KR101196201B1 - Scratch resistant propylene polymer composition - Google Patents

Abstract

Propylene compositions are disclosed that include propylene polymers, substantially linear ethylene polymers, linear ethylene polymers or mixtures thereof, low molecular weight polymers and optionally fillers. The propylene polymer composition exhibits improved processability with a good balance of stiffness and toughness, and improved scratch resistance in injection molded articles.

Scratch Resistance, Propylene Polymers, Stiffness, Toughness, Injection Molding

Description

Scratch resistant propylene polymer composition {SCRATCH RESISTANT PROPYLENE POLYMER COMPOSITION}

The present invention relates to a propylene polymer composition comprising a propylene polymer, a polyolefin elastomer and a low molecular weight polymer. The present invention includes a propylene polymer, a substantially linear ethylene polymer or a linear ethylene polymer, and a low molecular weight polymer, and exhibits well harmonized stiffness and toughness and improved processability, which exhibits improved scratch resistance in injection molded articles. Propylene polymer composition.

Propylene polymers have been used in many applications in the form of molded products, films, sheets, etc. because of their excellent molding processability, toughness, moisture resistance, oil resistance, chemical resistance, low specific gravity, and low cost. The use of propylene polymers is expanding at an increasing rate in automotive interior and exterior applications, housing and covers of electrical installations, as well as other household and personal products.

However, polypropylene has poor or inadequate heat resistance, stiffness, scratch resistance and impact resistance. These deficiencies hinder the development of new applications of polypropylene, especially those that have traditionally been injection molded. In order to overcome this drawback, in particular inadequate impact resistance, polypropylene has been blended with a rubbery elastic material such as ethylene-propylene copolymer rubber, ethylene-propylene-diene copolymer rubber or ethylene-butene copolymer rubber. For example, USP 5,391,618, which discloses a low crystalline polypropylene polymer composition comprising an ethylene alpha-olefin copolymer, USP 5,576,374 and ethylene, which discloses a polypropylene polymer composition comprising a substantially linear ethylene polymer; See USP 5,639,829 which discloses a propylene polymer composition comprising a 1-butene random copolymer. However, while impact properties are improved, these propylene polymer compositions do not blend well with stiffness and toughness. USP 6,300,419 discloses blends of high crystalline propylene polymers with large amounts of substantially linear ethylene polymers or linear ethylene polymers to achieve good scratch resistance.

In view of conventional propylene polymers and blends thereof, it is highly desirable to provide cost-effective propylene polymer compositions exhibiting well matched stiffness, toughness and improved processability that exhibit scratch resistance in injection molded articles.

The present invention relates to such a preferred propylene polymer composition. This composition exhibits well matched stiffness and impact strength and improved scratch resistance in injection molded articles, where good processability is preferably combined.

In one embodiment, the present invention provides a kit comprising (a) a propylene polymer; (b) (i) density is less than about 0.93 g / cm 3, (ii) molecular weight distribution (M _w / M _n ) is less than about 3.0, and (iii) the composition distribution branching is greater than 30%. , Substantially linear ethylene polymers, linear ethylene polymers or mixtures thereof; (c) low molecular weight polymers; And (d) optionally a filler.

In a further embodiment, the propylene polymer composition of the present invention comprises (b) a substantially linear ethylene polymer and / or a linear ethylene polymer having a weight average molecular weight of 40,000 to 180,000; And (c) a low molecular weight polymer having a weight average molecular weight of 500 to 70,000, wherein the average molecular weight of (b) versus the average molecular weight of (c) is at least 1.5.

In another embodiment of the present invention, the propylene polymer is preferably a homopolymer of propylene or a copolymer of propylene with C ₂ or C ₄ to C ₂₀ alpha-olefins.

In another embodiment of the invention, the substantially linear ethylene polymer or linear ethylene polymer is preferably a copolymer of ethylene and propylene, 1-butene, 1-hexene, 4-methyl-1-pentene or 1-octene.

In another embodiment of the invention, the low molecular weight polymer preferably has a molecular weight of 500 to 70,000, preferably animal wax, plant wax, carnauba wax, candelilla wax, Japan wax, beeswax, broad wax, Petroleum waxes, paraffin waxes, microcrystalline waxes, petrolatum waxes, polyolefin waxes, oxidized polyolefin waxes, higher fatty acid waxes, higher fatty acid ester waxes, styrene oligomers, amorphous poly-alpha-olefins, or mixtures thereof. Preferably, the low molecular weight polymer is polyethylene wax, polypropylene wax, polyethylene-propylene wax, polyethylene-butylene wax, polyethylene-hexylene wax, polyethylene-octylene wax, or mixtures thereof. Alternatively, the low molecular weight polymer may further comprise a polar comonomer (e.g., unsaturated carboxylic acid, carboxylic ester, carboxylic acid salt, or mixtures thereof) of up to 5% by weight, based on the weight of the low molecular weight polymer. Included in quantity.

In another embodiment of the invention, the filler is preferably talc, wollastonite, clay, monolayer cation exchange layered silicate material or mixtures thereof.

In a further embodiment of the invention, the propylene polymer composition further comprises (e) low density polyethylene, linear low density polyethylene, high density polyethylene, polystyrene, polycyclohexylethane, polyester, ethylene / styrene copolymer, ordered polypropylene, rule Further polymers selected from array polystyrene, ethylene / propylene copolymers, ethylene / propylene / diene terpolymers or mixtures thereof.

In a further embodiment of the invention, the propylene polymer composition further comprises a slip agent (eg, erucamide, oleamide, linoleamide or stearamide), an ultraviolet (UV) stabilizer, pigment (s), or mixtures thereof. It includes.

Other embodiments of the invention comprise (a) a propylene polymer; (b) (i) density is less than about 0.93 g / cm 3, (ii) molecular weight distribution (M _w / M _n ) is less than about 3.0, and (iii) the composition distribution branching is greater than 30%. , Substantially linear ethylene polymers, linear ethylene polymers or mixtures thereof; (c) low molecular weight polymers; And (d) optionally mixing the filler.

Other embodiments of the invention comprise (A) (a) a propylene polymer; (b) (i) density is less than about 0.93 g / cm 3, (ii) molecular weight distribution (M _w / M _n ) is less than about 3.0, and (iii) the composition distribution branching is greater than 30%. , Substantially linear ethylene polymers, linear ethylene polymers or mixtures thereof; (c) low molecular weight polymers; And (d) optionally a propylene polymer comprising a filler; And (B) molding or extruding the propylene polymer composition into a molded or extruded product.

Other embodiments of the invention comprise (a) a propylene polymer; (b) (i) density is less than about 0.93 g / cm 3, (ii) molecular weight distribution (M _w / M _n ) is less than about 3.0, and (iii) the composition distribution branching is greater than 30%. , Substantially linear ethylene polymers, linear ethylene polymers or mixtures thereof; (c) low molecular weight polymers; And (d) optionally a filler, a propylene polymer composition in the form of a molded or extruded product.

Component (a) in the propylene polymer composition of the present invention is a propylene polymer, preferably a high crystalline propylene polymer. Suitable propylene polymers for use in the present invention are well known in the literature and can be prepared by known techniques. Generally, the propylene polymers are in the same configuration, but other forms (eg, regular or hybrid) can also be used. The propylene polymers used in the present invention are preferably homopolymers of polypropylene or more preferably copolymers of propylene and alpha-olefins (preferably C ₂ or C ₄ to C ₂₀ alpha-olefins), for example Random or block copolymer. The alpha-olefins are present in the propylene copolymer of the present invention in an amount of up to 20 mol%, preferably up to 15 mol%, even more preferably up to 10 mol%, most preferably up to 5 mol%.

Examples of C ₂ or C ₄ to C ₂₀ alpha-olefins for constructing copolymers of propylene and alpha-olefins are ethylene, 1-butene, 1-pentene, 1-hexene, 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, vinylcyclopentene, vinylcyclohexene and vinylnorbornene, wherein the alkyl branch position is not specified but is generally at least position 3 of the alkene.

The propylene polymer of the present invention is slurry polymerized by various methods, for example in one or multiple stages, using a metallocene catalyst or a so-called Ziegler-Natta catalyst (usually comprising a solid transition metal component comprising titanium). , Gas phase polymerization, bulk phase polymerization, solution polymerization or mixed polymerization thereof. In particular, the catalyst comprises titanium, magnesium and halogen as essential components; Organoaluminum compounds as organometallic components; And optionally a solid composition of titanium trichloride containing an electron donor (as a transition metal / solid component). Preferred electron donors are organic compounds containing nitrogen atoms, phosphorus atoms, sulfur atoms, silicon atoms or boron atoms, and silicon compounds, ester compounds or ether compounds containing these atoms are preferred.

High crystalline polypropylene is often prepared by reacting propylene with a suitable molecular weight modifier under a catalyst in a polymerization reactor. Nucleating agents are added after the reaction to promote crystallization. The polymerization catalysts must exhibit high activity and be capable of producing highly stereoregular polymers. The reactor system must be able to remove the heat of polymerization from the reaction mass so that the temperature and pressure of the reaction can be adjusted appropriately.

An excellent review of various polypropylene polymers is contained in Modern Plastics Encyclopedia / 89, mid October 1988 Issue, Volume 65, Number 11, pp. 86-92. The molecular weight of the propylene polymer for use in the present invention is conveniently indicated using melt flow measurement, which is sometimes referred to as melt flow rate (MFR) or melt index (MI) under a load of 2.16 kg at 230 ° C. according to ASTM D 1238. . The melt flow rate is inversely proportional to the molecular weight of the polymer. Therefore, the larger the molecular weight, the lower the melt flow rate, but the relationship is not linear. Melt flow rates of the propylene polymers useful herein are generally greater than 0.1 g / 10 minutes (g / 10 minutes), preferably greater than 0.5 g / 10 minutes, more preferably greater than 1 g / 10 minutes, even more preferred. Preferably greater than 10 g / 10 min. Melt flow rates of the propylene polymers useful herein are generally less than 200 g / 10 minutes, preferably less than 100 g / 10 minutes, more preferably less than 75 g / 10 minutes, even more preferably less than 50 g / 10 minutes. .

As component (a) the propylene polymer may also be characterized by its crystalline structure.

One method of characterizing crystallinity is pulse nuclear magnetic resonance (NMR) in Polymer Journal Volume 3, 448-462 (1972) by K. Fujimoto, T. Nishi and R. Kado. ), Wherein the crystalline phase (I), intermediate phase (II) and amorphous phase (III) are determined. Preferably the weight ratio of crystalline phase (I) / intermediate phase (II) is greater than 4, preferably greater than 5, more preferably greater than 8 and most preferably greater than 10. The content of amorphous phase (III) is at least 1% by weight, preferably at least 2% by weight, more preferably at least 5% by weight, even more preferably at least 10% by weight, most preferably at least 15% by weight. The content of amorphous phase (III) is less than 40% by weight, preferably less than 30% by weight, more preferably less than 25% by weight, even more preferably less than 20% by weight, most preferably less than 15% by weight.

Generally, in pulsed NMR determinations, energy pulses are applied to emit high resolution polymer samples at specific temperature intervals (Kelvin temperature, ° K) over a range of temperatures. The generated energy is monitored in the time domain (microsecond time scale). The energy / time curve is a measure of the time required for a polymer to return from its excited energy state to its bottom energy level. This is called a free induction decay (FID) curve. The curve is then mathematically analyzed with a fast Gaussian equation (usually related to determinism), a slow Gaussian equation, and one exponential equation. The latter two formulas are generally associated with the polymer amorphous phase and the intermediate phase between the crystalline phase and the amorphous phase, respectively. These equations are used to calculate coefficients that characterize the appropriate amplitude and time components of the FID curve. The coefficients are then placed in a matrix and undergo a regression process such as partial least squares. Crystalline, amorphous and intermediate phases are calculated and reported as weight percent as a function of temperature ° K.

However, a more preferred method of determining the crystallinity of propylene polymers is by differential scanning calorimetry (DSC). A small sample (mg size) of propylene polymer is sealed in an aluminum DSC pan. The sample is placed in a DSC cell with nitrogen purging at 25 cm per minute and cooled to about -100 ° C. The thermal history of the standard is determined for the sample by heating to 225 ° C. at 10 ° C. per minute. The sample is then cooled to about −100 ° C. and reheated to 225 ° C. at 10 ° C. per minute. The observed heat of fusion (ΔH _observations ) of the second scan is recorded. The observed heat of fusion is related to the crystallinity (% by weight) based on the weight of the polypropylene sample by the following equation:

In the above formula, the heat of fusion of coarse polypropylene (ΔH coarse _PP ) is described in B. Wunderlich, Macromolecular Physisc, Volume 3, Crystal Melting, Academic Press, New York, 1980, p. 48. As reported, 165 J per gram of polymer.

The crystallinity of the high crystalline propylene polymer determined by DSC is at least 54% by weight, preferably at least 58% by weight, more preferably at least 64% by weight, even more preferably 68% by weight based on the weight of the high crystalline propylene polymer. As mentioned above, most preferably 70 weight% or more. The crystallinity of the high crystalline propylene polymer determined by DSC is 100 wt% or less, preferably 90 wt% or less, more preferably 80 wt% or less, most preferably 75 wt% or less, based on the weight of the high crystalline propylene polymer. to be.

Some or all of the propylene polymers of the present invention may be graft modified. Preferred graft modifications of polypropylene are grafted to polypropylene as described above, which contain one or more carbonyl groups (-C═O) in addition to one or more ethylenically unsaturated groups (eg, one or more double bonds). Is achieved by any unsaturated organic compound to be. Representative unsaturated organic compounds containing one or more carbonyl groups are carboxylic acids, anhydrides, esters, and metal and nonmetal salts thereof. Preferably, the organic compound contains ethylenically unsaturated groups conjugated with carbonyl groups. Representative compounds include maleic acid, fumaric acid, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, methyl crotonic acid and cinnamic acid, and if any, anhydrides, esters and salt derivatives thereof. Maleic anhydride is a preferred unsaturated organic compound containing at least one ethylenically unsaturated group and at least one carbonyl group.

Unsaturated organic compounds containing one or more carbonyl groups can be grafted to polypropylene by any known technique, such as those taught in USP 3,236,917 and USP 5,194,509. For example, the polymer is introduced into a two roll mixer and mixed at a temperature of 60 ° C. The unsaturated organic compound is then added together with the free radical initiator (eg benzoyl peroxide) and the components are mixed at 30 ° C. until the grafting is complete. Alternatively, the reaction temperature is higher (eg 210 ° C. to 300 ° C.) and no free radical initiators are used or at reduced concentrations. Another and preferred grafting method is taught in US Pat. No. 4,905,541, which uses a twin screw liquefaction extruder as a mixing machine. The polypropylene and unsaturated organic compounds are mixed and reacted in the extruder at the temperature at which the reactants are dissolved in the presence of free radical initiators. Preferably, the unsaturated organic compound is injected into the zone maintained under pressure in the extruder.

The unsaturated organic compound content of the grafted polypropylene is at least 0.01% by weight, preferably at least 0.1% by weight, more preferably at least 0.5% by weight, most preferably 1% by weight, based on the combined amount of the polypropylene and the organic compound. That's it. The maximum amount of unsaturated organic compound content may vary depending on circumstances, but typically does not exceed 10% by weight, preferably does not exceed 5% by weight, more preferably based on the combined amount of polypropylene and organic compound Does not exceed 2% by weight and most preferably does not exceed 1% by weight.

The propylene polymer or the graft-modified propylene polymer is used in an amount sufficient to provide the desired processability and well matched stiffness and toughness in the propylene polymer blend composition of the present invention. The graft-modified propylene polymer, if present, is 100% by weight of the total amount of propylene polymer, preferably 50% by weight or less, more preferably 30% by weight or less, even more preferably 20% by weight or less Most preferably in an amount of up to 10% by weight. Generally, the propylene polymer, the graft-modified propylene polymer or mixtures thereof is at least 40 parts by weight, preferably at least 45 parts by weight, more preferably at least 50 parts by weight, even more preferably based on the weight of the total composition. Is used in an amount of at least 55 parts by weight, most preferably at least 60 parts by weight. Generally, the propylene polymer, the graft-modified propylene polymer or mixtures thereof is 95 parts by weight or less, preferably 90 parts by weight or less, more preferably 85 parts by weight or less, even more preferred based on the weight of the total composition. Preferably in an amount of 80 parts by weight or less, most preferably 75 parts by weight or less.

Component (b) in the composition of the present invention is a polyolefin elastomer. Suitable polyolefin elastomers include one or more C ₂ -C ₂₀ alpha-olefins in polymerized form, having a glass transition temperature (T _g ) of less than 25 ° C., preferably less than 0 ° C., most preferably less than −25 ° C. T _g is the temperature or temperature range in which a polymeric material exhibits a sudden change in its physical properties, including, for example, mechanical strength. T _g can be determined by a differential scanning calorimeter. Examples of polymers of the type in which the polyolefin elastomer of the invention is selected include copolymers of alpha-olefins, such as ethylene and propylene, ethylene and 1-butene, ethylene and 1-hexene or ethylene and 1-octene copolymers, and Terpolymers of ethylene, propylene and diene comonomers such as hexadiene or ethylidene norbornene.

Preferably, the polyolefin elastomer is one or more substantially linear ethylene polymers or one or more linear ethylene polymers (S / LEP), or mixtures of one or more thereof. Substantially linear ethylene polymers and linear ethylene polymers are known. Substantially linear ethylene polymers and methods for their preparation are fully described in US Pat. No. 5,272,236 and USP 5,278,272. Linear ethylene polymers and methods for their preparation are disclosed in US Pat. No. 3,645,992; USP 4,937,299; USP 4,701,432; USP 4,937,301; USP 4,935,397; USP 5,055,438; EP 129,368; EP 260,999; And WO 90/07526.

As used herein, a "linear ethylene polymer" refers to an ethylene having a linear backbone (ie, no crosslinking), no long chain branching, a narrow molecular weight distribution, and a narrow compositional distribution for alpha-olefin copolymers. Refers to a homopolymer or a copolymer of ethylene and one or more alpha-olefin comonomers. Also, as used herein, "substantially linear ethylene polymer" has a linear backbone, has a specific and limited amount of long chain branching, a narrow molecular weight distribution, and a narrow compositional distribution for alpha-olefin copolymers. A homopolymer of ethylene or a copolymer of ethylene and one or more alpha-olefin comonomers.

The short chain branching of the linear copolymer arises from the alkyl side groups resulting from the polymerization of the deliberately added C ₃ -C ₂₀ alpha-olefin comonomers. Narrow compositional distribution is also sometimes called homogeneous short chain branching. Narrow compositional distribution and homogeneous short chain branching indicate that the alpha-olefin comonomers are irregularly distributed within a given copolymer of ethylene and alpha-olefin comonomers, and substantially all copolymer molecules have the same ethylene to comonomer ratio Indicates. The narrow degree of composition distribution is represented by the value of the composition distribution branching (CDBI) or sometimes called the short chain branching distribution. CDBI is defined as the weight percent of polymer molecules having a comonomer content within 50% of the intermediate comonomer molar content. CDBI is readily available using temperature rising elution fractionation, as described, for example, in Wilde's Journal of Polymer Science, Polymer Physics Edition, Volume 20, page 441 (1982) or USP 4,798,081. Is calculated. The CDBI of the substantially linear ethylene polymer and linear ethylene copolymer of the present invention is greater than 30%, preferably greater than 50%, more preferably greater than 90%.

Long chain branches in a substantially linear ethylene polymer are polymer branches, not short chain branches. Typically, long chain branches are formed by in situ production of oligomeric alpha-olefins by beta-hydride removal in the growing polymer chain. The resulting species are relatively high molecular weight vinyl terminal hydrocarbons, which produce large alkyl side groups upon polymerization. Long chain branching can be further defined as hydrocarbon branching to the polymer backbone, where the chain length is n-2 carbon atoms, where n is the carbon number of the largest alpha-olefin comonomers intentionally added to the reactor. Preferred long-chain branches in the homopolymer of ethylene or in the copolymer of ethylene and at least one C ₃ -C ₂₀ alpha-olefin comonomer have preferably at least 20 carbon atoms in the polymer backbone in which the branch is located. Long chain branches can be characterized using only ¹³ C nuclear magnetic resonance spectroscopy or together with gel permeation chromatography-laser light scattering (GPC-LALS) or similar analytical techniques. The substantially linear ethylene polymer contains at least 0.01 long chain branches per 1000 carbons, preferably 0.05 long chain branches per 1000 carbons. Generally, substantially linear ethylene polymers contain up to 3 long chain branches per 1000 carbons, preferably up to 1 long chain branch per 1000 carbons.

Preferred substantially linear ethylene polymers are prepared using metallocene-based catalysts that can readily polymerize high molecular weight alpha-olefin copolymers under process conditions. As used herein, a copolymer is meant that can be prepared by polymerizing two or more intentionally added comonomer polymers, such as ethylene and one or more other C ₃ -C ₂₀ comonomers. Preferred linear ethylene polymers can be prepared in a similar manner using metallocene-based or vanadium-based catalysts, for example under conditions that do not allow polymerization of monomers which are not intentionally added to the reactor. Other basic features of substantially linear ethylene polymers or linear ethylene polymers include low residue content (ie, low concentrations of catalyst used to prepare the polymer, unreacted comonomers and low molecular weight oligomers prepared during polymerization). There is a regulated molecular structure that provides excellent processability even though the molecular weight distribution is narrower than conventional olefin polymers.

Substantially linear ethylene polymers or linear ethylene polymers used in the practice of the present invention are substantially linear ethylene homopolymers or linear ethylene homopolymers, preferably substantially linear ethylene polymers or linear ethylene polymers weighing from 50 to 95 weight. %, And 5-50%, preferably 10-25%, by weight of one or more alpha-olefin comonomers. The comonomer content in the substantially linear ethylene polymer or the linear ethylene polymer is generally calculated according to ASTM D-2238, Method B and can be measured using infrared spectroscopy, based on the amount added to the reactor. Typically, the substantially linear ethylene polymer or linear ethylene polymer is a copolymer of ethylene and at least one C ₃ -C ₂₀ alpha-olefin, preferably a copolymer of ethylene and at least one C ₃ -C ₁₀ alpha-olefin and more Preferably a copolymer of ethylene with at least one comonomer selected from the group consisting of propylene, 1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene. Most preferably the copolymers are ethylene and 1-octene copolymers.

The density of such substantially linear ethylene polymers or linear ethylene polymers is at least 0.850 g / cm 3, preferably at least 0.860 g / cm 3. In general, the density of such substantially linear ethylene polymers or linear ethylene polymers is at most 0.935 g / cm 3, preferably at most 0.900 g / cm 3. The melt flow ratio of the substantially linear ethylene polymer, measured as I ₁₀ / I ₂ , is at least 5.63, preferably 6.5 to 15, more preferably 7 to 10. I ₂ is measured according to ASTM D 1238 under conditions of 190 ° C. and 2.16 kg mass. I ₁₀ is measured according to ASTM designation D 1238 under conditions of 190 ° C. and 10.0 kg mass.

The molecular weight distribution (M _w / M _n ) of the substantially linear ethylene polymer is the weight average molecular weight (M _w ) divided by the number average molecular weight (M _n ). M _w and M _n are measured by gel permeation chromatography (GPC). For substantially linear ethylene polymers, the I ₁₀ / I ₂ ratio represents the degree of long chain branching. That is, the greater the I ₁₀ / I ₂ ratio, the more long chain branches are present in the polymer. M _w / M _n of a preferred, substantially linear ethylene polymer is related to I ₁₀ / I ₂ by the formula M _w / M _n ≦ (I ₁₀ / I ₂ ) -4.63. In general, the M _w / M _n of the substantially linear ethylene polymer is at least 1.5, preferably at least 2.0 and at most 3.5, more preferably at most 3.0. In the most preferred embodiment, the substantially linear ethylene polymer is also characterized by one differential scanning calorimeter (DSC) melting peak.

The preferred I ₂ melt index of this substantially linear ethylene polymer or linear ethylene polymer is from 0.01 g / 10 min to 100 g / 10 min, more preferably from 0.1 g / 10 min to 10 g / 10 min.

The preferred M _w of this substantially linear ethylene polymer or linear ethylene polymer is 180,000 or less, preferably 160,000 or less, more preferably 140,000 or less and most preferably 120,000 or less. The preferred M _w of this substantially linear ethylene polymer or linear ethylene polymer is at least 40,000, preferably at least 50,000, more preferably at least 60,000, even more preferably at least 70,000 and most preferably at least 80,000.

Substantially linear ethylene polymers or linear ethylene polymers are used in the blends of the present invention in amounts that preferably combine processability and impact resistance. Generally, the substantially linear ethylene polymer or linear ethylene polymer is at least 1 part by weight, preferably at least 2 parts by weight, more preferably at least 3 parts by weight, even more preferably 4 parts by weight, based on the weight of the total composition. Or more, most preferably 5 parts by weight or more. Generally, the substantially linear ethylene polymer or linear ethylene polymer is at most 20 parts by weight, preferably at most 17 parts by weight, more preferably at least 15 parts by weight, even more preferably 12 parts by weight based on the weight of the total composition. Or more, most preferably in an amount of 10 parts by weight or less.

Component (c) of the present invention is a low molecular weight polymer (LMP). The low molecular weight polymer is not particularly limited, and any known low molecular weight polymer may optionally be used. Preferred examples of low molecular weight polymers are animal and plant waxes, carnauba wax, candelilla wax, Japan wax, beeswax, broad wax, petroleum wax, paraffin wax, microcrystalline wax, petrolatum wax, polyolefin wax, oxidized polyolefin wax, higher fatty acid wax , And higher fatty acid ester waxes. In addition, as the resin having the same properties as the wax, styrene oligomers and amorphous poly-alpha-olefins are preferably used. These low molecular weight polymers can be used alone or together.

Preferred low molecular weight polyolefins, sometimes referred to as polyolefin waxes, include polyethylene wax or polypropylene wax or copolymers thereof (eg, polyethylene-propylene wax, polyethylene-butylene wax, polyethylene-hexylene wax, and polyethylene-octylene wax). . Particularly suitable polyolefin waxes are polyethylene waxes. As used herein, the term polyolefin wax is a low molecular weight polyolefin having a molecular weight of 500 to 70,000. Such polyolefin waxes are well known to those skilled in the art and are commercially available. The polyolefin wax is preferably based on olefins having 2 to 18 carbon atoms, more preferably 2 to 8 carbon atoms, and most preferably 2 to 4 carbon atoms. Polyolefin waxes may also have small amounts of polar comonomers, such as unsaturated carboxylic acids, carboxylic esters or carboxylic acid salts. Such functional groups will generally be in amounts of at least 0.01% and at most 5% by weight, based on the weight of the low molecular weight polymer.

The weight average molecular weight of the low molecular weight polymer of the present invention is at least 500, preferably at least 1,000, more preferably at least 2,000, even more preferably at least 5,000, most preferably at least 10,000. The low molecular weight polymer of the present invention has a weight average molecular weight of 70,000 or less, preferably 60,000 or less, more preferably 40,000 or less, even more preferably 30,000 or less, most preferably 20,000 or less.

The low molecular weight polymer is present in an amount of at least 0.5 parts by weight, preferably at least 1 part by weight, more preferably at least 1.5 parts by weight, most preferably at least 2 parts by weight, based on the weight of the total composition. The low molecular weight polymer is present in an amount of up to 10 parts by weight, preferably up to 9 parts by weight, more preferably up to 8 parts by weight, most preferably up to 7 parts by weight based on the weight of the total composition.

Preferably, the low molecular weight polymer is compatible with component (b) polyolefin elastomer. In other words, when the two components are melt blended, they preferably form a single phase. Furthermore, in the present invention, the molecular weight ratio of component (b) to component (c) is at least 1.5, preferably at least 5, more preferably at least 10, even more preferably at least 20 and most preferably at least 40. It is preferable.

Optionally, the propylene polymer composition comprises component (d) fillers, examples being calcium carbonate, talc, clay, mica, wollastonite, hollow glass beads, titanium oxide, silica, carbon black, glass fibers or potassium titanate. Preferred fillers are talc, wollastonite, clay, monolayer cation exchange layered silicate material or mixtures thereof. Talc, wollastonite and clay are commonly known fillers for various polymer resins. For example, USP 5,091,461 and USP 3,424,703; EP 639,613 A1; And EP 391,413, their suitability as fillers of these materials and polymeric resins is generally described.

Preferred talc and clays with very low free metal oxide contents are not calcined. The most suitable inorganic talc is a hydrated magnesium silicate, generally represented by the formula 3MgO-4SiO ₂ -H ₂ O. The composition of talc can vary somewhat depending on where they are buried. Montana talc is very close to the theoretical composition, for example. Suitable inorganic talc of this type are VANTALC F2003 available from Orlinger and JETFIL ™ 700C available from Minerals Technology.

Examples of preferred cation exchange layered silicate materials include biophylate, kaolinite, dickalite or talc layers; Smectite clay; Vermiculite clay; mica; Divalent mica; Margarite; Kenialite; Octosilicates; Cannemite; And macatite. Preferred cation exchange layered silicate materials are smectite clays including montmorillonite, bidelite, saponite and hectorite.

The average length to thickness ratio (L / T) of the preferred filler is preferably from 1 to 10,000, providing a desirable level of physical and other property requirements such as toughness and stiffness (elastic modulus). Several various cation exchange layered silicate materials, talc, wollastonite, clay and mixtures thereof have been found to be particularly suitable.

The suitability of the cation exchange layered silicate material filler in maintaining the desired levels of toughness and stiffness of molded articles made from resins has been shown to be a function of the average L / T of filler particles while at the same time obtaining fillers of uniformly small particle size. Very preferred are compositions for introducing fillers having an average L / T of at least 1, preferably at least 15, more preferably at least 50, even more preferably at least 100 and most preferably at least 200, as measured according to the techniques described below. Do. For the maximum level of L / T ratio, it has been found to have a value of 10,000 or less, preferably 5,000 or less, more preferably 1,000 or less, even more preferably 500 or less and most preferably 200 or less.

Non-cationic exchange layered silicate material fillers such as calcium carbonate, talc, clay, mica, wollastonite, hollow glass beads, titanium oxide, silica, carbon black, in maintaining the desired level of toughness and rigidity of molded articles made from resins, Suitability of glass fibers or potassium titanate, etc.) has been shown to be a function of the average L / T of filler particles while at the same time obtaining a uniform small particle size filler. Very preferred are compositions which introduce fillers having an average L / T of at least 1, preferably at least 1.5, more preferably at least 2, even more preferably at least 3 and most preferably at least 4, as measured according to the techniques described below. Do. At the maximum level of L / T ratio, it has been found to have a value of 30 or less, preferably 20 or less, more preferably 15 or less, even more preferably 10 or less and most preferably 4 or less.

To determine the particle size and L / T ratio, the length of the filler (or the longest dimension, such as the diameter of the platelet particles) and its thickness (the shortest of the two measurable dimensions) produced the filler modified polymer resin sample. And measuring the particle dimensions of the dispersed particles from the digitized image generated by reverse scattering electron imaging using a scanning electron microscope, and analyzing the digitized image in an image analyzer. Preferably, the size of the image is at least 10 times the maximum particle size size.

Propylene polymer compositions within the scope of the present invention generally have a number average particle size of 10 μm or less, preferably 3 μm or less, more preferably 2 μm or less, as measured by reverse scattering electron imaging using a scanning electron microscope. More preferably, the inorganic filler which is 1.5 micrometers or less, most preferably 1.0 micrometer or less is used. In general, smaller average particle sizes (if available) of at least 0.001 μm, preferably at least 0.01 μm, more preferably at least 0.1 μm, most preferably at least 0.5 μm, can be used very suitably.

Fillers can be used to optimally match the toughness and rigidity of the propylene polymer composition according to the invention. If present, the filler is at least 1 part by weight, preferably at least 3 parts by weight, more preferably at least 5 parts by weight, even more preferably at least 10 parts by weight, most preferably 15 parts by weight based on the total weight of the composition It is used in an amount greater than one part. Generally, the amount of filler is 50 parts by weight or less, preferably 40 parts by weight or less, more preferably 30 parts by weight or less, more preferably 25 parts by weight or less, more preferably 20 parts by weight based on the total weight of the composition. It has been found to be sufficient to use amounts up to parts by weight, most preferably up to 15 parts by weight.

Optionally, the propylene polymer composition further comprises additional polymers which are resins other than components (a), (b) and (c) above. Preferred further polymers are polyethylene, preferably low density polyethylene (LDPE), linear low density polyethylene (LLDPE), high density polyethylene (HDPE), polystyrene, polycyclohexylethane, polyester (e.g. polyethylene terephthalate), ethylene / styrene air Coalescing, ordered PP, ordered PS, ethylene / propylene copolymers, EPDM and mixtures thereof. If present, the additional polymer is used in an amount of at least 1 part by weight, preferably at least 3 parts by weight, more preferably at least 5 parts by weight, most preferably at least 7 parts by weight, based on the weight of the total composition. In general, the additional polymer is used in an amount of up to 40 parts by weight, preferably up to 30 parts by weight, more preferably up to 20 parts by weight, most preferably up to 15 parts by weight based on the weight of the total composition.

The composition of the present invention may comprise a slip agent. Preferred slip agents are saturated fatty acid amides or ethylenebis (amide), unsaturated fatty acid amides or ethylenebis (amide) or mixtures thereof. Saturated fatty acids useful in the present invention essentially follow the empirical formula RC (O) NHR ¹ , wherein R is a saturated alkyl group of 10 to 26 carbon atoms and R ¹ is independently hydrogen or a saturated alkyl group of 10 to 26 carbon atoms. Compounds following the empirical formula are, for example, palmitamide, stearamide, arachidamide, behenamide, stearyl stearamide, palmityl palmitamide, stearyl arachidamide and mixtures thereof.

Saturated ethylenebis (amide) useful in the present invention essentially follows the empirical formula RC (O) NHCH ₂ CH ₂ NHC (O) R, wherein R is as defined above. Examples of compounds which follow the empirical formulas are stearamidoethylsteaaramide, stearamidoethylpalmitamide, palmitamidoethylstearicamide and mixtures thereof.

Unsaturated fatty acids useful in the present invention are essentially of the formula R ₂ C (O) NHR ³ , wherein R ² is an unsaturated alkyl group having 10 to 26 carbon atoms, and R ³ is independently hydrogen or an unsaturated alkyl group having 10 to 26 carbon atoms. Follow. Examples of compounds following the empirical formula are oleamide, erucamide, linoleamide and mixtures thereof.

Unsaturated ethylenebis (amide) useful in the present invention is essentially of the formula R ⁴ C (O) NHCH ₂ CH ₂ NHC (O) R ⁴ , wherein R ⁴ is a saturated or unsaturated alkyl group having 10 to 26 carbon atoms, provided that ^At least one of ⁴ is unsaturated). Examples of the compound according to the above empirical formula include erucamidoethylerucamide, oleamidoethyl oleamide, erucamidoethyl oleamide, oleamidoethyl erucamide, stearamidoethyl erucamide, eruk Amidoethylpalmitamide, palmitamidoethyloleamide and mixtures thereof.

Generally preferred concentrations of saturated fatty acid amides or ethylene-bis (amides) are 0 to 0.5 parts by weight, preferably 0.0025 to 0.25 parts by weight and most preferably 0.015 to 0.15 parts by weight, based on the weight of the total composition. Generally, the preferred concentration of unsaturated fatty acid amides or ethylene-bis (amides) is 0 to 1 parts by weight, preferably 0.05 to 0.75 parts by weight and most preferably 0.1 to 0.3 parts by weight based on the weight of the total composition.

In addition, the claimed propylene polymer compositions may also optionally contain one or more additives commonly used in this type of propylene polymer composition. Non-limiting examples of preferred additives of this type include fire resistant additives, stabilizers, colorants, antioxidants, antistatic agents, rheology enhancers, mold release agents (e.g. metal stearates such as calcium stearate, magnesium stearate), nucleating agents. And clearing agents. Preferred examples of the additive are fire resistant additives, and non-limiting examples thereof include halogenated hydrocarbons, halogenated carbonate oligomers, halogenated diglycidyl ethers, organophosphorus compounds, fluorinated olefins, metal salts of antimony oxide and aromatic sulfur, or mixtures thereof. Can be used. In addition, compounds may be used that stabilize the polymer composition against degradation caused by, but not limited to, heat, light and oxygen, or mixtures thereof.

Such additives, if used, are at least 0.01 parts by weight, preferably at least 0.1 parts by weight, more preferably at least 1 part by weight, more preferably at least 2 parts by weight, most preferably based on the weight of the total composition. It may be present in an amount of at least 5 parts by weight. Generally, the additive is 25 parts by weight or less, preferably 20 parts by weight or less, more preferably 15 parts by weight or less, more preferably 12 parts by weight or less, most preferably 10, based on the total amount of the composition of the composition. It is present in an amount of up to parts by weight.

The preparation of the propylene polymer compositions of the present invention may be carried out by dry blending the individual components and then melt blending directly in an extruder used to produce a finished product (e.g., automotive parts) or a separate extruder (e.g. Banbury mixers) may be implemented by any suitable mixing means known in the art, including premixing. Dry blends of this composition can also be injection molded directly without melt mixing in advance. Alternatively, the propylene polymer and polyolefin elastomer can be made in the same reactor.

The propylene polymer composition of the present invention is thermoplastic. When heated to soften or melt, the polymer blend compositions of the invention may be subjected to conventional techniques such as extrusion, injection molding, gas injection molding, calendering, vacuum molding, thermoforming, extrusion and / or blow molding alone. Or may be used together or formed. The polymer blend compositions may also be molded, spun or stretched into films, fibers, multilayer laminates or extrusion sheets, or may be combined with one or more organic or inorganic materials in any machine suitable for this purpose. The propylene polymer composition of the present invention is preferably injection molded. Some processed products include automotive interior and exterior components such as bumper beams, bumper fascia, pillars and instrument panels; Electrical appliance housings and covers; And other household and personal products (eg, home appliance housings, housewares, freezer containers, and crates); Lawn and garden furniture; And building and structure sheets.

To illustrate the practice of the present invention, examples of preferred embodiments are described below. However, these examples do not in any way limit the scope of the invention.

Examples 1-8 were natural propylene polymer compositions formulated in a Werner and Pfleiderer ZSK-40, 40 mm twin screw extruder. Talc, if used, was fed through an auxiliary feeder and the remaining ingredients were preblended before being fed to the extruder. Examples 1-8 did not contain any pigments or UV stabilizers. The following were the compounding conditions in the ZSK-40 extruder for Examples 1-8: Barrel temperature distribution: 170 ° C, 180 ° C, 190 ° C, 195 ° C, 200 ° C, 205 ° C, and 205 ° C; Die temperature: 210 ° C .; Melting point: 225 ° C .; Feed rate: 75 kg / h; Screw speed: 500 revolutions / minute (rpm); Die pressure: 13 bar; Torque: 28%. The die had nine holes. The extrudate was cooled in strand form and ground as pellets. The compositions of Examples 1-8 are listed in Table 1 below, where parts are parts by weight based on the total weight of the composition.

Examples 9 and 10 were the colorant and slip / UV stabilizer master batch, respectively. These were blended on a Werner Ant Flyder ZSK-25, 25 mm twin screw extruder. The ingredients were preblended before feeding to the extruder. The following were the compounding conditions in the ZSK-25 extruder for Examples 9 and 10: Barrel temperature distribution: 86 ° C., 132 ° C., 169 ° C., 174 ° C., 175 ° C., 184 ° C., and 197 ° C .; Die temperature: 205 ° C .; Melting point: 200 ° C .; Feed rate: 12 kg / h; Screw speed: 300 revolutions / minute (rpm); Die pressure: 3 bar; Torque: 32%. The die had three holes. The extrudate was cooled in strand form and ground as pellets. The compositions of Examples 9 and 10 are listed in Table 2 below, where parts are parts by weight based on the total weight of the master batch.

Examples 11-18 show natural propylene polymer composition pellets (Examples 1-8), colorant master batch ("Color MB") pellets (Example 9) and slip / UV stabilizer master batches ("slip / UV MB). ") A mixture of pellets (Example 10). Example 11 was a mixture of the pellets of Examples 9 and 10 and the pellets of Example 1 pre-blended, and Example 12 was a mixture of the pellets of Examples 9 and 10 and the pellets of Example 2 pre-blended Examples 13-18 were analogous mixtures based on the pellets of Examples 3-8 pre-blended with the examples of Examples 9 and 10. After pre-blended pellet mixture Examples 11-18 were dried at 80 ° C. for 2 hours, the test pieces were injection molded in a Krauss Mafei injection molding machine having the following molding conditions: barrel temperature distribution: 200 ° C., 210 ° C., 220 ° C., 230 ° C., and 195 ° C .; Injection rate: 40%; Injection pressure: 160 bar; Back pressure: 0; Cooling time: 42 seconds; And molding temperature: 50 ° C. The test pieces were plaques with two embedded textures or grains, each of 18 cm x 7.5 cm in size. Crystals were Opel N111 and Opel N127.

The compositions of Examples 11-18 are given in Table 3 below in parts by weight based on the weight of the total composition.

"PP-1" in Tables 1 to 3 comprises 8.5% by weight of ethylene, has a density of 0.9 g / cm 3, a molecular weight of about 300,000, MFR of 7 g / 10 min at 230 ° C. under a load of 2.16 kg, and more Propylene copolymers available as C704-07 from The Dow Chemical Company (unless otherwise indicated, molecular weight refers to weight average molecular weight);

“PP-2” comprises 10% by weight of ethylene, has a density of 0.9 g / cm 3, molecular weight of about 200,000, MFR of 44 g / 10 min at 230 ° C. under a load of 2.16 kg, and C705 from The Dow Chemical Company Propylene copolymers available as -44 NA HP;

"SLEP-1" has a density of 0.868 g / cm 3, a molecular weight of about 160,000, an MFR of 0.5 g / 10 min at 190 ° C. under a load of 2.16 kg, and AFFINITY ™ EG 8150 from The Dow Chemical Company A substantially linear ethylene-octene copolymer available as polyolefin elastomer;

“HDPE” is a high density polyethylene powder having a density of 0.96 g / cm 3 and an MFR of 1.1 at 190 ° C. under a load of 2.16 kg;

"Talc" is a high purity asbestos-free hydrated magnesium silicate, available as MISTRON ™ G7C from Luzenac Benelux;

“Erucamide” is available as ARMOSLIP ™ from Akzo Nobel Polymer Chemicals;

"CHIMASORB ™ 119" is a high molecular weight, hindered amine light stabilizer available as Cimach FL from Ciba Spezialiteitenchemie AG;

"IRGANOX ™ B215" is composed of tris (2,4-di-tert-butylphenyl) phosphate and tetrakis (methylene (3,5-di-tert-butyl-4-hydroxyhydrocinnamate) ) 2: 1 blend of methane and available as Irganox B215 from Ciba Specialty Chemicals;

"LMP-1" is a low molecular weight high density oxidized polyethylene homopolymer available as A-C 395A from AC Wax with a molecular weight of about 40,000;

"LMP-2" is a low molecular weight ethylene zinc acrylate zinc ionomer available as ACLYN ™ 295A from AC wax with a molecular weight of about 40,000;

"LMP-3" is a low molecular weight ethylene homopolymer available as POLYWAX ™ 3000 from Baker Petrolyte, having a molecular weight of about 3,000;

“LMP-4” is a low molecular weight, substantially linear ethylene-octene copolymer having a density of 0.88 g / cm 3, a MI of 190 g at 190 ° C. under a load of 2.16 kg, and a molecular weight of about 10,000;

“LMP-5” is a low molecular weight, substantially linear ethylene-octene copolymer having a density of 0.87 g / cm 3, a MI of 190 g at 190 ° C. under a load of 2.16 kg, and a molecular weight of about 10,000;

“LMP-6” is a low molecular weight, substantially linear ethylene-octene copolymer having a density of 0.874 g / cm 3, a MI at 190 ° C. of 500 g / 10 min under a load of 2.16 kg, and a molecular weight of about 20,000;

"LMP-7" has a density of 0.955 g / cm 3, a MFR of 25 g / 10 min at 190 ° C. under a load of 2.16 kg, and a molecular weight, available as HDPE 25055E Resin from Dow Chemical Company Low molecular weight HDPE having a narrow molecular weight distribution of about 50,000;

"Pigment" is White 6-1 available as TIOXIDE ™ RFC-5 from Tioxide, Brown available as SICOTAN ™ gelb K2111F from BASF. (Brown) 24, Blue 29-1 available as Ultra Marine Blue CM05-D from Holliday, available as BAYFERROX ™ 130M-PL from Bayer Red 101-1 MG, Black 7-3 MG available as 33% black and 66% MGSTRAR ™ from Ardo.

Example 1 ^* 2 3 4 5 6 7 8 ingredient PP-1 53.75 53.75 53.75 53.75 53.75 53.75 53.75 53.75 PP-2 22 20 20 20 20 20 20 20 SLEP-1 5 5 5 5 5 5 5 5 talc 16 16 16 16 16 16 16 16 Irganox B215 3 3 3 3 3 3 3 3 Erucamide 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 LMP-1 2 LMP-2 2 LMP-3 2 LMP-4 2 LMP-5 2 LMP-6 2 LMP-7 2 ^* Not an embodiment of the invention

Example 9 ^* 10 ^* ingredient  PP-2 20 68.58  HDPE 32 15.71  Erucamide 10  Upskirt 199 5.71 Pigment  White 6-1 32.34  Brown 24 9.51  Blue 29-1 2.81  Red 101-1 mg 0.87  Black 7-3 mg 2.47 ^* Not an embodiment of the invention

Example 11 ^* 12 13 14 15 16 17 18 ingredient Example 1 Residual amount Example 2 Residual amount Example 3 Residual amount Example 4 Residual amount Example 5 Residual amount Example 6 Residual amount Example 7 Residual amount Example 8 Residual amount Example 9 3.125 3.125 3.125 3.125 3.125 3.125 3.125 3.125 Example 10 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 ^* Not an embodiment of the invention

The following scratch resistance test was performed for Examples 11 to 18 and the results are reported in Table 4 below.

"Scratch resistance" is determined according to GME 60280 of General Motors, GM, where a grid of 20 scratches is made with a test needle (a 1 mm diameter scraper pen). The distance between the scratches is 2 mm. The load is 15 Newtons (N) instead of the 5 N specified in the test method. The L value is measured before and after scraping on a Data Color spectrometer. Delta L (DL) is determined according to the following equation:

DL = L _{scratch value} -L _{scratch value}

Test plaques were tested at the end near the gate and at the end far from the gate and the average of these two values is reported in Table 4 below.

Example 11 ^* 12 13 14 15 16 17 18 Average scratch resistance, DL Opel N111 1.645 0.8675 1.0195 1.1005 1.03 0.801 0.832 0.722 Opel N127 3.6285 1.7115 2.141 2.4895 2.1245 1.922 1.8625 1.6075 ^* Not an embodiment of the invention

Examples 19 to 22 are prepared by the same method as Examples 1 to 8.

The compositions of Examples 19-22 are given in Table 5 below in parts by weight based on the weight of the total composition.

In Table 5 below, “PP-3” comprises 15% by weight of ethylene, has a density of 0.9 g / cm 3, a molecular weight of about 170,000, an MFR of 12 g / 10 min at 230 ° C. under a load of 2.16 kg, and more Propylene copolymers available as C715-12 N HP from Dow Chemical Company;

"SLEP-2" comprises about 20% by weight of 1-octene, has a density of 0.868 g / cm 3, a molecular weight of about 90,000, MFR at 190 ° C. under a load of 2.16 kg is 5.0 g / 10 min, more Dow A substantially linear saturated ethylene-octene copolymer available from Chemical Company as an affinity EG 8200 polyolefin elastomer;

“HDPE” is a high density polyethylene powder having a density of 0.96 g / cm 3 and an MFR of 1.1 at 190 ° C. under a load of 2.16 kg;

“LMP-8” is a VLDPE ethylene-butene copolymer produced by gas phase polymerization, having a density of 0.8985 g / cm 3, a molecular weight of about 50,000, and an MFR of 5.2 at 190 ° C. under a load of 2.16 kg.

Example 19 ^* 20 ^* 21 22 ingredient PP-2 22 61.8 PP-3 74.8 72.8 PP-1 52.8 SLEP-1 5 SLEP-2 9 9 10 talc 16 16 16 20 Irganox B215 0.2 0.2 0.2 0.2 HDPE 4 LMP-3 2 2 LMP-8 6 ^* Not an embodiment of the invention

Examples 23-26 are pre-blended pellet mixtures prepared by the same method as Examples 11-18 and injection molded into plaques.

The compositions of Examples 23 to 26 are given in Table 6 below in parts by weight based on the weight of the total composition.

ingredient 23 ^* 24 ^* 25 26 ingredient Example 19 Residual amount Example 20 Residual amount Example 21 Residual amount Example 22 Residual amount Example 9 3.125 3.125 3.125 3.125 Example 10 3.5 3.5 3.5 3.5 ^* Not an embodiment of the invention

The scratch resistance properties of Examples 23-26 are reported in Table 7 below:

Example 23 ^* 24 ^* 25 26 Average scratch resistance, DL Opel N111 2.407 2.259 1.106 1.607 Opel N127 4.139 3.47 2.887 2.778 ^* Not an embodiment of the invention

Examples 27 to 31 are prepared in the same manner as in Examples 1 to 8.

The compositions of Examples 27-31 are given in Table 8 below in parts by weight based on the weight of the total composition.

In Table 8 below, “LMP-9” is a low molecular weight ethylene homopolymer having a molecular weight of about 2,000 and available as Polywax 2000 from Baker Petrolite;

“LMP-10” is a low molecular weight branched polyalphaolefin having a molecular weight of about 1,500 to 5,000 and available as VYBAR ™ 260 from Baker Petrolite;

“LMP-11” is a low molecular weight polyethylene wax having a melting point of 70 to 110 ° C., a density of 750 to 900 kg / m 3, a molecular weight of about 800, and available as polyethylene wax 800 from Dow Chemical Company;

“LMP-12” is a low molecular weight polyethylene wax having a drop point of 115 ° C., a density of 0.93 g / cm 3, a molecular weight of about 40,000, available as AC 9A from AC wax.

Example 27 ^* 28 29 30 31 ingredient PP-1 53.75 53.75 53.75 53.75 53.75 PP-2 22 20 20 20 20 SLEP-1 5 5 5 5 5 talc 16 16 16 16 16 LLDPE 3 3 3 3 3 Irganox B215 0.1 0.1 0.1 0.1 0.1 Erucamide 0.15 0.15 0.15 0.15 0.15 LMP-9 2 LMP-10 2 LMP-11 2 LMP-12 2 ^* Not an embodiment of the invention

Examples 32-36 are pre-blended pellet mixtures prepared by the same method as Examples 11-18 and injection molded into plaques.

The compositions of Examples 32-36 are given in Table 9 in parts by weight based on the total weight of the composition.

Example 32 ^* 33 34 35 36 ingredient Example 27 Residual amount Example 28 Residual amount Example 29 Residual amount Example 30 Residual amount Example 31 Residual amount Example 9 3.125 3.125 3.125 3.125 3.125 Example 31 3.5 3.5 3.5 3.5 3.5 ^* Not an embodiment of the invention

The scratch resistance properties of Examples 32-36 are reported in Table 10 below:

Example 32 ^* 33 34 35 36 Average scratch resistance, DL Opel N111 1.209 0.233 0.426 0.432 1.156 Opel N127 3.736 0.712 2.136 1.095 2.905 ^* Not an embodiment of the invention

Claims (20)

Based on the total weight of the composition, (a) 40 to 95 parts by weight of propylene polymer; (b) (i) the density is less than 0.93 g / cm 3, (ii) the molecular weight distribution (M _w / M _n ) is less than 3.0,     (iii) 1 to 20 parts by weight of a substantially linear ethylene polymer, linear ethylene polymer or mixtures thereof, characterized in that the composition distribution branching degree is greater than 30%; (c) 0.5 to 10 parts by weight of a low molecular weight polymer; And (d) 0 to 25 parts by weight of the filler Propylene polymer composition comprising a. The method of claim 1, (b) the weight average molecular weight of the substantially linear ethylene polymer and / or the linear ethylene polymer is 40,000 to 180,000, (c) the weight average molecular weight of the low molecular weight polymer is from 500 to 70,000, A propylene polymer composition wherein the ratio of the average molecular weight of (b) to the average molecular weight of (c) is at least 1.5. The propylene polymer composition of claim 1 wherein the propylene polymer is a homopolymer of propylene. The propylene polymer composition of claim 1, wherein the propylene polymer is a copolymer of propylene and C ₂ or C ₄ to C ₂₀ alpha-olefins. The propylene polymer composition of claim 1, wherein the substantially linear ethylene polymer or linear ethylene polymer is a copolymer of ethylene and C ₃ to C ₂₀ alpha-olefins. The propylene polymer composition of claim 1 wherein the substantially linear ethylene polymer or linear ethylene polymer is a copolymer of ethylene and propylene, 1-butene, 1-hexene, 4-methyl-1-pentene or 1-octene. The low molecular weight polymer according to claim 1, wherein the low molecular weight polymer has a molecular weight of 500 to 70,000, animal wax, plant wax, carnauba wax, candelilla wax, Japan wax, beeswax, broad wax, petroleum wax, paraffin wax, microcrystalline wax , Propylene polymer composition which is petrolatum wax, polyolefin wax, oxidized polyolefin wax, higher fatty acid wax, higher fatty acid ester wax, styrene oligomer, amorphous poly-alpha-olefin, or mixtures thereof. The propylene polymer composition of claim 1, wherein the low molecular weight polymer is polyethylene wax, polypropylene wax, polyethylene-propylene wax, polyethylene-butylene wax, polyethylene-hexylene wax, polyethylene-octylene wax, or mixtures thereof. The propylene polymer composition of claim 8, wherein the low molecular weight polymer further comprises a polar comonomer in an amount of 0.01% to 5% by weight based on the weight of the low molecular weight polymer. 10. The propylene polymer composition of claim 9, wherein the polar comonomer is an unsaturated carboxylic acid, carboxylic acid ester, carboxylic acid salt, or mixtures thereof. The propylene polymer composition of claim 1 wherein the filler is present in an amount from 1 to 20 parts by weight. The propylene polymer composition of claim 11 wherein the filler is talc, wollastonite, clay, monolayer cation exchange layered silicate material, or mixtures thereof. 12. The propylene polymer composition of claim 11 wherein the filler is talc. (E) low density polyethylene, linear low density polyethylene, high density polyethylene, polystyrene, polycyclohexylethane, polyester, ethylene / styrene copolymer, ordered polypropylene, ordered polystyrene, ethylene / propylene copolymer, A propylene polymer composition further comprising 1 to 20 parts of an additional polymer selected from ethylene / propylene / diene terpolymers, or mixtures thereof. The propylene polymer composition according to claim 1, further comprising (f) 0.1 to 1 part of a slip agent selected from erucamide, oleamide, linoleamide or stearamide. The propylene polymer composition of claim 1, further comprising a pigment (s), an ultraviolet (UV) stabilizer, or a mixture thereof. Based on the total weight of the composition, (a) 40 to 95 parts by weight of propylene polymer; (b) (i) the density is less than 0.93 g / cm 3, (ii) the molecular weight distribution (M _w / M _n ) is less than 3.0,     (iii) 1 to 20 parts by weight of a substantially linear ethylene polymer, linear ethylene polymer or mixtures thereof, characterized in that the composition distribution branching degree is greater than 30%; (c) 0.5 to 10 parts by weight of a low molecular weight polymer; And (d) 0 to 25 parts by weight of the filler Method for producing a propylene polymer composition comprising the step of mixing. (A) based on the total weight of the composition,     (a) 40 to 95 parts by weight of propylene polymer;     (b) (i) the density is less than 0.93 g / cm 3, (ii) the molecular weight distribution (M _w / M _n ) is less than 3.0,         (iii) 1 to 20 parts by weight of a substantially linear ethylene polymer, linear ethylene polymer or mixtures thereof, characterized in that the composition distribution branching degree is greater than 30%;     (c) 0.5 to 10 parts by weight of a low molecular weight polymer; And     (d) 0 to 25 parts by weight of the filler Preparing a propylene polymer composition comprising; And (B) molding or extruding the propylene polymer composition into a molded or extruded product A method for producing a molded or extruded product of a propylene polymer composition comprising a. The propylene polymer composition of claim 1 in the form of a molded or extruded product. 20. An automobile bumper beam, an automobile bumper fascia, an automobile pillar, an automotive appliance plate, an electrical appliance housing, an electrical appliance cover, a home appliance housing, a freezer compartment, a crate. Crate, or molded or extruded product selected from lawn and garden furniture.