JPH10168251A - Propylene polymer composition and molded product thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymer composition which has a high melt strength and excellent processability and also can be used for producing a product which is excellent in transparency, stiffness and impact resistance, and a molded product thereof, by preparing a composition which comprises a propylene polymer, an ethylene polymer and a random copolymer of ethylene and an α-olefin. SOLUTION: This composition comprises (A) 40 to 96wt.% propylene polymer having a MFR (230 deg.C) of 0.01 to 20 and a loss tangent of 1.05 to 5.8, (B) 2 to 30wt.% ethylene polymer having a density of 0.905 to 0.950 and a MFR (190 deg.C) of 0.001 to 15 and (C) 2 to 30wt.% random copolymer of ethylene and an α-olefin having a density less than 0.891 and a MFR (190 deg.C) of 0.001 to 15. It is desirable that component A contains a high molecular weight component having a limiting viscosity of 8 to 30dl/g in an amount of 0.1 to 20wt.%, units derived from ethylene in an amount of 0.001 to 5 mole and a component soluble in decane at 64 deg.C in an amount of 0.1 to 25wt.%. It is also desirable that the difference in density between component B and component C is 0.045 to 0.087.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a propylene-based polymer composition having excellent transparency, excellent rigidity and impact resistance, high melt tension and excellent moldability, and a molded article thereof.

[0002]

BACKGROUND OF THE INVENTION Crystalline propylene polymers are excellent in rigidity, hardness, heat resistance and the like, and can be easily formed into a desired shape by various molding methods such as injection molding, calender molding and extrusion molding. Wider range of applications than conventional products because they are possible and inexpensive, such as housing for home appliances, films or sheets, containers, automotive interior applications, automotive exterior applications such as fenders, bumpers, side moldings, mudguards, mirror covers, and general miscellaneous goods Widely used for applications.

Since this crystalline propylene polymer is inferior in impact resistance, when it is conventionally used for the above-mentioned applications, the propylene polymer is generally added to polyethylene or rubber components such as polyisobutylene, Polybutadiene, amorphous or low-crystalline ethylene / propylene copolymer (EPR), etc. are blended.

In order to obtain a propylene-based polymer composition having sufficiently improved impact resistance by adding such a rubber component, it is necessary to add a large amount of a rubber component or to use a rubber component having a lower density. . However, when a large amount of a rubber component is contained in the propylene-based polymer composition, there is a problem that rigidity is reduced. Also, when a low-density rubber component is blended with the propylene-based polymer, the transparency of the propylene-based polymer composition may be reduced.

The present inventors have studied such a propylene-based polymer composition, and found that the angular velocity-dependent loss tangent ratio (tan δ _0.1 / tan δ ₁₀₀ ) measured as a propylene-based polymer, particularly with a melt viscoelastic apparatus, is high. A propylene-based polymer composition formed by using a propylene-based polymer as small as 1.05 to 5.8 and two types of ethylene-based polymers having different densities in a specific quantitative ratio has a high rigidity and a high impact resistance. And excellent transparency. Further, when the propylene polymer contains a high molecular weight component of [η] = 8 to 30 dl / g or more, and the high molecular weight component contains a trace amount of units derived from ethylene, the propylene polymer composition The present inventors have found that a product can exhibit even more excellent rigidity and impact resistance, and have completed the present invention.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a propylene polymer composition which is excellent in transparency, rigidity and impact resistance, has a high melt tension and excellent moldability, and a molded article thereof. .

[0007]

SUMMARY OF THE INVENTION The propylene polymer composition according to the present invention comprises: (A) (1) a melt flow rate (MFR) measured at 230 ° C. under a load of 2.16 kg of 0.01 to 20 g / 10 min. (2) angular velocity dependent loss tangent tan δ _0.1 measured at 200 ° C. and angular velocity ω = 10 ⁻¹ rad / sec;
° C, angular velocity dependent loss tangent measured at angular velocity ω = 10 ² rad / sec Loss tangent ratio to loss tangent tanδ ₁₀₀ (tanδ _0.1 / tanδ
₁₀₀ ) is from 1.05 to 5.8, and the propylene-based polymer 4
And 0 to 96 wt%, (B) (1) Density d ₁ is ^{0.905~0.950g / cm 3, (2)} 190 ℃, melt flow rate measured under a 2.16kg load (MFR ) Is 0.001 to 15 g / 10
(C) (1) a density d ₂ of less than 0.891 g / cm ³ ,
(2) An ethylene / α-olefin random copolymer 2 having a melt flow rate (MFFR) measured at 190 ° C. under a load of 2.16 kg of 0.001 to 15 g / 10 min.
30% by weight.

As described above, the propylene polymer (A) used in the present invention has (1) an MFR of 0.01 to 20 g.
/ 10 min, (2) the loss tangent ratio (tan [delta _0.1 / tan [delta ₁₀₀₎
Is from 1.05 to 5.8, and further contains (3) a unit derived from ethylene in an amount of 0.001 to 5 mol%, and (4) a decane-soluble component at 64 ° C. of 0.1 to 25 mol%. It is desirable to contain it in an amount of% by weight.

The propylene polymer (A) used in the present invention desirably contains a high molecular weight component having an intrinsic viscosity [η] of 8 to 30 dl / g in an amount of 0.1 to 20% by weight. In the present invention also the ethylene-based polymer and the density d ₁ of (B), the difference between the density d ₂ of the ethylene · alpha-olefin random copolymer _{(C) (d 1 -d 2} ) is 0.045～
It is desirably 0.087 g / cm ³ .

The present invention also provides a blow molded product, a film or sheet, and an injection molded product comprising the propylene polymer composition as described above.

[0011]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the propylene polymer composition according to the present invention will be described in detail. In the present invention, the term "polymerization" may be used in a broad sense including not only homopolymerization but also copolymerization, and the term "polymer" refers to not only homopolymers but also copolymers. May be used in a broad sense that includes

The propylene polymer composition according to the present invention comprises a propylene polymer as shown below and two types of ethylene polymers. Each of these components will be described.

(A) Propylene Polymer In the present invention, a propylene polymer (A) having the following properties (1) and (2) is used when forming a propylene polymer composition. . (1) The melt flow rate (MFR: ASTM D1238) measured at 230 ° C. under a load of 2.16 kg is 0.1%.
01 to 20 g / 10 min, preferably 0.01 to 18 g
g / 10 minutes, and more preferably 0.01 to 15 g / 10 minutes. (2) Angular velocity dependent loss tangent tanδ _0.1 measured at 200 ° C. and angular velocity ω = 10 ⁻¹ rad / sec, and angular velocity dependent loss tangent measured at 200 ° C. and angular velocity ω = 10 ² rad / sec.
loss tangent ratio of _{tanδ 100 (tanδ 0.1 / tanδ 100} ) is 1.
05 to 5.8, preferably 1.05 to 5.5, more preferably 1.05 to 5.0.

The angular velocity dependent loss tangent as described above can be measured using a melt viscoelasticity measuring device. Specifically, the propylene-based polymer is 2 mm thick and has a radius of 12.
It is formed into a 5 mm disc-shaped sheet, and the sheet is formed into a flat disc and a cone-shaped plate (with a radius of 12.
5 mm), and the plate is rotated at the above frequency (angular velocity ω) at 200 ° C. and measured under a constant strain.

The propylene polymer used in the present invention has a loss in melt viscoelasticity measured at a low speed (ω = 10 ^-1 rad / sec) and a high speed (ω = 10 ² rad / sec) as described above. It is characterized in that the tangent ratio (tan δ _0.1 / tan δ ₁₀₀ ) is as small as 1.05 to 5.8.

As described above, the loss tangent ratio (tanδ _0.1 / tanδ)
_A propylene-based polymer having a small value of ₁₀₀ ) is extremely excellent in rigidity. Even if the rigidity of the propylene-based polymer is lower than that before kneading by kneading with an ethylene-based polymer as described later, a composition showing sufficient rigidity for practical use. Things can be formed.

The propylene polymer having the above-mentioned loss tangent ratio can be produced by, for example, a multistage polymerization as described below. And usually about 6 to 10.

The propylene polymer (A) used in the present invention is characterized by having a low loss tangent ratio and containing a high molecular weight component, and in particular, has an intrinsic viscosity [η] (1
(Measured in decahydronaphthalene at 35 ° C) is 8 to 30 dl /
g preferably a high molecular weight component of 8 to 25 dl / g,
It is desirable that it be contained in an amount of 0.1 to 20% by weight, preferably 0.1 to 15% by weight.

When the propylene polymer (A) contains such a high molecular weight component, the propylene polymer composition of the present invention exhibits higher rigidity. The propylene polymer (A) used in the present invention has the above properties (1) and
In addition to (2), it is preferable to further satisfy the following properties (3) and (4). (3) 0.001 to 5 mol% of units derived from ethylene
Preferably 0.001 to 4 mol%, more preferably 0.0
(4) 0.1 to 25% by weight, preferably 0.1 to 20% by weight, more preferably 0.1 to 15% by weight of a decane-soluble component at 64 ° C. It is contained in the amount.

The unit derived from ethylene (3) is desirably contained in a high molecular weight component having a [η] of 8 to 30 dl / g in the propylene-based polymer. When the high molecular weight component of the propylene-based polymer contains the above-mentioned units derived from ethylene, a propylene-based polymer composition exhibiting particularly excellent impact resistance can be formed.

The amount of the decane-soluble component at 64 ° C. can be determined as follows. About 2 g of sample (propylene polymer) in about 500 ml of decane in a glass double tube thermostat
Are thoroughly weighed and completely dissolved by stirring at 140 ° C. for about 1 hour. Thereafter, the temperature of the solution was gradually lowered to 64 ° C. with stirring, and after the temperature of the solution became constant,
It can be obtained by continuing stirring all day and night, filtering out the precipitated decane-insoluble portion with a glass filter, and drying and weighing the filtrate.

The decane-insoluble component at 64 ° C. is obtained by completely dissolving the decane-insoluble portion (powder) collected by filtration in about 500 ml of decane at about 140 ° C. and reprecipitating in excess acetone. The decane-insoluble component obtained by filtration is dried in a vacuum drier at about 80 ° C. under reduced pressure for 24 hours to obtain.

The decane-soluble components at 64 ° C. are usually a rubber component and an atactic polypropylene component in a propylene-based polymer. The propylene polymer used in the present invention is desirably highly crystalline. Specifically, the crystallinity (stereoregularity) of a decane-insoluble component at 64 ° C. of the propylene polymer is measured. be able to.

It is desirable that the crystallinity of the decane-insoluble component at 64 ° C. measured by X-ray diffraction is 60% or more, preferably 65% or more, and more preferably 65 to 95%.

The pentad isotacticity value (mmmm fraction) [M ₅ ], which is an index of stereoregularity, is usually measured for a decane-insoluble component at 64 ° C. and a boiling heptane-insoluble component. 0.99, preferably 0.9
Desirably, it is 7 to 0.99.

Pentad isotacticity [M ₅ ]
, The peak intensity ratio in ¹³ C-NMR spectra [P
mmmm] / [Pw]. [Pmmmm] is the methyl group peak intensity of the third unit in the five isotactic bond chains of propylene units, and [Pw] is the methyl group peak intensity of all propylene units.

Further density of the propylene based polymer (A) used in the invention is preferably 0.885~0.91g / cm ³ preferably from 0.895 to 0.910 g / cm ^3. In the present invention, if the above characteristics are satisfied,
The propylene-based polymer (A) can be used without any particular limitation. For example, homopolypropylene, a copolymer of propylene with a small amount of another α-olefin can be used. The copolymer may be a random copolymer or a block copolymer.

Other α-olefins include, for example, ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl
1-pentene, 3-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene and the like. Two or more of these may be copolymerized. Of these, ethylene is preferred.

The propylene-based polymer may contain a very small amount of units derived from other monomers as long as the object of the present invention is not impaired. Examples of such other monomers include styrene and vinylcyclopentene. , Vinyl cyclohexane, vinyl compounds such as vinyl norbornane,
Vinyl esters such as vinyl acetate, unsaturated organic acids such as maleic anhydride or derivatives thereof, conjugated dienes, dicyclopentadiene, 1,4-hexadiene, dicyclooctadiene, methylene norbornene, 5-ethylidene-2-norbornene, etc. Non-conjugated polyenes and the like can be mentioned.

The propylene polymer used in the present invention may be a branched olefin such as 3-methyl-1-butene, 3,3-dimethyl-1-butene, 3-methyl-1-pentene,
Ethyl-1-pentene, 4-methyl-1-pentene, 3-methyl-1
-Hexene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 3,5 Homopolymer or copolymer such as 1,5-trimethyl-1-hexene, vinylcyclopentane, vinylcyclohexane, vinylcycloheptane, vinylnorbornane, allylnorbornane, styrene, dimethylstyrene, allylbenzene, allyltoluene, allylnaphthalene, vinylnaphthalene, etc. The coalescence may be contained as a prepolymer. Of these, 3-methyl
1-butene and the like are preferred. It is considered that the prepolymer derived from such a branched olefin acts as a nucleating agent for the propylene-based polymer.

In the present invention, the propylene-based polymer (A) is preferably a homopolypropylene or a random copolymer of propylene and a very small amount of ethylene as specified in the above (3), particularly preferably the random copolymer. Is preferred.

The method for producing the propylene-based polymer (A) is not particularly limited as long as it satisfies the above-mentioned properties. For example, the propylene-based polymer (A) may be produced by multistage polymerization of propylene using a catalyst for producing highly stereoregular polypropylene as described later. Obtainable.

In the present invention, each of the following steps may be carried out by a gas phase polymerization method or a liquid phase polymerization method such as a solution polymerization method or a suspension polymerization method. Further, the polymerization may be performed in any of a batch system, a semi-continuous system, and a continuous system. Each stage may be divided into a plurality of polymerization vessels, for example, 2 to 10 polymerization vessels.

As the polymerization medium, inert hydrocarbons may be used, and liquid propylene may be used as the polymerization medium. The polymerization conditions in each step are such that the polymerization temperature is about -50 to 2
00 ° C., preferably in the range of about 20-100 ° C., and the polymerization pressure is normal pressure to 100 kg / cm ^2, preferably about 2-50 kg / c
It is appropriately selected within the range of m ² G.

When propylene is subjected to multi-stage polymerization using the above-mentioned catalyst, propylene and other monomers as described above may be used at any stage or all stages as long as the object of the present invention is not impaired. May be copolymerized.

For example, in the first step, a polymer, preferably the above-mentioned high molecular weight component is produced, and in the presence of the obtained polymer,
The propylene-based polymer (A) can be formed by performing the second or higher stage polymerization under different polymerization conditions. Specifically, propylene is polymerized in the presence of a catalyst for producing highly stereoregular polypropylene, and the weight fraction (w ₁ ) based on the total amount of the finally obtained propylene-based polymer is 0.1%.
The high molecular weight component ([η] = 8) is adjusted to 1 to 20% by weight.
To 30 dl / g), and then a low molecular weight component ([η] = 0.5 to 3 dl / g) of 80 to 99.9% by weight based on the total amount of the propylene polymer finally obtained. Can be obtained.

The weight fraction (w ₁ ) of the high molecular weight component obtained in the first stage is determined by the multiple peaks (double peaks) obtained in the gel permeation chromatography (GPC) of the propylene polymer finally obtained. Among them, the peak corresponding to the high molecular weight polypropylene is separated assuming that the peak has a normal distribution, and can be calculated as a ratio of this area to the total peak area.

For example, it is preferable to carry out propylene polymerization in three or more stages to produce propylene polymers having different molecular weights in each stage. As an example of the production method, the intrinsic viscosity [η _1st ] is 8 to 30 d in the first stage.
l / g, preferably 8 to 25 dl / g, of polypropylene is produced in an amount of 0.1 to 20% by weight, preferably 0.1 to 15% by weight in the finally obtained propylene polymer, and then the second stage Intrinsic viscosity [η _2nd ] is 3 to 10 dl
/ G, preferably 4 to 9 dl / g, of 19.9 to 50% by weight in the finally obtained propylene polymer.
And in the third stage, the intrinsic viscosity [η _3rd ] is 0.8 to 4.0 dl / g, preferably 0.8 to 3.0 dl / g.
0 dl / g of polypropylene can be produced in an amount of 30 to 80% by weight in the finally obtained propylene polymer.

At this time, {([η _1st ] + [η _3rd ]) / 2} −
It is desirable to satisfy 1 ≦ [η _2nd ] ≦ {([η _1st ] + [η _3rd ]) / 2} +1. In each of the above stages, propylene can be homopolymerized, or propylene and other monomers can be copolymerized if necessary, but the first stage preferably produces a high molecular weight component containing a trace amount of ethylene. Is desirable.

The high molecular weight component obtained in the first stage may be produced as a prepolymer. The order of each stage is not particularly limited and may be performed in a different order from the above, but the above order is preferable.

The molecular weight of the polypropylene in each stage can be adjusted, for example, by changing the amount of hydrogen supplied to the polymerization system. In the present invention, in addition to the step of forming a propylene-based polymer component by such multi-stage polymerization, a propylene-ethylene copolymer rubber component is formed by further performing a copolymerization step of propylene and ethylene, and a propylene block copolymer is formed. Can also be manufactured.

In the present invention, when producing the above-mentioned propylene-based polymer, it is preferable to use a catalyst for producing polyolefin having high stereoregularity.
A solid titanium catalyst component containing magnesium, titanium, a halogen and an electron donor, (b) an organometallic compound, and (c) an organosilicon compound represented by the following formula (i) (c-
A catalyst comprising 1) or a compound (c-2) having two or more ether bonds existing through a plurality of atoms can be used.

[0043] In _{^{R a n Si (OR b)}} 4-n ... (i) ( wherein, n is 1, 2 or 3, at least one of R ^a is an secondary or tertiary hydrocarbon group , N is 2 or 3, ^Ra may be the same or different;
R ^b is a hydrocarbon group having 1 to 4 carbon atoms, and 4-n is 2
Or when it is 3, ^Rb may be the same or different. The solid titanium catalyst component (a) as described above can be prepared by contacting a magnesium compound, a titanium compound and an electron donor.

Examples of the magnesium compound include a magnesium compound having a reducing ability and a magnesium compound having no reducing ability. Examples of the magnesium compound having a reducing ability include a magnesium compound having a magnesium-carbon bond or a magnesium-hydrogen bond, and specific examples thereof include dimethylmagnesium, diethylmagnesium, dipropylmagnesium, dibutylmagnesium, diamilmagnesium, and dihexyl. Examples include magnesium, didecyl magnesium, ethyl magnesium chloride, propyl magnesium chloride, butyl magnesium chloride, hexyl magnesium chloride, amyl magnesium chloride, butyl ethoxy magnesium, ethyl butyl magnesium, butyl magnesium hydride, and the like.

Examples of the magnesium compound having no reducing ability include magnesium chloride, magnesium bromide,
Aliquots such as magnesium halides such as magnesium iodide and magnesium fluoride, alkoxymagnesium halides such as methoxymagnesium chloride, ethoxymagnesium chloride, isopropoxymagnesium chloride, butoxymagnesium chloride and octoxymagnesium chloride, phenoxymagnesium chloride, and methylphenoxymagnesium chloride Alkoxy magnesium such as roxy magnesium halide, ethoxy magnesium, isopropoxy magnesium, butoxy magnesium, n-octoxy magnesium, 2-ethylhexoxy magnesium,
Examples include allyloxymagnesium such as phenoxymagnesium and dimethylphenoxymagnesium, and magnesium carboxylate such as magnesium laurate and magnesium stearate.

The magnesium compound having no reducing ability may be a compound derived from a magnesium compound having reducing ability or a compound derived at the time of preparing a catalyst component. In order to derive a magnesium compound having no reducing ability from a magnesium compound having reducing ability, for example, a magnesium compound having reducing ability is converted into a polysiloxane compound, a halogen-containing silane compound, a halogen-containing aluminum compound, an ester, an alcohol,
The compound may be brought into contact with a compound having an active carbon-oxygen bond such as a halogen-containing compound or a ketone.

The magnesium compound can also be derived from magnesium metal during catalyst preparation. Magnesium compounds can be used in combination of two or more.

The magnesium compound as described above is
It may form a complex compound or a complex compound with another metal such as aluminum, zinc, boron, beryllium, sodium and potassium, or may be a mixture with another metal compound.

In the present invention, many magnesium compounds other than those described above can be used, but it is preferred that the finally obtained solid titanium catalyst component (a) be in the form of a halogen-containing magnesium compound. When using a halogen-free magnesium compound,
It is preferable to carry out a contact reaction with a halogen-containing compound in the process of preparing the catalyst component.

Of the above, a magnesium compound having no reducing ability is preferable, a halogen-containing magnesium compound is more preferable, and magnesium chloride, alkoxymagnesium chloride and allyloxymagnesium chloride are particularly preferable.

In the present invention, when preparing the catalyst component, the magnesium compound is preferably used in a liquid state.
When the magnesium compound is a solid among the above magnesium compounds, the magnesium compound can be made into a liquid state using an electron donor.

Of the above magnesium compounds,
When the magnesium compound is a solid, it can be made into a liquid state using an electron donor (liquefier). As the liquefying agent, alcohols, phenols, ketones, aldehydes, ethers, amines, pyridines and the like as described below as an electron donor, further, tetraethoxy titanium, tetra-n-propoxy titanium, tetra- i-
Metal acid esters such as propoxytitanium, tetrabutoxytitanium, tetrahexoxytitanium, tetrabutoxyzirconium, and tetraethoxyzirconium can also be used.

Of these, alcohols and metal acid esters are particularly preferably used. The liquefaction reaction of the solid magnesium compound is generally carried out by bringing the solid magnesium compound into contact with the above-mentioned liquefying agent and heating as necessary. This contact is usually performed at 0 to 200 ° C, preferably 20 to 180 ° C, more preferably 50 to 150 ° C.
Done at temperature.

In the liquefaction reaction, a hydrocarbon solvent or the like may coexist, for example, pentane, hexane,
Aliphatic hydrocarbons such as heptane, octane, decane, dodecane, tetradecane, and kerosene; alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, cyclooctane, and cyclohexene; dichloroethane, dichloropropane, and trichloroethylene And halogenated hydrocarbons such as chlorobenzene, and aromatic hydrocarbons such as benzene, toluene and xylene.

In preparing the solid titanium catalyst component (a), it is preferable to use, for example, a tetravalent titanium compound represented by the following formula as the titanium compound. Ti (OR) _g X _4-g (where R is a hydrocarbon group, X is a halogen atom, 0 ≦ g ≦
4. More specifically, titanium tetrahalides such as TiCl ₄ , TiBr ₄ and TiI ₄ , Ti (OCH ₃ ) Cl ₃ , Ti (OC ₂ H ₅ ) Cl
_{3, Ti (On-C 4} H 9) Cl 3, Ti (OC 2 H 5) Br 3, Ti (O-
iso-C ₄ H ₉₎ trihalide, alkoxy titanium such as _{Br 3, Ti (OCH 3)} 2 Cl 2, Ti (OC 2 H 5) 2 Cl 2, Ti (On
Dialkoxytitanium dihalides such as -C ₄ H ₉ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₂ Br ₂ , Ti (OCH ₃ ) ₃ Cl, Ti (OC _{2
H 5) 3 Cl, Ti (} On-C 4 H 9) 3 Cl, Ti (OC 2 H 5) 3 Br
Monohalogenated trialkoxy titanium such as Ti (OC
_{H 3) 4, Ti (OC} 2 H 5) 4, Ti (On-C 4 H 9) 4, Ti (O-is
and tetraalkoxy titanium such as o-C ₄ H ₉ ) ₄ and Ti (O-2-ethylhexyl) ₄ .

Of these, a halogen-containing titanium compound is preferable, a titanium tetrahalide is more preferable, and titanium tetrachloride is particularly preferable. These titanium compounds can be used in combination of two or more. Further, the titanium compound can be used after being diluted with a hydrocarbon compound or a halogenated hydrocarbon compound.

The electron donor used in the preparation of the solid titanium catalyst component (a) includes, for example, alcohol,
Examples include phenol, ketone, aldehyde, esters of organic or inorganic acids, organic acid halides, ethers, acid amides, acid anhydrides, ammonia, amines, nitriles, isocyanates, nitrogen-containing cyclic compounds, oxygen-containing cyclic compounds, and the like. More specifically, methanol, ethanol, propanol, pentanol, hexanol, octanol, 2-ethylhexanol, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropyl alcohol, isopropyl benzyl alcohol, etc. Alcohols having 1 to 18 carbon atoms, phenol,
Cresol, xylenol, ethylphenol, propylphenol, nonylphenol, cumylphenol,
C6 to C20 phenols which may have a lower alkyl group such as naphthol; C3 to C15 ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, acetylacetone and benzoquinone; acetaldehyde and propion Aldehyde, octyl aldehyde, benzaldehyde,
2-1 carbon atoms such as tolualdehyde and naphthaldehyde
5, aldehydes, methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, croton Ethyl acetate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate,
Propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate,
Amyl toluate, ethyl ethyl benzoate, methyl anisate, n-butyl maleate, diisobutyl methylmalonate, di-n-hexyl cyclohexenecarboxylate, diethyl nadicate, diisopropyl tetrahydrophthalate, diethyl phthalate, diisobutyl phthalate, phthalate Acid di-n-
Organic acid esters having 2 to 30 carbon atoms such as butyl, di-2-ethylhexyl phthalate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, ethyl carbonate, acetyl chloride, benzoyl chloride, toluic acid chloride, anisic acid chloride, etc. Acid halides having 2 to 15 carbon atoms, such as methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, anisole, diphenyl ether epoxy-p-menthane, etc., ethers having 2 to 20 carbon atoms, acetic acid amide, benzoic acid amide Acid amides such as toluic acid amide, acetic anhydride, phthalic anhydride, acid anhydrides such as benzoic anhydride, methylamine, ethylamine, dimethylamine, diethylamine,
Amines such as ethylenediamine, tetramethylenediamine, hexamethylenediamine, tributylamine and tribenzylamine, acetonitrile, benzonitrile,
Nitriles such as tolunitrile, pyrroles, methylpyrrole, pyrroles such as dimethylpyrrole, pyrroline,
Pyrrolidine, indole, pyridine, methylpyridine,
Pyridines such as ethylpyridine, propylpyridine, dimethylpyridine, ethylmethylpyridine, trimethylpyridine, phenylpyridine, benzylpyridine, and pyridine chloride; nitrogen-containing cyclic compounds such as piperidines, quinolines, and isoquinolines; tetrahydrofuran;
Examples include cyclic oxygen-containing compounds such as cineol, 1,8-cineole, pinolfuran, methylfuran, dimethylfuran, diphenylfuran, benzofuran, coumaran, phthalane, tetrahydropyran, pyran, and dihydropyran.

As the above-mentioned organic acid ester, a polycarboxylic acid ester having a skeleton represented by the following general formula can be mentioned as a particularly preferred example.

[0059]

Embedded image

Where R¹Is a substituted or unsubstituted hydrocarbon
Group, R^Two, R^Five, R⁶Is hydrogen or substituted or unsubstituted
A substituted hydrocarbon group, R^Three, R^FourIs hydrogen or substituted or
Is an unsubstituted hydrocarbon group, preferably at least
One is a substituted or unsubstituted hydrocarbon group. Also R
^ThreeAnd R^FourIs connected to each other to form a ring structure
Is also good. Hydrocarbon group R¹~ R⁶Is replaced
Substituents include heteroatoms such as N, O, S, for example,
COC, COOR, COOH, OH, SO _ThreeH,-
C—N—C—, NH_TwoAnd the like.

Specific examples of such a polycarboxylic acid ester include diethyl succinate, dibutyl succinate, diethyl methyl succinate, diisobutyl α-methylglutarate, diethyl methyl malonate, diethyl ethyl malonate, and isopropyl malonate. Diethyl acrylate, diethyl butylmalonate, diethyl phenylmalonate, diethyl diethylmalonate, diethyl dibutylmalonate, monooctyl maleate, dioctyl maleate, dibutyl maleate, dibutyl butyl maleate, diethyl butyl maleate, β-methyl glutar Aliphatic polycarboxylates such as diisopropyl acrylate, diallyl ethyl succinate, di-2-ethylhexyl fumarate, diethyl itaconate, dioctyl citraconic acid, diethyl 1,2-cyclohexanecarboxylate, 1,2-cyclohexane Diisobutyl hexanecarboxylate, diethyl tetrahydrophthalate, alicyclic polycarboxylic acid esters such as diethyl nadicate, monoethyl phthalate, dimethyl phthalate, methylethyl phthalate, monoisobutyl phthalate, diethyl phthalate, ethyl isobutyl phthalate, Di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, di-isobutyl phthalate, di-n-heptyl phthalate, di-2-ethylhexyl phthalate, di-n-octyl phthalate, dineopentyl phthalate, phthalic acid Aromatic polycarboxylic acid esters such as didecyl, benzyl butyl phthalate, diphenyl phthalate, diethyl naphthalene dicarboxylate, dibutyl naphthalene dicarboxylate, triethyl trimellitate, dibutyl trimellitate, and heterogeneous substances such as 3,4-furandicarboxylic acid Cyclic polycarboxylic acid esters and the like.

Examples of the polycarboxylic acid esters include long-chain dicarboxylic acids such as diethyl adipate, diisobutyl adipate, diisopropyl sebacate, di-n-butyl sebacate, di-n-octyl sebacate, and di-2-ethylhexyl sebacate. Acid esters may also be mentioned.

Further, as the electron donor, an organic silicon compound or a polyether compound as described later as the electron donor (c), water, or an anionic, cationic or nonionic surfactant may be used. it can.

In the present invention, it is preferable to use a carboxylic acid ester among the above, and it is particularly preferable to use a polyvalent carboxylic acid ester, especially a phthalic acid ester.

These electron donors can be used in combination of two or more kinds. When contacting the titanium compound, the magnesium compound and the electron donor as described above, silicon,
Other reaction reagents such as phosphorus and aluminum may be allowed to coexist, or a carrier-supported solid titanium catalyst component (a) can be prepared using a carrier.

Examples of such a carrier include Al ₂ O ₃ and Si.
O ₂ , B ₂ O ₃ , MgO, CaO, TiO ₂ , ZnO, Sn
Examples include resins such as O ₂ , BaO, ThO, and styrene-divinylbenzene copolymer. Of these,
Al ₂ O ₃ , SiO ₂ , and styrene-divinylbenzene copolymer are preferably used.

The solid titanium catalyst component (a) can be prepared by any method including known methods, and will be briefly described below with several examples. (1) A method in which a hydrocarbon solution of a magnesium compound containing an electron donor (liquefying agent) is contact-reacted with an organometallic compound to precipitate a solid, or a contact reaction is performed with a titanium compound while the solid is precipitated.

(2) A method comprising bringing a complex comprising a magnesium compound and an electron donor into contact with and reacting with an organometallic compound, followed by a contact reaction with a titanium compound. (3) In the contact substance between the inorganic carrier and the organomagnesium compound,
A method in which a titanium compound and an electron donor are contact-reacted.
At this time, the contact product may be previously contacted with a halogen-containing compound and / or an organometallic compound.

(4) A support carrying a magnesium compound is obtained from a mixture of a magnesium compound solution containing a liquefying agent and a hydrocarbon solvent as the case may be, an electron donor, and a carrier, and then a titanium compound is brought into contact therewith. Method.

(5) Magnesium compounds, titanium compounds,
A method in which a solution containing an electron donor and, in some cases, a hydrocarbon solvent is further contacted with a carrier. (6) A method of contacting a liquid organomagnesium compound with a halogen-containing titanium compound. At this time, the electron donor is used at least once.

(7) A method in which a liquid organomagnesium compound is brought into contact with a halogen-containing compound and then brought into contact with a titanium compound. In this process, the electron donor is used at least once.

(8) A method of contacting an alkoxy group-containing magnesium compound with a halogen-containing titanium compound. At this time, the electron donor is used at least once. (9) A method comprising bringing a complex comprising an alkoxy group-containing magnesium compound and an electron donor into contact with a titanium compound.

(10) A method comprising bringing a complex comprising an alkoxy group-containing magnesium compound and an electron donor into contact with an organometallic compound, followed by a contact reaction with a titanium compound. (11) A method of contacting and reacting a magnesium compound, an electron donor, and a titanium compound in an arbitrary order. Prior to this reaction, each component may be pretreated with a reaction aid such as an electron donor, an organometallic compound, or a halogen-containing silicon compound.

(12) A method in which a liquid magnesium compound having no reducing ability is reacted with a liquid titanium compound in the presence of an electron donor to precipitate a solid magnesium-titanium composite.

(13) A method of further reacting a titanium compound with the reaction product obtained in (12). (14) A method in which an electron donor and a titanium compound are further reacted with the reaction product obtained in (11) or (12).

(15) A method in which a solid obtained by pulverizing a magnesium compound, an electron donor and a titanium compound is treated with any of a halogen, a halogen compound or an aromatic hydrocarbon. Note that this method may include a step of pulverizing only the magnesium compound, a complex compound including the magnesium compound and the electron donor, or the magnesium compound and the titanium compound. Further, after the pulverization, a pretreatment with a reaction assistant may be performed, followed by a treatment with halogen or the like. As the reaction assistant, an organometallic compound or a halogen-containing silicon compound is used.

(16) A method in which a magnesium compound is pulverized and then brought into contact with a titanium compound. At the time of grinding and / or contacting the magnesium compound, an electron donor is used together with a reaction aid as necessary.

(17) A method of treating the compound obtained in the above (11) to (16) with a halogen, a halogen compound or an aromatic hydrocarbon. (18) A method in which a contact reaction product of a metal oxide, an organomagnesium and a halogen-containing compound is contacted with an electron donor and preferably a titanium compound.

(19) A method in which a magnesium compound such as a magnesium salt of an organic acid, alkoxymagnesium or aryloxymagnesium is brought into contact with a titanium compound, an electron donor and, if necessary, a halogen-containing hydrocarbon.

(20) A method in which a hydrocarbon solution containing a magnesium compound and an alkoxytitanium is brought into contact with an electron donor and, if necessary, a titanium compound. At this time, it is preferable to coexist a halogen-containing compound such as a halogen-containing silicon compound.

(21) A liquid magnesium compound having no reducing ability is reacted with an organometallic compound to precipitate a solid magnesium-metal (aluminum) complex, and then an electron donor and a titanium compound are removed. How to react.

The amount of each component used for the contact varies depending on the preparation method and cannot be specified unconditionally. For example, the amount of the electron donor is 0.01 per mol of the magnesium compound.
The titanium compound is present in an amount of from 0.01 to 1000 mol, preferably from 0.1 to 200 mol, preferably from 0.1 to 5 mol.
It is desirable to use them in molar amounts.

The solid titanium catalyst component (a) thus obtained contains magnesium, titanium, halogen and an electron donor. In the solid titanium catalyst component (a), halogen / titanium (atom) Ratio) is about 2
200 preferably about 4 to 100, the electron donor / titanium (molar ratio) is about 0.01 to 100, preferably about 0.02 to 10, and magnesium / titanium (atomic ratio) is about 1 to 100. Preferably, it is about 2 to 50.

In the present invention, the organometallic compound (b) is used together with the solid titanium catalyst component (a) as described above as a catalyst.
Is used. As the organometallic compound, a compound containing a metal selected from Groups I to III of the periodic table is preferable, and specific examples thereof include an organoaluminum compound shown below and a complex alkyl of a Group I metal and aluminum. Compound,
Organic metal compounds of Group II metals can be mentioned.

[0085] (b-1) the formula _{^{R 1 m Al (OR 2)}} n H p X q ( wherein, R ¹ and R ² are from 1 to 15 carbon atoms, preferably from 1 to 4 carbon Hydrogen groups, which may be the same or different, X represents a halogen atom,
0 <m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q is 0
≤q <3, and m + n + p + q = 3. ). (b-2) the general formula M ¹ AlR ¹ ₄ (wherein, M ¹ is Li, Na, a K, R ¹ is as defined above.) alkyl complex with Group I metals and aluminum represented by monster.

(B-3) Formula R ¹ R ² M ² (wherein R ¹ and R ² are the same as above, and M ² is M
g, Zn or Cd. A) a group II or group III dialkyl compound represented by the formula:

As the organoaluminum compound belonging to the above (b-1), for example, R ¹ _m Al (OR ² ) _3-m (where R ¹ and R ² are the same as above, and m is preferably 1.
5 ≦ m ≦ 3. A compound represented _{^{by), R 1 m AlX 3-}} m (R 1 is as defined above, X is halogen, m is preferably 0 <m <3.) A compound represented by, R ¹ _m AlH _3-m (R ¹ is the same as above, and m is preferably 2 ≦ m <3
It is. R ¹ _m Al (OR ² ) _n X _q (R ¹ and R ² are the same as above, X is a halogen, 0 <
m ≦ 3, 0 ≦ n <3, 0 ≦ q <3, and m + n +
q = 3. And the like.

As the aluminum compound belonging to (b-1), more specifically, trialkylaluminums such as triethylaluminum and tributylaluminum, trialkenylaluminums such as triisoprenylaluminum, diethylaluminum ethoxide, dibutylaluminum butoxide Dialkyl aluminum alkoxide, ethyl aluminum sesquiethoxide, etc.
Alkyl aluminum sesquialkoxides such as butyl aluminum sesquibutoxide, R ¹ _2.5 Al (OR ² )
Partially alkoxylated alkylaluminum having an average composition represented by _0.5 , dialkylaluminum halide such as diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide Alkyl aluminum sesquihalides, such as
Partially halogenated alkyl aluminum such as alkyl aluminum dihalide such as ethyl aluminum dichloride, propyl aluminum dichloride and butyl aluminum dibromide, dialkyl aluminum hydride such as diethyl aluminum hydride and dibutyl aluminum hydride, ethyl aluminum dihydride, and propyl aluminum Alkyl aluminum such as dihydride Other partially hydrogenated alkyl aluminum such as dihydride, ethyl aluminum ethoxycyclolide, butyl aluminum butoxycyclolide, partially alkoxylated and halogenated alkyl aluminum such as ethyl aluminum ethoxy bromide Can be mentioned.

Examples of the compound similar to (b-1) include an organic aluminum compound in which two or more aluminum atoms are bonded via an oxygen atom or a nitrogen atom. For example, (C ₂ H ₅ ) ₂ AlOAl (C ₂ H ₅ ) ₂ ,
(C ₄ H ₉ ) ₂ AlOAl (C ₄ H ₉ ) ₂ , (C ₂ H ₅ ) ₂ Al
Aluminoxanes such as N (C ₂ H ₅ ) Al (C ₂ H ₅ ) ₂ and methylaluminoxane can be mentioned.

Compounds belonging to the above (b-2) include Li
Al (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ can be exemplified.

Of these, organoaluminum compounds,
Particularly, trialkylaluminum is preferably used.
The organometallic compound (b) can be used in combination of two or more kinds.

In the present invention, (c) an organosilicon compound (c) as an electron donor is used together with (a) a solid titanium catalyst component as described above and (b) an organometallic compound.
-1) or a compound (c-2) having two or more ether bonds existing through a plurality of atoms is used.

The (c-1) organosilicon compound used in the present invention is represented by the following formula. R ^a _n Si (OR ^b) in _4-n ... (i) wherein, n = 1, 2 or 3, R ^a when n is 1 is a secondary or tertiary hydrocarbon radical, n is In the case of 2 or 3, at least one of Ra is ^a secondary or tertiary hydrocarbon group, and ^Ra may be the same or different;
R ^b is a hydrocarbon group having 1 to 4 carbon atoms, and 4-n is 2
Or when it is 3, ^Rb may be the same or different. In the organosilicon compound (c-1) represented by the formula (i), as the secondary or tertiary hydrocarbon group, those having a cyclopentyl group, a cyclopentenyl group, a cyclopentadienyl group or a substituent And a hydrocarbon group in which the carbon adjacent to the group or Si is secondary or tertiary.
More specifically, as the substituted cyclopentyl group, a 2-methylcyclopentyl group, a 3-methylcyclopentyl group, a 2-ethylcyclopentyl group, a 2-n-butylcyclopentyl group,
2,3-dimethylcyclopentyl group, 2,4-dimethylcyclopentyl group, 2,5-dimethylcyclopentyl group, 2,3-diethylcyclopentyl group, 2,3,4-trimethylcyclopentyl group, 2,3,5-trimethylcyclopentyl And a cyclopentyl group having an alkyl group such as a 2,3,4-triethylcyclopentyl group, a tetramethylcyclopentyl group, and a tetraethylcyclopentyl group.

Examples of the substituted cyclopentenyl group include a 2-methylcyclopentenyl group, a 3-methylcyclopentenyl group,
2-ethylcyclopentenyl group, 2-n-butylcyclopentenyl group, 2,3-dimethylcyclopentenyl group, 2,4-dimethylcyclopentenyl group, 2,5-dimethylcyclopentenyl group, 2,3,4-trimethyl Cyclopentenyl groups having an alkyl group such as a cyclopentenyl group, a 2,3,5-trimethylcyclopentenyl group, a 2,3,4-triethylcyclopentenyl group, a tetramethylcyclopentenyl group, and a tetraethylcyclopentenyl group are exemplified.

The substituted cyclopentadienyl group includes 2-
Methylcyclopentadienyl group, 3-methylcyclopentadienyl group, 2-ethylcyclopentadienyl group, 2-n-butylcyclopentenyl group, 2,3-dimethylcyclopentadienyl group, 2,4-dimethyl Cyclopentadienyl group, 2,5-
Dimethylcyclopentadienyl group, 2,3-diethylcyclopentadienyl group, 2,3,4-trimethylcyclopentadienyl group, 2,3,5-trimethylcyclopentadienyl group,
3,4-triethylcyclopentadienyl group, 2,3,4,5-tetramethylcyclopentadienyl group, 2,3,4,5-tetraethylcyclopentadienyl group, 1,2,3,4, Cyclopentadienyl groups having an alkyl group such as a 5-pentamethylcyclopentadienyl group and a 1,2,3,4,5-pentaethylcyclopentadienyl group are exemplified.

Examples of the hydrocarbon group in which the carbon adjacent to Si is a secondary carbon include i-propyl, s-butyl, s-amyl, α-methylbenzyl and the like. Examples of the hydrocarbon group in which the carbon adjacent to is a tertiary carbon include a t-butyl group, a t-amyl group, an α, α′-dimethylbenzyl group, an admantyl group, and the like.

The organosilicon compound (c) represented by the above formula (i)
-1) is, when n is 1, cyclopentyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, 2,3-dimethylcyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, iso-butyltriethoxysilane, t -Butyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornanetrimethoxysilane, 2-
Trialkoxysilanes such as norbornanetriethoxysilane can be exemplified.

When n is 2, dicyclopentyldiethoxysilane, t-butylmethyldimethoxysilane,
t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, dialkoxysilanes such as 2-norbornanemethyldimethoxysilane, and the following formula (ii) And the dimethoxy compounds shown.

[0099]

Embedded image

In the formula, R ^a and R ^c independently represent a cyclopentyl group, a substituted cyclopentyl group, a cyclopentenyl group, a substituted cyclopentenyl group, a cyclopentadienyl group, a substituted cyclopentadienyl group, or Si A hydrocarbon group in which carbon is a secondary or tertiary carbon.

Among them, dimethoxysilanes,
Particularly preferred are dimethoxysilanes represented by the formula (ii),
Specifically, dicyclopentyldimethoxysilane, di-t-
Butyldimethoxysilane, di (2-methylcyclopentyl) dimethoxysilane, di (3-methylcyclopentyl)
Dimethoxysilane, di-t-amyldimethoxysilane and the like are preferred.

The above organosilicon compounds (c-1) can be used in combination of two or more. In the compound having two or more ether bonds existing through a plurality of atoms (hereinafter sometimes referred to as a polyether compound) (c-2) used in the present invention, the atoms existing between these ether bonds are carbon atoms. , Silicon, oxygen, sulfur, phosphorus, boron and at least two atoms. Of these, a relatively bulky substituent at the atom between ether bonds, specifically a substituent having 2 or more carbon atoms, preferably 3 or more and having a linear, branched, or cyclic structure, more preferably a branched one. It is desirable that a substituent having a linear or cyclic structure is bonded. Further, a compound in which a plurality of, preferably 3 to 20, more preferably 3 to 10 and particularly preferably 3 to 7 carbon atoms are contained in an atom existing between two or more ether bonds is preferable.

As such a polyether compound,
For example, a compound represented by the following formula can be mentioned.

[0104]

Embedded image

In the formula, n is an integer of 2 ≦ n ≦ 10;
^{1 to} R ²⁶ are carbon, hydrogen, oxygen, halogen, nitrogen, sulfur,
At least one selected from phosphorus, boron and silicon
R ^{1 to} R ²⁶ , preferably R ^{1 to} R ^2n, may form a ring other than a benzene ring together, and may have an atom other than carbon in the main chain. May be included.

Among these, 1,3-diethers are preferably used, and in particular, 2,2-diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2-dicyclohexyl-1,3-dimethoxypropane, 2,2-bis (cyclohexylmethyl) -1,3-
Dimethoxypropane is preferably used.

These polyether compounds (c-2) can be used in combination of two or more. In the present invention, the above-mentioned organosilicon compound (c-1) and polyether compound (c-2) can be used in combination as the electron donor (c).

Further, an organosilicon compound represented by the following formula can be used in combination. R _n Si (OR ') in _4-n (wherein, R and R' is a hydrocarbon group, 0 <n <4
And the organosilicon compound represented by the formula does not include the organosilicon compound (c-1) represented by the formula (i). More specifically, trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diisopropyldimethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane, bis-tolyldimethoxysilane, bis m-tolyldimethoxysilane, bis-p-tolyldimethoxysilane, bis-p-tolyldiethoxysilane, bisethylphenyldimethoxysilane,
Ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, n-propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane, Methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, n-butyltriethoxysilane, phenyltriethoxysilane, γ-aminopropyltriethoxysilane, chlorotriethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane , Trimethylphenoxysilane, methyltriallyloxy silane, vinyl tris (β-methoxyethoxy silane), vinyl triacetoxy silane, and the like.

Further similar compounds include ethyl silicate,
Butyl silicate, dimethyltetraethoxydisiloxane, and the like can also be used. In the present invention, as described above, (a) a solid titanium catalyst component, (b) an organometallic compound,
When producing a propylene-based polymer using a catalyst comprising (c) an electron donor, preliminary polymerization may be carried out in advance.

The prepolymerization is carried out by (a) a solid titanium catalyst component, (b) an organometallic compound and, if necessary, (c)
The olefin is polymerized in the presence of the electron donor. As the prepolymerized olefin, ethylene, propylene, 1-butene, 1-octene, 1-hexadecene, linear olefins such as 1-eicosene, 3-methyl-1-butene, 3-methyl-
1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene,
Branched olefins such as 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, allylnaphthalene, allylnorbornane, styrene, dimethylstyrenes, vinylnaphthalenes, allyltoluenes And olefins having a branched structure such as allylbenzene, vinylcyclohexane, vinylcyclopentane, vinylcycloheptane, and allyltrialkylsilanes, and these may be copolymerized.

Of these, ethylene, propylene,
3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1
-Hexene, vinylcyclohexane, allyltrimethylsilane, dimethylstyrene and the like are preferably used.

In the preliminary polymerization, the solid titanium catalyst component (a)
About 0.1 to 1000 g / g, preferably 0.3 to 50 g / g
Desirably, the reaction is performed so that about 0 g of a polymer is generated. In the prepolymerization, the catalyst can be used at a considerably higher concentration than the catalyst concentration in the system in the main polymerization.

The solid titanium catalyst component (a) is usually used in an amount of about 0.01 to 2 in terms of titanium atom per liter of polymerization volume.
Desirably, it is used at a concentration of about 0.005 mmol, preferably about 0.05 to 100 mmol.

The organometallic compound (b) is generally used in an amount of about 0.1 to about 0.1 mol per mol of titanium atom in the solid titanium catalyst component (a).
It is desirable to use it in an amount of 100 mmol, preferably about 0.5 to 50 mmol.

The electron donor (c) may or may not be used at the time of prepolymerization, but it is preferably 0.1 to 50 mol, preferably 0.1 mol, per mol of titanium atom in the solid titanium catalyst component (a). It can be used in an amount of 5 to 30 mol, more preferably 1 to 10 mol.

The prepolymerization is preferably carried out under mild conditions by adding the prepolymerized olefin and the above-mentioned catalyst component to an inert hydrocarbon medium. Among the inert hydrocarbon media, aliphatic hydrocarbons are preferred.

The prepolymerization temperature may be a temperature at which the produced prepolymer is not substantially dissolved in the inert hydrocarbon medium, and is usually -20 to + 100 ° C, preferably -20.
To + 80 ° C, more preferably about 0 to + 40 ° C.

The prepolymerization can be carried out by a batch system, a continuous system, or the like. At the time of prepolymerization, the molecular weight can be adjusted using hydrogen or the like. In the present invention, in the process of producing the ethylene-propylene copolymer component (i) as described above,
Solid titanium catalyst component (a) (or prepolymerized catalyst)
Is converted to titanium atoms per liter of polymerization volume, from about 0.0001 to 50 mmol, preferably from about 0.001 to 1
It is desirable to use it in an amount of 0 mmol.

The organometallic compound (b) is preferably used in an amount of about 1 to 2000 mol, preferably about 2 to 500 mol, per 1 mol of titanium atom in the polymerization system. The electron donor (c) is an organometallic compound (b)
Is preferably used in an amount of about 0.001 to 50 mol, preferably about 0.01 to 20 mol, per 1 mol of metal atom.

When a prepolymerized catalyst is used, a solid titanium catalyst component (a) and an organometallic compound (b) can be newly added as necessary. The organometallic compound (b) in the pre-polymerization and the main polymerization may be the same or different.

The electron donor (c) is always used once in either pre-polymerization or main polymerization, and is used only in main polymerization or in both pre-polymerization and main polymerization. Can be The electron donor (c) in the pre-polymerization and the main polymerization may be the same or different.

When the above-mentioned catalyst is used, the crystallinity or stereoregularity index of the obtained propylene-based polymer does not decrease even when hydrogen is used during the polymerization, and the catalytic activity decreases. Not even.

Ethylene Polymer In the present invention, two kinds of ethylene polymers are used as described later, and these are especially ethylene and C3-C2.
It is a random copolymer with 0 α-olefin, and it is desirable that the elastomeric materials be used.

Examples of such α-olefins include propylene, 1-butene, 1-pentene, 1-hexene,
4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, and combinations thereof.

The ethylene polymer used in the present invention may contain a unit derived from another polymerizable monomer, if necessary, as long as the properties of the present invention are not impaired.

Examples of such other polymerizable monomers include:
For example, styrene, vinylcyclopentene, vinylcyclohexane, vinyl compounds such as vinylnorbornane, vinyl esters such as vinyl acetate, unsaturated organic acids such as maleic anhydride or derivatives thereof, conjugated dienes,
1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-
Hexadiene, 6-methyl-1,5-heptadiene, 7-methyl-
1,6-octadiene, dicyclopentadiene, cyclohexadiene, dicyclooctadiene, methylenenorbornene, 5-vinylnorbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene , 6-chloromethyl-5-isopropenyl
Non-conjugated polyenes such as 2-norbornene, 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,2-norbornadiene and combinations thereof And the like.

The ethylene polymer may contain units derived from such other polymerizable monomers in an amount of 10 mol% or less, preferably 5 mol% or less, more preferably 3 mol% or less.

For use in the present invention. The ethylene polymer (B) to be obtained has (1) a density d ₁ of 0.905 to 0.950 g / cm ³ ,
Preferably it is 0.905 to 0.945 g / cm ^3, more preferably 0.908 to 0.945 g / cm ³ . In this specification, the density is a value measured according to JIS K7112A method. (2) The melt flow rate (MFR) measured at 190 ° C under a load of 2.16 kg is 0.001 to 15 g / 10 min, preferably 0.005 to 15 g / 10 min, and more preferably 0.01 to 15 g / 10 min. 10 g / 10 min.

The refractive index of the ethylene polymer (B) is from 1.5050 to 1.5400, preferably 1.5070.
~ 1.5400, more preferably 1.5090 ~ 1.53
Desirably, it is 50.

Examples of the ethylene polymer (B) include an ethylene homopolymer produced by a high pressure method and an ethylene / α-olefin random copolymer produced by a high pressure method or a medium / low pressure method. Among them, an ethylene / α-olefin random copolymer is particularly preferable.

The ethylene / α-olefin random copolymer used as the ethylene polymer (B) contains 0.01 to 0.01 units derived from an α-olefin having 3 to 20 carbon atoms.
-5 mol%, preferably 0.5-4 mol%. The α-olefin is preferably an α-olefin having 4 to 10 carbon atoms, particularly an α-olefin having 4 to 8 carbon atoms.

Specifically, the ethylene / α-olefin random copolymer used as the ethylene-based polymer (B) includes ethylene / 1-hexene random copolymer and ethylene / 4-methyl-1-pentene random copolymer. Coalescence, ethylene ・ 1
-Butene random copolymer, ethylene / 1-octene random copolymer and the like are preferred.

The ethylene / α-olefin random copolymer (C) used in the present invention has the following features. (1) The density d ₂ is less than 0.891 g / cm ³ , preferably less than 0.889 g / cm ^3. Is 0.887
g / cm ³ . (2) The melt flow rate (MFR) measured at 190 ° C under a load of 2.16 kg is 0.001 to 15 g / 10 min, preferably 0.005 to 15 g / 10 min, and more preferably 0.01 to 15 g / 10 min. 10 g / 10 min.

The ethylene / α-olefin random copolymer (C) has a refractive index of 1.4700 to 1.495.
0, preferably 1.4720 to 1.4950, and more preferably 1.4750 to 1.4950.

Such an ethylene / α-olefin random copolymer (C) has a unit derived from ethylene of 7
In the amount of 0 to 90 mol%, preferably 70 to 88 mol%, the unit derived from the α-olefin having 3 to 20 carbon atoms is 70 to 90 mol%, preferably 70 to 88 mol%.
Is desirably contained.

The α-olefin is, among the above, an α-olefin having 3 to 10 carbon atoms, especially 4 to 8 carbon atoms.
Α-olefin is preferred. Specifically, as the ethylene / α-olefin random copolymer (C), an ethylene / butene random copolymer, an ethylene / octene random copolymer, or the like can be preferably used.

In the present invention, the ethylene polymer (B) and the ethylene / α-olefin random copolymer (C) having different densities as described above are used, and the density of the ethylene polymer (B) is different. and d _1, the difference between the density d ₂ of the ethylene · alpha-olefin random copolymer _{(C) (d 1 -d 2} )
g / cm ³ is 0.045 to 0.087, particularly 0.055 to 0.0
It is desirably 87.

The ethylene polymer (B) and the ethylene / α-olefin random copolymer (C) are
It can be produced by a conventionally known method using a vanadium-based catalyst, a titanium-based catalyst, a metallocene-based catalyst, or the like.

Propylene Polymer Composition The propylene polymer composition according to the present invention comprises the above-mentioned propylene polymer (A) in an amount of 40 to 96% by weight, preferably 50 to 90% by weight, more preferably 50 to 90% by weight. Is 60-9
0% by weight of the ethylene polymer (B) in an amount of 2 to 30%.
(C) 2-30% by weight, preferably 5-30% by weight of the ethylene / α-olefin random copolymer in an amount of 5% by weight, preferably 5-30% by weight, more preferably 10-30% by weight. , More preferably 5 to 25% by weight.

The two types of ethylene polymers selected to have different densities as described above have excellent kneading properties with the propylene polymer, and can form a micro-dispersed composition. From these components, a propylene-based polymer composition having excellent transparency, excellent rigidity and excellent impact resistance can be formed.

Further, the propylene polymer composition of the present invention formed from the propylene polymer (A) and the rubber components (B) and (C) as described above has a high melt tension and excellent molding properties. Shows sex.

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

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

Examples of other elastomers include amorphous elastic copolymers containing olefins other than the above ethylene polymers (B) and (C) as main components, conjugated diene rubbers, and the like.

The additives include nucleating agents, antioxidants,
Hydrochloric acid absorber, heat stabilizer, light stabilizer, ultraviolet absorber, lubricant, antistatic agent, flame retardant, pigment, dye, dispersant, copper inhibitor, neutralizer, foaming agent, plasticizer, air bubble inhibitor , Crosslinking agent,
Flowability improvers such as peroxides and weld strength improvers can be used.

The propylene 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, etc., and kneading the components. And obtained by melt-kneading with a single-screw extruder, a multi-screw extruder, a kneader, a Banbury mixer, or the like.

[0147] 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.

Molded Articles The propylene-based polymer composition of the present invention can be molded into molded articles of various shapes by adopting a known molding method without any particular limitation, and widely used in known applications as polyolefins. can do. Specifically as a molded product,
Examples include molded articles obtained by known thermoforming methods such as extrusion molding, injection molding, inflation molding, blow molding, extrusion blow molding, injection blow molding, press molding, calendar molding, and foam molding. Among these, injection molded articles, films or sheets, and blow molded articles are preferably provided.

The injection molded article can be produced by injection molding a propylene polymer composition into various shapes using a conventionally known injection molding apparatus under known conditions.
The injection molded article comprising the propylene polymer composition according to the present invention is hardly charged, has excellent rigidity, heat resistance, impact resistance, surface gloss, chemical resistance, abrasion resistance, etc., and has a trim for automobile interiors. Materials, automotive exterior materials, home appliance housing,
It can be widely used for containers and the like.

The injection molding of the propylene polymer composition is carried out 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.
The above-mentioned propylene-based polymer composition which is injection-molded at an injection pressure of excellent is excellent in moldability such as fluidity during injection molding.

The sheet and film molded articles made of the propylene-based polymer as described above are hardly charged, have rigidity such as tensile modulus, heat resistance, impact resistance, aging resistance, transparency, transparency, gloss, and the like. It has excellent rigidity, moisture resistance and gas barrier properties, and can be widely used as a packaging film. In particular, press-through packs (pr
ess through pack).

When extruding a propylene-based polymer, a conventionally known extruder and molding conditions can be employed. For example, a single screw extruder, a kneading extruder,
The molten propylene-based polymer composition can be extruded from a T-die or the like using a ram extruder, a gear extruder, or the like to form a sheet or a film (unstretched).

The stretched film is prepared by subjecting the above-mentioned extruded sheet or extruded film (unstretched) to a known stretching method such as a tenter method (longitudinal and transverse stretching, transverse and longitudinal stretching), a simultaneous biaxial stretching method and a uniaxial stretching method. It can be obtained by stretching.

The stretching ratio when stretching a sheet or an unstretched film is usually about 20 to 70 times in the case of biaxial stretching, and usually about 2 to 10 times in the case of uniaxial stretching. It is desirable to obtain a stretched film having a thickness of about 5 to 200 μm by stretching.

Further, an inflation film can be produced as a film-shaped molded product. Since the composition of the present invention has a high melt tension, drawdown hardly occurs during inflation molding.

The blow-molded article can be produced by blow-molding a propylene-based polymer composition using a conventionally known blow-molding apparatus under known conditions. For example, in extrusion blow molding, the propylene-based polymer composition is extruded from a die in a molten state at a resin temperature of 100 ° C. to 300 ° C. to form a tubular parison, and then the parison is held in a mold having a desired shape, followed by air. Is blown into the mold at a resin temperature of 130 ° C. to 300 ° C. to produce a hollow molded article. The stretching (blow) magnification is preferably about 1.5 to 5 times in the lateral direction.

In the injection blow molding, the propylene polymer composition is injected into a parison mold at a resin temperature of 100 ° C. to 300 ° C. to form a parison, and then the parison is held in a mold having a desired shape. Blow molding can be manufactured by blowing air and mounting the resin at a resin temperature of 120 ° C to 300 ° C on a mold. Then, a hollow molded product is obtained. The stretching (blow) magnification is 1.1 to 1.8 times in the longitudinal direction,
Preferably, it is 1.3 to 2.5 times in the horizontal direction.

The blow-molded article comprising the propylene-based polymer composition according to the present invention has excellent rigidity, heat resistance and impact resistance, and also excellent moisture resistance. Molded articles comprising the propylene-based polymer composition according to the present invention as described above can be used for a wide range of applications requiring high rigidity, such as housings, home appliance applications such as washing tubs, uniaxially stretched films, Film applications such as biaxially stretched films and blown films, sheet applications such as calender molding and extrusion molding, container applications such as bags and retort containers, such as automotive interior applications such as trims, instrument panels and column covers, fenders, bumpers, and side moldings , Mud guards, mirror covers, etc., and can be suitably used for general exterior goods.
It can also be used for medical and scientific instruments such as syringes, test tubes, pipettes and animal gauges.

[0159]

The propylene polymer composition according to the present invention is excellent in transparency, rigidity and impact resistance, and has high melt tension and excellent moldability. Such a propylene-based polymer composition is useful for various uses,
In particular, it is suitable for use in blow molded articles, films or sheets, and injection molded articles.

[0160]

EXAMPLES Next, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples.

The components used in the following Examples and Comparative Examples are shown below. (A) Propylene polymer homo PP-1 (homo polypropylene) (1) MFR = 2.5 g / 10 min (2) Loss tangent ratio (tan δ _0.1 / tan δ ₁₀₀ ) = 2.5 (5) High molecular weight component ( Intrinsic viscosity [η] = 9.9 dl / g) Content = 7.8% by weight (6) Density d = 0.906 g / cm ³ Homo PP-2 (Homo polypropylene) (1) MFR = 2.1 g / 10 min (2) Loss tangent ratio (tan δ _0.1 / tan δ ₁₀₀ ) = 6.9 (5) High molecular weight component (intrinsic viscosity [η] = 10.2 dl / g)
Content = 8.3% by weight (6) Density d = 0.906 g / cm ³ Random PP-1 (propylene / ethylene random copolymer) (1) MFR = 2.1 g / 10 min (2) Loss tangent ratio ( tan δ _0.1 / tan δ ₁₀₀ ) = 2.1 (3) Ethylene unit content = 0.02 mol% (4) 64 ° C. decane soluble component (DS ₆₄ ) content = 2.1% by weight (5) High molecular weight component (extreme) (Viscosity [η] = 10.1 dl / g)
Content = 8.2% by weight (6) Density d = 0.905 g / cm ³ Random PP-2 (propylene / ethylene random copolymer) (1) MFR = 1.8 g / 10 min (2) Loss tangent ratio ( tan δ _0.1 / tan δ ₁₀₀ ) = 1.5 (3) Ethylene unit content = 0.04 mol% (4) 64 ° C. decane soluble component (DS ₆₄ ) content = 2.5% by weight (5) High molecular weight component (extreme) (Viscosity [η] = 11.2 dl / g)
Content = 8.5% by weight (6) Density d = 0.904 g / cm ³ (B) Ethylene polymer Ethylene / hexene random copolymer (1) Density d ₁ = 0.910 g / cm ³ (2) MFR (3) Ethylene unit content = 97 mol% (4) Refractive index n _D = 1.5135 Ethylene / 4-methyl-1-pentene random copolymer (1) Density d ₁ = 0. 930 g / cm ³ (2) MFR = 3.5 g / 10 min (3) Ethylene unit content = 99.2 mol% (4) Refractive index n _D = 1.5229 (C) Ethylene / α-olefin random copolymer EBR-1 (random ethylene-butene copolymer) (1) Density d ₂ = 0.861 g / cm ³ (2) MFR = 0.5 g / 10 min (3) Ethylene unit content = 82 mol% (4) Refraction Rate n _D = 1.4818 EBR-2 (ethylene / butene random copolymer) (1) Density d ₂ = 0.902 g / cm ³ (2) MFR = 0.6 g / 10 min (3) Ethylene unit content = 95 mol% (4) Refractive index n _D = 1.5035

[0162]

Examples 1-2 Each component as shown in Table 1 was charged at 230 ° C.
To obtain a propylene-based polymer composition.

The obtained propylene-based polymer composition was
Press molding was performed at 30 ° C., and the bending strength, impact strength, and transparency were evaluated by the following evaluation methods. Table 1 shows the results. (1) Bending test (flexural modulus: FM) In accordance with ASTM C790, a 2 mm-thick test piece injection-molded under predetermined conditions was measured under the conditions of a span of 32 mm and a bending speed of 5 mm / min. . (2) Impact strength (IZ) Measured at 0 ° C. using a 3 mm thick test piece (post-notch) in accordance with ASTM D256. (3) Transparency (haze) According to ASTM D1003-52, the thickness is 0.5 mmt.
Of the test specimen of Nippon Denshoku Industries Co., Ltd.
It measured using DH-20D. (4) Melt tension (MT) Melt tension (MT) is measured as stress when a molten sample is stretched at a constant speed. Specifically, a melt tension tester (manufactured by Toyo Seiki) was used to measure the temperature 2
Under conditions of 30 ° C., a nozzle diameter of 2.1 mm, and an extrusion speed of 15 mm / min, the extruded strand is wound at a winding speed of 200 mm.
It was measured as the tension applied to the monofilament when wound at rpm. (5) Refractive index (n _D ) In accordance with ASTM D542, a sodium wire (λ ₀ = 5) was measured using an Abbe refractometer 2T (manufactured by Atago Co., Ltd.).
89.3 nm).

[0164]

Comparative Examples 1-3 Examples 1 were prepared from the components shown in Table 1.
A propylene polymer composition was obtained in the same manner as described above. Table 1 shows the results.

[0165]

[Table 1]

[0166]

Examples 3 to 5 Example 1 was prepared from the components shown in Table 2.
A propylene polymer composition was obtained in the same manner as described above. Table 2 shows the results.

[0167]

Comparative Example 4 A propylene polymer composition was obtained from the components shown in Table 2 in the same manner as in Example 1. Table 2 shows the results
Shown in

[0168]

[Table 2]

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[Procedure amendment]

[Submission date] January 22, 1997

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0163

[Correction method] Change

[Correction contents]

The obtained propylene-based polymer composition was
Press molding was performed at 30 ° C., and the bending strength, impact strength, and transparency were evaluated by the following evaluation methods. Table 1 shows the results. (1) Bending test (bending elastic modulus: FM) in compliance with ASTM D 790, using a test piece having a thickness of 2mm was injection-molded under predetermined conditions, a span of 32 mm, the bending measured under the conditions of speed of 5 mm / min did. (2) Impact strength (IZ) Measured at 0 ° C. using a 3 mm thick test piece (post-notch) in accordance with ASTM D256. (3) Transparency (haze) According to ASTM D1003-52, the thickness is 0.5 mmt.
Of the test specimen of Nippon Denshoku Industries Co., Ltd.
It measured using DH-20D. (4) Melt tension (MT) Melt tension (MT) is measured as stress when a molten sample is stretched at a constant speed. Specifically, a melt tension tester (manufactured by Toyo Seiki) was used to measure the temperature 2
Under conditions of 30 ° C., a nozzle diameter of 2.1 mm, and an extrusion speed of 15 mm / min, the extruded strand is wound at a winding speed of 200 mm.
It was measured as the tension applied to the monofilament when wound at rpm. (5) Refractive index (n _D ) In accordance with ASTM D542, a sodium wire (λ ₀ = 5) was measured using an Abbe refractometer 2T (manufactured by Atago Co., Ltd.).
89.3 nm).

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 23:08) B29K 23:00 B29L 22:00

Claims (7)

[Claims] (A) (1) The melt flow rate (MFR) measured at 230 ° C. under a load of 2.16 kg is 0.01 to 1.
(2) 200 ° C., angular velocity ω = 10 ⁻¹
angular velocity dependent loss tangent measured in rad / sec tanδ _0.1
Loss tangent ratio (tan δ) of the angular velocity dependent loss tangent tanδ ₁₀₀ measured at 200 ° C. and angular velocity ω = 10 ² rad / sec.
_0.1 / tan δ ₁₀₀ ) is from 1.05 to 5.8, and 40 to 96% by weight of the propylene polymer; and (B) (1) the density d ₁ is from 0.905 to 0.950 g / cm ³ ; (2) The melt flow rate (MFR) measured at 190 ° C. under a load of 2.16 kg is 0.001 to 15 g / 10
(C) (1) a density d ₂ of less than 0.891 g / cm ³ ,
(2) An ethylene / α-olefin random copolymer 2 having a melt flow rate (MFFR) measured at 190 ° C. under a load of 2.16 kg of 0.001 to 15 g / 10 min.
30% by weight of a propylene polymer composition. 2. (A) (1) The melt flow rate (MFR) measured at 230 ° C. under a load of 2.16 kg is 0.01 to less.
(2) 200 ° C., angular velocity ω = 10 ⁻¹
angular velocity dependent loss tangent measured in rad / sec tanδ _0.1
Loss tangent ratio (tan δ) of the angular velocity dependent loss tangent tanδ ₁₀₀ measured at 200 ° C. and angular velocity ω = 10 ² rad / sec.
_0.1 / tan δ ₁₀₀ ) is from 1.05 to 5.8, (3) contains 0.001 to 5 mol% of units derived from ethylene, and (4) contains 0.1% of a decane-soluble component at 64 ° C. 40 to 96% by weight of a propylene polymer contained in an amount of 1 to 25% by weight
(B) (1) the density d ₁ is 0.905 to 0.950 g / cm ³ , and (2) the melt flow rate (MFR) measured at 190 ° C. under a load of 2.16 kg is 0.001. ~ 15g / 10
(C) (1) a density d ₂ of less than 0.891 g / cm ³ ,
(2) An ethylene / α-olefin random copolymer 2 having a melt flow rate (MFFR) measured at 190 ° C. under a load of 2.16 kg of 0.001 to 15 g / 10 min.
30% by weight of a propylene polymer composition. 3. The propylene polymer (A) according to claim 1, wherein the propylene polymer contains a high molecular weight component having an intrinsic viscosity [η] of 8 to 30 dl / g in an amount of 0.1 to 20% by weight. 2
A propylene-based polymer composition according to item 1. 4. The ethylene polymer and the density d ₁ of (B), the difference between the density d ₂ of the ethylene · alpha-olefin random copolymer _{(C) (d 1 -d 2} ) is 0.045 to 0 0.087g / cm
Propylene-based polymer composition according to any one of claims 1 to 3, characterized in that it is ^3. 5. A blow molded article comprising the propylene polymer composition according to claim 1. 6. A film or sheet comprising the propylene polymer composition according to claim 1. 7. An injection molded article comprising the propylene-based polymer composition according to claim 1.