuous ethylene inserts is the ethylene of that polymer. Unless the content is very high, it means that it is very low, if any, in the copolymer.

In one aspect of the invention, the second thermoplastic component preferably comprises a copolymer containing propylene and at least one α-olefin. As used herein, unless otherwise stated, copolymers can contain two, three or more different monomer units (ie, copolymers are terpolymers and four or more different monomer units. Including polymers containing). For example, one preferred copolymer is a propylene-containing elastomer containing at least about 50% by weight of the unit derived from the propylene monomer and at least about 5% by weight of one or more comonomer other than propylene, for example, a unit derived from ethylene. (That is, the propylene-containing elastomer can be an ethylene elastomer containing at least about 50% by weight of propylene). The propylene-containing elastomer can have an ethylene concentration of less than about 40% by weight based on the total weight of the propylene-containing elastomer. The propylene-containing elastomer contains an ethylene content of preferably at least about 5% by weight, more preferably at least about 7% by weight, and even more preferably about 9% by weight, based on the total weight of the propylene-containing elastomer. Propylene-containing elastomers are also, based on the total weight of the propylene-containing elastomer, less than about 40% by weight, more preferably less than about 30% by weight, even more preferably less than about 20% by weight, most preferably less than about 15% by weight ethylene. Can have a concentration. For example, the ethylene concentration is about 5 to about 40% by weight, more preferably about 7 to about 30% by weight, more preferably about 7 to about 20% by weight, and most preferably about 9 to about 9 to about 9 to about 40% by weight based on the total weight of the propylene-containing elastomer. It can be in the range of about 15% by weight.

The second polymer component (eg, ethylene elastomer or even propylene-containing elastomer) has a peak melting temperature of less than about 105 ° C., preferably less than about 100 ° C., more preferably less than about 90 ° C., most preferably less than about 82 ° C. It may include a polymer having (measured at a rate of about 10 ° C./min for a 3 mg sample of a polymer initially cooled at a rate of -10 ° C./min from 230 ° C. to about 0 ° C. by differential scanning calorimetry). Yes (eg peak melting temperature can be less than about 65 ° C.).

The propylene elastomer selected for the second polymer component has a Shore A hardness of at least about 45, preferably at least about 55, more preferably at least about 60, still more preferably at least about 65, according to ASTM D2240-05. Can be done. Shore A hardness can also be less than about 95, preferably less than about 90, more preferably less than about 85, even more preferably less than about 80. For example, the hardness (shore A unit) of the propylene elastomer can be in the range of about 65 to about 95, more preferably about 65 to about 85, and even more preferably about 65 to about 80.

Examples of suitable propylene elastomers that can be used in the second polymer component include more than about 50% by weight (eg, more than 60% by weight) of propylene monomer and about 5% by weight of ethylene monomer and about 35 to about 130. Examples thereof include soft thermoplastic resins that can be characterized by a peak melting temperature of ° C. (eg, about 40 to about 110 ° C.) (measured by differential scanning calorimetry). Such elastomers are commercially available from THE DOW CHEMICAL COMPANY under the name VERSIFY® (including, for example, 2400, 3000, 3200, 3300, 3401 and 4301) and from EXXON MOBIL CHEMICAL COMPANY under the name VISTAMAXX®. ing.

Olefin block copolymer / LOA / α-olefin interpolymer Olefin block polymer / ethylene / α-olefin interpolymer In one aspect of the present invention, the second polymer component comprises a multi-block polymer having a large number of blocks including a hard block having a relatively high crystallinity and a soft block having a lower crystallinity than the hard block. Can be done. A multi-block polymer (eg, a multi-block olefin-based polymer) is essentially a homopolymer containing one (eg, one) α-olefin monomer, a copolymer containing two α-olefin monomers, or three or more. It can be a terpolymer containing the above-mentioned monomers (typically, it contains at least two kinds of monomers which are α-olefins and can even contain three kinds of α-olefins), or four kinds or more. It can also contain the α-olefin monomer of. Multiblock homopolymers can include hard and soft blocks containing the same monomer, the difference between these blocks being the regularity of the monomers (eg, hard blocks are more regularly oriented monomers than soft blocks). Hard blocks have a higher degree of crystallinity because they can contain). Olefin block copolymers can include blocks with different concentrations of monomers. For example, the olefin block copolymer has a high concentration (for example, more than about 80% by weight, preferably more than about 90% by weight, more preferably more than about 95% by weight, most preferably more than about 99% by weight, or more of the olefin block copolymer. Is 100% by weight) than one or more hard blocks containing a first α-olein-based monomer and a low concentration of a second α-olefin-based monomer, and one or more hard blocks described above. It can have one or more soft blocks containing a low concentration of the first α-olefin. Preferably, the first α-olefin is a lower α-olefin (LOA), which is ethylene or propylene, so the olefin-based block copolymer is an LOA / α-olefin interpolymer. Although not limited, olefin block copolymers are ethylene / α. It can be a olefin interpolymer or a propylene / α-olefin interpolymer. Examples of LOA / α-olefin interpolymers that can be used in the second polymer component are PCT International Patent Application Publication Publication WO2006 / 102155A2 (filed March 15, 2006), WO2006 / 101966A1 (filed March 15, 2006). ) And WO 2006/101932A2 (filed March 15, 2006), all of which are incorporated herein by reference in their entirety.

Ethylene / α-olefin interpolymer Ethylene / α-olefin interpolymers suitable for use in the second polymer component are polymerized forms characterized by a large number of blocks or segments of two or more polymerized monomer units with different chemical or physical properties. Ethylene and one or more copolymerizable α-olefin comonomer (block interpolymer), preferably a multi-block copolymer.

Representative, but not limited to, ethylene / α-olefin interpolymers suitable for use in the polymer compositions of the present invention are characterized by a melting point Tm higher than the melting point of a random copolymer having the same density d. Can be done. For example, an ethylene / α-olefin interpolymer has at least one melting point Tm (° C.) and a density d (g / cm).³), And the numerical values of the variables have the following relationship: Tm 1000 (d) -800, preferably Tm -2002.9 + 4538.5 (d) -2422.2 (d).², More preferably Tm -6288.1 + 13141 (d) -6720.3 (d)²Most preferably, Tm 858.91-11825.3 (d) +112.8 (d).²Matches.

Preferably, the ethylene / α-olefin interpolymer suitable for use in the polymer compositions of the present invention has a Mw / Mn of about 1.7 to about 3.5, at least one melting point Tm (° C.) and a density d ( g / cm³), And the numerical values of the variables have the following relationship: Tm 1000 (d) -800, preferably Tm&gt; -2002.9 + 4538.5 (d) -2422.2 (d).², More preferably Tm -6288.1 + 13141 (d) -6720.3 (d)²Most preferably, Tm 858.91-11825.3 (d) +112.8 (d).²Matches.

Crystallinity As can be seen from this description, the first polymer component, the second polymer component, or a portion of both, includes a crystalline portion of the material. Preferably, some of the first polymer components have a relatively high crystallinity and some of the second polymer components have a relatively low crystallinity, or both. For example, the crystallinity of the first polymer component can be greater than about 12%, preferably greater than about 15%, more preferably greater than about 20%, most preferably greater than about 24% (eg, greater than about 35%). .. The crystallinity of the second polymer component can be less than about 30%, preferably less than about 14%, more preferably less than about 11%, most preferably less than about 9% (eg less than about 7%).

Percent crystallinity in the present specification can be measured by differential scanning calorimetry according to ASTM D3418.03 or ISO 11357-3. As an example, a 1 mg size polymer sample is sealed in an aluminum DSC pan. 25 cm³Place the sample in the DSC cell while purging nitrogen at / min and cool to -100 ° C. A standard thermal history is established for this sample by heating to 225 ° C. at 10 ° C./min. The sample is then cooled to 100 ° C. (at 10 ° C./min) and reheated to 225 ° C. at 10 ° C./min. Record the heat of fusion observed for the second scan (ΔH)_Observation). The observed heat of fusion is expressed by the following formula:

<maths num="6"></maths>

[In the formula, ΔH_KnownThe value of is the default reference value described in the literature on polymers] Is related to the degree of crystallinity (%) based on the weight of the sample. For example, the heat of fusion of isotactic polypropylene has been reported in B. Wunderlich, Macromolecular Physics, Volume 3, Crystal Melting, Academic Press, New York, 1980, p.48, ΔH._Known= 165 joules / g (polypropylene polymer); heat of fusion of polyethylene is F. Rodriguez, Principles of Polymer Systems, 2^nd Reported in Edition, Hemisphere Publishing Corporation, Washington, 1982, p.54, H_Known= 287 joules / g (polyethylene polymer). ΔH for polymers containing more than about 50 mol% propylene monomer_Known= 165 J / g, ΔH for polymers containing more than about 50 mol% ethylene monomer_KnownA value of = 287 J / g can be used.

Reinforcement material The compositions of the present invention include reinforcing materials, in particular one or more glass fiber materials (eg, short glass fibers, long glass fibers or both) or other fibers (eg steel, carbon, etc. or otherwise), talc. Further includes reinforcements (eg, talc, wollastonite, etc. or otherwise), or combinations thereof. Preferably, the fibers are distributed substantially uniformly throughout the final composition. However, it may be possible to selectively place the fibers in one or more predetermined positions within the composition.

Fiber reinforced plastics, glass fibers or both are at least about 5% by weight, preferably at least about 10% by weight, more preferably at least about 15% by weight, most preferably at least about 20% by weight, based on the total weight of the polymer composition. Can be present at the concentration of. Fiber reinforced plastics, fiberglass or both are less than about 70% by weight, preferably less than about 50% by weight 5, more preferably less than about 45% by weight, most preferably less than about 40% by weight, based on the total weight of the polymer composition. It can be present at a concentration of (eg, less than about 35% by weight).

It will be found that in the final composition obtained (eg in the resulting composition or in articles obtained after a molding process such as injection molding), the fiber length can be reduced relative to the raw fiber length. The average fiber length in the final composition can be greater than about 0.5 mm, preferably greater than about 1 mm, more preferably greater than about 2 mm. For example, the average fiber length can be in the range of about 0.5 to about 5 mm or about 1 mm to about 3 mm. In the final composition, the glass fibers can also have a shorter length, for example the glass fibers can have an average length of about 1 to about 2 mm or even less. Preferably at least about 50% by weight of the fiber is longer than 1 mm, more preferably at least about 65% by weight (or even about 75% by weight) is longer than about 1 mm. Fiber diameters typically range from about 3 to about 100 microns, more specifically from about 5 to about 25 microns (eg, about 17 microns). Without limitation, the glass can be one or more of E-glass, S-glass, T-glass, AR-glass, C-glass, R-glass and the like.

In addition, the polymer composition is optionally one or more additives such as surfactants, flexibility-imparting agents, coupling agents, flame retardants, ignition resistant additives, stabilizers, colorants, antioxidants. It is believed that agents, mold release agents, antistatic agents, antislip agents (ie, antislip agents), flow enhancers, nucleating agents, clarifying agents or any combination thereof can be included. One or more pigments or colorants can be added to the polymer composition so that, for example, the part or member is "molded-in-color". As an example, a colorant can be added to the fiber reinforced plastic. One of the preferred additives is a colorant, which, when included, has a relatively small weight percentage (eg, less than about 5% by weight, or even less than about 1% by weight) of the total composition obtained. Exists. For example, the colorant can be a colorant for achieving a black appearance, a gray flannel appearance, or the like. Preferred examples of additives are ignitable additives such as halogenated hydrocarbons, halogenated carbonate oligomers, halogenated diglycidyl ethers, organic phosphorus compounds, fluorinated olefins, antimony oxide and metal salts of aromatic sulfur (s). However, but not limited to these, or mixtures thereof can also be used. In addition, compounds that stabilize the thermoplastic resin composition against degradation caused by heat, light and oxygen or a mixture thereof (but not limited to these) can also be used. One of the preferred additives is an antioxidant, which, when included, is typically included in a relatively small weight percentage (eg, less than about 1 or 2% by weight) of the total polymer composition. .. An example of a preferred commercial antioxidant is IRGANOX B225 Antioxidant, which is commercially available from Ciba Specialty Chemicals Corporation. The Irganox B225 Antioxidant is the Irganox 1010 Antioxidant (Tetrakis (Methylene (3,5-di-t-Butyl-4-hydroxyhydrocinnamate)) 1 part methane and Irgafos. It is a blend with 1 part of 168 (tris (2,4-t-butylphenyl) phosphite). Another preferred additive is a mold release agent (eg, wax, mold release agent, slip aid, etc. or otherwise). One of the preferred mold release agents is a nitrogen or ammonia group containing compound such as amine or amide. One of the preferred amide-containing compounds is ethylene bisstearamid (EBS). Another preferred category of mold release agents is "stearic acid esters", such as glycerol monostearate commercially available from Danisco or Ciba Specialty Chemicals under the trade name Atmer. One of the preferred nitrogen-containing compounds, which is a wax, is elquamid (commercially available from Chemtura Corporation, Middlebury, Connectticut) sold under the trade name KENAMIDE ULTRA E.

One of the preferred additives is a coupling agent such as a grafted polypropylene coupling agent such as maleic anhydride, a grafted polypropylene coupling agent (eg Chemtura Polybond 3200 or Arkema OREVAC CA-100). The polymer composition of the present invention may or may not optionally contain a coupling agent. When included, the coupling agent is present in the total composition obtained in an amount of less than about 5% by weight, more preferably less than about 2% by weight. For example, the coupling agent can be present in an amount of at least about 0.01% by weight or even at least about 0.1% by weight of the total composition.

As described herein, the polymeric compositions of the present invention include a first polymeric component, a second polymeric component and a fiber reinforced material. It can be seen that the ratio of the first polymer component to the second polymer component is greater than 10:42, more specifically greater than 10:27. Preferably, the ratio of the first polymer component to the second polymer component is in the range of about 10: 2 to about 10:42, more preferably about 10: 2 to about 10:27.

Polymer composition obtained in the present invention is desired in the compound in which is blended can be prepared according to any suitable method to achieve the correct properties. A combination of two or more components (eg, a first polymer component and a reinforcing material) can be blended prior to feeding the material to the processing equipment (eg prior to introduction into the injection molding machine). Alternatively, or in addition, two or more of the ingredients may be blended together in the processing apparatus. For example, the polymeric components of the resulting composition do not melt blend with each other until they enter the processing equipment (eg, inside a screw and barrel assembly, mixing nozzle, injection molding machine, etc.). The preparation of the compositions of the present invention can be dry blended, melt blended or blended with two or more individual components, either directly or in another device in a device used to manufacture a finished product (eg, an automotive part). It can be done using any suitable mixing means, including dry blending and melt blending (eg, premixing in a Banbury mixer). The dry blend of the composition can also be injection molded directly without performing a pre-melt blending step. In one preferred embodiment, the formation of the polymer composition is a mixture of at least two components (eg, a second polymer component and a reinforcing material concentrate) in the molding machine or at least three components (eg, a first polymer component, a second. Including mixing (eg, blending in a press) of a polymer component and reinforcing material in a molding machine. Optionally or further, two or more components may be premixed in the compounding unit prior to mixing in the molding machine.

As mentioned above, the components in the polymer composition are also in mixers such as Banbury mixers or extruders such as kneaders, single screw compound extruders, twin screw extruders, heated double roll machines and the like. It can also be blended or melt-blended inside. In one aspect of the invention, after blending the ingredients, the blended polymeric material can be pelletized to form granules or pellets that can be fed to the molding machine. A large amount (eg, greater than 5 kg, preferably greater than 20 kg or even greater than 250 kg) of pellets or granules can be placed in a container and stored or transported before molding the article.

When softened or melted by application of heat, the polymer compositions of the present invention use conventional techniques such as compression molding, injection molding, gas assisted injection molding, rolling, vacuum forming, thermoforming, extrusion, blow molding. It can be processed into articles, either alone or in combination. The polymeric composition can also be molded, spun or stretched onto films, fibers, multilayer laminates or extruded sheets on any machine suitable for such purposes, or one or more. It can also be blended with organic or inorganic substances. In a particularly preferred embodiment, the polymeric compositions of the invention are preferably injection molded with or without an accompanying insert (eg, as part of an insert molding process) to form a molded article or an overmolded article. Injection molding as part of.

In one preferred embodiment, the first polymer component and the second polymer component (eg, an elastomer) may not be premixed with each other in the molten state prior to feeding them into an apparatus for producing the article. Conceivable. To be precise, they are mixed with each other and then subjected to melt blending only upon introduction into the device (eg, at the time of mixing in the screw and barrel assembly of an injection molding machine).

Reinforcing materials can be added in loose individual states or can also be added as bundles of material (eg fibers). Preferably, the reinforcing material comprises a cohesive material dispersed in a matrix of polymeric materials that is compatible or identical to other polymeric components of the resulting composition (eg, the first polymeric component). Place in the mixture as part of the form of sex concentrate. As an example, a fiber (eg, glass fiber) reinforcing material in which the fiber phase is dispersed in a polymer matrix phase (a matrix phase containing one or more of the polymer materials described herein, such as polypropylene homopolymers). It is considered that concentrate can be used. The fibrous phase is present in an amount of at least about 20% by weight, more preferably more than 50% by weight (eg, about 50 to about 90% by weight, for example about 60% by weight) of the concentrate. An example of such a concentrate of fiber reinforced plastics is described in US Patent Application No. 60 / 890,002 (filed August 16, 2007), which is hereby cited by reference for all purposes. Incorporate in the book.

In a typical aspect, the polymer composition can include a first polymer component, a second polymer component containing ethylene, and a reinforcing material concentrate containing a polymer matrix containing a reinforcing material and an additional polymer material. Conceivable. In another typical embodiment, the polymer composition can include a reinforcing material concentrate containing a second polymer component containing ethylene and a polymer matrix containing a first polymer component.

One approach to improving one or more of the properties is to use pretreated or otherwise modified fibers. For example, one approach is to coat the fibers with a chemical agent (eg, a coupling agent, a surface property modifier, a stabilizer or other suitable agent). As one embodiment, the fiber is used to physically, chemically or physically and chemically improve the strength of the subsequent interfacial bond with the polymer matrix, to protect the fiber surface from damage, or both. Can be treated with a sizing agent. Sizing agents typically include suitable film-forming agents, coupling agents (eg silanes such as alkoxysilanes) and optionally lubricants or other agents. It may be possible to include a coupling agent as described above (including, for example, a maleic anhydride grafted polypropylene coupling agent) as at least a portion of the sizing agent.

The fibers can be provided as individual fibers, such as chopped fibers and / or continuous fibers, which are randomly oriented with each other, aligned axially with each other, woven, or any combination thereof, and they are subsequently provided. Can be dispersed in a polymer matrix (eg, including a thermoplastic polymer matrix, such as polypropylene homopolymers or copolymers). It is also believed that the fibers can be provided in the form of fiber bundles in which the fibers are generally aligned in the axial direction.

The fiber reinforced material concentrate material in the present invention can have any suitable size or shape. In general, fiber reinforced concentrate concentrate materials are elongated (eg, like rods), granular, substantially symmetrical in shape with respect to at least one axis, and substantially asymmetric in shape with respect to at least one axis. It can be substantially solid, porous, or any combination thereof. The individual particles of the fiber reinforced material concentrate material have maximum dimensions (eg, length, diameter, height, width, thickness, etc.) of about 5 mm or more, more specifically about 8 mm or more, and even more limited. Can be about 10 mm or more. Smaller dimensions, such as less than about 1 mm, and more specifically less than about 0.5 mm, are also possible.

One approach for producing fiber reinforced material concentrates is to impregnate the fiber bundles with a polymer, such as by the pull-fusion technique disclosed in the prior art. See, for example, US Pat. No. 5,834,056, "Process and Appliance for Fiber Bundle Impregnation," which is incorporated herein by reference for all purposes.

In general, the present invention contemplates a method of manufacturing an article in which a first polymer component, a second polymer component and a reinforcing material concentrate are supplied from individual sources (eg, hoppers) into the screw barrel assembly of the processing equipment. To do. As the material travels along the assembly, it is subjected to shear forces and heat and melt-blended with each other. Optionally, a mixing nozzle is also used in the device to aid in melt blending. The resulting melt-blended component is introduced into a molding tool that molds the material (eg, a die, a mold, or other structure that shapes the introduced material).

Advantageously, surprisingly, the properties desired by the disclosed proportions of fiber reinforced material concentrate, the first polymer component and the second polymer component (eg low gloss and improved scratch resistance, scratch resistance, etc. It has been found that low temperature ductility and dimensional stability can be achieved. As an example, articles formed compositions from the present invention have superior grain reproduction (eg, low gloss) and improved resistance to articles compared to the article forming compositions known in the art. It provides an article with a surface that is both scratchy and soft to the touch. More specifically, articles formed from the compositions of the present invention using a tool having an N111 texture (eg, Opel N111 texture) are about 0.6 to about 1.7 GU, more specifically about 0. Improved gloss properties in the range of 9 to about 1.4 GU (according to ASTM D-542) (eg gloss is micromat (micro) It was found that (measured with N111 texture with matt)) can be realized. Furthermore, articles formed using the compositions of the present invention have been found to be able to achieve the following improvements in properties; scratch resistance (eg, scratches at 6N by GMW 14688 are less than about 2 GU, and in some cases about 0.05 to about. 1GU); Scratch resistance [eg, scratches at 10 N measured for articles with N111 texture with micromats by PV3952 are less than about 1 dL, more typically less than about 0.5 dL; scratches at 10 N by PV3952. (Article formed with Audi K42 texture) less than about 0.4 dL]; dimensional stability (eg shrinkage less than about 5%, in some cases 0.1 to about 1%; inflow by ASTM D-696 The linear expansion rate (CLTE) of is about 25 to about 50 mm / mm ° C, more specifically about 30 to about 45 mm / mm ° C; ASTM The coefficient of linear expansion (CLTE) of the cross flow according to D-696 is about 40 to about 70 mm / mm ° C., more specifically about 45 to about 65 mm / mm ° C.) or a combination thereof. Preferably, the polymer composition is free of grafted copolymers, free of inorganic fillers (eg talc), free of glass particles other than glass fibers, free of peroxides, or any combination thereof. Results are obtained.

The polymer compositions of the present invention have many advantageous uses. Accordingly, the present invention contemplates articles manufactured using methods that include one or more molding steps of this composition for forming the compositions and articles of the invention. These articles are typically molded. They can have a substantially constant shape along their length (eg by extrusion). They can have a shape that varies throughout the article (eg, can have a shape that includes one or more surfaces that are flat, three-dimensionally curved, or a combination thereof). The article here can be a composite article. These can be insert-molded, overmolded, or both articles. For example, the present invention can be used as part of various products, while already being particularly suitable for use in the formation of articles such as trays, tables, plates, lawns and garden furniture, shoes, boots, etc. know. Polymer compositions are also used in automotive parts such as dashboards, consoles, armrests, switch covers, brake levers, shift levers, knobs, handles, control buttons, trim panels, seat back covers, instrument housings, cup holders, panels, sun visors. , Rearview mirror housing, fascia (eg bumper fascia), automotive equipment, automotive cowl, console (eg center overhead, floor assembly or both), instrument panel, glove box assembly including doors, knee bolster assembly or instrument panel fixing assembly Alternatively, it can be used to form a structural member.

The materials obtained by the teachings herein have the following properties: inflow flexural modulus in the range of about 200 to about 4000 MPa, more specifically about 350 to about 3500 MPa (measured according to ISO 178); about 50. Cross-flow flexural modulus in the range of ~ about 2500 MPa, more specifically about 150 to about 1950 MPa (measured according to ISO 178); average bending in the range of about 50 to about 3000 MPa, more specifically about 150 to about 2000 MPa. Modulus (measured according to ISO 178); about 5 to about 50 kJ / m², More limitedly about 11-about 45 kJ / m²Notched Charpy impact at room temperature in the range of (measured according to ISO 179-1eU); about 1 to about 35 kJ / m², More limitedly about 4 to about 28 kJ / m²Notched Charpy Impact at 20 ° C. (measured according to ISO 179-1eU); friction coefficient in the range of about 0.2 to about 0.7, more specifically about 0.1 to about 0.6. (Coefficient of static friction) (according to ASTM D-1894); and the coefficient of friction (coefficient of dynamics) in the range of about 0.5 to about 0.75, and more specifically about 0.2 to about 0.5 (ASTM D- It has any combination of at least one, two (and, more specifically, at least three or all) of (measured according to 1894). The average flexural modulus is the average of the inflow and crossflow modulus. As an example, the average flexural modulus can be determined by cutting a test piece from a molded plaque having a film gate on one side. A test piece cut along the direction of the film gate is used for measuring the inflow elastic modulus, and a test piece cut perpendicular to the flow is used for measuring the cross-flow elastic modulus.

<p>Examples 1-6 Examples (EX.) 1-6 are produced by injection molding the compositions in Table I. A first polymer component (polypropylene homopolymer), a second polymer component (propylene-ethylene elastomer) and a reinforcing material concentrate (including long glass fibers and an additional first polymer component polypropylene) are dry blended and then DEMAG. Gold for forming a test sample after being placed in a 100 injection molding machine and melt-blended therein (ie, after the solid dry blend pellets after being placed in the screw of the injection molding machine have been melted and blended). Inject into the mold cavity. The data in Table I show the expected results.</p><p><tables num="1"></tables></p><p>Examples 7 to 15 Examples 7 to 15 are produced using the formulations shown in Table II and the same methods as in Examples 1 to 6. In addition to the first component, the second component and the reinforcing material, Examples 7 to 15 also include a color concentrate. The color concentrate is dry-blended with other ingredients before being placed in the DEMAG injection molding machine. The data in Table II show the expected results.</p><p><tables num="2"></tables></p><p>Examples (EX.) 16-23 and Comparative Examples (CE) 24 Molded parts are manufactured by injection molding the compositions in Table III using the same methods used in Examples 7-15. In Examples 16-22, the second polymer component is S / LEP, specifically an ethylene-octene copolymer. Example 23 uses a propylene-ethylene elastomer as the second polymer component, and Comparative Example 24 is a comparative example in which talc is contained instead of the reinforcing material concentrate containing long glass fibers.</p><p> S / LEP-A is a copolymer containing about 59% by weight of ethylene monomer units and about 41% by weight of octene monomer units. This ethylene elastomer has a specific gravity of about 0.868 as measured according to ASTM D792; a Shore A hardness of about 70 as measured according to ASTM D2240; a peak melting temperature of about 55 ° C. as measured by the differential scanning calorie method; measured according to ASTM D790. (Tested with 2% split wire using compression molded sample) Bending elasticity is about 14.4 MPa; melt flow rate measured at 190 ° C./2.16 kg according to ASTM D1238; about 0.5 g / 10 min; according to ASTM D638 The tensile strength at 100% strain measured at a strain rate of 510 mm / min is about 2.6 MPa; the breaking point tensile strength measured at a strain rate of 510 mm / min according to ASTM D638 is about 9.5 MPa; 510 mm / min according to ASTM D638. The breaking point tensile elongation measured at a strain rate of minutes is about 810%; and the Vicar softening point measured according to ASTM D1525 is about 46 ° C.</p><p> S / LEP-B is a copolymer containing about 59% by weight of ethylene monomer units and about 41% by weight of octene monomer units. This ethylene elastomer has a specific gravity of about 0.870 as measured according to ASTM D792; a Shore A hardness of about 66 as measured according to ASTM D2240; a peak melting temperature as measured by the differential scanning calorimeter of about 59 ° C.; as measured according to ASTM D790. (Tested with 2% split wire using compression molded sample) Bending elasticity is about 10.8 MPa; melt flow rate measured at 190 ° C./2.16 kg according to ASTM D1238; about 5.0 g / 10 min; 510 mm according to ASTM D638 Tensile strength at 100% strain measured at a strain rate of / min is about 2.3 MPa; breaking point tensile strength at breaking point measured at a strain rate of 510 mm / min according to ASTM D638; 510 mm / min according to ASTM D638. The breaking point tensile elongation measured at the strain rate of is about 1100%; and the Vicar softening point measured according to ASTM D1525 is about 37 ° C.</p><p> S / LEP-C is a copolymer containing about 59% by weight of ethylene monomer units and about 41% by weight of octene monomer units. This ethylene elastomer has a specific gravity measured according to ASTM D792 of about 0.870; a Shore A hardness measured according to ASTM D2240 of about 72; a peak melting temperature measured by differential scanning calorimetry of about 60 ° C.; measured according to ASTM D790 ( Tested with 2% split wire using compression molded sample) Bending elasticity is about 12.1 MPa; melt flow rate measured at 190 ° C. / 2.16 kg according to ASTM D1238; about 30 g / 10 min; 510 mm / min according to ASTM D638 The tensile strength at 100% strain measured at strain rate is about 3.3 MPa; the breaking point tensile elongation measured at a strain rate of 510 mm / min according to ASTM D638 is about 1000%; and the Vicar softening point measured according to ASTM D1525 is about. It is 41 ° C.</p><p> Elastomer A is a propylene-ethylene copolymer containing about 15% by weight of ethylene monomer units and about 85% by weight of propylene units. Elastomer A has a specific gravity of about 0.876 measured according to ASTM D792; durometer hardness measured according to ASTM D2240 of about 72 and Shore D of about 19; expected peak melting temperature measured by differential scanning calorific value is about 30-about. 50 ° C; Crystalline measured by Differential Scanning Calorie Measurement Method (10 ° C./min) is about 14%; Measured according to ISO 178 (tested with 1% split line using injection molded sample) Bending elasticity is about 8 MPa; Melt flow rate measured at 230 ° C./2.16 kg according to ASTM D1238 is about 8 g / 10 min; yield point tensile stress measured according to ISO 527-1, -2 is about 1.5 MPa; according to ISO 527-1, -2 The measured breaking point tensile stress is about 2.05 MPa; the breaking point tensile elongation measured according to ISO 527-1, -2 is about 250%.</p><p> Elastomer B is a propylene-ethylene copolymer containing about 9% by weight of ethylene monomer units and about 91% by weight of propylene units. Elastomer B has a specific gravity of about 0.863 measured according to ASTM D792; a durometer hardness measured according to ASTM D2240 of about 95 Shore A and about 43 Shore D; an expected peak melting temperature of about 85 ° C. as measured by the differential scanning calorific value measurement method. Crystalline degree measured by differential scanning calorific value measurement method (10 ° C./min) is about 30%; Bending elasticity measured according to ISO 178 (tested with 1% split line using injection molded sample) is about 105 MPa; ASTM D1238 The melt flow rate measured at 230 ° C./2.16 kg according to is about 8 g / 10 min; the yield point tensile stress measured according to ISO 527-1, -2 is about 7.0 MPa; measured according to ISO 527-1, -2. Breaking point tensile stress is about 15.5 MPa; breaking point tensile elongation measured according to ISO 527-1, -2 is more than about 640%; Viker softening point measured according to ASTM D1525 is about 64 ° C.</p><p> Elastomer C is a propylene-ethylene copolymer containing about 5% by weight of ethylene monomer units and about 95% by weight of propylene units. Elastomer C has a specific gravity of about 0.888 measured according to ASTM D792; a durometer hardness measured according to ASTM D2240 of about 96 and Shore D of about 54; an expected peak melting temperature measured by differential scanning calorific value of about 115 ° C.; Crystalline measured by differential scanning calorie measurement (10 ° C./min) is about 44%; measured according to ISO 178 (tested with 1% split line using injection molded sample) bending elasticity is about 400 MPa; according to ASTM D1238 Melt flow rate measured at 230 ° C./2.16 kg is about 8 g / 10 min; yield point tensile stress measured according to ISO 527-1, -2 is about 16 MPa; break point tension measured according to ISO 527-1, -2 The stress is about 23 MPa; the breaking point tensile elongation measured according to ISO 527-1, -2 is more than about 630%; the Vicar softening point measured according to ASTM D1525 is about 98 ° C.</p><p> Elastomer D is a propylene-ethylene copolymer containing about 12% by weight of ethylene monomer units and about 88% by weight of propylene units. Elastomer D has a specific gravity of about 0.864 as measured according to ASTM D792; a durometer hardness of about 70 as measured according to ASTM D2240; an expected peak melting temperature of about 50 ° C. as measured by differential scanning calorimetry; Crystalline measured by (10 ° C./min) is about 14%; bending elasticity measured according to ISO 178 (tested with 1% split line using injection molded sample) is about 32 MPa; 230 ° C./2 according to ASTM D1238. Melt flow rate measured at 16 kg is about 25 g / 10 min; yield point tensile stress measured according to ISO 527-1, -2 is about 2.8 MPa; break point tensile elongation measured according to ISO 527-1, -2 More than 67%; Viker softening point measured according to ASTM D1525 is less than about 30 ° C.</p><p> Elastomer E is a propylene-ethylene copolymer containing more than about 9% by weight of ethylene monomer units and about 91% by weight of propylene units. Elastomer E has a specific gravity of about 0.876 as measured according to ASTM D792; durometer hardness as measured according to ASTM D2240: Shore A about 94 and Shore D about 42; expected peak melting temperature measured by differential scanning calorific value measurement is about 80 ° C.; Crystalline measured by differential scanning calorie measurement (10 ° C./min) is about 29%; measured according to ISO 178 (tested with 1% split line using injection molded sample) bending elasticity is about 108 MPa; according to ASTM D1238 Melt flow rate measured at 230 ° C./2.16 kg is about 25 g / 10 min; yield point tensile stress measured according to ISO 527-1, -2 is about 7 MPa; break point tension measured according to ISO 527-1, -2 The stress is about 12 MPa; the breaking point tensile elongation measured according to ISO 527-1, -2 is more than about 630%; the Vicar softening point measured according to ASTM D1525 is about 60 ° C.</p><p> PP-A is a polypropylene homopolymer containing at least 95% by weight isotactic polypropylene. PP-A has a density of about 0.900 g / cm measured according to ISO 1183.³The impact strength with Charpy notch at 23 ° C. measured according to ISO 179 / eA is about 2.5 KJ / m.²The peak melting temperature measured by the differential scanning calorimetry is over about 160 ° C; the expected crystallization measured by the differential scanning calorimetry is over about 50%; the bending elasticity measured according to ISO 178 is about 1650 MPa; ISO 1133. The melt flow rate measured at 230 ° C./2.16 kg was about 52 g / 10 min; the yield point tensile stress measured according to ISO 527-1, -2 was about 37.0 MPa; measured according to ISO 527-1, -2. Yield point tensile elongation is about 9%; Viker softening point measured according to ASTM D1525 is about 156 ° C.</p><p> PP-B is a polypropylene homopolymer containing at least 95% by weight isotactic polypropylene. PP-B has a density of about 0.90 g / cm measured according to ISO 1183.³The impact strength with Charpy notch at 23 ° C. measured according to ISO 179-1 / 1eA is about 2.5 KJ / m.²The peak melting temperature measured by the differential scanning calorimetry is over about 156 ° C; the expected crystallization measured by the differential scanning calorimetry is over about 50%; the bending elasticity measured according to ISO 178 is about 1650 MPa; ISO 1133. The melt flow rate measured at 230 ° C./2.16 kg was about 52 g / 10 min; the yield point tensile strength measured according to ISO 527-2 was about 37 MPa; the yield point tensile elongation measured according to ISO 527-2 was about 9. %; The Vicar softening point measured according to ASTM D1525 is about 152 ° C.</p><p> PP-C is an impact resistant polypropylene copolymer containing an isotactic polypropylene phase and an elastomer copolymer phase. PP-A has a density of about 0.900 g / cm measured according to ISO 1183.³The impact strength with Charpy notch at 23 ° C. measured according to ISO 179 / eA is about 4KJ / m.²The peak melting temperature measured by the differential scanning calorimetry is over about 152 ° C; the expected crystallization measured by the differential scanning calorimetry is over about 45% by weight; the bending elasticity measured according to ISO 178 is about 1450 MPa; ISO. Melt flow rate measured at 230 ° C / 2.16 kg according to 1133 is about 44 g / 10 min; yield point tensile stress measured according to ISO 527-1, -2 is about 28.0 MPa; measured according to ISO 527-1, -2 The yield point tensile elongation was about 7%; the Vicar softening point measured according to ASTM D1525 was about 152 ° C.</p><p> PP-D is an impact resistant polypropylene homopolymer containing at least 80% by weight isotactic polypropylene and an elastomer copolymer phase. PP-C has a density of about 0.90 g / cm measured according to ISO 1183.³The impact strength with Charpy notch at 23 ° C. measured according to ISO 179-1 / 1eA is about 10 KJ / m.²The peak melting temperature measured by the differential scanning calorimetry is over about 156 ° C; the expected crystallization measured by the differential scanning calorimetry is over about 45% by weight; the bending elasticity measured according to ISO 178 is about 1450 MPa; ISO. Melt flow rate measured at 230 ° C. / 2.16 kg according to 1133 is about 12 g / 10 min; yield point tensile strength measured according to ISO 527-2 is about 28 MPa; yield point tensile elongation measured according to ISO 527-2 is about 8%; Viker softening point measured according to ASTM D1525 is about 152 ° C.</p><p> CC-A is a color concentrate. CC-B and CC-C are color concentrates containing colorants, UV stabilizers and slip agents in polypropylene carriers.</p><p> Reinforcing material concentrate-A is a concentrate containing about 60% by weight of long glass fibers and about 40% by weight of PP-B.</p><p> Reinforcement Concentrate-B, Reinforcement Concentrate-C and Reinforcement Concentrate-D all contain approximately 60% by weight of long glass fibers, approximately 2% by weight of coupling agent, and melt flow rate (230 ° C. according to ISO 1133). / 2.16 kg) contains about 36% by weight of polypropylene (eg PP-B) in excess of about 40g / 10 minutes and a heat stabilizer with a concentration of less than about 2% by weight.</p><p> The first polymer component, the second polymer component and the reinforcing material concentrate are dry blended, placed in a Demag 100 injection molding machine, melt blended therein, and then in a mold cavity for forming a test sample. Inject into. The data in Table III show the expected results. C. which does not contain long glass fibers. E. 24 has a low heat deflection temperature and a low vicar softening point as well as poor glossiness, scratch resistance and scratch resistance.</p><p> D9100.05, D8507.15 and D9530.05 are ethylene / α-olefin interpolymers which are blocks having at least one hard block and at least a plurality of soft blocks. These block copolymers are commercially available from The Dow Chemical Company under the trade name INFUSE® and include ethylene and octene monomers. The properties of these interpolymers are shown in Table IV below.</p><p><tables num="3"></tables></p><p><tables num="4"></tables></p><p>Examples 25-31 Molded parts are manufactured by injection molding the compositions in Table V using the same methods used in Examples 7-15. In Examples 25-31, the second polymer component is a propylene-ethylene elastomer.</p><p> The first polymer component, the second polymer component and the reinforcing material concentrate are dry blended, placed in a Demag 100 injection molding machine, melt blended therein, and then in a mold cavity for forming a test sample. Inject into. The data in Table V show the expected results.</p><p>Examples 32 to 35 Molded parts are manufactured by injection molding the compositions in Table VI using the same methods used above. Example 32 comprises a propylene-ethylene elastomer, Example 33 comprises an S / LEP, Example 34 comprises a block copolymer, and Example 35 is a Nordel® IP4770P elastomer commercially available from The Dow Chemical Company. including.</p><p> Nordel® IP4770P is an ethylene propylene diene polymer (EPDM rubber) containing about 70% by weight ethylene, about 25% by weight of propylene and about 5% by weight of diene (eg, ethylidene norbornene). Nordel IP4770P is a random copolymer, ASTM D1646 (ML at 125 ° C.)₁₊₄) Is about 70 (the expected melt index measured at 190 ° C. / 2.16 kg according to ISO 1133 is less than about 0.2 g / 10 min).</p><p> The first polymer component, the second polymer component and the reinforcing material concentrate are dry blended, placed in a Demag 100 injection molding machine, melt blended therein, and then in a mold cavity for forming a test sample. Inject into. The data in Table VI show the expected results.</p><p><tables num="5"></tables></p><p>Examples 36-39 and Comparative Example 40 Molded parts are manufactured by injection molding the compositions in Table VII using the same methods used in Examples 7-15. Example 36 comprises a propylene-ethylene elastomer and Examples 37-39 comprises S / LEP. Comparative Example 40 is available from Bassell (Italy), C.₂About 40% by weight and C₃About 60% by weight of rubber-like C₂-C₃Includes the copolymer SOFTELL CA02A. These examples are also in Color Concentrate (CC-C), Orevac CA® 100, a maleic anhydride grafted polypropylene available from Arkema Inc (Philadelphia, PA, USA) and in thermoplastic carriers. Also includes CMPP 13.00, which is a concentrate of additive packages containing heat stabilizers.</p><p><tables num="6"></tables></p><p> The first polymer component, the second polymer component, glass fiber, maleic acid grafted PP, color concentrate and additive package concentrate are blended in a twin screw extruder to melt blend the material and then pellet or Extrude into granules. The pellet or granule is then placed in a Demag 100 injection molding machine, melted in it and then injected into a mold cavity for forming a test sample.</p><p> The data in Table VIII show the expected results for Examples 36-39 and Comparative Example 40. Comparative Example 40 requires a high concentration of SOFTELL CA02A to achieve a flexural modulus comparable to that of a sample containing a propylene elastomer or S / LEP. Comparative Example 40 also has an undesirably low melt flow rate. The higher melt flow rates of Examples 36-39 are preferred for these polymer compositions.</p><p> It should be understood that various components can be replaced, added or removed from the formulation without departing from the scope of the invention. Further, the weight percentage of the component and the value of the described property are 5% or less or more than 5% of the described value, 10% or less or more than 10%, 25% or less or more than 25% or 50% or less or more than 50%. It is thought that it can be different. For example, a value of 10 can vary by 10% and can range from about 9 to about 11.</p><p><tables num="7"></tables></p><p><tables num="8"></tables></p><p> As long as any lower limit and any upper limit are separated by at least 2 units, any numerical value described herein includes all values in 1 unit increments from the lower limit to the upper limit. As an example, if the amount of a component or the value of a process variable such as temperature, pressure, time, etc. is stated to be, for example, 1-90, preferably 20-80, more preferably 30-70. It means explicitly listing values such as 15-85, 22-68, 43-51, 30-32, etc. in the specification. For values less than 1, one unit is considered to be 0.0001, 0.001, 0.01 or 0.1 as appropriate. Although only these are specifically represented, it can be considered that all possible combinations of numerical values between the listed minimum and maximum values are similarly explicitly stated in the present application. It can be seen that the teaching of the quantity expressed as "parts by weight" in the present specification also means the same range expressed in terms of% by weight. Therefore, when the range is represented by "x parts by weight of the obtained polymer blend composition" in the detailed description of the invention, the same enumerated amount range of x is also included in the weight% of the obtained polymer blend composition. It is also considered to be taught in.</p><p> Unless otherwise noted, all ranges include all numbers between end points. The use of "about" or "approximately" with respect to a range applies to both ends of the range. Therefore, "about 20 to 30" means covering "about 20 to about 30" including at least the specified endpoints.</p><p> The disclosure of all articles and references, including patent applications and publications, is incorporated herein by reference for all purposes. The term "becomes essential from" to describe a combination is used to describe the identified element, component or process and other elements that do not substantially affect the basic novel properties of this combination. It shall include elements, components or steps. The use of the term "contains" or "contains" to describe a combination of elements, components or steps herein also means an embodiment consisting essentially of the elements, components or steps.</p><p> Multiple elements, components or steps can be represented by a singular overall element, component or process. Alternatively, a singular overall element, component or process may be divided into separate elements, components or processes. Disclosure of the singular (a or an) describing an element, component or process does not mean excluding additional elements, components or processes. All references to elements or metals belonging to a particular group herein refer to the Periodic Table of the Elements, published and copyrighted by CRC Press, Inc. in 1989. All references to one or more groups shall relate to one or more groups shown in this Periodic Table of the Elements using the IUPAC system for numbering the groups.</p><p> As used herein, the terms "polymer" and "polymerization" are generic and include, or both, more specific examples of "homomopolymers and copolymers" and "homomopolymerization and copolymerization", respectively. be able to.</p><p> It can be seen that the above description is provided for illustration purposes only and is not limiting. Many embodiments and applications other than those described herein will be apparent to those skilled in the art upon reading the description. Therefore, the scope of the present invention is not determined by referring to the above description, but by referring to the attached scope of claims together with the entire range of contents equivalent to those in which the scope of claims can be enjoyed. Should be. The disclosure of all articles and references, including patent applications and publications, is incorporated herein by reference for all purposes. The following omissions in the claims regarding any aspect of the subject matter disclosed herein are not waivers of such subject matter, and the present inventors have disclosed such subject matter of the present invention. It should not be considered not to be considered part of. The present invention and related aspects thereof are listed below. Aspect 1. (A) First polymer component containing a relatively hard thermoplastic resin; (b) Containing a thermoplastic resin relatively softer than the first polymer component and propylene elastomer, substantially linear or A second polymer component selected from the linear ethylene polymer (S / LEP) or the group consisting of both (the S / LEP has an ethylene concentration of about 40 to about 85% by weight based on the total weight of the S / LEP). It contains an α-olefin comonomer having 4 to 20 carbon atoms; the propylene elastomer contains propylene and one or more α-olefin comonomer having 2 or 4 to 20 carbon atoms and is about 20 based on the total weight of the propylene elastomer. A polymer composition having a soft-touch feel, comprising a blend of at least one fortifier (having a comonomer concentration of less than% by weight). Aspect 2. The polymer composition according to embodiment 1, wherein the first polymer component is present in an amount of about 3 to about 70% by weight based on the total weight of the composition. Aspect 3. The polymer composition according to aspect 1 or 2, wherein the second polymer component is present in an amount of about 10 to about 90% by weight based on the total weight of the composition. Aspect 4. The at least one reinforcing material is the total weight group of the polymer composition. The polymer composition according to any one of aspects 1 to 3, which comprises glass fibers present in a concentration of about 5 to about 40% by weight. Aspect 5. In any of embodiments 1 to 4, wherein the second polymer component comprises S / LEP and the ratio of the first polymer component to the second polymer component is in the range of about 10:42 to about 10: 2. The polymer composition described. Aspect 6. The invention according to any one of embodiments 1 to 5, wherein the second polymer component comprises a propylene elastomer and the ratio of the first polymer component to the second polymer component is in the range of about 10:42 to about 10: 2. Polymer composition. Aspect 7. The soft thermoplastic resin is about 0.850 to about 0.900 g / cm.³The polymer composition according to any of aspects 1-6, comprising S / LEP having a density of and a melt index of about 0.2 to about 40 (measured at 190 ° C., 2.16 kg according to ASTM D-1238-04). .. Aspect 8. The S / LEP is i) Melt flow ratio I₁₀/ I₂5.63; ii) Equation M_w/ M_nI₁₀/ I₂Molecular weight distribution defined by -4.63 (M)_w/ M_n); And iii) Approximately 4 × 10⁶Dyne / cm²The polymer composition according to any of aspects 1-7, characterized by a higher gross melt fracture initiation critical shear stress. Aspect 9. The S / LEP has (i) a density of 0.85 to 0.92 g / cm.³(Ii) Extreme viscosity number [η] (measured in decalin at 135 ° C.) 0.1 to 10 dl / g; (iii) Weight average molecular weight (Mw) Log average molecular weight (Mn) ratio Mw / Mn (by GPC) Measurements) 1.2-4; or (iv) Ratio of (MFR10 under 10 kg load) to (MFR2 under 2.16 kg load) measured at 190 ° C. (MFR10 / MFR2) 8-50 (MFR10 and MFR2 are MFR10 and MFR2) The polymer composition according to any of aspects 1-8, characterized in one or any combination of (measured by ASTM D-1238 at 190 ° C. with loads of 10 kg and 2.16 kg, respectively). Aspect 10. The ratio of the first polymer component to the second polymer component ranges from about 5: 1 to about 1: 4.2; the first polymer component is about 3 to about 50 parts by weight of the composition. The second polymer component is present in an amount of about 4 to about 20% by weight of ethylene and in an amount of about 10 to about 70 parts by weight of the composition; the second polymer component is present. Shore A hardness of about 65-about 95 (ASTM) The polymer composition according to any one of aspects 1 to 9 having (according to D-2240). Aspect 11. The polymer composition according to any one of aspects 1 to 10, wherein the ratio of the first polymer component to the second polymer component is about 10:27 to about 10: 2. Aspect 12. The polymer composition according to any one of aspects 1 to 11, wherein the first polymer component comprises a polypropylene homopolymer, a polypropylene random copolymer, an impact resistant polypropylene polymer or any combination thereof. Aspect 13. The polymer composition according to any one of aspects 1 to 12, wherein the first polymer component comprises a polypropylene homopolymer present in a concentration of about 20 to about 50% by weight based on the total weight of the polymer composition. Aspect 14. The second polymer component is an ethylene-octene copolymer containing S / LEP, and the S / LEP contains about 50 to about 70% by weight of ethylene based on the total weight of the ethylene-octene copolymer, and the ethylene-octene copolymer. Melt flow rate (ASTM) of about 1 to about 30 g / 10 minutes The polymer composition according to any of aspects 1 to 13 having (measured according to D-1238 (190 ° C., 2.16 kg)). Aspect 15. Shore A hardness (ASTM) in which the second polymer component is from about 65 to about 95. The polymer composition according to any one of aspects 1 to 14 having (according to D-2240). Aspect 16. The polymer composition according to any one of aspects 1 to 15, wherein the polymer composition has a total ethylene concentration of about 2 to about 10% by weight based on the total weight of the polymer composition. Aspect 17. The second polymer component comprises a propylene elastomer, and the propylene elastomer has an ethylene concentration of about 4 to about 20% by weight and a propylene concentration of about 80 to about 96% by weight based on the total weight of the propylene elastomer. -The polymer composition according to any of aspects 1-16, which is an ethylene copolymer. Aspect 18. The propylene elastomer is a low elastic ethylene-propylene copolymer (LEEP copolymer), and the LEEP copolymer has the following properties: (i) melting point is in the range of less than 110 ° C to lower limit; (ii) elastic pair 500. The relationship of% tensile modulus is elasticity 0.935M + 12 (elasticity is expressed as a percentage, M is 500% tensile modulus expressed in megapascal (MPa)); (iii) flexural modulus vs. 500% tensile The relationship of elastic modulus is bending elastic modulus 4.2e^0.27M+50 (bending modulus is expressed in MPa, M is 500% tensile modulus expressed in MPa); (iv) heat of fusion is more than 1.0 joule / g at the lower limit and less than 125 J / g at the upper limit; (V) Triad Tacticity (Carbon-13 Nuclear Magnetic Resonance (v)¹³(Measured by C NMR) is&gt; 75%; (vi) tacticity index m / r ranges from lower limit 4 to upper limit 12; (vii) for 2,1-insertion of propylene monomer in fully inserted propylene. Reverse Insertion Based on Propene Unit Ratio (¹³(Measured by C NMR) is greater than 0.5%; (viii) Ratio of reverse-inserted propylene units based on 1,3-insertion of propylene monomer in total inserted propylene (viii)¹³(Measured by C NMR) is greater than 0.05%; (ix) at least 75% by weight of the copolymer is soluble in two adjacent temperature fractions of thermal fractionation performed by heating in hexanes by 8 ° C. Intermolecular tacticity such as (x) reactive ratio product r₁r₂Is less than 1.5; (xi) molecular weight distribution Mw / Mn ranges from lower limit 1.5 to upper limit 40; (xii) molecular weight is 15,000 to 5,000,000; (xiii) solid Proton nuclear magnetic resonance (¹1 H NMR) relaxation time is less than 18 ms (ms); (xiv) elasticity is less than 30% or less than 20% or less than 10% or less than 8% or less than 5%; or (xv) 500% The polymer composition according to any one of aspects 1 to 17, having one or any combination of tensile elastic moduli of more than 0.5 MPa, more than 0.8 MPa, more than 1.0 MPa, or more than 2.0 MPa. Aspect 19. The propylene elastomer is a region error ethylene-propylene copolymer (R-EPE copolymer), and the R-EPE copolymer has the following properties: i) Ethylene-derived units are at least about 0.1% by weight and about 14.6 ppm. And about the same intensity corresponding to a region error of about 15.7 ppm¹³It has a C NMR peak; ii) a propylene-derived unit of at least about 60% by weight and an ethylene-derived unit of at least about 0.1% by weight, and a skewness index S of more than about -1.20._ixIii) The unit derived from propylene is at least about 60% by weight and the unit derived from ethylene is at least about 0.1% by weight, and the DSC curve is essentially unchanged._meAnd T which decreases as the amount of ethylene in the copolymer increases_maxIV) The weight average molecular weight is the same except that the unit derived from propylene is at least about 60% by weight and the unit derived from ethylene is at least about 0.1% by weight and is produced using a Ziegler-Natta catalyst. It has an X-ray diffraction pattern showing more γ-type crystals than the propylene / ethylene copolymer to the extent; or v) at least about 60% by weight of propylene-derived units and at least about 0.1% by weight of ethylene-derived units. The polymer composition according to any one of embodiments 1 to 18, which has one or any combination having a B value of more than about 1.4 when the ethylene content of the R-EPE copolymer is at least about 3% by weight. .. Aspect 20. The polymer composition according to any one of aspects 1 to 19, wherein the S / LEP is present at a concentration of about 20 to about 45% by weight based on the total weight of the polymer composition. Aspect 21. A molded article having at least one component comprising the polymer composition according to any of aspects 1-20. Aspect 22. A method for producing a molded product, wherein the part of the molded product contains the polymer composition according to any one of aspects 1 to 20. Aspect 23. The method a) prepares about 3 to about 60 parts by weight of a first material containing at least a portion of a relatively hard thermoplastic; b) a propylene elastomer, substantially linear or linear ethylene. About 10 to about 70 parts by weight of a second material containing at least a part of a polymer (S / LEP) or a relatively soft thermoplastic resin selected from the group consisting of both is prepared (the S / LEP is S). / Contains an α-olefin comonomer having 4 to 20 carbon atoms having an ethylene concentration of about 40 to about 85% by weight based on the total weight of LEP, and the propylene elastomer contains propylene and one or more carbon atoms of 2 or carbon atoms. (Contains 4 to 20 α-olefin comonomers and has a comonomer concentration of less than about 20% by weight based on the total weight of the propylene elastomer); c) A third material containing a reinforcing material concentrate containing at least one reinforcing material. Prepare about 20 to about 75 parts by weight; d) Blend the first material, the second material and the third material to form a blend. ; And e) The method for producing a molded product according to aspect 22, comprising the step of molding the blend in a molding tool to form an article. Aspect 24. 23. The method of aspect 23, wherein the reinforcing material concentrate comprises at least a portion of glass fiber and polypropylene. Aspect 25. The method according to any of aspects 23 or 24, wherein the at least one reinforcing material is present at a concentration of about 30 to about 90% by weight based on the total weight of the reinforcing material concentrate. Aspect 26. The method according to any of aspects 23 to 25, wherein the at least one reinforcing material is present in an amount of about 5 to about 40% by weight based on the total weight of the molded product. Aspect 27. The method according to any one of aspects 23 to 26, wherein the propylene elastomer has a crystallinity lower than that of the relatively hard thermoplastic resin. Aspect 28. The method according to any of aspects 23-27, wherein the molded product further comprises a coupling agent. Aspect 29. Any of aspects 23-28, wherein the method further comprises the step of simultaneously blending two or more of the first material, the second material or the third material prior to the blending step. The method described in. Aspect 30. 23 to 29, wherein the method substantially does not include a step of blending any two of the first material, the second material and the third material before the blending step. The method described in either. Aspect 31. i) Prepare a first material containing a relatively hard thermoplastic resin selected from polypropylene homopolymers, impact resistant polypropylene copolymers, polypropylene random copolymers or any combination thereof; ii) S / LEP, propylene elastomer Alternatively, a second material containing a relatively soft thermoplastic resin selected from both is prepared; iii) at least one kind of reinforcing material is prepared; iv) the first material, the second material, and the above. The reinforcing materials are mixed to form a polymer composition; v) the polymer composition is pelletized to form pellets or granules that can be fed to a thermoplastic resin molding machine; and vi) at least 5 kg of the pellets or Put the granule in the container A method for producing a part containing the composition according to any one of aspects 1 to 20, which comprises the steps described above. Aspect 32. 31. The method of aspect 31, wherein the method further comprises a step of injection molding the polymer composition. Aspect 33. 31. The method of aspect 31 or 32, wherein the injection molding step comprises forming an article by single shot injection molding. Aspect 34. Aspect 31 in which the mixing step includes a step of mixing the reinforcing material with at least a part of the first material, at least a part of the second material, or both before the step of preparing the reinforcing material. The method according to any one of ~ 33. Aspect 35. One of aspects 31 to 34, wherein the mixing step includes a step of mixing the second material with at least a part of the first material before the step of preparing the at least one kind of reinforcing material. The method described.</p>