JP2003221477A - ETHYLENE/alpha-OLEFIN COPOLYMER COMPOSITION AND ITS USE - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ethylene/α-olefin copolymer composition improving the rigidity, especially elongation at a tensile break point and low-temperature impact strength of a polypropylene resin, when the copolymer composition is used as a modifier, and excellent in productivity and operability not to cause problems such as blocking during its use as a modifier, and to provide a polypropylene resin composition containing the ethylene/α-olefin copolymer composition. <P>SOLUTION: A composition (i) comprising 30-80 wt.% specific ethylene/α- olefin copolymer [A], 1-69 wt.% specific ethylene/α-olefin copolymer [B], and 1-69 wt.% specific low density polyethylene [C], a composition (ii) obtainable by crosslinking the composition (i), and a composition (iii) comprising a propylene copolymer (D) and the composition (ii) are provided. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an ethylene / α-olefin copolymer composition useful as a modifier for resins such as polypropylene, and the ethylene / α-olefin copolymer composition.
-The present invention relates to a propylene-based polymer composition containing an olefin copolymer composition.

[0002]

2. Description of the Related Art Conventionally, for the purpose of improving impact resistance of polypropylene resin, a method of blending an elastomer such as ethylene / propylene copolymer or ethylene / butene copolymer as a modifier with the polypropylene resin is well known. ing.

However, when an elastomer is blended with a polypropylene resin, the rigidity of the resin is lowered, so that the blending amount of the elastomer is limited. Further, for example, a resin molded product such as a polypropylene resin molded product may be required to have not only impact resistance at room temperature but also impact resistance at low temperature. The low-temperature impact resistance does not always match the impact resistance at room temperature, and in order to enhance such low-temperature impact resistance, it is conceivable to use a soft rubber as a modifier. If is added to the polypropylene resin, the rigidity of the molded product will be impaired, and the same problems as described above will occur.

Therefore, there is a demand for a modifier capable of maintaining a high level of balance between rigidity and impact resistance.
On the other hand, it is known that the above-mentioned resin molded body is not destroyed in practical use. For this reason, it is required for the resin molded product to have high strength at break and high impact strength while maintaining high rigidity, that is, resin modification with a high level of balance between rigidity and elongation at tensile break. The appearance of agents was sought.

Japanese Unexamined Patent Publication (Kokai) No. 6-192500 discloses an ethylene / α-containing polypropylene polymer having specific properties.
It is disclosed that a composition having a well-balanced physical properties of rigidity and impact resistance is obtained by blending an olefin copolymer. However, this composition is insufficient in terms of the balance between rigidity and low temperature impact strength, and rigidity and tensile elongation characteristics, and improvements have been demanded.

Further, when the resin is modified in this way, some of the resin modifiers cause blocking at the supply part of the kneader, such as a hopper, at the time of kneading, which deteriorates the productivity. In addition, the physical properties of the obtained modified product may not be constant.

For this reason, problems such as blocking occur when the elongation of the tensile breaking point and the impact resistance at low temperature are modified while the rigidity of the resin such as polypropylene resin is maintained and the modifier is used. The advent of a resin modifier that is difficult and has excellent productivity and workability has been eagerly awaited.

The applicant of the present invention discloses, as such a resin modifier, a specific [A] ethylene and an α-olefin copolymer having 4 to 20 carbon atoms in JP-A-10-273563. A composition comprising a specific [B] ethylene and an α-olefin copolymer having 3 to 20 carbon atoms or a specific [C] high density polyethylene is proposed. However, even if these compositions are used for modification, it is not always possible to obtain a resin composition having an excellent balance of impact resistance and flexural modulus.

[0009]

DISCLOSURE OF THE INVENTION The present invention is intended to solve the problems associated with the prior art as described above, and when used as a modifier, the rigidity of a resin such as polypropylene resin, In particular, ethylene / α-olefin copolymers that can improve tensile elongation at break and impact resistance at low temperatures, and are less prone to problems such as blocking when used as a modifier and have excellent productivity and workability. The purpose is to provide a composition. Another object of the present invention is to provide a polypropylene resin composition containing the above ethylene / α-olefin copolymer composition.

[0010]

Means for Solving the Problems Ethylene according to the present invention
The α-olefin copolymer composition comprises [A] ethylene and
A copolymer with an α-olefin having 4 to 20 carbon atoms, wherein the content of the structural unit (a) derived from (i) ethylene is 6
The content of the structural unit (b) derived from an α-olefin having 0 to 80 mol% and a carbon number of 4 to 20 is in the range of 20 to 40 mol%, and (ii) the density is 0.863 g / cm ³ or less. Yes, (ii
i) The intrinsic viscosity [η] measured in decalin at 135 ° C. is in the range of 0.1 to 10.0 dl / g, and (iv) the glass transition temperature measured by a differential scanning calorimeter (DSC) is −60. ℃ or less, the crystallinity is 10% or less, (v) ¹³ C-
The intensity ratio of T _{alpha beta} for T _{alpha alpha} in the NMR spectrum _(T αβ / T αα) is 0.5 or less, (vi) ¹³ C-
NMR spectrum and the following general formula (1)

[0011]

[Chemical 2]

(In the formula, [P _E ] is the content mole fraction of the structural unit derived from ethylene in the copolymer,
[P _O ] is the mole fraction of the constituent units derived from α-olefin in the copolymer, and [P _OE ] is the number of ethylene / α-olefin chains with respect to all the dyad chains in the copolymer. And is determined by ¹³ C-NMR spectrum. ), The B value calculated from 0.9 to 1.5 is 30 to 80% by weight of an ethylene / α-olefin copolymer,

[B] (a ') ethylene and (b') carbon number 3 to 2
A copolymer with at least one compound selected from the group consisting of 0-α-olefins and cyclic olefin compounds, wherein (i) the density is in the range of 0.860 to 0.900 g / cm ³ , ii) The melt flow rate at 190 ° C. under a load of 2.16 kg is in the range of 0.3 to 50 g / 10 minutes,
(iii) Ethylene · α in which the temperature (Tm) at the maximum peak position and the density (d) in the endothermic curve measured by a differential scanning calorimeter (DSC) satisfy the relationship represented by Tm <400 × d-250. Olefin-based copolymer 1-69% by weight
When,

[C] (i) Density is 0.910 to 0.930 g / c
It is characterized in that it is in the range of m ³ and (ii) is composed of 1 to 69% by weight of low-density polyethylene having a melt flow rate at 190 ° C. and a load of 2.16 kg of 0.3 to 50 g / 10 minutes. .

The above-mentioned ethylene / α- according to the present invention
Regarding the density Da of the olefin copolymer [A] and the density Db of the ethylene / α-olefin copolymer [B], Da <Db
It is characterized by the relationship of.

The above-mentioned ethylene / α-related to the present invention
The olefin copolymer composition is the above-mentioned ethylene / α-
It is characterized by being obtained by melt-mixing the olefin copolymer [A], the ethylene / α-olefin copolymer [B] and the low density polyethylene [C].

The above-mentioned ethylene / α- according to the present invention
The olefin copolymer composition is the above-mentioned ethylene / α-
It is characterized by being obtained by subjecting a mixture of an olefin copolymer [A], an ethylene / α-olefin copolymer [B] and a low density polyethylene [C] to a crosslinking treatment.

The above-mentioned crosslinked ethylene / α-olefin copolymer composition according to the present invention comprises (i) 190 ° C.
Melt flow rate at 2.16 kg load is 0.3
When the frequency dependence of the melt viscosity (η ^* ) at 190 ° C. was measured, the melt viscosity was η ^{* 1} at a low frequency (ω ₁ = 0.0158 rad / sec). And the melt viscosity η ^{* 2} at high frequency (ω ₂ = 398 rad / sec)
It is characterized in that (η ^{* 1} / η ^{* 2} ) is 4 or more.

The ethylene / α-olefin copolymer composition as described above is useful as a resin modifier. The crosslinked ethylene / α-olefin copolymer composition as described above is further useful as a resin modifier.

The propylene-based polymer composition according to the present invention comprises a propylene-based polymer [D] and the ethylene / α-olefin copolymer composition (ethylene / α-olefin copolymer [A] and ethylene / α -A composition of an olefin copolymer [B] and a low density polyethylene [C]), wherein the content of the propylene polymer [D] is 98 to 60% by weight, and ethylene / α-olefin The content of the copolymer [A], the ethylene / α-olefin copolymer [B] and the low density polyethylene [C] (total of [A], [B] and [C]) is 2 to 40.
It is characterized in that it is wt%.

The propylene-based polymer composition according to the present invention comprises a propylene-based polymer [D] and the crosslinked ethylene / α-olefin copolymer composition (ethylene / α-olefin copolymer [A]). Ethylene / α-olefin copolymer
[B] and a low-density polyethylene [C] cross-linked ethylene / α-olefin copolymer), wherein the content of the propylene-based polymer [D] is 98 to 60% by weight, and ethylene The content of α-olefin copolymer [A], ethylene / α-olefin copolymer [B] and low density polyethylene [C] (total of [A], [B] and [C]) is 2 to 40. It is characterized in that it is wt%.

230 ° C. of the propylene-based polymer [D],
Melt flow rate (MFR) under 2.16 kg load
Is preferably 0.01 g / 10 minutes or more. In addition, the above-mentioned propylene-based polymer composition has a peak of the attenuation rate due to the glass transition temperature of the propylene-based polymer [D] and an ethylene / α
-Olefin copolymer composition (ethylene / α-olefin copolymer [A] and ethylene / α-olefin copolymer
It is preferable that there is a peak of an attenuation rate due to the glass transition temperature of [B] and the composition of the ethylene copolymer [C], and both peaks are separated.

230 ° C. of the propylene-based polymer [D],
Melt flow rate (MFR) under 2.16 kg load
Is preferably 0.01 g / 10 minutes or more. Further, the propylene-based polymer composition has a peak of attenuation rate due to the glass transition temperature of the propylene-based polymer [D] and crosslinked ethylene / α- when the temperature dependence of the elastic modulus is measured. Olefin copolymer composition (ethylene / α
-The glass transition temperature of the crosslinked ethylene / α-olefin copolymer composition consisting of the olefin copolymer [A], the ethylene / α-olefin copolymer [B] and the low density polyethylene [C] It is preferable that there is a peak of attenuation rate and both peaks are separated.

The ethylene / α-olefin copolymer composition according to the present invention and its use will be specifically described below.

Ethylene / α-olefin Copolymer Composition The ethylene / α-olefin copolymer composition according to the present invention is an ethylene / α-olefin copolymer [A]: 30 to 8
0% by weight, preferably 30 to 75% by weight, more preferably 30 to 70% by weight, ethylene / α-olefin copolymer [B]: 1 to 69% by weight, preferably 5 to 60% by weight,
More preferably 10 to 50% by weight, low density polyethylene
[C]: 1 to 69% by weight, preferably 10 to 60% by weight,
More preferably, it comprises 20 to 50% by weight. (Note that
Ethylene / α-olefin copolymer [A] and ethylene / α-
The total of the olefin copolymer [B] and the ethylene copolymer [C] is 100% by weight. )

The ethylene / α-olefin copolymer [A] used in the present invention is an ethylene-α-olefin having 4 to 20 carbon atoms.
It is a copolymer with an olefin.

Specific examples of the α-olefin having 4 to 20 carbon atoms include 1-butene, 1-pentene, 1-hexene,
3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1
-Pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-one 1-octene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-
Dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like can be mentioned. Of these, 1-butene 1-hexene and 1-octene are preferable.

(I) Ethylene / α-olefin copolymer [A]
Content of each structural unit in the ethylene / α-olefin copolymer used in the present invention
The content of the structural unit (a) derived from ethylene in [A] is 60 to 80 mol%, preferably 65 to 75 mol%, and the structural unit (a) derived from an α-olefin having 4 to 20 carbon atoms ( The content of b) is 20 to 40 mol%, preferably 25.
Is about 35 mol%. When the content of each constituent unit is within the above range, a composition having excellent blocking properties can be obtained. (ii) Density Ethylene / α-olefin copolymer used in the present invention
[A] has a density of 0.863 g / cm ³ or less, preferably 0.855 to 0.860 g / cm ³ . (iii) Intrinsic viscosity ethylene / α-olefin copolymer used in the present invention
[A] has an intrinsic viscosity [η] measured in decalin of 135 ° C. of 0.1 to 10.0 dl / g, preferably 0.5 to 8 dl.
/ g, more preferably 1 to 6 dl / g. (iv) Glass transition temperature and crystallinity Ethylene / α-olefin copolymer used in the present invention
[A] has a glass transition temperature of −60 ° C. or lower, preferably −65 ° C. or lower, and a crystallinity of 10% or lower, preferably 5% or lower, as measured by a differential scanning calorimeter (DSC). (v) T _αβ / T _αα Ethylene / α-olefin copolymer used in the present invention
[A] is, T _.alpha..beta intensity ratio T _{alpha alpha} in the ¹³ C-NMR spectrum _(T αβ / T αα) is 0.5 or less, preferably 0.2 or less, and more preferably less than 0.01.

Here, T in the ¹³ C-NMR spectrum
_αα and T _αβ are peak intensities of CH ₂ in a structural unit derived from an α-olefin having 4 or more carbon atoms,
As shown below, it means two types of CH ₂ having different positions with respect to the tertiary carbon.

[0030]

[Chemical 3]

The intensity ratio of T _αβ / T _αα is obtained as follows. The ¹³ C-NMR spectrum of the ethylene / α-olefin copolymer [A] is measured using, for example, a JEOL-GX270 NMR measuring device manufactured by JEOL Ltd. The measurement is hexachlorobutadiene / d ₆ -benzene = 2/1 (volume ratio) adjusted to a sample concentration of 5% by weight.
67.8 MHz, 25 ° C., and d ₆ -benzene (128 ppm) as a standard. The ¹³ C-NMR spectrum measured was analyzed by Lindemann Adams (Analysis Chemistr
y43, P1245 (1971)), JCRandall (Review Macromolecu
lar Chemistry Physics, C29, 201 (1989)) to determine the T _αβ / T _αα intensity ratio.

The ethylene / α-olefin copolymer [A] used in the present invention has a B value represented by the following general formula (1) of 0.9 to 1.5, preferably 1.0 to 1. .2.

[0033]

[Chemical 4]

(In the formula, [P _E ] is the mole fraction of the structural unit derived from ethylene in the copolymer,
[P _O ] is the mole fraction of the constituent units derived from α-olefin in the copolymer, and [P _OE ] is the ethylene / α-olefin chain to the total dyad chain in the copolymer. It is a ratio of numbers and is determined by ¹³ C-NMR spectrum. )

This B value is an index showing the distribution state of ethylene and the α-olefin having 4 to 20 carbon atoms in the ethylene / α-olefin copolymer [A], and JCRandall (Macr
omolecules, 15, 353 (1982)), J. Ray (Macromolecules,
10, 773 (1977)).

The larger the above B value, the shorter the block-like chain of the ethylene or α-olefin copolymer,
The distribution of ethylene and α-olefin is uniform, indicating that the composition distribution of the copolymer rubber is narrow. As the B value becomes smaller than 1.0, the compositional distribution of the ethylene / α-olefin copolymer becomes wider and the handleability may deteriorate.

Method for producing ethylene / α-olefin copolymer [A] Such an ethylene / α-olefin copolymer [A] is
Ethylene and carbon number 4-20 in the presence of metallocene catalyst
It can be produced by copolymerizing with α-olefin.

Such a metallocene catalyst is formed from a metallocene compound (a) and an organoaluminumoxy compound (b) and / or a compound (c) which reacts with the metallocene compound (a) to form an ion pair. It may also be formed from the organoaluminum compound (d) together with (a), (b) and / or (c).

Each of these components will be described below. (A) Metallocene Compound The metallocene compound (a) forming the metallocene catalyst used in the present invention is a metallocene compound of a transition metal selected from Group 4 of the periodic table, and specifically, represented by the following general formula (2): expressed.

MLx (2) [In the general formula (2), M is a transition metal selected from Group 4 of the periodic table, x is the valence of the transition metal M, and L is a ligand. In the general formula (2), specific examples of the transition metal represented by M include zirconium, titanium and hafnium.

In the general formula (2), L is a ligand that coordinates with the transition metal M, and at least one of these ligands L is a ligand having a cyclopentadienyl skeleton. The ligand having this cyclopentadienyl skeleton may have a substituent. Examples of the ligand L having a cyclopentadienyl skeleton include cyclopentadienyl group, methylcyclopentadienyl group, ethylcyclopentadienyl group, n- or i-propylcyclopentadienyl group, n-, alkyl such as i-, sec-, t-, butylcyclopentadienyl group, dimethylcyclopentadienyl group, methylpropylcyclopentadienyl group, methylbutylcyclopentadienyl group, methylbenzylcyclopentadienyl group, etc. Examples include cycloalkyl-substituted cyclopentadienyl group; indenyl group, 4,5,6,7-tetrahydroindenyl group, fluorenyl group and the like.

The group having a cyclopentadienyl skeleton may be substituted with a halogen atom or a trialkylsilyl group. When the compound represented by the general formula (2) has two or more groups having a cyclopentadienyl skeleton as the ligand L, the groups having two cyclopentadienyl skeletons are ethylene, They may be bonded via an alkylene group such as propylene; a substituted alkylene group such as isopropylidene or diphenylmethylene; a substituted silylene group such as a silylene group or a dimethylsilylene group, a diphenylsilylene group, or a methylphenylsilylene group.

Ligands other than those having a cyclopentadienyl skeleton (ligands having no cyclopentadienyl skeleton) L are hydrocarbon groups having 1 to 12 carbon atoms,
Alkoxy group, aryloxy group, sulfonic acid-containing group (-
SO ₃ R ^a ; 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, an aryl group substituted with an alkyl group, or the like. ), A halogen atom or a hydrogen atom.

Examples of the hydrocarbon group having 1 to 12 carbon atoms include alkyl group, cycloalkyl group, aryl group and aralkyl group. Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl Examples thereof include an alkyl group such as a group; a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group; an aryl group such as a phenyl group and a tolyl group; and an aralkyl group such as a benzyl group and a neofil group.

Examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group and the like. A phenoxy group etc. are mentioned as an aryloxy group. The sulfonic acid-containing group (-SO ₃ R ^a), methanesulfonate group, p- toluenesulfonate group, trifluoromethanesulfonate group, such as p- chlorobenzene sulfonate group.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine. The metallocene compound represented by the general formula (2) is more specifically represented by the following general formula (3) when the valence of the transition metal is 4, for example.

R ² _k R ³ _l R ⁴ _m R ⁵ _n M (3) [In the general formula (3), M is the same transition metal as in the general formula (2), and R ² is a cyclopentadienyl skeleton. Is a group (ligand) having R ³ , R ⁴ and R ⁵ are each independently a group (ligand) having or not having a cyclopentadienyl skeleton. k is an integer of 1 or more, k + l + m + n
= 4. ]

Examples of the metallocene compound (a) include bis (cyclopentadienyl) zirconium dichloride, bis (methylcyclopentadienyl) zirconium dichloride, bis (ethylcyclopentadienyl) zirconium dichloride, bis (n). -Propylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride,
Bis (n-hexylcyclopentadienyl) zirconium dichloride, bis (methyl-n-propylcyclopentadienyl) zirconium dichloride, bis (methyl-n-butylcyclopentadienyl) zirconium dichloride,
Bis (dimethyl-n-butylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dibromide, bis (n-butylcyclopentadienyl) zirconium methoxychloride, bis (n-butylcyclopenta) Dienyl) zirconium ethoxy chloride, bis (n-butylcyclopentadienyl) zirconium butoxycyclolide, bis (n-butylcyclopentadienyl) zirconium ethoxide, bis (n-butylcyclopentadienyl) zirconium methyl chloride, bis (N-Butylcyclopentadienyl) zirconium dimethyl, bis (n-butylcyclopentadienyl) zirconium benzyl chloride, bis (n-butylcyclopentadienyl) zirconium dibenzyl, bis (n-butylcyclopentadienyl) The Benzalkonium phenyl chloride, and bis (n- butylcyclopentadienyl) zirconium hydride chloride. In the above example, the disubstituted product of the cyclopentadienyl ring is
Includes 1,2- and 1,3-substitutes.

In the present invention, a metallocene compound (a) in which zirconium metal is replaced with titanium metal or hafnium metal in the above zirconium compound can be used.

Further, as the metallocene compound (a),
R in the general formula (3)², R³, R ^FourAnd R^FiveLess
Two, for example R²And R³Is cyclopentadieni
A group (ligand) having a skeleton of at least 2
Groups are alkylene groups, substituted alkylene groups, silylene groups
Or bridging, such as via a substituted silylene group.
Examples of the metallocene compounds of the type:
At this time R^FourAnd R^FiveAre the same or different from each other
The cyclopentadiene described in the general formula (2)
It is the same as the ligand L other than the ligand having a skeleton.

Examples of the bridge-type metallocene compound (a) include ethylenebis (indenyl) dimethylzirconium, ethylenebis (indenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-fluorenyl) zirconium dichloride, diphenylsilylenebis ( Examples thereof include indenyl) zirconium dichloride, methylphenylsilylenebis (indenyl) zirconium dichloride, and metallocene compounds represented by the following general formula (4) described in JP-A-4-268307.

[0052]

[Chemical 5]

In the above general formula (4), M ¹ is a metal of Group 4 of the periodic table, specifically titanium, zirconium,
Hafnium etc. are mentioned. In the general formula (4),
R ¹ and R ² may be the same or different from each other,
Hydrogen atom; alkyl group having 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms; alkoxy group having 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms; aryl group having 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms An aryloxy group having 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms; 2 to 10 carbon atoms, preferably 2
~ 4 alkenyl group; 7-40 carbon atoms, preferably 7-10 arylalkyl group; 7-40 carbon atoms,
It is preferably an alkylaryl group having 7 to 12; an arylalkenyl group having 8 to 40 carbon atoms, preferably 8 to 12 carbon atoms; or a halogen atom, preferably a chlorine atom.

Further, in the general formula (4), R ³ and R ⁴ are hydrogen atom; halogen atom, preferably fluorine atom, chlorine atom or bromine atom; optionally halogenated carbon atom number 1 to 10, preferably having 6 to 10 carbon atoms, preferably C6-8 aryl _{^{group;; -N (R 10) 2}} , -SR 10, -OSi (R 10) 3, - 1~4 alkyl groups
Si (R ¹⁰ ) ₃ or —P (R ¹⁰ ) ₂ group. R ¹⁰ above
Is a halogen atom, preferably a chlorine atom;
10, preferably 1 to 3 alkyl groups; or 6 to 10 carbon atoms, preferably 6 to 8 aryl groups. R ³ and R ⁴ may be the same as or different from each other, and particularly preferably a hydrogen atom.

Further, in the general formula (4), R ⁵ and R ⁶ include the same groups as those exemplified for R ³ and R ⁴ excluding a hydrogen atom. R ⁵ and R ⁶ may be the same or different and are preferably the same. R ⁵ and R ⁶ are preferably an alkyl group having 1 to 4 carbon atoms or a halogen-substituted alkyl group, specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group or trifluoromethyl. And the like, and a methyl group is particularly preferable. In the general formula (4), R ⁷ is

[0056]

[Chemical 6] ^{-B (R 11) -, -} Al (R 11) -, - Ge -, - Sn-,
-O -, - S -, - SO -, - SO 2 -, - N (R 11)
-, - CO -, - P (R 11) - or ^{-P (O) (R 11)} - is.

R ¹¹ , R ¹² and R ¹³ are hydrogen atoms;
Halogen atom; 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms
An alkyl group of, more preferably a methyl group; a fluoroalkyl group having 1 to 10 carbon atoms, preferably a CF ₃ group;
An aryl group having 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms;
Fluoroaryl group having 6 to 10 carbon atoms, preferably pentafluorophenyl group; alkoxy group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, particularly preferably methoxy group; 2 to 10 carbon atoms, preferably 2 An alkenyl group having 4 to 4 carbon atoms; an arylalkyl group having 7 to 40 carbon atoms, preferably 7 to 10 carbon atoms; 8 to 40 carbon atoms, preferably 8 to
12 arylalkenyl groups; or 7 to 4 carbon atoms
0, preferably 7 to 12 alkylaryl groups.

"R ¹¹ and R ¹² " or "R ¹¹ and R ¹³ " may form a ring together with the atom to which they are bonded. R ¹¹ , R ¹² and R ¹³ may be the same or different from each other.

The above M ² is silicon, germanium or tin, preferably silicon or germanium.
The above R ⁷ is -C (R ¹¹ ) (R ¹² )-, -Si (R ¹¹ ) (R ¹² ).
^{-, - Ge (R 11)} (R 12) -, - O -, - S -, - SO
It is preferably —, —P (R ¹¹ ) — or —P (O) (R ¹¹ ) —.

In the above general formula (4), R ⁸ and R ⁹
Are the same as those for R ¹¹ . R ⁸ and R ⁹ may be the same as or different from each other. m and n are each 0, 1 or 2, preferably 0 or 1, and m + n is 0, 1 or 2, preferably 0 or 1. m and n may be the same as or different from each other.

The metallocene compound (a) represented by the general formula (3) includes rac-ethylene-bis (2-methyl-1-indenyl) -zirconium-dichloride and rac-dimethylsilylene-bis (2). -Methyl-1-indenyl) -zirconium-dichloride and the like can be used.

The metallocene compound (a) represented by the general formula (3) can be produced by a known method (see, for example, JP-A-4-268307). Furthermore, as the metallocene compound (a) represented by the general formula (3), a metallocene compound represented by the following general formula (5) can be used.

[0063]

[Chemical 7]

In the above general formula (5), M represents a transition metal atom of Group 4 of the periodic table, and specifically, titanium, zirconium, hafnium or the like. In the general formula (5),
R ¹ and R ² are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or 1 carbon atom.
To 20 halogenated hydrocarbon groups, silicon-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups or phosphorus-containing groups, specifically, halogen atoms such as fluorine, chlorine, bromine and iodine; methyl, Ethyl, propyl, butyl, hexyl, cyclohexyl, octyl, nonyl, dodecyl,
Alkyl groups such as eicosyl, norbornyl and adamantyl, alkenyl groups such as vinyl, propenyl and cyclohexenyl, arylalkyl groups such as benzyl, phenylethyl and phenylpropyl, phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl and propylphenyl, A hydrocarbon group having 1 to 20 carbon atoms such as an aryl group such as biphenyl, naphthyl, methylnaphthyl, anthracenyl and phenanthryl; 1 to 20 carbon atoms in which the hydrocarbon group is substituted with a halogen atom.
Halogenated hydrocarbon groups of monohydrocarbon-substituted silyl such as methylsilyl and phenylsilyl, dihydrocarbon-substituted silyl such as dimethylsilyl and diphenylsilyl, trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl, triphenylsilyl, dimethyl Trihydrocarbon-substituted silyls such as phenylsilyl, methyldiphenylsilyl, tritolylsilyl, and trinaphthylsilyl; hydrocarbon-substituted silyl silyl ethers such as trimethylsilyl ether; silicon-substituted alkyl groups such as trimethylsilylmethyl; silicon-substituted aryls such as trimethylsilylphenyl. Groups, such as silicon-containing groups; hydroxy groups, alkoxy groups such as methoxy, ethoxy, propoxy, butoxy, phenoxy, methylphenoxy, dimethylpheno Oxygen-containing groups such as aryloxy groups such as Si and naphthoxy, arylalkoxy groups such as phenylmethoxy and phenylethoxy; Sulfur-containing groups such as substituents in which oxygen of the oxygen-containing groups is substituted with sulfur; Amino groups, methylamino Alkylamino groups such as dimethylamino, diethylamino, dipropylamino, dibutylamino, dicyclohexylamino, phenylamino,
Examples thereof include nitrogen-containing groups such as arylamino groups or alkylarylamino groups such as diphenylamino, ditolylamino, dinaphthylamino, and methylphenylamino; phosphorus-containing groups such as phosphino groups such as dimethylphosphino and diphenylphosphino.

Of these, a hydrocarbon group is preferable, and an alkyl group having 1 to 3 carbon atoms such as methyl, ethyl or propyl is particularly preferable. In the general formula (5), R ³ ,
R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms. Examples of these include the same as those for R ¹ and R ² . Of these, hydrogen, a hydrocarbon group or a halogenated hydrocarbon group is preferable.

Further, at least one set of R ³ and R ⁴ , R ⁴ and R ⁵ , and R ⁵ and R ⁶ may combine with each other to form a monocyclic aromatic ring. Examples of the ligand containing include those represented by the following general formulas (6) to (8).

[0067]

[Chemical 8]

The metallocene compound (a) represented by the general formula (5) is a hydrocarbon group among R ³ , R ⁴ , R ⁵ and R ⁶ (groups other than groups forming an aromatic ring) or When there are two or more kinds of halogenated hydrocarbon groups, these may be bonded to each other to form a ring. When R ⁶ is a substituent other than an aromatic group, it is preferably a hydrogen atom.

In the general formula (5), X ¹ and X ² are
Each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group or a sulfur-containing group.

A halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms,
Specific examples of the oxygen-containing group include R ¹ and R ² described above.
Examples of the same as those exemplified in.

The sulfur-containing groups include R ¹ and R ² described above.
Groups similar to, and methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate, p-toluene sulfonate, trimethylbenzene sulfonate, triisobutylbenzene sulfonate, p-chlorobenzene sulfonate. Phonate,
Sulfonate groups such as pentafluorobenzene sulfonate, methyl sulfinate, phenyl sulfinate, benzene sulfinate, p-toluene sulfinate, trimethylbenzene sulfinate, pentafluorobenzene sulfinate and other sulfinate groups Can be mentioned

In the general formula (5), Y is a divalent hydrocarbon group having 1 to 20 carbon atoms or 2 having 1 to 20 carbon atoms.
Divalent halogenated hydrocarbon group, divalent silicon-containing group, divalent germanium-containing group, divalent tin-containing group, -O-,-
CO -, - S -, - SO -, - SO 2 -, - NR 7 -, -
^{P (R 7) -, -} P (O) (R 7) -, - BR 7 - or -Al
R ⁷ — (wherein R ⁷ is a hydrogen atom, a halogen atom similar to the above R ¹ and R ² , a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms) . [R
₇ is a halogen atom similar to R ₁ and R ₂ and has 1 to 1 carbon atoms.
It is a hydrocarbon group having 20 or a halogenated hydrocarbon group having 1 to 20 carbon atoms. ]

Specific examples of such Y include methylene, dimethylmethylene, 1,2-ethylene, dimethyl-1,2-
Ethylene, 1,3-trimethylene, 1,4-tetramethylene, 1,
1-carbon atoms such as alkylene groups such as 2-cyclohexylene and 1,4-cyclohexylene, aryl alkylene groups such as diphenylmethylene and diphenyl-1,2-ethylene
20 divalent hydrocarbon groups; halogenated hydrocarbon groups obtained by halogenating the above C 1-20 divalent hydrocarbon groups such as chloromethylene; methylsilylene, dimethylsilylene, diethylsilylene, di (n- Propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, methylphenylsilylene, diphenylsilylene, di (p-tolyl) silylene, di (p-chlorophenyl) silylene, and other alkylsilylenes, alkylarylsilylenes, aryls A divalent silicon-containing group such as a silylene group, an alkyldisilirene such as tetramethyl-1,2-disilirene, or tetraphenyl-1,2-disilirene, an alkylaryldisilirene, an aryldisilirene group; the above divalent silicon-containing group A divalent germanium-containing group in which silicon in the group is replaced by germanium; Such divalent tin-containing group substituents of the silicon-containing groups is replaced with tin and the like.

Of these, a divalent silicon-containing group, a divalent germanium-containing group and a divalent tin-containing group are preferable, and a divalent silicon-containing group is more preferable, and an alkylsilylene group and an alkylaryl group are particularly preferable. A silylene group and an arylsilylene group are preferable.

In the compound represented by the general formula (5), two of R ³ , R ⁴ , R ⁵ and R ⁶ containing R ³ are alkyl groups having 1 to 20 carbon atoms. And R ³ and R ⁵ , or R ³ and R ⁶ are preferably alkyl groups. This alkyl group is preferably a secondary or tertiary alkyl group, and such an alkyl group may be substituted with a halogen atom or a silicon-containing group. Examples of the halogen atom and the silicon-containing group include the substituents exemplified for R ¹ and R ² . Furthermore, R ³ ,
Of R ⁴ , R ⁵ and R ⁶ , the groups other than the alkyl group are preferably hydrogen atoms. As the alkyl group having 1 to 20 carbon atoms, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, tert-butyl group, pentyl group , Hexyl group, cyclohexyl group, heptyl group, octyl group, nonyl group, dodecylaicosyl group, norbornyl group, adamantyl group and other chain alkyl groups and cyclic alkyl groups; benzyl group, phenylethyl group, phenylpropyl group, tolylmethyl group And the like, and may contain a double bond or a triple bond.

Further, two groups selected from R ³ , R ⁴ , R ⁵ and R ⁶ may be bonded to each other to form a monocyclic or polycyclic ring other than an aromatic ring. Specific examples of such a metallocene compound (a) include rac-dimethylsilylene-bis (4,7-dimethyl-1-indenyl) zirconium dichloride and rac-dimethylsilylene-bis (2,4,7-trimethyl-). 1-indenyl) zirconium dichloride, rac-
Examples thereof include dimethylsilylene-bis (2,4,6-trimethyl-1-indenyl) zirconium dichloride.

It is also possible to use the metallocene compound (a) in which zirconium metal is replaced with titanium metal or hafnium metal in the above compounds. The metallocene compound (a) is usually used as a racemate, but R type or S type can also be used.

Further, as the metallocene compound (a) represented by the general formula (5), R ³ is phenyl group, α-naphthyl group, β-naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group, acenaphthyl group, phenalenyl group. A metallocene compound (a) which is an aryl group having 6 to 16 carbon atoms, such as a group (perinaphthenyl group) and an aceanthrylenyl group, can also be preferably used. These aryl groups may be substituted with the same halogen atom as R ¹ , a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms. this house,
Particularly, a phenyl group and a naphthyl group are preferable.

Specific examples of such a metallocene compound include rac-dimethylsilylene-bis (4-phenyl-1-indenyl) zirconium dichloride and 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-anthracenyl) -1-indenyl) zirconium dichloride and the like can be mentioned.

Further, in the above compound, a transition metal compound in which zirconium metal is replaced with titanium metal or hafnium metal can be used. Moreover, the transition metal compound represented by the following general formula (9) can also be used.

[0081]

[Chemical 9]

In the general formula (9), M is a transition metal atom of Group 4 of the periodic table, specifically titanium, zirconium or hafnium, preferably zirconium. In the general formula (9), R ^{1 s} may be the same or different, at least one of which is an aryl group having 11 to 20 carbon atoms, and 1 has 1 carbon atom.
2-40 arylalkyl groups, 13-40 carbon atoms
Is an arylalkenyl group of, an alkylaryl group having 12 to 40 carbon atoms, or a silicon-containing group, or at least two adjacent groups of the groups represented by R ¹ together with the carbon atoms to which they are bonded, It forms one or more aromatic or aliphatic rings. In this case, the ring formed by R ¹ is the number of carbon atoms in all including carbon atoms to which R ¹ is attached is 4 to 20.

An example in which at least two adjacent groups of the groups represented by R ¹ together with the carbon atoms to which they are bonded form one or more aromatic rings or aliphatic rings is a fused phenyl group. , Condensed cyclohexyl group, condensed cyclopentadienyl group, condensed dihydrocyclopentadienyl group, condensed indenyl group, condensed tetrahydroindenyl, condensed fluorenyl group, condensed tetrahydrofluorenyl group, condensed octa A hydrofluorenyl group etc. are mentioned.

These groups are substituted with a chain alkyl group, a cyclic alkyl group, a halogen atom, a halogen-substituted alkyl group, an aryl group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group or a phosphorus-containing group. Good. Aryl group, arylalkyl group, arylalkenyl group, an alkylaryl group and an aromatic ring, R ¹ other than R ¹ to form an aliphatic ring is a hydrogen atom, a halogen atom, an alkyl number of 1 to 10 carbon atoms A group or a silicon-containing group.

Examples of the aryl group having 11 to 20 carbon atoms include biphenylyl, anthryl and phenanthryl. Examples of the arylalkyl group having 12 to 40 carbon atoms include phenanthrylmethyl, phenanthrylethyl, Examples thereof include phenanthrylpropyl, and examples of the arylalkenyl group having 13 to 40 carbon atoms include vinylphenanthryl and the like, which has 12 carbon atoms.
Examples of the alkylaryl group of -40 include methylphenanthryl, ethylphenanthryl, propylphenanthryl, and the like, and halogen atoms include fluorine, chlorine, bromine, iodine, and the like, and the number of carbon atoms is 1. ~ 1
Examples of the alkyl group of 0 include methyl, ethyl, propyl,
Butyl, hexyl, cyclohexyl, octyl, nonyl and the like can be mentioned.

The silicon-containing groups include methylsilyl, phenylsilyl, dimethylsilyl, diethylsilyl, diphenylsilyl, trimethylsilyl, triethylsilyl,
Examples include groups such as tripropylsilyl, tricyclohexylsilyl, triphenylsilyl, dimethylphenylsilyl, methyldiphenylsilyl, tritolylsilyl, and trinaphthylsilyl.

The above alkyl group, aryl group, arylalkyl group, arylalkenyl group and alkylaryl group may be substituted with halogen. In the general formula (9), R ^{2 s} may be the same as or different from each other, and have a hydrogen atom, a halogen atom, or a carbon atom number of 1.
An alkyl group having 10 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, and 8 to 40 carbon atoms.
Is an arylalkenyl group, an alkylaryl group having 7 to 40 carbon atoms, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group.

In addition, R²Of the groups shown in
At least two groups, together with the carbon atom to which they are attached
To form one or more aromatic or aliphatic rings.
May be. In this case, R²The ring formed by is R²
The total number of carbon atoms is 4 including the carbon atoms bound by
To 20 and R forming an aromatic ring or an aliphatic ring. ²
R other than²Is a hydrogen atom, halogen atom, or carbon atom
1 to 10 alkyl groups or silicon-containing groups.

The group formed by the two groups represented by R ² forming one or more aromatic rings or aliphatic rings includes a mode in which the fluorenyl group has the following structure. Be done.

[0090]

[Chemical 10]

Examples of the alkyl group having 1 to 10 carbon atoms and the halogen atom include the same groups and atoms as described above. Examples of the aryl group having 6 to 20 carbon atoms include phenyl, biphenylyl, α- or β-naphthyl,
Examples of the arylalkyl group having 7 to 40 carbon atoms include benzyl, phenylethyl, phenylpropyl, phenanthrylmethyl, phenanthrylethyl, and phenanthrylpropyl. Examples of the arylalkenyl group having 8 to 40 atoms include styryl and vinylphenanthryl, and examples of the alkylaryl group having 7 to 40 carbon atoms include tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl and propylphenyl. , Methylnaphthyl, methylphenanthryl, ethylphenanthryl, propylphenanthryl, and the like. Examples of the alkenyl group having 2 to 10 carbon atoms include vinyl, propenyl, cyclohexenyl, and the like, and a silicon-containing group. As above Examples of the oxygen-containing group include a hydroxy group, an alkoxy group such as methoxy, ethoxy, propoxy and butoxy, an aryloxy group such as phenoxy, methylphenoxy, dimethylphenoxy and naphthoxy, an aryl such as phenylmethoxy and phenylethoxy. Examples of the sulfur-containing group include a substituent in which oxygen of the oxygen-containing group is replaced with sulfur, and methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate, p-toluene. Sulfonate groups such as sulfonate, trimethylbenzene sulfonate, triisobutylbenzene sulfonate, p-chlorobenzene sulfonate, pentafluorobenzene sulfonate, methyl sulphinate, phenyl Examples thereof include sulfinate groups such as ruffinate, benzenesulfinate, p-toluenesulfinate, trimethylbenzenesulfinate, and pentafluorobenzenesulfinate, and nitrogen-containing groups include amino groups, methylamino, dimethylamino, diethylamino. , Alkylamino groups such as dipropylamino, dibutylamino, dicyclohexylamino, phenylamino, diphenylamino,
Examples thereof include arylamino groups such as ditolylamino, dinaphthylamino, and methylphenylamino, and alkylarylamino groups. Examples of the phosphorus-containing group include dimethylphosphino and diphenylphosphino.

Of these, R ² is preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms such as methyl, ethyl or propyl.

A preferable example of the fluorenyl group having R ² as the substituent is a 2,7-dialkyl-fluorenyl group, and the alkyl group of the 2,7-dialkyl in this case is a carbon atom. Examples thereof include alkyl groups having a number of 1 to 5.

The above-mentioned R ¹ and R ² may be the same or different from each other. In the general formula (9), R ³ and R ⁴ may be the same as or different from each other, and have the same hydrogen atom, halogen atom and carbon atom number of 1 to 1 as described above.
An alkyl group of 0, an aryl group having 6 to 20 carbon atoms,
Alkenyl group having 2 to 10 carbon atoms, 7 carbon atoms
˜40 arylalkyl group, C 8-40 arylalkenyl group, C 7-40 alkylaryl group, silicon-containing group, oxygen-containing group, sulfur-containing group, nitrogen-containing group or phosphorus-containing group. is there.

At least one of R ³ and R ⁴ is preferably an alkyl group having 1 to 3 carbon atoms. In the general formula (9), X ¹ and X ² may be the same or different from each other, and are a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogen having 1 to 20 carbon atoms. A hydrocarbon group, an oxygen-containing group, a sulfur-containing group or a nitrogen-containing group, or a conjugated diene residue formed from X ¹ and X ^2, and specifically, a halogen atom, an oxygen-containing group, a sulfur-containing group As the nitrogen-containing group, the same atom or group as described above can be exemplified.

The hydrocarbon group having 1 to 20 carbon atoms includes alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, octyl, nonyl, dodecyl, eicosyl, norbornyl and adamantyl; vinyl, propenyl, cyclo Alkenyl groups such as hexenyl; arylalkyl groups such as benzyl, phenylethyl, phenylpropyl; phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, α- or β-naphthyl, methylnaphthyl, anthryl, phenanthryl, benzyl. Phenyl,
Examples thereof include aryl groups such as pyrenyl, acenaphthyl, phenalenyl, aceanthrylenyl, tetrahydronaphthyl, indanyl and biphenylyl, and the like, and the number of carbon atoms is 1
Examples of the halogenated hydrocarbon group having 20 to 20 include groups obtained by substituting the above hydrocarbon group having 1 to 20 carbon atoms with halogen.

[0097] X ¹ and Examples of the conjugated diene residue formed by X ² Prefecture, eta ^{4-1,4-diphenyl-1,3-butadiene,} eta ⁴ -
1,3-butadiene, η ⁴ -1,4-dibenzyl-1,3-butadiene, η 4-1-phenyl-1,3-pentadiene, η ⁴ -3-methyl-
1,3-pentadiene, η ⁴ -1,4-bis (trimethylsilyl)
-1,3-butadiene, 2,3-dimethylbutadiene, η ⁴ -2,4-
Hexadiene, isoprene and the like can be mentioned.

The conjugated diene residue formed from X ¹ and X ² includes 1,3-butadiene, 2,4-hexadiene, 1-phenyl-1,3-pentadiene, and the remaining 1,4-diphenylbutadiene. Groups are preferred, these residues also having 1 carbon atom
It may be substituted with a hydrocarbon group of 10 to 10. Of these, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a sulfur-containing group is preferable.

In the general formula (9), Y is a divalent hydrocarbon group having 1 to 20 carbon atoms, or 1 to 20 carbon atoms.
A divalent halogenated hydrocarbon group, a divalent silicon-containing group,
Divalent germanium-containing group, divalent tin-containing group, -O
-, - CO -, - S -, - SO -, - SO 2 -, - NR
^{5 -, - P (R 5} ) -, - P (O) (R 5) -, - BR 5 -
Or —AlR ⁵ — (wherein R ⁵ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms),
Specifically, methylene, dimethylmethylene, 1,2-ethylene, dimethyl-1,2-ethylene, 1,3-trimethylene, 1,4-
Divalent carbon atoms having 1 to 20 carbon atoms such as alkylene groups such as tetramethylene, 1,2-cyclohexylene and 1,4-cyclohexylene, aryl alkylene groups such as diphenylmethylene and diphenyl-1,2-ethylene. Hydrogen group; halogenated hydrocarbon group obtained by halogenating the above divalent hydrocarbon group having 1 to 20 carbon atoms such as chloromethylene; methylsilylene, dimethylsilylene, diethylsilylene, di (n-propyl) silylene, di (I-propyl) silylene,
Alkylsilylene such as di (cyclohexyl) silylene, methylphenylsilylene, diphenylsilylene, di (p-tolyl) silylene, di (p-chlorophenyl) silylene, alkylarylsilylene, arylsilylene group,
Tetramethyl-1,2-disilirene, tetraphenyl-1,2-
Divalent silicon-containing groups such as alkyldisilylene such as disilylene, alkylaryldisilirene, and aryldisilirene groups; Divalent germanium-containing groups obtained by substituting germanium for silicon in the above divalent silicon-containing groups; Examples thereof include a divalent tin-containing group obtained by substituting tin for silicon in the silicon-containing group.

Of these divalent groups, those in which the shortest linking part of —Y— represented by the general formula (9) is composed of 1 or 2 atoms are preferable. Also, R
⁵ is a halogen atom similar to the above, having 1 to 2 carbon atoms
It is a hydrocarbon group of 0 or a halogenated hydrocarbon group having 1 to 20 carbon atoms.

Of these, Y is preferably a divalent hydrocarbon group having 1 to 5 carbon atoms, a divalent silicon-containing group or a divalent germanium-containing group, and preferably a divalent silicon-containing group. More preferably, alkylsilylene,
Particularly preferred is alkylarylsilylene or arylsilylene.

Further, in the zirconium compound as described above, a compound in which zirconium is replaced by titanium or hafnium can be mentioned. Among the zirconium compounds mentioned above, for example, dimethylsilylene (2,7-dimethyl-4,5- (2-methyl-benzo) -1-indenyl) (2,7-di-t-butyl-9-fluorenyl) The structural formula of zirconium dichloride is shown below.

[0103]

[Chemical 11]

In addition, dimethylsilylene (2,6-dimethyl-
4,5- (1-Methyl-benzo) -1-indenyl) (2,7-di-t-
The structural formula of butyl-9-fluorenyl) zirconium dichloride is shown below.

[0105]

[Chemical 12]

These catalysts are disclosed in Japanese Patent Application No. 8-187563 (Japanese Patent Application Laid-Open No. 9-235313) filed by the present applicant.
(See Japanese Patent Laid-Open Publication). Further, in the present invention, the compound represented by the following general formula (10) can be used as the metallocene compound (a).

LaMX ₂ (10) [In the general formula (10), M is a metal of Group 4 or the lanthanide series of the periodic table. La is a derivative of the delocalized π-bonding group, and is a group that imparts a constrained geometric shape to the metal M active site. Each X is independently hydrogen, halogen or a hydrocarbon group containing 20 or less carbon, silicon or germanium, a silyl group or a germyl group. ]

Among the compounds represented by the general formula (10), the compound represented by the following general formula (11) is preferable.

[0109]

[Chemical 13]

In the general formula (11), M is titanium, zirconium or hafnium, and X is the same as in the general formula (10). Cp is a cyclopentadienyl group that is π-bonded to M. In the general formula (11), Z is oxygen, sulfur, boron or an element of Group 4 of the periodic table (for example, silicon, germanium or tin), Y is a ligand containing nitrogen, phosphorus, oxygen or sulfur, and Z and A condensed ring may be formed with Y.

Examples of the compound represented by the general formula (11) include (dimethyl (t-butylamide) (tetramethyl
Examples include -η ⁵ -cyclopentadienyl) silane) titanium dichloride, ((t-butylamido) (tetramethyl-η ⁵ -cyclopentadienyl) -1,2-ethanediyl) titanium dichloride and the like. In addition, in the above metallocene compound, a compound in which titanium is replaced with zirconium or hafnium can be given.

The metallocene compound (a) represented by the general formula (10) or (11) is a zirconocene having a central metal atom of zirconium and having a ligand containing at least two cyclopentadienyl skeletons. Compounds are preferably used. The general formula (4) or (5)
In the metallocene compound (a) represented by, the central metal atom is preferably titanium.

In the present invention, the metallocene compound (a) may be used alone or in combination of two or more kinds. Further, the metallocene compound (a) may be diluted with a hydrocarbon or a halogenated hydrocarbon and used. Furthermore, the metallocene compound (a) can also be used in contact with a carrier.

The carrier used is an inorganic or organic compound and has a particle size of 10 to 300 μm, preferably 2
A granular or fine particle solid of 0 to 200 μm is used. Among these, porous oxides are preferable as the inorganic carrier, and specifically, SiO ₂ , Al ₂ O ₃ , MgO, Zr
O ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, Th
O2, etc., or mixtures thereof, for example, SiO ₂ -MgO,
SiO ₂ -Al ₂ O ₃ , SiO ₂ -TiO ₂ , SiO ₂ -V
_{2 O 5, SiO 2 -Cr 2} O 3, can be exemplified SiO ₂ -TiO ₂ -MgO and the like. Among these, SiO ₂ and A
It is preferable that the main component is at least one component selected from the group consisting of l ₂ O ₃ .

The inorganic oxide contains a small amount of Na ₂ C.
O ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ SO ₄ ,
Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg (NO ₃ ) ₂ ,
Carbonate such as Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O, Li ₂ O,
It does not matter if it contains sulfates, nitrates or oxides. Although such a carrier has different properties depending on its type and production method, the carrier preferably used in the present invention has a specific surface area of 50 to 1000 m ² / g, preferably 100 to 1000 m ² / g.
700 m ² / g and pore volume of 0.3 to 2.5 cm ³ /
It is preferably g. The carrier is 10 if necessary.
It is used by firing at 0 to 1000 ° C, preferably 150 to 700 ° C.

Further, examples of the carrier which can be used in the present invention include granular or fine particle solids of an organic compound having a particle size of 10 to 300 μm. These organic compounds include ethylene, propylene, 1-butene, 4-methyl-1-pentene and the like having 2 to 14 carbon atoms.
Examples of the (co) polymer produced by using α-olefin as the main component or the polymer or copolymer produced by using vinylcyclohexane or styrene as the main component.

Organoaluminum Oxy Compound (b) The organoaluminum oxy compound (b) may be a known aluminoxane or a benzene-insoluble organoaluminum oxy compound (b). Such known aluminoxane is specifically represented by the following general formula (12) or (13).

[0118]

[Chemical 14]

[In the general formulas (12) and (13), R is a hydrocarbon group such as a methyl group, an ethyl group, a propyl group and a butyl group, preferably a methyl group and an ethyl group, and particularly preferably a methyl group. And m is an integer of 2 or more, preferably 5 to 40. In the general formula (12) or (13), the aluminoxane is an alkyloxyaluminum unit represented by the general formula (OAl (R ¹ )) and the general formula (OAl (R ² )).
An alkyloxyaluminum unit represented by (where
R ¹ and R ² can be the same hydrocarbon groups as R, and R ¹ and R ² represent different groups. ) May be formed from a mixed alkyloxyaluminum unit.

Organoaluminum oxy compound (b)
May contain a small amount of an organic compound component of a metal other than aluminum. The aluminoxane as described above can be prepared, for example, by the following method. (1) Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, ceric chloride hydrate, etc. A method of recovering a hydrocarbon solution by adding an organoaluminum compound such as trialkylaluminum to the hydrocarbon medium suspension and reacting the same. (2) A method in which water, ice, or steam is directly applied to an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether, or tetrahydrofuran to recover it as a hydrocarbon solution. (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 organic metal component. Alternatively, the solvent or unreacted organoaluminum compound may be removed by distillation from the recovered solution of the aluminoxane, and then redissolved in the solvent.

Specific examples of the organoaluminum compound used when preparing the aluminoxane include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, and triisopropylaluminum.
n-butyl aluminum, triisobutyl aluminum,
Trisec-butylaluminum, tritert-butylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum and other trialkylaluminums; tricyclohexylaluminum, tricyclooctylaluminum and other tricycloalkylaluminums; dimethylaluminum Chloride, diethylaluminum chloride,
Dialkyl aluminum halides such as diethyl aluminum bromide and diisobutyl aluminum chloride;
Dialkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride; dialkyl aluminum alkoxides such as dimethyl aluminum methoxide and diethyl aluminum ethoxide; and dialkyl aluminum aryloxides such as diethyl aluminum phenoxide.

Of these, trialkylaluminum and trialkylaluminum are particularly preferable. Further, as the organoaluminum compound, a compound represented by the general formula (1
4)

[0124] _{(i-C 4 H 9)} x Al y (C 5 H 10) z ... (14) (x, y, z are each a positive number, a is z ≧ 2x) isoprenylaluminum represented by Can also be used.

The organoaluminum compound as described above is
Used alone or in combination. As a solvent used in the preparation of aluminoxane, aromatic hydrocarbons such as benzene, toluene, xylene, cumene, and cymene, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, octadecane, etc. Aliphatic hydrocarbons such as hydrogen, cyclopentane, cyclohexane, cyclooctane, and methylcyclopentane, petroleum fractions such as gasoline, kerosene, and light oil, or halogens of the above aromatic hydrocarbons, aliphatic hydrocarbons, and alicyclic hydrocarbons. In particular, hydrocarbon solvents such as chlorinated compounds and brominated compounds are mentioned. In addition, ethers such as ethyl ether and tetrahydrofuran can also be used.
Of these solvents, aromatic hydrocarbons are particularly preferable.

In the benzene-insoluble organoaluminum oxy compound, the Al component soluble in benzene at 60 ° C. is 10% or less, preferably 5% or less in terms of Al atom.
It is particularly preferably 2% or less and insoluble or hardly soluble in benzene.

The solubility of such an organoaluminum oxy compound in benzene is 10 mg of the organoaluminum oxy compound corresponding to 100 mg of Al.
After suspending in 0 ml of benzene and mixing under stirring at 60 ° C. for 6 hours, hot filtration was carried out at 60 ° C. using a G-5 glass filter with a jacket, and the solid portion separated on the filter was washed with 60 parts. It is determined by measuring the abundance (x mmol) of Al atoms present in the entire filtrate after washing four times with 50 ml of benzene at 50 ° C. (x%).

Ionized Ionic Compound (c) As the ionized ionic compound (sometimes referred to as ionic ionized compound or ionic compound) (c),
Examples thereof include Lewis acids, ionic compounds, borane compounds, and carborane compounds.

As the Lewis acid, Mg-containing Lewis acid, A
1-containing Lewis acid, B-containing Lewis acid and the like can be mentioned, and among these, B-containing Lewis acid is preferable. The B-containing Lewis acid is a compound represented by BR ₃ (R represents a phenyl group which may have a substituent such as a fluorine atom, a methyl group or a trifluoromethyl group or a fluorine atom). ,
Specifically, trifluoroboron, triphenylboron, tris (4-fluorophenyl) boron, tris (3,
5-difluorophenyl) boron, tris (4-fluoromethylphenyl) boron, tris (pentafluorophenyl) boron, tris (p-tolyl) boron, tris (o-tolyl) boron, tris (3,5-dimethylphenyl) Examples include boron.

The ionic compound is a salt composed of a cationic compound and an anionic compound, and the anion reacts with the metallocene compound (a) to cationize the metallocene compound (a) to form an ion pair. Has the function of stabilizing the transition metal cation species.
Examples of such anions include an organic boron compound anion, an organic arsenic compound anion, and an organic aluminum anion, and those which are relatively bulky and stabilize the transition metal cation species are preferable. Examples of the cation include a metal cation, an organometallic cation, a carbonium cation, a tripium cation, an oxonium cation, a sulfonium cation, a phosphonium cation, and an ammonium cation. More specifically, it is a triphenylcarbenium cation, a tributylammonium cation, an N, N-dimethylammonium cation, a ferrocenium cation, or the like.

Specific examples of such an ionic compound include N, N-dialkylanilinium salts, dialkylammonium salts, trialkylsubstituted ammonium salts such as triarylphosphonium salts, triethylammonium tetra (phenyl) boron, Trialkyl ammonium tetra (phenyl) boron, tri (n-butyl) ammonium tetra (phenyl) boron and other trialkyl-substituted ammonium salts, di (1-propyl) ammonium tetra (pentafluorophenyl) boron, dicyclohexylammonium tetra (phenyl) Examples thereof include dialkyl ammonium salts such as boron.

As the ionic compound containing a boron atom, triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate,
Ferrocenium tetra (pentafluorophenyl) borate and the like can also be mentioned.

Examples of the borane compound include decaborane (14); bis [tri (n-butyl) ammonium] nonaborate, bis [tri (n-butyl) ammonium] decaborate, bis [tri (n-butyl) ammonium] bis ( Examples thereof include metal borane anion salts such as dodeca hydride dodecaborate) nickelate (III).

Examples of the carborane compound include 4-carbanonaborane (14) and 1,3-dicarbanonaborane (1
3), salts of metal carborane anions such as bis [tri (n-butyl) ammonium] bis (undecahydride-7-carboundecaborate) nickelate (IV).

The above-mentioned ionized ionic compound (c) is used alone or in combination of two or more kinds. The organoaluminum oxy compound (b) and the ionized ionic compound (c) can also be used by supporting them on the carrier compound.

When preparing the metallocene catalyst, the organoaluminum compound (d) may be used, if necessary, together with the organoaluminum oxy compound (b) or the ionized ionic compound (c).

Organoaluminum compound (d) Organoaluminum compound (d) optionally used
For example, an organoaluminum compound represented by the following general formula (15) can be exemplified.

R ¹ _n AlX _3-n (15) [In the formula (15), R ¹ is a hydrocarbon group having 1 to 12 carbon atoms, X is a halogen atom or a hydrogen atom, and n is
Is 1 to 3. ]

In the above general formula (15), R ¹ is a hydrocarbon group having 1 to 12 carbon atoms, for example, an alkyl group, a cycloalkyl group or an aryl group.
Methyl group, ethyl group, n-propyl group, isopropyl group,
Isobutyl group, pentyl group, hexyl group, octyl group,
Examples include a cyclopentyl group, a cyclohexyl group, a phenyl group and a tolyl group.

Such an organoaluminum compound (d)
Specifically, the following compounds may be mentioned. Trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, and tri-2-ethylhexylaluminum; alkenylaluminums such as isoprenylaluminum; dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutyl. Dialkyl aluminum halides such as aluminum chloride and dimethyl aluminum bromide; alkyl aluminum sesquihalides such as methyl aluminum sesquichloride, ethyl aluminum sesquichloride, isopropyl aluminum sesquichloride, butyl aluminum sesquichloride, ethyl aluminum sesquibromide; methyl Aluminum dichloride,
Alkyl aluminum dihalides such as ethyl aluminum dichloride, isopropyl aluminum dichloride, and ethyl aluminum dibromide; alkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride.

Further, as the organoaluminum compound (d), compounds represented by the following general formula (16) can also be mentioned.

R ¹ _n AlY _3-n (16) (In the formula (16), R ¹ is the same as above, and Y is -OR.
² group, -OSiR ³ ₃ group, -OAlR ⁴ ₂ group, -NR ⁵ ₂ group, -
SiR ⁶ ₃ group or —N (R ⁷ ) AlR ⁸ ₂ group, n is 1 to
2, R ² , R ³ , R ⁴ and R ⁸ are a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a cyclohexyl group, a phenyl group, etc., and R ⁵ is a hydrogen atom, a methyl group, an ethyl group, isopropyl group. Group, phenyl group, trimethylsilyl group and the like, and R ⁶ and R ⁷ are methyl group, ethyl group and the like. )

As such an organoaluminum compound
Specifically, the following compounds may be mentioned. (1) R¹ _nAl (OR²)_3-nA compound represented by, for example
Dimethyl aluminum methoxide, diethyl aluminum
Mutethoxide, diisobutylaluminum methoxide
What (2) R¹ _nAl (OSiR³ ₃)_3-nCompounds represented by
Speaking of Et₂Al (OSiMe₃), (Iso-Bu)₂Al (OS
iMe₃), (Iso-Bu)₂Al (OSiEt₃)Such; (3) R¹ _nAl (OAlR^Four ₂)_3-nCompounds represented by
Speaking of Et₂AlOAlEt ₂, (Iso-Bu)₂AlOAl
(iso-Bu)₂Such; (4) R¹ _nAl (NR^Five ₂)_3-nA compound represented by, for example
Me₂AlNEt₂, Et₂AlNHMe, Me₂AlN
HEt, Et₂AlN (SiMe₃)₂, (Iso-Bu) ₂Al
N (SiMe₃)₂Such; (5) R¹ _nAl (SiR⁶ ₃)_3-nA compound represented by
Ba (iso-Bu)₂AlSiMe₃Etc; (6) R¹ _nAl
(N (R⁷) AlR⁸ ₂)_3-n A compound represented by, for example, Et₂
AlN (Me) AlEt₂ , (Iso-Bu)₂AlN (Et)
Al (iso-Bu)₂Such.

Among the organoaluminum compounds represented by the above general formulas (15) and (16), the general formula R ¹³ A
l, R ¹ _n Al (OR ² ) _3-n , R ¹ _n Al (OAlR ⁴ ₂ ) _3-n
The compound represented by is preferable, and the compound in which R is an isoalkyl group and n = 2 is particularly preferable.

Copolymerization of Ethylene / α-Olefin Copolymer [A] In the present invention, the metallocene compound (a) as described above is used.
In the presence of a catalyst formed from an organoaluminum oxy compound (b) and / or an ionizable ionic compound (c), and optionally an organoaluminum compound (d),
Ethylene and an α-olefin having 4 to 20 carbon atoms are usually copolymerized in a liquid phase. At this time, a hydrocarbon solvent is generally used, but an α-olefin may be used as a solvent.

This copolymerization can be carried out by any of batch method, semi-continuous method and continuous method. When carrying out the copolymerization by the batch method, the catalyst components are used in the following concentrations.

When a metallocene catalyst comprising the metallocene compound (a) and the organoaluminum oxy compound (b) or the ionizable ionic compound (c) is used, the concentration of the metallocene compound (a) in the polymerization system is Usually 0.00005
˜0.1 mmol / liter (polymerization volume), preferably 0.0001 to 0.05 mmol / liter. The organoaluminum oxy compound (b) is supplied in an amount of 1 to 10000, preferably 10 to 5000, in terms of molar ratio of aluminum atom to transition metal in the metallocene compound in the polymerization system (Al / transition metal).

In the case of the ionized ionic compound (c), the molar ratio of the ionized ionic compound (c) to the metallocene compound (a) in the polymerization system (ionized ionic compound (c) / metallocene compound (a)) is used. , 0.5 to 20, preferably 1 to
Supplied in quantities of 10.

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

The copolymerization reaction usually has a reaction temperature of -20 to 20.
+ 150 ° C., preferably 0 to 120 ° C., more preferably 0 to 100 ° C.
0 kgf / cm ² , gauge pressure) or less, preferably more than 4.
It is carried out under the conditions of 9 MPa (50 kgf / cm ² , gauge pressure) or less.

Ethylene and α-olefin are supplied to the polymerization system in such an amount that the ethylene / α-olefin copolymer [A] having the above-mentioned specific composition can be obtained. A molecular weight modifier such as hydrogen may be used in the copolymerization.

By copolymerizing ethylene and α-olefin as described above, a polymerization solution containing an ethylene / α-olefin copolymer [A] is usually obtained. This polymerization liquid is treated by a conventional method to obtain an ethylene / α-olefin copolymer [A].

Ethylene / α-olefin copolymer [B] Ethylene / α-olefin copolymer used in the present invention
[B] is a copolymer of ethylene and at least one compound selected from the group consisting of α-olefins having 3 to 20 carbon atoms and cyclic olefin compounds.

Specific examples of the α-olefin include propene, 1-butene, 1-pentene, 1-hexene and 3-methyl-1.
-Butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-
Dimethyl-1-pentene, 4-ethyl-1-hexene 1-octene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-
Dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like can be mentioned. Of these, propene, 1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene are preferably used.

As the cyclic olefin, the following general formula (1
The cyclic olefin represented by 7) or (18) may be mentioned.

[0156]

[Chemical 15]

In the above general formula (17), n is 0 or 1, m is 0 or a positive integer, and k is 0 or 1. When k is 1, the ring represented by k is a 6-membered ring, and when k is 0, this ring is a 5-membered ring. R ^{1 to} R ¹⁸ and R ^a and R ^b are each independently a hydrogen atom, a halogen atom or a hydrocarbon group. Here, the halogen atom is a fluorine atom, a chlorine atom,
It is a bromine atom or an iodine atom.

Further, in the general formula (17), R ¹⁵
And R ¹⁶ , R ¹⁷ and R ¹⁸ , R ¹⁵ and R ¹⁷ , R ¹⁶ and R ¹⁸ , R ¹⁵ and R ¹⁸ , or R ¹⁶ and R ¹⁷ are bonded to each other. They (in cooperation with each other) may form a monocyclic or polycyclic group, and the monocyclic or polycyclic ring thus formed may have a double bond.

[0159]

[Chemical 16]

In the general formula (18), p and q
Are each independently 0 or a positive integer, and r and s are each independently 0, 1 or 2. Also, R
^{21 to} R ³⁹ are each independently a hydrogen atom, a halogen atom,
It is a hydrocarbon group or an alkoxy group.

Here, the halogen atom is represented by the above general formula (1
It is the same as the halogen atom in 7). Moreover, as a hydrocarbon group, a C1-C20 alkyl group, a C3-C15 cycloalkyl group, or an aromatic hydrocarbon group is usually mentioned. More specifically, the number of carbon atoms is 1-2.
Examples of the alkyl group of 0 include a methyl group, an ethyl group, a propyl group, an isopropyl group, an amyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group and an octadecyl group. These alkyl groups may be substituted with a halogen atom.

Examples of the cycloalkyl group include a cyclohexyl group, examples of the aromatic hydrocarbon group include an aryl group and an aralkyl group, and specific examples include a phenyl group, a tolyl group, a naphthyl group, a benzyl group, Examples thereof include a phenylethyl group.

Examples of the alkoxy group include a methoxy group, an ethoxy group and a propoxy group. Where R ²⁹
And the carbon atom to which R ³⁰ is bonded and the carbon atom to which R ³³ is bonded or the carbon atom to which R ³¹ is bonded,
They may be bonded directly or via an alkylene group having 1 to 3 carbon atoms. That is, when the above two carbon atoms are bonded via an alkylene group, R ²⁹ and R
³³ , or R ³⁰ and R ³¹ cooperate with each other to form a methylene group (-CH _2- ), an ethylene group (-CH ₂ CH _2- ) or a propylene group (-CH ₂ CH ₂ CH _2- ). Forming an alkylene group.

Further, when r = s = 0, R ³⁵ and R ³² or R ³⁵ and R ³⁹ may be bonded to each other to form a monocyclic or polycyclic aromatic ring. The above general formula (1
Specific examples of the cyclic olefin represented by 7) or (18) include bicyclo-2-heptene derivative (bicyclohept-2-ene derivative), tricyclo-3-decene derivative, tricyclo-3-undecene derivative, tetracyclo -3-
Dodecene derivative, pentacyclo-4-pentadecene derivative, pentacyclopentadecadiene derivative, pentacyclo-3-pentadecene derivative, pentacyclo-3-hexadecene derivative, pentacyclo-4-hexadecene derivative, hexacyclo-4-heptadecene derivative, heptacyclo-5-eicosene Derivatives, heptacyclo-4-eicosene derivatives, heptacyclo-5-heneicosene derivatives, octacyclo-5-
Docosene derivative, nonacyclo-5-pentacosene derivative,
Nonacyclo-6-hexacocene derivative, cyclopentadiene-acenaphthylene adduct, 1,4-methano-1,4,4a, 9a-tetrahydrofluorene derivative, 1,4-methano-1,4,4a, 5,10,1
Examples thereof include 0a-hexahydroanthracene derivatives.

Low Density Polyethylene [C] The low density polyethylene [C] used in the present invention is a copolymer of ethylene and at least one compound selected from α-olefins having 3 to 20 carbon atoms.

Specific examples of the α-olefin include propene, 1-butene, 1-pentene, 1-hexene and 3-methyl-1.
-Butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-
Dimethyl-1-pentene, 4-ethyl-1-hexene 1-octene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-
Dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like can be mentioned. Of these, propene, 1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene are preferably used.

(I) Ethylene / α-olefin copolymer
Density of [B] and low density polyethylene [C] Ethylene / α-olefin copolymer used in the present invention
The density of [B] is 0.860 to 0.900 g / cm ³ , preferably 0.865 to 0.895 g / cm ³ , and more preferably 0.8.
It is in the range of 870 to 0.890 g / cm ³ . The density of the low density polyethylene [C] used in the present invention is 0.91.
0 to 0.930 g / cm ³ , preferably 0.915 to 0.930
g / cm ³ , more preferably 0.915 to 0.925 g / cm ³
Is in the range. Ethylene / α-olefin copolymer [B]
When the density of the low-density polyethylene [C] is in such a range, a composition having an excellent balance between rigidity and impact resistance when blended with a resin such as polypropylene as a resin modifier is obtained. You can do it. (ii) Melt flow rate (MFR) of ethylene / α-olefin copolymer [B] and low-density polyethylene [C] Ethylene / α-olefin copolymer used in the present invention
[B] and low density polyethylene [C] at 190 ° C, 2.16
The melt flow rate under a load of kg is 0.3 to 50.
g / 10 minutes, preferably 0.5 to 20 g / 10 minutes.

The ethylene / α-olefin copolymer [B] used in the present invention is measured by the maximum peak position temperature and the density differential scanning calorimeter (DSC) in addition to the above (i) to (ii). The temperature at the maximum peak position (T
m) and the density (d) are Tm <400 × d-250, preferably Tm <450 × d-297, more preferably Tm <
500 × d-344, particularly preferably Tm <550 × d
-391, is satisfied.

Further, ethylene / α-used in the present invention
The olefin copolymer [B] has a melt tension (MT) at room temperature.
And the melt flow rate (MFR) measured at 190 ° C. under a load of 2.16 kg preferably satisfy the relationship of MT ≦ 2.2 × MFR ^−0.84 .

Further, ethylene / α used in the present invention
In the -olefin copolymer [B], the n-decane-soluble component amount fraction (W (wt%)) and the density at room temperature are (a) MFR ≤
At 10 g / 10 minutes, W <80 × exp (−100 (d−0.8
8)) + 0.1, preferably W <60 × exp (−100 (d−
0.88)) + 0.1, more preferably W <40 × exp (-1
00 (d−0.88)) + 0.1, and (b) MFR> 10 g / 10 min, W <80 × (MF
R-9) ^0.26 xexp (-100 (d-0.88)) + 0.1, more preferably satisfying the relationship.

Method for producing ethylene / α-olefin copolymer [B] Such an ethylene / α-olefin copolymer [B] is
Any of vanadium-based catalysts, metallocene-based catalysts and the like may be used without any particular limitation. For example, in the presence of the above-mentioned metallocene-based catalyst, ethylene and C3-20
It can be produced by copolymerizing at least one compound selected from the group consisting of α-olefins or cyclic olefins. Examples of the metallocene catalyst include the following compounds.

Bis (cyclopentadienyl) zirconium dichloride, bis (methylcyclopentadienyl) zirconium dichloride, bis (ethylcyclopentadienyl) zirconium dichloride, bis (n-propylcyclopentadienyl) zirconium dichloride, bis ( n-
Butylcyclopentadienyl) zirconium dichloride, bis (n-hexylcyclopentadienyl) zirconium dichloride, bis (methyl-n-propylcyclopentadienyl) zirconium dichloride, bis (methyl-n
-Butylcyclopentadienyl) zirconium dichloride, bis (dimethyl-n-butylcyclopentadienyl)
Zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dibromide, bis (n-butylcyclopentadienyl) zirconium methoxychloride,
Bis (n-butylcyclopentadienyl) zirconium ethoxy chloride, bis (n-butylcyclopentadienyl) zirconium butoxycyclolide, bis (n-butylcyclopentadienyl) zirconium ethoxide, bis (n-butylcyclopentadiene) (Enyl) zirconium methyl chloride, bis (n-butylcyclopentadienyl) zirconium dimethyl, bis (n-butylcyclopentadienyl) zirconium benzyl chloride, bis (n-butylcyclopentadienyl) zirconium dibenzyl, bis (n -Butylcyclopentadienyl) zirconium phenyl chloride, bis (n-butylcyclopentadienyl) zirconium hydride chloride, etc. In the above example, the disubstituted product of the cyclopentadienyl ring includes 1,2- and 1,3-substituted products. Further, in the present invention, in the zirconium compound as described above, a metallocene compound in which zirconium metal is replaced with titanium metal or hafnium metal can be used.

Method for producing low-density polyethylene [C] Such low-density polyethylene [C] can be obtained by a conventionally known production method. That is, the low density polyethylene [C] can be produced by copolymerizing ethylene with a small amount of α-olefin in the presence of a catalyst. Specific examples of the catalyst include (1) a titanium-based catalyst composed of a solid titanium catalyst component and an organoaluminum compound, (2) a vanadium-based catalyst composed of a soluble vanadium compound and an organoaluminum compound, and (3) Examples thereof include metallocene catalysts.

The ethylene / α-olefin copolymer composition of the present invention as described above is useful as a modifier of impact resistance and rigidity of a thermoplastic resin. Examples of such a thermoplastic resin include polyolefin, polyamide, polyester, polystyrene, polyvinyl chloride, polyvinyl alcohol, and the like. When modifying the polar group-containing thermoplastic resin, the ethylene / α-olefin copolymer composition of the present invention may be graft-modified with an unsaturated carboxylic acid.

Ethylene / α-olefin copolymer composition
Crosslinking method of the ethylene / α-olefin copolymer composition according to the present invention is a crosslinked product of the above-mentioned ethylene / α-olefin copolymer [A], ethylene / α-olefin copolymer [B] and low density. It is obtained by heat-treating a mixture of polyethylene [C] in the presence of the following organic peroxide to crosslink it.

Here, "heat-treating" means kneading in a molten state. Specific examples of the organic peroxide include dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane and 2,5- Dimethyl-2,5-di- (tert-butylperoxy) hexyne-3,1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) -3,3 , 5-trimethylcyclohexane, n-butyl-4,4-bis (tert-butylperoxy) valerate,
Benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide,
Examples thereof include tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, tert-butyl cumyl peroxide.

Such an organic peroxide is the total of the object to be treated, that is, the total of the ethylene / α-olefin copolymer [A], the ethylene / α-olefin copolymer [B] and the low density polyethylene [C]. It is used in an amount of 0.02 to 3 parts by weight, preferably 0.05 to 1 part by weight, based on 100 parts by weight.

In the present invention, in the crosslinking treatment with the above organic peroxide, sulfur, p-quinonedioxime, p,
p'-dibenzoylquinone dioxime, N-methyl-N,
Peroxy crosslinking aids such as N'-m-phenylene dimaleimide, or polyfunctional methacrylate monomers such as divinylbenzene, triallyl cyanurate, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, acrylic methacrylate, etc. A multifunctional vinyl monomer such as vinyl butyrate or vinyl stearate may be incorporated.

A uniform and mild crosslinking reaction can be expected by using a compound such as the above-mentioned crosslinking aid.
Such a crosslinking aid or a compound such as a polyfunctional vinyl monomer may be added to 100 parts by weight of the whole object to be treated.
It is usually used in an amount of 2 parts by weight or less, more preferably 0.3 to 1 part by weight.

Further, in order to accelerate the decomposition of the organic peroxide, triethylamine, tributylamine, 2,4,6
-A tertiary amine such as tri (dimethylamino) phenol, or a decomposition accelerator such as a naphthenate such as aluminum, cobalt, vanadium, copper, calcium, zirconium, manganese, magnesium, lead or mercury may be used.

The heat treatment in the present invention is preferably carried out in a non-open type apparatus, and is preferably carried out in an atmosphere of an inert gas such as nitrogen or carbon dioxide gas. The temperature is in the range of from the melting point of the ethylene-based copolymer [C] to 300 ° C, usually 150 to 250 ° C, preferably 170 ° C to
225 ° C. The kneading time is usually 1 to 20 minutes, preferably 1 to 10 minutes. Further, the shear force applied is, 10～100,000Sec ^-1 as the shear rate is preferably 100~50,000sec ^-1.

As the kneading device, a mixing roll, an intensive mixer (for example, Banbury mixer, kneader), a single-screw or twin-screw extruder and the like can be used.

According to the present invention, the ethylene / α-olefin copolymer [A], the ethylene / α-olefin copolymer [B] and the low density polyethylene are subjected to the heat treatment described above.
A crosslinked ethylene / α-olefin copolymer composition consisting of [C] is obtained.

According to the present invention, the cross-linked ethylene / α-olefin copolymer composition obtained by the above heat treatment has a melt flow rate of 0.3 to 30 g / 10 minutes at 190 ° C. and a load of 2.16 kg, Preferably 1.0-
It is in the range of 20g / 10 minutes.

Further, according to the present invention, the cross-linked ethylene / α-olefin copolymer composition obtained by the above heat treatment has a frequency ω ₁ when the melt viscosity (η ^* ) at 190 ° C. is measured. (= 0.0158ra
Melt viscosity (η ^{* 1} ) at d / sec) and frequency ω ₂ (= 398ra)
d / sec) melt viscosity (η ^{* 2} ) ratio: η ^{* 1} / η ^{* 2} is 4
Or more, preferably 6 or more.

Such a crosslinked ethylene of the present invention
The α-olefin copolymer composition is more useful than the ethylene / α-olefin copolymer composition as a modifier for impact resistance and rigidity of a thermoplastic resin. Examples of such a thermoplastic resin include polyolefin, polyamide, polyester, polystyrene, polyvinyl chloride, polyvinyl alcohol, and the like. When modifying the polar group-containing thermoplastic resin, the ethylene / α-olefin copolymer composition of the present invention may be graft-modified with an unsaturated carboxylic acid.

To modify a resin such as polypropylene using the ethylene / α-olefin copolymer composition and the crosslinked ethylene / α-olefin copolymer composition according to the present invention as a modifier, From the heat treatment of the ethylene / α-olefin copolymer composition and its crosslinked product, pellets are molded by extrusion molding or injection molding,
The pellets may be melt-blended with the resin to be modified.

When the ethylene / α-olefin copolymer composition and the crosslinked product thereof according to the present invention are used as a modifier, it is preferable to use an apparatus such as an extruder for continuously kneading and discharging. It is desirable to carry out the kneading at a temperature not lower than the melting point or softening point of the resin to be discharged and not higher than 400 ° C.

When the ethylene / α-olefin copolymer composition according to the present invention is used as a modifier, the impact resistance and the tensile elongation strength at low temperature are improved while maintaining the rigidity of the resin such as polypropylene resin. Can be quality.

Crosslinked ethylene / α-according to the present invention
When the olefin copolymer composition is used as a modifier, it is possible to further modify the impact resistance at low temperature and the tensile elongation strength of the polypropylene resin, as compared with the ethylene / α-olefin copolymer composition.

Resin Modification Method The resin modification method according to the present invention comprises melt-blending the pellet comprising the ethylene / α-olefin copolymer composition and the crosslinked product thereof with the resin to be modified. It has a feature. According to such a modification method, it is possible to obtain a resin composition having excellent balance between rigidity and strength at break / impact strength during blocking of the thermoplastic resin, without blocking. Therefore, such a modification method is excellent in productivity and operability of the modified thermoplastic resin.

Propylene-Based Polymer Composition The propylene-based polymer composition according to the present invention is a composition comprising a propylene-based polymer [D], the ethylene / α-olefin copolymer composition and a cross-linked product thereof. is there.

The content of the propylene polymer [D] in the propylene polymer composition is 98 to 60% by weight,
The content is preferably 95 to 65% by weight, and the ethylene / α-olefin copolymer composition and the crosslinked product thereof are 2 to 40% by weight.
%, Preferably 5 to 35% by weight.

Such a propylene polymer composition is
When the temperature dependence of the elastic modulus was measured and plotted every 3 ° C., the peak of the attenuation rate (tan δ) due to the glass transition temperature of the propylene polymer [D] and the ethylene / α-olefin copolymer composition It is preferable that there is a peak of attenuation rate (tan δ) due to the glass transition temperature of the compound and its crosslinked product, and both peaks are separated. In addition, the case where two peaks clearly appear, that is, the case where a saddle exists between the highest points of the two peaks is “separated”.
To determine. The propylene-based polymer composition having such two "separated" peaks has excellent impact resistance and rigidity.

When such two distinct peaks do not appear and the peaks are “fused”, impact resistance and rigidity of such a propylene polymer composition may deteriorate. .

As the propylene polymer [D], 23
MFR measured at 0 ° C, 2.16kg load is 0.01g / 10
Min or more, preferably 0.5 to 200 g / 10 min, more preferably 1 to 200 g / 10 min.

By using such a propylene-based polymer, a propylene-based polymer composition having an excellent balance of rigidity, elongation at break at tensile strength and / or low-temperature impact resistance and excellent fluidity can be obtained.

Propylene Polymer [D] The propylene polymer [D] is a homopolymer of propylene,
Or propylene and ethylene or 4 to 2 carbon atoms
It is a copolymer with 0 α-olefin. As the α-olefin having 4 to 20 carbon atoms, ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1
-Octene, 1-decene, 1-dodecene, 1-tetradecene, 1
-Hexadecene, 1-octadecene, 1-eicosene and the like. These α-olefins may be used alone or in combination of two or more. These α
-The olefin may form a random copolymer with propylene, or may form a block copolymer.

In the present invention, a propylene homopolymer, a crystalline propylene / ethylene block copolymer having an ethylene content of 2 to 40 mol%, and a crystalline propylene / ethylene random copolymer having an ethylene content of 0.5 to 10 mol%. Coalescence is preferred.

When the above-mentioned ethylene / α-olefin copolymer composition and its crosslinked product are used, especially MFR
When blended with a propylene-based polymer [D] of 4 g / 10 min or more, the above-mentioned ethylene / α-olefin copolymer composition maintains the rigidity of the polymer itself, especially at break strength and low temperature. It is possible to obtain a composition having a modified impact resistance. Further, the crosslinked ethylene / α-olefin copolymer composition makes it possible to obtain a composition in which the strength at break and the impact resistance at low temperature are further modified.

Further, such a propylene polymer [D]
Has a density of usually 0.885 to 0.910 g / cm ³ , preferably 0.890 to 0.910 g / cm ³ , and more preferably 0.89.
It is preferably in the range of 5 to 0.910 g / cm ³ .

Further, such a propylene polymer
The refractive index of [D] is usually 1.490 to 1.510, preferably 1.495 to 1.510, more preferably 1.500 to.
It is in the range of 1.510.

The propylene polymer [D] having such characteristics can be produced by various methods.
For example, a catalyst formed from a solid titanium catalyst component and an organometallic compound catalyst component, or a highly active titanium catalyst formed from both components and an electron donor, or a catalyst formed from a metallocene compound and an aluminoxane, or It can be produced using a catalyst obtained by mixing these catalysts. Further, when the propylene-based polymer [E] is a block copolymer, it can be produced by using a different catalyst selected from the above-mentioned catalysts for each stage in multi-stage polymerization.

Preparation of Propylene Polymer Composition As a method for preparing the olefin resin composition of the present invention,
The propylene-based polymer [D] and the ethylene / α-olefin copolymer composition and the cross-linked product thereof described above are conventionally known such as a mixing method using an internal mixer such as a Banbury mixer, a kneader or an intermix. It can be manufactured by kneading by a method.

In the preparation of the propylene polymer composition according to the present invention, within the range that does not impair the object of the present invention,
A styrene thermoplastic elastomer may be added. Examples of the styrene-based thermoplastic elastomer include a block copolymer of styrenes and a conjugated diene compound.

As the styrenes, styrene and α-
Methylstyrene, p-methylstyrene, pt-butylstyrene, alkyl styrene, p-methoxystyrene, vinylnaphthalene and combinations thereof.
Of these, styrene is preferred.

As the conjugated diene compound, butadiene,
Isoprene, piperylene, methylpentadiene, phenylbutadiene, 3,4-dimethyl-1,3-hexadiene, 4,5-
Examples include diethyl-1,3-octadiene and combinations thereof. Of these, butadiene and isoprene are preferable.

Specific examples of the styrene thermoplastic elastomer include styrene / butadiene diblock copolymer, styrene / butadiene / styrene triblock copolymer, styrene / isoprene diblock copolymer, and styrene / isoprene.・ Styrene triblock copolymer, styrene / butadiene diblock copolymer hydrogenated product, styrene / butadiene / styrene triblock copolymer hydrogenated product, styrene / isoprene diblock copolymer hydrogenated product, styrene Examples thereof include hydrogenated products of isoprene-styrene triblock copolymer.

In the present invention, the weight ratio of the structural unit derived from the styrene compound to the structural unit derived from the conjugated diene compound is 10/90 to 65/35, preferably 20/90.
It is desirable to use a styrene-based thermoplastic elastomer of 80 to 50/50.

The molecular structure of the styrene thermoplastic elastomer may be linear, branched, radial or a combination thereof. Further, in the present invention, in addition to the ethylene / α-olefin copolymer composition and the propylene-based polymer [D], a nucleating agent, an antioxidant,
Hydrochloric acid absorber, softener, light stabilizer, ultraviolet absorber, lubricant,
Anti-aging agent, processing aid, heat stabilizer, weathering stabilizer, antistatic agent, flame retardant, pigment, dye, dispersant, copper damage inhibitor, neutralizing agent, foaming agent, plasticizer, antifoaming agent, crosslinking Additives such as agents, flowability improvers such as peroxides, weld strength improvers, antifogging agents and the like can be added within a range that does not impair the object of the present invention. Further, a known inorganic filler such as talc or glass fiber may be blended. In this case, the inorganic filler is 1 part by weight with respect to 100 parts by weight of the propylene polymer composition.
It is preferably mixed in an amount of about 40 parts by weight.

The propylene polymer composition according to the present invention can be formed into a film, a sheet, or a film by a molding method such as extrusion molding, injection molding, inflation molding or calender molding.
It can be molded into various molded products such as pipes. The obtained molded product is also excellent in strain recovery and the like.

[0212]

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

The physical properties of each resin component were evaluated as follows. 1. Physical properties of ethylene / α-olefin copolymer [A] [Density] 190 ° C., the strand after MFR measurement under a load of 2.16 kg is heat-treated at 120 ° C. for 1 hour and gradually cooled to room temperature over 1 hour. It was measured by a density gradient tube method. [Α-olefin content, T _αβ / T _αα , B value] ¹³ C-
Determined by NMR spectrum. [Intrinsic viscosity [η]] Measured in decalin at 135 ° C. [Mw / Mn] GPC (gel permeation chromatography) with orthodichlorobenzene solvent,
It was measured at 140 ° C. [MFR ₁₀ / MFR ₂ ] MFR ₁₀ at a load of 10 kg at 190 ° C. according to ASTM D-1238 and 2.
The MFR ₂ under a load of 16 kg was measured and the ratio was calculated. When this ratio is large, it indicates that the fluidity of the polymer when melted is excellent, that is, the processability is high. [Glass transition temperature] Endothermic curve when the temperature is raised from room temperature to 200 ° C. at 30 ° C./minute, held for 5 minutes, lowered to −150 ° C. at 10 ° C./minute, and then raised to 10 ° C./minute. I asked from. [Crystallinity] The amount of heat of fusion per unit weight was determined from the endothermic peak during DSC measurement, and this was divided by the amount of heat of fusion of polyethylene crystals of 70 cal / g.

2. Ethylene / α-olefin copolymer
[B], low density polyethylene [C] and propylene polymer
Physical properties of [D] [Density] MFR measurement at 190 ℃, 2.16kg load
Heat the subsequent strands at 120 ° C for 1 hour and
Measured by the density gradient tube method after slowly cooling to room temperature
did. [Α-olefin content]¹³According to the C-NMR spectrum
Decided. [Melt tension (MT)] The molten polymer is stretched at a constant speed.
It is determined by measuring the stress when stretched. Heavy
Toyo Seiki Seisakusho Co., Ltd.
Manufactured by using MT measuring device, resin temperature 190 ° C, extrusion speed 1
5 mm / min, winding speed 10-20 m / min, nozzle diameter
The measurement was performed under the conditions of 2.09 mmφ and a nozzle length of 8 mm. [MFR] According to ASTM D-1238, the specified temperature
MFR at 2.16kg load in degrees ₂Was measured. [Softening point (Tm)] Obtain the endothermic curve of DSC and determine the maximum peak
The temperature at the black position is Tm. For measurement, sample the aluminum pan
The temperature at 200 ° C at 10 ° C / min.
After holding for 5 minutes, cool down to room temperature at 20 ° C / minute, and
It was determined from the endothermic curve when the temperature was raised at 10 ° C./min.

3. Crosslinked ethylene / α-olefin
Physical properties of copolymer composition [MFR] According to ASTM D-1238, the specified temperature
MFR at 2.16kg load in degrees ₂Was measured. [Melt viscosity] An RDS apparatus was used. The measurement conditions are 190 ℃,
Frequency is 0.0158-398 rad / sec at 10% strain
Melt viscosity (η^*) Was measured. Low lap
Wave number (ω₁= 0.0158 rad / sec) melt viscosity: η^{* 1}
And high frequency (ω₂= 398 rad / sec) melt viscosity: η^{* 2}
Ratio of (η^{* 1}/ Η^{* 2}) Was calculated.

Production Example 1 845 ml of hexane was inserted at 23 ° C. into a SUS autoclave equipped with a stirrer and having a capacity of 2 liters, which had been sufficiently replaced with nitrogen. 120 ml of 1-butene was inserted into this autoclave while rotating a stirrer and cooling with ice water. Next, the autoclave is heated to an internal temperature of 100 ° C.,
Furthermore, it was pressurized with ethylene so that the total pressure would be 8 kg / cm ² . When the internal pressure of the autoclave reached 8 kg / cm ² , 1.0 of triisobutylaluminum (TIBA) was added.
The mM / ml decane solution was pressed with 1.0 ml nitrogen. Next, the previously prepared methylaluminoxane was added to A
0.3 mM in terms of l, rac-dimethylsilylene-bis [1- (2-
Methyl-4-phenyl-indenyl)] zirconium dichloride in an amount of 0.001 mM A toluene solution of 0.3 ml was introduced into the autoclave with nitrogen to initiate polymerization.

Then, for 30 minutes, the internal temperature of the autoclave is adjusted to 6
The temperature was adjusted to 0 ° C., and ethylene was directly supplied so that the pressure became 8 kg. After 30 minutes from the start of polymerization, 5 ml of methanol was inserted into the autoclave by a pump to stop the polymerization, and the autoclave was depressurized to atmospheric pressure. 2 l of acetone was poured into the reaction solution while stirring.

1 part of the rubber-ball-shaped polymer containing the obtained solvent was added.
When dried at 30 ° C. for 13 hours at 600 torr, an ethylene / 1-butene copolymer 54 containing 34 mol of 1-butene was obtained.
g was obtained.

The resulting ethylene / 1-butene copolymer (A-
Table 1 shows the basic characteristics of 1). The composition of the copolymer is
As shown in (Table-1), the types of monomers,
In the same manner except that the charged amount was changed, ethylene / α-olefin copolymers (A-2) to (A-4), ethylene / α-olefin copolymers (B-1) to (B-2 ), And ethylene-based polymers
(C-1) to (C-2) were obtained. The resulting copolymer (A-2) ~ (A-4),
The basic characteristics of (B-1) to (B-2) and (C-1) to (C-2) are shown in (Table-
It is shown in 1).

[0220]

[Table 1]

Example 1 70% by weight of ethylene / 1-butene copolymer (A-1), 10% by weight of ethylene / 1-butene copolymer (B-1), 20 low density polyethylene (C-1) Single screw extruder (thermo 20m
mφ) was melt-kneaded at 200 ° C. and pelletized to obtain an ethylene copolymer composition (E).

A pellet blocking test was performed on the obtained pellets of the ethylene copolymer composition (E) to evaluate the blocking property. The results are shown in (Table-2). [Pellet blocking test] Pellets were placed in a polyethylene bag and placed in an oven set at 35 ° C for 10
After standing for 72 hours under a load of 0 g / cm ² , the blocking state of the taken-out pellets was evaluated as follows.

[0223] ◎: Almost no blocking ○: Can be easily loosened by hand △: Can be pressed and loosened by hand ×: Pellets are fused and become veil-like

Example 2 70% by weight of ethylene / 1-butene copolymer (A-1), 10% by weight of ethylene / 1-butene copolymer (B-1) and 20% by weight of low density polyethylene (C-1) % Organic peroxide (2,5-dimethyl-2,5-di- (tert-butylperoxy) hexyne-
3) Add 0.1 parts by weight of uniaxial extruder (thermo 20 mm
φ) was melt-kneaded at 200 ° C. and pelletized to obtain an ethylene copolymer composition (F). A pellet blocking test was conducted in the same manner as in Example 1. Pellet blocking was less likely to occur and workability was better than that of the ethylene-based copolymer composition (E).

Examples 3 to 6 A pellet blocking test was conducted in the same manner as in Example 1 with the formulations shown in Table 2 below. In all cases, pellet blocking was unlikely to occur and workability was good. The results are shown in (Table-2).

Comparative Examples 1 to 4 A pellet blocking test was conducted in the same manner as in Example 1 with the formulations shown in Table 2 below. Except for Examples 1 to 6,
Workability was poor. The results are shown in (Table-2).

[0227]

[Table 2]

Example 7 Obtained ethylene / α-olefin copolymer composition (E)
To 30% by weight, homopolymer made by Grand Polymer Co., Ltd. [brand name: Grand Polypro ^™ J139, M
FR = 55 g / 10 min (230 ° C.)] (D) 70% by weight, as stabilizers calcium stearate 0.1% by weight, Irganox 1010 0.1% by weight, Irganox 168
0.1% by weight was added, and the mixture was melt-kneaded at 200 ° C. using a twin-screw extruder and pelletized by a pelletizer. The obtained pellets were injection molded at 230 ° C. using an injection molding machine, and the breaking strength, flexural modulus, impact strength, and viscoelasticity were measured by the evaluation methods shown below. The results (Table-3)
Shown in.

[Strength at Break (TS)] ASTM D 6
According to No. 38, the measurement was performed at room temperature. [Flexural Modulus (FM)] According to ASTM D 790, a 2 mm-thick test piece injection-molded under predetermined conditions was used and measured under conditions of a span of 32 mm and a bending speed of 5 m / min. [Impact strength (IZ)] According to ASTM D 256, using a test piece (rear notch) having a thickness of 3 mm, -30 ° C
It was measured at. [Viscoelasticity] 1 using RDSII made by Rheometrics
The temperature dependence of the dynamic viscoelasticity was measured at a frequency of 0 rad / sec from −80 to 50 ° C., and the peak of the attenuation rate (tan δ) due to the glass transition temperature of the polypropylene polymer [D] and the ethylene -It was judged whether the peak of the attenuation rate (tan δ) due to the glass transition temperature of the crosslinked product of the α-olefin copolymer composition [E] was separated or fused.

Example 8 Crosslinked ethylene / α-olefin copolymer composition
A molded body was produced in the same manner as in Example 7 except that (F) was used, and the same evaluation as in Example 7 was performed. The results (Table-
3).

Example 9 Cross-linked ethylene / α- with different contents of α-olefin
A molded article was produced in the same manner as in Example 7 except that the olefin copolymer composition (G) was used, and the same evaluation as in Example 7 was performed. The results are shown in (Table 3).

Example 10 Cross-linked ethylene / α- with different contents of α-olefin
A molded product was produced in the same manner as in Example 7 except that the olefin copolymer composition (H) was used, and the same evaluation as in Example 7 was performed. The results are shown in (Table 3).

Example 11 Crosslinked ethylene / α-olefins having different contents of α-olefin
A molded product was produced in the same manner as in Example 7 except that the olefin copolymer composition (I) was used, and the same evaluation as in Example 7 was performed. The results are shown in (Table 3).

Example 12 Cross-linked ethylene / α- with different contents of α-olefin
A molded product was produced in the same manner as in Example 7 except that the olefin copolymer composition (J) was used, and the same evaluation as in Example 7 was performed. The results are shown in (Table 3).

Comparative Example 5 A molded article was prepared in the same manner as in Example 7 except that the crosslinked ethylene / α-olefin copolymer composition (K) having a different content of α-olefin was used. The same evaluation as in 7 was performed. The results are shown in (Table 3).

Comparative Example 6 A molded article was prepared in the same manner as in Example 7 except that the ethylene / α-olefin copolymer composition (L) was used, and the same evaluation as in Example 7 was performed. The results are shown in (Table 3).

Comparative Example 7 Cross-linked ethylene / α- with different contents of α-olefin
A molded product was produced in the same manner as in Example 7 except that the olefin copolymer composition (M) was used, and the same evaluation as in Example 7 was performed. The results are shown in (Table 3).

Comparative Example 8 A molded product was produced in the same manner as in Example 7 except that the ethylene / α-olefin copolymer composition (N) was used, and the same evaluation as in Example 7 was performed. The results are shown in (Table 3).

[0239]

[Table 3] As is clear from (Table 3), the propylene-based polymer compositions obtained in Examples 7 to 12 were
The balance of strength at break, flexural modulus and impact resistance was excellent.

The ethylene / α-olefin copolymer composition of the present invention comprises a specific ethylene / α-olefin copolymer and a specific ethylene-based copolymer, so that it is possible to use a thermoplastic resin, particularly polypropylene. When it is used as a modifier, it is possible to improve the balance between the rigidity of the resin and the strength at break / impact strength, and since it does not cause blocking during modification, it has good workability. Further cross-linked ethylene / α-olefin copolymer composition, than the above ethylene / α-olefin copolymer composition,
It is possible to improve the balance between the rigidity, strength at break, and impact resistance of polypropylene.

In the method for modifying a resin according to the present invention, since the ethylene / α-olefin copolymer composition and the cross-linked product thereof as described above are used as a modifier, when modifying the thermoplastic resin, Blocking is less likely to occur,
Excellent operability and productivity of modified thermoplastic resin.

Since the propylene-based polymer composition of the present invention contains the specific ethylene / α-olefin copolymer and the specific ethylene-based copolymer, the rigidity of the resin and the strength at break / impact resistance Excellent strength balance.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4F071 AA15X AA18 AA20 AA21X                       AA82 AA86 AA87 AA88 AA89                       AF15 AF20 AF23 AH04 AH19                       BA01 BB05 BB06 BB09 BC01                       BC05                 4J002 BB05W BB05X BB05Y BB052                       BB10W BB10X BB10Y BB121                       BB141 BB202 FD010 GG02                       GL00

Claims (12)

[Claims] 1. [A] ethylene and α having 4 to 20 carbon atoms
-A copolymer with an olefin, wherein the content of the structural unit (a) derived from ethylene (i) is 60 to 80 mol% and the structural unit derived from an α-olefin having 4 to 20 carbon atoms (b )
Content of 20-40 mol%, and (ii) density of 0.86
3 g / cm ³ or less, (iii) the intrinsic viscosity [η] measured in decalin at 135 ° C. is 0.1 to 10.0 dl / g, and (i)
v) A glass transition temperature of at -60 ° C. or less as measured by a differential scanning calorimeter (DSC), crystallinity of 10% or less, the T _.alpha..beta for T _{alpha alpha} in (v) ¹³ C-NMR spectrum The intensity ratio (T _αβ / T _αα ) is 0.5 or less, and (vi) ¹³ C-NMR spectrum and the following general formula (1): (In the formula, [P _E ] is the content mole fraction of the structural unit derived from ethylene in the copolymer, and [P _O ] is the content of the structural unit derived from α-olefin in the copolymer. Is the mole fraction, [P _OE ] is the total dyad in the copolymer
It is the ratio of the number of ethylene / α-olefin chains to the chain. ), An ethylene / α-olefin copolymer 30 to 80 satisfying the relationship that the B value is 0.9 to 1.5
% By weight, [B] (a ') ethylene, and (b') carbon number 3-20
A copolymer with at least one compound selected from the group consisting of α-olefins and cyclic olefin compounds, wherein (i) the density is in the range of 0.860 to 0.900 g / cm ³ , ) The melt flow rate at 190 ° C. under a load of 2.16 kg is in the range of 0.3 to 50 g / 10 minutes, and (iv)
The temperature (Tm) and the density (d) at the maximum peak position in the endothermic curve measured by a differential scanning calorimeter (DSC) are
1 to 69% by weight of an ethylene / α-olefin copolymer satisfying the relationship represented by Tm <400 × d-250,
[C] (i) Density is in the range of 0.910 to 0.930 g / cm ³ , (ii) Melt flow rate at 190 ° C. and 2.16 kg load is in the range of 0.3 to 50 g / 10 minutes. An ethylene / α-olefin copolymer composition comprising 1 to 69% by weight of low-density polyethylene. 2. The density Da of the ethylene / α-olefin copolymer [A] and the density Db of the ethylene / α-olefin copolymer [B] described in the preceding paragraph are characterized by the relationship of Da <Db. An ethylene / α-olefin copolymer composition. 3. The ethylene / α- according to claim 1 or 2.
A resin modifier comprising an olefin copolymer composition. 4. The ethylene / α-olefin copolymer composition according to claim 1, which is obtained by a crosslinking treatment. 5. (i) at 190 ° C. and under a load of 2.16 kg
Melt flow rate is in the range of 0.3 to 30 g / 10 min.
(Ii) melt viscosity at 190 ° C (η^*) Frequency dependence
Low frequency (ω1 = 0.158 rad /
sec) Melt viscosity η^{* 1}And high frequency (ω₂= 398rad / se
Melt viscosity η in c)^{* 2}Ratio (η^{* 1}/ η ^{* 2}) Is 4 or more
Crosslinked ethylene according to claim 4, characterized in that
-Α-olefin copolymer composition. 6. A resin modifier comprising the crosslinked ethylene / α-olefin copolymer composition according to claim 4 or 5. 7. A composition comprising a propylene polymer [D], the ethylene / α-olefin copolymer [A], an ethylene / α-olefin copolymer [B] and a low density polyethylene [C]. The content of (i) propylene polymer [D] is 9
8-60% by weight, ethylene / α-olefin copolymer
Content of [A], ethylene / α-olefin copolymer [B] and low density polyethylene [C] ([A], [B] and [C]
The total) is from 2 to 40% by weight, the propylene-based polymer composition. 8. A propylene-based polymer [D] at 230 ° C.,
Melt flow rate (MFR) under 2.16 kg load
Is 0.01 g / 10 minutes or more.
The propylene-based polymer composition described in 1. 9. When the temperature dependence of the elastic modulus is measured, the peak of the attenuation rate due to the glass transition temperature of the propylene-based polymer [D] and the ethylene / α-olefin copolymer composition (ethylene / α-olefin copolymer a composition of α-olefin copolymer [A], ethylene / α-olefin copolymer [B], and low-density polyethylene [C]), and a peak of the attenuation factor due to the glass transition temperature, and The propylene-based polymer composition according to claim 7 or 8, wherein peaks are separated. 10. A propylene-based polymer [D] and the crosslinked ethylene / α-olefin copolymer (ethylene / α-
A cross-linked ethylene / α-olefin copolymer composition comprising an olefin copolymer [A], an ethylene / α-olefin copolymer [B] and a low density polyethylene [C], Content of propylene-based polymer [D] is 98
A propylene-based polymer composition, wherein the content of the crosslinked ethylene / α-olefin copolymer composition is 2 to 40% by weight. 11. When the temperature dependence of the elastic modulus is measured,
There is a peak of decay rate due to the glass transition temperature of the propylene-based polymer [D] and a peak of decay rate due to the glass transition temperature of the crosslinked ethylene / α-olefin copolymer composition, Moreover, both peaks are separated, The propylene polymer composition according to claim 8 or 10. 12. A molded article made of the propylene-based polymer composition according to claim 7.