JPH11209532A - Propylene polymer composition and injection molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a propylene polymer composition having well-balanced impact resistance and hardness and excellent rigidity and toughness. SOLUTION: This propylene polymer composition is composed of (A) 40-90 wt.% of a propylene polymer having an MFR(melt flow rate)(230 deg.C, 2.16 kg load) of 0.1-1,000 g/10 min and composed of 0.1-20 wt.% of a component soluble in decane at 64 deg.C and 99.9-80 wt.% of a component insoluble in decane at 64 deg.C and having a pentad isotacticity of 0.96-0.99, (B) 5-35 wt.% of an ethylene.α- olefin copolymer composition composed of 100 pts.wt. of a copolymer of ethylene and a 4-20C α-olefin, having a density of 0.860-0.900 g/cm<3> and a melt flow rate of 0.05-50 g/10 min (190 deg.C, 2.16 kg load) and satisfying the formula Tm<400×d-250, (in the formula, Tm is the maximum peak temperature of an endothermic curve measured by a differential scanning calorimeter and (d) is density) and 0.001-5 pts.wt. of a crystal nucleation agent and (C) 5-25 wt.% of an inorganic filler.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a propylene polymer composition capable of forming a molded article having excellent rigidity and impact resistance and also having excellent toughness, and an injection molded article thereof.

[0002]

TECHNICAL BACKGROUND OF THE INVENTION Polyolefins, polyesters,
Since thermoplastic resins such as polyamide and polyacetal have excellent workability, chemical resistance, electrical properties, mechanical properties, etc., they can be used for injection molded products, hollow molded products, films,
It is processed into sheets and used for various purposes. However, impact resistance may not be sufficient for some applications.

As a method for improving the impact resistance and the like of a molded article made of such a thermoplastic resin, for example, a modifier such as a low-crystalline ethylene / α-olefin copolymer is blended with the thermoplastic resin. Methods for making compositions are known. However, in the conventional modifier, the balance between the impact resistance and the hardness may not be good depending on the use.

The inventors of the present invention have conducted intensive studies in view of such circumstances, and have found that an ethylene copolymer composition comprising a specific ethylene / α-olefin copolymer and a crystal nucleating agent has been modified into a thermoplastic resin. It has been found that a composition excellent in the balance between impact resistance and hardness and excellent in rigidity and toughness can be obtained by using as a filler and adding an inorganic filler to complete the present invention. Was.

[0005]

An object of the present invention is to provide a propylene polymer composition and a propylene polymer composition capable of forming a molded article having an excellent balance between impact resistance and hardness and excellent rigidity and toughness. The purpose of the present invention is to provide an injection-molded product comprising:

[0006]

SUMMARY OF THE INVENTION The propylene polymer composition according to the present invention comprises: [A] (A-1) having a melt flow rate at 230 ° C. and a load of 2.16 kg in the range of 0.1 to 1000 g / 10 minutes; (A-2) 64 ° C decane-soluble component; 0.1 to 20% by weight and 64 ° C
(A-3) a propylene polymer having a pentad isotacticity of the decane-insoluble component in the range of 0.96 to 0.99, which is in the range of 0.96 to 0.99; (B) (B-1) a copolymer of ethylene and an α-olefin having 4 to 20 carbon atoms, wherein (i) a density of 0.860 to 0.900 g / cm ³ (Ii) the melt flow rate at 190 ° C. under a load of 2.16 kg is in the range of 0.05 to 50 g / 10 minutes; and (iii) the temperature at the maximum peak position in the endothermic curve measured by a differential scanning calorimeter. (Tm (° C)) and density (d (g / c
m ³ )), an ethylene / α-olefin copolymer satisfying the following relationship: Tm <400 × d-250; 100 parts by weight; (B-2) a crystal nucleating agent; 0.001 to 5 parts by weight An ethylene / α-olefin copolymer composition comprising:
5 to 35% by weight, and [C] an inorganic filler; 5 to 25% by weight ([A], [B], [C]
Is 100% by weight).

Further, an injection-molded article according to the present invention is characterized by comprising the propylene-based polymer composition.

[0008]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the propylene polymer composition and the injection molded article according to the present invention will be specifically described.

The propylene polymer composition according to the present invention comprises an ethylene / α-olefin copolymer composition comprising a propylene polymer (A), an ethylene / α-olefin copolymer and a crystal nucleating agent. B) and an inorganic filler (C).

First, each component forming the polypropylene copolymer composition according to the present invention will be described. [Propylene-based polymer (A)] The propylene-based polymer used in the present invention comprises a specific decane-insoluble component at 64 ° C and 64 ° C.
A propylene polymer having a decane-soluble component.

The propylene polymer (A) has a melt flow rate (MFR: 230 in accordance with ASTM D1238).
° C, measured under a load of 2.16 kg) is 0.1 to 1000 g / 10
Min, preferably 0.1 to 500 g / 10 min, more preferably 1 to 500 g / 10 min.

Further, such a propylene-based polymer (A) contains (1) a decane-insoluble component at 64 ° C. of 99.9 to 80%.
(2) 0.1 to 20% by weight, preferably 0.1 to 20% by weight of a decane-soluble component at 64 ° C in an amount of 99.9 to 82% by weight, more preferably 99.9 to 85% by weight. It is contained in an amount of 18% by weight, more preferably 0.1 to 15% by weight.

In the present invention, the propylene-based polymer 6
The 4 ° C decane-soluble component and the insoluble component are separated as follows. That is, two samples are placed in 500 ml of decane.
g and 0.05 g of a stabilizer and stirred at 145 ° C. until melting. After melting, the melting temperature was adjusted to 64 ° C., and the mixture was stirred at 64 ° C. for 2 hours.
The mixture is filtered with a filtration filter heated to. By such an operation, it is separated into a filtrate side (a component soluble in decane at 64 ° C.) and a precipitate (a component insoluble in decane at 64 ° C.). The precipitate was again added to 500 ml of decane together with a stabilizer, and stirred at 145 ° C. until it was melted. At the time of melting, the melting temperature was adjusted to 64 ° C.
After stirring at 2 ° C. for 2 hours, the mixture may be filtered through a filter heated to 64 ° C.

[0014] 64 The ° C. decane insoluble component present invention, 64 ° C.-decane-insoluble component of the propylene polymer (A) has, pentad isotacticity (mm
mm fraction) is 0.96 to 0.99, preferably 0.96.
It is in the range of 5 to 0.99, more preferably 0.97 to 0.99. Pentad isotacticity (mm
mm fraction) is P _mmmm in the ¹³ C-NMR spectrum.
(Absorption intensity derived from the methyl unit of the third unit in the buoy having five units of propylene units consecutively and isotactically bonded) and P _w (the absorption intensity derived from all the methyl groups of the propylene unit) are represented by the following formulas. Desired.

Mmmm fraction = P _mmmm / P _w ¹³ C-NMR measurement is performed, for example, as follows. That is, 0.35 g of a sample is dissolved by heating in 2.0 ml of hexachlorobutadiene. This solution was filtered through a glass filter (G2), and then deuterated benzene 0.5.
ml and add to an NMR tube with an inner diameter of 10 mm. Then, using a GX-500 type NMR measuring device manufactured by JEOL Ltd., ¹³ C-NMR is measured at 120 ° C. The number of integration is 10,000 or more.

In the present invention, the propylene-based polymer (A) is insoluble in decane at 64 ° C. as long as it satisfies the above-mentioned characteristics. Or a copolymer of

Other olefins include, for example, ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene,
1-octene, 1-decene, 1-dodecene, 1-hexadecene,
Α-olefins such as 4-methyl-1-pentene; vinyl compounds such as vinylcyclopentene, vinylcyclohexane and vinylnorbornane; vinyl esters such as vinyl acetate; unsaturated organic acids such as maleic anhydride and derivatives thereof.

Of these, it is desirable to use a homopolypropylene. The polypropylene component forming the 64 ° C. decane-insoluble component is, for example, 3-methyl-1
-Butene, 3,3-dimethyl-1-butene, 3-methyl-1-pentene, 3-methyl-1-hexene, 3,5,5-trimethyl-1-hexene, vinylcyclopentene, vinylcyclohexane, vinylnorbornane, etc. May be contained, for example, as a prepolymer formed by prepolymerization. When such a prepolymer is contained in a small amount, for example, about 1 ppm to 3% by weight, This is preferable because the crystallization speed increases.

64 ° C. Decane-Insoluble Component The propylene polymer (A) has a decane-soluble component at 64 ° C.
The rubber component of the propylene-based polymer (A), which usually comprises a propylene / ethylene copolymer component and a very small amount of atactic polypropylene, but as long as the object of the present invention is not impaired, the olefins and It may contain units derived from polyenes.

The propylene-based polymer (A) may be composed of the above-mentioned 64 ° C. decane-insoluble component and the 64 ° C. decane-soluble component, and the preparation method is not particularly limited. For example, a crystalline propylene polymer (A-1) such as a homopolypropylene manufactured separately in advance, and a low crystalline or amorphous propylene polymer (A-2) such as a propylene / ethylene copolymer. Is blended to form a propylene-based polymer (A) composed of the specific 64 ° C decane-insoluble component and the 64 ° C decane-soluble component as described above. Further, such a propylene-based polymer (A)
Is used when producing a polypropylene-based resin composition together with other components (B) and (C).
(A-1) and a low-crystalline or amorphous propylene-based polymer (A
-2) may be formed as a blend or may be formed before blending with other components.

The propylene-based polymer (A) (for example, a propylene-based block copolymer) may be produced by forming the above-mentioned 64 ° C. decane-insoluble component and 64 ° C. decane-soluble component by polymerization.

The propylene-based block copolymer produced by such polymerization is further added to the above-mentioned crystalline propylene-based polymer (A-1) and / or a low-crystalline or amorphous propylene-based polymer (A-2). ) May be added.

In the present invention, the propylene block copolymer as described above, the crystalline propylene polymer (A-1)
, Low crystalline or amorphous propylene polymer (A-2)
Can be appropriately used in combination of two or more.

In the present invention, if the propylene-based polymer (A) satisfying the above conditions can be obtained, the propylene-based block copolymer or the crystalline propylene-based polymer (A- 1) The method for producing the low-crystalline or non-crystalline propylene-based polymer (A-2) is not particularly limited, but is preferably produced as follows.

When the propylene polymer (A) is directly produced by polymerization, it is preferable to use an olefin polymerization catalyst such as a titanium catalyst. When the propylene-based polymer (A) is prepared by blending, a blend raw material such as a crystalline propylene-based polymer (A-1) or a low-crystalline or amorphous propylene-based polymer (A-2) is used. The polymer is preferably produced using the olefin polymerization catalyst.

[Ethylene / α-olefin copolymer composition (B)] The ethylene / α-olefin copolymer composition (B) used in the present invention is an ethylene / α-olefin copolymer (B-1). ) And a nucleating agent (B-2).

Ethylene / α-olefin copolymer (B-1) The ethylene / α-olefin copolymer (B-1) used in the present invention comprises ethylene and an α-olefin having 4 to 20 carbon atoms. Is a random copolymer. Here, as the α-olefin having 4 to 20 carbon atoms, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1- Examples include tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, and the like.

Ethylene / α-olefin copolymer (B-1)
In the above, the constituent unit derived from ethylene is 55 to 99% by weight, preferably 65 to 98% by weight, more preferably 7 to 99% by weight.
0 to 96% by weight, having 4 to 20 carbon atoms
Is from 1 to 45% by weight, preferably from 2 to 35% by weight, more preferably from 4 to 3% by weight.
Desirably, it is present in a proportion of 0% by weight.

Composition of ethylene / α-olefin copolymer
Weighs about 200 mg of copolymer in a 10 mmφ sample tube.
Trial dissolved uniformly in 1 ml of hexachlorobutadiene
Charge ¹³The C-NMR spectrum was measured at a measurement temperature of 120 ° C.
Constant frequency 25.05 MHz, spectrum width 1500 Hz
 , Pulse repetition time 4.2 sec., Pulse width 6 μsec.
It is determined by measuring under constant conditions.

Such an ethylene / α-olefin copolymer has a density of 0.860 to 0.900 g / cm ³ , preferably 0.870 to 0.900 g / cm ³ , more preferably 0.870 to 0.990 g / cm ³ . The melt flow rate (MFR) at 190 ° C. under a load of 2.16 kg is 0.05 to 50 g / 10 min, preferably 0.1 to 40 g / 10 min, and more preferably 0.895 g / cm ^3. Is 1-2
The temperature (Tm (° C.)) and the density (d (g / cm ³ )) at the maximum peak position in the endothermic curve measured by a differential scanning calorimeter (DSC) are desirably within 0 g / 10 min. , Tm <400 × d-250, preferably Tm <450 × d-297, more preferably Tm <500 × d-344, and particularly preferably Tm <550 × d-391.

In the present invention, the density, MFR and Tm are measured as follows. Density density (g / cm ³ ) is measured with a density gradient tube after heat treating a strand obtained at the time of MFR measurement at 190 ° C. with a load of 2.16 kg at 120 ° C. for 1 hour, gradually cooling to room temperature over 1 hour, and then using a density gradient tube. did.

MFR MFR (g / 10 min) was measured at 190 ° C. and 2.16 k in accordance with ASTM D1238-65T.
Measured under g load conditions.

The temperature at the maximum peak position (Tm (° C.)) of the endothermic curve measured by Tm DSC is as follows.
The temperature was raised to 200 ° C. at 0 ° C./min, kept at 200 ° C. for 5 minutes, lowered to room temperature at 20 ° C./min, and then reduced to 10 ° C./min.
It is obtained from an endothermic curve when the temperature is raised in minutes. The measurement was performed using a DSC-7 type device manufactured by PerkinElmer.

Crystal nucleating agent (B-2) As the crystal nucleating agent, various conventionally known crystal nucleating agents can be used without any particular limitation. Among them, the following nucleating agents can be exemplified as preferred nucleating agents.

[0035]

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Wherein R ¹ is oxygen, sulfur or a hydrocarbon group having 1 to 10 carbon atoms, R ² and R ³ are hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, and R ² , R ³ may be different even in the same kind, R ² to each other, may have a ring by bonding R ³ s or R ² and R ^3, M is
It is a 1-3 valent metal atom, and n is an integer of 1-3. ) Specifically, sodium-2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate, sodium-2,2'-ethylidene-bis (4,6-di-t- (Butylphenyl) phosphate, lithium-2,2'-methylene-bis-
(4,6-di-t-butylphenyl) phosphate, lithium
-2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate, sodium-2,2'-ethylidene-bis (4-i
-Propyl-6-t-butylphenyl) phosphate, lithium-2,2'-methylene-bis (4-methyl-6-t-butylphenyl) phosphate, lithium-2,2'-methylene-bis (4
-Ethyl-6-t-butylphenyl) phosphate, calcium-bis [2,2'-thiobis (4-methyl-6-t-butylphenyl) phosphate], calcium-bis [2,2'-thiobis ( 4-ethyl-6-t-butylphenyl) phosphate]
, Calcium-bis [2,2'-thiobis- (4,6-di-t-butylphenyl) phosphate], magnesium-bis [2,2'-thiobis (4,6-di-t-butylphenyl) Phosphate], magnesium-bis [2,2'-thiobis- (4-t-
Octylphenyl) phosphate], sodium-2,
2'-butylidene-bis (4,6-di-methylphenyl) phosphate, sodium-2,2'-butylidene-bis (4,6-di-
(t-butylphenyl) phosphate, sodium-2,2'-
t-octylmethylene-bis (4,6-di-methylphenyl) phosphate, sodium-2,2'-t-octylmethylene-
Bis (4,6-di-t-butylphenyl) phosphate, calcium-bis- (2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate), magnesium-bis [2 ,
2'-methylene-bis (4,6-di-t-butylphenyl) phosphate], barium-bis [2,2'-methylene-bis (4,6
-Di-t-butylphenyl) phosphate], sodium
-2,2'-methylene-bis (4-methyl-6-t-butylphenyl)
Phosphate, sodium-2,2'-methylene-bis (4-
Ethyl-6-t-butylphenyl) phosphate, sodium (4,4'-dimethyl-5,6'-di-t-butyl-2,2'-biphenyl) phosphate, calcium-bis [(4,4 '-Dimethyl-6,6'-di-t-butyl-2,2'-biphenyl) phosphate], sodium-2,2'-ethylidene-bis (4-m-butyl-
6-t-butylphenyl) phosphate, sodium-2,
2'-methylene-bis (4,6-di-methylphenyl) phosphate, sodium-2,2'-methylene-bis (4,6-di-ethylphenyl) phosphate, potassium-2,2'-ethylidene -Bis (4,6-di-t-butylphenyl) phosphate,
Calcium-bis [2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate], magnesium-bis [2,2'-ethylidene-bis (4,6-di-t-butylphenyl) )
Phosphate], barium-bis [2,2'-ethylidene-
Bis (4,6-di-t-butylphenyl) phosphate],
Aluminum-tris [2,2'-methylene-bis (4,6-di-t-
Butylfel) phosphate] and aluminum-
Tris [2,2′-ethylidene-bis (4,6-di-t-butylphenyl) phosphate] and mixtures of two or more thereof can be exemplified. Particularly, sodium-2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate is preferred.

[0037]

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(Wherein R ⁴ is hydrogen or C 1 -C 1)
0 is a hydrocarbon group, M is a metal atom having 1 to 3 valences, and n is an integer of 1 to 3. Specifically, sodium-bis (4-t-butylphenyl) phosphate, sodium-bis (4-methylphenyl) phosphate, sodium-bis (4-ethylphenyl) phosphate,
Sodium-bis (4-i-propylphenyl) phosphate, sodium-bis (4-t-octylphenyl) phosphate, potassium-bis (4-t-butylphenyl) phosphate, calcium-bis (4-t- Butylphenyl) phosphate, magnesium-bis (4-t-butylphenyl) phosphate, lithium-bis (4-t-butylphenyl) phosphate, aluminum-bis (4-t
-Butylphenyl) phosphate and mixtures of two or more thereof. Especially sodium
-Bis (4-t-butylphenyl) phosphate is preferred.

[0039]

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(Wherein R ⁵ is hydrogen or C 1 -C 1)
0 hydrocarbon group. ) Specifically, 1,3,2,4-dibenzylidene sorbitol, 1,3-benzylidene-2,4-p-methylbenzylidene sorbitol, 1,3-benzylidene-2,4-p
-Ethylbenzylidene sorbitol, 1,3-p-methylbenzylidene-2,4-benzylidene sorbitol, 1,3-p-ethylbenzylidene-2,4-benzylidene sorbitol, 1,3-p
-Methylbenzylidene-2,4-p-ethylbenzylidene sorbitol, 1,3-p-ethylbenzylidene-2,4-p-methylbenzylidene sorbitol, 1,3,2,4-di (p-methylbenzylidene) sorbitol, 1,3,2,4-di (p-ethylbenzylidene) sorbitol, 1,3,2,4-di (pn-propylbenzylidene) sorbitol, 1,3,2,4-di (pi-propylbenzylidene) sorbitol 1,3,2,4-di (pn-butylbenzylidene) sorbitol, 1,3,2,4-di (ps-butylbenzylidene) sorbitol, 1,3,2,4-di (pt-butylbenzylidene) Sorbitol, 1,3,2,4-di (2 ', 4'-dimethylbenzylidene) sorbitol, 1,3,2,4-di (p-methoxybenzylidene) sorbitol, 1,3,2,4-di ( p-ethoxybenzylidene) sorbitol, 1,3-benzylidene-2-4-p-
Chlorbenzylidene sorbitol, 1,3-p-chlorobenzylidene-2,4-benzylidene sorbitol, 1,3-p-chlorobenzylidene-2,4-p-methylbenzylidene sorbitol, 1,3-p-chlorobenzylidene-2, 4-p-ethylbenzylidene sorbitol, 1,3-p-methylbenzylidene-2,4-p-
Chlorbenzylidene sorbitol, 1,3-p-ethylbenzylidene-2,4-p-chlorobenzylidene sorbitol and
Examples thereof include 1,3,2,4-di (p-chlorobenzylidene) sorbitol and a mixture of two or more of these. Particularly, 1,3,2,4-
Dibenzylidene sorbitol, 1,3,2,4-di (p-methylbenzylidene) sorbitol, 1,3,2,4-di (p-ethylbenzylidene) sorbitol, 1,3-p-chlorobenzylidene-
Preferred are 2,4-p-methylbenzylidene sorbitol, 1,3,2,4-di (p-chlorobenzylidene) sorbitol and mixtures of two or more thereof.

Examples of other nucleating agents include metal salts of aromatic carboxylic acids and aliphatic carboxylic acids.
Examples thereof include aluminum benzoate, aluminum pt-butylbenzoate, sodium adipate, sodium thiophenecarboxylate, and sodium pyrrolecarboxylate.

Ethylene / α-olefin copolymer composition
Preparation of Ethylene / α-Olefin Copolymer Composition (B) Used in the Present Invention
(B-1); 100 parts by weight of a polyolefin crystal nucleating agent (B-
2); 0.005 to 5 parts by weight, preferably 0.01 to 2 parts by weight.

Such an ethylene / α-olefin copolymer composition (B) may contain a weather-resistant stabilizer, a heat-resistant stabilizer, an antistatic agent, an anti-slip agent, an anti-slip agent, as long as the object of the present invention is not impaired. Blocking agent, anti-fogging agent, lubricant, pigment,
Additives such as dyes, plasticizers, antioxidants, hydrochloric acid absorbents, antioxidants and the like may be added as necessary. Also,
Small amounts of other synthetic resins can be blended without departing from the spirit of the present invention.

Such an ethylene / α-olefin copolymer composition (B) can be produced by any known method. For example, ethylene / α-olefin copolymer (B-1) ), A crystal nucleating agent for polyolefin (B-2), and other components to be added as desired, are obtained by melt-kneading using an extruder, a kneader or the like.

Further, such an ethylene / α-olefin copolymer composition can be blended with various thermoplastic resins as an impact modifier. [Inorganic filler (C)] Specific examples of the inorganic filler used in the present invention include natural silicic acids or silicates such as fine powder talc, kaolinite, calcined clay, vilophyllite, sericite, and wollastonite. Carbonates such as precipitated calcium carbonate, heavy calcium carbonate and magnesium carbonate, hydroxides such as aluminum hydroxide and magnesium hydroxide, oxides such as zinc oxide, zinc oxide and magnesium oxide, hydrous calcium silicate and hydrous silicate Powdered filler such as synthetic silicic acid or silicate such as aluminum, hydrous silicic acid, silicic anhydride, flake-like filler such as mica, basic magnesium sulfate whisker, calcium titanate whisker, aluminum borate whisker, sepiolite, PMF (Processed Mi
For example, fibrous fillers such as neral fiber, zonotolite, potassium titanate, and elestadite, and balun fillers such as glass balun and fly ash balun can be used. Two or more of the above-mentioned inorganic fillers may be used in combination.

In the present invention, talc is preferably used among these, and fine talc having an average particle size of 0.01 to 10 μm is particularly preferably used. The average particle size of talc can be measured by a liquid phase sedimentation method.

The inorganic filler, particularly talc, used in the present invention may be untreated or may be surface-treated in advance. Specific examples of the surface treatment include a chemical or physical treatment using a treating agent such as a silane coupling agent, a higher fatty acid, a fatty acid metal salt, an unsaturated organic acid, an organic titanate, a resin acid, or polyethylene glycol. Can be By using talc subjected to such a surface treatment, it is possible to obtain a polypropylene composition having excellent weld strength, paintability, and moldability.

In the present invention, together with such an inorganic filler, an organic filler such as high styrenes, lignin, and re-rubber can be used. [Preparation of propylene-based polymer composition] The propylene-based polymer composition according to the present invention comprises the propylene-based polymer (A) in an amount of 40 to 90% by weight, preferably 50 to 9% by weight.
0% by weight, more preferably 55 to 90% by weight, particularly preferably 55 to 85% by weight, ethylene (α) -α-
35% by weight, preferably 28% to 10% by weight, more preferably 26% to 10% by weight, particularly preferably 25% to 10% by weight of the olefin copolymer composition, It is contained in an amount of 25 to 10% by weight, preferably 20 to 5% by weight. The above (A), (B),
The total of (C) is 100% by weight.

The use of the propylene-based polymer composition of the present invention formed from the above-described components makes it possible to obtain a molded article having excellent impact resistance and rigidity and excellent toughness.

The propylene polymer composition according to the present invention is excellent in moldability because the propylene polymer (A) containing a rubber component having a low ethylene content is used. In particular, when used for injection molding, the molded article has excellent fluidity at the time of molding, so that an injection-molded article having a flow mark that is less conspicuous and excellent in appearance can be formed.

The propylene-based polymer composition according to the present invention may contain other resins and other thermoplastics, if necessary, in addition to the components described above, as long as the object of the present invention is not impaired. It may contain an elastomer, various additives, and the like.

For example, as other resins, a thermoplastic resin or a thermosetting resin can be used. Specifically, α-olefin homopolymers or copolymers such as poly 1-butene and the like, Copolymers of α-olefins and vinyl compounds, modified olefin polymers such as maleic anhydride-modified polypropylene, nylon, polycarbonate, ABS, polystyrene, polyvinyl chloride, polyphenylene oxide, petroleum resin, phenol resin, etc. it can.

Examples of other elastomers include olefin elastomers other than the above (B), that is, amorphous elastic copolymers containing olefin as a main component, olefin thermoplastic elastomers, and conjugated diene rubbers.

As additives, antioxidants, hydrochloric acid absorbers, heat stabilizers, light stabilizers, ultraviolet absorbers, lubricants, antistatic agents, flame retardants, pigments, dyes, dispersants, copper damage inhibitors,
Neutralizing agents, foaming agents, plasticizers, air bubble inhibitors, crosslinking agents, flow improvers such as peroxides, weld strength improvers, and the like can be used.

The propylene-based polymer composition according to the present invention is prepared by charging the above components simultaneously or sequentially into a Henschel mixer, a V-type blender, a tumbler blender, a ribbon blender, or the like, and kneading them. And obtained by melt-kneading with a single-screw extruder, a multi-screw extruder, a kneader, a Banbury mixer, or the like.

Among these, when equipment having excellent kneading performance such as a multi-screw extruder, a kneader, and a Banbury mixer is used, a high-quality propylene-based polymer composition in which each component is more uniformly dispersed can be obtained. Is preferred.

The propylene-based polymer composition according to the present invention can be molded into molded articles of various shapes by employing a known molding method without any particular limitation. Among these, it is preferable to mold into an injection molded product.

The injection molding of the propylene polymer composition is performed by
Usually at a resin temperature of 200 to 250 ° C. and usually 800 to 1400 kg / cm ^2, depending on the shape of the injection molded product obtained.
Of the injection pressure.

The obtained injection-molded article is excellent in impact resistance and rigidity, excellent in toughness, inconspicuous in flow marks, and excellent in appearance. The injection molded article of the propylene-based polymer composition according to the present invention can be used for a wide range of applications, such as housings, home appliances such as washing tubs, uniaxially stretched films, biaxially stretched films, and blown films. Such as film applications, sheet applications such as calender molding, extrusion molding, etc., container applications such as bags, retort containers, containers, etc., automotive interior applications such as trims, instrument panels, column covers, fenders, bumpers, side moldings, mudguards, mirror covers It can be suitably used for exterior applications of automobiles and general goods.

Among the above, applications that can effectively utilize characteristics that are excellent in rigidity, heat resistance, impact resistance, and toughness and excellent in appearance, such as fenders, bumpers, side moldings, mudguards, and mirror covers It can be suitably used as interior and exterior parts for automobiles, parts for home appliances such as housings and washing tubs, and materials for containers such as bags and containers.

[0061]

The use of the propylene polymer composition according to the present invention makes it possible to obtain a molded article having excellent rigidity and impact resistance and excellent toughness. Further, the propylene-based polymer composition according to the present invention is excellent in moldability, particularly in injection moldability, and can form an injection-molded article with inconspicuous flow marks.

[0062]

EXAMPLES Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.

In this specification, the physical properties of the composition were measured as follows. Flexural modulus (FM) According to ASTM C790, a 1/8 inch thick test piece was used, and the span was 51 mm and the bending speed was 20 mm /
It was measured under the condition of minutes.

Izod Impact Test (IZ) Measured at 23 ° C. using a 1/4 inch thick test piece (post notch) in accordance with ASTM D256.

Rockwell hardness (HR) According to ASTM D785, thickness 2 mm × length 120
The measurement was performed using a square plate having a size of 130 mm × 130 mm.

[0066]

Example 1 The melt flow rate (MFR ₂₃₀ ) at 230 ° C. under a load of 2.16 kg was 10 g / 10 min, the amount of decane-soluble component at 64 ° C. was 0.4% by weight, and the amount of decane-insoluble component at 64 ° C. was 99.6%.
Homopolypropylene (A-1) having a pentad isotacticity (mmmm fraction) of a decane-insoluble component of 0.9% by weight of 64% at 64 ° C .; 70 parts by weight, a density of 0.886 g / cm ³ and a temperature of 190 ° C. 2.
Melt flow rate (MFR ₁₉₀ ) at 16kg load is 4g / 10
Minute, ethylene-butene copolymer (b-1) having a temperature (Tm) at the maximum peak position of 71.8 ° C. in an endothermic curve measured by a differential scanning calorimeter, and Na-2,2′-methylene-bis ( 4,6-di
-t-butylphenyl) phosphate (crystal nucleating agent), wherein the nucleating agent is compounded in an amount of 0.2 part by weight with respect to 100 parts by weight of the ethylene / butene copolymer. (B-1); 20 parts by weight, and talc (trade name: Micellon, manufactured by Hayashi Kasei, average particle diameter: 1.4 μm);
Parts by weight were melt-kneaded at 200 ° C. to prepare a propylene-based polymer composition.

The obtained propylene polymer composition was subjected to a resin temperature of 200 ° C., an injection pressure of 1000 kg / cm ² and a mold temperature of 4
Injection molding was performed at 0 ° C. The flexural modulus, Izod impact test, and Rockwell hardness of the obtained molded product were measured. Table 1 shows the results.

[0068]

Example 2 In Example 1, the density was 0.887 g / cm ³ , 190 instead of the ethylene / butene copolymer composition (B-1).
Ethylene-octene copolymer having a melt flow rate (MFR ₁₉₀ ) at 4 ° C. and a load of 2.16 kg of 4 g / 10 min, and a temperature (Tm) at a maximum peak position of 83.8 ° C. in an endothermic curve measured by a differential scanning calorimeter ( b-2) and a nucleating agent,
Ethylene / octene copolymer composition (B-2) containing 0.2 parts by weight of a crystal nucleating agent per 100 parts by weight of ethylene / octene copolymer (b-2); 20 parts by weight was used. Except for the above, a propylene-based polymer composition was prepared in the same manner as in Example 1.

The obtained propylene polymer composition was injection molded in the same manner as in Example 1, and the flexural modulus, Izod impact test, and Rockwell hardness were measured. Table 1 shows the results.

[0070]

Example 3 The homopolypropylene (A-
1); 30 parts by weight, a melt flow rate (MFR ₂₃₀ ) at 230 ° C. under a load of 2.16 kg of 22 g / 10 min, a decane-soluble component at 64 ° C. of 10.8% by weight, and a decane-insoluble component at 64 ° C. of 89.2% A propylene block copolymer (A-2) having a pentad isotacticity (mmmm fraction) of 0.978% of a decane-insoluble component at 64 ° C. of 64% by weight; and 44 parts by weight of ethylene / butene copolymer used in Example 1. 16 parts by weight of the combined composition (B-1) and 10 parts by weight of talc used in Example 1 were melt-kneaded at 200 ° C. to prepare a propylene-based polymer composition.

The obtained propylene polymer composition was injection molded in the same manner as in Example 1, and the obtained molded product was measured for flexural modulus, Izod impact test, and Rockwell hardness. Table 1 shows the results.

[0072]

Comparative Example 1 The homopolypropylene (A-
1); 70 parts by weight, density 0.886g / cm ³ , 190 ℃, 2.16kg
Melt flow rate under load (MFR ₁₉₀ ) is 4g / 10min,
An ethylene / butene copolymer (b-1) having a temperature (Tm) at the maximum peak position of 71.8 ° C. in an endothermic curve measured by a differential scanning calorimeter; 20 parts by weight, and talc used in Example 1; Parts by weight were melt-kneaded at 200 ° C. to prepare a propylene-based polymer composition.

The obtained propylene polymer composition was injection molded in the same manner as in Example 1, and the obtained molded product was measured for flexural modulus, Izod impact test, and Rockwell hardness. Table 1 shows the results.

[0074]

Comparative Example 2 The homopolypropylene (A-
1); 70 parts by weight, density 0.887 g / cm ³ , 190 ° C, 2.16 kg
An ethylene / octene copolymer (b-2) having a melt flow rate under load of 4 g / 10 min and a temperature (Tm) at a maximum peak position of 83.8 ° C. in an endothermic curve measured by a differential scanning calorimeter; Parts and talc used in Example 1;
10 parts by weight were melt-kneaded at 200 ° C. to prepare a propylene-based polymer composition.

The obtained propylene polymer composition was injection molded in the same manner as in Example 1, and the obtained molded product was measured for flexural modulus, Izod impact test, and Rockwell hardness. Table 1 shows the results.

[0076]

Comparative Example 3 The homopolypropylene (A-
1); 80 parts by weight of the ethylene / octene copolymer (b)
-2) and 20 parts by weight were melt-kneaded at 200 ° C. to prepare a propylene-based polymer composition.

The obtained propylene polymer composition was injection-molded in the same manner as in Example 1, and the obtained molded product was measured for flexural modulus, Izod impact test, and Rockwell hardness. Table 1 shows the results.

[0078]

Comparative Example 4 Homopolypropylene (A-1); 40 parts by weight, propylene block copolymer (A-2); 44 parts by weight, ethylene / butene copolymer composition (B-1); 16 parts by weight Were melt-kneaded at 200 ° C. to prepare a propylene polymer composition.

The obtained propylene polymer composition was injection-molded in the same manner as in Example 1, and the obtained molded product was measured for flexural modulus, Izod impact test, and Rockwell hardness. Table 1 shows the results.

[0080]

[Table 1]

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Claims (2)

[Claims] 1. [A] (A-1) a melt flow rate at 230 ° C. under a load of 2.16 kg is in the range of 0.1 to 1000 g / 10 minutes, and (A-2) a decane-soluble component at 64 ° C .; 0.1-20% by weight and 64 ° C
(A-3) a propylene polymer having a pentad isotacticity of the decane-insoluble component in the range of 0.96 to 0.99, which is in the range of 0.96 to 0.99; (B) (B-1) a copolymer of ethylene and an α-olefin having 4 to 20 carbon atoms, wherein (i) a density of 0.860 to 0.900 g / cm ³ (Ii) the melt flow rate at 190 ° C. under a load of 2.16 kg is in the range of 0.05 to 50 g / 10 minutes; and (iii) the temperature at the maximum peak position in the endothermic curve measured by a differential scanning calorimeter. (Tm (° C)) and density (d (g / c
m ³ )), an ethylene / α-olefin copolymer satisfying the following relationship: Tm <400 × d-250; 100 parts by weight; (B-2) a crystal nucleating agent; 0.001 to 5 parts by weight An ethylene / α-olefin copolymer composition comprising:
5 to 35% by weight, and [C] an inorganic filler; 5 to 25% by weight ([A], [B], [C]
Is a total of 100% by weight). 2. An injection molded article comprising the propylene polymer composition according to claim 1.