JP5843782B2 - Impact resistant polyolefin composition - Google Patents

Description

The present invention relates to an impact resistant thermoplastic polyolefin composition. In particular, the present invention relates to a composition comprising a propylene polymer component, a copolymer of ethylene and a C ₄ -C ₁₀ -α-olefin, other polyolefin elastomeric or plastomer based material, and filler material.

  To achieve a good balance of stiffness (high flexural modulus) and impact resistance in thermoplastic polymer composition technology, a propylene polymer, generally a homopolymer or a copolymer with a small amount of a comonomer, and an elastomeric system Combining with ethylene copolymers is known. For specific applications, it is also desirable that the thermal shrinkage is low. In fact, these properties provide high form stability to the final products obtained from these compositions.

In particular, WO 03/075511 and WO 2005/121240 include a copolymer of a propylene polymer component, ethylene and one or more C ₄ -C ₁₀ -α-olefins, other elastomeric or plastomer based polyolefins and mineral fillers. Polyolefin compositions with low heat shrinkage and excellent mechanical properties are described. As shown in the examples of these documents, using the technical solution disclosed therein, flexural modulus significantly greater than 1000 MPa only when about 20 wt% mineral based filler is added. A value is obtained. Also, the melt flow rate (MFR) of these high flexural modulus compositions is relatively small.

Select a specific propylene polymer and ethylene / alpha-olefin copolymer, other characteristics, by combining the ratio of the various components, the desired mechanical properties (especially flexural modulus and Aizo' preparative impact strength) of the balance of the composition It was revealed that favorable fluidity in the molten state and low heat shrinkage can be achieved.

  Due to their mechanical and physical properties, the polyolefin compositions according to the invention are used in particular in the automotive field, in particular in the manufacture of door trims.

Thus, the present invention is all expressed in weight percent,
A) 40-75%, preferably 45-65%, of a polypropylene component consisting of a propylene homopolymer, a propylene copolymer with other α-olefins, or combinations thereof, comprising at least 85% by weight of propylene, The MFRL value is 90 g / 10 min or more, preferably 100 g / 10 min or more, and preferably at most 2500 g / 10 min, and the solubility in xylene at room temperature is less than 20% by weight;
B) 3 to 20%, a copolymer of ethylene and one or more _C 4 _{-C 10 -α-} olefin) contains a _C 4 _{-C 10 -α-} olefin 15 to 35% by weight, at room temperature The solubility in xylene is greater than 50% by weight and the intrinsic viscosity of the xylene soluble fraction is preferably 2.5-4 dl / g;
C) 10-35%, preferably 10-30% of one or more elastomeric or plastomer polymers different from B) with a Shore A hardness of 90 points or more, preferably less than 80 points;
D) 5 to 25%, preferably 6 to 20% mineral filler, preferably talc;
E) Copolymers containing from 0.5 to 5% C) different ethylene and propylene and optionally 0.5 to 5% by weight diene, having an ethylene content of 20 to 70% by weight at room temperature A composition having a solubility in xylene greater than 50% by weight and an intrinsic viscosity of the xylene-soluble fraction of 4-9 dl / g,
A), B), C), D), E) relates to a composition wherein the amount is A) + B) + C) + D and, if necessary, a value relative to the total weight of E).

  From the above definition it is clear that "copolymer" includes polymers containing multiple types of comonomers.

  The composition of the present invention may also comprise a nucleating agent F), if necessary, in a preferred amount of 0.01 to 0.5 parts by weight per 100 parts by weight of A) + B) + C) + D) and E) if necessary. Can be included.

  The MFR value of the composition of the present invention is preferably 20 g / 10 min or more, more preferably 23 g / 10 min or more, for example, in the range of 20 to 60 g / 10 min, particularly in the range of 23 to 60 g / 10 min.

  Therefore, the composition of the present invention can be easily converted into various kinds of final products and semi-finished products by injection molding method due to its relatively high MFR value and the above balanced properties.

  Mixing various propylene homopolymers and / or copolymers having different MFRL values (MFR-L values) determines the MFRL value of component A).

In such cases, the MFRL value of A) is easily derived from the correlation between the MFR of the known polyolefin composition and the MFR of each component, based on the amount of the single polymer and the MFRL value, respectively. For example, in the case of bipolymer components A1 and A2, this correlation is expressed as:
ln MFR ^A = [WA ¹ / ( WA ¹ + WA ² )] × ln MFR ¹ + [WA ² / (WA ¹ + WA ² )] × ln MFR ²

Where WA ¹ and WA ² represent the weights of the components A ¹ ) and A ² ), respectively, MFR ^A represents the calculated MFR of A), MFR ¹ and MFR ² represent the components A ¹ ) and A ² ), respectively. Represents the MFR of A ² ).

Therefore, the MFRL value for a single polymer is less than 90 g / 10 min. Therefore, the definition of the MFRL value of component A) includes the above calculated value. The amount of fraction (XI) insoluble in xylene at room temperature of component B) preferably satisfies the following formula:
(XI) <1.14 × B ₂ −34

Wherein, B ₂ in the amount of ethylene in component B), is obtained in weight percent relative to the weight of B).

The amount of component (A) soluble in xylene at room temperature is 20% or less, preferably 10% by weight or less, as described above. Usually component (A) comprises (i) a propylene homopolymer, preferably having a solubility in xylene at room temperature of less than 10% by weight, more preferably less than 5%, even more preferably less than 3%, (ii) propylene and at least Selected from a copolymer of a kind of α-olefin of the formula H ₂ CH═CHR, wherein R is H or a C _2-8 linear or branched alkyl group, or a combination of (i) and (ii) It is.

  Preferably the copolymer of propylene (ii) comprises at least 90% propylene and its solubility in xylene at room temperature is preferably less than 15% by weight, more preferably less than 10%, even more preferably less than 8% . The α-olefin is preferably ethylene, butene-1, pentene-1,4-methylpentene-1, hexene-1, octene-1, or a combination thereof, and more preferably propylene ( The copolymer of ii) is a copolymer of propylene and ethylene.

  As mentioned above, components (B) and (C) are partially soluble in xylene at room temperature. The content of the component (B) or (C) soluble in xylene at room temperature is preferably about 50 to 95% by weight, more preferably 55 to 95% by weight.

The C ₄ -C ₁₀ -α-olefin in component (B) is generally an olefin of formula H ₂ CH═CHR where R is a C _2-8 linear or branched alkyl group. ).
Representative examples of the C ₄ -C ₁₀ -α-olefin of component (B) include 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene and 1-octene. Is particularly preferred.

  The composition of the present invention can be produced by melt blending components (A), (B), (C) and (D), and if necessary, components (E) and / or (F).

All compositions of the present invention are expressed in weight percent,
From A ^I) 60 of 85%, a propylene homopolymer, propylene copolymers with other α- olefin or a polypropylene component comprising a combination thereof, comprises at least 85 wt% propylene, MFRL value 20 g / 10 Min. And the solubility in xylene at room temperature is less than 20% by weight;
B ^I ) a copolymer of 15-40% ethylene and one or more C ₄ -C ₁₀ -α-olefins, containing 15-35% by weight C ₄ -C ₁₀ -α-olefins, to xylene at room temperature A masterbatch composition (1) comprising a solubility exceeding 50% by weight and an xylene-soluble fraction having an intrinsic viscosity of 2.5 to 4 dl / g,
It can also be produced by melt blending with other polyolefin components, component (D), and if necessary (F).

The preferred polymer type and comonomer type and amount for the masterbatch component (A ^I ) and the fraction soluble in xylene at room temperature are the same as those described above for component (A).

The type and amount of comonomer for the masterbatch component (B ^I ) and the amount of fraction soluble in xylene at room temperature are the same as those described above for component (B).

  The DSC melting peak melting enthalpy value ΔHm that can be detected at a temperature between 100 and 130 ° C. of the masterbatch composition (I) is preferably 1 J / g or more.

  The elastomeric or plastomer-based polymer C) can be any elastomeric or plastomer-based polymer commonly used to change the mechanical properties of polyolefins.

“Plastomer-based” includes a specific grade of material that has properties intermediate between thermoplastic and elastomeric materials, commonly referred to as “plastomers”. Such plastomers can have a wide range of densities (up to about 0.925 g / cm ³ ) and can have a higher degree of crystallinity than conventional elastomers.

Whether it is an elastomeric or plastomer based material, the component C) preferably has at least one of the following characteristics in addition to the Shore A hardness of 90 points or less:
-Flexural modulus (iso-178A): 200 MPa or less, preferably 170 MPa or less, most preferably 100 MPa or less;
-Shore D hardness: 50 points or less, more preferably 45 points or less, most preferably 32 points or less;
-X-ray crystallinity: 0 to 40%, more preferably 0 to 30%.
Preferred examples of C) are:
1) most 45% by weight, in particular 10 to 42 wt% of olefin comonomer, preferably _C 3 _{-C 10 -α-} olefin, in particular comprises a butene-1 or octene-1, Shore A hardness below 90 points An ethylene copolymer,
2) A propylene copolymer containing at most 40% by weight of an olefin comonomer, preferably ethylene or C ₄ -C ₁₀ -α-olefin, and having a Shore A hardness of 90 points or less.

The density of the ethylene copolymer 1) is usually from 0.86 to 0.925 g / cm ³ .

A specific example of copolymer 1) comprises 63.5% by weight ethylene and 36.5% by weight octene-1 ( ¹³ C-NMR analysis), with a hardness of 72 Shore A points at 20 Shore D points, Melting point is 60 ° C., MFR is 30 g / 10 min (ASTM-D1238, 190 ° C./2.16 kg), intrinsic viscosity is 0.9 dl / g, and density according to ASTM-D792 is 0.87 g. / Ml of copolymer.

  This is sold by Dow Chemical Company under the trade name Engage 8407 (R).

  Another example of copolymer 1) contains 62% by weight ethylene and 38% by weight octene-1 (IR analysis), has a hardness of 21 Shore D points and 75 Shore A points and a melting point of 60 ° C. , A copolymer having an MFR of 5 g / 10 min (ASTM-D1238, 190 ° C./2.16 kg) and a density of 0.87 g / ml according to ASTM-D792.

  This is sold by Dow Chemical Company under the trade name Engage 8200 (R).

  Other polymeric materials of this type sold by Dow under the trade name Affinity can also be suitably used.

Another example of copolymer 1) contains 61% by weight ethylene and 39% by weight octene-1 (IR analysis), has a hardness of 20 Shore D points and 75 Shore A points, and a melting point of 55 ° C. , A copolymer having a density of 0.868 g / cm ³ and an MFR of 0.5 g / 10 min (ASTM-D1238, 190 ° C./2.16 kg) according to ASTM-D792.

  It is sold by Dow Chemical Company under the trade name Engage 8150 (R).

Another specific example of the copolymer 1) is a hardness of 56 Shore A points, a melting point of 36 ° C., a density of 0.86 g / cm ^{3 according to} ASTM-D792, and an MFR of 1.2 g / 10 min (ASTM -D1238, 190 ° C./2.16 kg), an ethylene and butene-1 copolymer having an intrinsic viscosity of 1.5 dl / g.

This is sold under the trade name ENR7467 (R) by Dow Chemical Company.

Another specific example of the copolymer 1) is that the hardness is 30 Shore D point and 85 Shore A point, the flexural modulus is 22.8 MPa (ASTM-D790), the melting point is 60 ° C., and the density is measured by ASTM-D792. Is a copolymer of ethylene and butene-1 having a viscosity of 0.88 g / cm ³ and an intrinsic viscosity of 1.6 dl / g.

  This is sold by Exxon Chemical Company under the trade name of Exact 4033 (R).

  Examples of preferred propylene copolymers 2) are propylene copolymers comprising 0.1 to 40% by weight, more preferably 0.1 to 25% by weight of olefin comonomers, in particular ethylene.

The density of the propylene copolymer 2) is usually from 0.850 to 0.890 g / cm ³ , in particular from 0.855 to 0.885 g / cm ³ . When measured as X-ray crystallinity, these usually exhibit a crystallinity of 0 to relatively low, for example, 0 to 25%.

  Other typical properties of the propylene copolymer 2) are as follows.

-Shore A hardness: preferably 88 points or less, more preferably 75 points or less;
A melting point measured by differential scanning calorimetry (DSC) at a heating / cooling rate of 10 to 20 ° C .: 105 ° C. or less, preferably 90 ° C. or less;
-Heat of fusion measured by DSC under the above conditions; 75 J / g or less;
-Mw / Mn (Mw = weight average molecular weight, Mn = number average molecular weight, both measured by gel permeation chromatography at 135 ° C. in trichlorobenzene): 1.5-5, more preferably 1.5 ~ 3.5.

  Suitable propylene copolymers 2) are plastomers Vistamax (R) and Versify (R), sold by Exxon Mobil Chemical and Dow Chemical, and Notio (R) polymers sold by Mitsui Petrochemical. .

  The above copolymers 1) and 2) are usually produced by polymerization in the presence of a single site catalyst, in particular in the presence of a metallocene catalyst and a geometrically constrained catalyst.

  Particularly preferred as component C) is the aforementioned copolymer 1). Such copolymers usually have an intrinsic viscosity of 2 dl / g or less. Since this copolymer is very soluble, such intrinsic viscosity substantially corresponds to the intrinsic viscosity of the fraction soluble in xylene at room temperature.

  In general, components (A), (B), (C) and (E) can be produced separately using known polymerization methods.

The masterbatch composition (I) is preferably produced by sequential polymerization. Specifically, the masterbatch composition (I) is produced in a separate step in which the components (A ^I ) and (B ^I ) are continuous, and the first step is the previous step. It is preferred to produce by sequential polymerization consisting of at least two sequential steps performed in independent steps except that it is performed in the presence of the polymer formed in the step and the catalyst used. This catalyst is added only in the first step, but its activity is so high that it is maintained in all subsequent steps.

  This polymerization may be continuous or batchwise, but in a known manner, in the liquid phase in the presence or absence of an inert diluent, or in the gas phase, or gas-liquid mixing Done by law.

  However, the reaction time, pressure, and temperature of these polymerization steps are not so important, but the temperature is highest when the temperature is 50 to 100 ° C. The pressure may be atmospheric pressure or higher.

  The molecular weight is adjusted with known regulators, in particular with hydrogen.

  In order to produce components (A), (B) and (E), it is preferred to carry out the polymerization in the presence of a stereoselective Ziegler-Natta catalyst.

  Accordingly, component B) is preferably produced using a Ziegler-Natta catalyst for the polymerization and component C) is preferably produced using a single site catalyst for the polymerization. This catalyst is known.

Known conventional molecular weight self-adjusting agents such as chain transfer agents (eg hydrogen or ZnEt ₂ ) can be used.

  Examples of preferred Ziegler-Natta catalysts include supported catalyst systems containing a trialkylaluminum compound and optionally an electron donor, or a Ti halide or halogen-alcolate supported on anhydrous magnesium chloride and an electron donor compound if necessary. Examples of the solid catalyst component. Catalysts having the above characteristics and polymerization methods using such catalysts are well known in the patent literature. Particularly preferred are the catalysts and polymerization processes described in USP 4,399,054 and EP-A-45977. Other examples are found in USP 4,472,524.

These catalysts can also be contacted in advance with a small amount of olefin (prepolymerization). If necessary, the mineral filler (D) added to the composition of the present invention includes talc, CaCO ₃ , silica, mica, wollastonite (CaSiO ₃ ), clay, diatomaceous earth, titanium oxide, and zeolite. Talc is preferred. Usually, this mineral filler is in the form of particles having an average diameter in the range of 0.1 to 5 micrometers.

  Useful nucleating agents (E) include, for example, metal salts of carboxylic acids, dibenzyl sorbitol derivatives, alkali metal salts of phosphoric acid, and the like.

  Specific examples of the nucleating agent include sodium benzoate, aluminum adipate, aluminum pt-butylbenzoate, 1,3,2,4-dibenzylidene sorbitol, 1,3,2,4-bis (p -Methyl-benzylidene) sorbitol, 1,3,2,4-bis (p-ethylbenzylidene) sorbitol, 1,3-p-chlorobenzylidene-2,4-p-methylbenzylidene) sorbitol, sodium bis (4-t -Butylphenyl) phosphate, sodium bis (4-t-methylphenyl) phosphate, potassium bis (4,6-di-t-butylphenyl) phosphate, sodium 2,2'-methylene-bis (4,6-di-) t-butylphenyl) phosphate, sodium 2,2′-ethylidene-bis (4,6-di-t-butylpheny ) Phosphate, and the like.

  The composition of the present invention may also contain conventionally used additives such as antioxidants, light stabilizers, heat stabilizers, colorants and the like.

  As described above, the composition of the present invention is obtained by melt blending components (A), (B), (C) and (D), and if necessary, components (E) and / or (F), or a masterbatch. Composition (I) can be prepared by melt blending with other polyolefin components, component (D) and / or component (F) if necessary. Any known mixing device equipped with a mixer such as a closed mixer or an extruder can be used. For example, a Banbury mixer or a single screw bus extruder or a twin screw Maris type or Werner type extruder can be used.

  The present invention also provides a final product, in particular a door trim comprising the above polyolefin composition.

  The practice and advantages of the present invention are illustrated in the following examples.

  These examples are for illustrative purposes only and do not limit the scope of the invention in any way.

The following analytical methods are used to evaluate the properties of the polymer composition.
Melt flow rate: Unless otherwise specified, measured according to ASTM-D1238, Condition L (ie 230 ° C., 2.16 kg load) [η] Intrinsic viscosity: measured at 135 ° C. in tetrahydronaphthalene Content of ethylene and butene: R. Spectroscopy Flexural modulus: ISO178
Tensile strength at break: ISO 527
Elongation at break: ISO 527
Notched Izod impact test: ISO180 / 1A
Shore A and D Hardness: ASTM-D2240
Glossiness

Ten rectangular test pieces (55 × 60 × 1 mm) of each polymer to be tested were produced by injection molding under the following conditions using an injection press / Batterenfeld BA500CD.
Screw speed: 120rpm
Back pressure: 10 bar
Mold temperature: 40 ℃
Melting temperature: 260 ° C
Injection time: 3 seconds
First residence time: 5 seconds
Second residence time: 5 seconds
Cooling time (after second residence time): 10 seconds

  The value of the injection pressure needs to be sufficient for the mold to be completely filled within the above time.

  The ratio of the light beam reflected from the surface of the measurement specimen was measured with a gloss meter at an incident angle of 60 °. The values shown in Table III correspond to the average gloss of 10 test pieces for each test polymer.

  The gloss meter to be used is a photometer Zane Toner ZGM1020 type or 1022 type with an incident angle set to 60 °. The measurement principle is described in ASTM-D2457. The apparatus is calibrated using a sample having a known gloss level.

Xylene soluble and insoluble fractions 2.5 g of polymer and 250 cm ³ of xylene are placed in a glass flask equipped with a freezer and a magnetic stirrer. The temperature is raised to the boiling point of the solvent over 30 minutes. The clear solution thus obtained is then placed under reflux and stirred for a further 30 minutes. The closed flask is placed in an ice-water bath for 30 minutes and then placed in a constant temperature water bath at 25 ° C. for another 30 minutes. The solid thus produced is filtered through a quick filter paper. A 100 cm ³ filtrate is placed in a pre-weighed aluminum container, which is heated on a hot plate under a stream of nitrogen to evaporate the solvent. The vessel is then placed in an 80 ° C. vacuum oven and waited until a constant weight is reached. The weight percent of polymer soluble in xylene at room temperature is then calculated.

  The weight percent of the polymer insoluble in xylene at room temperature is considered the crystallizable portion of the polymer. This value also substantially corresponds to the isotacticity index determined by extraction with boiling n-heptane, which by definition is the isotacticity index of polypropylene.

Heat shrinkage in the vertical and horizontal directions Using a 100 x 200 x 2.5 mm plate using an injection molding machine "Sandlet Series 7-190" (190 indicates that the clamping force is 190 tons) Mold.
The injection conditions are as follows.
Melting temperature = 250 ° C .;
Mold temperature = 40 ° C .;
Injection time = 8 seconds;
Residence time = 22 seconds;
Screw diameter = 55mm

The plate is measured with calipers 48 hours after molding. The shrinkage rate is given by the following equation.

Longitudinal shrinkage = (200−measured value) / 200 × 100
Lateral shrinkage = (100−measured value) / 100 × 100

In the formula, 200 is the length (mm) in the vertical direction of the plate measured immediately after molding.
100 is the horizontal length (mm) of the plate measured immediately after molding.

  The measured value is the length of the plate in the relevant direction.

Measurement of melting peak and melting enthalpy (ΔHm) by differential scanning calorimetry (DSC) The apparatus used is a Perkin Elmer Diamond DSC. The polymer sample is heated to 230 ° C. at a rate of 10 ° C./min and maintained in a nitrogen stream at 230 ° C. for 5 minutes, then cooled to 20 ° C. at a rate of 10 ° C./min and maintained at this temperature for 5 minutes. To crystallize the sample. The sample is then melted again to 230 ° C. at a heating rate of 10 ° C./min. This melting scan is recorded to obtain a thermogram from which the strongest peak temperature and melting enthalpy between 100-130 ° C. is read.

Preparation of Master Batch Composition (I) Three master batch compositions are prepared. The solid catalyst component used in the polymerization is a highly stereoselective Ziegler-Natta catalyst component supported on magnesium chloride as described in Example 5, lines 48-55 of European Patent EP 728769. Triethylaluminum (TEAL) is used as a cocatalyst and dicyclopentyldimethoxysilane (DCPMS) is used as an external donor.

  The solid catalyst component is contacted with TEAL and DCPMS at 12 ° C. for 24 minutes. The weight ratio between TEAL and the solid catalyst component and the weight ratio between TEAL and DCPMS are 20 and 10, respectively.

  This catalyst system is then prepolymerized in a suspension in liquid propylene at 20 ° C. for about 5 minutes and then charged to the first polymerization reactor.

Polymerization Polymerization is carried out continuously in two connected reactors with means for transferring the product from one reactor to the next reactor. The first reactor is a liquid phase reactor and the second reactor is a fluidized bed gas phase reactor. Component (A ^I ) is produced in the first reactor and component (B ^I ) is produced in the second reactor.

Component (A ^I ) is a propylene homopolymer, Component (B ^I ) is an ethylene / butene-1 copolymer.

  The temperature and pressure are kept constant throughout the reaction period. Hydrogen is used as an automatic molecular weight regulator.

  The gas phase (propylene, ethylene, butene, and hydrogen) is continuously analyzed by gas chromatography.

  Table I shows the polymerization conditions and the molar ratio of the reactants, and the composition of the resulting copolymer.

  The polymer particles exiting the second reactor are subjected to steam treatment to remove reactive monomers and volatile materials and then dried.

  The polymer particles are then placed on a rotating drum where 0.05 wt.% Paraffinic oil ROL / OB30 (density according to ASTM-D1298: 0.842 kg / l (20 ° C.), pour point of ASTM-D97: −10 ), 0.15 wt% Irganox (R) B215 (consisting of about 34% Irganox (R) 1010 and 66% Irgaphos (R) 168), and 0.04 wt% DHT-4A Mix with (hydrotalcite).

  Irganox 1010 described above is 2,2-bis [3-[, 5-bis (1,1-dimethylethyl) -4-hydroxyphenyl) -1-oxopropoxy] methyl] -1,3-propanediyl- 3,5-Bis (1,1-dimethylethyl) -4-hydroxybenzenepropanoate and Irgaphos 168 is tris (2,4-di-tert-butylphenyl) phosphite.

  The polymer particles are then extruded from a screw extruder under nitrogen at a melting temperature of 200-250 ° C.

  The characteristics of the polymer composition shown in Table II are obtained by measuring the polymer thus extruded.

Examples 1 and 2 and Comparative Example 1
Masterbatch compositions 1-3 produced as described above are extruded under the above conditions and mechanically mixed with the other ingredients. The ratio of the polyolefin component used in these examples is the amount of components A), B), C), E) of the final composition obtained by collecting the contributions of the polyolefin component, and the correlation of the MFR logarithm described above. Table III shows the calculated MFRL values for A).

The following polyolefin components are used.
PP: a propylene homopolymer having an MFRL value of 2000 g / 10 min and a solubility in xylene at room temperature of 2.3% by weight;
EG8407: Engagement 8407 as described above;
ENR7467: Engagement ENR7467 as described above;
Heco: 67% by weight propylene homopolymer having an MFRL value of 9 g / 10 min and a solubility in xylene at room temperature of 2% by weight;
Polyolefin composition comprising an ethylene / propylene copolymer comprising 33% by weight, 38% by weight of ethylene, having a solubility in xylene at room temperature of 84% by weight and an intrinsic viscosity of the xylene soluble fraction of 7.5 dl / g Things (heterophase blend).

  EG8407 and ENR7467 together constitute component C) of the composition of the present invention.

In addition to the above polyolefin components, talc and nucleating agent corresponding to components D) and F) , respectively, are added.

  The talc D) used is Neotalc UNI from Neotalc Industries.

  The amount of D) is also shown in Table III.

Sodium-2,2′-methylene-bis (4,6-di-t-butylphenyl) -phosphate (trade name NA11, manufactured by Asahi Denka Kogyo) is used as the nucleating agent F 1 ). The amount of F) in the compositions of all examples is 0.1 parts by weight with respect to 100 parts by weight of A) + B) + C) + D) + E).

The properties of the final composition thus obtained are shown in Table IV.
For comparison, Tables III and IV are blended with the same ingredients as in Examples 1 and 2, but with a MFRL of 15 g / 10 (as weight percent)
A ¹⁾ 74% of a propylene homopolymer a is 1.7% solubility in xylene at room temperature MFRL value at 20 g / 10 min;
B ¹ ) a copolymer of ethylene and butene-1 containing 26%, 21% butene-1 and having a solubility in xylene at room temperature of 51% and an xylene-soluble fraction having an intrinsic viscosity of 1.2 dl / g The data of the composition obtained using the masterbatch composition of the comparative example 1 which consists of are shown.

Claims (10)

A) 40-75% by weight of a polypropylene component consisting of a propylene homopolymer, comprising at least 85% by weight of propylene,
For each polymer component of the n types of polymer components constituting the polypropylene component, MFR (MFR ¹ ,... MFR ⁿ ) measured under ASTM-D1238, condition L (230 ° C., 2.16 kg load) , respectively ,
The weight ratio (WA ¹ / W ^total ,... WA ⁿ / W ^total ) obtained by dividing the weight of each polymer component (WA ¹ ..., WA ⁿ ) by the total weight (W ^total ) of the polypropylene component was obtained,
Following formula:
ln MFR ^A = [WA ¹ / W ^total ] × ln MFR ¹ + ... + [WA ⁿ / W ^total ] × ln MFR ⁿ
Shown in, MFR is a natural logarithm and MFR values calculated from the total (ln MFR ^A) of the product of the weight ratio ^(MFR A) is 90 g / 10 min or more,
Having a solubility in xylene at room temperature of less than 20% by weight;
B) A copolymer of 3 to 20% by weight of ethylene and one or more C ₄ -C ₁₀ -α-olefins, comprising 15 to 35% by weight of C ₄ -C ₁₀ -α-olefins, and xylene at room temperature Having an intrinsic viscosity greater than 50% by weight and an intrinsic viscosity of the xylene soluble fraction of 2.5-4 dl / g;
C) 10 to 35% by weight of one or more elastomeric or plastomer based polymers different from B) having a Shore A hardness of 90 points or less;
D) 5-25% by weight mineral filler, selected from the group consisting of talc, CaCO ₃ , silica, mica, wollastonite (CaSiO ₃ ), clay, diatomaceous earth, titanium oxide, zeolite. With materials;
E) 0.5-5% by weight of a copolymer comprising ethylene and propylene different from C) having an ethylene content of 20-70% by weight and a solubility in xylene at room temperature of greater than 50% by weight; A polyolefin composition comprising an xylene-soluble fraction having an intrinsic viscosity of 4-9 dl / g,
A composition wherein the amount of A), B), C), D) and E) is a value relative to the total weight of A) + B) + C) + D) + E).
The polyolefin composition according to claim 1, further comprising 0.01 to 0.5 parts by weight of a nucleating agent F) with respect to 100 parts by weight of A) + B) + C) + D ) + E). MFRL value polyolefin composition according to claim 1 which is the 10 g / 10 minutes or more. The amount of fraction (XI) insoluble in xylene at room temperature of component B) satisfies the following formula (XI) <1.14 × B ₂ −34
(Wherein B ₂ is the amount of ethylene in component B) expressed as a percentage by weight relative to the weight of component B))
The polyolefin composition according to claim 1. According to any one of claims 1 to 4 A manufacturing method A ^I) of 60 to 85 wt% of the polyolefin composition, a propylene homopolymer chromatography or Ranaru polypropylene component, at least 85 wt% Contains propylene, has an MFRL value of 20 g / 10 min or more as measured under ASTM-D1238, Condition L (230 ° C., 2.16 kg load), and has a solubility in xylene at room temperature of less than 20% by weight. ;
B ^I ) a copolymer of 3-20% by weight of ethylene and one or more C ₄ -C ₁₀ -α-olefins, comprising 15-35% by weight of C ₄ -C ₁₀ -α-olefins, at room temperature Having a solubility in xylene of greater than 50% by weight and an intrinsic viscosity of the xylene soluble fraction of 2.5-4 dl / g;
Only including,
The master batch composition in which the A ^I ) component becomes a part of the A) component and the B ^I ) component becomes the B component, the remainder of the A) component, the C) component, and the E) component. another method for manufacturing the polyolefin component and the melt-blending Lupo Li olefin composition from that comprising.   The method according to claim 5, wherein the master batch composition has an MFRL value of 2 g / 10 min or more.   The method according to claim 5, wherein ΔHm of the DSC melting peak detected at a temperature between 100 and 130 ° C. of the masterbatch composition is 1 J / g or more. It said masterbatch composition The method of claim 5 obtained by polymerization in the presence of a Ziegler-Natta catalyst supported on MgCl _2. A product comprising the polyolefin composition according to any one of claims 1 to 4 .   The product of claim 9 in the form of a door trim.