JP2001106841A - Syndiotactic polypropylene based composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a syndiotactic polypropylene based compositions which excels in heat resistance, flexibility, impact resistance and mar resistance. SOLUTION: This syndiotactic polypropylene based composition comprises (A) a syndiotactic polypropylene polymer composed of (a) propylene units of a substantially syndiotactic structure and, if necessary, (b) ethylene units and/or (c) 4-20C α-olefin units and contains 90-100 mol% units (a), 0-10 mol% units (b), and 0-9.5 mol% units (c) and having an intrinsic viscosity [η] in the range of 0.5-10 dl/g, (B) an α-olefin polymer having a Young' modulus of not higher than 400 MPa, and (C) a filler at a weight ratio [(A)/(B)] of polymer (A) to polymer (B) of 90/10 to 10/90 and filler (C) in an amount of 1-1,000 pts.wt. based on 100 pts.wt. sum of polymer (A) and polymer (B).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a syndiotactic polypropylene composition, and more particularly, to a syndiotactic polypropylene composition having excellent heat resistance, flexibility, impact resistance, and scratch resistance.

[0002]

BACKGROUND OF THE INVENTION Isotactic polypropylene is excellent in rigidity, hardness, heat resistance and the like, and conventionally used for a wide range of applications. For example, it is used for housing of household electric appliances, film and sheet use, container use, car interior use, car exterior use such as fender, bumper, side molding, mudguard, mirror cover, and general miscellaneous goods.

Since isotactic polypropylene is inferior in impact resistance, when conventionally used for the above-mentioned applications, polyisobutylene, polybutadiene, polyethylene or an elastomer component such as amorphous or low-crystalline ethylene / propylene is used. It is known that a polypropylene composition is blended with a copolymer (EPR) or the like to impart flexibility and improve impact resistance. There is also known a polypropylene-based composition in which a filler is added together with an elastomer component in order to compensate for the reduced scratch resistance due to the incorporation of the elastomer component.

However, in the conventionally known isotactic polypropylene-based composition formed from the above-described components, a large amount of an elastomer component must be blended in order to maintain a high level of impact resistance. Insufficient heat resistance and scratch resistance. On the other hand, if a large amount of a filler is blended to compensate for the scratch resistance, the filler becomes hard and lacks flexibility.

[0005] Syndiotactic polypropylene is
It is known that it can be obtained by low-temperature polymerization in the presence of a catalyst comprising a vanadium compound, ether and organoaluminum. However, the polymer obtained by this method has a low syndiotacticity and is not sufficiently flexible.

In recent years, JA Ewen et al. Have reported that a syndiotactic triad fraction of 0.7 in the presence of a transition metal catalyst having an asymmetric ligand and an aluminoxane catalyst.
It has been discovered that polypropylene having a high syndiotacticity exceeding 0.1% can be obtained (J. Am. Chem. So
c., 1988, 110, 6255-6256). The polymer obtained by the method of JA Ewen et al. Had a high syndiotacticity and an elastic property than isotactic polypropylene, but this was used as a soft molding material, for example, When it is intended to be used in a field where soft vinyl chloride, vulcanized rubber or the like is used, its flexibility, rubber elasticity and mechanical strength are not sufficient.

The inventors of the present invention have conducted intensive studies in view of such circumstances, and have found that a syndiotactic polypropylene composition comprising a specific syndiotactic propylene polymer, an α-olefin polymer, and a filler has a high heat resistance. The present invention was found to be excellent in balance among flexibility, impact resistance and scratch resistance, and completed the present invention.

[0008]

That is, an object of the present invention is to provide a syndiotactic polypropylene composition excellent in heat resistance, flexibility, impact resistance and scratch resistance.

[0009]

SUMMARY OF THE INVENTION The syndiotactic polypropylene composition according to the present invention comprises (A) a repeating unit (a) derived from propylene and, if necessary, a repeating unit (b) derived from ethylene and / or a carbon atom. Number 4-20
Wherein the repeating unit (a) is contained in a proportion of 90 to 100 mol%, and the repeating unit (b) is contained in a proportion of 0 to 10 mol%. A substantially syndiotactic structure containing unit (c) in a proportion of 0 to 9.5 mol% and having an intrinsic viscosity [η] of 0.5 to 10 dl / g measured in decalin at 135 ° C. And (B) α- having 2 to 20 carbon atoms.
At least one repeating unit derived from an α-olefin selected from olefins, and one of the at least one repeating unit is 50 to 10
0% by mole, Young modulus 150M
A weight ratio of the above-mentioned syndiotactic propylene polymer (A) and the above-mentioned α-olefin polymer (B), which contains an α-olefin polymer of not more than Pa and a filler (C) ｛(A) / ( B) is in the range of 90/10 to 10/90, and the total amount of the syndiotactic propylene polymer (A) and the α-olefin polymer (B) is 100
It is characterized in that the filler (C) is contained at a ratio of 1 to 1000 parts by weight with respect to parts by weight.

[0010] In an embodiment of the syndiotactic polypropylene composition according to the present invention, the (A) syndiotactic propylene polymer has a syndiotacticity of 0.6 or more as viewed in a propylene triad chain;
The α-olefin polymer (B) has an intrinsic viscosity [η] measured in decalin at 135 ° C. of 0.01 to 10 dl /.
g, the molecular weight distribution (Mw / Mn) determined by gel permeation chromatography is 4 or less, the glass transition temperature is -5 ° C or less, and the filler (C) is an inorganic filler. Some are agents.

In the present invention, the (B) α-olefin polymer contains 50 to 99 repeating units derived from ethylene.
A copolymer containing at least 1 mol% of a repeating unit derived from at least one kind of α-olefin selected from α-olefins having 3 to 20 carbon atoms in a proportion of 1 to 50 mol%; Preferably, the (B) α-olefin polymer comprises at least one kind of ethylene and α-olefin having 4 to 20 carbon atoms in a proportion of 50 to 99 mol% of repeating units derived from propylene. 1-5 repeating units derived from α-olefin
It is also preferable that the copolymer is contained at a ratio of 0 mol%.

The (B) α-olefin polymer is, for example, (a) a transition metal compound represented by the following general formula (I) or (II), and (b) (b-1) a transition metal compound ( a) a compound which reacts with the transition metal in a) to form an ionic complex (hereinafter sometimes referred to as “ionized ionic compound”), (b-2) an organic aluminum oxy compound,
(B-3) one obtained by polymerizing or copolymerizing an α-olefin having 2 to 20 carbon atoms in the presence of a metallocene catalyst comprising at least one compound selected from organoaluminum compounds. is there;

[0013]

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(In the formulas (I) and (II), M is Ti, Z
r, Hf, Rn, Nd, Sm or Ru, and Cp ¹
And Cp ² may be the same or different from each other,
A cyclopentadienyl group, an indenyl group, a fluorenyl group or a derivative group thereof, which is π-bonded to M;
X ¹ and X ² may be the same or different from each other and are an anionic ligand or a neutral Lewis base ligand, and 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, G
e, Si or Sn atom or a group containing these atoms. The syndiotactic polypropylene composition according to the present invention has an excellent balance of heat resistance, flexibility, impact resistance, and scratch resistance.

[0015]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the syndiotactic polypropylene composition of the present invention will be described in detail.

The syndiotactic polypropylene composition according to the present invention contains a specific syndiotactic propylene polymer (A), a specific α-olefin polymer (B), and a filler (C). I have.

First, each component contained in the syndiotactic polypropylene composition according to the present invention will be described. (A) Syndiotactic propylene polymer The syndiotactic propylene polymer (A) is a propylene homopolymer or a propylene random copolymer obtained from propylene and ethylene or an α-olefin having 4 to 20 carbon atoms. It is a polymer. The syndiotactic propylene polymer (A) comprises a repeating unit (a) derived from propylene and, if necessary, a repeating unit (b) derived from ethylene and / or 4 carbon atoms.
Repeating units (c) derived from α-olefins of from 20 to 20
Wherein the repeating unit (a) is contained in an amount of 90 to 100 mol%, preferably 92 to 100 mol%.
Mol%, more preferably 92 to 98 mol%, and the repeating unit (b) is contained in an amount of 0 to 10 mol%, preferably 0 to 8 mol%, more preferably 0.2 to 8 mol%.
And the repeating unit (c) is contained at a ratio of 0 to 9.5 mol%, preferably 0 to 8.5 mol%, more preferably 0 to 7 mol%.

The α-olefin having 4 to 20 carbon atoms includes 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-pentene,
Examples thereof include 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene, among which 1-butene is preferable.

This syndiotactic propylene polymer (A) has an intrinsic viscosity [η] measured in decalin at 135 ° C. of 0.5 to 10 dl / g, preferably 1.0 to 10 dl / g.
6 dl / g, more preferably in the range of 1.0 to 4 dl / g. When the intrinsic viscosity is in such a range, the syndiotactic propylene polymer (A)
Has good fluidity, is easily blended with other components, and tends to give a molded article having excellent mechanical strength from the obtained composition.

Further, the repeating unit chain derived from propylene constituting the syndiotactic propylene polymer (A) used in the present invention has substantially a syndiotactic structure, and is syndiotactic as viewed from the triad chain of propylene. City is 0.6 or more, preferably 0.7
As described above, when the syndiotacticity is in such a range, the crystallization speed is high and the workability is excellent. In addition,
In the present specification, substantially having a syndiotactic structure means that the syndiotacticity of the propylene in the triad chain is 0.6 or more.

The triad syndiotacticity (hereinafter sometimes referred to as “rr fraction”) of the syndiotactic propylene polymer (A) is determined by measuring the ¹³ C-NMR spectrum and the triad syndiotacticity of the polymer (A). According to the following formula (1), the strength (area) ratio of the side chain methyl group of the second unit of the three chain portions of the head-to-tail bonded propylene unit is obtained.

Rr fraction = PPP (rr) / {PPP (mm) + PPP (mr) + PPP (rr)} (1) (where PPP (mm), PPP (mr) and PPP (rr) are These are the areas of the measured methyl groups in the second unit of the three-chain part of the propylene unit head-to-tail bond observed in the following shift region of the ¹³ C-NMR spectrum.)

[0023]

[Table 1]

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

[0025]

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In the methyl carbon region (19 to 23 pp)
In m), in addition to the side chain methyl groups of the propylene units in the three head-to-tail bonded propylene chains, peaks of the side chain methyl groups of the propylene units in the other chains as described below are observed. When determining the rr fraction, the peak area of such a methyl group that is not based on three chains of propylene units is corrected as follows. P represents a repeating unit derived from propylene, and E represents a repeating 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 this 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 region, 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, in the positionally irregular units represented by the following partial structures (i), (ii) and (iii), which are contained in a small amount in the ethylene / ethylene random copolymer: Peaks derived from the methyl groups CE to E ′ 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 were observed at 17.3 ppm and 17.0 ppm, respectively, in the methyl groups in the position irregular units (i) to (iii). Is not observed.

[0032]

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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 is determined by the peak based on the αβ methylene carbon in the structure (ii) (34.3p
pm and around 34.5 ppm).

The peak area of the methyl group D is represented by the structure (iii)
The peak based on the adjacent methine group of the methyl group E (3
(Around 3.3 ppm). The peak area of the methyl group E is determined by the adjacent methine carbon (33.
(Around 7 ppm).

The peak area of the methyl group E can be determined from the peak area of the adjacent methine carbon (around 33.3 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 can be obtained. .

Each carbon peak in the spectrum can be assigned with reference to the literature (Polymer, 30, 1350 (1989)). Production of syndiotactic propylene polymer (A) When producing such a syndiotactic propylene polymer (A), α-
The metallocene catalyst used for the production of the olefin polymer (B) is preferably used.

In the production of the syndiotactic propylene polymer (A), JP-A-2-41303, JP-A-41305, JP-A-2-274703 and JP-A-2-274703 are used in place of the above catalyst system. JP-A-2-274704, JP-A-3-179005, JP-A-3-1790
06, JP-A-4-69394, JP-A-5-1
The catalyst system described in JP-A-7589 or JP-A-8-120127 can also be used.

Further, the above-mentioned document "J. Am. Chem. Soc., 1988," by JA Ewen et al.
110, 6255-6256 '' can also be used,
Further, even if the compound has a structure different from that of the compound described in the literature, when a homopolymer of propylene is produced, the syndiotactic triad fraction (A. Zam
belli et al Macromolecules vol 6 687 (1973); vol 8 925
(1975)) can be used as long as the catalyst system gives a polymer having a relatively high syndiotacticity of, for example, about 0.5 or more. Examples of such a catalyst system include a catalyst system comprising a crosslinked transition metal compound having asymmetrical ligands and a promoter such as organoaluminum.

Examples of the bridged transition metal compound having asymmetrical ligands constituting such a catalyst system include diphenylmethylene (cyclopentadienyl) (fluorenyl) hafnium dichloride and diphenylmethylene described in the above-mentioned literature. Methylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, isopropyl (cyclopentadienyl-1-fluorenyl) hafnium dichloride, isopropyl (cyclopentadienyl-1-fluorenyl) zirconium dichloride, (t-butylamido) dimethyl (fluorenyl) Silane titanium dimethyl, diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride and the like can be mentioned.

The co-catalyst used in such a catalyst system includes ionized ionic compounds and organic compounds similar to those constituting the metallocene-based catalyst used in the production of the α-olefin polymer (B) described later. Examples include an aluminum oxy compound (also referred to as an aluminoxane or an alumoxane) and an organic aluminum compound.

When the syndiotactic propylene polymer (A) used in the present invention is produced in the presence of the above-mentioned catalyst, propylene and, if necessary, ethylene and a carbon atom having 4 to 20 carbon atoms are used. And at least one α-olefin selected from the above α-olefins is finally polymerized so as to have the above-mentioned properties. The polymerization can be carried out by any of a liquid phase polymerization method such as suspension polymerization and solution polymerization or a gas phase polymerization method.

In the liquid phase polymerization method, as a polymerization medium, aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane. Hydrogen; aromatic hydrocarbons such as benzene, toluene and xylene; inert hydrocarbon solvents such as halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane or mixtures thereof, and propylene as a polymerization medium It can also be used.

The polymerization is preferably carried out at a temperature of usually -50 to 100 ° C., preferably 0 to 90 ° C. when carrying out the suspension polymerization method, and when carrying out the solution polymerization method.
Usually, it is desirable to carry out at a temperature of 0 to 250 ° C, preferably 20 to 200 ° C. When carrying out the gas phase polymerization, the polymerization is usually carried out at 0 to 120 ° C., preferably at 20 to 1 ° C.
Preferably, it is performed at a temperature of 00 ° C. The polymerization is usually carried out at normal pressure to 100 kg / cm ² , preferably at normal pressure to 50 kg / cm ² .
It is performed under a pressure of kg / cm ² .

The polymerization can be carried out by any of batch, semi-continuous and continuous methods. Further, the polymerization can be performed in two or more stages having different reaction conditions. The molecular weight of the resulting syndiotactic propylene polymer (A) can be adjusted by allowing hydrogen to be present in the polymerization system or by changing the polymerization temperature and the polymerization pressure.

(B) α-Olefin Polymer The α-olefin polymer (B) is a homopolymer of one kind of α-olefin selected from α-olefins having 2 to 20 carbon atoms, or a polymer having 2 carbon atoms. A copolymer of two or more α-olefins selected from α-olefins having from 20 to 20 carbon atoms, wherein at least one repeating unit is derived from an α-olefin selected from α-olefins having 2 to 20 carbon atoms.
And at least one of the one or more kinds of repeating units is contained in a proportion of 50 to 100 mol%, preferably 60 to 90 mol%, more preferably 65 to 85 mol%. I have.

The α-olefin polymer (B) containing the α-olefin component at such a ratio has good compatibility with the syndiotactic propylene polymer (A), and the resulting syndiotactic polypropylene The composition tends to exhibit sufficient flexibility and impact resistance.

The α-olefin polymer (B) is amorphous and has a Young's modulus of 150 MPa or less, preferably 50 MPa or less. The Young's modulus of the syndiotactic propylene polymer (A) is usually 300 MPa or more.

Examples of the α-olefin polymer (B) include an ethylene / propylene copolymer (the α-olefin described first as a main component, hereinafter the same), an ethylene / butene copolymer, Ethylene-pentene copolymer, ethylene-4-methyl-1-pentene copolymer,
Ethylene / hexene copolymer, ethylene / heptene copolymer, ethylene / octene copolymer, ethylene / nonene copolymer, ethylene / decene copolymer, ethylene / norbornene copolymer, ethylene / tetracyclododecene copolymer Copolymer, ethylene / butadiene copolymer, ethylene / isoprene copolymer, ethylene / 1,5-hexadiene copolymer, ethylene / acrylic acid copolymer, ethylene / methacrylic acid copolymer, ethylene / acrylic acid ester copolymer Copolymer, binary ethylene copolymers such as ethylene / methacrylic acid ester copolymer, isotactic propylene
Ethylene copolymer, atactic propylene / ethylene copolymer, syndiotactic propylene / ethylene copolymer, isotactic propylene / butene copolymer, atactic propylene / butene copolymer,
Syndiotactic propylene / butene copolymer, isotactic propylene / pentene copolymer, atactic propylene / pentene copolymer, syndiotactic propylene / pentene copolymer, isotactic propylene / hexene copolymer, attack Tic propylene / hexene copolymer, syndiotactic propylene / hexene copolymer, isotactic propylene / heptene copolymer, atactic propylene / heptene copolymer, syndiotactic propylene / heptene copolymer, isotactic Propylene / octene copolymer, atactic propylene / octene copolymer, syndiotactic propylene / octene copolymer, isotactic propylene / decene copolymer, ATA Tic propylene / decene copolymer, syndiotactic propylene / decene copolymer, isotactic propylene / styrene copolymer, atactic propylene / styrene copolymer, syndiotactic propylene / styrene copolymer, isotactic Propylene-norbornene copolymer,
Atactic propylene / norbornene copolymer, syndiotactic propylene / norbornene copolymer, isotactic propylene / tetracyclododecene copolymer, atactic propylene / tetracyclododecene copolymer, syndiotactic propylene / tetra Cyclododecene copolymer, isotactic propylene / butadiene copolymer, atactic propylene / butadiene copolymer, syndiotactic propylene / butadiene copolymer, isotactic propylene / isoprene copolymer, atactic propylene / Isoprene copolymer, syndiotactic propylene / isoprene copolymer, isotactic propylene / 1,5-hexadiene copolymer, atactic propylene / 1,5-hexa Binary propylene copolymers such as ene copolymers, syndiotactic propylene / 1,5-hexadiene copolymers, ethylene / propylene / norbornene copolymers, ethylene / butene / norbornene copolymers, ethylene / octene / Norbornene copolymer, ethylene / propylene / tetracyclododecene copolymer,
Ethylene-butene-tetracyclododecene copolymer, ethylene-octene-tetracyclododecene copolymer, ethylene-propylene-butadiene copolymer, ethylene-
Butene-butadiene copolymer, ethylene-octene-butadiene copolymer, ethylene-propylene-isoprene copolymer, ethylene-butene-isoprene copolymer, ethylene-octene-isoprene copolymer, ethylene-propylene-ethylidene norbornene copolymer Polymers, ethylene-butene-ethylidene norbornene copolymer, ethylene-octene-ethylidene norbornene copolymer, etc.
Primary ethylene copolymer, isotactic propylene / butene / ethylene copolymer, atactic propylene / butene / ethylene copolymer, syndiotactic propylene / butene / ethylene copolymer, isotactic propylene / octene / ethylene Copolymer, atactic propylene / octene / ethylene copolymer,
Syndiotactic propylene / octene / ethylene copolymer, isotactic propylene / octene /
Ethylene copolymer, atactic propylene / octene / ethylene copolymer, syndiotactic propylene / octene / ethylene copolymer, isotactic propylene / norbornene / ethylene copolymer, atactic propylene / norbornene / ethylene copolymer , Syndiotactic Propylene Norbornene
Ethylene copolymer, isotactic propylene / tetracyclododecene / ethylene copolymer, atactic propylene / tetracyclododecene / ethylene copolymer, syndiotactic propylene / tetracyclododecene / ethylene copolymer, iso Tactic propylene / butadiene / ethylene copolymer, atactic propylene / butadiene / ethylene copolymer, syndiotactic propylene / butadiene / ethylene copolymer, isotactic propylene / isoprene / ethylene copolymer, atactic propylene / Ternary propylene copolymers such as isoprene / ethylene copolymer and syndiotactic propylene / isoprene / ethylene copolymer are exemplified.

Such an α-olefin polymer (B)
Is the intrinsic viscosity [η] measured in 135 ° C. decalin,
Usually 0.01 to 10 dl / g, preferably 0.5 to 10 dl / g
dl / g, more preferably in the range of 1 to 8 dl / g. When the intrinsic viscosity [η] of the α-olefin polymer (B) is within the above range, syndiotactic polymer having excellent properties such as weather resistance, ozone resistance, heat aging resistance, low temperature properties, and dynamic fatigue resistance. It becomes a tick polypropylene composition.

The α-olefin polymer (B) has a single glass transition temperature and a differential scanning calorimeter (DS)
It is desirable that the glass transition temperature (Tg) measured by C) is usually -5C or lower, preferably -10C or lower, more preferably -20C or lower. When the glass transition temperature (Tg) of the α-olefin polymer (B) is within the above range, excellent cold resistance and low-temperature properties are obtained.

The molecular weight distribution (Mw / M) measured by gel permeation chromatography (GPC)
n, in terms of polystyrene, Mw: weight average molecular weight, Mn:
(Number average molecular weight) is preferably 4.0 or less,
More preferably, it is 3.5 or less.

Production of α-Olefin Polymer (B) Such α-olefin polymer (B) has a carbon number of 2 to 2 in the presence of, for example, a metallocene catalyst shown below.
It is obtained by (co) polymerizing at least one α-olefin selected from α-olefins of 0.

As such a metallocene-based catalyst,
(A) a transition metal compound represented by the following general formula (I) or (II), and (b) (b-1) the transition metal compound (a)
A compound which forms an ionic complex by reacting with a transition metal M therein, (b-2) an organic aluminum oxy compound, (b-3)
At least one catalyst system comprising at least one compound selected from organoaluminum compounds is exemplified.

First, the transition metal compound represented by the general formula (I) used in the present invention will be described.

[0055]

Embedded image

In the formula (I), M is Ti, Zr, Hf, R
n, Nd, Sm or Ru, preferably Ti,
Zr or Hf. Cp ¹ and Cp ² may be the same or different from each other, and are a cyclopentadienyl group, an indenyl group, a fluorenyl group, or a derivative group thereof bonded to M by π. More specifically, Cp ¹ and Cp ² are ligands that coordinate to a transition metal, and include cyclopentadienyl, indenyl, 4,5,6,7-tetrahydroindenyl, and fluorenyl groups. It is a ligand having a dienyl skeleton, and the ligand having a cyclopentadienyl skeleton may have a substituent such as an alkyl group, a cycloalkyl group, a trialkylsilyl group, or a halogen atom.

X ¹ and X ² may be the same or different from each other, and are an anionic ligand or a neutral Lewis base ligand, specifically, a hydrocarbon having 1 to 12 carbon atoms. Group, alkoxy group, aryloxy group, sulfonic acid-containing group (-SO ₃ ^Ra , where ^Ra 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 alkyl group. And a halogen atom, a hydrogen atom and the like.

Z is C, O, B, S, Ge, Si or
Is Sn or a group containing these atoms, for example, carbon
A divalent hydrocarbon group having 1 to 20 atoms, 1 to 2 carbon atoms
A divalent halogenated hydrocarbon group of 0, containing divalent silicon
Group, divalent germanium-containing group, divalent tin-containing group,-
CO-, -SO-, -SO_Two-, -BR^b-(R
^bIs a hydrogen atom, a halogen atom, a carbon atom having 1 to 20 carbon atoms.
Hydrogen groups, halogenated hydrocarbons having 1 to 20 carbon atoms
Group).

Specific examples of the transition metal compound represented by the general formula (I) include diphenylmethylene (cyclopentadienyl) (fluorenyl) hafnium dichloride and diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium. Dichloride, isopropyl (cyclopentadienyl-1-fluorenyl) hafnium dichloride, isopropyl (cyclopentadienyl-1-fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) fluorenyl zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2,7-dimethyl-4-
Ethylindenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis (1- (2,7-dimethyl-4-n-propylindenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2,7- Dimethyl-4-i-propylindenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2,7-dimethyl-4-n-butylindenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1
-(2,7-dimethyl-4-sec-butylindenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2,7-dimethyl-4-t-butylindenyl)｝ zirconium dichloride, rac- Dimethylsilylene-bis ｛1- (2,7-dimethyl-4-n
-Pentylindenyl) zirconium dichloride, rac-
Dimethylsilylene-bis {1- (2,7-dimethyl-4-n-hexylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-cyclohexylindenyl)} zirconium Dichloride, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-methylcyclohexylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-phenylethylindene) Nil)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2,7-dimethyl-4-phenyldichloromethylindenyl)｝ zirconium dichloride, rac-
Dimethylsilylene-bis {1- (2,7-dimethyl-4-chloromethylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-trimethylsilylenemethylindenyl)} Zirconium dichloride, r
ac-dimethylsilylene-bis {1- (2,7-dimethyl-4-trimethylsiloxymethylindenyl)} zirconium dichloride, rac-diethylsilylene-bis {1- (2,7-dimethyl-4)
-i-propylindenyl) zirconium dichloride, ra
c-di (i-propyl) silylenebis ｛1- (2,7-dimethyl-4-i-
Propylindenyl) zirconium dichloride, rac-
Di (n-butyl) silylenebis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride, rac-di
(Cyclohexyl) silylenebis ｛1- (2,7-dimethyl-4-i-
Propylindenyl) zirconium dichloride, rac-
Methylphenylsilylenebis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride, rac-methylphenylsilylenebis {1- (2,7-dimethyl-4-t-butylindenyl) ｝ Zirconium dichloride, rac-diphenylsilylenebis ｛1- (2,7-dimethyl-4-t-butylindenyl)｝ zirconium dichloride, rac-diphenylsilylenebis ｛1- (2,7-dimethyl-4-i- (Propylindenyl) zirconium dichloride, rac-diphenylsilylene bis 1- (2,7-dimethyl-4-ethylindenyl) zirconium dichloride, rac-di (p-tolyl) silylene bis 1- (2,7- Dimethyl-4-i-propylindenyl)｝ zirconium dichloride, rac-di (p-chlorophenyl) silylene bis ｛1- (2,7-dimethyl-4-i-propylindenyl)｝ zirconium dichloride, rac-dimethylsilylene bis ｛1-
(2-methyl-4-i-propyl-7-ethylindenyl)｝ zirconium dibromide, rac-dimethylsilylene-bis ｛1-
(2,7-dimethyl-4-i-propyl-1-indenyl)｝ zirconium dimethyl, rac-dimethylsilylene-bis ｛1- (2,7-
Dimethyl-4-i-propyl-1-indenyl) zirconium methyl chloride, rac-dimethylsilylene-bis {1- (2,7-
Dimethyl-4-i-propyl-1-indenyl) zirconium
-Bis {1- (trifluoromethanesulfonato)}, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-i-propyl-
1-indenyl) {zirconium-bis {1- (p-phenylsulfinato)}, rac-dimethylsilylene-bis {1- (2-phenyl-4-i-propyl-7-methyl-1-indenyl)} Zirconium dichloride, (cyclopentadienyl) (fluorenyl) hafnium dichloride, (cyclopentadienyl)
(Fluorenyl) zirconium dichloride, bis ｛1- (2,7
-Dimethyl-4-ethylindenyl) zirconium dichloride, bis (cyclopentadienyl) hafnium dichloride, bis (cyclopentadienyl) zirconium dichloride, bisindenylhafnium dichloride, bisindenylzirconium dichloride, bis ｛1- ( 2,7-dimethyl-4-n-propylindenyl) zirconium dichloride, bis 1- (2,7-dimethyl-4-i-propylindenyl) zirconium dichloride, bis 1- (2,7- Dimethyl
-4-n-butylindenyl) zirconium dichloride, bis {1- (2,7-dimethyl-4-sec-butylindenyl)} zirconium dichloride, bis {1- (2,7-dimethyl-4-t) -Butylindenyl)｝ zirconium dichloride, bis ｛1- (2,
7-dimethyl-4-n-pentylindenyl)｝ zirconium dichloride, bis ｛1- (2,7-dimethyl-4-n-hexylindenyl)｝ zirconium dichloride, bis ｛1- (2,7-dimethyl- 4-cyclohexylindenyl)｝ zirconium dichloride, bis ｛1- (2,7-dimethyl-4-methylcyclohexylindenyl)｝ zirconium dichloride, bis ｛1- (2,7-
Dimethyl-4-phenylethylindenyl) zirconium dichloride, bis {1- (2,7-dimethyl-4-phenyldichloromethylindenyl)} zirconium dichloride, bis {1- (2,7-dimethyl-4-) Chloromethylindenyl) zirconium dichloride, bis {1- (2,7-dimethyl-4-trimethylsilylenemethylindenyl)} zirconium dichloride, bis {1- (2,7-dimethyl-4-trimethylsiloxymethylindenyl) )｝ Zirconium dichloride, bis ｛1-
(2,7-dimethyl-4-ethylindenyl)｝ zirconium dichloride, bis ｛1- (2-methyl-4-i-propyl-7-ethylindenyl)｝ zirconium dibromide, bis ｛1- (2, 7-
Dimethyl-4-i-propyl-1-indenyl)｝ zirconium dimethyl, bis ｛1- (2,7-dimethyl-4-i-propyl-1-indenyl)｝ zirconium methyl chloride, bis ｛1- (2,
7-dimethyl-4-i-propyl-1-indenyl)｝ zirconium-bis ｛1- (trifluoromethanesulfonato), bis ｛1
-(2,7-dimethyl-4-i-propyl-1-indenyl)｝ zirconium-bis ｛1- (p-phenylsulfinato)｝, bis ｛1
-(2-phenyl-4-i-propyl-7-methyl-1-indenyl)｝
Zirconium dichloride and the like can be mentioned.

Further, a transition metal compound in which the zirconium metal is replaced with a titanium metal or a hafnium metal in the above-mentioned zirconium compound can also be exemplified.

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

[0062]

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In the formula (II), M is a transition metal of Group 4 of the periodic table or a lanthanide series, and specifically, Ti, Z
r, Hf, Rn, Nd, Sm or Ru, preferably Ti, Zr, Hf.

Cp ¹ is a cyclopentadienyl group, an indenyl group, a fluorenyl group or a derivative group thereof bonded to M by π. More specifically, Cp ¹ is a ligand that coordinates to a transition metal, and is a ligand having 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.

X ¹ and X ² may be the same or different from each other and are an anionic ligand or a neutral Lewis base ligand, specifically, a hydrogen atom, a halogen atom,
It is a hydrocarbon group containing 0 or less carbon atoms, a silyl group containing 20 or less silicon atoms, or a germyl group containing 20 or less germanium atoms.

Z is carbon, oxygen, sulfur, boron or an element of group 14 of the periodic table (for example, silicon, germanium or tin), preferably any of carbon, oxygen and silicon, which are alkyl groups, It may have a substituent such as an alkoxy group, and these substituents may be bonded to each other to form a ring. Further, Z and Y may form a condensed ring.

Specific examples of the transition metal complex represented by the above general formula (II) include (t-butylamido) dimethyl (fluorenyl) silanetitanium dimethyl and (t-butylamido) dimethyl (fluorenyl) silanetitanium dichloride , (T-butylamido) dimethyl (fluorenyl) silane zirconium dimethyl, (t-butylamido) dimethyl (fluorenyl) silane zirconium dichloride, dimethyl (t-
Butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) silylene) titanium dichloride, ｛(t-butylamide)
(Tetramethyl-η ⁵ -cyclopentadienyl) -1,2-ethanediyl titanium dichloride, dimethyl (phenylamide) (tetramethyl-η ⁵ -cyclopentadienyl) silylene titanium dichloride, dimethyl (t- Butyramide)
(Tetramethyl-η ⁵ -cyclopentadienyl) silylene｝
Titanium dimethyl, dimethyl (4-methylphenylamide)
(Tetramethyl-η ⁵ -cyclopentadienyl) silylene｝
Titanium dichloride, ｛dimethyl (t-butylamide) (η ^5-
(Cyclopentadienyl) silylene｝ titanium dichloride,
{Tetramethyl (t-butylamido) (tetramethyl-eta ⁵ - cyclopentadienyl) Jishiriren} titanium dichloride,
(t-butylamido) dimethyl (fluorenyl) silanetitanium dimethyl and the like.

The above transition metal compounds can be used alone or in combination of two or more. Particulate carrier The transition metal 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.

Next, the component (b) forming the metallocene catalyst, that is, the ionized ionic compound (b-1), the organic aluminum oxy compound (b-2) and the organic aluminum compound (b-3) will be described.

(B-1) Ionized Ionic Compound The ionized ionic compound (b-1) is a compound which reacts with the transition metal in the transition metal compound (a) to form an ionic complex. Compounds are disclosed in
JP-A-501950, JP-A-1-502036, JP-A-3-179005, JP-A-3-179
No. 006, JP-A-3-207703, JP-A-3-207704, US Pat. No. 5,321,106, etc., Lewis acids, ionic compounds, borane compounds and carborane compounds can be exemplified.

Examples of the Lewis acid include BR_Three(Where R is
Substitution of nitrogen atom, methyl group, trifluoromethyl group, etc.
A phenyl group or a fluorine atom which may have a group
You. ), For example, trifluoro
Roboron, triphenylboron, tris (4-fluorofuran
Enyl) boron, tris (3,5-difluorophenyl) bo
Ron, tris (4-fluoromethylphenyl) boron,
Lis (pentafluorophenyl) boron, tris (p-to
Ril) boron, tris (o-tolyl) boron, tris (3,
5-dimethylphenyl) boron, MgCl_Two, Al_TwoO_Three,
SiO_Two-Al_TwoO _ThreeAnd the like.

Examples of the ionic compound include trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts, dialkylammonium salts, and triarylphosphonium salts. Specifically, the trialkyl-substituted ammonium salt includes, for example, triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, tri (n-butyl) ammonium tetra (phenyl) boron and the like. Examples of the dialkylammonium salt include di (1-
Propyl) ammonium tetra (pentafluorophenyl) boron, dicyclohexylammonium tetra (phenyl) boron and the like. Further, as ionic compounds, triphenylcarbenium tetrakis (pentafluorophenyl) borate, tri-n-butylammonium tetrakis (pentafluorophenyl) borate,
N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, ferrocenium tetra (pentafluorophenyl) borate and the like can also be mentioned.

As the 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).

Examples of the carborane compound include 4-carbanonaborane (14), 1,3-dicarbanonaborane (13), and bis [tri (n-butyl) ammonium] bis (undecahydride-7-carboundecaborate) Nickelates (I
V), dodecaborane, 1-carboundecaborane, bis-n-
Butyl ammonium (1-carbedodeca) borate, tri
n-butylammonium (7,8-dicarbaundeca) borate, tri-n-butylammonium (trideca hydride)
-7-carboundeca) borate and the like, and salts of metal carborane anions.

The ionized ionic compound (b-
1) can be used alone or in combination of two or more. The ionized ionic compound (b-1) can be used by being supported on the above-mentioned particulate carrier.

(B-2) Organoaluminum oxy compound (b-2) The organoaluminum oxy compound may be a conventionally known aluminoxane.
A benzene-insoluble organic aluminum oxy compound as exemplified in JP-A-87-87 may be used.

The known aluminoxane is specifically represented by the following general formula.

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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 or more, more preferably 5 to 40, particularly preferably 10 to 40.

The aluminoxane has the formula (OAl (R
¹⁾ represented alkyloxy aluminum units and formula (OAl (R ²⁾ represented alkyloxy aluminum units (where they are in) is in), R ¹ and R ² are the same hydrocarbon group as R, R ¹ And R ² represent different groups.).

A conventionally known aluminoxane can be produced, for example, by the following method. (1) Compounds containing water of adsorption or salts containing water of crystallization such as hydrated magnesium chloride, hydrated copper sulfate, hydrated aluminum sulfate, hydrated nickel sulfate, hydrated cerous chloride A method of adding an organoaluminum compound such as trialkylaluminum to a hydrocarbon medium suspension of the above to react. (2) A method in which water, ice or steam is allowed to directly act on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran. (3) A method of reacting an organoaluminum compound such as trialkylaluminum with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene or toluene.

The aluminoxane may contain a small amount of an organic metal component. Alternatively, the solvent or unreacted organoaluminum compound may be removed from the recovered solution of aluminoxane by distillation, and then redissolved in a solvent or suspended in a poor solvent of aluminoxane.

As the organoaluminum compound used in preparing the aluminoxane, the same compounds as the below-mentioned organoaluminum compound (b-3) can be mentioned. The above-mentioned organoaluminum compounds can be used alone or in combination.

Solvents used for the preparation of aluminoxane include aromatic hydrocarbons such as benzene, toluene, xylene, cumene and cymene; and aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane. Alicyclic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane and methylcyclopentane; petroleum fractions such as gasoline, kerosene and light oil or halides of the above aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbons (E.g., chlorinated products, brominated products, etc.). Others
Ethers such as ethyl ether and tetrahydrofuran can also be used. Among these solvents, aromatic hydrocarbons and aliphatic hydrocarbons are particularly preferred.

Such an organoaluminum oxy compound (b-2) can be used by being supported on the above-mentioned particulate carrier. Organoaluminum Compound (b-3) 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 general formula (III).

R ³ _n AlX _3-n (III) (wherein, R ³ is a hydrocarbon group having 1 to 12 carbon atoms, X is a halogen atom or a hydrogen atom, and n is 1 to 3)
3. In the above general formula (III), R ³ has 1 to 1 carbon atoms.
2 hydrocarbon groups such as an alkyl group, a cycloalkyl group or an aryl group, specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an isobutyl group,
Examples include a pentyl group, a hexyl group, an octyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group and a tolyl group.

Such an organoaluminum compound (b-
Specific examples of 3) include the following compounds. Trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, tri (2-ethylhexyl) aluminum, tridecylaluminum; alkenylaluminum such as isoprenylaluminum; dimethylaluminumchloride, diethylaluminumchloride Dialkylaluminum halides such as diisopropylaluminum chloride, diisobutylaluminum chloride and dimethylaluminum bromide; alkylaluminum halides such as methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride and ethylaluminum sesquibromide Alkyl aluminum dihalides such as methylaluminum dichloride, ethylaluminum dichloride, isopropylaluminum dichloride and ethylaluminum dibromide; alkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride.

As the organoaluminum compound (b-3), a compound represented by the following general formula (IV) can also be used. R ³ _n AlL _3-n (IV) (wherein R ³ is the same as above, L is —OR ⁴ group,
OSiR ⁵ ₃ group, -OAlR ⁶ ₂ group, -NR ⁷ ₂ group, -S
iR ⁸ ₃ group or -N (R ⁹⁾ is AlR ¹⁰ ₂ group, n represents 1
And R ⁴ , R ⁵ , R ⁶ and R ¹⁰ are a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a cyclohexyl group, a phenyl group and the like, R ⁷ is a hydrogen atom,
Examples include a methyl group, an ethyl group, an isopropyl group, a phenyl group, and a trimethylsilyl group, and R ⁸ and R ⁹ are a methyl group, an ethyl group, and the like. ) Among such organoaluminum compounds, R ³ _n
A compound represented by Al (OAlR ⁴ ₂ ) _3-n , for example, Et
₂ AlOAlEt ₂ , (iso-Bu) ₂ AlOAl (iso-B
u) _{2 and the} like are preferred.

[0090] Among the organic aluminum compounds represented by the general formula (III) and (IV), the general formula R ³ ₃ Al
Are preferred, and particularly preferred are compounds wherein R ³ is an isoalkyl group.

In the present invention, as the catalyst for producing the α-olefin polymer (B), the above-mentioned metallocene catalyst is preferably used. It is also possible to use a titanium-based catalyst comprising a solid titanium catalyst component and an organoaluminum compound, and a vanadium-based catalyst comprising a soluble vanadium compound and an organoaluminum compound.

In the present invention, at least one or more α-olefins selected from α-olefins having 2 to 20 carbon atoms are usually copolymerized in the liquid phase in the presence of the above-mentioned metallocene catalyst. In this case, a hydrocarbon solvent is generally used, but propylene may be used as the solvent.
The copolymerization can be carried out by either a batch method or a continuous method.

In the case where the copolymerization is carried out by a batch method using a metallocene catalyst, the transition metal compound (a) in the polymerization system usually has a concentration of 0.00000 per liter of polymerization volume.
It is used in an amount of 5 to 1 mmol, preferably 0.0001 to 0.5 mmol.

The ionized ionic compound (b-1) has a molar ratio ((b-1) / (a)) of the ionized ionic compound to the transition metal compound (a) of 0.5 to 20, preferably 1 It is used in such an amount as to be.

Organic aluminum oxy compound (b-2)
Is the molar ratio (Al / M) of the aluminum atom (Al) to the transition metal atom (M) in the transition metal compound (a).
And is used in such an amount as to be 1 to 10000, preferably 10 to 5000.

The organoaluminum compound (b-3) is
Usually about 0 to 5 mmol per liter of polymerization volume, preferably
Or about 0 to 2 mmol.
The (co) polymerization reaction is usually carried out at a temperature of -20 to 150 ° C.
Preferably 0 to 120 ° C, more preferably 0 to 100 ° C
In the range, the pressure exceeds 0 to ~ 80 kg / cm ^Two, Preferred
Or more than 0 to 50kg / cm^TwoUnder the condition of
Done.

The reaction time (average residence time when the polymerization 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 1 hour. .5 hours.

At least one α-olefin selected from α-olefins having 2 to 20 carbon atoms is used in an amount such that the above-mentioned α-olefin polymer (B) having a specific composition can be obtained. It is supplied to the polymerization system. At the time of copolymerization, a molecular weight regulator such as hydrogen can be used.

By polymerizing at least one α-olefin selected from α-olefins having 2 to 20 carbon atoms as described above, the α-olefin polymer (B)
Is usually obtained as a polymerization solution containing the same. This polymerization solution is treated by a conventional method, and the α-olefin copolymer (B)
Is obtained.

(C) Filler As the filler (C) used in the present invention, various fillers such as conventionally known inorganic fillers and organic fillers are not particularly limited. Used. Preferred fillers are exemplified below.

As the inorganic filler, fine powder talc,
Silicates such as kaolinite, calcined clay, pyrophyllite, sericite, wollastonite; carbonates such as precipitated calcium carbonate, heavy calcium carbonate and magnesium carbonate; hydroxides such as aluminum hydroxide and magnesium hydroxide; oxidation Oxides such as titanium, zinc oxide, zinc oxide, magnesium oxide and aluminum oxide; sulfates such as calcium sulfate, barium sulfate and magnesium sulfate; hydrous calcium silicate, hydrous aluminum silicate, hydrous silicic acid,
Silicic acid or silicate such as silicic anhydride; powdered filler such as finely divided silica or carbon black; flake-shaped filler such as mica or glass flake; basic magnesium sulfate whisker; calcium titanate whisker;
Aluminum borate whisker, sepiolite, PMF
(Processed Mineral Fiber), zonotolite, potassium titanate, erestadite, glass fiber, carbon fiber, and other fibrous fillers, and glass balun, fly ash balun, and other balun-like fillers.

Examples of the organic filler include isotactic polypropylene, polystyrene, polyacetal,
Polyphenylene ether, polybutylene terephthalate, polyphenylene sulfide, polyarylate, polyamide, polyester, acrylonitrile-butadiene-styrene (ABS resin), polyvinyl alcohol,
Examples include polycarbonate and acrylic resin. Among them, polyamide, polyester, polyvinyl alcohol, polycarbonate, and acrylic resin are particularly preferable.

(1) As the polyamide, hexamethylenediamine, decamethylenediamine, dodecamethylenediamine, 2,2,4- or 2,4,4-trimethylhexamethylenediamine, 1,3- or 1,4-bis Aliphatic, alicyclic or aromatic diamines such as (aminomethyl) cyclohexane, bis (p-aminocyclohexylmethane), m- or p-kisylylenediamine, and adipic acid, suberic acid, sebacic acid, and cyclohexanedicarboxylic acid Polycondensates with aliphatic, alicyclic or aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid; condensates of aminocarboxylic acids such as ε-aminocaproic acid and 11-aminoundecanoic acid; ε-caprolactam; -Ring-opening polymers of lactams such as laurolactam, copolymerized polyamides composed of these components, and mixtures of these polyamides It is below.

Specific examples of such polyamides include:
Nylon 6, Nylon 66, Nylon 610, Nylon 9, Nylon 11, Nylon 12, Nylon 6/66,
Nylon 66/610, nylon 6/11, etc.
Particularly, nylon 6 and nylon 66 are preferable.

(2) Polyesters include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenoxyethanedicarboxylic acid; succinic acid, glutaric acid, adipic acid, sebacine Aliphatic dicarboxylic acids such as acid, azelaic acid and decane dicarboxylic acid; dicarboxylic acids such as alicyclic dicarboxylic acid such as cyclohexane dicarboxylic acid, and ethylene glycol, propylene glycol, tetramethylene glycol, heptamethylene glycol, diethylene glycol, triethylene glycol , Tetraethylene glycol, trimethylene glycol (propanediol), pentanediol, neopentyl glycol, hexamethylene glycol, dodecamethylene glycol, etc. Alicyclic glycols such as cyclohexanedimethanol; bisphenols; diol compounds such as aromatic diols such as hydroquinone, and, if necessary, trimethylolmethane.
Polycondensates with polyfunctional hydroxy compounds such as trimethylolethane and trimethylolpropane.

Specifically, polyethylene terephthalate, polyethylene isophthalate, polyethylene naphthalate and the like can be mentioned. (3) As the polyvinyl alcohol, a conventionally known polyvinyl alcohol can be used without particular limitation. Usually, a polyvinyl acetate having a saponification degree of 80% or more is used. If necessary, a copolymer with ethylene or methyl methacrylate may be used, or a part thereof may be acetalized, formalized, or etherified with polyvinyl alcohol, depending on the intended use.

As such polyvinyl alcohol, those having a degree of polymerization of about 1000 or more and a degree of saponification of about 95 mol% are preferably used. (4) As the polycarbonate, a conventionally known polycarbonate obtained from a dihydric phenol such as bisphenol A and a carbonic acid diester or phosgene is used.

Examples of the dihydric phenol include 1,2-bis (4-hydroxyphenyl) propane (bisphenol A), 1,1-bis (4-hydroxyphenyl) methane, and 1,1-bis
Bis (hydroxyaryl) alkanes such as (4-hydroxyphenyl) ethane and 2,2-bis (4-hydroxyphenyl) butane; bis (hydroxyaryl) cyclohexane such as 1,1-bis (4-hydroxyphenyl) cyclohexane Alkanes; dihydroxyaryl ethers such as 4,4'-dihydroxydiphenyl ether; dihydroxydiaryl sulfides;

These dihydric phenols may be used in combination of two or more, if necessary. Usually, bisphenol A or those containing bisphenol A as a main component and containing a small amount of another dihydric phenol are used. Is done.

Examples of the carbonic acid diester include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, bis (diphenyl) carbonate,
Diethyl carbonate and the like. Of these, diphenyl carbonate is preferably used.

The polycarbonate may be treated with an end capping agent such as an allyloxy compound or a monocarboxy compound, if necessary. (5) Acrylic resins include (co) polymers of methacrylates such as polymethyl methacrylate (PMMA), (co) polymers of acrylates, and (meth) acrylates and α-methylstyrene. And the like.

Composition The syndiotactic polypropylene-based composition according to the present invention comprises the above-mentioned syndiotactic propylene polymer (A), the above-mentioned α-olefin polymer (B) and the above-mentioned filler (C). The weight ratio {(A) / (B)} between the tactic propylene polymer (A) and the α-olefin polymer (B) is 90/10 to 10/90, preferably 80/20 to 20/80, More preferably 75 /
25 to 40/60, and the filler (C) is added in an amount of 1 to 10 based on 100 parts by weight of the total amount of the syndiotactic propylene polymer (A) and the α-olefin polymer (B).
The content is preferably 00 parts by weight, preferably 10 to 600 parts by weight, more preferably 30 to 300 parts by weight.

When the filler is an organic filler, the syndiotactic propylene polymer (A) and
It is desirably contained in an amount of 1 to 300 parts by weight, preferably 1 to 200 parts by weight, based on 100 parts by weight in total with the α-olefin polymer (B).

The syndiotactic propylene polymer (A) and α-olefin polymer (B) are used in the proportions as described above.
And a syndiotactic polypropylene-based composition containing a filler (C), heat resistance, flexibility, impact resistance,
It tends to have excellent scratch resistance.

Further, the melt tension (MT) of the syndiotactic polypropylene composition according to the present invention is described.
Is usually 0.5 to 10 g, preferably 1 to 10 g, and is excellent in moldability such as film moldability. The melt tension (MT) was measured at a measurement temperature of 20 using a melt tension tester (manufactured by Toyo Seiki Seisaku-sho, Ltd.).
It is determined as the tension applied to the filament when the strand extruded under the condition of 0 ° C. and the extrusion speed of 15 mm / min is taken out at a constant speed (10 m / min).

Syndiotactic polypropylene series
Production of the product The syndiotactic polypropylene-based composition as described above can be produced by various known methods using the above-mentioned components in the above-described quantitative ratios, for example, a Henschel mixer,
It is manufactured by a method of mixing with a V-blender, a ribbon blender, 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 grinding. be able to.

The syndiotactic polypropylene composition contains a heat-resistant stabilizer, a weather-resistant stabilizer, an antistatic agent, a lubricant, a slip agent, as long as the object of the present invention is not impaired.
A nucleating agent, a flame retardant, an oil agent, a pigment, a dye, a rust inhibitor, "another copolymer" described in detail below, and the like can be blended as long as the object of the present invention is not impaired.

Other Copolymers The syndiotactic polypropylene composition according to the present invention may contain "other copolymers" as necessary.

Examples of such “other copolymers” include an aromatic hydrocarbon block copolymer (D) which may be hydrogenated and an ethylene / α-olefin block copolymer (described later). E), ethylene / triene copolymer (F), ethylene / styrene copolymer, ethylene / triene copolymer
And diene copolymers. These copolymers are used alone or in combination of two or more.

These "other copolymers" are used in an amount of usually 0 to 40 parts by weight, preferably 0 to 3 parts by weight, per 100 parts by weight of the syndiotactic polypropylene composition of the present invention.
It is used in a proportion of 0 parts by weight.

When the “other copolymer” is used in the above ratio, a composition capable of producing a molded article having an excellent balance of rigidity, hardness and impact resistance can be obtained. Aromatic hydrocarbon block copolymers which may be hydrogenated
(D) The aromatic hydrocarbon-based block copolymer (D) which may be hydrogenated as required in the present invention comprises a block polymer unit (X) derived from aromatic vinyl and a conjugated diene And an aromatic vinyl / conjugated diene block copolymer (D1) or a hydrogenated product thereof (D2).

The form of the aromatic vinyl / conjugated diene block copolymer (D1) having such a structure is, for example, X (Y
X) _n or (XY) _n (n is an integer of 1 or more). Among them, a block copolymer in the form of X (YX) _n , particularly XYX, is preferable, and specifically, in the form of polystyrene-polybutadiene (or polyisoprene or polyisoprene-butadiene) -polystyrene. Styrene block copolymers are preferred.

In such an aromatic hydrocarbon block copolymer, the aromatic vinyl block polymerization unit (X), which is a hard segment, exists as a cross-linking point of the conjugated diene block polymerization unit (Y), and physical crosslinking ( Domain). Conjugated diene block polymer units (Y) existing between the aromatic vinyl block polymer units (X)
Is a soft segment and has rubber elasticity.

Specific examples of the aromatic vinyl forming the aromatic vinyl block polymerized unit (X) include styrene, α-methylstyrene, 3-methylstyrene, p-methylstyrene, and 4-propyl Styrene, 4-dodecylstyrene, 4-cyclohexylstyrene, 2-ethyl-4-
Styrene derivatives such as benzylstyrene and 4- (phenylbutyl) styrene are exemplified. Of these, styrene is preferred.

Further, the conjugated diene block polymerization unit (Y)
Examples of the conjugated diene that forms are butadiene, isoprene, pentadiene, 2,3-dimethylbutadiene, and combinations 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 a proportion 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 (D1) has an aromatic vinyl block polymerization 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.

The aromatic vinyl / conjugated diene block copolymer (D1) has a melt flow rate (MFR; AS
TM D 1238, 200 ° C, load 2.16 kg)
Usually 5 g / 10 min or more, preferably 5 to 100 g /
10 minutes.

Various methods can be used for producing the above-mentioned aromatic vinyl / conjugated diene block copolymer (D1). For example, (1) an alkyllithium compound such as n-butyllithium is used as an initiator. A method of sequentially polymerizing an aromatic vinyl compound and then a conjugated diene,
(2) a method of polymerizing an aromatic vinyl compound and then a conjugated diene and coupling them with a coupling agent; and (3) a method of sequentially polymerizing a conjugated diene and then an aromatic vinyl compound using a lithium compound as an initiator. Can be mentioned.

The hydrogenated aromatic vinyl / conjugated diene block copolymer (D2) is obtained by hydrogenating the above aromatic vinyl / conjugated diene block copolymer (D1) by a known method. Can be obtained by Hydrogenated aromatic vinyl / conjugated diene block copolymer (D2)
Usually has a hydrogenation rate of 90% or more.

This hydrogenation rate is determined by subtracting the total amount of carbon-carbon double bonds in the conjugated diene block polymerization unit (Y) before hydrogenation by 10%.
This is a value when 0% is set. Such aromatic vinyl
Specific examples of the hydrogenated product of the conjugated diene block copolymer (D2) include a hydrogenated product of a styrene-isoprene block copolymer (SEP) and a hydrogenated product of a styrene-isoprene-styrene block copolymer (SEP). SEPS; polystyrene / polyethylene / propylene / polystyrene block copolymer), hydrogenated styrene / butadiene block copolymer (SEBS; 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 T
R (manufactured by Shell Chemical Co., Ltd.), Solprene (manufactured by Philips Petro Rifam), Europrene SOLT (manufactured by Anich), Tufprene (manufactured by Asahi Kasei Kogyo), Solprene-T (manufactured by Nippon Elastomer), JSR- TR (manufactured by Nippon Synthetic Rubber Co., Ltd.), Electrification STR (manufactured by Denki Kagaku Kogyo Co., Ltd.), Quintac (manufactured by Zeon Corporation), Clayton G (manufactured by Shell Chemical Co., Ltd.), Tuftec (Asahi Kasei Kogyo Co., Ltd.) Co., Ltd.) (all trade names).

The hydrogenated product (D2) of the aromatic vinyl / conjugated diene block copolymer includes, among these, SEB
S and SEPS are preferably used. The aromatic hydrocarbon-based block copolymer (D) which may be hydrogenated is usually 0 to 30% by weight, preferably 0 to 25% by weight based on 100 parts by weight of the syndiotactic polypropylene composition. It is desirable to use in proportion. When the aromatic hydrocarbon-based block copolymer (D) which may be hydrogenated is used at the above ratio, a composition capable of preparing a molded article having an excellent balance of rigidity, hardness and impact resistance is obtained. Can be

Ethylene / α-olefin block copolymer
(E) The ethylene / α-olefin block copolymer (E) optionally used in the present invention comprises 0 to 20 mol% of a repeating unit derived from an α-olefin having 3 to 10 carbon atoms.
And a crystalline polyethylene portion consisting of 100 to 80 mol% of a repeating unit derived from ethylene;
And a low-crystalline copolymer part or an amorphous copolymer part containing two or more kinds of repeating units derived from α-olefins of from 20 to 20.

In the present invention, a repeating unit derived from ethylene is contained in a proportion of 30 to 95 mol% and has 3 carbon atoms.
70 to 5 repeating units derived from olefins of
An ethylene / α-olefin block copolymer containing at a mole percentage is preferred. In particular, a repeating unit derived from ethylene is contained in a proportion of 60 to 90 mol%, and a repeating unit derived from an olefin having 3 to 20 carbon atoms is 40%.
An ethylene / α-olefin block copolymer containing 10 to 10 mol% is preferred.

Here, as the α-olefin having 3 to 20 carbon atoms, specifically, propylene, 1-butene, 1-butene,
Pentene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-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.

In the crystalline polyethylene part, two or more kinds of repeating units derived from the above α-olefin having 3 to 20 carbon atoms may be contained. Further, the ethylene / α-olefin block copolymer (E) used in the present invention may contain a repeating unit derived from a diene compound having 4 to 20 carbon atoms at a ratio of 5 mol% or less. .

Specific examples of the diene compound include 1,3-butadiene, 1,3-pentadiene, 1,4-pentadiene, 1,3-hexadiene, 1,4-hexadiene, 1,5-hexadiene, and 4-diene.
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-
Examples thereof include 1,6-undecadiene, 1,7-octadiene, 1,9-decadiene, isoprene, butadiene, ethylidene norbornene, vinyl norbornene, and dicyclopentadiene.

The ethylene / α-olefin block copolymer (E) has a melt flow rate (MFR;
(ASTM D 1238, 190 ° C, load 2.16 kg)
Is usually 0.0001 to 500 g / 10 min, preferably 0.1 g.
0001-300 g / 10 min, more preferably 0.00
01 to 200 g / 10 min, and the density (ASTMD
1505) is 0.85 to 0.90 g / cm ³ , preferably 0.85 to 0.89 g / cm ³ , and more preferably 0.86 to 0.89 g / cm ³ .

The degree of crystallinity of the boiling heptane-insoluble component in the ethylene / α-olefin block copolymer (E) 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 (E) is prepared as follows. That is, 3 g of the 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 5 ° 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. An n-decane suspension containing the precipitated polymer (23 ° C. decane-insoluble component) was added to G-4 (or G-
After filtration and separation 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 (E) is usually 0.8
It is at least 6 g / cm ³ , preferably at least 0.87 g / cm ³ .

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

In the present invention, the amount of n-decane-soluble component at 23 ° C. of the ethylene / α-olefin block copolymer (E) 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.
t-butyl-4-methylphenol 20 mg, n-decane 50
Add 0 ml and heat and dissolve 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 an n-decane solution containing the dissolved polymer were subjected to G-4
(Or G-2) through a glass filter.
The solution obtained in this way is 10 mmHg, 150 ° C.
The polymer dissolved in the n-decane solution was dried by heating under the conditions described above until the amount was determined. The weight of the polymer was determined as the decane-soluble component at 23 ° C., and the weight of the ethylene / α-olefin block copolymer (E) was determined. C. The amount of n-decane-soluble component is calculated as a percentage based on the weight of the polymer sample.

The ethylene / α-olefin block copolymer (E) can be prepared by a conventionally known method. The ethylene / α-olefin block copolymer (E) is preferably used in a proportion of usually 0 to 40% by weight, preferably 0 to 35% by weight, based on 100 parts by weight of the syndiotactic polypropylene composition. Ethylene / α-olefin block copolymer (E)
When the above is used in the above proportion, a composition which can prepare a molded article having an excellent balance of rigidity, hardness and impact resistance can be obtained.

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

Specific examples of the triene include 6,10-dimethyl-1,5,9-undecatriene, 4,8-dimethyl-1,4,8-decatriene and 5,9-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-
Non-conjugated trienes such as 4-ethylidene-1,7-nonadiene and 4-ethylidene-1,7-undecadiene; and conjugated trienes such as 1,3,5-hexatriene. These trienes can be used alone or in combination of two or more.

The above-mentioned trienes are described, for example, in EP06
It can be prepared by a conventionally known method as described in 91354A1 and WO96 / 20150.

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

The 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) is preferably used at a ratio of usually 0 to 40% by weight, preferably 0 to 35% by weight, based on 100 parts by weight of the syndiotactic polypropylene composition. When the ethylene / triene copolymer (F) is used in the above ratio, a composition that can prepare a molded article having an excellent balance of rigidity, hardness and impact resistance is obtained.

Molded Articles The syndiotactic polypropylene-based composition according to the present invention as described above can be widely used for conventionally known polyolefin applications. For example, various shapes including sheets, unstretched or stretched films, filaments and the like can be used. It can be used after being molded into a molded article.

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. The obtained molded article is exemplified.

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 molded article, its shape and product type are not particularly limited.For example, floor sheets, sound insulation sheets, sheets such as decorative sheets, floor tiles, wallpaper, gaskets, desk mats, Examples include films such as wrap films and shrink films, pipes, hoses, wire coatings, filaments, and the like, and sheets, films, and filaments are particularly preferable.

When extruding the syndiotactic polypropylene composition, a conventionally known extruder and molding conditions can be employed, such as a single screw extruder, a kneading extruder, a ram extruder, a gear extruder. The molten syndiotactic polypropylene composition can be extruded from a T-die or the like using a machine or the like to form a sheet or film (unstretched).

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

The stretching ratio for stretching a sheet or an unstretched film is usually about 20 to 70 times in the case of biaxial stretching and 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.

An inflation film can also be produced as a film-shaped molded product. When the syndiotactic polypropylene composition according to the present invention is blown, drawdown hardly occurs.

The sheet and the film formed from the syndiotactic polypropylene composition according to the present invention as described above are hardly charged, have flexibility such as tensile modulus, heat resistance, impact resistance, aging resistance, and the like. It has excellent rigidity, moisture resistance and gas barrier properties, and can be used widely.

The filament can be produced, for example, by extruding a molten syndiotactic polypropylene-based composition through a spinneret. The filament thus obtained may be further drawn. This stretching may be performed to such an extent that at least one axis direction of the filament is molecularly oriented, and it is usually desirable to perform the stretching at a magnification of about 5 to 10 times. The filament comprising the syndiotactic polypropylene-based composition according to the present invention is hardly charged, and is excellent in rigidity, heat resistance and impact resistance.

An injection molded article can be produced by injection molding a syndiotactic polypropylene composition into various shapes using a conventionally known injection molding apparatus under known conditions. The injection molded article comprising the syndiotactic polypropylene composition according to the present invention is hardly charged, and has rigidity, heat resistance, impact resistance, surface gloss, chemical resistance,
It is excellent in abrasion resistance and the like, and 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 syndiotactic polypropylene composition using a conventionally known blow molding apparatus under known conditions.

For example, in extrusion blow molding, the above syndiotactic polypropylene composition is treated at a resin temperature of 100
Extruded from a die in a molten state at a temperature of from 300 ° C. to 300 ° C. to form a tubular parison. Then, the parison was held in a mold having a desired shape, and then air was blown into the parison.
A hollow molded body can be manufactured by mounting the mold at 0 ° C. The stretching (blow) magnification is 1.5 in the horizontal direction.
It is desirably about 5 times.

In the injection blow molding, the syndiotactic polypropylene composition is used at a resin temperature of 100.
The parison is molded by injecting it into a parison mold at a temperature of about 300 ° C. to 300 ° C., and then the parison is held in a mold having a desired shape. A molded article can be manufactured.

The stretching (blow) magnification is 1.1 to 1.1 in the longitudinal direction.
It is desirable that the ratio be 1.8 times and 1.3 to 2.5 times in the horizontal direction. The blow molded article comprising the syndiotactic polypropylene composition according to the present invention is excellent in rigidity, heat resistance and impact resistance, and also excellent in moisture resistance.

Examples of the press-molded body include a mold stamping-molded 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 integrated molding (mold stamping molding) according to the present invention. It can be formed of a syndiotactic polypropylene-based composition.

Specific examples of such a molded stamping molded body include interior materials for automobiles such as door trims, rear package trims, seat back garnishes, and instrument panels.

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

[0170] The press-formed product comprising the syndiotactic polypropylene composition according to the present invention is hardly charged, and has improved rigidity, heat resistance, impact resistance, aging resistance, surface gloss, chemical resistance, abrasion resistance and the like. Are better.

[0171]

From the syndiotactic polypropylene composition of the present invention, a molded article having a good balance of impact resistance, flexibility, heat resistance and scratch resistance can be obtained.

[0172]

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

Hereinafter, physical test conditions and the like will be described. 1. Tensile modulus (Young modulus); JIS K
Measured at 23 ° C. using a JIS No. 3 dumbbell at a span distance of 30 mm and a pulling speed of 30 mm / min in accordance with 6301. 2. Martens hardness (1 / mm): Using a Martens hardness scratch hardness tester manufactured by Tokyo Ikki, a groove width generated when a sample having a thickness of 3 mm was scratched by applying a load of 20 g of a scratch indenter to the test piece, The reciprocal was calculated. 3. Needle penetration temperature (° C); in accordance with JIS K7196,
Using a test piece having a thickness of 2 mm, a pressure of ² kg / cm ² was applied to a 1.8 mmφ plane indenter at a heating rate of 5 ° C./min, and the needle entry temperature (° C.) was determined from a TMA curve. 4. Haze (%): Digital turbidimeter (NDH-20D) manufactured by Nippon Denshoku Industries Co., Ltd., using a test piece having a thickness of 1 mm.
Was measured. 5. Melting point (Tm) and glass transition temperature (Tg); DS
An endothermic curve of C is obtained, and the temperature at the maximum peak position is defined as Tm.

For the measurement, the sample was packed in an aluminum pan,
The temperature was raised to 200 ° C. at a rate of 200 ° C./min.
It was determined from an endothermic curve when the temperature was raised at 0 ° C./min.

From the endothermic peak at the time of DSC measurement, the heat of fusion per unit weight is obtained, and this is divided by the heat of fusion of polyethylene crystal of 70 cal / g to obtain the crystallinity (%). Can be. 6. Intrinsic viscosity [η]: measured at 135 ° C. in decalin. 7. Molecular weight distribution (Mw / Mn): measured at 140 ° C. in an orthodichlorobenzene solvent using GPC (gel permeation chromatography).

[0176]

[Synthesis Example 1] Syndiotactic polypropylene
According to the method described in adult Hei 2-274763 discloses, using diphenylmethylene (cyclopentadienyl) catalysts consisting of fluorenyl zirconium dichloride and methylaluminoxane, syndiotactic by bulk polymerization of propylene in the presence of hydrogen Tic polypropylene was obtained. The melt flow index of the resulting syndiotactic polypropylene was 4.4 g / 10 min, the intrinsic viscosity [η] was 1.6 dl / g, the molecular weight distribution by GPC was 2.3, and ¹³ C-NMR. Was 0.823, the Tm was 127 ° C., and the Tc was 57 ° C. as measured by differential scanning calorimetry.

[0177]

Example 1 30 parts by weight of the syndiotactic polypropylene obtained in Synthesis Example 1 above were mixed with ethylene octene.
70 parts by weight of -1 copolymer and 300 parts by weight of calcium carbonate (average particle diameter: 60 μm) were melt-kneaded to obtain a syndiotactic polypropylene composition. Table 2 shows the obtained results.

[0178]

Examples 2 to 5 Syndiotactic polypropylene compositions were obtained in the same manner as in Example 1 except that the compositions were changed as shown in Table 2. The average particle diameter of the talc used was 2.5 μm, and the average particle diameter of the aluminum hydroxide was 4 μm. Table 2 shows the obtained results.

[0179]

Comparative Examples 1 and 2 An isotactic polypropylene composition was obtained in the same manner as in Example 1 except that the composition was changed as shown in Table 2. The melt flow index of the isotactic polypropylene used was 8.6 g.
/ 10 min, the molecular weight distribution by GPC is 5.4, the isotactic triad fraction measured by ¹³ C-NMR is 0.96, and the Tm measured by differential scanning calorimetry is 161 ° C. And Tc was 115 ° C. Table 2 shows the obtained results.

[0180]

[Table 2]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification FI FI Theme Court ゛ (Reference) C08L 23/14 C08L 23/14 (72) Inventor Ryoji Mori 6-1, Waki, Waki-machi, Kuga-gun, Yamaguchi Prefecture No. 2 Mitsui Chemicals Co., Ltd. F-term (reference) 4J002 BB05X BB07X BB08X BB10X BB12W BB123 BB13X BB14W BB14X BB15W BB15X BB17X BC033 BE023 BG003 DJBN 136 153 003 003 003 003 DJ046 DJ056 DK006 DL006 FA016 FA046 FA066 FD013 FD016 GG01 GN00 GQ00 4J028 AA01A AB00A AB01A AC01A AC10A AC28A AC45A AC49A BA00A BA01B BB00A BB01B BC12B BC15B BC16B BC17B BC19B BC20B BC25B CA24C CA25C CA27C CA28C CA29C CB09C CB15C EB02 EB04 EB05 EB07 EB08 EB09 EB10 EB13 EB14 EB16 EB18 EB21 EB25 EC01 EC02 EC04 GA04 GA06 GA12 GA13 GA14 GA19

Claims (5)

[Claims] (A) a repeating unit (a) derived from propylene and, if necessary, a repeating unit (b) derived from ethylene and / or a repeating unit derived from an α-olefin having 4 to 20 carbon atoms. (C), wherein the repeating unit (a) is 90 to 100 mol%, the repeating unit (b) is 0 to 10 mol%, and the repeating unit (c) is 0 to 9 mol%. 5 mol%, 13
The intrinsic viscosity [η] measured in decalin at 5 ° C. is 0.5 to
A syndiotactic propylene polymer having a substantially syndiotactic structure in the range of 10 dl / g, and (B) at least a repeating unit derived from an α-olefin selected from α-olefins having 2 to 20 carbon atoms. An α-olefin polymer composed of at least one kind, containing at least one kind of the at least one kind of repeating unit at a ratio of 50 to 100 mol%, and having a Young's modulus of 150 MPa or less; ) A filler; and a weight ratio of the syndiotactic propylene polymer (A) and the α-olefin polymer (B) ｛(A) /
(B)｝ is in the range of 90/10 to 10/90, and the filler (C) is based on 100 parts by weight of the total amount of the syndiotactic propylene polymer (A) and the α-olefin polymer (B). ) In an amount of 1 to 1000 parts by weight. 2. The (A) syndiotactic propylene polymer has a syndiotacticity of 0.6 or more as viewed from the triad chain of propylene, and the α-olefin polymer (B) has a decalinicity of 135 ° C. Intrinsic viscosity [η] measured in solution is 0.01 to 10 dl /
g, the molecular weight distribution (Mw / Mn) determined by gel permeation chromatography is 4 or less, the glass transition temperature is -5 ° C or less, and the filler (C) is an inorganic filler. The syndiotactic polypropylene-based composition according to claim 1, which is: 3. The (B) α-olefin polymer has at least one kind selected from α-olefins having 3 to 20 carbon atoms in a proportion of 50 to 99 mol% of repeating units derived from ethylene. The syndiotactic polypropylene composition according to claim 1 or 2, which is a copolymer containing a repeating unit derived from an α-olefin of 1 to 50 mol%. 4. The (B) α-olefin polymer comprises at least one repeating unit derived from propylene in an amount of 50 to 99 mol% and selected from ethylene and α-olefins having 4 to 20 carbon atoms. The syndiotactic polypropylene-based composition according to claim 1 or 2, which is a copolymer containing the repeating unit derived from the α-olefin in a proportion of 1 to 50 mol%. 5. The (B) α-olefin polymer is
(A) a transition metal compound represented by the following general formula (I) or (II), and (b) (b-1) the transition metal compound (a)
A metallocene-based catalyst comprising at least one compound selected from the group consisting of: a compound which reacts with a transition metal therein to form an ionic complex; (b-2) an organic aluminum oxy compound; and (b-3) an organic aluminum compound. The syndiotactic polypropylene composition according to any one of claims 1 to 4, which is obtained by polymerizing or copolymerizing an α-olefin having 2 to 20 carbon atoms in the presence. (In the formulas (I) and (II), M is Ti, Zr, Hf, R
n, Nd, Sm or Ru, Cp ¹ and Cp ²
Are cyclopentadienyl groups, indenyl groups, fluorenyl groups or derivative groups thereof which are the same or different from each other and are π-bonded to M, and X ¹ and X ^1
2 may be the same or different from each other and are an anionic ligand or a neutral Lewis base ligand, and Y is a ligand containing a nitrogen atom, an oxygen atom, a phosphorus atom or a sulfur atom. , Z is a C, O, B, S, Ge, Si or Sn atom or a group containing these atoms. )