JP2000191851A - Propylene based polymer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide propylene based polymer compositions excellent in rigidity, impact resistance, and surface hardness. SOLUTION: Propylene compositions comprise (A) 30-90 wt.% propylene based polymer composed of propylene or propylene and a 2-10C (excluding 3C64 deg.C decalin soluble) α-olefin and having (a) an intrinsic viscosity (in decalin at 135 deg.C) of 0.8-5.0 dl/g, (b) a 64 deg.C decalin insoluble component of 99.5-80 wt.%, (c) a 64 deg.C decalin soluble component of 0.5-20 wt.%, and (d) an α-olefin content in the component of 0-50 mol%, and (B) 10-70 wt.% amorphous α-olefin copolymer containing (e) not less than 20 mol% α-olefin component units and having (f) no substantially observable fusion peak by a DSC, (g) an intrinsic viscosity of 0.01-10 dl/g, (h) a molecular weight distribution by GPC of not greater than 4, and (i) a glass transition temperature (Tg) of not higher than 40 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a propylene-based polymer composition, and more particularly to a propylene-based polymer composition having excellent rigidity, impact resistance, surface hardness, and surface hardness.

[0002]

BACKGROUND OF THE INVENTION Polypropylene is excellent in rigidity, hardness, heat resistance, etc., can be easily formed into a desired shape by various molding methods such as injection molding, calender molding, extrusion molding, and is inexpensive. For a wide range of applications, such as home appliance housing, film applications,
It is widely used for container applications, automotive interior applications, automotive exterior applications such as fenders, bumpers, side moldings, mudguards, mirror covers, and general miscellaneous goods.

[0003] Further, in the field of molded articles of polypropylene, various improvements have been made so far in order to open up new markets and respond to market demands in accordance with such various uses. The improvement is in the resin manufacturing process, mixing of resins, and mixing with additives. Polypropylene or polyethylene or rubber components such as polyisobutylene, polybutadiene, amorphous or low-crystalline ethylene-propylene copolymer (EPR), etc. Is also known to improve impact resistance and surface hardness. There is also known a polypropylene composition in which an inorganic filler such as talc or a crystal nucleating agent is added to polypropylene together with a rubber component in order to compensate for the rigidity that is reduced by compounding the rubber component.

On the other hand, there is a demand from the market for lighter and thinner molded products, and in order to achieve these and obtain molded products having sufficient strength, rigidity is required.
There is a need for a polypropylene composition having an improved impact resistance balance (excellent in both rigidity, impact resistance and surface hardness).

[0005]

SUMMARY OF THE INVENTION The present invention is to solve the above-mentioned problems associated with the prior art, and provides a propylene polymer composition having excellent rigidity, impact resistance and surface hardness. It is intended to be.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in order to solve the problems.
Provide a propylene-based polymer composition having the following characteristics: (i) propylene or propylene and carbon number 2
A propylene-based polymer comprising α-olefins (excluding 3 carbon atoms) and having the following characteristics:
A) Intrinsic viscosity (in decalin at 135 ° C) [η] of 0.8 to
5.0 dl / g b) 99.5 to 80% by weight of 64 ° C decane-insoluble component, c) 0.5 to 20% by weight of 64 ° C decane-soluble component, and d) Α- having 2 to 10 carbon atoms
Olefin (excluding 3 carbon atoms) content is 0 to 50 mol%. (ii) 10 to 70% by weight of an amorphous α-olefin copolymer having the following characteristics: e) An amount of 20 mol% or more of the component unit (A) derived from an α-olefin having 3 to 20 carbon atoms. (The total amount of the component unit (a) and the other component units in the copolymer (ii) is 1
00 mol%. F) a melting peak measured by a differential scanning calorimeter (DSC) is not substantially observed; g) an intrinsic viscosity [η] measured in decalin at 135 ° C. in the range of 0.01 to 10 dl / g. H) the molecular weight distribution by GPC is 4 or less, and i) the glass transition temperature Tg is 40 ° C. or less. A propylene polymer composition comprising:

The present invention further provides a propylene polymer composition wherein the propylene polymer (i) further has the following characteristics. j) Melting point Tm (° C.) measured by a differential scanning calorimeter
Is 150 <Tm <173, and k) the isotacticity of the boiling heptane-insoluble component of 64 ° C. decane-insoluble component is 0.90 or more as viewed in the propylene triad chain.

Further, the present invention provides the above-mentioned amorphous α-olefin copolymer (ii), comprising the above-mentioned α-olefin and another monomer, the following components (a), (b) and (c): And a propylene-based polymer composition using a copolymer obtained by polymerization in the presence of at least one catalyst system comprising at least one compound selected from the group consisting of (d) and (d). (A): transition metal complex represented by the following formula (I) or formula (II)

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[In the formulas (I) and (II), M is Ti, Zr,
Hp, Rn, Nd, Sm or Ru, Cp1 and Cp2 are a cyclopentadienyl group, an indenyl group, a fluorenyl group or a derivative thereof bonded to M by π, and X1 and X2 are anionic groups. A ligand or a neutral Lewis base ligand, Y is a ligand containing a nitrogen atom, an oxygen atom, a phosphorus atom, or a sulfur atom, and Z is C, O, B, S, Ge, Si or It is a Sn atom or a group containing these atoms. (B): a compound that reacts with the transition metal M in the component (a) to form an ionic complex (c): an organoaluminum compound (d): aluminoxane.

In the present invention, the propylene polymer composition further comprises an ethylene / α-olefin random copolymer (A) and an optionally hydrogenated aromatic hydrocarbon block copolymer (B). ), Ethylene / α-olefin block copolymer (C), ethylene / styrene copolymer (D), ethylene / diene copolymer (E), and ethylene / triene copolymer (F). Provided is a propylene-based polymer composition containing one type of copolymer. And this invention provides the molded object which consists of said polymer composition.

[0011]

DETAILED DESCRIPTION OF THE INVENTION The propylene-based polymer composition of the present invention will be specifically described below.

Propylene Polymer Composition The propylene polymer composition according to the present invention comprises: (i) propylene, or propylene and carbon number 2
A propylene-based polymer comprising α-olefins (excluding 3 carbon atoms) and having the following characteristics:
A) Intrinsic viscosity (in decalin at 135 ° C) [η] of 0.8 to
5.0 dl / g b) 99.5 to 80% by weight of 64 ° C decane-insoluble component, c) 0.5 to 20% by weight of 64 ° C decane-soluble component, and d) Α- having 2 to 10 carbon atoms
Olefin (excluding 3 carbon atoms) content is 0 to 50 mol%. (ii) 10 to 70% by weight of an amorphous α-olefin copolymer having the following characteristics: e) An amount of 20 mol% or more of the component unit (A) derived from an α-olefin having 3 to 20 carbon atoms. (The total amount of the component unit (a) and the other component units in the copolymer (ii) is 1
00 mol%. F) a melting peak measured by a differential scanning calorimeter (DSC) is not substantially observed; g) an intrinsic viscosity [η] measured in decalin at 135 ° C. in the range of 0.01 to 10 dl / g. H) the molecular weight distribution by GPC is 4 or less, and i) the glass transition temperature Tg is 40 ° C. or less. And a propylene polymer composition comprising:

First, the components (i) and (ii) contained in the propylene polymer composition will be described.

(I) Propylene Polymer The propylene polymer (i) may be a homopolymer of propylene, and may be propylene and a polymer having 2 to 10 carbon atoms (however,
) May be a block copolymer with an α-olefin. Examples of the α-olefin include α-olefins such as ethylene, butene-1, pentene-1, hexene-1,4-methylpentene-1, and octene-1. Among them, ethylene and octene-1 are preferred.

The propylene polymer (i) of the present invention comprises a)
Intrinsic viscosity (in 135 ° C decalin) [η] is 0.8 to 5.0
dl / g, preferably in the range of 1.0 to 5.0 dl / g, more preferably in the range of 1.0 to 4.0 dl / g. Is 99.
5) to 82% by weight, more preferably 99.5 to 84% by weight;
20% by weight, preferably 5 to 20% by weight, and more preferably 8 to 20% by weight, and d) an α-olefin having 2 to 10 carbon atoms in the decane-soluble component at 64 ° C. 0 to 50 mol%, preferably 0 to 48 mol)
l%, more preferably in the range of 0 to 45 mol%.

Such a propylene-based polymer accounts for 30 to 90% by weight, preferably 40 to 90% by weight, more preferably 50 to 90% by weight in the propylene-based polymer composition.
Contains.

The propylene polymer (i) at 64 ° C. for the decane fractionation is specifically prepared by immersing 5 g of a sample (propylene polymer) in 200 cc of boiling decane for 5 hours and dissolving it. The solid phase thus precipitated can be obtained by filtering the precipitated solid phase through a G4 glass filter, and drying the solid phase (insoluble component) and the filtrate (soluble component).

In the above propylene polymer (i),
Melting point T measured by differential scanning calorimeter (DSC)
m (° C.) is 150 <Tm <173, preferably 155 <T
m <173, more preferably 160 <Tm <173, and when the melting point is in such a range, the rigidity and heat resistance are excellent.

The decane-insoluble component at 64 ° C. of the propylene-based polymer (i) is determined based on the amount of the boiling heptane-insoluble component as described above.
Usually, the content is 80% by weight or more, preferably 85% by weight or more, more preferably 90% by weight or more, still more preferably 93% by weight or more, and particularly preferably 94% by weight or more.

The boiling heptane-insoluble component is the above-mentioned 6
Soxhlet extraction of 1.5 g of 4 ° C decane-insoluble component with heptane for 6 hours or more was obtained as an extraction residue, and the amount of boiling heptane-insoluble component was determined by assuming that the 64 ° C decane-soluble component was also soluble in boiling heptane. It is calculated.

The propylene polymer (i) of 64
The isotacticity of the propylene in the heptane-insoluble component in terms of triad triad chain is at least 0.9, preferably at least 0.95, and the isotacticity is within such a range. It has a high conversion speed and excellent workability.

Here, the isotacticity of the propylene triad chain will be described. Below,
A case where a small amount of ethylene is contained as a copolymer monomer will be described.

The triad tacticity of this propylene-based polymer [i] is determined by the ¹³ C-NMR spectrum of the copolymer and the second unit of the three-chain part of the head-to-tail bonded propylene unit according to the following formula (1). Is determined as the strength (area) ratio of the side chain methyl group.

[0024]

(Equation 1)

(Where PPP (mm), PPP (mr), PPP
(rr) is the area of the side-chain methyl group of the second unit of the three-chain part of the head-tail bonded propylene unit observed in the following shift region of the ¹³ C-NMR spectrum. )

[0026]

[Table 1]

Such PPP (mm), PPP (mr), PP
P (rr) represents a head-to-tail bonded propylene 3 unit chain having the following structure.

[0028]

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In the methyl carbon region (19 to 23 ppm)
In addition to the above, in addition to the side chain methyl groups of the propylene units in the three head-to-tail bonded propylene chains, the following side chain methyl group peaks of the propylene units in other chains are observed. When obtaining the mm fraction, the peak area of such a methyl group not based on three chains of propylene units is corrected as follows. Hereinafter, E indicates a unit derived from ethylene.

In the second region, the propylenes have a head-
A peak derived from the side chain methyl group of the second unit (propylene unit) in the tail-linked PPE 3 chain is observed.
The area of the methyl group peak can be determined from the peak area of the methine group (resonating around 30.6 ppm) of the second unit (propylene unit) in the PPE chain.

In the third area, the second in the EPE3 chain
A peak derived from the side chain methyl group of the unit (propylene unit) is observed. The peak area of this methyl group is
The methine group (3) of the second unit (propylene unit) in the chain
(Resonance around 2.9 ppm).

In the second region and the third region, the position irregularity represented by the following partial structures (i), (ii) and (iii) contained in a small amount in the propylene / ethylene random copolymer: Peaks derived from the methyl groups CE to E 'in the unit are observed.

In the second region, a methyl group C peak, a methyl group D peak and a methyl group D ′ peak are observed,
In the region, a methyl group E peak and a methyl group E ′ peak are observed.

The methyl group A peak and the methyl group B peak in the methyl groups in the position irregular units (i) to (iii)
Observed at 17.3 ppm and 17.0 ppm, respectively,
It is not observed in three regions.

[0035]

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The peak area of the methyl group C can be determined from the peak area of the adjacent methine group (resonating at around 31.3 ppm). The peak area of the methyl group D has the structure (ii)
Can be determined from 1/2 of the sum of the peak areas of the peaks (around 34.3 ppm and around 34.5 ppm) based on the αβ methylene carbon.

The peak area of the methyl group D ′ is determined by the structure (iii)
Of the methine group adjacent to the methyl group E ′ (3
(Around 3.3 ppm). The peak area of the methyl group E was calculated from the adjacent methine carbon (33.7p
pm). The peak area of the methyl group E ′ is determined by the adjacent methine carbon (33.
(Around 3 ppm).

Accordingly, by subtracting these peak areas from the total peak areas of the second and third regions, the peak area of the side chain methyl group of the second propylene unit in the three head-to-tail bonded propylene unit chains is obtained. be able to. Note that each carbon peak in the spectrum is
30,1350 (1989) can be referred to.

The component soluble in decane at 64 ° C. of the propylene polymer (i) has an intrinsic viscosity (in decalin at 135 ° C.) [η].
But 2.0 to 20 dl / g, preferably 2.5 to 10 d
l / g, more preferably 2.5 to 8.0 dl / g, particularly preferably 2.9 to 7.0 dl / g, and having 2 to 2 carbon atoms.
It contains 5 to 29 mol%, preferably 10 to 25 mol% of units derived from 10 α-olefins (excluding 3 carbon atoms).

The decane-soluble component at 64 ° C. is a rubber component of the propylene-based polymer (i) and is usually propylene and an α-olefin having 2 to 10 carbon atoms (however, α-olefin excluding 3 carbon atoms).
-Olefins, especially ethylene) and a very small amount of atactic polypropylene, but other olefins such as those shown at 64 ° C insoluble components, as long as the object of the present invention is not impaired. It may contain units derived from polyenes.

In producing such a propylene-based polymer, it can be produced using, for example, a known titanium-based catalyst or a known metallocene-based catalyst as a catalyst. Here, the production using a Ti-based catalyst will be briefly described. The Ti-based catalyst for olefin polymerization comprises [Ia] a solid titanium catalyst component (a) containing magnesium, titanium, halogen and an electron donor as essential components;
I] an organometallic catalyst component (b) and [III] a silicon compound (c) represented by the following formula (V) or a compound (d) having two or more ether bonds existing through a plurality of atoms.
And formed from _{R a nSi (OR b) 4} - n ... (V)

Wherein n is 1, 2 or 3, and when n is 1, _Ra is a secondary or tertiary hydrocarbon group;
When n is 2 or 3, at least one of R _a is a secondary or tertiary hydrocarbon group, R _a may be the same or different, and R _b has 1 to 4 carbon atoms. When 4-n is 2 or 3 in the hydrocarbon group, R _b may be the same or different. The olefin polymerization catalyst may be prepolymerized as described below.

The solid titanium catalyst component (a) as described above
Can be prepared by contacting a magnesium compound, a titanium compound and an electron donor as described below. As the titanium compound used for preparing the solid titanium catalyst component (a), specifically, for example, the following formula (V
The tetravalent titanium compound represented by I) can be mentioned.

Ti (OR)_gX_4-g (VI) (In the formula (VI), R is a hydrocarbon group, and X is a halogen atom.
And g is 0 ≦ g ≦ 4. ) As such a titanium compound, specifically, TiC
l_Four, TiBr_Four, TiI_Four Titanium tetrahalide such as;
 Ti (OCH_Three) Cl_Three, Ti (OC_TwoH_Five) Cl_Three, Ti (On-C_Four
H₉) Cl3, Ti (OC_TwoH_Five) Br_Three, Ti (O-iso-C_FourH₉) Br
_ThreeTrihalogenated alkoxytitanium such as Ti (OC
H_Three)_Two Cl _Two, Ti (OC_TwoH_Five)_TwoCl_Two, Ti (On-C_FourH₉)_TwoC
l_Two, Ti (OC_TwoH_Five)_TwoBr_TwoDihalogenated dialkoxy
Si titanium; Ti (OCH_Three)_ThreeCl, Ti (OC_TwoH_Five)_ThreeCl,
Ti (On-C_FourH₉)_ThreeCl, Ti (OC_TwoH_Five)_ThreeThings such as Br
Halogenated trialkoxytitanium; Ti (OCH_Three)_Four,
Ti (OC_TwoH_Five)_Four, Ti (On-C_FourH₉)_Four, Ti (O-iso-C_FourH
₉)_Four, Ti (O-2-ethylhexyl)_FourSuch as tetraalkoxy
Examples thereof include titanium.

Of these, halogen-containing titanium compounds are preferable, titanium tetrahalides are more preferable, and titanium tetrachloride is particularly preferable. These titanium compounds may be used alone or in combination of two or more. Further, these titanium compounds may be diluted with a hydrocarbon compound or a halogenated hydrocarbon compound.

Examples of the magnesium compound used for preparing the solid titanium catalyst component (a) include a reducing magnesium compound and a non-reducing magnesium compound.

Here, examples of the magnesium compound having a reducing property include a magnesium compound having a magnesium-carbon bond or a magnesium-hydrogen bond. Specific examples of such a reducing magnesium compound include dimethyl magnesium, diethyl magnesium, dipropyl magnesium,
Dibutyl magnesium, diamyl magnesium, dihexyl 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. it can. These magnesium compounds can be used alone or may form a complex compound with the organometallic compound. Further, these magnesium compounds may be liquid or solid, or may be derived by reacting metallic magnesium with a corresponding compound. Furthermore, it can be derived from metallic magnesium during the catalyst preparation using the above-mentioned method.

Specific examples of the non-reducing magnesium compound include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, and magnesium fluoride; methoxy magnesium chloride,
Alkoxy magnesium halides such as ethoxy magnesium chloride, isopropoxy magnesium chloride, butoxy magnesium chloride, octoxy magnesium chloride;
Allyloxymagnesium halides such as phenoxymagnesium chloride, methylphenoxymagnesium chloride;
Ethoxymagnesium, isopropoxymagnesium,
Butoxymagnesium, n-octoxymagnesium, 2-
Examples thereof include alkoxymagnesium such as ethylhexoxymagnesium; allyloxymagnesium such as phenoxymagnesium and dimethylphenoxymagnesium; and magnesium carboxylate such as magnesium laurate and magnesium stearate.

The non-reducing magnesium compound may be a compound derived from the above-mentioned reducing magnesium compound or a compound derived during the preparation of the catalyst component. In order to derive a non-reducing magnesium compound from a reducing magnesium compound, for example, a magnesium compound having a reducing property is converted into a halogen, a polysiloxane compound, a halogen-containing silane compound, a halogen-containing aluminum compound, an alcohol, an ester. And a compound having an active carbon-oxygen bond, such as ketone, aldehyde and the like.

In the present invention, in addition to the above-mentioned magnesium compound having a reducing property and the magnesium compound having no reducing property, a magnesium compound is a complex compound, a double compound or another compound of the above-mentioned magnesium compound and another metal. It may be a mixture with a metal compound. Further, two or more of the above compounds may be used in combination.

As the magnesium compound used for preparing the solid titanium catalyst component (a), many magnesium compounds other than those described above can be used. , Preferably in the form of a halogen-containing magnesium compound,
Therefore, when a halogen-free magnesium compound is used, it is preferable to carry out a contact reaction with a halogen-containing compound during the preparation.

Among the above-mentioned magnesium compounds, a magnesium compound having no reducing property is preferable, a halogen-containing magnesium compound is more preferable, and magnesium chloride, alkoxymagnesium chloride and allyloxymagnesium chloride are particularly preferable.

The solid titanium catalyst component (a) used in the present invention is formed by bringing the above-mentioned magnesium compound into contact with the above-mentioned titanium compound and an electron donor.

Examples of the electron donor used in the preparation of the solid titanium catalyst component (a) include the following compounds. Methylamine, ethylamine,
Dimethylamine, diethylamine, ethylenediamine,
Amines such as tetramethylenediamine, hexamethylenediamine, tributylamine and tribenzylamine;
Pyrroles such as pyrrole, methylpyrrole and dimethylpyrrole; pyrroline; pyrrolidine; indole; pyridine, methylpyridine, ethylpyridine, propylpyridine, dimethylpyridine, ethylmethylpyridine, trimethylpyridine, phenylpyridine, benzylpyridine,
Pyridines such as pyridine chloride; nitrogen-containing cyclic compounds such as piperidines, quinolines, and isoquinolines; tetrahydrofuran, 1,4-cineole, 1,8-cineole, pinolfuran, methylfuran, dimethylfuran, diphenylfuran, benzofuran, Cyclic oxygenates such as coumaran, phthalane, tetrahydropyran, pyran, ditedropyran;

Methanol, ethanol, propanol,
Alcohols having 1 to 18 carbon atoms such as pentanol, hexanol, octanol, 2-ethylhexanol, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropyl alcohol, isopropylbenzyl alcohol; phenol; C6-C20 which may have a lower alkyl group such as cresol, xylenol, ethylphenol, propylphenol, nonylphenol, cumylphenol and naphthol
Phenols having 3 to 3 carbon atoms such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, acetylacetone and benzoquinone
15 ketones;

C2-15 aldehydes such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, naphthaldehyde; 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, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, benzoic acid Octyl, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethyl benzoate, methyl anisate, n-butyl maleate, methyl Rumaron diisobutyl, cyclohexene carboxylic di n- hexyl, nadic diethyl, tetrahydrophthalic acid diisopropyl, diethyl phthalate, diisobutyl phthalate, di n- butyl,
Di-2-ethylhexyl phthalate, γ-butyrolactone, δ-
C2-30 organic acid esters such as valerolactone, coumarin, phthalide, ethyl carbonate;

Acetyl chloride, benzoyl chloride,
2 carbon atoms such as toluic acid chloride and anisic acid chloride
To 15 acid halides; methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, anisole, diphenyl ether epoxy-p-
Ethers having 2 to 20 carbon atoms such as menthane; 2-isopentyl-2-isopropyl-1,3-dimethoxypropane, 2,2-
Isobutyl-1,3-dimethoxypropane, 2,2-isopropyl-1,3-dimethoxypropane, 2-cyclohexylmethyl-
2-isopropyl-1,3-dimethoxypropane, 2,2-isopentyl-1,3-dimethoxypropane, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclohexyl-
2-isopropyl-1,3-dimethoxypropane, 2-cyclopentyl-2-isopropyl-1,3-dimethoxypropane, 2,2-
Dicyclopentyl-1,3-dimethoxypropane, 1,2-bis-
Methoxymethyl-bicyclo- [2,2,1] -heptane, diphenyldimethoxysilane, isopropyl-t-butyldimethoxysilane, 2,2-diisobutyl-1,3-dimethoxycyclohexane, 2-isopentyl-2-isopropyl-1, Diethers such as 3-dimethoxycyclohexane; acid amides such as acetic acid amide, benzoic acid amide and toluic acid amide; nitriles such as acetonitrile, benzonitrile and tolunitrile; acid anhydrides such as acetic anhydride, phthalic anhydride and benzoic anhydride Objects are used.

As the electron donor, a silicon compound represented by the following general formula (V) can be used. When the above-mentioned titanium compound, magnesium compound and electron donor are brought into contact with each other, a carrier-supported solid titanium catalyst component (a) can be prepared using the following carrier compound.

As such a carrier compound, Al ₂ O
₃ , SiO ₂ , B ₂ O ₃ , MgO, CaO, TiO ₂ ,
Resins such as ZnO, ZnO ₂ , SnO ₂ , BaO, ThO, and styrene-divinylbenzene copolymer can be given. Among these carrier compounds, preferably, SiO ₂ , Al ₂ O ₃ , MgO, ZnO, ZnO _{2 and the} like can be mentioned.

The above components may be brought into contact with each other in the presence of another reaction reagent such as silicon, phosphorus, and aluminum. The solid titanium catalyst component (a) can be produced by, for example, contacting a titanium compound, a magnesium compound and an electron donor as described above,
As a manufacturing method, any method including a known method can be adopted.

A specific method for producing the solid titanium catalyst component (a) will be briefly described below with several examples. (1) A method in which a solution comprising a magnesium compound, an electron donor, and a hydrocarbon solvent is contact-reacted with an organometallic compound to precipitate a solid, or a contact reaction is performed with a titanium compound while the solid is precipitated.

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

(4) An inorganic or organic carrier carrying a magnesium compound is obtained from a mixture of a magnesium compound, an electron donor, and optionally a solution containing a hydrocarbon solvent, and an inorganic or organic carrier. How to make contact.

(5) Magnesium compounds, titanium compounds,
A method for obtaining a solid titanium catalyst component carrying magnesium and titanium by contacting a solution containing an electron donor, and optionally a hydrocarbon solvent, with an inorganic or organic carrier.

(6) A method of contacting a liquid state 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 state organomagnesium compound is brought into contact with a halogen-containing compound and then brought into contact with a titanium compound.
At this time, the electron donor is used at least once.

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

(10) A method comprising bringing a complex comprising an alkoxy group-containing magnesium compound and an electron donor into contact with an organometallic compound and then reacting 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. In this reaction, each component may be pretreated with an electron donor and / or a reaction auxiliary such as an organometallic compound or a halogen-containing silicon compound. In this method, the electron donor is preferably used at least once.

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

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

(15) A method in which a solid obtained by pulverizing a magnesium compound, preferably an electron donor, and a titanium compound is treated with any of a halogen, a halogen compound and an aromatic hydrocarbon. In this method,
The method may include a step of pulverizing only the magnesium compound, a complex compound composed of the magnesium compound and the electron donor, or a magnesium compound and the titanium compound. Further, after the pulverization, a preliminary treatment with a reaction aid may be performed, followed by a treatment with a halogen or the like. Examples of the reaction aid include an organometallic compound and a halogen-containing silicon compound.

(16) A method of pulverizing a magnesium compound and then contacting and reacting with a titanium compound. At this time, it is preferable to use an electron donor or a reaction assistant at the time of pulverization and / or contact / reaction.

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

(19) A method of reacting a magnesium compound such as a magnesium salt of an organic acid, alkoxymagnesium or aryloxymagnesium with a titanium compound and / or a halogen-containing hydrocarbon and preferably an electron donor.

(20) A method of contacting a hydrocarbon solution containing at least a magnesium compound and alkoxytitanium with a titanium compound and / or an electron donor. At this time, it is preferable to coexist a halogen-containing compound such as a halogen-containing silicon compound.

(21) A liquid magnesium compound having no reducing ability is reacted with an organometallic compound to precipitate a solid magnesium / metal (aluminum) composite,
Next, a method of reacting an electron donor and a titanium compound.

The amount of each of the above components used in preparing the solid titanium catalyst component (a) depends on the preparation method and cannot be specified unconditionally. For example, the amount of the electron donor is 0.01 per mole of the magnesium compound. It is used in an amount of from 10 to 10 mol, preferably from 0.1 to 5 mol, and the titanium compound is used in an amount of from 0.01 to 1000 mol, preferably from 0.1 to 200 mol.

The solid titanium catalyst component (a) thus obtained contains magnesium, titanium, halogen and an electron donor as essential components. In this solid titanium catalyst component (a), the halogen / titanium (atomic ratio) is in the range of about 2 to 200, preferably about 4 to 100, and the electron donor / titanium (molar ratio) is about 0.0.
1-100, preferably in the range of about 0.02-10, magnesium / titanium (atomic ratio) of about 1-100,
Preferably, it is in the range of about 2 to 50.

[II] As the organometallic catalyst component (b),
Organometallic compounds of metals of Groups I to III of the Periodic Table are used, and specifically, compounds represented by the following formulas (b-1) to (b-3) are used. (b-1) the general formula _{(R 1) m Al (O} (R 2)) n H p X q ( wherein, R ₁ and R ₂ are from 1 to 15 carbon atoms, preferably 1 to 4 X may be the same or different, and 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. The organoaluminum compound represented by).

(B-2) Group I represented by the general formula: M ₁ Al (R ₁ ) ₄ (where M ₁ is Li, Na, K, and R ₁ is the same as described above) Complex alkylated product of metal and aluminum.

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

As the organoaluminum compound belonging to the above (b-1), the following compounds can be exemplified. Formula (R ₁ ) _m Al (O (R ₂ )) _3-m (VII) (wherein R ₁ and R ₂ are the same as described above, and m is preferably a number of 1.5 ≦ m ≦ 3) A compound represented by the general formula (R ₁ ) _m AlX _3-m (VIII) (wherein R ₁ is the same as described above, X is a halogen, and m is preferably 0 <m. <3.> A compound represented by the general formula (R ₁ ) _m AlH _3-m (IX) (wherein R ₁ is the same as described above, and m is preferably 2 ≦
m <3. A compound represented by the general formula (R ₁ ) _m Al (O (R ₂ )) _{n Xq} (X) (wherein R ₁ and R ₂ are the same as described above, X is a halogen, 0 < m ≦ 3, 0 ≦ n <3, 0 ≦ q <3, and m + n + q = 3).

As the aluminum compound belonging to (b-1), more specifically, trialkylaluminum such as triethylaluminum and tributylaluminum; trialkenylaluminum such as triisoprenylaluminum; diethylaluminum ethoxide and dibutylaluminum butoxide Dialkylaluminum alkoxides such as; ethylaluminum sesquiethoxide;
Alkyl aluminum sesquialkoxides such as butyl aluminum sesquibutoxide; (R ₁ ) _2.5 Al (OR
₂ ) Partly alkoxylated alkylaluminum having an average composition represented by _0.5 or the like; dialkylaluminum halides such as diethylaluminum chloride, dibutylaluminum chloride, and diethylaluminum bromide; ethylaluminum sesquichloride, butylaluminum sesquichloride, ethyl Alkyl aluminum sesquihalides such as aluminum sesquibromide; partially halogenated alkyl aluminum such as alkyl aluminum dihalides such as ethyl aluminum dichloride, propyl aluminum dichloride and butyl aluminum dibromide; dialkyl such as diethyl aluminum hydride and dibutyl aluminum hydride Aluminum hydride; ethyl aluminum dihydride, propyl alcohol Other partially hydrogenated alkylaluminum such as alkylaluminum dihydride such as mini-um dihydride; ethylaluminum ethoxy chloride, butyl aluminum butoxide cycloalkyl chloride,
Mention may be made of partially alkoxylated and halogenated alkylaluminums such as ethylaluminum ethoxybromide.

Compounds similar to (b-1) include acids
Two or more aluminum atoms are bonded through an element atom or nitrogen atom
Organic aluminum compounds. This
Examples of the compound such as (C)_TwoH_Five)_TwoAl
OAl (C_TwoH_Five)_Two, (C_FourH₉)_TwoAlOAl (C
_FourH₉)_Two, (C_TwoH_Five)_TwoAlN (C_TwoH_Five) Al (C
_TwoH_Five) _TwoAnd methyl aluminoxane, etc.
And luminoxane.

Compounds belonging to the above (b-2) include L
iAl (C_TwoH_Five)_Four , LiAl (C ₇H₁₅)_Four Etc.
I can do it. Of these, organic aluminum
Compounds are preferably used. In the present invention, the organometallic compound
It is also possible to use two or more types in combination.

In forming the olefin polymerization catalyst,
The silicon compound (c) used as the catalyst component [III] is represented by the following formula (V). _{R a nSi (OR b) 4} - in _n ... (V) (wherein, n is 1, 2 or 3, when n is 1, R
_a is a secondary or tertiary hydrocarbon group, and when n is 2 or 3, at least one of R _a is a secondary or tertiary hydrocarbon group, R _a is independently identical or different R _b is a hydrocarbon group having 1 to 4 carbon atoms,
When n is 2 or 3, R _b may be the same or different. )

In the silicon compound (c) represented by the formula (V), the secondary or tertiary hydrocarbon group may be a cyclopentyl group, a cyclopentenyl group, a cyclopentadienyl group or a group having a substituent. Or S
and a hydrocarbon group in which the carbon adjacent to i is secondary or tertiary. More specifically, as the substituted cyclopentyl group, 2-methylcyclopentyl group, 3-methylcyclopentyl group, 2-ethylcyclopentyl group, 2-n-butylcyclopentyl group, 2,3-dimethylcyclopentyl group, 2,4-dimethyl Cyclopentyl group, 2,5-dimethylcyclopentyl group, 2,3-diethylcyclopentyl group, 2,3,4-trimethylcyclopentyl group, 2,3,5-trimethylcyclopentyl group, 2,3,4-triethylcyclopentyl group, tetra Examples thereof include a cyclopentyl group having an alkyl group such as a methylcyclopentyl 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 A cyclopentenyl group 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 may be exemplified. it can.

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

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

When n is 1, the silicon compound (c) represented by the formula (V) is cyclopentyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, 2,3-dimethylcyclopentyltrimethoxysilane. Silane, cyclopentyltriethoxysilane, iso-butyltriethoxysilane, t-butyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornanetrimethoxysilane,
Trialkoxysilanes such as 2-norbornanetriethoxysilane are exemplified.

When n is 2, dicyclopentyldiethoxysilane, t-butylmethyldimethoxysilane,
Examples include dialkoxysilanes such as t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, and 2-norbornanemethyldimethoxysilane.

In the formula (V), when n is 2, the silicon compound (c) is preferably a dimethoxy compound represented by the following formula (XI).

Embedded image

In the formula, R _p and R _s each independently represent a cyclopentyl group, a substituted cyclopentyl group, a cyclopentenyl group, a substituted cyclopentenyl group, a cyclopentadienyl group, a substituted cyclopentadienyl group, or
A hydrocarbon group in which the carbon adjacent to Si is a secondary carbon or a tertiary carbon.

Examples of the silicon compound represented by the formula (XI) include, for example, dicyclopentyldimethoxysilane, dicyclopentenyldimethoxysilane, dicyclopentadienyldimethoxysilane, di-t-butyldimethoxysilane, 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 (2,4-dimethylcyclopentenyl) dimethoxysilane, di (2,5-dimethylcyclopentenyl) dimethoxysilane, di (2,3,4-trimethylcyclopentenyl) dimethoxysilane, di (2, 3,5-trimethylcyclopentenyl) dimethoxysilane, di (2,3,4-to Ethylcyclopentenyl) dimethoxysilane, di (tetramethylcyclopentenyl) dimethoxysilane, di (tetraethylcyclopentenyl) dimethoxysilane, di (2-methylcyclopentadienyl) dimethoxysilane, di (3-methylcyclopentadienyl) dimethoxy Silane, 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-trimethylcyclopentadienyl) 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-pentamethylcyclopentadi Enyl) dimethoxysilane, di (1,2,3,4,
5-pentaethylcyclopentadienyl) dimethoxysilane, di-t-amyl-dimethoxysilane, di (α, α'-dimethylbenzyl) dimethoxysilane, di (admantyl) dimethoxysilane, admantyl-t-butyldimethoxysilane, cyclopentyl- t-butyldimethoxysilane, diisopropyldimethoxysilane, dis-butyldimethoxysilane, dis-amyldimethoxysilane, isopropyl-s
-Butyldimethoxysilane and the like.

When n is 3, tricyclopentylmethoxysilane, tricyclopentylethoxysilane, dicyclopentylmethylmethoxysilane, dicyclopentylethylmethoxysilane, dicyclopentylmethylethoxysilane, cyclopentyldimethylmethoxysilane, cyclopentyldiethylmethoxysilane, Monoalkoxysilanes such as cyclopentyldimethylethoxysilane are exemplified.

Of these, dimethoxysilanes, particularly dimethoxysilanes represented by the formula (XI), are preferred. Specifically, dicyclopentyldimethoxysilane, di-t-butyldimethoxysilane, di (2-methylcyclopentyl) dimethoxysilane , Di (3-methylcyclopentyl) dimethoxysilane and di-t-amyldimethoxysilane are preferred. Two or more silicon compounds (c) can be used in combination.

Compound (d) having two or more ether bonds existing through a plurality of atoms used in the present invention
(Hereinafter sometimes referred to as polyether compound), the atoms existing between these ether bonds are carbon, silicon,
1 selected from the group consisting of oxygen, sulfur, phosphorus, and boron
The number of atoms is 2 or more.

Of these, a relatively bulky substituent at an atom between ether bonds, specifically a substituent having at least 2 carbon atoms, preferably at least 3 carbon atoms, having a linear, branched or cyclic structure, Preferably, a substituent having a branched or cyclic structure is bonded. Further, the atom existing between two or more ether bonds may have a plurality of, preferably 3 to
20, more preferably 3 to 10, particularly preferably 3 to 7
Are preferred. Such a polyether compound is represented, for example, by the following formula (XII).

[0099]

Embedded image

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

As the above polyether compound,
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-dimethoxypropane, 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 -Screw (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-diiso Neopentyloxyethane, 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-diisobutyldi Oxyheptane,

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-
Butyl bis (methoxymethyl) silane, cyclohexyl
-t-butylbis (methoxymethyl) silane, i-propyl-
t-butylbis (methoxymethyl) silane and the like.

Of these, 1,3-diethers are preferably used. In particular, 2,2-diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2-Dicyclohexyl-1,3-dimethoxypropane and 2,2-bis (cyclohexylmethyl) -1,3-dimethoxypropane are preferably used. These polyether compounds (d) can be used in combination of two or more kinds.

The olefin polymerization catalyst used in the present invention may be preliminarily polymerized. Specifically, the catalyst for olefin polymerization is [Ib] a prepolymerized catalyst component obtained by prepolymerizing an olefin in the presence of the solid titanium catalyst component (a) and the organometallic catalyst component (b). And [II]
It is formed from the organometallic catalyst component (b) and [III] the silicon compound (c) or the polyether compound (d).

The prepolymerized olefins include ethylene,
Propylene, 1-butene, 1-octene, 1-hexadecene,
Linear olefins such as 1-eicosene, the following formula (XIII)
Alternatively, a branched olefin represented by (XIV) can be used.

[0108]

Embedded image(Wherein X is a cycloalkyl group, an aryl group, or-
MR₁R_TwoR_ThreeAnd M represents carbon or silicon;
R₁And R_TwoRepresents a hydrocarbon group; _ThreeIs hydrogen or charcoal
Represents a hydride group. )

As the branched olefin as described above,
Specifically, 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, vinylcyclohexane,
Examples include olefins having a branched structure such as vinylcyclopentane, vinylcycloheptane, and allyltrialkylsilanes.

Among these, 3-methyl-1-butene, 3
-Methyl-1-pentene, 3-ethyl-1-hexene, vinylcyclohexane, allyltrimethylsilane, dimethylstyrene and the like are preferable, and 3-methyl-1-butene, vinylcyclohexane and allyltrimethylsilane are more preferable,
3-Methyl-1-butene is particularly preferred. Among the above, propylene and ethylene are preferably used as the prepolymerized olefin. The prepolymerized olefin can be used in combination of two or more kinds.

In the prepolymerization, the catalyst can be used at a considerably higher concentration than the catalyst concentration in the system in the main polymerization of propylene. The concentration of the solid titanium catalyst component (a) in the prepolymerization is usually about 0.01 to 200 mmol, preferably about 0.05 to 100 mmol, in terms of titanium atoms, per liter of the polymerization solvent described below. desirable.

The organometallic catalyst component (b) may be used in such an amount that a polymer is produced in an amount of 0.1 to 1000 g, preferably 0.3 to 500 g, per 1 g of the solid titanium catalyst component (a). It is generally desirable to use about 0.1 to 100 mmol, preferably about 0.5 to 50 mmol, per 1 mol of titanium atoms in the titanium catalyst component (a).

In the prepolymerization, an electron donor (e) may be used together with the solid titanium catalyst component (a) and the organometallic catalyst component (b). As the electron donor (e), specifically, the electron donor shown at the time of preparing the solid titanium catalyst component (a), the silicon compound (c) shown as the catalyst component [III], and the polyether compound (d) ) And the above-mentioned organosilicon compounds represented by the following formula (V).

[0114] _{R a nSi (OR b) 4} - in _n ... (V) (wherein, n is 1, 2 or 3, when n is 1, R
_a is a secondary or tertiary hydrocarbon group, and when n is 2 or 3, at least one of Ra is a secondary or tertiary hydrocarbon group, R _a is optionally substituted by one or more identical R _b is a hydrocarbon group having 1 to 4 carbon atoms,
When n is 2 or 3, R _b may be the same or different. 0 <n <4. Incidentally, the organosilicon compound represented by the formula (V) may include the silicon compound (c) in some cases.

Specific examples of such organosilicon compounds include trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diisopropyldimethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane. Silane, bis-o-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-aminopropyltri Ethoxysilane, chlorotriethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane, ethyl silicate, butyl silicate, trimethylphenoxysilane, methyltriaryloxy (allyloxy) silane, vinyl tris (β-methoxyethoxy silane), vinyl Examples include triacetoxysilane, dimethyltetraethoxydisiloxane, and the like.

The electron donor (e) may be used in combination of two or more kinds. The electron donor (e) is used in an amount of from 0.1 to 50 mol, preferably from 0.5 to 30 mol, more preferably from 1 to 50 mol, per 1 mol of titanium atoms in the solid titanium catalyst component (a).
It can be used as needed in an amount of from 10 to 10 mol.

The prepolymerization is preferably carried out under mild conditions by adding an olefin and the above catalyst component to an inert hydrocarbon medium. Examples of the inert hydrocarbon medium include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane; and benzene. , Aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as ethylene chloride and chlorobenzene, and contact products thereof. Among these, it is particularly preferable to use an aliphatic hydrocarbon.

The reaction temperature at the time of the prepolymerization may be any temperature at which the resulting prepolymer does not substantially dissolve in the inert hydrocarbon medium, and is usually about -20 to + 100 ° C, preferably about -100 ° C. 20 to + 80 ° C, more preferably 0 to +
It is desirable to be in the range of 40 ° C. During prepolymerization,
Molecular weight regulators such as hydrogen can also be used.

In the preliminary polymerization, the solid titanium catalyst component (a)
About 0.1 to 1000 g per gram, preferably about 0.3 to 5
It is desirable to carry out such that 00 g of the polymer is produced.
If the prepolymerization amount is too large, the (co)
The production efficiency of the polymer may be reduced, and when a film or the like is formed from the obtained (co) polymer, fish eyes may be easily generated. The prepolymerization can be performed in a batch system or a continuous system.

The olefin polymerization catalyst used in the present invention may be the above-mentioned [Ia] solid titanium catalyst component or [Ib]
A pre-polymerization catalyst component, [II] an organometallic catalyst component, and [II]
I] It is formed from a silicon compound (c) or a polyether compound (d). When the prepolymerization catalyst component [Ib] is used, the organometallic catalyst component (b) during the prepolymerization is used.
And the same organic metal catalyst component as used in the main polymerization can be used.

When producing propylene homopolymer for blending by polymerizing propylene using the olefin polymerization catalyst as described above, the solid titanium catalyst component [Ia] (or the prepolymerization catalyst component [Ib]) is used. )
Is usually about 0.0001 to 50 mmol, preferably about 0.0001 to 50 mmol, in terms of titanium atom in the titanium atom (or [Ib]) in the catalyst component [Ia] per liter of polymerization volume in the polymerization system. Desirably, it is present in an amount of about 0.001 to 10 mmol. Organometallic catalyst component [II]
Is used in such an amount that the metal atom in the catalyst component [II] is usually about 1 to 2000 mol, preferably about 2 to 500 mol, per 1 mol of titanium atom in the polymerization system.
The catalyst component [III] is used in an amount of usually about 0.001 to 50 mol, preferably about 0.01 to 20 mol, per 1 mol of the metal atom in the organometallic catalyst component [II]. .

The polymerization temperature is usually about -50 to 200 ° C,
Preferably at about 20-100 ° C., the polymerization pressure is usually from normal pressure to 100 kg / cm ² , preferably from about ^{2 to} 50 kg / cm ² .
cm ² . The polymerization can be performed in a gas phase or a liquid phase, and can be performed in any of a batch system, a semi-continuous system, and a continuous system. At the time of polymerization, the molecular weight of the obtained polymer can be adjusted using hydrogen. When the polymerization takes a reaction form of slurry polymerization or solution polymerization, an inert hydrocarbon as shown in the preparation of the prepolymerization catalyst component [Ib] can be used as a reaction solvent.

In the above polymerization step, a small amount of other olefins or dienes as described above can be copolymerized with propylene as long as the object of the present invention is not impaired. The content of the unit derived from the other olefins is desirably less than 5 mol%, preferably 0 to 4 mol%, and particularly preferably 0 to 2 mol%. Using the above olefin polymerization catalyst, propylene and, C _{2 ~ 10} alpha-olefin, preferably by copolymerizing ethylene propylene · C _{2 ~ 10} α- olefin copolymer for blending (noncrystalline or low crystalline In producing the polymer, the solid titanium catalyst component [Ia] (or the prepolymerization catalyst component [I
It is desirable that b)) and the organometallic catalyst component [II] be present in the reaction system in the same amounts as in the production of the polypropylene. The catalyst component [III] is an organometallic catalyst component [II]
The amount is usually about 0.001 to 50 mol, preferably about 0.01 to 20 mol, per 1 mol of the metal atom therein.

[0124] propylene and, C _{2 ~ 10} alpha-olefins,
Preferably, at the time of copolymerization with ethylene, the above-mentioned other olefins and / or polyenes can be used if necessary. This polymerization is usually carried out usually in the form of a solution polymerization. You can do it too. When the reaction mode of the solution polymerization is adopted, the above-mentioned inert hydrocarbon can be used as a reaction solvent. The polymerization can be carried out by any of batch, semi-continuous and continuous methods.

When hydrogen is used at the time of polymerization, the molecular weight of the low-crystalline copolymer or amorphous copolymer obtained can be adjusted by the amount of hydrogen added. The polymerization temperature is usually about -50 to 200 ° C., preferably about 20 to 100 ° C., the polymerization pressure is usually atmospheric pressure to 100 kg / cm ^2, preferably about to 50 kg / cm ^2.

Amorphous α-olefin-based copolymer (ii) Amorphous α-olefin-based copolymer of the present invention (ii) An amorphous α-olefin-based copolymer having the following characteristics. e) The component unit (A) derived from the α-olefin having 3 to 20 carbon atoms is contained in an amount of 20 mol% or more, (the component unit (A) in the copolymer (ii) and the other component units). The total amount of
00 mol%. F) a melting peak measured by a differential scanning calorimeter (DSC) is not substantially observed; g) an intrinsic viscosity [η] measured in decalin at 135 ° C. in the range of 0.01 to 10 dl / g. H) the molecular weight distribution by GPC is 4 or less, and i) the glass transition temperature Tg is 40 ° C. or less.

The α-olefin having 3 to 20 carbon atoms (A) of the present invention is more preferably an α-olefin having 3 to 12 carbon atoms, and is preferably propylene, 1-butene, 4-methylpentene-1, 1-olefin. At least one olefin selected from hexene, 1-octene and 1-decene is preferred. The remaining component units of these component units derived from α-olefins are components derived from monomers other than α-olefin (A) having 3 to 20 carbon atoms, and include monomers that can be copolymerized with various α-olefins. Preferred examples include ethylene, a polyene unsaturated compound having two or more double bonds (ethylenically unsaturated compound), and the like.

Specifically, ethylene, ethylidenebornene, dicyclopentadiene, butadiene, isoprene, 4,8-dimethyl-1,4,8-decatriene, 4-ethylidene-8-methyl-1,7-nonadiene A preferable example is a polyene-based unsaturated compound having at least one double bond having at least one double bond selected from the above. Ethylene component unit content in the total amount of component units of ethylene and the polyene unsaturated compound having two or more double bonds is 30 mol% to 90 mol%, preferably 40 mol% to 90 mol%. Is desirable. Also,
Carbon number 3 other than α-olefin (a) having 3 to 20 carbon atoms
~ 20 α-olefins (II) may be used as the remaining component units.

Amorphous α-olefin copolymer of the present invention
(ii) contains component units (a) derived from an olefin having 3 to 20 carbon atoms in an amount of 20 mol% or more (the total component unit amount in the copolymer (ii) is 100 mol%). )But,
Preferably, it is contained in an amount of 50 to 99 mol%, and the component unit derived from a monomer different from (a) is 1 to 5
Desirably, it is contained at 0 mol%.

The amorphous α-olefin copolymer of the present invention
(ii) is characterized in that f) a melting peak measured by a differential scanning calorimeter (DSC) is not substantially observed. The meaning that a melting peak is not substantially observed is as follows.
Regardless of whether the peak is sharp or broad,
It means that a peak recognizable as an endothermic peak is not substantially recognized.

The amorphous α-olefin copolymer of the present invention
(ii) is characterized in that g) intrinsic viscosity [η] measured in decalin at 135 ° C. is 0.01 to 10 dl / g, preferably 0.05 to 10 dl / g, more preferably 0.1 to 10 dl / g. 〜１０10 dl / g.

The amorphous α-olefin copolymer of the present invention
(ii) is characterized in that h) the molecular weight distribution by GPC is 4 or less. The molecular weight distribution was determined by the ratio (Mw / M) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by gel permeation chromatography (GPC).
n), but this value is 4 or less, preferably 1 to
4, more preferably 1-3.

Further, the amorphous α-olefin copolymer (ii) of the present invention is characterized in that i) the glass transition temperature Tg is 40 ° C. or lower. The glass transition temperature Tg is preferably 23 ° C. or lower, more preferably 10 ° C. or lower. Production of amorphous α-olefin copolymer (ii)

The method for producing such an amorphous α-olefin-based copolymer (ii) can be appropriately selected by those skilled in the art. To give a preferred example, the above-mentioned carbon number 3-20
Of α-olefin and ethylene, a polyene unsaturated compound having two or more double bonds (ethylenically unsaturated compound), and the like, in the presence of a metallocene catalyst shown below.

As such a metallocene catalyst, a transition metal complex (a) represented by the following formula (I) or (II):

[0136]

Embedded image

[In the formulas (I) and (II), M is Ti, Z
r, Hf, Rn, Nd, Sm or Ru, and Cp ¹
And Cp ² are a cyclopentadienyl group, an indenyl group, a fluorenyl group or a derivative group thereof bonded to M by π, X ¹ and X ² are an anionic ligand or a neutral Lewis base ligand Y is a ligand containing a nitrogen atom, an oxygen atom, a phosphorus atom, or a sulfur atom, and Z is a C, O, B, S, Ge, Si or Sn atom or a group containing these atoms. It is. And 1 selected from the following components (b), (c) and (d):
At least one catalyst system consisting of one or more compounds is used. (B): a compound that reacts with the transition metal M in the component (a) to form an ionic complex (also referred to as an ionized ionic compound) (c): an organoaluminum compound (d): an aluminoxane.

First, the transition metal complex (a) represented by the following formula (I) used in the present invention will be described.

Embedded image

In the formula (I), M is a transition metal belonging to Group 4 of the periodic table or a lanthanide series, and specifically, Ti, Z
r, Hf, Rn, Nd, Sm, and Ru, preferably Ti, Zr, and Hf, and Cp ¹ is a cyclopentadienyl group, an indenyl group, a fluorenyl group, or a derivative thereof, which is π-bonded to M. X ¹ and X ² are
An anionic ligand or a neutral Lewis base ligand,
Y is a ligand containing a nitrogen, oxygen, phosphorus, or sulfur atom, and Z is carbon, oxygen, sulfur, boron or an element of Group 14 of the periodic table (eg, silicon, germanium or tin). Yes, preferably one of carbon, oxygen and silicon, Z may have a substituent, and Z and Y may form a condensed ring.

More specifically, Cp ¹ is a ligand which coordinates to a transition metal, and has a cyclopentadienyl skeleton such as a cyclopentadienyl group, an indenyl group, a fluorenyl group or a derivative group thereof. The ligand having a cyclopentadienyl skeleton may have a substituent such as an alkyl group, a cycloalkyl group, a trialkylsilyl group, and a halogen atom.

Z is C, O, B, S, Ge, Si,
It is an atom selected from Sn, and Z may have a substituent such as an alkyl group or an alkoxy group, and the substituents of Z may combine with each other to form a ring.

X ¹ and X ² are anionic ligands or neutral Lewis base ligands, which may be the same or different and are each a hydrogen atom or a halogen atom,
Or a hydrocarbon, silyl or germyl group containing up to 20 carbon, silicon or germanium atoms.

Specific examples of the compound represented by the formula (I) include (dimethyl (t-butylamide) (tetramethyl-η5-cyclopentadienyl) silylene) titanium dichloride, ((t-butylamide) (Tetramethyl-
η5-cyclopentadienyl) -1,2-ethanediyl) titanium dichloride, (dimethyl (phenylamide) (tetramethyl-η5-cyclopentadienyl) silylene) titanium dichloride, (dimethyl (t-butylamide) (tetramethyl- η5-cyclopentadienyl) silylene) titanium dimethyl, (dimethyl (4-methylphenylamide) (tetramethyl-η5-cyclopentadienyl) silylene) titanium dichloride, (dimethyl (t-butylamide) (η5-
Cyclopentadienyl) silylene) titanium dichloride,
(Tetramethyl (t-butylamide) (tetramethyl-η5
-Cyclopentadienyl) disilylene) titanium dichloride.

In the present invention, a transition metal compound represented by the following formula (II) can also be used.

Embedded image

[In the formula (II), M is Ti, Zr, Hf, R
n, Nd, Sm or Ru, preferably Ti, Z
r or Hf, and Cp ¹ and Cp ² are a cyclopentadienyl group, an indenyl group, a fluorenyl group or a derivative group thereof bonded to M by π, and X ¹ and X ²
Is an anionic ligand or a neutral Lewis base ligand, and Z is a C, O, B, S, Ge, Si or Sn atom or a group containing these atoms, preferably one O, Si or C. ]

In the formula (II), the bonding group Z is preferably C, O,
It is preferably one atom selected from B, S, Ge, Si, and Sn, and this atom may have a substituent such as an alkyl group or an alkoxy group, and the substituents of Z are mutually bonded. To form a ring. Of these, Z is preferably selected from O, Si and C.

Cp1 and Cp2 are ligands that coordinate to the transition metal, and include cyclopentadienyl group, indenyl group, 4,5,
A ligand having a cyclopentadienyl skeleton such as a 6,7-tetrahydroindenyl group or a fluorenyl group, and the ligand having a cyclopentadienyl skeleton includes an alkyl group, a cycloalkyl group, and a trialkylsilyl group. And a substituent such as a halogen atom.

X ¹ and X ² are anionic ligands or neutral Lewis base ligands, and specifically include a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group and a sulfone group. Acid-containing group (—SO ₃ R _a , where R _a is an alkyl group, an alkyl group substituted with a halogen atom, an aryl group, an aryl group substituted with a halogen atom, or an aryl group substituted with an alkyl group. ), A halogen atom, a hydrogen atom and the like.

The following are examples of metallocene compounds in which M is zirconium and contains two ligands having a cyclopentadienyl skeleton. Cyclohexylidene-bis (indenyl) dimethyl zirconium, cyclohexylidene-bis (indenyl) zirconium dichloride, isopropylidene-bis (indenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-fluorenyl) zirconium dichloride, diphenylsilylene-bis ( Indenyl) zirconium dichloride, methylphenylsilylene-bis (indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-
1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (4,7-dimethyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,4,7-trimethyl-1-indenyl) zirconium dichloride, rac
-Dimethylsilylene-bis (2,4,6-trimethyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-
Bis (4-phenyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (α -Naphthyl) -1-
Indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (β-naphthyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-
Bis (2-methyl-4- (1-anthryl) -1-indenyl) zirconium dichloride and the like.

Further, metallocene compounds in which zirconium metal is replaced with titanium metal or hafnium metal in the above compounds can also be exemplified.

The metallocene compounds as described above can be used alone or in combination of two or more. The metallocene compound as described above can be used by being supported on a particulate carrier.

As such a particulate carrier, Si is used.
O ₂ , Al ₂ O ₃ , B ₂ O ₃ , MgO, ZrO ₂ , CaO, T
inorganic carriers such as iO ₂ , ZnO, SnO ₂ , BaO, and ThO, polyethylene, polypropylene, poly-1-butene,
Organic carriers such as poly-4-methyl-1-pentene and styrene-divinylbenzene copolymer can be used. These particulate carriers can be used alone or in combination of two or more.

In the present invention, the above-mentioned metallocene catalyst is preferably used as the olefin polymerization catalyst.

Next, a metallocene catalyst is formed (b): a compound which reacts with the transition metal M in the component (a) to form an ionic complex, that is, an ionized ionic compound, and (c): an organoaluminum The compound and (d): aluminoxane (aluminum oxy compound) will be described.

(B) Ionized Ionic Compound The ionized ionic compound is a compound which reacts with the transition metal M in the transition metal complex component (a) to form an ionic complex. Examples include Lewis acids, ionic compounds, borane compounds and carborane compounds.

As the Lewis acid, compounds represented by BR ₃ (where R is a phenyl group which may have a substituent such as a fluorine atom, a methyl group, a trifluoromethyl group or a fluorine atom). For example, trifluoroboron, triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl)
Boron, tris (4-fluoromethylphenyl) boron,
Tris (pentafluorophenyl) boron, tris (p-
And tris (o-tolyl) boron and tris (3,5-dimethylphenyl) boron.

Examples of the ionic compound include trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts, dialkylammonium salts, and triarylphosphonium salts. Specifically, the trialkyl-substituted ammonium salts include, for example, triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, tri (n-butyl) boron.
And ammonium tetra (phenyl) boron. Examples of the dialkyl ammonium salt include di (1-propyl) ammonium tetra (pentafluorophenyl) boron and dicyclohexylammonium tetra (phenyl) boron. Further, examples of the ionic compound include triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylaniliniumtetrakis (pentafluorophenyl) borate, and ferrocenium tetra (pentafluorophenyl) borate.

As a borane compound, decaborane (1
4), bis [tri (n-butyl) ammonium] nonaborate, bis [tri (n-butyl) ammonium] decaborate, bis [tri (n-butyl) ammonium] bis (dodecahydride dodecaborate) nickelate (II
And salts of metal borane anions such as I).

As the carborane compound, 4-carbanonaborane (14), 1,3-dicarbanonaborane (13), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carboundecaborate) Salts of metal carborane anions such as nickelate (IV) are exemplified.

The ionized ionic compound as described above is
They can be used alone or in combination of two or more.
The organic aluminum oxy compound or the ionized ionic compound can be used by being supported on the above-mentioned particulate carrier.

In forming the catalyst, the following organic aluminum compound (c) may be used together with the organic aluminum oxy compound or the ionized ionic compound.

(C) Organoaluminum Compound As the organoaluminum compound, a compound having at least one Al-carbon bond in a molecule can be used. Examples of such a compound include an organoaluminum compound represented by the following formula (b-1) represented by the following general formula.

(R ₁ ) _m Al (O (R ₂ )) _n H _p X _q (b-1) (wherein, R ₁ and R ₂ may be the same or different from each other, and the number of carbon atoms is Usually 1 to 15, preferably 1 to 4
X represents a halogen atom, and m represents 0
<M ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, and q is 0 ≦
q <3, and m + n + p + q =
3. (D) Organoaluminum oxy compound (aluminoxane)
) (D) an organoaluminum oxy-compound may be a conventionally known aluminoxane, also JP-A 2-7868
It may be a benzene-insoluble organic aluminum oxy compound as exemplified in JP-A-7.

The conventionally known aluminoxane (alumoxane) is specifically represented by the following general formulas (XV-1) and (XV-
It is a compound represented by 2).

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In the formula, R is a hydrocarbon group such as a methyl group, an ethyl group, a propyl group and a butyl group, preferably a methyl group, an ethyl group, and particularly preferably a methyl group. m is an integer of 2 or more, preferably 5 to 40.

The organic aluminum oxy compound may contain a small amount of an organic compound component of a metal other than aluminum. In the present invention, the above-mentioned metallocene-based catalyst is preferably used as the catalyst (olefin-based catalyst) for producing the amorphous α-olefin-based copolymer (ii). In addition to the catalyst, a titanium catalyst comprising a conventionally known solid titanium catalyst component and an organoaluminum compound, and a vanadium catalyst comprising a soluble vanadium compound and an organoaluminum compound can also be used.

In the present invention, the above α-olefin having 3 to 20 carbon atoms is used in the presence of the above-mentioned metallocene catalyst.
Ethylene, a polyene unsaturated compound having two or more double bonds, and the like are usually copolymerized in a liquid phase. In this case, a hydrocarbon solvent is generally used, but the α-olefin may be used as the solvent. The copolymerization can be carried out by either a batch method or a continuous method.

When the copolymerization is carried out by a batch method using a metallocene catalyst, the concentration of the metallocene compound in the polymerization system is usually 0.00005 per liter of polymerization volume.
-1 mmol, preferably 0.0001-0.5 mmol.

The organoaluminum oxy compound has a molar ratio (Al / M) of aluminum atom (Al) to transition metal atom (M) in the metallocene compound of 1 to 1000.
It is used in such an amount that it becomes 0, preferably 10-5000.

The ionized ionic compound has a molar ratio of the ionized ionic compound to the metallocene compound (ionized ionic compound / metallocene compound) of 0.5 to 2
It is used in an amount such that it becomes 0, preferably 1 to 10.

When an organoaluminum compound is used, it is used in an amount of usually about 0 to 5 mmol, preferably about 0 to 2 mmol, per liter of polymerization volume.

In the copolymerization reaction, the temperature is usually -20 to 15
0 ° C, preferably 0 to 120 ° C, more preferably 0 to
In the range of 100 ° C., the pressure exceeds 0 and is ~ 80 kg / cm
² , preferably above 0 and up to 50 kg / cm ² .

The reaction time (average residence time when the copolymerization is carried out by a continuous method) varies depending on conditions such as the catalyst concentration and the polymerization temperature, but is usually 5 minutes to 3 hours, preferably 10 minutes to 10 minutes. 1.5 hours.

The above-mentioned copolymerizing monomers such as α-olefin, ethylene, and a polyene unsaturated compound having two or more double bonds include the α-olefin / ethylene / polyene unsaturated compound having a specific composition as described above. The copolymer (amorphous α-olefin copolymer) (ii) is supplied to the polymerization system in such an amount as to obtain the copolymer. In the copolymerization,
Molecular weight regulators such as hydrogen can also be used.

As described above, when a copolymerizing monomer such as ethylene, the above α-olefin, and a polyene unsaturated compound having two or more double bonds is copolymerized, an amorphous α-olefin copolymer is obtained. The combination (ii) is usually obtained as a polymerization solution containing the same. This polymerization liquid is treated by a conventional method to obtain an amorphous α-olefin copolymer (ii).

A molded article comprising such a propylene-based polymer composition can be obtained by melt flow rate (ASTM D 1238,230).
° C, load 2.16 kg) is usually 0.0001 to 1000 g /
10 minutes, preferably 0.0001 to 900 g / 10 minutes,
More preferably, it is 0.0001 to 800 g / 10 minutes.

<Production of Propylene-Based Polymer Composition> The above-mentioned propylene-based polymer composition can be prepared by mixing the components with various known methods such as a Henschel mixer, a V-blender, a ribbon blender, and the like. It can be manufactured by employing a method of mixing with a tumbler blender or the like, or a method of mixing and kneading with a single-screw extruder, a twin-screw extruder, a kneader, a Banbury mixer or the like, followed by granulation or pulverization.

The propylene polymer composition includes a heat stabilizer, a weather stabilizer, an antistatic agent, a pigment, a dye, a rust inhibitor, an inorganic filler, a nucleating agent described in detail below, and other additives. A "polymer" (elastomer) and the like can be blended within a range that does not impair the object of the present invention. Inorganic fillers Specific examples of inorganic fillers include fine powdered talc, kaolinite, calcined clay, virophyllite, sericite, natural silicic acid or silicate such as wollastonite, precipitated calcium carbonate, heavy calcium carbonate, Carbonates such as magnesium carbonate, hydroxides such as aluminum hydroxide and magnesium hydroxide, oxides such as zinc oxide, zinc white and magnesium oxide, synthetic silica such as hydrous calcium silicate, hydrous aluminum silicate, hydrous silicic acid, and silicic anhydride Powdered filler such as silicate, flaked filler such as mica, basic magnesium sulfate whisker, calcium titanate whisker, aluminum borate whisker, sepiolite, PMF (Processed Mineral Fibe
r), fibrous fillers such as zonotolite, potassium titanate, and elestadite, and balun fillers such as glass balun and fly ash balun.

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

The inorganic filler, especially talc, used in the present invention may be untreated or surface-treated in advance. Examples of the surface treatment include, specifically, 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. By using talc subjected to such a surface treatment, it is possible to obtain a polypropylene composition having excellent weld strength, paintability, and moldability.

The inorganic fillers described above may be used in combination of two or more. In the present invention, together with such an inorganic filler, an organic filler such as high styrenes, lignin, and recycled rubber can be used. As the nucleating agent, various conventionally known nucleating agents are used without any particular limitation. Among them, a nucleating agent represented by the following formula (XVI) can be exemplified as a preferable nucleating agent.

[0182]

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[0183] (wherein, R ³¹ is oxygen, sulfur or a hydrocarbon group having 1 to 10 carbon atoms, R ^32, R ³³ is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, R ^32, R ³³ may be heterologous be homologous, R ³² to each other, may be R ³³ s or R ³² and R ³³ are combined to have a cyclic, M is a monovalent to trivalent metal atom And n 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- Screw-
(4,6-di-t-butylphenyl) phosphate, lithium
-2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate, sodium-2,2'-ethylidene-bis (4-i
-Propyl-6-t-butylphenyl) phosphate, lithium-2,2'-methylene-bis (4-methyl-6-t-butylphenyl) phosphate, lithium-2,2'-methylene-bis (4
-Ethyl-6-t-butylphenyl) phosphate, calcium-bis [2,2'-thiobis (4-methyl-6-t-butylphenyl) phosphate], calcium-bis [2,2'-thiobis ( 4-ethyl-6-t-butylphenyl) phosphate]
, Calcium-bis [2,2'-thiobis- (4,6-di-t-butylphenyl) phosphate], magnesium-bis [2,2'-thiobis (4,6-di-t-butylphenyl) Phosphate], magnesium-bis [2,2'-thiobis- (4-t-
Octylphenyl) phosphate], sodium-2,
2'-butylidene-bis (4,6-di-methylphenyl) phosphate, sodium-2,2'-butylidene-bis (4,6-di-
(t-butylphenyl) phosphate, sodium-2,2'-
t-octylmethylene-bis (4,6-di-methylphenyl) phosphate, sodium-2,2'-t-octylmethylene-
Bis (4,6-di-t-butylphenyl) phosphate, calcium-bis- (2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate), magnesium-bis [2 ,
2'-methylene-bis (4,6-di-t-butylphenyl) phosphate], barium-bis [2,2'-methylene-bis (4,6
-Di-t-butylphenyl) phosphate], sodium
-2,2'-methylene-bis (4-methyl-6-t-butylphenyl)
Phosphate, sodium-2,2'-methylene-bis (4-
Ethyl-6-t-butylphenyl) phosphate, sodium (4,4'-dimethyl-5,6'-di-t-butyl-2,2'-biphenyl) phosphate, calcium-bis [(4,4 '-Dimethyl-6,6'-di-t-butyl-2,2'-biphenyl) phosphate], sodium-2,2'-ethylidene-bis (4-m-butyl-
6-t-butylphenyl) phosphate, sodium-2,
2'-methylene-bis (4,6-di-methylphenyl) phosphate, sodium-2,2'-methylene-bis (4,6-di-ethylphenyl) phosphate, potassium-2,2'-ethylidene -Bis (4,6-di-t-butylphenyl) phosphate,
Calcium-bis [2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate], magnesium-bis [2,2'-ethylidene-bis (4,6-di-t-butylphenyl) )
Phosphate], barium-bis [2,2'-ethylidene-
Bis (4,6-di-t-butylphenyl) phosphate],
Aluminum-tris [2,2'-methylene-bis (4,6-di-t-
Butylfel) phosphate] and aluminum-
Tris [2,2′-ethylidene-bis (4,6-di-t-butylphenyl) phosphate] and mixtures of two or more thereof can be exemplified. Particularly, sodium-2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate is preferred.

[0185]

Embedded image

(Wherein R ³⁴ is hydrogen or C 1 -C 1)
0 is a hydrocarbon group, M is a metal atom having 1 to 3 valences, and n is an integer of 1 to 3. ) Specifically, sodium-bis (4-t-butylphenyl)
Phosphate, sodium-bis (4-methylphenyl) phosphate, sodium-bis (4-ethylphenyl) phosphate, sodium-bis (4-i-propylphenyl) phosphate, sodium-bis (4-t-
Octylphenyl) phosphate, potassium-bis (4
-t-butylphenyl) phosphate, calcium-bis (4-t-butylphenyl) phosphate, magnesium
-Bis (4-t-butylphenyl) phosphate, lithium-bis (4-t-butylphenyl) phosphate, aluminum-bis (4-t-butylphenyl) phosphate and mixtures of two or more thereof can do. Particularly, sodium-bis (4-t-butylphenyl) phosphate is preferred.

[0187]

Embedded image (In the formula, R ³⁵ is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms.)

More specifically, 1,3,2,4-dibenzylidene sorbitol, 1,3-benzylidene-2,4-p-methylbenzylidene sorbitol, 1,3-benzylidene-2,4-p-ethylbenzylidene Sorbitol, 1,3-p-methylbenzylidene-2,4
-Benzylidene sorbitol, 1,3-p-ethylbenzylidene-2,4-benzylidene sorbitol, 1,3-p-methylbenzylidene-2,4-p-ethylbenzylidene sorbitol, 1,3
-p-ethylbenzylidene-2,4-p-methylbenzylidene sorbitol, 1,3,2,4-di (p-methylbenzylidene) sorbitol, 1,3,2,4-di (p-ethylbenzylidene) sorbitol, 1,3,2,4-di (pn-propylbenzylidene) sorbitol, 1,3,2,4-di (pi-propylbenzylidene) sorbitol, 1,3,2,4-di (pn-butylbenzylidene) sorbitol 1,3,2,4-di (ps-butylbenzylidene) sorbitol, 1,3,2,4-di (pt-butylbenzylidene) sorbitol, 1,3,2,4-di (2 ', 4' -Dimethylbenzylidene)
Sorbitol, 1,3,2,4-di (p-methoxybenzylidene)
Sorbitol, 1,3,2,4-di (p-ethoxybenzylidene)
Sorbitol, 1,3-benzylidene-2-4-p-chlorobenzylidenesorbitol, 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-
Chlorbenzylidene sorbitol and 1,3,2,4-di (p-
Chlorbenzylidene) sorbitol and mixtures of two or more thereof, especially 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-chlorobenzylidene) sorbitol and the like A mixture of two or more of the above is preferred.

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

Other Copolymers The propylene-based polymer composition according to the present invention may contain "other copolymers" (elastomer, resin for elastomer) as required.

Examples of such "other copolymers" include ethylene / α-olefin random copolymer (A), optionally hydrogenated aromatic hydrocarbon block copolymer (B), ethylene copolymer -Α-olefin block copolymer (C), ethylene-styrene-based copolymer (D), ethylene-diene copolymer (E), ethylene-triene copolymer (F) and the like. These copolymers are used alone or in combination of two or more.

These “other copolymers” are a total of 100% by weight of the propylene polymer (i) and the amorphous α-olefin copolymer (ii) contained in the polypropylene composition of the present invention. It may be contained in an amount of usually 0 to 40 parts by weight based on parts. Also, these "other copolymers"
Is usually 0 to 3 in total in the propylene polymer composition.
It may be contained in an amount of 0% by weight. When other copolymers are used in the above amounts, a composition capable of producing a molded article having an excellent balance of rigidity, transparency, impact resistance and surface hardness can be obtained.

Ethylene / α-olefin random copolymer
Combined (A) The ethylene / α-olefin random copolymer (A) used in the present invention has a density of 0.860 g / cm.
³ or more and less than 0.895 g / cm ³ , preferably 0.86 g / cm ³
0 to 0.890 g / cm ³ and a melt flow rate (MFR; ASTM D 1238, 190 ° C., load 2.16 kg) of 0.
A soft ethylene / α-olefin copolymer having a weight of 5 to 30 g / 10 min, preferably 1 to 20 g / 10 min is desirable.

The α-olefin to be copolymerized with ethylene is an α-olefin having 3 to 20 carbon atoms, and specifically, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, -Octene, 1-nonene, 1-decene,
1-undecene, 1-dodecene, 1-hexadedecene, 1-octadecene, 1-nonadecene, 1-eicosene, 4-methyl-1-
Penten and the like. Among them, α-olefins having 3 to 10 carbon atoms are preferable. These α-
The olefins are used alone or in combination of two or more.

The ethylene / α-olefin random copolymer (A) contains 60 to 90 units of units derived from ethylene.
It is desirable to contain 10 to 40 mol% of units derived from an α-olefin having 3 to 20 carbon atoms in an amount of mol%.

The ethylene / α-olefin random copolymer (A) contains, besides these units, units derived from other polymerizable monomers within a range not to impair the object of the present invention. Is also good.

[0197] Such other polymerizable monomers include:
For example, vinyl compounds such as styrene, vinylcyclopentene, vinylcyclohexane, and vinylnorbornane; vinyl esters such as vinyl acetate; unsaturated organic acids such as maleic anhydride or derivatives thereof; butadiene;
Conjugated dienes such as isoprene, pentadiene and 2,3-dimethylbutadiene; 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-isopropylene-2-norbornene, 2,3-diisopropylidene-5-norbornene, 2- Non-conjugated polyenes such as ethylidene-3-isopropylidene-5-norbornene and 2-propenyl-2,2-norbornadiene.

The ethylene / α-olefin random copolymer (A) contains units derived from such other polymerizable monomers in an amount of at most 10 mol%, preferably at most 5 mol%, more preferably at most 3 mol%. May be contained.

Specific examples of the ethylene / α-olefin random copolymer (A) include an ethylene / propylene random copolymer, an ethylene / 1-butene random copolymer, and an ethylene / propylene / 1-butene random copolymer. Polymers include ethylene / propylene / ethylidene norbornene random copolymer, ethylene / 1-hexene random copolymer, ethylene / 1-octene random copolymer and the like. Among these, ethylene / propylene random copolymer, ethylene / 1-butene random copolymer,
Ethylene / 1-hexene random copolymer, ethylene / 1-
Octene random copolymers and the like are particularly preferably used. Two or more of these copolymers may be used in combination.

Further, the ethylene.α-
The olefin random copolymer (A) generally has a crystallinity of 40% or less, preferably 0 to 39%, more preferably 0 to 35% as measured by X-ray diffraction.

The above-mentioned ethylene / α-olefin random copolymer can be produced by a conventionally known method using a vanadium catalyst, a titanium catalyst or a metallocene catalyst.

The ethylene / α-olefin random copolymer (A) is usually contained in the propylene polymer composition in an amount of 0%.
It may be present in an amount of up to 40% by weight, preferably 0 to 35% by weight. When the ethylene / α-olefin random copolymer (A) is used in the above amount, a composition capable of preparing a molded article having excellent balance of rigidity and hardness, transparency, impact resistance, and surface hardness can be obtained. .

Aromatic hydrocarbons which may be hydrogenated
Lock Copolymer (B) The aromatic hydrocarbon-based block copolymer (B) which may be hydrogenated, which is used as an elastomer in the present invention, comprises:
A block polymerized unit (X) derived from aromatic vinyl,
Aromatic vinyl / conjugated diene block copolymer (B) comprising a block polymer unit (Y) derived from a conjugated diene
1) and its hydrogenated product (B2).

The form of the aromatic vinyl / conjugated diene block copolymer (B1) having such a structure is, for example, X (Y
X) n or (XY) n [n is an integer of 1 or more]. Among these, a block copolymer in the form of X (YX) n, particularly XYX is preferred, and specifically, in the form of polystyrene-polybutadiene (or polyisoprene or polyisoprene-butadiene) -polystyrene. Styrene block copolymers are preferred.

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

As the aromatic vinyl forming the above-mentioned block polymerized unit (X), specifically, in addition to styrene, α-methylstyrene, 3-methylstyrene, p-methylstyrene, 4-propylstyrene And styrene derivatives such as 4-dodecylstyrene, 4-cyclohexylstyrene, 2-ethyl-4-benzylstyrene, and 4- (phenylbutyl) styrene. Of these, styrene is preferred.

Examples of the conjugated diene forming the block polymerized unit (Y) include butadiene, isoprene, pentadiene, 2,3-dimethylbutadiene and a combination thereof. Of these, butadiene or isoprene or a combination of butadiene and isoprene is preferred.

When the conjugated diene block polymerization unit (Y) is derived from butadiene and isoprene, the unit preferably contains the unit derived from isoprene in an amount of 40 mol% or more.

The conjugated diene block polymerization unit (Y) comprising butadiene / isoprene copolymerization unit
Is a random copolymerized unit of butadiene and isoprene,
It may be either a block copolymer unit or a tapered copolymer unit.

The aromatic vinyl / conjugated diene block copolymer (B1) has an aromatic vinyl block polymerized unit (X) content of 22% by weight or less, preferably 5 to 22% by weight. . The content of the aromatic vinyl polymerized unit can be measured by a conventional method such as infrared spectroscopy and NMR spectroscopy.

Further, the melt flow rate (MFR; ASTM) of the aromatic vinyl / conjugated diene block copolymer (B1)
D 1238, 200 ° C, load 2.16 kg) is usually 5 g / 10 min or more, preferably 5 to 100 g / 10 min.

As the method for producing the above-mentioned aromatic vinyl / conjugated diene block copolymer (B1), various methods can be mentioned. For example, (1) an alkyllithium compound such as n-butyllithium is used as an initiator. As 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, and (3) using a lithium compound as an initiator. , A conjugated diene, and then a method of sequentially polymerizing an aromatic vinyl compound.

The hydrogenated aromatic vinyl / conjugated diene block copolymer (B2) is obtained by hydrogenating the above aromatic vinyl / conjugated diene block copolymer (B1) by a known method. Can be obtained by Hydrogenated aromatic vinyl / conjugated diene block copolymer (B2)
Usually has a hydrogenation rate of 90% or more.

This hydrogenation ratio is a value when the total amount of carbon-carbon double bonds in the conjugated diene block polymerization unit (Y) is 100%. Specific examples of the hydrogenated product (B2) of the aromatic vinyl / conjugated diene block copolymer include a hydrogenated product of a styrene / isoprene block copolymer (SEP) and a styrene / isoprene / styrene block copolymer. Hydrogenated polymer (SEPS; polystyrene / polyethylene / propylene / polystyrene block copolymer),
Hydrogenated styrene-butadiene block copolymer (SE
BS; polystyrene / polyethylene / butylene / polystyrene block copolymer) and the like. More specifically, HYBRAR [manufactured by Kuraray Co., Ltd.], Clayton [manufactured by Shell Chemical Co., Ltd.], Carifrex TR [shell chemical] Co., Ltd.], Solprene [Philippe Petro Rifum Co., Ltd.], Europrene SOLT [Aniche Co., Ltd.], Tufprene [Asahi Kasei Kogyo Co., Ltd.], Solprene-T [Nihon Elastomer Co., Ltd.], JSR-TR [Nihon Gosei Rubber Co., Ltd.], Electrification STR
And Quintac [manufactured by Zeon Corporation], Clayton G [manufactured by Shell Chemical Co., Ltd.], Tuftec [manufactured by Asahi Chemical Industry Co., Ltd.] (all trade names) and the like.

As the hydrogenated product (B2) of the aromatic vinyl / conjugated diene block copolymer, SEB
S and SEPS are preferably used. The optionally hydrogenated aromatic hydrocarbon block copolymer (B) may be contained in the polypropylene composition in an amount of usually 0 to 30% by weight, preferably 0 to 25% by weight. . Aromatic hydrocarbon-based block copolymer (B) which may be hydrogenated
Is used in the above amounts, a composition is obtained which can prepare a molded article having an excellent balance of rigidity and hardness, transparency, impact resistance and surface hardness.

Ethylene / α-olefin block copolymer
Combined (C) ethylene • α- used as an elastomer in the present invention
The olefin block copolymer (C) has 3 carbon atoms.
0 to 20% by mole of a structural unit derived from olefin, and 100 to 80% of a structural unit derived from ethylene.
And a low-crystalline copolymer part or an amorphous copolymer part containing two or more structural units derived from an olefin having 2 to 20 carbon atoms.

In the present invention, the constitutional unit derived from ethylene is contained in an amount of 30 to 95 mol%, and has 3 carbon atoms.
A structural unit derived from an olefin of from 20 to 70 to 5
Ethylene / α-olefin block copolymers contained in an amount of mol% are preferred. In particular, ethylene · α in which the constituent unit derived from ethylene is contained in an amount of 60 to 90 mol% and the constituent unit derived from an olefin having 3 to 20 carbon atoms is contained in an amount of 40 to 10 mol%.
-Olefin block copolymers are preferred.

Here, specific examples of the olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene and 3-methyl-1-pentene.
Pentene, 1-octene, 3-methyl-1-butene, 1-decene, 1-dodecene, 1-tetradodecene, 1-hexadecene,
1-octadecene, 1-eicosene, cyclopentene, cycloheptene, norbornene, 5-ethyl-2-norbornene, tetracyclododecene, 2-ethyl-1,4,5,8-dimethano-1,2,3,4,4a , 5,8,8a-octahydronaphthalene and the like.

The structural unit derived from an olefin having 3 to 20 carbon atoms or ethylene may be contained in two or more kinds. The ethylene / α-olefin block copolymer used in the present invention has 4 carbon atoms.
To 20 diene compounds may be contained in an amount of 5 mol% or less.

Specific examples of such a diene compound include 1,3-butadiene, 1,3-pentadiene, 1,4-pentadiene, 1,3-hexadiene, 1,4-hexadiene, 1,5- Hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-
1,4-hexadiene, 6-methyl-1,6-octadiene, 7-methyl-1,6-octadiene, 6-ethyl-1,6-octadiene, 6-propyl-1,6-octadiene, 6-butyl- 1,6-octadiene, 6-methyl-1,6-nonadiene, 7-methyl-1,6
-Nonadiene, 6-ethyl-1,6-nonadiene, 7-ethyl-
1,6-nonadiene, 6-methyl-1,6-decadiene, 7-methyl-1,6-decadiene, 6-methyl-1,6-undecadiene,
Examples thereof include 1,7-octadiene, 1,9-decadiene, isoprene, butadiene, ethylidene norbornene, vinyl norbornene, and dicyclopentadiene.

The ethylene / α-olefin block copolymer (C) has a melt flow rate (MF
R; ASTM D 1238, 190 ℃, load 2.16kg) is usually 0.00
01-500 g / 10 min, preferably 0.0001-3
00g / 10 min, more preferably 0.0001 to 20
0 g / 10 min, and the density (ASTM D 1505)
0.85 to 0.90 g / cm ³ , preferably 0.85 to
0.89 g / cm ³ , more preferably 0.86 to 0.1 g / cm ³ .
Desirably, it is 89 g / cm ³ .

The crystallinity of the boiling heptane insoluble component in the copolymer (C) measured by an X-ray diffraction method is usually 0 to 30%, preferably 0 to 28%, more preferably 0 to 25%. .

The boiling heptane-insoluble component of the ethylene / α-olefin block copolymer (C) is prepared as follows. That is, 3 g of a polymer sample, 20 mg of 2,6-di-tert-butyl-4-methylphenol and 500 ml of n-decane were placed in a 1-liter flask equipped with a stirrer,
Heat and dissolve on a 45 ° C. oil bath. After the polymer sample is dissolved, it is cooled to room temperature over about 8 hours, and then kept on a 23 ° C. water bath for 8 hours. The n-decane suspension containing the precipitated polymer (23 ° C. decane-insoluble component) was prepared using G-4 (or G
After filtering and separating through a glass filter of -2) and drying under reduced pressure, 1.5 g of the polymer is subjected to Soxhlet extraction using heptane for 6 hours or more to obtain a boiling heptane-insoluble component.

The degree of crystallinity is measured as follows using the boiling heptane-insoluble component obtained as described above as a sample. That is, a sample was formed into a square plate having a thickness of 1 mm by a pressure molding machine at 180 ° C., and immediately thereafter, measured using a press sheet obtained by cooling with water using a Rotaflex RU300 measuring device manufactured by Rigaku Corporation. (Output 50 kV, 250 mA). As a measuring method at this time, a transmission method is used, and the measurement is performed while rotating the sample.

The density of the boiling heptane-insoluble component of the ethylene / α-olefin block copolymer (C) used in the present invention is usually 0.86 g / cm ³ or more, preferably 0.87 g / cm ³ or more.

The amount of the n-decane-soluble component at 23 ° C. of the ethylene / α-olefin block copolymer (C) was as follows:
It is in the range of 0.1-99%, preferably 0.5-99%, more preferably 1-99%.

In the present invention, the amount of the n-decane-soluble component at 23 ° C. of the ethylene / α-olefin block copolymer is as follows:
It is measured as follows. That is, 3 g of the polymer sample and 2,6-di-ter were placed in a 1-liter flask equipped with a stirrer.
20 mg of t-butyl-4-methylphenol and 500 ml of n-decane are added and dissolved by heating on an oil bath at 145 ° C. After the polymer sample is dissolved, it is cooled to room temperature over about 8 hours, and then kept on a 23 ° C. water bath for 8 hours. The precipitated polymer and the n-decane solution containing the dissolved polymer are separated by filtration through a G-4 (or G-2) glass filter. The solution obtained in this way was 10 mmHg, 1
The polymer dissolved in the n-decane solution was dried by heating under the condition of 50 ° C. until the amount was determined, and the weight of the polymer was determined as a 23 ° C. decane-soluble component, and the weight of the ethylene / α-olefin block copolymer was determined at 23 ° C. The amount of n-decane soluble component is calculated as a percentage based on the weight of the polymer sample.

Ethylene used in the present invention is
The α-olefin block copolymer (C) can be prepared by a conventionally known method. Ethylene α-
The olefin block copolymer (C) is used in the propylene polymer composition in an amount of usually 0 to 40% by weight, preferably 0 to 40% by weight.
It may be included in an amount of 35% by weight. Ethylene ・ α
-When the olefin block copolymer (C) is used in the above-mentioned amount, a composition that can prepare a molded article having an excellent balance of rigidity, transparency, impact resistance, and surface hardness can be obtained.

Ethylene / Styrene Copolymer (D) The ethylene / styrene copolymer (D) used as the elastomer in the present invention is a random copolymer of ethylene and styrene or a derivative thereof.

Examples of the styrene or its derivative copolymerized with ethylene include, in addition to styrene, α
Styrene derivatives such as methylstyrene, 3-methylstyrene, p-methylstyrene, 4-propylstyrene, 4-dodecylstyrene, 4-cyclohexylstyrene, 2-ethyl-4-benzylstyrene, and 4- (phenylbutyl) styrene; No. In the present invention, styrene is preferred.

The ethylene / styrene copolymer (D) is
It is desirable to contain units derived from ethylene in an amount of 5 to 99 mol% and units derived from styrene and / or styrene derivatives in an amount of 1 to 95 mol%.
The ethylene / styrene copolymer (D) may have one or more units derived from styrene or a derivative thereof.

The ethylene / styrene copolymer (D) is
A density of 0.85 to 1.02 g / cm3, preferably
86 to 1.02 g / cm @ 3 and a melt flow rate (MFR; ASTM D 1238, 190 DEG C., load 2.16 kg) of 0.0
01 to 500 g / 10 min, preferably 0.001 to 30
Desirably, it is 0 g / 10 minutes.

The crystallinity of the ethylene / styrene copolymer (D) measured by X-ray diffraction is usually 80% or less, preferably 0 to 75%, more preferably 0 to 70%. .

The ethylene / styrene copolymer (D) as described above can be prepared by a conventionally known method. The ethylene / styrene copolymer (D) may be contained in the propylene polymer composition in an amount of usually 0 to 40% by weight, preferably 0 to 35% by weight. When the ethylene / styrene-based copolymer (D) is used in the above amount, a composition that can prepare a molded article having an excellent balance of rigidity, transparency, impact resistance, and surface hardness can be obtained.

Ethylene / diene copolymer (E) The ethylene / diene copolymer (E) used as the elastomer in the present invention is a random copolymer of ethylene and diene.

As the diene to be copolymerized with ethylene,
Specifically, non-conjugated dienes such as dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylene norbornene, and ethylidene norbornene; butadiene;
Conjugated dienes such as isoprene; Of these, butadiene and isoprene are preferred. These dienes can be used alone or in combination of two or more.

In the ethylene / diene copolymer (E) used in the present invention, the content of the structural unit derived from diene is usually 0.1 to 30 mol%, preferably 0.1 to 30 mol%.
-20 mol%, more preferably 0.5-15 mol%. The iodine value is usually 1-1.
50, preferably 1 to 100, more preferably 1 to 5
Desirably, it is 0. The intrinsic viscosity [η] of the ethylene / diene copolymer (E) measured in decahydronaphthalene at 135 ° C. is 0.01 to 10 dl / g, preferably 0.05 to 10 dl / g, more preferably 0.
It is desirable to be in the range of 1 to 10 dl / g. Such an ethylene / diene copolymer (E) can be prepared by a conventionally known method.

The ethylene / diene copolymer (E) may be contained in the propylene-based polymer composition in an amount of usually 0 to 40% by weight, preferably 0 to 35% by weight. When the ethylene-diene copolymer (E) is used in the above amount, a composition that can prepare a molded article having an excellent balance of rigidity and hardness, transparency, impact resistance, and surface hardness can be obtained.

Ethylene / triene copolymer (F) The ethylene / triene copolymer (F) used as the elastomer in the present invention is a random copolymer of ethylene and triene.

Specific examples of the triene to be copolymerized with ethylene include 6,10-dimethyl-1,5,9-undecatriene, 4,8-dimethyl-1,4,8-decatriene, -Dimethyl-1,4,8-decatriene, 6,9-dimethyl-1,5,8-decatriene, 6,8,9-trimethyl-1,5,8-decatriene, 6-ethyl-10-methyl-1 , 5,9-Undecatriene, 4-ethylidene-1,6-octadiene, 7-methyl-4-ethylidene-1,6-
Octadiene, 4-ethylidene-8-methyl-1,7-nonadiene (EMND), 7-methyl-4-ethylidene-1,6-nonadiene, 7-ethyl-4-ethylidene-1,6-nonadiene, 6,7 -
Dimethyl-4-ethylidene-1,6-octadiene, 6,7-dimethyl-4-ethylidene-1,6-nonadiene, 4-ethylidene-
1,6-decadiene, 7-methyl-4-ethylidene-1,6-decadiene, 7-methyl-6-propyl-4-ethylidene-1,6-octadiene, 4-ethylidene-1,7-nonadiene, 8- Methyl
-4-ethylidene-1,7-nonadiene, 4-ethylidene-1,7-
A non-conjugated triene such as undecadiene; a conjugated triene such as 1,3,5-hexatriene; These trienes can be used alone or in combination of two or more.

The above-mentioned triene is, for example, EP0
It can be prepared by a conventionally known method as described in JP 691354A1 and WO96 / 20150.

In the ethylene / triene copolymer (F) used in the present invention, the content of the structural unit derived from triene is usually 0.1 to 30 mol%, preferably 0.1 to 20 mol%, and more preferably 0.1 to 20 mol%. Preferably, it is in the range of 0.5 to 15 mol%. It is desirable that the iodine value is usually 1 to 200, preferably 1 to 100, and more preferably 1 to 50.

Also, ethylene / triene copolymer (F)
Has an intrinsic viscosity [η] measured in decahydronaphthalene at 135 ° C. of 0.01 to 10 dl / g, preferably 0.1 to 10 dl / g.
05 to 10 dl / g, more preferably 0.1 to 10 d / g
It is desirably within the range of 1 / g.

The ethylene / triene copolymer (F) as described above can be prepared by a conventionally known method. The ethylene / triene copolymer (F) may be contained in the propylene-based polymer composition in an amount of usually 0 to 40% by weight, preferably 0 to 35% by weight. ethylene·
When the triene copolymer (F) is used in the above amount,
As a result, a composition that can prepare a molded article having an excellent balance of rigidity and hardness, transparency, impact resistance, and surface hardness can be obtained.

Molded article The propylene polymer composition according to the present invention as described above can be widely used for conventionally known polyolefin applications. In particular, the polyolefin composition can be used, for example, in a sheet, unstretched or stretched film, filament, It can be used after being molded into molded articles of other various shapes.

Specific examples of the molded body include known thermoforming methods such as extrusion molding, injection molding, inflation molding, blow molding, extrusion blow molding, injection blow molding, press molding, vacuum molding, calendar molding, and foam molding. And a molded article obtained by the above method. The molded product will be described below with reference to several examples.

When the molded article according to the present invention is, for example, an extruded article, its shape and product type are not particularly limited, but for example, sheets, films (unstretched), pipes,
Examples include hoses, wire coatings, and filaments, and particularly preferred are sheets, films, and filaments.

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

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

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

Also, an inflation film can be produced as a film-shaped molded product. Drawdown hardly occurs during inflation molding. Sheets and film molded articles made of the propylene polymer composition according to the present invention as described above are difficult to be charged, and have rigidity such as tensile elasticity, heat resistance, impact resistance, surface hardness, aging resistance, and transparency. It is excellent in transparency, transparency, gloss, rigidity, moisture resistance and gas barrier properties, and can be widely used as a packaging film. Particularly, since it has excellent moisture-proof properties, it is suitably used for press-through packs used for packaging tablets, capsules and the like of chemicals.

The filament molding can be produced, for example, by extruding a molten propylene polymer composition through a spinneret. The filament thus obtained may be further drawn. This stretching may be carried out so that at least the uniaxial direction of the filament is molecularly oriented, and is usually desirably performed at a magnification of about 5 to 10 times. The filament made of the propylene-based polymer composition according to the present invention is hardly charged, and is excellent in transparency, rigidity, heat resistance, impact resistance, and surface hardness.

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

The blow molded article can be produced by blow molding a propylene-based polymer composition using a conventionally known blow molding apparatus under known conditions.

For example, in extrusion blow molding, the propylene polymer composition is extruded from a die in a molten state at a resin temperature of 100 ° C. to 300 ° C. to form a tubular parison, and then the parison is held in a mold having a desired shape. Then, air is blown into the mold at a resin temperature of 130 ° C. to 300 ° C. to form a hollow molded body.
The stretching (blow) magnification is desirably about 1.5 to 5 times in the lateral direction.

In injection blow molding, the propylene polymer composition was injected into a parison mold at a resin temperature of 100 ° C. to 300 ° C. to form a parison, and the parison was held in a mold having a desired shape. After that, air is blown into the mold at a resin temperature of 120 ° C to 300 ° C, whereby a hollow molded body can be manufactured. The stretching (blow) magnification is 1.1 to 1.8 times in the longitudinal direction and 1.3 to 2.2 in the lateral direction.
Preferably, it is 5 times.

The blow molded article comprising the propylene polymer composition according to the present invention is excellent in transparency, rigidity, heat resistance, impact resistance, surface hardness, and moisture resistance.

Examples of the press-formed body include a mold stamping-formed body. For example, the base material and the skin material are simultaneously press-formed and the base material of the present invention is subjected to composite integral forming (mold stamping forming) according to the present invention. It can be formed of a propylene-based polymer composition.

Specific examples of such a molded stamping molded body include automotive interior materials such as door trim, rear package trim, seat back garnish, and instrument panel.

The propylene-based polymer composition according to the present invention exhibits transparency and high rigidity. For example, even if it contains an elastomer component, it exhibits sufficiently high rigidity, so that it can be used for various high rigidity applications. . For example, it can be suitably used particularly for applications such as interior and exterior materials of automobiles, housings of home appliances, and various containers.

The press-formed body comprising the propylene-based polymer composition according to the present invention is hardly charged, and has rigidity, heat resistance, transparency, impact resistance, surface hardness, aging resistance, surface gloss, chemical resistance, and Excellent abrasion properties.

The propylene-based polymer composition according to the present invention is transparent and flexible, so that it can be suitably used for the following applications, for example. (1) Film: multilayer stretched film, multilayer unstretched film, laminate film, shrink film, stretch film, wrap film, protect film,
Retort film, porous film, barrier film, metallized film, agricultural film (2) Sheets and sheet molded products: wallpaper, foamed sheet,
Wire covering materials, prestar packaging materials, trays, stationery supplies, toys, cosmetic containers, medical equipment, detergent containers, flooring materials, cushion flooring materials, decorative sheets, shoe soles

(3) Blow molded product: bottle (4) Extruded product: tube, wire covering material, cable covering material, pipe, gasket material (5) Fiber: fiber, flat yarn (6) Nonwoven fabric and nonwoven fabric product: nonwoven fabric , Filters (7) Injection molded products: automotive interior skin materials, automotive exterior materials,
Sundries, home appliances, caps, containers, pallets (8) Modifiers: adhesives, lubricant additives, hot melt adhesives, toner release agents, pigment dispersants, asphalt modifiers (9 ) Others: Sealant, vacuum formed body, powder slash body

[0264]

According to the present invention, there can be obtained a propylene-based polymer composition capable of obtaining a molded article excellent in rigidity, impact resistance, surface hardness and the like in a well-balanced manner.

[0265]

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

Hereinafter, physical property test conditions and the like will be described. Tensile test In the following examples, each physical property was measured as follows. (1) Flexural Modulus (FM) A flexural modulus (FM) was measured using a test piece having a thickness of 1/8 inch under the conditions of a span of 51 mm and a bending speed of 20 mm / min in accordance with ASTM C790. (2) Izod Impact Strength (IZ) Measured at 23 ° C. using a 片 inch thick test piece (post notch) in accordance with ASTM D256. (3) Rockwell hardness (HR) 2 mm thick x 120 mm long according to ASTM D785
× Measured using a 130 mm wide square plate.

The melting point (Tm) and the glass transition temperature (T
g) The endothermic curve of DSC is determined, and the temperature at the maximum peak position is determined by Tm.
And Further, when the base line is inflected, the intersection between the initial baseline and the inflection point is defined as Tg. For the measurement, the sample was packed in an aluminum pan, heated to 200 ° C. at 100 ° C./min, kept at 200 ° C. for 5 minutes, and then −1 at 10 ° C./min.
The temperature was lowered to 50 ° C. and then determined from an endothermic curve when the temperature was raised at 10 ° C./min.

From the endothermic peak at the time of DSC measurement, the heat of fusion per unit weight is determined, and this is divided by the heat of fusion of polyethylene crystal 70 cal / g to obtain
The crystallinity (%) can be determined.

The intrinsic viscosity [η] was measured at 135 ° C. in decalin. The measurement was performed at 140 ° C. using an Mw / Mn GPC (gel permeation chromatography) in an orthodichlorobenzene solvent.

[0270]

Synthesis Example 1 Preparation of solid titanium catalyst component 95.2 g of anhydrous magnesium chloride, 442 ml of decane and 390 ml of 2-ethylhexyl alcohol.
6 g was reacted at 130 ° C. for 2 hours to form a homogeneous solution. 21.3 g of phthalic anhydride was added to this solution, and the mixture was further stirred and mixed at 130 ° C. for 1 hour. Was dissolved. After cooling the thus obtained homogeneous solution to room temperature, 150 ml of this homogeneous solution was placed in 400 ml of titanium tetrachloride kept at -20 ° C.
0 ml was added dropwise over 1 hour. After completion of the charging, the temperature of the mixture was raised to 110 ° C. over 4 hours. When the temperature reached 110 ° C., 10.44 g of diisobutyl phthalate (DIBP) was added, and the mixture was kept at the same temperature for 2 hours. Stirring was maintained.

After completion of the reaction for 2 hours, a solid portion was collected by hot filtration, and the solid portion was resuspended in 550 ml of titanium tetrachloride, and then heated again at 110 ° C. for 2 hours. . After 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 prepared by the above operation was stored as a decane slurry, and a part of this was dried for the purpose of examining the catalyst composition. The composition of the solid titanium catalyst component thus obtained was as follows: 2.3% by weight of titanium, 61% by weight of chlorine, 19% by weight of magnesium, DIBP1
2.5% by weight.

Preliminary polymerization of solid titanium catalyst component In a 400-ml four-neck glass reactor equipped with a stirrer, 100 ml of purified hexane, 10 mmol of triethylaluminum, 2.0 mmol of dicyclopentyldimethoxysilane (DCPMS) and 400 mmol of the above were placed in a nitrogen atmosphere. After adding 1.0 mmol of the solid titanium catalyst component in terms of titanium atoms, propylene was supplied to the reactor at a rate of 3.2 liter / hour for 1 hour. Polymerization temperature is 20 ° C
Kept. When the supply of propylene was completed, the inside of the reactor was purged with nitrogen, and a washing operation including removal of the supernatant and addition of purified hexane was performed twice, followed by resuspension with purified hexane and transfer of the whole amount to the catalyst bottle. As a result, a prepolymerized catalyst was obtained.

The propylene polymer (ia) <block poly
Propylene> Polymerization In a 17 liter autoclave, propylene 3
After charging Kg and 120 liters of hydrogen and raising the temperature to 60 ° C., 15 mmol of triethylaluminum, 15 mmol of dicyclopentyldimethoxysilane (DCPMS) and 0.05 mmol of a prepolymerized catalyst in terms of titanium atom were added.
i was charged. After the temperature was raised to 70 ° C., the temperature was maintained for 35 minutes to perform propylene homopolymerization. After the completion of the homopolymerization, the vent valve was opened, and unreacted propylene was depressurized until the pressure in the polymerization reactor became normal pressure.

After the depressurization was completed, ethylene and propylene were subsequently copolymerized. That is, ethylene is 150Nl / h
r, propylene was supplied to the polymerization reactor at a rate of 1050 Nl / hr. The vent opening of the polymerization vessel was adjusted so that the pressure in the polymerization vessel was 10 kg / cm 2 · G. The temperature is maintained at 70 ° C. and 80
Polymerization was performed for minutes. The polymerization reaction was stopped by adding a small amount of ethanol, and the unreacted gas in the polymerization vessel was purged.
The resulting white powder was dried at 80 ° C. under reduced pressure. [Η] of the obtained polymer = 1.6 dl / g, Tm = 167 ° C., 64
The content of soluble components in tecan is 10.1 wt% and the ethylene content is 2%.
The content of the insoluble component in 0 mol% at 64 ° C. was 89.9% by weight, and the isotacticity of the boiling heptane insoluble component in the 64 ° C. insoluble component as observed in the triad chain of propylene was 0.99.

[0275]

[Synthesis Example 2] Propylene polymer (ib) <Homopolypro
Pyrene> was polymerized by a known method using a homopolymerized Ti-based catalyst. [Η] = 1.7 dl / g, Tm = 169 ° C., 64 ° C. Tecan-soluble component content of the obtained polymer is 1.5% by weight, 64 ° C. Tecan-insoluble component content is 98.5% by weight, and 64 ° C. The isotacticity of the boiling heptane-insoluble component in the insoluble component as observed in the triad chain of propylene was 0.99.

[0276]

[Synthesis Example 3] Atactic propylene / ethylene copolymerization
Synthesis of Compound (iia) To a 1.5-liter autoclave dried under reduced pressure and purged with nitrogen, 750 ml of heptane was added at room temperature, followed by 1.0 mmol / ml of triisobutylaluminum (hereinafter abbreviated as TIBA) in toluene. 0.3 ml of the solution was converted to aluminum atoms so that the amount became 0.3 mmol, 30 liters of propylene (25 ° C., 1 atm) were inserted with stirring, and the temperature was raised to reach 60 ° C. I let it. Then, the inside of the system was ethylene with 5.9 kg / cm2.
3.75 ml of a toluene solution of (dimethyl (t-butylamide) (tetramethyl-η5-cyclopentadienyl) silane) dichloride titanium (0.0001 mM / ml) synthesized by a known method. Solution of (triphenylcarbenium tetra (pentafluorophenyl) borate) in toluene (0.001 mM / m
l) was added to initiate copolymerization of propylene and ethylene. The catalyst concentration at this time was (dimethyl (t-butylamide) (tetramethyl-η5-cyclo
-Pentadienyl) silane) dichloride titanium is 0.1%.
0005 mmol / l, triphenylcarbenium tetra (pentafluorophenyl) borate
02 mmol / l.

During the polymerization, the internal pressure was maintained at 5.9 kg / cm 2 G by continuously supplying ethylene. Fifteen minutes after the start of the polymerization, the polymerization reaction was stopped by adding methyl alcohol. After depressurization, the polymer solution was taken out, and the polymer solution was washed with an aqueous solution obtained by adding 5 ml of concentrated hydrochloric acid to 1 liter of water at a ratio of 1: 1. Transferred to the aqueous phase. After the catalyst mixed solution was allowed to stand, the aqueous phase was separated and removed, and further washed twice with distilled water, and the polymerization liquid phase was separated into oil and water. Next, the polymerization liquid phase separated from the oil and water was brought into contact with three times the volume of acetone under vigorous stirring to precipitate a polymer, which was then sufficiently washed with acetone, and a solid part (copolymer) was collected by filtration. 130 ° C, 350mmH under nitrogen flow
g for 12 hours. The yield of the propylene / ethylene copolymer obtained as described above was 29 g,
The intrinsic viscosity [η] measured in decalin at 5 ° C. is 3.2 dl.
/ G, the glass transition temperature Tg is -22 ° C, and the ethylene content is 16.0 mol% (ethylene: 11.3 wt%).
The activity was 310 kg / mmol Zr · hr, and the molecular weight distribution (Mw / Mn) measured by GPC was 2.6. Further, the melting peak measured by DSC was not substantially observed.

[0278]

[Synthesis Example 4] Atactic propylene / ethylene copolymerization
Synthesis of Compound (iib) The same operation as in Synthesis Example 1 was performed except that the amount of propylene was changed to 28.5 liters (25 ° C., 1 atm). The yield of the obtained propylene / ethylene copolymer was 39 g, the intrinsic viscosity [η] measured in 135 ° C. decalin was 2.9 dl / g, the glass transition temperature Tg was −31 ° C., The ethylene content is 24 mol% (ethylene: 17.4% by weight) and the activity is 412 k
g / mmol · Zr · hr, and the molecular weight distribution by GPC was 2.4.

The melting peak measured by DSC was not substantially observed.

[0280]

[Synthesis Example 5] Both isotactic propylene and ethylene
Synthesis of Polymer (iiia) 750 ml of heptane was added at room temperature to a 1.5-liter autoclave which had been dried under reduced pressure and purged with nitrogen, and then a 1.0 mmol / ml toluene solution of triisobutylaluminum (hereinafter abbreviated as TIBA) was added. 0.3 ml of aluminum atoms was added so that the amount became 0.3 mmol, and 34 liters (25 ° C., 1 atm) of propylene were inserted with stirring, and the temperature was raised to reach 60 ° C. Thereafter, the inside of the system was pressurized with ethylene to 5.9 kg / cm 2 G, and rac-dimethylsilylenebis # 1 synthesized by a known method was used.
-(2-methyl-4-phenylindenyl) zirconium dichloride in toluene solution (0.0001 mM / m
3.75 ml of l) and 9.38 ml of a toluene solution of methylaluminoxane (0.01 mM / ml) were added to initiate copolymerization of propylene and ethylene. At this time, the catalyst concentration was 0.0005 mmol / liter of rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride and 0.125 mmol / liter of methylaluminoxane with respect to the whole system. Met. During the polymerization, the internal pressure was maintained at 5.9 kg / cm 2 G by continuously supplying ethylene. Fifteen minutes after the start of the polymerization, the polymerization reaction was stopped by adding methyl alcohol.

After depressurizing, the polymer solution was taken out, and the polymer solution was added with “1 liter of water and 5 ml of concentrated hydrochloric acid.
The polymer solution was washed with an aqueous solution containing 1 ml of a 1: 1 ratio, and the catalyst residue was transferred to the aqueous phase. After allowing the catalyst mixed solution to stand, the aqueous phase was separated and removed, and further washed twice with distilled water to separate the polymerization liquid phase from oil and water. Next, the polymer liquid phase separated from the oil and water was brought into contact with a three-fold amount of acetone under vigorous stirring to precipitate a polymer, and then thoroughly washed with acetone, and a solid part (copolymer) was collected by filtration. It dried at 130 degreeC and 350 mmHg for 12 hours under nitrogen flow.
The yield of the propylene / ethylene copolymer obtained as described above was 20 g, the intrinsic viscosity [η] measured in 135 ° C. decalin was 2.1 dl / g, and the glass transition temperature Tg was −34 ° C. The ethylene content was 18.0 mol% (ethylene: 12.8% by weight), and the activity was 21.
The molecular weight distribution by GPC was 2 kg / mmol Zr · hr and was 2.4. The melting peak measured by DSC was observed at a maximum of 76 ° C.

[0282]

[Synthesis Example 6] Both isotactic propylene and ethylene
The same operation as in Synthesis Example 5 was performed except that the synthetic propylene of the polymer (iiib) was changed to 28 liters (25 ° C., 1 atm). The yield of the obtained propylene / ethylene copolymer was 26 g, the intrinsic viscosity [η] measured in decalin at 135 ° C. was 2.8 dl / g,
The glass transition temperature Tg was -47 ° C, the ethylene content was 30 mol% (ethylene: 22.2 wt%), the activity was 276 kg / mmol Zr · hr, and the molecular weight distribution by GPC was 2.7. The melting peak measured by DSC was observed but broad, but could not be quantified.

[0283]

Example 1 80 parts by weight of the propylene polymer (ia) obtained in Synthesis Example 1 and 20 parts by weight of the atactic propylene / ethylene copolymer (iia) obtained in Synthesis Example 3 were kneaded. To obtain a propylene polymer composition at a resin temperature of 2
Injection molding was performed under the conditions of 00 ° C., an injection pressure of 1000 kg / cm 2, and a mold temperature of 40 ° C. Bending test of the obtained injection molded product,
The impact strength and surface hardness were evaluated. Table 2 shows the results.

[0284]

Example 2 Example 1 was repeated except that the propylene polymer obtained in Synthesis Example 1 was replaced with the propylene polymer (ib) obtained in Synthesis Example 2. .
Table 2 shows the results.

[0285]

Example 3 In Example 1, the propylene-based polymer obtained in Synthesis Example 2 was replaced with the propylene-based polymer (ib) obtained in Synthesis Example 2, and the atactic propylene polymer obtained in Synthesis Example 3 was used. The procedure was performed in the same manner as in Example 1, except that the atactic propylene (iib) obtained in Synthesis Example 4 was changed from the ethylene copolymer. Table 2 shows the results.

[0286]

Example 4 60 parts by weight of the propylene polymer (ia) obtained in Synthesis Example 1 above, 20 parts by weight of the atactic propylene / ethylene copolymer (iia) obtained in Synthesis Example 3, and talc (Hayashi) A propylene polymer composition was obtained by kneading 20 parts by weight of Kasei (Miselton) and evaluated. Table 2 shows the results
Shown in

[0287]

Comparative Example 1 In Example 1, except that the atactic propylene / ethylene copolymer obtained in Synthesis Example 3 was changed to the isotactic propylene / ethylene copolymer (iiia) obtained in Synthesis Example 5 This was performed in the same manner as in Example 1. Table 2 shows the results.

[0288]

Comparative Example 2 In Example 1, the propylene-based polymer obtained in Synthesis Example 2 was replaced with the propylene-based polymer (ib) obtained in Synthesis Example 2, and the atactic propylene polymer obtained in Synthesis Example 3 was used. The isotactic propylene / ethylene copolymer obtained in Synthesis Example 5 from the ethylene copolymer (iii
Except having changed to a), it carried out similarly to Example 1. Table 2 shows the results.

[0289]

Comparative Example 3 The procedure of Example 1 was repeated, except that the propylene polymer obtained in Synthesis Example 1 was replaced with the propylene polymer (ib) obtained in Synthesis Example 2. The isotactic propylene / ethylene copolymer obtained in Synthesis Example 6 from the ethylene copolymer (iii
Except having changed to b), it carried out similarly to Example 1. Table 2 shows the results.

[0290]

[Table 2]

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Claims (11)

[Claims] (I) propylene or a propylene polymer comprising propylene and an α-olefin having 2 to 10 carbon atoms (excluding 3 carbon atoms) and having the following characteristics: 30 to 90% by weight; a) Intrinsic viscosity (in 135 ° C decalin) [η] of 0.8 to
5.0 dl / g b) 99.5 to 80% by weight of 64 ° C decane-insoluble component, c) 0.5 to 20% by weight of 64 ° C decane-soluble component, and d) Α- having 2 to 10 carbon atoms
Olefin (excluding 3 carbon atoms) content is 0 to 50 mol%. (ii) 10 to 70% by weight of an amorphous α-olefin copolymer having the following characteristics: e) An amount of 20 mol% or more of the component unit (A) derived from an α-olefin having 3 to 20 carbon atoms. (The total amount of the component unit (A) and the other component units in the copolymer (ii) is 1
00 mol%. F) a melting peak measured by a differential scanning calorimeter (DSC) is not substantially observed; g) an intrinsic viscosity [η] measured in decalin at 135 ° C. in the range of 0.01 to 10 dl / g. H) the molecular weight distribution by GPC is 4 or less, and i) the glass transition temperature Tg is 40 ° C. or less. A propylene polymer composition comprising: 2. The propylene polymer composition according to claim 1, wherein said (i) propylene polymer further has the following characteristics. j) Melting point Tm (° C.) measured by a differential scanning calorimeter
Is 150 <Tm <173, and k) the isotacticity of the boiling heptane-insoluble component of 64 ° C. decane-insoluble component is 0.90 or more as viewed in the propylene triad chain. 3. The propylene-based composition according to claim 1, wherein the other component units in the (ii) amorphous α-olefin-based copolymer include a component unit derived from ethylene. Polymer composition. 4. In the above (ii) amorphous α-olefin-based copolymer, the α-olefin having 3 to 20 carbon atoms is propylene, 1-butene, 4-methylpentene-1, 1-hexene, At least one selected from -octene and 1-decene
The propylene polymer composition according to any one of claims 1 to 3, which is a kind of olefin. 5. The (ii) amorphous α-olefin-based copolymer comprises an α-olefin having 3 to 20 carbon atoms, ethylene,
At least two or more selected from ethylidene norbornene, dicyclopentadiene, butadiene, isoprene, 4,8-dimethyl-1,4,8-decatriene, and 4-ethylidene-8-methyl-1,7-nonadiene 2
The propylene-based polymer composition according to any one of claims 1 to 4, which is a copolymer with a polyene-based unsaturated compound having a heavy bond. 6. The amorphous α-olefin copolymer (ii)
Contains a component unit (A) derived from an olefin having 3 to 20 carbon atoms in an amount of 50 to 99 mol%, and the propylene-based polymer composition according to any one of claims 1 to 5, wherein object. 7. The amorphous α-olefin copolymer (ii)
Is a component unit (A) derived from an α-olefin having 3 to 20 carbon atoms in an amount of 50 to 99 mol%, and an α-olefin having 3 to 20 carbon atoms.
-3 to 2 carbon atoms other than the olefin-derived component unit (A)
A copolymer containing 0 to 50 mol% of α-olefin-derived component unit (b) (total component amount in the copolymer (ii) is 100 mol%). The propylene polymer composition according to claim 6, characterized in that: 8. The amorphous α-olefin copolymer (ii)
Is a copolymer containing 50 to 99 mol% of a component unit (A) derived from an α-olefin having 3 to 20 carbon atoms and 1 to 50 mol% of an ethylene component unit (the copolymer (ii)
The content of all components in the composition is 100 mol%. 7. The propylene-based polymer composition according to claim 6, wherein 9. The amorphous α-olefin copolymer (ii)
Is a catalyst comprising at least one of the following components (a) and one or more compounds selected from the following components (b), (c) and (d): A propylene-based polymer composition according to any one of claims 1 to 8, which is obtained by polymerizing in the presence of a propylene-based polymer; (a) the following formula (I) or (II): The transition metal complex represented by) [In the formulas (I) and (II), M is Ti, Zr, Hf, Rn,
Nd, Sm or Ru, Cp1 and Cp2 are a cyclopentadienyl group, an indenyl group, a fluorenyl group or a derivative group thereof bonded to M by π;
1 and X2 are anionic ligands or neutral Lewis base ligands, Y is a ligand containing a nitrogen, oxygen, phosphorus, or sulfur atom, and Z is C, O,
It is a B, S, Ge, Si or Sn atom or a group containing these atoms. (B): a compound that reacts with the transition metal M in the component (a) to form an ionic complex (c): an organoaluminum compound (d): aluminoxane. 10. The propylene polymer composition further comprises:
Ethylene / α-olefin random copolymer (A),
Aromatic hydrocarbon block copolymer (B) which may be hydrogenated, ethylene / α-olefin block copolymer (C), ethylene / styrene copolymer (D), ethylene / diene copolymer The propylene-based polymer composition according to any one of claims 1 to 9, comprising (E) and at least one copolymer selected from ethylene-triene copolymer (F). object. 11. A molded article comprising the propylene polymer composition according to any one of claims 1 to 10.