JPH09328598A - Propylene-base polymer composition and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a propylene-base polymer composition capable of yielding injection-moldings which are excellent in stiffness and impact resistance, particularly in injection-moldability, have few noticeable flow marks and stones, and are excellent in appearance, and its use. SOLUTION: The propylene-base polymer composition suitable for injection- moldings comprises (A) 30-95wt.% propylene block copolymer which (1) contains 2-36wt.% of a 64 deg.C decane-soluble component, (2) the 64 deg.C decane-soluble component containing 20-55mol% of units derived from ethylene, (3) the ratio of η*(0.01) measured at an angular velocity ω of 0.01 rad/s to η*(100) measured at an angular velocity ω of 100 rad/s being 50 or more in a frequency viscoelasticity measurement of the 64 deg.C decane-soluble component at 200 deg.C, (B) 5-70wt.% ethylene-α-olefin random copolymer and/or styrene-base block copolymer, and (C) 0-25wt.% inorganic filler.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a propylene-based polymer composition which is excellent in rigidity and impact resistance, particularly excellent in injection moldability, and which is capable of forming an injection-molded article having a flow mark that is inconspicuous and an excellent appearance. And its use.

[0002]

BACKGROUND OF THE INVENTION Polypropylene has excellent rigidity, hardness and heat resistance, and can be easily formed into a desired shape by various molding methods such as injection molding, calender molding and extrusion molding, and at a low cost. Widely used in a wide range of applications, such as home appliance housings, film or sheet applications, containers, automotive interior applications, fenders, bumpers, side moldings, mudguards, mirror covers, and other automotive exterior goods, general miscellaneous goods, etc. Has been done.

Polypropylene or a rubber component such as polyisobutylene, polybutadiene, an amorphous or low crystalline ethylene / propylene copolymer (EPR) is blended with polypropylene according to various uses to improve impact resistance. Polypropylene compositions are also known.
Further, as a polypropylene composition containing polypropylene and a rubber component, in addition to the above blend,
Polymerization of crystalline polypropylene component, ethylene
Propylene block copolymers that form propylene copolymer components are also known.

In the polypropylene composition as described above,
The impact strength can be improved by increasing the molecular weight of the polypropylene component or the rubber component, but when the polypropylene composition is molded, particularly when injection-molded, the fluidity of the molten resin is lowered and the moldability is deteriorated. Flow marks are likely to appear in the injection molded product according to the flow direction of the molten resin. In an injection molded product such as an automobile bumper, if the flow mark is conspicuous, there is a problem in that the appearance is inferior and the commercial value thereof is lowered.

Also, "porosity" may be seen on the surface of a film or sheet obtained by injection molding of a polypropylene composition. If the "porosity" is large, the external appearance is inferior and the commercial value is lowered as in the above case. However, if the amount of the rubber component is increased in order to improve the impact resistance, the “bugs” tend to increase.

The present inventor has been made in view of the above-mentioned prior art, and is excellent in rigidity and impact resistance, particularly in injection moldability, and is excellent in appearance with flow marks and spots being inconspicuous. When a propylene block copolymer capable of obtaining an injection-molded article was studied, a viscosity η * measured at an angular velocity ω = 0.01 rad / s
Ratio of (ω _0.01 ) and viscosity η * (ω ₁₀₀ ) measured at angular velocity ω = 100 rad / s η * (ω _0.01 ) / η *
(Ω ₁₀₀ ) is _{50 to 10} ⁵ and a propylene block copolymer containing a specific amount of a decane-soluble component (rubber component) at 64 ° C., an ethylene / α-olefin random copolymer and / or a styrene block The propylene-based polymer composition containing a copolymer has been found to satisfy the above-mentioned characteristics, and the present invention has been completed.

[0007]

An object of the present invention is to provide a propylene-based polymer composition which is excellent in rigidity and impact resistance, particularly in injection moldability, and which is capable of producing an injection-molded article in which flow marks and spots are less noticeable and which has an excellent appearance. It is intended to provide a product and its use.

[0008]

SUMMARY OF THE INVENTION The propylene polymer composition according to the present invention comprises (A) (1) a decane-soluble component at 64 ° C. in an amount of 2 to 36% by weight, and (2) the decane-soluble component is ethylene. (3) the decane-soluble component has an angular velocity of ω 0.01 rad at 200 ° C.
Viscosity η * (ω _0.01 ) measured in / s and angular velocity ω 10
Ratio η * with viscosity η * (ω ₁₀₀ ) measured at 0 rad / s
(Ω _0.01 ) / η * (ω ₁₀₀ ) of 50 or more, a propylene block copolymer; 30 to 95% by weight, and (B) an ethylene / α-olefin random copolymer (B-
1) and / or styrene block copolymer (B-2)
5 to 70% by weight, and (C) an inorganic filler; 0 to 25% by weight.

The propylene polymer composition according to the present invention is preferably used by molding it into an injection molded product, and is particularly suitable as an injection molded product for automobile interior and exterior products. Further, the propylene polymer composition according to the present invention can be suitably used for film or sheet applications.

[0010]

DETAILED DESCRIPTION OF THE INVENTION The propylene polymer composition according to the present invention and its use will be specifically described below.

The propylene-based polymer composition according to the present invention comprises (A) a specific propylene block copolymer,
(B) Ethylene / α-olefin random copolymer (B-
1) and / or styrene block copolymer (B-2)
And (C) inorganic filler as required.

First, the (A) propylene block copolymer will be described below. (A) Propylene Block Copolymer The propylene block copolymer used in the present invention is (1) a decane-soluble component at 64 ° C. in an amount of 2 to 36% by weight.
It is preferably contained in an amount of 5 to 30% by weight, more preferably 5 to 25% by weight, and the decane-soluble component satisfies the following properties (2) and (3).

The propylene block copolymer has a temperature of 64 ° C.
Specifically, the amount of the decane component in Example 2 was such that 5 g of the sample (propylene block copolymer) was immersed in 200 cc of boiling decane for 5 hours to dissolve it, then cooled to 64 ° C., and the precipitated solid phase was G4. It can be determined by filtering with a glass filter, separating into a solid phase (insoluble component) and a filtrate (soluble component), and evaporating the solution from the filtrate.

The 64 ° C. decane-soluble component is a rubber component in the propylene block copolymer, and is usually ethylene.
Propylene copolymers and atactic polypropylene. (2) The decane-soluble component at 64 ° C contains 20 to 55 mol% of units derived from ethylene, preferably 20 units.
˜50 mol%, more preferably 25 to 50 mol%. The ethylene unit content in the decane-soluble component at 64 ° C can be determined by measuring ¹³ C-NMR by a conventional method. (3) The decane-soluble component at 64 ° C has a viscosity η * (ω _0.01 ) measured at an angular velocity of ω = 0.01 rad / s at 200 ° C.
And the viscosity η * measured at an angular velocity ω = 100 rad / s
The ratio of (ω ₁₀₀ ) to η * (ω _0.01 ) / η * (ω ₁₀₀ ) is 5
It is 0 or more, preferably 80 or more, more preferably 100 or more and 10 ⁵ or less.

The angular velocity-dependent viscosities η * (ω _0.01 ) and η * (ω ₁₀₀ ) of the decane-soluble component at 64 ° C. were measured using a viscoelasticity measuring device (rheometer; manufactured by Rheometrics Co., Ltd.) in the form of parallel discs. 2 between plates (radius 12.5 mm)
mm-thick disc-shaped sample (64 ° C decane soluble component molded disc)
And the plate is rotated at a corresponding angular velocity ω at 200 ° C., and the viscosity is measured.

Angular velocity ω of decane-soluble component at 64 ° C.
The viscosity ratio η * (ω _0.01 ) / η * (ω ₁₀₀ ) measured at _0.01 rad / s and 100 rad / s is an index of the molecular weight distribution of the component.

In the propylene block copolymer used in the present invention, the decane-soluble component at 64 ° C. has a viscosity ratio η * (ω
_0.01 ) / η * (ω ₁₀₀ ) value is as large as 50 or more, and the molecular weight distribution is wide.

The viscosity ratio of the decane-soluble component at 64 ° C. contained in the conventionally known propylene block copolymer is 10
About 30. The propylene block copolymer containing the specific 64 ° C. decane-soluble component as described above is excellent in rigidity and impact resistance, and particularly excellent in injection moldability, and is excellent in appearance with less noticeable flow marks and spots. It is possible to manufacture a molded product that has

In the propylene block copolymer used in the present invention, the intrinsic viscosity [η] of the decane-insoluble component (solid phase portion) at 64 ° C. is 0.1 to 6 dl / g, preferably 0.1 to 6. 4 dl / g, more preferably 0.5-4
It is desirable that it is dl / g. In this specification,
The intrinsic viscosity [η] is a value measured in decalin at 135 ° C.

The propylene block copolymer is a decane-insoluble component and a boiling heptane-insoluble component of 80 to 1
It is desirable to contain it in an amount of 00% by weight, preferably 85 to 100% by weight (boiling heptane extraction residual rate).

Furthermore, the stereoregularity index value of the boiling heptane-insoluble component pentad isotacticity [M ₅ ] (mm
mm fraction) is 0.95-0.99, preferably 0.97.
It is desirable that it is ˜0.99. The crystallinity of the boiling heptane-insoluble component measured by the X-ray diffraction method is 60% or more, preferably 65% or more, and more preferably 65 to 95%.
It is desirable that

This pentad isotacticity is
It is determined as the peak intensity ratio [Pmmmm] / [Pw] in the ¹³ C-NMR spectrum of the boiling heptane-insoluble component. Here, [Pmmmm] is the methyl group peak intensity of the third unit in the isotactic bond 5 chain of propylene units, and [Pw] is the methyl group peak intensity of all propylene units.

The boiling heptane-insoluble component of the decane-insoluble component is a suspension of the decane-insoluble component in n-decane in G-4 (or G-
After separating by filtration with a glass filter of 2) and drying under reduced pressure, 1.5 g of a sample is obtained as a residue of extraction after Soxhlet extraction with heptane for 6 hours or longer.

Melt flow rate (MFR: ASTM D123) of the propylene block copolymer according to the present invention
8; 230 ℃, under 2.16kg load) 0.1-150g
/ 10 minutes, preferably 0.5 to 150 g / 10 minutes, and the bulk specific gravity is 0.35 g / ml or more, preferably 0.38 g / ml or more.

The propylene block copolymer according to the present invention is produced by a multi-stage polymerization including polymerization of propylene and copolymerization of ethylene and propylene as described below,
Although it contains units derived from propylene and ethylene, it may contain units derived from other copolymerizable monomers as long as the object of the present invention is not impaired. Α-olefins such as 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-hexadecene, 4-methyl-1-pentene,
It may contain units derived from vinyl compounds such as vinylcyclopentene, vinylcyclohexane and vinylnorbornane, vinyl esters such as vinyl acetate, unsaturated organic acids such as maleic anhydride or derivatives thereof.

The propylene block copolymer used in the present invention 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 and the like may be contained as a prepolymer formed by prepolymerization.

The propylene block copolymer as described above is produced, for example, by using a catalyst as described below to produce (i) an ethylene / propylene copolymer component, (ii) a polypropylene component, and (iii) Then, it can be obtained by producing an ethylene / propylene copolymer component. This will be specifically described below.

In the present invention, the term "polymerization" means
The term "polymer" may be used to mean not only homopolymerization but also copolymerization, and the term "polymer" may be used to include not only homopolymer but also copolymer.

In the present invention, each of the following steps may be carried out by any of a gas phase polymerization method, a solution polymerization method, a suspension polymerization method and the like. An inert hydrocarbon may be used as the polymerization medium, or liquid propylene may be used as the polymerization medium. The polymerization may be carried out by any of batch system, semi-continuous system and continuous system.

The polymerization conditions in each step are that the polymerization temperature is about −
50 to 200 ° C., preferably in the range of about 20 to 100 ° C.,
The polymerization pressure is normal pressure to 100 kg / cm ^2, preferably about 2 to
It is appropriately selected within the range of 50 kg / cm ² G.

First, in the present invention, ethylene and propylene are copolymerized in the presence of a catalyst so that the intrinsic viscosity [η ₁ ] is 3 to 30 dl / g, preferably 4 to 25 dl / g, more preferably 5 to 25 dl / g. g of low crystalline or amorphous ethylene
A propylene copolymer component (i) (high molecular weight rubber component) is produced.

Amorphous ethylene / propylene copolymer component
(i) At the time of production, other monomers as described above may be copolymerized with ethylene and propylene, if necessary, as long as the object of the present invention is not impaired.

In this step, an ethylene / propylene copolymer component (i) containing 10 to 70 mol% of units derived from ethylene, preferably 10 to 60 mol%, more preferably 15 to 55 mol% is produced. It is preferable.

In this step, the ethylene / propylene copolymer component (i) is finally obtained in a propylene block copolymer of 0.1 to 33.1% by weight, preferably 0.1 to 32% by weight. Is 0.1 to 30% by weight
It is desirable to manufacture it so that it is contained in the amount of. The content (% by weight) of the high molecular weight ethylene / propylene copolymerization component (i) will be referred to as w ₁ below.

In the present invention, when the propylene block copolymer is produced, ethylene and propylene are first copolymerized, so that hydrogen is not mixed in the polymerization system and a high molecular weight ethylene / propylene copolymer component (rubber) is prepared. Ingredients) can be produced.

In the above step, the molecular weight of the ethylene / propylene copolymerization component (i) can be adjusted by allowing hydrogen to be present in the reaction system, but it is preferable not to use hydrogen.

In the present invention, the production process of the ethylene / propylene copolymerization component (i) can be carried out in two or more stages by changing the polymerization conditions. In the present invention, after the low crystalline or amorphous ethylene / propylene copolymer component (i) is produced as described above, the crystalline polypropylene component (ii) is then produced.

In the production process of the polypropylene component (ii),
In the presence of the ethylene / propylene copolymerization component (i) obtained above, it is preferable to carry out homopolymerization of propylene to produce homopolypropylene, but if crystalline polypropylene can be obtained, propylene and a small amount of the above-mentioned substances can be produced. Such other monomers may be copolymerized. Specifically, it may contain units derived from other monomers in an amount of less than 10 mol%.

In the step of producing the polypropylene component (ii), hydrogen can be used to control the melt flow rate of the propylene block copolymer obtained. In the present invention, it is preferable to use hydrogen in the production process of the polypropylene component (ii) so that the propylene block copolymer having the melt flow rate value as described above is finally obtained.

The production process of the polypropylene component (ii) can be carried out in two or more steps by changing the polymerization conditions. Such a crystalline polypropylene component (ii) is contained in the finally obtained propylene block copolymer in an amount of 65 to 98% by weight, preferably 70 to 95% by weight, more preferably 75% by weight.
It is desirable to manufacture such that it is contained in an amount of ˜95% by weight.

In the present invention, ethylene and propylene are then copolymerized in the presence of the ethylene / propylene copolymerization component (i) and the crystalline polypropylene component (ii) obtained above to obtain a low crystalline or non-crystalline compound. A crystalline ethylene / propylene copolymerization component (iii) is produced.

In the step of producing the ethylene / propylene copolymerization component (iii), the intrinsic viscosity [η ₂ ] is 1 to 4 dl / g, preferably 1.2 to 4 dl / g, and more preferably 1.2 to 3.8 dl.
/ G of low crystalline or amorphous ethylene / propylene copolymer component (low molecular weight rubber component) is produced.

This ethylene / propylene copolymer component (ii
The intrinsic viscosity [η ₂ ] of i) can be calculated from the following formula. (W _m / w _f ) · log [η _m ] + (w ₂ / w _f ) · log [η ₂ ]
= Log [η _f ] where w _m + w ₂ = w _f w _m ; propylene obtained at the end of the production process of the ethylene / α-olefin copolymerization component (i) and the polypropylene component (ii). Block copolymer intermediate 6
4 ° C. Decane soluble component amount (wt%) w ₂ ; Content of ethylene / propylene copolymer component (iii) in the propylene block copolymer finally obtained (wt%) w _f ; Amount of decane-soluble component at 64 ° C in propylene block copolymer (wt%) [η _m ]; Intrinsic viscosity of decane-soluble component at 64 ° C [η _f ]; Intrinsic viscosity of decane-soluble component at 64 ° C In the step of producing the ethylene / α-olefin copolymerization component (iii), a low molecular weight ethylene / propylene copolymerization component is produced, and the intrinsic viscosity [η ₂ ] thereof is obtained in the step (i) as described above. It is smaller than the intrinsic viscosity [η ₁ ] of the high molecular weight ethylene / propylene copolymer component to be obtained, and specifically, the ratio of the intrinsic viscosity [η ₂ ] and the above [η ₁ ] ([η ₂ ] /
[Η ₁ ]) is 0.35 or less, preferably 0.25 or less.

Ethylene / α-olefin copolymerization component (ii
In the production process of i), ethylene and propylene are copolymerized to obtain 10 to 70 mol% of units derived from ethylene.
Preferably 10-60 mol%, more preferably 15-55
It is preferable to produce the ethylene / propylene copolymer component contained in an amount of mol%. If necessary, the above-mentioned other monomers may be copolymerized with ethylene and propylene as long as the object of the present invention is not impaired.

Ethylene / α-olefin copolymerization component (ii
In the production process of i), the molecular weight of the ethylene / propylene copolymerization component can be adjusted by using hydrogen, and a low molecular weight ethylene / propylene copolymerization component having the above-mentioned intrinsic viscosity in the presence of hydrogen can be produced. Preferably.

In this step, the low molecular weight ethylene / propylene copolymer component (iii) as described above is contained in the propylene block copolymer finally obtained in an amount of 1.9 to 34.9% by weight, preferably 3 to 3% by weight. It is desirable to manufacture such that it is contained in an amount of 34.9% by weight. The content (% by weight) of the ethylene / α-olefin copolymerization component (iii) in the finally obtained propylene block copolymer can also be determined from the polymerization amount.

In the present invention, in the finally obtained propylene block copolymer, the content of the ethylene / propylene copolymerization component (iii) (w ₂ ) of the high molecular weight ethylene / propylene copolymerization component (i) is The ratio w ₂ / w ₁ to the content (w ₁ ) is 1 or more, preferably 1.5 or more.

This production process can be carried out in two or more stages by changing the polymerization conditions. In the present invention, when producing the propylene block copolymer as described above, it is preferable to use a catalyst for producing a polyolefin having high stereoregularity. For example, (a) a solid containing magnesium, titanium, halogen and an electron donor. Titanium catalyst component,
(B) an organometallic compound, and (c) an organosilicon compound (c-1) represented by the following formula (i) or a compound (c-2) having two or more ether bonds existing through a plurality of atoms. When,
A catalyst consisting of can be used.

R ^a _n Si (OR ^b ) _4-n ... (i) (where n is 1, 2 or 3 and at least one of R ^a is a secondary or tertiary hydrocarbon group) , N is 2 or 3, R ^a 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 thereof include allyloxy magnesium such as phenoxy magnesium and dimethylphenoxy magnesium, and magnesium carboxylates 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 the 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 used as a polysiloxane compound, a halogen-containing silane compound, a halogen-containing aluminum compound, an ester, an alcohol,
It 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 metallic magnesium 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 mentioned above can be used, but it is preferable that the finally obtained solid titanium catalyst component (a) is in the form of a halogen-containing magnesium compound. When using a halogen-free magnesium compound,
It is preferable to carry out a catalytic reaction with a halogen-containing compound in the process of preparing the catalyst component.

Among the above, a magnesium compound having no reducing ability is preferable, a halogen-containing magnesium compound is more preferable, and magnesium chloride, alkoxy magnesium chloride, and aryloxy magnesium chloride are particularly preferable.

In the present invention, the magnesium compound is preferably used in a liquid state when preparing the catalyst component,
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.

Among the magnesium compounds as described above,
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 this liquefaction reaction, a hydrocarbon solvent 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.

When the solid titanium catalyst component (a) is prepared, 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
Mono-halogenated 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, halogen-containing titanium compounds are preferable, titanium tetrahalides are more preferable, and titanium tetrachloride is particularly preferable. These titanium compounds can be used in combination of two or more. Further, the titanium compound may be diluted with a hydrocarbon compound or a halogenated hydrocarbon compound and used.

The electron donor used in the preparation of the solid titanium catalyst component (a) is, 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 to 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 polyvalent carboxylic acid ester having a skeleton represented by the following general formula can be mentioned as a particularly preferable example.

[0065]

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
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 polycarboxylic acid ester include diethyl succinate, dibutyl succinate, diethyl methylsuccinate, diisobutyl α-methylglutarate, diethyl methylmalonate, diethyl ethylmalonate and isopropylmalon. Acid diethyl, diethyl butylmalonate, diethyl phenylmalonate, diethyl diethylmalonate, diethyl dibutylmalonate, monooctyl maleate, dioctyl maleate, dibutyl maleate, dibutyl butylmaleate, diethyl butylmaleate, β-methylglutar Acid diisopropyl, ethyl succinate, di-2-ethylhexyl fumarate, diethyl itaconate, aliphatic polycarboxylic acid esters such as dioctyl citracone, diethyl 1,2-cyclohexanecarboxylate, 1,2-cyclyl 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 ester 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. Mention may also be made of acid esters and the like.

Further, as the electron donor, an organosilicon compound or a polyether compound as described below 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 the carboxylic acid ester among the above, and it is particularly preferable to use the polyvalent carboxylic acid ester, especially the phthalic acid ester.

Two or more of these electron donors can be used in combination. 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 thereof include resins such as O ₂ , BaO, ThO, and styrene-divinylbenzene copolymer. Of these,
Al ₂ O ₃ , SiO ₂ , and a styrene-divinylbenzene copolymer are preferably used.

The solid titanium catalyst component (a) can be prepared by employing any method including known methods, but a brief description will be given below with some 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 in which a complex consisting of a magnesium compound and an electron donor is brought into contact with an organometallic compound to cause a reaction, and then a titanium compound is brought into a catalytic reaction. (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) After a magnesium compound-supported carrier is obtained from a mixture of a magnesium compound solution containing a liquefying agent and a hydrocarbon solvent, an electron donor, and a carrier, a titanium compound is then contacted. Method.

(5) magnesium compound, titanium compound,
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 a titanium compound is brought into contact therewith. In this process, the electron donor is used at least once.

(8) A method of bringing an alkoxy group-containing magnesium compound into contact 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 of bringing a complex comprising an alkoxy group-containing magnesium compound and an electron donor into contact with an organometallic compound and then contacting 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 of reacting a liquid magnesium compound having no reducing ability with a liquid titanium compound in the presence of an electron donor to precipitate a solid magnesium-titanium complex.

(13) A method of further reacting the reaction product obtained in (12) with a titanium compound. (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 of treating a solid material obtained by pulverizing a magnesium compound, an electron donor and a titanium compound with either 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. In addition, after pulverization, a pretreatment with a reaction aid may be performed, and then a treatment with halogen or the like may be performed. As the reaction aid, an organic metal compound or a halogen-containing silicon compound is used.

(16) A method in which a magnesium compound is pulverized and then contacted 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 (11) to (16) above with halogen or 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, alkoxy magnesium, aryloxy magnesium or the like is brought into contact with a titanium compound, an electron donor and optionally a halogen-containing hydrocarbon.

(20) A method of bringing a hydrocarbon solution containing a magnesium compound and alkoxytitanium into contact with an electron donor and, if necessary, a titanium compound. At this time, it is preferable to coexist with 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 added. How to react.

The amount of each component used for contact varies depending on the preparation method and cannot be specified unconditionally. For example, the amount of 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 (atoms) 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 as a catalyst together with the solid titanium catalyst component (a) as described above.
Is used. As the organometallic compound, those containing a metal selected from Group I to Group III of the periodic table are preferable, and specifically, the following organoaluminum compounds and complex alkyls of Group I metal and aluminum are shown. Compound,
Examples thereof include organometallic compounds of Group II metals.

(B-1) General formula R ¹ _m Al (OR ² ) _n H _p X _q (In the formula, R ¹ and R ² are carbonized containing usually 1 to 15, preferably 1 to 4 carbon atoms. 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. ).

[0092] (b-2) the general formula M ¹ AlR ¹ ₄ (wherein, M ¹ is Li, Na, a K, R ¹ is as defined above.) And a group I metal and aluminum represented by Complex alkylated product.

(B-3) General 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 (R ¹ and R ² are the same as above, and m is preferably 1.
5 ≦ m ≦ 3. R ¹ _m AlX _3-m (R ¹ is the same as defined above, X is halogen, and m is preferably 0 <m <3), 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.

Specific examples of the aluminum compound belonging to (b-1) include trialkylaluminums such as triethylaluminum and tributylaluminum, trialkenylaluminums such as triisoprenylaluminum, diethylaluminum ethoxide and dibutylaluminum butoxide. Dialkyl aluminum alkoxide, ethyl aluminum sesquiethoxide,
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 organoaluminum compound in which two or more aluminum atoms are bound to each other 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.

Among 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, (a) the solid titanium catalyst component as described above, (b) the organometallic compound, and (c) the organosilicon compound (c) as the electron donor are used as the catalyst.
-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.

The substituted cyclopentenyl group includes 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.

Examples of the substituted cyclopentadienyl group include 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 group, s-butyl group, s-amyl group and α-methylbenzyl group. Examples of the hydrocarbon group whose carbon adjacent to is a tertiary carbon include t-butyl group, t-amyl group, α, α′-dimethylbenzyl group, and admantyl group.

The organosilicon compound represented by the above formula (i) (c
-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.

[0106]

Embedded image

In the formula, R ^a and R ^c are each independently adjacent to 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 secondary carbon or tertiary carbon.

Examples of the dimethoxy compound represented by the formula (ii) include dicyclopentyldimethoxysilane, dicyclopentenyldimethoxysilane, dicyclopentadienyldimethoxysilane, di-t-butyldimethoxysilane and di (2- Methylcyclopentyl) dimethoxysilane, di (3-methylcyclopentyl) dimethoxysilane, di (2-ethylcyclopentyl) dimethoxysilane,
Di (2,3-dimethylcyclopentyl) dimethoxysilane,
Di (2,4-dimethylcyclopentyl) dimethoxysilane,
Di (2,5-dimethylcyclopentyl) dimethoxysilane,
Di (2,3-diethylcyclopentyl) dimethoxysilane,
Di (2,3,4-trimethylcyclopentyl) dimethoxysilane, di (2,3,5-trimethylcyclopentyl) dimethoxysilane, di (2,3,4-triethylcyclopentyl) dimethoxysilane, di (tetramethylcyclopentyl) dimethoxysilane , Di (tetraethylcyclopentyl) dimethoxysilane, di (2-methylcyclopentenyl) dimethoxysilane, di (3-methylcyclopentenyl) dimethoxysilane, di (2-ethylcyclopentenyl) dimethoxysilane, di (2-n-butylcyclo) Pentenyl) dimethoxysilane, di (2,3-dimethylcyclopentenyl) dimethoxysilane, di (2,4-dimethylcyclopentenyl) dimethoxysilane, di (2,5-dimethylcyclopentenyl) dimethoxysilane, di (2,3, 4-trimethylcyclopentenyl)
Dimethoxysilane, di (2,3,5-trimethylcyclopentenyl) dimethoxysilane, di (2,3,4-triethylcyclopentenyl) dimethoxysilane, di (tetramethylcyclopentenyl) dimethoxysilane, di (tetraethylcyclopentenyl) dimethoxy Silane, di (2-methylcyclopentadienyl) dimethoxysilane, di (3-methylcyclopentadienyl) dimethoxysilane, di (2-ethylcyclopentadienyl) dimethoxysilane, di (2-n-butylcyclopentenyl) ) Dimethoxysilane, di (2,3-dimethylcyclopentadienyl) dimethoxysilane, di (2,4-dimethylcyclopentadienyl) dimethoxysilane, di (2,5-dimethylcyclopentadienyl) dimethoxysilane, di (2,3-diethylcyclopentadienyl) dimethoxysilane, di (2,3,4-trimethyl) Dicyclopentadienyl) dimethoxysilane, di (2,3,5-trimethylcyclopentadienyl) dimethoxysilane, di (2,3,4-triethylcyclopentadienyl) dimethoxysilane, di (2,3,4 , 5-Tetramethylcyclopentadienyl) dimethoxysilane, di (2,3,4,5-tetraethylcyclopentadienyl) dimethoxysilane, di (1,2,3,4,5-pentamethylcyclopentadienyl) ) Dimethoxysilane, di (1,2,
3,4,5-pentaethylcyclopentadienyl) dimethoxysilane, di-t-amyl-dimethoxysilane, di (α, α'-dimethylbenzyl) dimethoxysilane, di (admantyl) dimethoxysilane, admantyl-t-butyldimethoxy Examples include silane, cyclopentyl-t-butyldimethoxysilane, diisopropyldimethoxysilane, di-s-butyldimethoxysilane, di-s-amyldimethoxysilane, and isopropyl-s-butyldimethoxysilane.

In the above formula (i), when n is 3, tricyclopentylmethoxysilane, tricyclopentylethoxysilane, dicyclopentylmethylmethoxysilane, dicyclopentylethylmethoxysilane, dicyclopentylmethylethoxysilane, cyclopentyldimethylmethoxysilane. Examples include monoalkoxysilanes such as silane, cyclopentyldiethylmethoxysilane, and cyclopentyldimethylethoxysilane.

Among these, 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 compound (c-1) may be used in combination of two or more kinds. 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.

[0113]

Embedded image

In the formula, n is an integer of 2 ≦ n ≦ 10, and R
^{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.

As the polyether compound as described above,
Specifically, 2- (2-ethylhexyl) -1,3-dimethoxypropane, 2-isopropyl-1,3-dimethoxypropane, 2
-Butyl-1,3-dimethoxypropane, 2-s-butyl-1,3-dimethoxypropane, 2-cyclohexyl-1,3-dimethoxypropane, 2-phenyl-1,3-dimethoxypropane, 2-cumyl-1 , 3-Dimethoxypropane, 2- (2-phenylethyl) -1,3-dimethoxypropane, 2- (2-cyclohexylethyl) -1,3-dimethoxypropane, 2- (p-chlorophenyl) -1,3- Dimethoxypropane, 2- (diphenylmethyl) -1,3-dimethoxypropane, 2- (1-naphthyl) -1,3-
Dimethoxypropane, 2- (2-fluorophenyl) -1,3-
Dimethoxypropane, 2- (1-decahydronaphthyl) -1,3
-Dimethoxypropane, 2- (pt-butylphenyl) -1,3-
Dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane, 2,2-diethyl-1,3-dimethoxypropane,
2,2-dipropyl-1,3-dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane, 2,2-dibutyl-1,3-
Dimethoxypropane, 2-methyl-2-propyl-1,3-dimethoxypropane, 2-methyl-2-benzyl-1,3-dimethoxypropane, 2-methyl-2-ethyl-1,3-dimethoxypropane,
2-methyl-2-isopropyl-1,3-dimethoxypropane, 2-
Methyl-2-phenyl-1,3-dimethoxypropane, 2-methyl
-2-Cyclohexyl-1,3-dimethoxypropane, 2,2-bis (p-chlorophenyl) -1,3-dimethoxypropane, 2,2-
Bis (2-cyclohexylethyl) -1,3-dimethoxypropane, 2-methyl-2-isobutyl-1,3-dimethoxypropane, 2-methyl-2- (2-ethylhexyl) -1,3-dimethoxypropane, 2 , 2-Diisobutyl-1,3-dimethoxypropane, 2,2-diphenyl-1,3-dimethoxypropane, 2,2-dibenzyl-1,3-dimethoxypropane, 2,2-bis (cyclohexylmethyl) -1, 3-dimethoxypropane, 2,2-diisobutyl-1,3-diethoxypropane, 2,2-diisobutyl-
1,3-dibutoxypropane, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, 2- (1-methylbutyl) -2-
Isopropyl-1,3-dimethoxypropane, 2- (1-methylbutyl) -2-s-butyl-1,3-dimethoxypropane, 2,2-di
-s-butyl-1,3-dimethoxypropane, 2,2-di-t-butyl-1,3-dimethoxypropane, 2,2-dineopentyl-1,3-
Dimethoxypropane, 2-isopropyl-2-isopentyl-
1,3-dimethoxypropane, 2-phenyl-2-isopropyl-
1,3-dimethoxypropane, 2-phenyl-2-s-butyl-1,3-
Dimethoxypropane, 2-benzyl-2-isopropyl-1,3-
Dimethoxypropane, 2-benzyl-2-s-butyl-1,3-dimethoxypropane, 2-phenyl-2-benzyl-1,3-dimethoxypropane, 2-cyclopentyl-2-isopropyl-1,3-dimethoxypropane, 2-Cyclopentyl-2-s-butyl-1,3-
Dimethoxypropane, 2-cyclohexyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclohexyl-2-s-butyl-1,3-dimethoxypropane, 2-isopropyl-2-s-butyl-1,3-dimethoxy Propane, 2-cyclohexyl-2-cyclohexylmethyl-1,3-dimethoxypropane, 2,3-diphenyl-1,4-diethoxybutane, 2,3-dicyclohexyl-1,4-diethoxybutane, 2,2- Dibenzyl-1,4-diethoxybutane, 2,3-dicyclohexyl-1,4-diethoxybutane, 2,3-diisopropyl-1,4-diethoxybutane, 2,2
-Bis (p-methylphenyl) -1,4-dimethoxybutane, 2,
3-bis (p-chlorophenyl) -1,4-dimethoxybutane,
2,3-bis (p-fluorophenyl) -1,4-dimethoxybutane, 2,4-diphenyl-1,5-dimethoxypentane, 2,5-diphenyl-1,5-dimethoxyhexane, 2,4-diisopropyl -1,5-dimethoxypentane, 2,4-diisobutyl-1,5-dimethoxypentane, 2,4-diisoamyl-1,5-dimethoxypentane, 3-methoxymethyltetrahydrofuran, 3-methoxymethyldioxane, 1,3- Diisobutoxypropane, 1,2-diisobutoxypropane, 1,2-diisobutoxyethane, 1,3-diisoamyloxypropane, 1,3-diisoneopentyloxyethane, 1,3-dineopentyloxypropane , 2,2-tetramethylene-1,3-dimethoxypropane, 2,2
-Pentamethylene-1,3-dimethoxypropane, 2,2-hexamethylene-1,3-dimethoxypropane, 1,2-bis (methoxymethyl) cyclohexane, 2,8-dioxaspiro [5,
5] undecane, 3,7-dioxabicyclo [3,3,1] nonane, 3,7-dioxabicyclo [3,3,0] octane, 3,3-diisobutyl-1,5-oxononane, 6, 6-diisobutyldioxyheptane, 1,1-dimethoxymethylcyclopentane,
1,1-bis (dimethoxymethyl) cyclohexane, 1,1-bis (methoxymethyl) bicyclo [2,2,1] heptane, 1,1
-Dimethoxymethylcyclopentane, 2-methyl-2-methoxymethyl-1,3-dimethoxypropane, 2-cyclohexyl-
2-ethoxymethyl-1,3-diethoxypropane, 2-cyclohexyl-2-methoxymethyl-1,3-dimethoxypropane,
2,2-diisobutyl-1,3-dimethoxycyclohexane, 2-
Isopropyl-2-isoamyl-1,3-dimethoxycyclohexane, 2-cyclohexyl-2-methoxymethyl-1,3-dimethoxycyclohexane, 2-isopropyl-2-methoxymethyl-1,3-dimethoxycyclohexane, 2-isobutyl-2 -Methoxymethyl-1,3-dimethoxycyclohexane, 2-cyclohexyl-2-ethoxymethyl-1,3-diethoxycyclohexane, 2-cyclohexyl-2-ethoxymethyl-1,3-dimethoxycyclohexane, 2-isopropyl-2- Ethoxymethyl-1,3-diethoxycyclohexane, 2-isopropyl-
2-ethoxymethyl-1,3-dimethoxycyclohexane, 2-
Isobutyl-2-ethoxymethyl-1,3-diethoxycyclohexane, 2-isobutyl-2-ethoxymethyl-1,3-dimethoxycyclohexane, tris (p-methoxyphenyl) phosphine, methylphenylbis (methoxymethyl) silane, diphenyl Bis (methoxymethyl) silane, methylcyclohexylbis (methoxymethyl) silane, di-t-
Butylbis (methoxymethyl) silane, cyclohexyl
-t-butylbis (methoxymethyl) silane, i-propyl-
Examples thereof include t-butylbis (methoxymethyl) silane.

Of these, 1,3-diethers are preferably used, particularly 2,2-diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2, 2-dicyclohexyl-1,3-dimethoxypropane, 2,2-bis (cyclohexylmethyl) -1,3-
Dimethoxypropane is preferably used.

Two or more kinds of these polyether compounds (c-2) can be used in combination. 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 the propylene block copolymer is produced by using a catalyst composed of (c) an electron donor, preliminary polymerization can be carried out in advance.

The prepolymerization is carried out by (a) a solid titanium catalyst component, (b) an organometallic compound, and (c) if necessary.
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,
4,4-Dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, allylnaphthalene, allylnorbornane, styrene, dimethylstyrenes, vinylnaphthalenes, allyltoluenes, allylbenzene, vinyl Olefin having a branched structure such as cyclohexane, vinylcyclopentane, vinylcycloheptane, and allyltrialkylsilanes can be used, and these may be copolymerized.

Among these, propylene and 3-methyl-1
-Butene, 3-methyl-1-pentene, 3-ethyl-1-hexene, vinylcyclohexane, allyltrimethylsilane,
Dimethylstyrene and the like are preferably used.

Prepolymerization is carried out by 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. If the amount of prepolymerization is too large, the production efficiency of the (co) polymer in the main polymerization may decrease, and the (co) polymer obtained
When a film or the like is molded from the polymer, fish eyes are likely to occur.

In the prepolymerization, the catalyst can be used at a much higher concentration than the catalyst concentration in the system in the main polymerization.
It is desirable that the solid titanium catalyst component (a) is used in a concentration of usually about 0.01 to 200 mmol, preferably about 0.05 to 100 mmol, in terms of titanium atom, per liter of polymerization volume.

The organometallic compound (b) is generally used in an amount of about 0.1 to 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 during the prepolymerization, but is preferably 0.1 to 50 mol, preferably 0.1 to 50 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 catalyst component to an inert hydrocarbon medium. As the inert hydrocarbon medium,
For example, propane, butane, pentane, hexane, heptane, octane, decane, dodecane, kerosene and other aliphatic hydrocarbons, cyclopentane, cyclohexane, methylcyclopentane and other alicyclic hydrocarbons, benzene, toluene, xylene and other aromatic hydrocarbons. Hydrocarbons, halogenated hydrocarbons such as ethylene chloride and chlorobenzene, and mixtures thereof can be used. It is particularly preferable to use an aliphatic hydrocarbon.

The prepolymerization temperature may be a temperature at which the produced prepolymer does not substantially dissolve 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 batchwise or continuously. During the prepolymerization, the molecular weight can be adjusted by 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)
In terms of titanium atoms per liter of polymerization volume is about 0.0001 to 50 mmol, preferably about 0.001 to 1
It is desirable to use it in an amount of 0 mmol.

The organometallic compound (b) is desirably used in an amount of about 1 to 2000 mol, preferably about 2 to 500 mol, based on 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 the prepolymerization catalyst is used, the solid titanium catalyst component (a) and the organometallic compound (b) can be newly added if necessary. The organometallic compound (b) at the time of prepolymerization and at the time of main polymerization may be the same or different.

The electron donor (c) is always used once in either the prepolymerization or the main polymerization and is used only in the main polymerization, or in both the prepolymerization and the main polymerization. To be The electron donors (c) at the time of prepolymerization and at the time of main polymerization may be the same or different.

Each of the catalyst components as described above is added to the following process for producing the crystalline polypropylene component (ii) and / or
Alternatively, it may not be newly added in the production process of the ethylene / α-olefin copolymerization component (iii), but may be appropriately added.

When the above-mentioned catalyst is used, the crystallinity or stereoregularity index of the obtained propylene block copolymer does not decrease even when hydrogen is used during the polymerization, and the catalytic activity decreases. There is nothing to do.

Further, in the present invention, since the propylene block copolymer can be produced in a high yield per unit amount of the solid titanium catalyst component, the amount of the catalyst in the propylene block copolymer, particularly the halogen content is relatively reduced. Can be made. Therefore, the operation of removing the catalyst in the propylene block copolymer can be omitted, and when molding a molded product using this propylene block copolymer, rust is unlikely to occur in the mold.

(B-1) Ethylene / α-olefin random
Copolymer The ethylene / α-olefin random copolymer used in the present invention is a random copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms, and is preferably an elastomer.

The ethylene / α-olefin random copolymer (B-1) has 60 to 9 units derived from ethylene.
It is desirable to contain a unit derived from an α-olefin having 3 to 10 carbon atoms in an amount of 0 to 40 mol% in an amount of 0 to 40 mol%.

Examples of such α-olefins include propylene, 1-butene, 1-pentene, 1-hexene,
Examples include 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-hexadodecene, 4-methyl-1-pentene and the like.

Of these, α-containing 4 to 10 carbon atoms
Olefin is preferred. Further, the ethylene / α-olefin random copolymer (B-1) used in the present invention contains a unit derived from another polymerizable monomer, if necessary, as long as the characteristics of the present invention are not impaired. May be.

Examples of such other polymerizable monomer 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 the like.

The ethylene / α-olefin random copolymer (B-1) contains a unit derived from such other polymerizable monomer in an amount of 10 mol% or less, preferably 5 mol% or less, more preferably 3 mol% or less. It may be contained in the amount of.

The ethylene / α-olefin random copolymer (B-1) may contain two or more kinds of units derived from C3 to C20, and units derived from other polymerizable monomers. 2 or more types may be contained.

The ethylene / α-olefin random copolymer (B-1) used in the present invention has a melt flow rate (M
FR: ASTM D1238; 190 ° C., under 2.16 kg load) is 0.01 to 100 g / 10 minutes, preferably 0.0
It is preferably 5 to 50 g / 10 minutes.

The intrinsic viscosity [η] (measured in decalin of 135 ° C.) of the ethylene / α-olefin random copolymer (B-1) is preferably 1 to 5 dl / g. The glass transition point Tg is preferably −50 ° C. or lower, and the density is preferably 0.850 to 0.900 g / cm ³ .

In the present invention, the ethylene / α-olefin random copolymer (B-1) is specifically an ethylene / propylene random copolymer, an ethylene / 1-butene random copolymer, or an ethylene / propylene random copolymer. 1-butene random copolymer, ethylene / propylene / ethylidene norbornene random copolymer, ethylene / 1-hexene random copolymer, ethylene / 1-octene random copolymer, and the like. A 1-butene random copolymer, an ethylene / 1-octene random copolymer, an ethylene / 1-hexene random copolymer and the like are particularly preferably used.

The ethylene / α-olefin random copolymer (B-1) as described above is excellent in compatibility with the propylene block copolymer, and is excellent in rigidity and impact resistance from each of these components. It is also possible to form a propylene-based polymer composition which is excellent in fluidity and also excellent in fluidity.

In the present invention, two or more ethylene / α-olefin random copolymers may be used in combination. The ethylene / α-olefin random copolymer (B
-1) can be produced by a conventionally known method using a vanadium catalyst, a titanium catalyst, a metallocene catalyst, or the like.

(B-2) Styrenic Block Copolymer The styrene block copolymer used in the present invention (B-2)
Is preferably composed of block polymer units derived from aromatic vinyl and block polymer units derived from conjugated diene.

Specific examples of the aromatic vinyl forming the styrene block copolymer include styrene, α-methylstyrene, 3-methylstyrene, p-methylstyrene,
4-propylstyrene, 4-dodecylstyrene, 4-cyclohexylstyrene, 2-ethyl-4-benzylstyrene, 4-
(Phenylbutyl) styrene, 1-vinylnaphthalene, 2-
Vinyl naphthalene and the like. Of these, styrene is preferred.

The styrenic block copolymer used in the present invention contains 5 to 80 aromatic vinyl block polymer units.
% By weight, preferably 15-80% by weight. The content of the aromatic vinyl unit, infrared spectroscopy,
It can be measured by a conventional method such as NMR spectroscopy.

Examples of the conjugated diene include butadiene, isoprene, pentadiene, 2,3-dimethylbutadiene and combinations thereof. Among these, isoprene or a combination of butadiene and isoprene is preferable.

When the conjugated diene block polymerized unit is formed of butadiene and isoprene, it is preferable that the unit derived from isoprene is contained in an amount of 40 mol% or more.

Further, the conjugated diene block polymer unit composed of the butadiene / isoprene copolymer unit may be any of a random copolymer unit of butadiene and isoprene, a block copolymer unit or a tapered copolymer unit.

In the present invention, some or all of the carbon-carbon double bonds in this conjugated diene block polymerized unit may be hydrogenated. The hydrogenation rate is determined according to the desired heat resistance, weather resistance, etc., but 50% or more, preferably 70%
It may be the above. When the resin composition according to the present invention is particularly required to have heat resistance and weather resistance, this hydrogenation rate is set to 80.
% Is preferable.

The styrenic block copolymer composed of the aromatic vinyl block polymerized units (X) and the conjugated diene block polymerized units (Y) has a form of, for example, X (YX) _n or (XY) _n. [N is an integer of 1 or more].

Of these, X (YX) _{n is} particularly preferable in the form of XYX, and specifically, polystyrene-polyisoprene (or isoprene-butadiene) -polystyrene block copolymer is preferable.

In such a styrene block copolymer, the aromatic vinyl block unit (X), which is a hard segment, exists as a bridging point of the conjugated diene rubber block unit (Y) to form a physical crosslink (domain). Is forming. The conjugated diene rubber block unit (Y) existing between the aromatic vinyl block units (X) is a soft segment and has rubber elasticity.

The styrene block copolymer used in the present invention can be produced by various methods. For example, (1) n-butyllithium and other alkyllithium compounds can be used. As an initiator, a method of sequentially polymerizing an aromatic vinyl compound and then a conjugated diene, (2) a method of polymerizing an aromatic vinyl compound and then a conjugated diene, and coupling this with a coupling agent, (3) starting a lithium compound Examples of the agent include a method of sequentially polymerizing a conjugated diene and then an aromatic vinyl compound.

The copolymerized diene unit of the styrene block copolymer thus obtained is hydrogenated by a known method, if necessary. In the present invention, as the styrene block copolymer (B-2), specifically, styrene
Isoprene block copolymer (SI) and its hydrogenated product (SEP), styrene / isoprene / styrene block copolymer (SIS) and its hydrogenated product (SEPS; polystyrene / polyethylene / propylene / polystyrene block copolymer), Styrene-butadiene block copolymer (SB) and its hydrogenated product (SEB), styrene
Examples thereof include butadiene / styrene block copolymer (SBS) and hydrogenated products thereof (SEBS; polystyrene / polyethylene / butylene / polystyrene block copolymer), and more specifically, HYBRAR (Kuraray Co., Ltd.).
), Kraton (Shell Chemical Co., Ltd., trade name), Califlex TR (Shell Chemical Co., Ltd.),
Sorprene (Phillip Petroleum Co., Ltd.), Europrene SOLT (Aniche Co., Ltd.), Toughprene (Asahi Kasei Co., Ltd.), Sorprene-T (Nippon Elastomer Co., Ltd.), JSRTR (Nippon Synthetic Rubber Co., Ltd.), Electrified STR
(Manufactured by Denki Kagaku), Quintac (manufactured by Zeon Corporation),
Kraton G (manufactured by Shell Chemical Co., Ltd.), Tuftec (manufactured by Asahi Kasei Co., Ltd.) (these product names) and the like can be mentioned.

In the present invention, among these, styrene / isoprene / styrene block copolymer (SIS) or SEPS (polystyrene / polypropylene / polystyrene / polystyrene block copolymer) which is a hydrogenated product of SIS is preferable. Used as. This SI
It is desirable that S or SEPS contain polystyrene units in an amount of 5 to 80% by weight, preferably 15 to 80% by weight, as described above.

SIS or SE used in the present invention
Melt flow rate of PS: MFR (ASTM D12
38; 200 ° C, 2.16 kg load) is usually 0.1 to 1
50 g / 10 minutes, and the intrinsic viscosity [η] (135 ° C. in decalin) is 0.01 to 10 dl / g, preferably 0.08 to
It is preferably 7 dl / g.

The crystallinity measured by the X-ray diffraction method of SIS or SEPS is 0 to 10%, preferably 0.
It is desirable that the content is ˜7%, more preferably 0 to 5%. The density is preferably 0.88 to 0.94 g / cm ³ .

The above styrene block copolymers may be used in combination of two or more kinds. Further, in the present invention, the ethylene / α-olefin random copolymer (B-1) and the styrene block copolymer (B-2) may be used in combination.

(C) Inorganic Filler When forming a propylene-based polymer composition from the above components, an inorganic filler can be used if necessary.

As the inorganic filler, specifically, fine powder talc, kaolinite, calcined clay, bilophyllite,
Natural silicic acid or silicate such as sericite and wollastonite, precipitated calcium carbonate, heavy calcium carbonate, carbonate such as magnesium carbonate, hydroxide such as aluminum hydroxide and magnesium hydroxide, zinc oxide, zinc oxide, oxidation Oxides such as magnesium, powdered fillers such as synthetic silicic acid or silicate such as hydrous calcium silicate, hydrous aluminum silicate, hydrous silicic acid, and silicic acid, flake-like fillers such as mica, basic magnesium sulfate whisker, calcium titanate Whisker, aluminum borate whisker, sepiolite, PMF (Processed Mineral Fi
ber), zonotolite, potassium titanate, fibrous filler such as elestadite, and balun-like filler such as glass balun and fly ash baln can be used.

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

The inorganic filler used in the present invention, especially talc, may be untreated or may be surface-treated in advance. Specific examples of the surface treatment include 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. Is mentioned. When talc subjected to such a surface treatment is used, a propylene polymer composition excellent in weld strength, coatability and moldability can be obtained.

Two or more kinds of the above-mentioned inorganic fillers may be used in combination. In the present invention, together with such an inorganic filler, an organic filler such as high styrenes, lignin, and recycled rubber can be used.

Propylene-Based Polymer Composition The propylene-based polymer composition according to the present invention contains the above-mentioned (A) propylene block copolymer in an amount of 30 to 95% by weight, preferably 35 to 95% by weight, The amount of the ethylene / α-olefin random copolymer (B) and / or the styrene block copolymer (B) is preferably 5 to 70% by weight, preferably 5 to 65% by weight, and more preferably 40 to 95% by weight. Is contained in an amount of 5 to 60% by weight, and further contains (C) an inorganic filler in an amount of 0 to 25 if necessary.
It is contained in an amount of% by weight.

The propylene-based polymer composition of the present invention formed from the propylene block copolymer (A) and the elastomer component (B) as described above is excellent in heat resistance and rigidity, and particularly impact resistance. It has excellent impact resistance at low temperatures, and exhibits excellent moldability, especially injection moldability.

The polypropylene resin composition according to the present invention contains, in addition to the above-mentioned components, other resins, other elastomers, various types, etc., if necessary, as long as the object of the present invention is not impaired. It may contain additives and the like.

For example, as the other resin, a thermoplastic resin or a thermosetting resin can be used. Specifically, α-olefin homopolymer or α-olefin copolymer such as poly 1-butene, A copolymer of α-olefin and vinyl monomer, a modified olefin polymer 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 (B) as a main component, conjugated diene rubbers, and the like. As the additive, a nucleating agent, an antioxidant, a hydrochloric acid absorbent, a heat stabilizer, a light stabilizer, an ultraviolet absorber, a lubricant, an antistatic agent, a flame retardant, a pigment, a dye, a dispersant, a copper damage inhibitor, A neutralizing agent, a foaming agent, a plasticizer, an anti-foaming agent, a cross-linking agent, a flowability improving agent such as peroxide, a weld strength improving agent and the like can be used. For example, as the nucleating agent, poly-3-methyl-1-butene contained as a prepolymer in the propylene block copolymer can be preferably cited. Furthermore, various conventionally known nucleating agents can be used without particular limitation, and among them, the following nucleating agents can be preferably used.

[0173]

Embedded image (In the formula, 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 and R ³ are the same kind. Or R ^{2 s} , R ^{2 s} , R ^{3 s} or R ² and R ³ may be bonded to form a ring, M is a monovalent metal atom, and n is It is an integer of 1 to 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) phosphonate], magnesium-bis [2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate Fate], 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.

Of these, sodium-2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate is particularly preferable.

[0175]

Embedded image (In the formula, R ⁴ is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, M is a metal atom having a valence of 1 to 3, 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 can do.

Among these, sodium-bis (4-t
-Butylphenyl) phosphate is preferred.

[0177]

[Chemical 6] (In the formula, R ⁵ is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms.) Specifically, 1,3,2,4-dibenzylidene sorbitol,
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-benzylidenesorbitol, 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-chlorobenzylidene 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-chlorobenzylidene sorbitol, 1,3-p-ethylbenzylidene-2,4-p-chlorobenzylidene sorbitol and 1,3,2,4-di (p-chlorobenzylidene) sorbitol and these And a mixture of two or more of the above.

Of these, 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-2,4-p-methylbenzylidene sorbitol, 1,3,2,4-di (p- (Chlorbenzylidene) sorbitol and mixtures of two or more thereof are preferred.

Examples of the nucleating agent include metal salts of aromatic carboxylic acids or aliphatic carboxylic acids, such as aluminum benzoate, aluminum pt-butylbenzoate, sodium adipate, sodium thiophenecarboxylate, and pillow. Examples thereof include sodium recarboxylate. In addition, an inorganic compound such as talc described below can also be used as a nucleating agent.

In the propylene polymer composition according to the present invention, the nucleating agent as described above is added to the propylene polymer (A) 100.
With respect to parts by weight, 0.001 to 10 parts by weight, preferably 0.00.
It is desirable that the content is 01 to 5 parts by weight, more preferably 0.1 to 3 parts by weight.

When the propylene polymer composition contains a nucleating agent, the crystal grains can be made finer and the crystallization rate can be improved to enable high speed molding.

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

Among these, when a device having excellent kneading performance such as a multi-screw extruder, a kneader, or a Banbury mixer is used, a high quality polypropylene resin composition in which the respective components are more uniformly dispersed can be obtained. It is possible and preferable.

When the propylene polymer composition is prepared as described above, the respective components can be kneaded with excellent dispersibility. Applications The propylene-based polymer composition according to the present invention can be molded into various shaped articles by employing known molding methods without particular limitation.

Of these, injection molding is preferable. Injection molding of a propylene-based polymer composition is usually performed at a resin temperature of 200 to 250 ° C., and usually 800 to 1400 kg / depending on the shape of the injection molded product obtained.
Injection molded with an injection pressure of cm ² .

The propylene polymer composition according to the present invention is excellent in moldability such as fluidity during injection molding. In particular, from the propylene-based polymer composition according to the present invention, it is possible to obtain an injection-molded article having excellent appearance in which flow marks and spots are not noticeable.

The injection-molded article of the polypropylene resin composition according to the present invention can be used in a wide variety of applications, for example, in household appliances such as housings and washing tubs,
Uniaxially stretched films, biaxially stretched films, film applications such as inflation films, calendar molding, sheet applications by extrusion molding, bags, container applications such as retort containers, for example, automobile interior applications such as trims, instrument panels, column covers, fenders, etc. It can be suitably used for automobile exterior applications such as bumpers, side moldings, mudguards, and mirror covers, and general miscellaneous goods applications.

Among the above, the applications that can effectively utilize the characteristics that are excellent in rigidity, heat resistance and impact resistance and have excellent appearance, such as fenders, bumpers, side moldings, mudguards, mirror covers, etc. It can be suitably used as an automobile interior / exterior component.

[0189]

EFFECT OF THE INVENTION The propylene polymer composition according to the present invention is capable of forming an injection-molded article which is excellent in rigidity, heat resistance and impact resistance, and which is excellent in the appearance of flow marks and spots. You can

[0190]

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

The production examples of the propylene block copolymers used in Examples and Comparative Examples are shown below.

[0192]

Production Example 1 Production of Propylene Block Copolymer (A-1) [Preparation of Solid Titanium Catalyst Component (a)] Anhydrous magnesium chloride 95.2 g, decane 442 ml and 2-ethylhexyl alcohol 390.6 g at 130 ° C. After heating for 2 hours to obtain a uniform solution, phthalic anhydride 2
1.3 g was added and further stirred at 130 ° C. for 1 hour to dissolve phthalic anhydride.

200 m of titanium tetrachloride kept at -20 ° C
75 ml of the above homogeneous solution cooled to room temperature were added dropwise to 1 liter over 1 hour. After the completion of charging, the temperature of this mixed solution was raised to 110 ° C over 4 hours, and when it reached 110 ° C, diisobutyl phthalate (DIBP) 5.22 was added.
g was added, and the mixture was kept stirring at the same temperature for 2 hours.
After the completion of the reaction for 2 hours, a solid part was collected by hot filtration, and the solid part was resuspended in 275 ml of titanium tetrachloride.
The mixture was again held at 110 ° C. for 2 hours with stirring. After the completion of the reaction, the solid portion was collected again by hot filtration, and sufficiently washed with decane and hexane at 110 ° C. until no free titanium compound was detected in the solution.

The solid titanium catalyst component (a) obtained by the above operation was stored as a decane slurry. The composition of the solid titanium catalyst component (dry) (a) is titanium 2.
3% by weight, chlorine 62% by weight, magnesium 19% by weight,
It was 13.5% by weight of DIBP.

[Prepolymerization of solid titanium catalyst component (a)] In a 400 ml four-neck glass reactor equipped with a stirrer,
In a nitrogen atmosphere, 100 ml of purified hexane, 10 mmol of triethylaluminum, 2.0 mmol of dicyclopentyldimethoxysilane (DCPMS) and 1.0 mmol of the above solid titanium catalyst component (a) in terms of titanium atom were added, and then 3.2 liters were added. Propylene was fed at a rate of / hour for 1 hour. The polymerization temperature was kept at 20 ° C.

When the supply of propylene was completed, the inside of the reactor was replaced with nitrogen, and the washing operation consisting of removal of the supernatant and addition of purified hexane was carried out twice, and the resulting prepolymerized catalyst was purified with purified hexane. The whole was resuspended and transferred to a catalyst bottle.

[Polymerization] (i) Copolymerization of Propylene and Ethylene 3 kg of propylene in an autoclave having an internal volume of 17 liters
And then ethylene with a partial pressure of 2 kg / cm^Two-Becomes G
As supplied. After heating to 50 ° C, triethylal
Minium 5 mmol, dicyclopentyl dimethoxy sila
(DCPMS) 5 mmol and the reserve obtained above
Polymerization catalyst was charged in an amount of 0.05 mmol in terms of titanium atom,
Hold at the same temperature for 5 minutes and co-weigh propylene and ethylene
I went together. Ethylene partial pressure is 2 kg / cm during polymerization^Two-G
So that ethylene was fed. ([Η₁] = 15dl /
g, w₁(= 4.23% by weight) After the completion of the copolymerization, the vent valve is opened and the pressure inside the polymerization vessel is normal pressure.
Depressurize until
Removed. (ii) Polymerization of propylene Next, charge 3 kg of propylene and 180 liters of hydrogen.
Then, the temperature was raised to 70 ° C. and held for 45 minutes. After the reaction,
Open the vent valve and purge unreacted gas until normal pressure is reached.
I did it. (iii) Copolymerization of ethylene and propylene Next, ethylene was added at 360 l / hr and propylene was added at 8
40 liters / hr, hydrogen 180 liters / hr
Supplied to the combiner. Pressure in the polymerization vessel is 10kg / cm ^Two-G
The vent opening was adjusted so that Keep temperature at 70 ℃
Then, polymerization was carried out for 50 minutes. ([Η_Two] = 3 dl / g, w_Two
= 8.47 wt%) Add a small amount of ethanol to stop the polymerization reaction,
The unreacted gas inside was purged.

The white powdery polymer thus produced was subjected to 80% under reduced pressure.
It was dried at ° C. The polymer yield was 2643 g. The MFR of the obtained polymer was 45 g / 10 minutes, the bulk specific gravity was 0.43 g / ml, and the decane-soluble component amount at 64 ° C. was 12.7% by weight. The 64 ° C. decane-soluble component has an intrinsic viscosity [η] of 7.2 dl / g and an ethylene unit content of 4
1 mol% and the viscosity ratio η * (ω measured at 200 ° C.
_0.01 ) / η * (ω ₁₀₀ ) was 5000. 64
The boiling heptane extraction residual ratio (insoluble component amount) in the decane-insoluble component at 9 ° C was 95.3%, and the [M ₅ ] value of the boiling heptane-insoluble component was 0.991.

[0199]

[Production Example 2] Production of propylene block copolymer (A-2) [Polymerization] 3 kg of propylene and 120 liters of hydrogen were charged into an autoclave having an internal volume of 17 liters, the temperature was raised to 60 ° C, and then triethylaluminum 5 Mmol, dicyclopentyldimethoxysilane (DCPMS) 5 mmol and the prepolymerization catalyst obtained in Example 1 were charged in an amount of 0.05 mmol in terms of titanium atom. After raising the temperature to 70 ° C,
This was kept for 25 minutes to polymerize propylene. After the completion of propylene polymerization, the vent valve was opened and unreacted propylene was purged until the pressure inside the polymerization vessel became normal pressure.

After completion of depressurization, copolymerization of ethylene and propylene was subsequently carried out. Then, ethylene was supplied to the polymerizer in an amount of 360 liter / hr and propylene was supplied in an amount of 840 liter / hr (hydrogen was not supplied). The vent opening was adjusted so that the pressure in the polymerization vessel was 10 kg / cm ² -G. The temperature was kept at 70 ° C. and polymerization was carried out for 90 minutes. The polymerization reaction was stopped by adding a small amount of ethanol, and the unreacted gas in the polymerization vessel was purged.

The white powdery polymer thus produced was subjected to 80% under reduced pressure.
It was dried at ° C. The polymer yield was 2560 g. The MFR of the obtained polymer was 45 g / 10 minutes, the bulk specific gravity was 0.44 g / ml, and the amount of decane-soluble component at 64 ° C. was 11.4% by weight. The 64 ° C. decane-soluble component has an intrinsic viscosity [η] of 6.6 dl / g and an ethylene unit content of 4
1 mol% and the viscosity ratio η * (ω measured at 200 ° C.
_0.01 ) / η * (ω ₁₀₀ ) was 25. In addition, the boiling heptane extraction residual ratio (insoluble component amount) in the decane insoluble component at 64 ° C
Is 95.0%, and the [M ₅ ] value of the boiling heptane-insoluble component is 0.1.
99.

[0202]

Examples 1 to 3 The propylene block copolymer (A-1) obtained in Production Example 1 and 2 parts of each component shown in Table 1 were used.
Melt kneading at 00 ° C. to prepare a propylene polymer composition.

The propylene polymer composition thus obtained was injected at an injection pressure of 1000 kg / cm ² , a resin temperature of 200 ° C. and a mold temperature of 4
Injection molding was performed at 0 ° C. The bending test, impact strength, and appearance of the injection molded product were evaluated as follows. The results are shown in Table 1. Flexural Modulus (FM) According to ASTM C790, a test piece having a thickness of 1/8 inch was used and measured under conditions of a span of 51 mm and a bending speed of 20 mm / min. Izod impact strength (IZ) Based on ASTM D258, it measured at -30 degreeC using the test piece (rear notch) of thickness 1/4 inch. Appearance (Spots) In the T-die extrusion-molded film (thickness 60 μm × length 10 cm × width 10 cm), spots having a size of 300 μm or more were counted. Appearance (Flow Mark) The appearance (flow mark) of the injection-molded square plate (thickness 2 mm × length 30 cm × width 12 cm) was visually evaluated.

⊙ No flow mark or extremely inconspicuous ○… Flow mark is inconspicuous △… Flow mark is slightly conspicuous ×… Flow mark is conspicuous

[0205]

Reference Example 1 The propylene block copolymer (A-1) obtained in Production Example 1 was injection molded in the same manner as in Example 1,
The bending test, impact strength, and appearance of the injection molded product were evaluated as follows. The results are shown in Table 1.

[0206]

Comparative Examples 1 to 3 The propylene block copolymer (A-2) obtained in Production Example 2 and each of the components shown in Table 1 were mixed.
Melt kneading at 00 ° C. to prepare a propylene polymer composition.

Injection molding was carried out in the same manner as in Example 1, and the bending test, impact strength and appearance of the injection molded product were evaluated as follows. The results are shown in Table 1.

[0208]

[Table 1]

Claims (4)

[Claims] 1. (A) (1) A decane-soluble component at 64 ° C. is contained in an amount of 2 to 36% by weight, and (2) the decane-soluble component is in an amount of 20 to 55 mol% of a unit derived from ethylene. And (3) the decane-soluble component has a viscosity η * (ω _0.01 ) measured at an angular velocity of ω _0.01 rad / s at 200 ° C.,
Viscosity η * (ω ₁₀₀ ) measured at angular velocity ω ₁₀₀ rad / s
Propylene block copolymer having a ratio η * (ω _0.01 ) / η * (ω ₁₀₀ ) of 50 or more; 30 to 95% by weight
And (B) ethylene / α-olefin random copolymer (B-
1) and / or styrene block copolymer (B-2)
5 to 70% by weight, and (C) an inorganic filler; 0 to 25% by weight, a propylene polymer composition. 2. An injection-molded article comprising the propylene polymer composition according to claim 1. 3. The injection-molded article according to claim 2, which is an automobile interior / exterior article. 4. A film or sheet comprising the propylene-based polymer composition according to claim 1.